Patent Grant
10938032
The present disclosure is directed to carbon-based energy storage devices and methods of manufacture of the same. The worldwide market for electronics such as power tools, smartphones, grid stabilization devices, electric vehicles, and laptops is continually growing and evolving. Many such devices rely upon energy storage devices for portability and rechargeability. However, such electrical devices are currently limited by existing batteries and capacitors with low energy densities and power densities, short life cycles, and high recharge times.
The present disclosure discloses a fast-charging hybrid battery to replace lithium-ion batteries in portable electronics and electric vehicles. The battery can be referred to as a M2+/M3+ hybrid battery. Hybrid batteries consistent with the present disclosure can deliver more than 250 watt hours per kilogram of energy, which is comparable with or superior to state-of-the-art lithium-ion batteries, yet they can be recharged in just a few minutes compared with the hours required for recharging lithium-ion batteries. Provided herein are fast-charging energy devices capable of replacing lithium-ion batteries in portable electronics and electric vehicles.
One aspect provided herein is an energy storage device comprising: a first electrode comprising: a graphene sheet; a layered double hydroxide coupled to the graphene sheet; a binder; a conductive additive; and a first current collector; a second electrode comprising a hydroxide, and a second current collector; a separator; and an electrolyte. In some embodiments, a percentage by mass or volume of the graphene sheet in the first electrode is at most about 5%. In some embodiments, the graphene sheet comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the graphene sheet comprises a nanosheet, a microsheet, a platelet, or any combination thereof. In some embodiments, the layered double hydroxide comprises a metallic layered double hydroxide comprising an aluminum-based layered double hydroxide, a barium-based layered double hydroxide, a bismuth-based layered double hydroxide, a cadmium-based layered double hydroxide, calcium-based layered double hydroxide, a chromium-based layered double hydroxide, cobalt-based layered double hydroxide, a copper-based layered double hydroxide, an indium-based layered double hydroxide, an iron-based layered double hydroxide, a lead-based layered double hydroxide, a manganese-based layered double hydroxide, a mercury-based layered double hydroxide, a nickel-based layered double hydroxide, a strontium-based layered double hydroxide, a tin-based layered double hydroxide, a zinc-based layered double hydroxide, or any combination thereof. In some embodiments, the layered double hydroxide comprises an M2+ metal cation, an M3+ metal cation, a hydroxide ion, an octahedral site with a trivalent metal cation, an octahedral site with a divalent metal cation, a water molecule, an anion, or any combination thereof. In some embodiments, the M2+ metal cation comprises barium, cadmium, calcium, cobalt, copper (II), iron (II), lead (II), magnesium, mercury (I), mercury (II), nickel, strontium, tin, zinc, or any combination thereof. In some embodiments, the M3+ metal cation comprises aluminum, bismuth, chromium (III), iron (III), or any combination thereof. In some embodiments, the anion comprises nitrate, sulfate, carbonate, chloride, bromide, or any combination thereof. In some embodiments, the binder comprises a polymeric binder. In some embodiments, the polymeric binder comprises polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), polyethylene glycol (PEG), alginic acid (ALG or sodium alginate), polypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene) (PEDOT), a sulfonated tetrafluoroethylene based fluoropolymer-copolymer (Nafion®), polytetrafluoroethylene (Teflon®), polydopamine (PD), polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN), carbonyl β-cyclodextrin (C—B—CD), or any combination thereof. In some embodiments, the conductive additive comprises a zero-dimensional carbon additive, a one-dimensional carbon additive, a two-dimensional carbon additive, a three-dimensional carbon additive, or any combination thereof. In some embodiments, the zero-dimensional carbon additive comprises carbon black, acetylene black, or both. In some embodiments, the one-dimensional carbon additive comprises a carbon fiber, an activated carbon fiber, a carbon nanotube, an activated carbon nanotube, a carbon nanoplatelet, an activated carbon nanoplatelet, a carbon nanoribbon, an activated carbon nanoribbon, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a nanosheet, a microsheet, a platelet, or any combination thereof. In some embodiments, the three-dimensional carbon additive comprises graphite, carbon foam, activated carbon, graphene foam, carbon aerogel, graphene aerogel, porous carbon, a buckminsterfullerene, an interconnected corrugated carbon-based network, or any combination thereof. In some embodiments, the energy storage device stores energy through both oxidation-reduction (redox) reactions and ion adsorption. In some embodiments, at least one of the first current collector and the second current collector comprises a foam, a foil, a mesh, an aerogel, or any combination thereof. In some embodiments, at least one of the first current collector and the second current collector comprises a copper-based current collector, a nickel-based current collector, a zinc-based current collector, a graphite-based current collector, a stainless steel-based current collector, a brass-based current collector, a bronze-based current collector, or any combination thereof. In some embodiments, a concentration by mass, by volume, or both of the graphene sheet in the first electrode is about 0.1% to about 10%. In some embodiments, a concentration by mass, by volume, or both of the layered double hydroxide in the first electrode is about 1% to about 80%. In some embodiments, a concentration by mass, by volume, or both of the binder in the first electrode is about 1% to about 20%. In some embodiments, a concentration by mass, by volume, or both of the conductive additive in the first electrode is about 1% to about 30%. In some embodiments, the separator comprises a membrane separator, a cellulose separator, an organic polymeric separator, an inorganic polymer separator, a microporous separator, a woven separator, a non-woven separator, or any combination thereof. In some embodiments, the separator has a thickness of about 10 μm to about 30 μm. In some embodiments, the electrolyte comprises: a hydroxide; an additive; a stabilizer; a hydrogen evolution inhibitor; and a conductivity enhancer. In some embodiments, the electrolyte comprises: a hydroxide; an additive; a stabilizer; a hydrogen evolution inhibitor; a conductivity enhancer, or any combination thereof. In some embodiments, the hydroxide ion comprises aluminum hydroxide, barium hydroxide, benzyltrimethylammonium hydroxide, beryllium hydroxide, cadmium hydroxide, cesium hydroxide, calcium hydroxide, cerium(III) hydroxide, chromium acetate hydroxide, chromium(III) hydroxide, cobalt(II) hydroxide, cobalt(III) hydroxide, copper(I) hydroxide, copper(II) hydroxide, curium hydroxide, gallium(III) hydroxide, germanium(II) hydroxide, gold(III) hydroxide, indium(III) hydroxide, iron(II) hydroxide, iron(III) oxide-hydroxide, lanthanum hydroxide, lead(II) hydroxide, lead(IV) hydroxide, lithium hydroxide, magnesium hydroxide, manganese(II) hydroxide, mercury(II) hydroxide, metal hydroxide, nickel(II) hydroxide, potassium hydroxide, rubidium hydroxide, sodium hydroxide, strontium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, thallium hydroxide, thallium(I) hydroxide, thallium(III) hydroxide, tin(II) hydroxide, uranyl hydroxide, zinc hydroxide, zirconium(IV) hydroxide, or any combination thereof. In some embodiments, the additive comprises calcium hydroxide, calcium titanate, calcium zincate, potassium fluoride, sodium phosphate tribasic, potassium phosphate, sodium fluoride, potassium borate, potassium carbonate, or any combination thereof. In some embodiments, the stabilizer comprises zinc oxide, zinc hydroxide, sodium zincate, potassium zincate, bismuth oxide, cadmium oxide, indium sulfate, lead oxide, a metallic zinc powder, or any combination thereof. In some embodiments, the hydrogen evolution inhibitor comprises bismuth oxide, cadmium oxide, a conductive ceramic, lead oxide, a metallic zinc powder antimony sulfate, gallium hydroxide, indium sulfate, lithium hydroxide, or any combination thereof. In some embodiments, the conductivity enhancer comprises a conductive ceramic. In some embodiments, the conductive ceramic comprises a dielectric ceramic, a piezoelectric ceramic, or a ferroelectric ceramic. In some embodiments, the conductive ceramic comprises lead zirconate titanate (PZT), barium titanate(BT), strontium titanate (ST), calcium titanate (CT), magnesium titanate (MT), calcium magnesium titanate (CMT), zinc titanate (ZT), lanthanum titanate (LT), and neodymium titanate (NT), barium zirconate (BZ), calcium zirconate (CZ), lead magnesium niobate (PMN), lead zinc niobate (PZN), lithium niobate (LN), barium stannate (BS), calcium stannate (CS), magnesium aluminium silicate, magnesium silicate, barium tantalate, titanium dioxide, niobium oxide, zirconia, quartz, silica, sapphire, beryllium oxide, zirconium tin titanate, Indium tin oxide (ITO), lanthanum-doped strontium titanate (SLT), yttrium-doped strontium titanate (SYT), yttria-stabilized zirconia (YSZ), gadolinium-doped ceria (GDC), lanthanum strontium gallate magnesite (LSGM), or any combination thereof. In some embodiments, a concentration by mass, by volume, or both by mass of the hydroxide within the electrolyte is about 22% to about 91%. In some embodiments, a concentration by mass, by volume, or both by mass of the additive within the electrolyte is about 5% to about 16%. In some embodiments, a concentration by mass, by volume, or both by mass of the stabilizer within the electrolyte is about 1% to about 5%. In some embodiments, a concentration by mass, by volume, or both by mass of the hydrogen evolution inhibitor within the electrolyte is about 1% to about 5%. In some embodiments, a concentration by mass, by volume, or both by mass of the conductivity enhancer within the electrolyte is about 1% to about 5%. In some embodiments, a concentration by volume of the hydroxide within the electrolyte is about 220 g/L to about 900 g/L. In some embodiments, a concentration by volume of the additive within the electrolyte is about 30 g/L to about 160 g/L. In some embodiments, a concentration by volume of the stabilizer within the electrolyte is about 10 g/L to about 40 g/L. In some embodiments, the energy storage device has a gravimetric energy density of about 200 Wh/kg to about 800 Wh/kg. In some embodiments, the energy storage device has a volumetric energy density of about 400 Wh/L to about 1,600 Wh/L. In some embodiments, the energy storage device has a gravimetric power density of about 2.5 kW/kg to about 12 kW/kg. In some embodiments, the energy storage device has an internal resistance of about 1 mOhm to about 60 mOhm. In some embodiments, the energy storage device has a charge capacity percentage after about 10 minutes of about 23% to about 90%. In some embodiments, the energy storage device has a charge capacity of about 45 mAh to about 5,000 mAh.
Another aspect provided herein is a method of forming an electrode comprising: forming a first dispersion comprising a three-dimensional carbon additive, a first precursor to trivalent ions, a precursor to divalent ions, and a first solvent; forming a second dispersion comprising a second solvent and a conductive additive comprising a zero-dimensional carbon additive, a one-dimensional carbon additive, a two-dimensional carbon additive, a three-dimensional carbon additive, or any combination thereof; adding the second dispersion to the first dispersion to form a third dispersion; adding a reducing agent to the third dispersion; heating the third dispersion; cooling the third dispersion; centrifuging the third dispersion with a third solvent; drying the third dispersion; and depositing the dried third dispersion and a binder onto a current collector. In some embodiments, the three-dimensional carbon additive comprises graphite, carbon foam, activated carbon, graphene foam, carbon aerogel, graphene aerogel, porous carbon, an interconnected corrugated carbon-based network, or any combination thereof. In some embodiments, the zero-dimensional carbon additive comprises carbon black, acetylene black, or both. In some embodiments, the one-dimensional carbon additive comprises a carbon fiber, an activated carbon fiber, a carbon nanotube, an activated carbon nanotube, a carbon nanoplatelet, an activated carbon nanoplatelet, a carbon nanoribbon, an activated carbon nanoribbon, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a nanosheet, a microsheet, a platelet, or any combination thereof. In some embodiments, the first precursor to trivalent ions comprises a metal salt. In some embodiments, the first precursor to trivalent ions comprises aluminum nitrate, aluminum acetate, aluminum chloride, aluminum sulfate, aluminum carbonate, aluminum bromide, bismuth nitrate, bismuth acetate, bismuth chloride, bismuth sulfate, bismuth carbonate, bismuth bromide, chromium nitrate, chromium acetate, chromium chloride, chromium sulfate, chromium carbonate, chromium bromide, iron nitrate, iron acetate, iron chloride, iron sulfate, iron carbonate, iron bromide, or any combination thereof. In some embodiments, the first precursor to trivalent ions comprises a powder, a liquid, a paste, a gel, a dispersion, or any combination thereof. In some embodiments, the precursor to divalent ions comprises a metal salt. In some embodiments, the precursor to divalent ions comprises zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride, zinc bromide, barium nitrate, barium sulfate, barium carbonate, barium chloride, barium bromide, cadmium nitrate, cadmium sulfate, cadmium carbonate, cadmium chloride, cadmium bromide, calcium nitrate, calcium sulfate, calcium carbonate, calcium chloride, calcium bromide, cobalt nitrate, cobalt sulfate, cobalt carbonate, cobalt chloride, cobalt bromide, copper nitrate, copper sulfate, copper carbonate, copper chloride, copper bromide, iron nitrate, iron sulfate, iron carbonate, iron chloride, iron bromide, lead nitrate, lead sulfate, lead carbonate, lead chloride, lead bromide, magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium chloride, magnesium bromide, mercury nitrate, mercury sulfate, mercury carbonate, mercury chloride, mercury bromide, nickel nitrate, nickel sulfate, nickel carbonate, nickel chloride, nickel bromide, strontium nitrate, strontium sulfate, strontium carbonate, strontium chloride, strontium bromide, tin nitrate, tin sulfate, tin carbonate, tin chloride, tin bromide, or any combination thereof. In some embodiments, the reducing agent comprises urea, or any combination thereof. In some embodiments, the binder comprises a polymeric binder. In some embodiments, the polymeric binder comprises polyvinylidene fluoride, carboxymethyl cellulose, polyacrylic acid, polyethylene glycol, alginic acid, polypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene), a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer (Nafion®), polytetrafluoroethylene (Teflon®), polydopamine, polyvinylpyrrolidone, polyacrylonitrile, carbonyl β-cyclodextrin, or any combination thereof. In some embodiments, the current collector comprises a foam, a foil, a mesh, an aerogel, or any combination thereof. In some embodiments, the current collector comprises a copper-based current collector, a nickel-based current collector, a zinc-based current collector, a graphite-based current collector, a stainless steel-based current collector, a brass-based current collector, a bronze-based current collector, or any combination thereof. In some embodiments, a concentration by mass of the three-dimensional carbon additive within the first dispersion is about 1% to about 5%. In some embodiments, a concentration by mass of the first precursor to trivalent ions within the first dispersion is about 2% to about 8%. In some embodiments, a concentration by mass of the precursor to divalent ions within the first dispersion is about 5% to about 20%. In some embodiments, a concentration by mass of the conductive additive within the second dispersion is about 1% to about 5%. In some embodiments, a concentration by mass of the reducing agent within the third dispersion is about 4% to about 14%. In some embodiments, a concentration by mass of the three-dimensional carbon additive within the third dispersion is about 1% to about 5%. In some embodiments, a concentration by mass of the first precursor to trivalent ions within the third dispersion is about 5% to about 20%. In some embodiments, a concentration by mass of the precursor to divalent ions within the third dispersion is about 12% to about 48%. In some embodiments, a concentration by mass of the conductive additive within the third dispersion is about 1% to about 5%. In some embodiments, a concentration by mass of the reducing agent within the third dispersion is about 9% to about 36%. In some embodiments, a concentration by mass of the binder within the electrode is about 1% to about 50%. In some embodiments, the first solvent comprises water, N-methyl-2-pyrrolidone, acetone, ethanol, isopropanol, or any combination thereof. In some embodiments, the second solvent comprises water, N-methyl-2-pyrrolidone, acetone, ethanol, isopropanol, or any combination thereof. In some embodiments, the third solvent comprises water, N-methyl-2-pyrrolidone, acetone, ethanol, isopropanol, or any combination thereof. In some embodiments, the first dispersion further comprises a second precursor to trivalent ions. In some embodiments, the second precursor to trivalent ions comprises a metal salt. In some embodiments, the second precursor to trivalent ions comprises aluminum nitrate, aluminum acetate, aluminum chloride, aluminum sulfate, aluminum carbonate, aluminum bromide, bismuth nitrate, bismuth acetate, bismuth chloride, bismuth sulfate, bismuth carbonate, bismuth bromide, chromium nitrate, chromium acetate, chromium chloride, chromium sulfate, chromium carbonate, chromium bromide, iron nitrate, iron acetate, iron chloride, iron sulfate, iron carbonate, iron bromide, or any combination thereof. In some embodiments, a concentration by mass of the second precursor to trivalent ions within the third dispersion is about 4% to about 16%. In some embodiments, forming the first dispersion occurs in a vessel that is at least partially enclosed. In some embodiments, forming the first dispersion comprises: mixing the three-dimensional carbon additive and the first solvent; mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent; and mixing the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive, and the first solvent. In some embodiments, mixing the three-dimensional carbon additive and the first solvent occurs over a period of time of about 5 minutes to about 20 minutes. In some embodiments, mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent occurs over a period of time of about 5 minutes to about 20 minutes. In some embodiments, mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent comprises mixing the precursor to trivalent ions into the three-dimensional carbon additive and the first solvent in two or more portions. In some embodiments, mixing the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive, and the first solvent occurs over a period of time of about 1 minute to about 10 minutes. In some embodiments, heating the third dispersion comprises heating the third dispersion at a first temperature for a first time period, heating the third dispersion at a second temperature for a second time period, and heating the third dispersion at a third temperature for a third time period. In some embodiments, heating the third dispersion comprises heating the third dispersion in an autoclave. In some embodiments, autoclave comprises a Teflon-lined stainless steel autoclave. In some embodiments, the first temperature is about 10° C. to about 50° C. In some embodiments, the second temperature is about 90° C. to about 360° C. In some embodiments, the third temperature is about 90° C. to about 360° C. In some embodiments, the first time period is about 15 minutes to about 60 minutes. In some embodiments, the second time period is about 600 minutes to about 2,400 minutes. In some embodiments, the third time period is about 15 minutes to about 60 minutes. In some embodiments, cooling the third dispersion comprises cooling the third dispersion at a temperature of about −60° C. to about −200° C. In some embodiments, cooling the third dispersion comprises cooling the third dispersion at a temperature of about −60° C. to about
Another aspect provided herein is a method of forming an energy storage device, the method comprising: forming a first electrode; forming a second electrode; and stacking the first electrode, a separator, and the second electrode to form a pouch cell. In some embodiments, the method further comprises sealing the pouch cell. In some embodiments, sealing the pouch cell is performed by a heat sealer, a vacuum sealer, or any combination thereof. In some embodiments, the method further comprises adding an electrolyte to the pouch cell. In some embodiments, the method further comprises allowing the pouch cell to rest for a period of time of about 1 minute to about 10 minutes. In some embodiments, the method further comprises vacuum sealing of the pouch cell. In some embodiments, the method further comprises performing a formation cycle of the pouch cell in open air and at ambient temperature. In some embodiments, the method further comprises cutting the pouch cell, degassing the pouch cell, and resealing the pouch cell. In some embodiments, the method is not performed in a dry room or a clean room.
Another aspect provided herein is an energy charging and discharging device configured for parallel charging and series discharging, the device comprising: a first energy storage device having a negative terminal and a positive terminal; a second energy storage device having a negative terminal and a positive terminal; a third energy storage device having a negative terminal and a positive terminal; a switch configured: in a first position to connect the negative terminal of the first energy storage device with the positive terminal of the third energy storage device and connect the positive terminal of the first energy storage device with the negative terminal of the second energy storage device; in a second position to connect the negative terminal of the first energy storage device with the negative terminal of the second energy storage device, connect the positive terminal of the first energy storage device with the positive terminal of the second energy storage device, and connect the negative terminal of the first energy storage device with the positive terminal of the second energy storage device and the positive terminal of the third energy storage device; wherein at least one of the first energy storage device, the second energy storage device, or the third energy storage device comprises an energy storage device comprising: a first electrode comprising: a graphene sheet; a layered double hydroxide coupled to the graphene sheet; a binder; a conductive additive; and a first current collector; and a second electrode comprising: a hydroxide; and a second current collector; a separator; and an electrolyte. In some embodiments, the switch comprises two or more switches. In some embodiments, the switch comprises a double-pull double-throw switch.
In another aspect, disclosed herein is an electrode comprising: a graphene sheet; a layered double hydroxide coupled to the graphene sheet; a binder; a conductive additive; and a current collector. In some embodiments, the graphene sheet comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the graphene sheet comprises a nanosheet, a microsheet, a platelet, or any combination thereof.
In some embodiments, the layered double hydroxide comprises a metallic layered double hydroxide comprising an aluminum-based layered double hydroxide, a barium-based layered double hydroxide, a bismuth-based layered double hydroxide, a cadmium-based layered double hydroxide, calcium-based layered double hydroxide, a chromium-based layered double hydroxide, cobalt-based layered double hydroxide, a copper-based layered double hydroxide, an indium-based layered double hydroxide, an iron-based layered double hydroxide, a lead-based layered double hydroxide, a manganese-based layered double hydroxide, a mercury-based layered double hydroxide, a nickel-based layered double hydroxide, a strontium-based layered double hydroxide, a tin-based layered double hydroxide, a zinc-based layered double hydroxide, or any combination thereof. In some embodiments, the layered double hydroxide comprises an M2+ metal cation, an M3+ metal cation, a hydroxide ion, an octahedral site with a trivalent metal cation, an octahedral site with a divalent metal cation, a water molecule, an anion, or any combination thereof. In some embodiments, the M2+ metal cation comprises barium, cadmium, calcium, cobalt, copper (II), iron (II), lead (II), magnesium, mercury (I), mercury (II), nickel, strontium, tin, zinc, or any combination thereof. In some embodiments, the M3+ metal cation comprises aluminum, bismuth, chromium (III), iron (III), or any combination thereof. In some embodiments, the anion comprises nitrate, sulfate, carbonate, chloride, bromide, or any combination thereof. In some embodiments, the binder comprises a polymeric binder. In some embodiments, the polymeric binder comprises polyvinylidene fluoride, carboxymethyl cellulose, polyacrylic acid, polyethylene glycol, alginic acid, polypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene), a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer (Nafion®, polytetrafluoroethylene (Teflon®, polydopamine, polyvinylpyrrolidone, polyacrylonitrile, carbonyl β-cyclodextrin, or any combination thereof. In some embodiments, the conductive additive comprises a zero-dimensional carbon additive, a one-dimensional carbon additive, a two-dimensional carbon additive, a three-dimensional carbon additive, or any combination thereof. In some embodiments, the zero-dimensional carbon additive comprises carbon black, acetylene black, or both. In some embodiments, the one-dimensional carbon additive comprises a carbon fiber, an activated carbon fiber, a carbon nanotube, an activated carbon nanotube, a carbon nanoplatelet, an activated carbon nanoplatelet, a carbon nanoribbon, an activated carbon nanoribbon, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a nanosheet, a microsheet, a platelet, or any combination thereof. In some embodiments, the three-dimensional carbon additive comprises graphite, carbon foam, activated carbon, graphene foam, carbon aerogel, graphene aerogel, porous carbon, a buckminsterfullerene, an interconnected corrugated carbon-based network, or any combination thereof. In some embodiments, the current collector comprises a foam, a foil, a mesh, an aerogel, or any combination thereof. In some embodiments, the current collector comprises a copper-based current collector, a nickel-based current collector, a zinc-based current collector, a graphite-based current collector, a stainless steel-based current collector, a brass-based current collector, a bronze-based current collector, or any combination thereof. In some embodiments, a concentration by mass, by volume, or both of the graphene sheet in the first electrode is about 0.1% to about 10%. In some embodiments, a concentration by mass, by volume, or both of the layered double hydroxide in the first electrode is about 1% to about 80%. In some embodiments, a concentration by mass, by volume, or both of the binder in the first electrode is about 1% to about 20%. In some embodiments, a concentration by mass, by volume, or both of the conductive additive in the first electrode is about 1% to about 30%.
Another aspect provided herein is a method of fabricating battery electrodes comprising: providing electrode materials comprising: a layered double hydroxide composite; electrically conductive additives; and a polymer binder; mixing the electrode materials to form a slurry; providing an electrically conductive current collector substrate; cooling the slurry; centrifuging the slurry; drying the slurry; and applying the slurry to the electrically conductive current collector substrate to form an electrode. In some embodiments, the electrode materials include a conductive three-dimensional network of layered double hydroxide graphene composites. In some embodiments, the electrically conductive current collector substrate is zinc. In some embodiments, the method further includes stacking two electrodes separated by a battery electrode separator to form a pouch cell. In some embodiments, the pouch cell is fabricated in open air at an ambient temperature between 65° F. and 85° F. In some embodiments, a hybrid battery is constructed using the methods herein has an energy density from at least 250 Wh/kg to 425 Wh/kg and an energy density from about 600 Wh/L to 850 Wh/L. In some embodiments, a hybrid battery constructed using the methods herein has an energy density of from about 250 Wh/kg to 425 Wh/kg and a power density about 3.5 kW/kg to 5 kW/kg.
Those skilled in the art will appreciate the scope of the present disclosure and realize additional aspects thereof after reading the following detailed description in association with the accompanying drawings.
The features of the disclosure are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present disclosure will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the disclosure are utilized, and the accompanying drawings of which:
Energy storage devices, such as lithium-ion batteries, are widely used as energy storage devices in electronics. Although lithium-ion batteries exhibit high energy densities, such devices often exhibit low power densities, typically below 3 kW/kg, and high recharging times on the order of hours. Furthermore, lithium-ion batteries are flammable and suffer from induced ignition from overcharging and electrolyte breakdown. Such ignition is often caused by damage to the separator, which short circuits the battery. Separator damage may be induced by battery temperatures above its melting point or through impact. Furthermore, overcharging such lithium storage devices causes the lithium cobalt oxide therein to emit oxygen, which can react with the lithium cobalt oxide or the electrolyte, thereby increasing its resistance and generating sufficient heat to spark ignition. Additionally, overcharging lithium batteries breaks down and expands the organic molecules within the electrolyte, which can lead to explosion and leakage of the highly flammable electrolyte within.
As such, there is a long felt and unmet need for safe and powerful energy storage devices that are lightweight, structurally flexible, and exhibit high power densities, high energy densities, and extended cycle life spans. Furthermore, there is a current unmet need for electrode and electrolyte materials configured to store a large amount of energy in a short time and to slowly and controllably release the energy for use in an electronic device.
Comparison of Energy Storage Devices
Provided herein, per
Energy storage devices with higher gravimetric power densities and volumetric power densities recharge faster. Gravimetric power density is measured in units of power/mass (e.g., watts per kilogram [W/kg]). Volumetric power density is measured in units of power/volume (e.g., watts per liter [W/L]). In some embodiments, the gravimetric power density of an energy storage device is measured as a gravimetric power density of an entire cell including non-active materials. In some embodiments, the gravimetric power density of an energy storage device is measured as a gravimetric power density of only active materials in the electrodes. Alternatively, in some embodiments, the gravimetric power density of an energy storage device is measured by any standard means. In some embodiments, the volumetric power density of an energy storage device is measured as a volumetric power density of an entire cell including non-active materials. In some embodiments, the volumetric power density of an energy storage device is measured as a volumetric power density of only active materials. In some embodiments, the power density, the energy density, or both of an energy storage device is measured as an average among multiple energy storage device samples. Alternatively, in some embodiments, the volumetric power density of an energy storage device is measured by any standard means.
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As such, the energy storage devices disclosed herein are able to both recharge quickly and store large quantities of energy. Thus, due to their improved energy storage capabilities, the devices herein can be used in a broad range of applications including, for example, consumer electronics, military equipment, and transportation.
Energy Storage Devices
Provided herein are energy storage devices. In some embodiments, the energy storage devices herein are hybrid supercapacitors. In some embodiments, the energy storage devices herein comprise a first electrode, a second electrode, a separator, and an electrolyte. In some embodiments, the first electrode comprises a graphene sheet, a layered double hydroxide (LDH), a binder, a conductive additive, and a first current collector. In some embodiments, the second electrode comprises a hydroxide and a second current collector. In some embodiments, the energy storage devices herein stores charge electrostatically. In some embodiments, the energy storage devices herein stores charge electrochemically. In some embodiments, the energy storage devices herein stores charge electrostatically and electrochemically. The energy devices herein exhibit superior electrochemical performance and can be manufactured at large scales and at low cost.
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As shown in
In some embodiments, the secondary first electrode 510 comprises a redox active material 411 and a capacitive material 512. As shown, a first portion of the secondary first electrode 510 comprises the redox active material 411, and a second portion of the secondary first electrode 510 comprises the capacitive material 512. As shown, the redox active material 411 and the capacitive material 512 of the secondary first electrode 510 of the second energy storage device 500 are connected in series. In some embodiments, at least one of the secondary first electrode 510 and the second electrode 420 comprises a current collector. In some embodiments, the first portion of the current collector of the secondary first electrode 510 is coated with the redox active material 411, and the second portion of the current collector is coated with the capacitive material 512. In some embodiments, the first portion of the current collector of the secondary first electrode 510 is coated with a slurry comprising the redox active material 411, and the second portion of the current collector is coated with a slurry comprising the capacitive material 512. As shown, the first portion having the redox active material 411 and the second portion having the capacitive material 512 are connected in series.
In some embodiments, the electrochemical performance of the second energy storage device 500 can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the secondary first electrode 510. In some embodiments, the electrochemical performance of the second energy storage device 500 can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510. In some embodiments, the energy density of the second energy storage device 500 can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the secondary first electrode 510. In some embodiments, the energy density of the second energy storage device 500 can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510. In some embodiments, the power density of the second energy storage device 500 can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the secondary first electrode 510. In some embodiments, power density of the second energy storage device 500 can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510. In some embodiments, the internal resistance of the second energy storage device 500 can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the secondary first electrode 510. In some embodiments, internal resistance of the second energy storage device 500 can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510. In some embodiments, the charging and/or discharging times of the second energy storage device 500 can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the secondary first electrode 510. In some embodiments, charging and/or discharging times of the second energy storage device 500 can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510.
In some embodiments, increasing the ratio between the first portion and the second portion of the secondary first electrode 510 increases the energy density of the second energy storage device 500. In some embodiments, decreasing the ratio between the first portion and the second portion of the secondary first electrode 510 decreases the energy density of the second energy storage device 500. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510 increases the energy density of the second energy storage device 500. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510 decreases the energy density of the second energy storage device 500. In some embodiments, increasing the ratio between the first portion and the second portion of the secondary first electrode 510 decreases the power density of the second energy storage device 500. In some embodiments, decreasing the ratio between the first portion and the second portion of the secondary first electrode 510 increases the power density of the second energy storage device 500. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510 decreases the power density of the second energy storage device 500. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510 increases the power density of the second energy storage device 500. In some embodiments, increasing the ratio between the first portion and the second portion of the secondary first electrode 510 decreases the internal resistance of the second energy storage device 500. In some embodiments, decreasing the ratio between the first portion and the second portion of the secondary first electrode 510 increases the internal resistance of the second energy storage device 500. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510 decreases the internal resistance of the second energy storage device 500. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 of the secondary first electrode 510 increases the internal resistance of the second energy storage device 500. In some embodiments, increasing the ratio between the first portion and the second portion of the secondary first electrode 510 decreases the charging and/or discharging times of the second energy storage device 500. In some embodiments, decreasing the ratio between the first portion and the second portion of the secondary first electrode 510 increases the charging and/or discharging times of the second energy storage device 500. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 decreases the charging and/or discharging times of the second energy storage device 500. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 increases the charging and/or discharging times of the second energy storage device 500.
As shown in
In some embodiments, the tertiary first electrode 610A comprises a redox active material 411 and a capacitive material 512. As shown, a first portion of the tertiary first electrode 610A comprises the redox active material 411, and a second portion of the tertiary first electrode 610A comprises the capacitive material 512. As shown, the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A of the third energy storage device 600A are connected in parallel. In some embodiments, at least one of the tertiary first electrode 610A and the second electrode 420 comprises a current collector. In some embodiments, the first portion of the current collector of the tertiary first electrode 610A is coated with the redox active material 411, and the second portion of the current collector is coated with the capacitive material 512. In some embodiments, the first portion of the current collector of the tertiary first electrode 610A is coated with a slurry comprising the redox active material 411, and the second portion of the current collector is coated with a slurry comprising the capacitive material 512. As shown, the first portion having the redox active material 411 and the second portion having the capacitive material 512 are connected in parallel.
In some embodiments, the electrochemical performance of the third energy storage device 600A can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the tertiary first electrode 610A. In some embodiments, the electrochemical performance of the third energy storage device 600A can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A. In some embodiments, the energy density of the third energy storage device 600A can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the tertiary first electrode 610A. In some embodiments, energy density of the third energy storage device 600A can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A. In some embodiments, the power density of the third energy storage device 600A can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the tertiary first electrode 610A. In some embodiments, power density of the third energy storage device 600A can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A. In some embodiments, the internal resistance of the third energy storage device 600A can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the tertiary first electrode 610A. In some embodiments, internal resistance of the third energy storage device 600A can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A. In some embodiments, the charging and/or discharging times of the third energy storage device 600A can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the tertiary first electrode 610A. In some embodiments, charging and/or discharging times of the third energy storage device 600A can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A.
In some embodiments, increasing the ratio between the first portion and the second portion of the tertiary first electrode 610A increases the energy density of the third energy storage device 600A. In some embodiments, decreasing the ratio between the first portion and the second portion of the tertiary first electrode 610A decreases the energy density of the third energy storage device 600A. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A increases the energy density of the third energy storage device 600A. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A decreases the energy density of the third energy storage device 600A. In some embodiments, increasing the ratio between the first portion and the second portion of the tertiary first electrode 610A decreases the power density of the third energy storage device 600A. In some embodiments, decreasing the ratio between the first portion and the second portion of the tertiary first electrode 610A increases the power density of the third energy storage device 600A. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A decreases the power density of the third energy storage device 600A. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A increases the power density of the third energy storage device 600A. In some embodiments, increasing the ratio between the first portion and the second portion of the tertiary first electrode 610A decreases the internal resistance of the third energy storage device 600A. In some embodiments, decreasing the ratio between the first portion and the second portion of the tertiary first electrode 610A increases the internal resistance of the third energy storage device 600A. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A decreases the internal resistance of the third energy storage device 600A. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 of the tertiary first electrode 610A increases the internal resistance of the third energy storage device 600A. In some embodiments, increasing the ratio between the first portion and the second portion decreases the charging and/or discharging times of the third energy storage device 600A. In some embodiments, decreasing the ratio between the first portion and the second portion increases the charging and/or discharging times of the third energy storage device 600A. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 decreases the charging and/or discharging times of the third energy storage device 600A. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 increases the charging and/or discharging times of the third energy storage device 600A.
As shown in
In some embodiments, the quaternary first electrode 610B comprises a redox active material 411 and a capacitive material 512. As shown, a first portion of the quaternary first electrode 610B comprises the redox active material 411, and a second portion of the quaternary first electrode 610B comprises the capacitive material 512. As shown, the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B of the third energy storage device 600B are connected in parallel. In some embodiments, at least one of the quaternary first electrode 610B and the second electrode 420 comprises a current collector. In some embodiments, the first portion of the current collector of the quaternary first electrode 610B is coated with the redox active material 411, and the second portion of the current collector is coated with the capacitive material 512. As shown, the first portion having the redox active material 411 and the second portion having the capacitive material 512 are connected in parallel.
In some embodiments, the electrochemical performance of the fourth energy storage device 600B can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the quaternary first electrode 610B. In some embodiments, the electrochemical performance of the fourth energy storage device 600B can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B. In some embodiments, the energy density of the fourth energy storage device 600B can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the quaternary first electrode 610B. In some embodiments, energy density of the fourth energy storage device 600B can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B. In some embodiments, the power density of the fourth energy storage device 600B can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the quaternary first electrode 610B. In some embodiments, power density of the fourth energy storage device 600B can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B. In some embodiments, the internal resistance of the fourth energy storage device 600B can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the quaternary first electrode 610B. In some embodiments, internal resistance of the fourth energy storage device 600B can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B. In some embodiments, the charging and/or discharging times of the fourth energy storage device 600B can be tuned by adjusting a ratio by mass, by volume, by surface area, or any combination thereof between the first portion and the second portion of the quaternary first electrode 610B. In some embodiments, charging and/or discharging times of the fourth energy storage device 600B can be tuned by adjusting a ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B.
In some embodiments, increasing the ratio between the first portion and the second portion of the quaternary first electrode 610B increases the energy density of the fourth energy storage device 600B. In some embodiments, decreasing the ratio between the first portion and the second portion of the quaternary first electrode 610B decreases the energy density of the fourth energy storage device 600B. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B increases the energy density of the fourth energy storage device 600B. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B decreases the energy density of the fourth energy storage device 600B. In some embodiments, increasing the ratio between the first portion and the second portion of the quaternary first electrode 610B decreases the power density of the fourth energy storage device 600B. In some embodiments, decreasing the ratio between the first portion and the second portion of the quaternary first electrode 610B increases the power density of the fourth energy storage device 600B. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B decreases the power density of the fourth energy storage device 600B. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B increases the power density of the fourth energy storage device 600B. In some embodiments, increasing the ratio between the first portion and the second portion of the quaternary first electrode 610B decreases the internal resistance of the fourth energy storage device 600B. In some embodiments, decreasing the ratio between the first portion and the second portion of the quaternary first electrode 610B increases the internal resistance of the fourth energy storage device 600B. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B decreases the internal resistance of the fourth energy storage device 600B. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 of the quaternary first electrode 610B increases the internal resistance of the fourth energy storage device 600B. In some embodiments, increasing the ratio between the first portion and the second portion decreases the charging and/or discharging times of the fourth energy storage device 600B. In some embodiments, decreasing the ratio between the first portion and the second portion increases the charging and/or discharging times of the fourth energy storage device 600B. In some embodiments, increasing the ratio between the redox active material 411 and the capacitive material 512 decreases the charging and/or discharging times of the fourth energy storage device 600B. In some embodiments, decreasing the ratio between the redox active material 411 and the capacitive material 512 increases the charging and/or discharging times of the fourth energy storage device 600B.
As shown in
As shown, the capacitive material 512 of the second electrode 420 of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, comprises zinc hydroxide, wherein the zinc hydroxide converts to zinc oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the zinc oxide hydroxide converts to zinc hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises aluminum hydroxide, wherein the aluminum hydroxide converts to aluminum oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the aluminum oxide hydroxide converts to aluminum hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises barium hydroxide, wherein the barium hydroxide converts to barium oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the barium oxide hydroxide converts to barium hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises bismuth hydroxide, wherein the bismuth hydroxide converts to bismuth oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the bismuth oxide hydroxide converts to bismuth hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises cadmium hydroxide, wherein the cadmium hydroxide converts to cadmium oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the cadmium oxide hydroxide converts to cadmium hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises calcium hydroxide, wherein the calcium hydroxide converts to calcium oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the calcium oxide hydroxide converts to calcium hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises chromium hydroxide, wherein the chromium hydroxide converts to chromium oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the chromium oxide hydroxide converts to chromium hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises cobalt hydroxide, wherein the cobalt hydroxide converts to cobalt oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the cobalt oxide hydroxide converts to cobalt hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises copper hydroxide, wherein the copper hydroxide converts to copper oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the copper oxide hydroxide converts to copper hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises indium hydroxide, wherein the indium hydroxide converts to indium oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the indium oxide hydroxide converts to indium hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises iron hydroxide, wherein the iron hydroxide converts to iron oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the iron oxide hydroxide converts to iron hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises lead hydroxide, wherein the lead hydroxide converts to lead hydroxide oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the lead oxide hydroxide converts to lead hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises manganese hydroxide, wherein the manganese hydroxide converts to manganese oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the manganese oxide hydroxide converts to manganese hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises mercury hydroxide, wherein the mercury hydroxide converts to mercury oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the mercury oxide hydroxide converts to mercury hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises nickel hydroxide, wherein the nickel hydroxide converts to nickel oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the nickel oxide hydroxide converts to nickel hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises strontium hydroxide, wherein the strontium hydroxide converts to strontium oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the strontium oxide hydroxide converts to strontium hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Alternatively, the capacitive material 512 of the second electrode 420 comprises tin hydroxide, wherein the tin hydroxide converts to tin oxide hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the tin oxide hydroxide converts to tin hydroxide during discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively.
Alternatively, per
In some embodiments, the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, comprise the LDH coupled to the graphene sheet. In some embodiments, the LDH coupled to the graphene sheet is an LDH-graphene composite. In some embodiments, the redox active material 411 comprises the LDH coupled to the graphene sheet and/or a binder. In some embodiments, the LDH is bonded to the graphene sheet. In some embodiments, the LDH is not bonded to the graphene sheet. In some embodiments, LDH is bonded to the graphene sheet by a covalent bond, an ionic bond, a dipole-dipole interaction (e.g., a hydrogen bond), or any combination thereof. In some embodiments, the graphene sheet comprises a nanosheet, a microsheet, a platelet, or any combination thereof.
In some embodiments, the unexpectedly superior electrochemical performance, such as the reduced charging and discharging times, exhibited by the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, herein is attributed to the composition by mass, by volume, or both of the graphene sheet within the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, of below about 10%. The concentration by mass, by volume, or both of the graphene sheet of below about 10% enables the graphene to serve as a substrate for LDH growth but prevents the formation of a complete matrix that limits the density of the LDH-graphene composite. The unexpectedly superior electrochemical performance exhibited by the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, is attributed to the composition by mass, by volume, or both of the graphene sheet of below about 10%. The concentration by mass, by volume, or both of the graphene sheet of below about 10% enables the graphene to serve as a substrate for LDH growth but does not form a complete matrix that limits the density of the LDH-graphene composite.
As shown, the electrolyte 430 comprises water, wherein the water converts to hydroxide during charging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, and wherein the hydroxide converts to water during the discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. In some embodiments, the electrolyte 430 comprises: a hydroxide, an additive, a stabilizer, a hydrogen evolution inhibitor, and a conductivity enhancer. In some embodiments, the electrolyte 430 comprises zinc oxide powder dissolved in an alkaline solution of 7.1 M potassium hydroxide in water.
In some embodiments, the electrolyte 430 comprises a hydroxide, an additive, a stabilizer, a hydrogen evolution inhibitor, and a conductivity enhancer. In some embodiments, the additive prevents corrosion of the active material. In some embodiments, the additive prevents corrosion of the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively.
In some embodiments, the stabilizer contributes to the redox reactions during energy storage and discharge. In some embodiments, the stabilizer prevents the dissolution of the first electrode. In some embodiments, the stabilizer is soluble in strong alkaline solutions. In some embodiments, the stabilizer comprises zinc oxide, which converts into zinc hydroxide or zincate during the redox reaction. In some embodiments, no or negligible net dissolution of zinc hydroxide into the electrolyte occurs.
In some embodiments, the separator comprises a membrane separator, a cellulose separator, an organic polymeric separator, an inorganic polymer separator, a microporous separator, a woven separator, a non-woven separator, or any combination thereof. In some embodiments, the separator has a bonding strength sufficient to withstand pressures and impacts without fracturing or separating from the electrode components. In some embodiments, the polymer has a melting point above ambient conditions. In some embodiments, the polymer has a melting point above 100° C.
In some embodiments, a ratio by mass or volume between the first portion and the second portion of the first electrode is about 0.1:1 to about 9:1. In some embodiments, a ratio by mass or volume between the first portion and the second portion of the first electrode is about 0.1:1 to about 0.2:1, about 0.1:1 to about 0.5:1, about 0.1:1 to about 1:1, about 0.1:1 to about 2:1, about 0.1:1 to about 3:1, about 0.1:1 to about 4:1, about 0.1:1 to about 5:1, about 0.1:1 to about 6:1, about 0.1:1 to about 7:1, about 0.1:1 to about 8:1, about 0.1:1 to about 9:1, about 0.2:1 to about 0.5:1, about 0.2:1 to about 1:1, about 0.2:1 to about 2:1, about 0.2:1 to about 3:1, about 0.2:1 to about 4:1, about 0.2:1 to about 5:1, about 0.2:1 to about 6:1, about 0.2:1 to about 7:1, about 0.2:1 to about 8:1, about 0.2:1 to about 9:1, about 0.5:1 to about 1:1, about 0.5:1 to about 2:1, about 0.5:1 to about 3:1, about 0.5:1 to about 4:1, about 0.5:1 to about 5:1, about 0.5:1 to about 6:1, about 0.5:1 to about 7:1, about 0.5:1 to about 8:1, about 0.5:1 to about 9:1, about 1:1 to about 2:1, about 1:1 to about 3:1, about 1:1 to about 4:1, about 1:1 to about 5:1, about 1:1 to about 6:1, about 1:1 to about 7:1, about 1:1 to about 8:1, about 1:1 to about 9:1, about 2:1 to about 3:1, about 2:1 to about 4:1, about 2:1 to about 5:1, about 2:1 to about 6:1, about 2:1 to about 7:1, about 2:1 to about 8:1, about 2:1 to about 9:1, about 3:1 to about 4:1, about 3:1 to about 5:1, about 3:1 to about 6:1, about 3:1 to about 7:1, about 3:1 to about 8:1, about 3:1 to about 9:1, about 4:1 to about 5:1, about 4:1 to about 6:1, about 4:1 to about 7:1, about 4:1 to about 8:1, about 4:1 to about 9:1, about 5:1 to about 6:1, about 5:1 to about 7:1, about 5:1 to about 8:1, about 5:1 to about 9:1, about 6:1 to about 7:1, about 6:1 to about 8:1, about 6:1 to about 9:1, about 7:1 to about 8:1, about 7:1 to about 9:1, or about 8:1 to about 9:1. In some embodiments, a ratio by mass or volume between the first portion and the second portion is about 0.1:1, about 0.2:1, about 0.5:1, about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, or about 9:1. In some embodiments, a ratio by mass or volume between the first portion and the second portion of the first electrode is at least about 0.1:1, about 0.2:1, about 0.5:1, about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, or about 8:1. In some embodiments, a ratio by mass or volume between the first portion and the second portion of the first electrode is at most about 0.2:1, about 0.5:1, about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, or about 9:1.
In some embodiments, a ratio by mass or volume of the redox active material to the capacitive material is about 0.1:1 to about 9:1. In some embodiments, a ratio by mass or volume of the redox active material to the capacitive material is about 0.1:1 to about 0.2:1, about 0.1:1 to about 0.5:1, about 0.1:1 to about 1:1, about 0.1:1 to about 2:1, about 0.1:1 to about 3:1, about 0.1:1 to about 4:1, about 0.1:1 to about 5:1, about 0.1:1 to about 6:1, about 0.1:1 to about 7:1, about 0.1:1 to about 8:1, about 0.1:1 to about 9:1, about 0.2:1 to about 0.5:1, about 0.2:1 to about 1:1, about 0.2:1 to about 2:1, about 0.2:1 to about 3:1, about 0.2:1 to about 4:1, about 0.2:1 to about 5:1, about 0.2:1 to about 6:1, about 0.2:1 to about 7:1, about 0.2:1 to about 8:1, about 0.2:1 to about 9:1, about 0.5:1 to about 1:1, about 0.5:1 to about 2:1, about 0.5:1 to about 3:1, about 0.5:1 to about 4:1, about 0.5:1 to about 5:1, about 0.5:1 to about 6:1, about 0.5:1 to about 7:1, about 0.5:1 to about 8:1, about 0.5:1 to about 9:1, about 1:1 to about 2:1, about 1:1 to about 3:1, about 1:1 to about 4:1, about 1:1 to about 5:1, about 1:1 to about 6:1, about 1:1 to about 7:1, about 1:1 to about 8:1, about 1:1 to about 9:1, about 2:1 to about 3:1, about 2:1 to about 4:1, about 2:1 to about 5:1, about 2:1 to about 6:1, about 2:1 to about 7:1, about 2:1 to about 8:1, about 2:1 to about 9:1, about 3:1 to about 4:1, about 3:1 to about 5:1, about 3:1 to about 6:1, about 3:1 to about 7:1, about 3:1 to about 8:1, about 3:1 to about 9:1, about 4:1 to about 5:1, about 4:1 to about 6:1, about 4:1 to about 7:1, about 4:1 to about 8:1, about 4:1 to about 9:1, about 5:1 to about 6:1, about 5:1 to about 7:1, about 5:1 to about 8:1, about 5:1 to about 9:1, about 6:1 to about 7:1, about 6:1 to about 8:1, about 6:1 to about 9:1, about 7:1 to about 8:1, about 7:1 to about 9:1, or about 8:1 to about 9:1. In some embodiments, a ratio by mass or volume of the redox active material to the capacitive material is about 0.1:1, about 0.2:1, about 0.5:1, about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, or about 9:1. In some embodiments a ratio by mass or volume of the redox active material to the capacitive material is at least about 0.1:1, about 0.2:1, about 0.5:1, about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, or about 8:1. In some embodiments, a ratio by mass or volume of the redox active material to the capacitive material is at most about 0.2:1, about 0.5:1, about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, or about 9:1.
In some embodiments, the separator has a thickness of about 10 μm (microns) to about 30 μm. In some embodiments, the separator has a thickness of about 10 μm to about 12 μm, about 10 μm to about 14 μm, about 10 μm to about 16 μm, about 10 μm to about 18 μm, about 10 μm to about 20 μm, about 10 μm to about 22 μm, about 10 μm to about 24 μm, about 10 μm to about 26 μm, about 10 μm to about 28 μm, about 10 μm to about 30 μm, about 12 μm to about 14 μm, about 12 μm to about 16 μm, about 12 μm to about 18 μm, about 12 μm to about 20 μm, about 12 μm to about 22 μm, about 12 μm to about 24 μm, about 12 μm to about 26 μm, about 12 μm to about 28 μm, about 12 μm to about 30 μm, about 14 μm to about 16 μm, about 14 μm to about 18 μm, about 14 μm to about 20 μm, about 14 μm to about 22 μm, about 14 μm to about 24 μm, about 14 μm to about 26 μm, about 14 μm to about 28 μm, about 14 μm to about 30 μm, about 16 μm to about 18 μm, about 16 μm to about 20 μm, about 16 μm to about 22 μm, about 16 μm to about 24 μm, about 16 μm to about 26 μm, about 16 μm to about 28 μm, about 16 μm to about 30 μm, about 18 μm to about 20 μm, about 18 μm to about 22 μm, about 18 μm to about 24 μm, about 18 μm to about 26 μm, about 18 μm to about 28 μm, about 18 μm to about 30 μm, about 20 μm to about 22 μm, about 20 μm to about 24 μm, about 20 μm to about 26 μm, about 20 μm to about 28 μm, about 20 μm to about 30 μm, about 22 μm to about 24 μm, about 22 μm to about 26 μm, about 22 μm to about 28 μm, about 22 μm to about 30 μm, about 24 μm to about 26 μm, about 24 μm to about 28 μm, about 24 μm to about 30 μm, about 26 μm to about 28 μm, about 26 μm to about 30 μm, or about 28 μm to about 30 μm. In some embodiments, the separator has a thickness of about 10 μm, about 12 μm, about 14 μm, about 16 μm, about 18 μm, about 20 μm, about 22 μm, about 24 μm, about 26 μm, about 28 μm, or about 30 μm. In some embodiments, the separator has a thickness of at least about 10 μm, about 12 μm, about 14 μm, about 16 μm, about 18 μm, about 20 μm, about 22 μm, about 24 μm, about 26 μm, or about 28 μm. In some embodiments, the separator has a thickness of at most about 12 μm, about 14 μm, about 16 μm, about 18 μm, about 20 μm, about 22 μm, about 24 μm, about 26 μm, about 28 μm, or about 30 μm.
First Electrodes
The electrodes herein exhibit superior electrochemical performance and can be manufactured at large scales and at low cost. In some embodiments, the first electrode is solid. In some embodiments, the first electrode is not a hydrogel.
In some embodiments, increasing the amount of LDH 702 increases the specific capacity for high energy density applications. In some embodiments, the first electrode 710 stores charge electrostatically through electric double layers on the surface of high surface area carbon and stores energy with electrochemical reactions through the LDH 702. In some embodiments, the LDH 702 provides a majority of the capacity of the first electrode 710. In some embodiments, the LDH 702 provides a majority of the battery-like energy storage of the first electrode 710. In some embodiments, zinc in the LDH is the chemically active material.
In some embodiments, the LDH 702 comprises an M2+ metal cation, an M3+ metal cation, a hydroxide ion, an octahedral site with a trivalent metal cation, an octahedral site with a divalent metal cation, a water molecule, an anion, or any combination thereof. In some embodiments, the M2+ metal cation comprises barium, cadmium, calcium, cobalt, copper (II), iron (II), lead (II), magnesium, mercury (I), mercury (II), nickel, strontium, tin, zinc, or any combination thereof. In some embodiments, the M3+ metal cation comprises aluminum, bismuth, chromium (III), iron (III), or any combination thereof. In some embodiments, the anion comprises nitrate, sulfate, carbonate, chloride, bromide, or any combination thereof. In some embodiments, the LDH 702 comprises a unique combination of divalent (e.g., zinc) and trivalent (e.g., bismuth) ions, both of which contribute to charge storage. In one example, the energy storage devices of the present disclosure comprise an LDH based on zinc (Zn2+) and bismuth (Bi3+).
In some embodiments, the LDH comprises divalent ions (e.g., zinc) and trivalent ions (e.g., bismuth), both of which contribute to energy storage. In some embodiments, the LDH enables electrostatic energy storage, electrochemical energy storage, or both. In some embodiments, the LDH comprises a chemically active material and a stabilizer to suppress hydrogen evolution.
In some embodiments, the LDH 702 comprises a metallic LDH comprising an aluminum-based LDH, a barium-based LDH, a bismuth-based LDH, a cadmium-based LDH, a calcium-based LDH, a chromium-based LDH, a cobalt-based LDH, a copper-based LDH, an indium-based LDH, an iron-based LDH, a lead-based LDH, a manganese-based LDH, a mercury-based LDH, a nickel-based LDH, a strontium-based LDH, a tin-based LDH, a zinc-based LDH, or any combination thereof.
In some embodiments, the graphene oxide sheets introduced during the LDH synthesis provide surfaces for LDH growth and are reduced to graphene sheets during the reaction, forming a conductive three-dimensional network of LDH-graphene composite 720. As shown in
In some embodiments, one or more graphene sheets 701 are introduced during the LDH 702 synthesis. In some embodiments, the one or more graphene sheets 701 provide surfaces for LDH 702 growth. In some embodiments, the one or more graphene sheets 701 are separated from each other. In some embodiments, the one or more graphene sheets 701 are not interconnected. In some embodiments, the one or more graphene sheets 701 do not form a matrix. In some embodiments, the graphene sheets 701 comprise graphene oxide sheets. In some embodiments, one or more graphene oxide sheets are reduced to graphene sheets 701 during the formation of the LDH 702. In some embodiments, the one or more graphene sheets 701 and LDH 702 form a conductive three-dimensional network. In some embodiments, a plurality of graphene sheets are arranged in layered configuration, wherein each layer is a graphene sheet.
In some embodiments, the graphene sheet is an excellent conductor of electricity and provides a substrate for the growth of LDH nanostructures. In some embodiments, graphene increases the surface area of the materials at the interface with the electrolyte. In some embodiments, the graphene further facilitates ion diffusion while also allowing free space to alleviate the volume changes of LDH during charge and discharge. In some embodiments, the graphene sheet comprises holey graphene, graphite nanoplatelets, thin layer graphite, carbon fibers, graphene fibers, carbon nanotubes, graphene nanoribbons, buckminsterfullerene, or any combination thereof. In some embodiments, the graphene sheet comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the graphene sheet comprises a plurality of graphene sheets. In some embodiments, the two-dimensional carbon additive comprises a nanosheet, a microsheet, a platelet, or any combination thereof. In some embodiments, the graphene sheet has a thickness of about 0.3 nm. In some embodiments, the graphene sheet has a thickness of at most about 0.3 nm.
In some embodiments, the unexpectedly superior electrochemical performance exhibited by the storage devices herein is attributed to the composition by mass, by volume, or both of the graphene sheet within the first electrode of below about 10%. The concentration by mass, by volume, or both of the graphene sheet of below about 10% enables the graphene to serve as a substrate for LDH growth but prevents the formation of a complete matrix that limits the density of the LDH-graphene composite 720. The unexpectedly superior electrochemical performance exhibited by the first electrode 710 is attributed to the composition by mass, by volume, or both of the graphene sheet 701 of below about 10%. The concentration by mass, by volume, or both of the graphene sheet 701 of below about 10% enables the graphene to serve as a substrate for LDH 702 growth but does not form a complete matrix that limits the density of the LDH-graphene composite 720.
In some embodiments, the basal plane of the graphene sheet 701 is the only face of the graphene sheet 701. In some embodiments, the graphene sheet 701 is a micro-scale graphene sheet 701. In some embodiments, the graphene sheet 701 is not a nano-scale graphene sheet 701. In some embodiments, the graphene sheet 701 is not a graphene flake or a graphene particle. In some embodiments, the graphene sheet 701 comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the graphene sheet comprises a nanosheet, a microsheet, a platelet, or any combination thereof. Graphene is an excellent conductor of electricity and is a great carrier for the growth of LDH nanostructures. In some embodiments, graphene increases accessibility of the electrolyte to the electrode. In some embodiments, graphene increases accessibility of the electrolyte to the electrode to provide a greater contact surface area with the electrolyte. In some embodiments, the increased accessibility facilitates ion diffusion while also allowing free space to alleviate the volume changes of LDH during charge and discharge.
In some embodiments, the binder 703 comprises a polymeric binder. In some embodiments, the polymeric binder comprises polyvinylidene fluoride, carboxymethyl cellulose, polyacrylic acid, polyethylene glycol, alginic acid, polypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene), a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer (Nafion®), polytetrafluoroethylene (Teflon®), polydopamine, polyvinylpyrrolidone, polyacrylonitrile, carbonyl β-cyclodextrin, or any combination thereof. In some embodiments, the binder 703 adheres the active and conductive materials to the current collector to allow flow of electrons from the external circuit to through electrode materials during charge and discharge of the energy storage device. In some embodiments, the binder 703 has a bonding strength sufficient to withstand pressures and effects without fracturing or separating from the current collector. In some embodiments, the binder 703 is a conductive polymer. In some embodiments, the binder 703 has a melting point above ambient conditions. In some embodiments, the polymer has a melting point above 100° C.
In some embodiments, the binder binds all components together and adheres them to the current collector. In some embodiments, the binder comprises a polymeric binder. In some embodiments, the polymeric binder comprises polyvinylidene fluoride, carboxymethyl cellulose, polyacrylic acid, polyethylene glycol, alginic acid, polypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene), a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer (Nafion®), polytetrafluoroethylene (Teflon®), polydopamine, polyvinylpyrrolidone, polyacrylonitrile, carbonyl β-cyclodextrin, or any combination thereof. In some embodiments, the binder adheres the components of the first electrode. In some embodiments, the binder adheres the components of the first electrode to the first current collector. In some embodiments, the binder adheres the graphene sheet, the LDH, and the conductive additive to the first current collector. In some embodiments, the polymeric binder has a bonding strength sufficient to withstand pressures and effects without fracturing or separating from the current collector. In some embodiments, the polymer is a conductive polymer. In some embodiments, the polymer has a melting point above ambient conditions. In some embodiments, the polymer has a melting point above 100° C.
In some embodiments, the conductive additives 704A, 704B, 704C, and 704D comprises a zero-dimensional carbon additive 704A, a one-dimensional carbon additive 704B, a two-dimensional carbon additive 704C, a three-dimensional carbon additive 704D, or any combination thereof. In some embodiments, the zero-dimensional carbon additive 704A comprises carbon black, acetylene black, or both. In some embodiments, the one-dimensional carbon additive 704B comprises a carbon fiber, an activated carbon fiber, a carbon nanotube, an activated carbon nanotube, a carbon nanoplatelet, an activated carbon nanoplatelet, a carbon nanoribbon, an activated carbon nanoribbon, or any combination thereof. In some embodiments, the two-dimensional carbon additive 704C comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the two-dimensional carbon additive 704C comprises a nanosheet, a microsheet, a platelet, or any combination thereof. In some embodiments, the three-dimensional carbon additive 704D comprises graphite, carbon foam, activated carbon, graphene foam, carbon aerogel, graphene aerogel, porous carbon, a buckminsterfullerene, or an interconnected corrugated carbon-based network. In some embodiments, the three-dimensional conductive additive enables electrochemical capacitor-like energy storage and rapid charging and discharging. In some embodiments, the conductive additives 704A, 704B, 704C, and 704D provide an electron superhighway for the transport of charge to and from the current collector during charge and discharge.
In some embodiments, the conductive additives 704A, 704B, 704C, and 704D provide the electrochemical capacitor-like energy storage, which enables rapid charging/discharging of the first electrode 710. The carbon additives serve to increase the conductivity of the electrode. The ratio by mass or volume between the conductive additives 704A and 704D, which are high surface area carbon materials, can be tuned to alter and improve performance of the first electrode 710. In some embodiments, increasing the amount of the conductive additive improves the rate capability of the first electrode 710 for high-power applications.
In some embodiments, the conductive additive increases the conductivity of the electrode. In some embodiments, the ratio by mass or volume between the conductive additive and the LDH can be tuned to alter the performance of the electrodes and energy storage devices. In some embodiments, increasing the amount of the conductive additive improves the rate capability of the energy storage device for high-power applications. In some embodiments, the conductive additive provides an electron superhighway for the transport of charge from and to the current collector during charge and discharge. In some embodiments, the conductive additive comprises carbon black, acetylene black, carbon nanotubes, carbon fibers, graphite, graphene, or any combination thereof.
In some embodiments, the conductive additive comprises a zero-dimensional carbon additive, a one-dimensional carbon additive, a two-dimensional carbon additive, a three-dimensional carbon additive, or any combination thereof. In some embodiments, the zero-dimensional carbon additive comprises carbon black, acetylene black, or both. In some embodiments, the one-dimensional carbon additive comprises a carbon fiber, an activated carbon fiber, a carbon nanotube, an activated carbon nanotube, a carbon nanoplatelet, an activated carbon nanoplatelet, a carbon nanoribbon, an activated carbon nanoribbon, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a nanosheet, a microsheet, a platelet, or any combination thereof. In some embodiments, the three-dimensional carbon additive comprises graphite, carbon foam, activated carbon, graphene foam, carbon aerogel, graphene aerogel, porous carbon, a buckminsterfullerene, an interconnected corrugated carbon-based network, or any combination thereof. In some embodiments, the conductive additive has thickness, height, width, or any combination thereof of at most about 3 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, or more including increments therein.
In some embodiments, the current collector transports the charge from the external circuit to the battery materials during charge and discharge. In some embodiments, the current collector allows the flow of electrons from the external circuit to through electrode materials during charge and discharge processes. In some embodiments, the current collector is formed of tin, zinc, copper, graphite, nickel, stainless steel, brass, bronze, or any combination thereof. In some embodiments, the current collector is a foil, a plate, a mesh, or a foam. In some embodiments, the current collector stores charge electrostatically in electric double layers. In some embodiments, the current collector 705 comprises a foam, a foil, a mesh, an aerogel, or any combination thereof. In some embodiments, the current collector 705 comprises a copper-based current collector, a zinc-based current collector, a graphite-based current collector, a nickel-based current collector, a stainless steel-based current collector, a brass-based current collector, a bronze-based current collector, or any combination thereof. In some embodiments, the current collector transports the charge from the external circuit to the battery materials during charge and discharge.
In some embodiments, per
In some embodiments, a concentration by mass, by volume, or both of the graphene sheet in the first electrode is sufficiently less than about 10%, such that the first electrode does not form a hydrogel. In some embodiments, a concentration by mass, by volume, or both of the graphene sheet in the first electrode is about 0.1% to about 10%. In some embodiments, a concentration by mass, by volume, or both of the graphene sheet in the first electrode is about 0.1% to about 0.2%, about 0.1% to about 0.5%, about 0.1% to about 1%, about 0.1% to about 2%, about 0.1% to about 3%, about 0.1% to about 4%, about 0.1% to about 5%, about 0.1% to about 6%, about 0.1% to about 7%, about 0.1% to about 8%, about 0.1% to about 10%, about 0.2% to about 0.5%, about 0.2% to about 1%, about 0.2% to about 2%, about 0.2% to about 3%, about 0.2% to about 4%, about 0.2% to about 5%, about 0.2% to about 6%, about 0.2% to about 7%, about 0.2% to about 8%, about 0.2% to about 10%, about 0.5% to about 1%, about 0.5% to about 2%, about 0.5% to about 3%, about 0.5% to about 4%, about 0.5% to about 5%, about 0.5% to about 6%, about 0.5% to about 7%, about 0.5% to about 8%, about 0.5% to about 10%, about 1% to about 2%, about 1% to about 3%, about 1% to about 4%, about 1% to about 5%, about 1% to about 6%, about 1% to about 7%, about 1% to about 8%, about 1% to about 10%, about 2% to about 3%, about 2% to about 4%, about 2% to about 5%, about 2% to about 6%, about 2% to about 7%, about 2% to about 8%, about 2% to about 10%, about 3% to about 4%, about 3% to about 5%, about 3% to about 6%, about 3% to about 7%, about 3% to about 8%, about 3% to about 10%, about 4% to about 5%, about 4% to about 6%, about 4% to about 7%, about 4% to about 8%, about 4% to about 10%, about 5% to about 6%, about 5% to about 7%, about 5% to about 8%, about 5% to about 10%, about 6% to about 7%, about 6% to about 8%, about 6% to about 10%, about 7% to about 8%, about 7% to about 10%, or about 8% to about 10%. In some embodiments, a concentration by mass, by volume, or both of the graphene sheet in the first electrode is about 0.1%, about 0.2%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, or about 10%. In some embodiments, a concentration by mass, by volume, or both of the graphene sheet in the first electrode is at least about 0.1%, about 0.2%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, or about 8%. In some embodiments, a concentration by mass, by volume, or both of the graphene sheet in the first electrode is at most about 0.2%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, or about 10%.
In some embodiments, a concentration by mass, by volume, or both of the LDH in the first electrode is about 1% to about 80%. In some embodiments, a concentration by mass, by volume, or both of the LDH in the first electrode is about 1% to about 5%, about 1% to about 10%, about 1% to about 20%, about 1% to about 30%, about 1% to about 40%, about 1% to about 50%, about 1% to about 60%, about 1% to about 70%, about 1% to about 80%, about 5% to about 10%, about 5% to about 20%, about 5% to about 30%, about 5% to about 40%, about 5% to about 50%, about 5% to about 60%, about 5% to about 70%, about 5% to about 80%, about 10% to about 20%, about 10% to about 30%, about 10% to about 40%, about 10% to about 50%, about 10% to about 60%, about 10% to about 70%, about 10% to about 80%, about 20% to about 30%, about 20% to about 40%, about 20% to about 50%, about 20% to about 60%, about 20% to about 70%, about 20% to about 80%, about 30% to about 40%, about 30% to about 50%, about 30% to about 60%, about 30% to about 70%, about 30% to about 80%, about 40% to about 50%, about 40% to about 60%, about 40% to about 70%, about 40% to about 80%, about 50% to about 60%, about 50% to about 70%, about 50% to about 80%, about 60% to about 70%, about 60% to about 80%, or about 70% to about 80%. In some embodiments, a concentration by mass, by volume, or both of the LDH in the first electrode is about 1%, about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 80%. In some embodiments, a concentration by mass, by volume, or both of the LDH in the first electrode is at least about 1%, about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, or about 70%. In some embodiments, a concentration by mass, by volume, or both of the LDH in the first electrode is at most about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 80%.
In some embodiments, a concentration by mass, by volume, or both of the binder in the first electrode is about 1% to about 20%. In some embodiments, a concentration by mass, by volume, or both of the binder in the first electrode is about 1% to about 2%, about 1% to about 5%, about 1% to about 8%, about 1% to about 10%, about 1% to about 12%, about 1% to about 14%, about 1% to about 16%, about 1% to about 18%, about 1% to about 20%, about 2% to about 5%, about 2% to about 8%, about 2% to about 10%, about 2% to about 12%, about 2% to about 14%, about 2% to about 16%, about 2% to about 18%, about 2% to about 20%, about 5% to about 8%, about 5% to about 10%, about 5% to about 12%, about 5% to about 14%, about 5% to about 16%, about 5% to about 18%, about 5% to about 20%, about 8% to about 10%, about 8% to about 12%, about 8% to about 14%, about 8% to about 16%, about 8% to about 18%, about 8% to about 20%, about 10% to about 12%, about 10% to about 14%, about 10% to about 16%, about 10% to about 18%, about 10% to about 20%, about 12% to about 14%, about 12% to about 16%, about 12% to about 18%, about 12% to about 20%, about 14% to about 16%, about 14% to about 18%, about 14% to about 20%, about 16% to about 18%, about 16% to about 20%, or about 18% to about 20%. In some embodiments, a concentration by mass, by volume, or both of the binder in the first electrode is about 1%, about 2%, about 5%, about 8%, about 10%, about 12%, about 14%, about 16%, about 18%, or about 20%. In some embodiments, a concentration by mass, by volume, or both of the binder in the first electrode is at least about 1%, about 2%, about 5%, about 8%, about 10%, about 12%, about 14%, about 16%, or about 18%. In some embodiments, a concentration by mass, by volume, or both of the binder in the first electrode is at most about 2%, about 5%, about 8%, about 10%, about 12%, about 14%, about 16%, about 18%, or about 20%.
In some embodiments, a concentration by mass, by volume, or both of the conductive additive in the first electrode is about 1% to about 30%. In some embodiments, a concentration by mass, by volume, or both of the conductive additive in the first electrode is about 1% to about 2%, about 1% to about 5%, about 1% to about 10%, about 1% to about 14%, about 1% to about 18%, about 1% to about 22%, about 1% to about 26%, about 1% to about 30%, about 2% to about 5%, about 2% to about 10%, about 2% to about 14%, about 2% to about 18%, about 2% to about 22%, about 2% to about 26%, about 2% to about 30%, about 5% to about 10%, about 5% to about 14%, about 5% to about 18%, about 5% to about 22%, about 5% to about 26%, about 5% to about 30%, about 10% to about 14%, about 10% to about 18%, about 10% to about 22%, about 10% to about 26%, about 10% to about 30%, about 14% to about 18%, about 14% to about 22%, about 14% to about 26%, about 14% to about 30%, about 18% to about 22%, about 18% to about 26%, about 18% to about 30%, about 22% to about 26%, about 22% to about 30%, or about 26% to about 30%. In some embodiments, a concentration by mass, by volume, or both of the conductive additive in the first electrode is about 1%, about 2%, about 5%, about 10%, about 14%, about 18%, about 22%, about 26%, or about 30%. In some embodiments, a concentration by mass, by volume, or both of the conductive additive in the first electrode is at least about 1%, about 2%, about 5%, about 10%, about 14%, about 18%, about 22%, or about 26%. In some embodiments, a concentration by mass, by volume, or both of the conductive additive in the first electrode is at most about 2%, about 5%, about 10%, about 14%, about 18%, about 22%, about 26%, or about 30%.
In some embodiments, the plurality of graphene sheets comprises about 5 layers to about 1,000,000,000 layers. In some embodiments, the plurality of graphene sheets comprises about 5 layers to about 10 layers, about 5 layers to about 100 layers, about 5 layers to about 1,000 layers, about 5 layers to about 10,000 layers, about 5 layers to about 100,000 layers, about 5 layers to about 1,000,000 layers, about 5 layers to about 10,000,000 layers, about 5 layers to about 100,000,000 layers, about 5 layers to about 1,000,000,000 layers, about 10 layers to about 100 layers, about 10 layers to about 1,000 layers, about 10 layers to about 10,000 layers, about 10 layers to about 100,000 layers, about 10 layers to about 1,000,000 layers, about 10 layers to about 10,000,000 layers, about 10 layers to about 100,000,000 layers, about 10 layers to about 1,000,000,000 layers, about 100 layers to about 1,000 layers, about 100 layers to about 10,000 layers, about 100 layers to about 100,000 layers, about 100 layers to about 1,000,000 layers, about 100 layers to about 10,000,000 layers, about 100 layers to about 100,000,000 layers, about 100 layers to about 1,000,000,000 layers, about 1,000 layers to about 10,000 layers, about 1,000 layers to about 100,000 layers, about 1,000 layers to about 1,000,000 layers, about 1,000 layers to about 10,000,000 layers, about 1,000 layers to about 100,000,000 layers, about 1,000 layers to about 1,000,000,000 layers, about 10,000 layers to about 100,000 layers, about 10,000 layers to about 1,000,000 layers, about 10,000 layers to about 10,000,000 layers, about 10,000 layers to about 100,000,000 layers, about 10,000 layers to about 1,000,000,000 layers, about 100,000 layers to about 1,000,000 layers, about 100,000 layers to about 10,000,000 layers, about 100,000 layers to about 100,000,000 layers, about 100,000 layers to about 1,000,000,000 layers, about 1,000,000 layers to about 10,000,000 layers, about 1,000,000 layers to about 100,000,000 layers, about 1,000,000 layers to about 1,000,000,000 layers, about 10,000,000 layers to about 100,000,000 layers, about 10,000,000 layers to about 1,000,000,000 layers, or about 100,000,000 layers to about 1,000,000,000 layers. In some embodiments, the plurality of graphene sheets comprises about 5 layers, about 10 layers, about 100 layers, about 1,000 layers, about 10,000 layers, about 100,000 layers, about 1,000,000 layers, about 10,000,000 layers, about 100,000,000 layers, or about 1,000,000,000 layers. In some embodiments, the plurality of graphene sheets comprises at least about 5 layers, about 10 layers, about 100 layers, about 1,000 layers, about 10,000 layers, about 100,000 layers, about 1,000,000 layers, about 10,000,000 layers, or about 100,000,000 layers. In some embodiments, the plurality of graphene sheets comprises at most about 10 layers, about 100 layers, about 1,000 layers, about 10,000 layers, about 100,000 layers, about 1,000,000 layers, about 10,000,000 layers, about 100,000,000 layers, or about 1,000,000,000 layers.
Layered Double Hydroxides
In some embodiments, the quantity of LDH in the electrodes can be used to tune the performance of the electrodes and energy storage devices. In some embodiments, increasing the amount of LDH increases the specific capacity for high energy density applications.
In some embodiments, the LDH is bonded to a graphene sheet. In some embodiments, the concentration by mass, by volume, or both of the graphene sheet of below about 10% enables the graphene to serve as a substrate for LDH growth but does not form a complete matrix that limits the density of the LDH-graphene composite 720. In some embodiments, the LDH is a nanofiber, a nanoplatelet, a nanoflower, a nanodot, a nanoparticle, or any combination thereof. In some embodiments, the LDH is a powder, a bulk material, a slurry, a paste, or a dispersion. In some embodiments, the LDH is synthesized as a powder that can be easily processed into slurries or pastes for large-scale electrode manufacturing.
In some embodiments, LDHs enable electrochemical storage in the first electrode.
The general formula of LDH 702 is:
[M2+1-xM3+x(OH)2]x+(Am−)x/m.nH2O
wherein M2+ is a bivalent cation, M3+ is a trivalent cation, and A is a counter anion with negative charge (m). In some embodiments, the LDH 702 has an octahedral structure, in which metal cations are accommodated in the centers of the edge-sharing octahedral, and wherein each cation contains six OH− ions that are pointed towards the corners and form infinite sheets. In some embodiments, the M2+ and M3+ cations are distributed in a uniform manner in the structural hydroxide layers of the LDH. In some embodiments, the LDH comprises a zinc-bismuth LDH, a bismuth hydroxide LDH, a ferric hydroxide LDH, a nickel hydroxide LDH, a nickel-cobalt LDH, or any combination thereof.
In the octahedral structure, the metal cations are accommodated in the centers of the edge-sharing octahedral. In some embodiments, each cation contains six OH− ions that are pointed towards the corners and form infinite sheets. One of the important structural characteristics of LDH materials is that the M2+ and M3+ cations are distributed in a uniform manner in the hydroxide layers.
In some embodiments, the metal cation 801 comprises an M2+ metal cation, an M3+ metal, or both. In some embodiments, the M2+ metal cation comprises barium, cadmium, calcium, cobalt, copper (II), iron (II), lead (II), magnesium, mercury (I), mercury (II), nickel, strontium, tin, zinc, or any combination thereof. In some embodiments, the M3+ metal cation comprises aluminum, bismuth, chromium (III), iron (III), or any combination thereof.
In some embodiments, the hydroxide ion 802 comprises aluminum hydroxide, ammonium hydroxide, arsenic hydroxide, barium hydroxide, beryllium hydroxide, bismuth(III) hydroxide, boron hydroxide, cadmium hydroxide, calcium hydroxide, cerium(III) hydroxide, cesium hydroxide, chromium(II) hydroxide, chromium(III) hydroxide, chromium(V) hydroxide, chromium(VI) hydroxide, cobalt(II) hydroxide, cobalt(III) hydroxide, copper(I) hydroxide, copper(II) hydroxide, gallium(II) hydroxide, gallium(III) hydroxide, gold(I) hydroxide, gold(III) hydroxide, indium(I) hydroxide, indium(II) hydroxide, indium(III) hydroxide, iridium(III) hydroxide, iron(II) hydroxide, iron(III) hydroxide, lanthanum hydroxide, lead(II) hydroxide, lead(IV) hydroxide, lithium hydroxide, magnesium hydroxide, manganese(II) hydroxide, manganese(III) hydroxide, manganese(IV) hydroxide, manganese(VII) hydroxide, mercury(I) hydroxide, mercury(II) hydroxide, molybdenum hydroxide, neodymium hydroxide, nickel oxo-hydroxide, nickel(II) hydroxide, nickel(III) hydroxide, niobium hydroxide, osmium(IV) hydroxide, palladium(II) hydroxide, palladium(IV) hydroxide, platinum(II) hydroxide, platinum(IV) hydroxide, plutonium(IV) hydroxide, potassium hydroxide, radium hydroxide, rubidium hydroxide, ruthenium(III) hydroxide, scandium hydroxide, silicon hydroxide, silver hydroxide, sodium hydroxide, strontium hydroxide, tantalum(V) hydroxide, technetium(II) hydroxide, tetramethylammonium hydroxide, thallium(I) hydroxide, thallium(III) hydroxide, thorium hydroxide, tin(II) hydroxide, tin(IV) hydroxide, titanium(II) hydroxide, titanium(III) hydroxide, titanium(IV) hydroxide, tungsten(II) hydroxide, uranyl hydroxide, vanadium(II) hydroxide, vanadium(III) hydroxide, vanadium(V) hydroxide, ytterbium hydroxide, yttrium hydroxide, zinc hydroxide, zirconium hydroxide. In some embodiments, the hydroxide ion 802 comprises cobalt(II) hydroxide. In some embodiments, the hydroxide ion 802 comprises cobalt(III) hydroxide. In some embodiments, the hydroxide ion 802 comprises copper(I) hydroxide. In some embodiments, the hydroxide ion 802 comprises copper(II) hydroxide. In some embodiments, the hydroxide ion 802 comprises nickel(II) hydroxide. In some embodiments, the hydroxide ion 802 comprises nickel(III) hydroxide.
In some embodiments, the hydroxide ion 802 comprises hydroxide nanoparticles, hydroxide nanopowder, hydroxide nanoflowers, hydroxide nanoflakes, hydroxide nanodots, hydroxide nanorods, hydroxide nanochains, hydroxide nanofibers, hydroxide nanoparticles, hydroxide nanoplatelets, hydroxide nanoribbons, hydroxide nanorings, hydroxide nanosheets, or a combination thereof. In some embodiments, the anion 806 comprises nitrate, sulfate, carbonate, chloride, bromide, or any combination thereof.
Electrolytes
In some embodiments, various electrolytes can be used in the energy storage devices herein. In some embodiments, per
In some embodiments, the electrolyte 430 comprises: a hydroxide, an additive, a stabilizer, a hydrogen evolution inhibitor, and a conductivity enhancer. In some embodiments, the electrolyte 430 comprises zinc oxide powder dissolved in an alkaline solution of 7.1 M potassium hydroxide in water.
Hydrogen evolution reaction is the production of hydrogen through the process of water electrolysis, which causes the desorption of molecules from the surface of an electrode of one of a first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. As such, in some embodiments, at least one of the additive, the stabilizer, and the hydrogen evolution inhibitor reduces and/or inhibits the evolution of hydrogen gas on the surface of the electrode of one of a first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. In some embodiments, at least one of the additive, the stabilizer, and the hydrogen evolution inhibitor prevents and/or reduces the decomposition of the electrolyte 430, the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, and the second electrode 420. In some embodiments, at least one of the additive, the stabilizer, and the hydrogen evolution inhibitor prevents and/or reduces the decomposition of the electrolyte 430, the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, and the second electrode 420 during charging, discharging, or both. In some embodiments, such decomposition prevention/reduction increases the discharge capacity of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, herein. In some embodiments, at least one of the additive, the stabilizer, and the hydrogen evolution inhibitor inhibit the active materials in the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, the second electrode 420, or both from dissolving into the electrolyte 430. In some embodiments, at least one of the additive, the stabilizer, and the hydrogen evolution inhibitor inhibit the active materials in the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, the second electrode 420, or both from dissolving into the electrolyte 430 during charging, discharging, or both. In some embodiments, at least one of the additive, the stabilizer, and the hydrogen evolution inhibitor enables zero net decomposition or dissolution of the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, the second electrode 420, or both. In some embodiments, such dissolution prevention/reduction increases the discharge capacity of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, herein.
Furthermore, dendrite formation on the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, the second electrode 420, or both during hydrogen evolution is detrimental to the stability of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively. Such sharp dendrites puncture components of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, such as the separators and current collectors. As such, in some embodiments, at least one of the additive and the hydrogen evolution inhibitor reduces and/or inhibits the formation of dendrites on the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, the second electrode 420, or both. In some embodiments, the reduced/inhibited dendrite formation enables the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, with increased stability and performance over a number of charging and discharging cycles.
In some embodiments, the stabilizer contributes to the redox reactions during charging and discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, herein. In some embodiments, the stabilizer suppresses hydrogen evolution during charging and discharging of the first, second, third, and fourth energy storage devices 400, 500, 600A, and 600B, respectively, herein. In some embodiments, the stabilizer is soluble in strong alkaline solutions. In one embodiment, the stabilizer comprises zinc oxide which converts into hydroxide or zincate during the redox reaction. In another embodiment, the stabilizer comprises bismuth. In some embodiments, the conductivity enhancer increases a conductivity of the primary, secondary, tertiary, and quaternary first electrodes 410, 510, 610A, and 610B, respectively, the second electrode 420, or both.
In some embodiments, the hydroxide ion comprises aluminum hydroxide, barium hydroxide, benzyltrimethylammonium hydroxide, beryllium hydroxide, cadmium hydroxide, cesium hydroxide, calcium hydroxide, cerium(III) hydroxide, chromium acetate hydroxide, chromium(III) hydroxide, cobalt(II) hydroxide, cobalt(III) hydroxide, copper(I) hydroxide, copper(II) hydroxide, curium hydroxide, gallium(III) hydroxide, germanium(II) hydroxide, gold(III) hydroxide, indium(III) hydroxide, iron(II) hydroxide, iron(III) oxide-hydroxide, lanthanum hydroxide, lead(II) hydroxide, lead(IV) hydroxide, lithium hydroxide, magnesium hydroxide, manganese(II) hydroxide, mercury(II) hydroxide, metal hydroxide, nickel(II) hydroxide, potassium hydroxide, rubidium hydroxide, sodium hydroxide, strontium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, thallium hydroxide, thallium(I) hydroxide, thallium(III) hydroxide, tin(II) hydroxide, uranyl hydroxide, zinc hydroxide, zirconium(IV) hydroxide, or any combination thereof.
In some embodiments, the additive comprises calcium hydroxide, calcium titanate, calcium zincate, potassium fluoride, sodium phosphate tribasic, potassium phosphate, sodium fluoride, potassium borate, potassium carbonate, or any combination thereof.
In some embodiments, the stabilizer comprises an electrochemical couple of the electrode. In some embodiments, the stabilizer comprises zinc oxide, zinc hydroxide, sodium zincate, potassium zincate, bismuth oxide, cadmium oxide, indium sulfate, lead oxide, a metallic zinc powder, or any combination thereof.
In some embodiments, the hydrogen evolution inhibitor comprises bismuth oxide, cadmium oxide, a conductive ceramic, lead oxide, a metallic zinc powder, antimony sulfate, gallium hydroxide, indium sulfate, lithium hydroxide, or any combination thereof.
In some embodiments, the conductivity enhancer comprises a conductive ceramic. In some embodiments, the conductive ceramic comprises a dielectric ceramic, a piezoelectric ceramic, or a ferroelectric ceramic. In some embodiments, the conductive ceramic comprises lead zirconate titanate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, calcium magnesium titanate, zinc titanate, lanthanum titanate, and neodymium titanate, barium zirconate, calcium zirconate, lead magnesium niobate, lead zinc niobate, lithium niobate, barium stannate, calcium stannate, magnesium aluminum silicate, magnesium silicate, barium tantalate, titanium dioxide, niobium oxide, zirconia, quartz, silica, sapphire, beryllium oxide, zirconium tin titanate, indium tin oxide, lanthanum-doped strontium titanate, yttrium-doped strontium titanate, yttria-stabilized zirconia, gadolinium-doped ceria, lanthanum strontium gallate magnesite, or any combination thereof.
In some embodiments, a concentration by mass of the hydroxide within the electrolyte is about 22% to about 91%. In some embodiments, a concentration by mass of the hydroxide within the electrolyte is about 22% to about 25%, about 22% to about 30%, about 22% to about 35%, about 22% to about 40%, about 22% to about 45%, about 22% to about 50%, about 22% to about 55%, about 22% to about 60%, about 22% to about 70%, about 22% to about 80%, about 22% to about 91%, about 25% to about 30%, about 25% to about 35%, about 25% to about 40%, about 25% to about 45%, about 25% to about 50%, about 25% to about 55%, about 25% to about 60%, about 25% to about 70%, about 25% to about 80%, about 25% to about 91%, about 30% to about 35%, about 30% to about 40%, about 30% to about 45%, about 30% to about 50%, about 30% to about 55%, about 30% to about 60%, about 30% to about 70%, about 30% to about 80%, about 30% to about 91%, about 35% to about 40%, about 35% to about 45%, about 35% to about 50%, about 35% to about 55%, about 35% to about 60%, about 35% to about 70%, about 35% to about 80%, about 35% to about 91%, about 40% to about 45%, about 40% to about 50%, about 40% to about 55%, about 40% to about 60%, about 40% to about 70%, about 40% to about 80%, about 40% to about 91%, about 45% to about 50%, about 45% to about 55%, about 45% to about 60%, about 45% to about 70%, about 45% to about 80%, about 45% to about 91%, about 50% to about 55%, about 50% to about 60%, about 50% to about 70%, about 50% to about 80%, about 50% to about 91%, about 55% to about 60%, about 55% to about 70%, about 55% to about 80%, about 55% to about 91%, about 60% to about 70%, about 60% to about 80%, about 60% to about 91%, about 70% to about 80%, about 70% to about 91%, or about 80% to about 91%. In some embodiments, a concentration by mass of the hydroxide within the electrolyte is about 22%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 70%, about 80%, or about 91%. In some embodiments, a concentration by mass of the hydroxide within the electrolyte is at least about 22%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 70%, or about 80%. In some embodiments, a concentration by mass of the hydroxide within the electrolyte is at most about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 70%, about 80%, or about 91%.
In some embodiments, a concentration by mass of the additive within the electrolyte is about 5% to about 16%. In some embodiments, a concentration by mass of the additive within the electrolyte is about 5% to about 6%, about 5% to about 7%, about 5% to about 8%, about 5% to about 9%, about 5% to about 10%, about 5% to about 11%, about 5% to about 12%, about 5% to about 13%, about 5% to about 14%, about 5% to about 15%, about 5% to about 16%, about 6% to about 7%, about 6% to about 8%, about 6% to about 9%, about 6% to about 10%, about 6% to about 11%, about 6% to about 12%, about 6% to about 13%, about 6% to about 14%, about 6% to about 15%, about 6% to about 16%, about 7% to about 8%, about 7% to about 9%, about 7% to about 10%, about 7% to about 11%, about 7% to about 12%, about 7% to about 13%, about 7% to about 14%, about 7% to about 15%, about 7% to about 16%, about 8% to about 9%, about 8% to about 10%, about 8% to about 11%, about 8% to about 12%, about 8% to about 13%, about 8% to about 14%, about 8% to about 15%, about 8% to about 16%, about 9% to about 10%, about 9% to about 11%, about 9% to about 12%, about 9% to about 13%, about 9% to about 14%, about 9% to about 15%, about 9% to about 16%, about 10% to about 11%, about 10% to about 12%, about 10% to about 13%, about 10% to about 14%, about 10% to about 15%, about 10% to about 16%, about 11% to about 12%, about 11% to about 13%, about 11% to about 14%, about 11% to about 15%, about 11% to about 16%, about 12% to about 13%, about 12% to about 14%, about 12% to about 15%, about 12% to about 16%, about 13% to about 14%, about 13% to about 15%, about 13% to about 16%, about 14% to about 15%, about 14% to about 16%, or about 15% to about 16%. In some embodiments, a concentration by mass of the additive within the electrolyte is about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, or about 16%. In some embodiments, a concentration by mass of the additive within the electrolyte is at least about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%. In some embodiments, a concentration by mass of the additive within the electrolyte is at most about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, or about 16%.
In some embodiments, a concentration by mass of the stabilizer within the electrolyte is about 1% to about 5%. In some embodiments, a concentration by mass of the stabilizer within the electrolyte is about 1% to about 1.5%, about 1% to about 2%, about 1% to about 2.5%, about 1% to about 3%, about 1% to about 3.5%, about 1% to about 4%, about 1% to about 4.5%, about 1% to about 5%, about 1.5% to about 2%, about 1.5% to about 2.5%, about 1.5% to about 3%, about 1.5% to about 3.5%, about 1.5% to about 4%, about 1.5% to about 4.5%, about 1.5% to about 5%, about 2% to about 2.5%, about 2% to about 3%, about 2% to about 3.5%, about 2% to about 4%, about 2% to about 4.5%, about 2% to about 5%, about 2.5% to about 3%, about 2.5% to about 3.5%, about 2.5% to about 4%, about 2.5% to about 4.5%, about 2.5% to about 5%, about 3% to about 3.5%, about 3% to about 4%, about 3% to about 4.5%, about 3% to about 5%, about 3.5% to about 4%, about 3.5% to about 4.5%, about 3.5% to about 5%, about 4% to about 4.5%, about 4% to about 5%, or about 4.5% to about 5%. In some embodiments, a concentration by mass of the stabilizer within the electrolyte is about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%. In some embodiments, a concentration by mass of the stabilizer within the electrolyte is at least about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, or about 4.5%. In some embodiments, a concentration by mass of the stabilizer within the electrolyte is at most about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%.
In some embodiments, a concentration by mass of the hydrogen evolution inhibitor within the electrolyte is about 1% to about 5%. In some embodiments, a concentration by mass of the hydrogen evolution inhibitor within the electrolyte is about 1% to about 1.5%, about 1% to about 2%, about 1% to about 2.5%, about 1% to about 3%, about 1% to about 3.5%, about 1% to about 4%, about 1% to about 4.5%, about 1% to about 5%, about 1.5% to about 2%, about 1.5% to about 2.5%, about 1.5% to about 3%, about 1.5% to about 3.5%, about 1.5% to about 4%, about 1.5% to about 4.5%, about 1.5% to about 5%, about 2% to about 2.5%, about 2% to about 3%, about 2% to about 3.5%, about 2% to about 4%, about 2% to about 4.5%, about 2% to about 5%, about 2.5% to about 3%, about 2.5% to about 3.5%, about 2.5% to about 4%, about 2.5% to about 4.5%, about 2.5% to about 5%, about 3% to about 3.5%, about 3% to about 4%, about 3% to about 4.5%, about 3% to about 5%, about 3.5% to about 4%, about 3.5% to about 4.5%, about 3.5% to about 5%, about 4% to about 4.5%, about 4% to about 5%, or about 4.5% to about 5%. In some embodiments, a concentration by mass of the hydrogen evolution inhibitor within the electrolyte is about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%. In some embodiments, a concentration by mass of the hydrogen evolution inhibitor within the electrolyte is at least about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, or about 4.5%. In some embodiments, a concentration by mass of the hydrogen evolution inhibitor within the electrolyte is at most about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%.
In some embodiments, a concentration by mass of the conductivity enhancer within the electrolyte is about 1% to about 5%. In some embodiments, a concentration by mass of the conductivity enhancer within the electrolyte is about 1% to about 1.5%, about 1% to about 2%, about 1% to about 2.5%, about 1% to about 3%, about 1% to about 3.5%, about 1% to about 4%, about 1% to about 4.5%, about 1% to about 5%, about 1.5% to about 2%, about 1.5% to about 2.5%, about 1.5% to about 3%, about 1.5% to about 3.5%, about 1.5% to about 4%, about 1.5% to about 4.5%, about 1.5% to about 5%, about 2% to about 2.5%, about 2% to about 3%, about 2% to about 3.5%, about 2% to about 4%, about 2% to about 4.5%, about 2% to about 5%, about 2.5% to about 3%, about 2.5% to about 3.5%, about 2.5% to about 4%, about 2.5% to about 4.5%, about 2.5% to about 5%, about 3% to about 3.5%, about 3% to about 4%, about 3% to about 4.5%, about 3% to about 5%, about 3.5% to about 4%, about 3.5% to about 4.5%, about 3.5% to about 5%, about 4% to about 4.5%, about 4% to about 5%, or about 4.5% to about 5%. In some embodiments, a concentration by mass of the conductivity enhancer within the electrolyte is about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%. In some embodiments, a concentration by mass of the conductivity enhancer within the electrolyte is at least about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, or about 4.5%. In some embodiments, a concentration by mass of the conductivity enhancer within the electrolyte is at most about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%.
In some embodiments, a concentration by volume of the hydroxide within the electrolyte is about 220 g/L to about 900 g/L. In some embodiments, a concentration by volume of the hydroxide within the electrolyte is about 220 g/L to about 250 g/L, about 220 g/L to about 300 g/L, about 220 g/L to about 350 g/L, about 220 g/L to about 400 g/L, about 220 g/L to about 450 g/L, about 220 g/L to about 500 g/L, about 220 g/L to about 550 g/L, about 220 g/L to about 600 g/L, about 220 g/L to about 700 g/L, about 220 g/L to about 800 g/L, about 220 g/L to about 900 g/L, about 250 g/L to about 300 g/L, about 250 g/L to about 350 g/L, about 250 g/L to about 400 g/L, about 250 g/L to about 450 g/L, about 250 g/L to about 500 g/L, about 250 g/L to about 550 g/L, about 250 g/L to about 600 g/L, about 250 g/L to about 700 g/L, about 250 g/L to about 800 g/L, about 250 g/L to about 900 g/L, about 300 g/L to about 350 g/L, about 300 g/L to about 400 g/L, about 300 g/L to about 450 g/L, about 300 g/L to about 500 g/L, about 300 g/L to about 550 g/L, about 300 g/L to about 600 g/L, about 300 g/L to about 700 g/L, about 300 g/L to about 800 g/L, about 300 g/L to about 900 g/L, about 350 g/L to about 400 g/L, about 350 g/L to about 450 g/L, about 350 g/L to about 500 g/L, about 350 g/L to about 550 g/L, about 350 g/L to about 600 g/L, about 350 g/L to about 700 g/L, about 350 g/L to about 800 g/L, about 350 g/L to about 900 g/L, about 400 g/L to about 450 g/L, about 400 g/L to about 500 g/L, about 400 g/L to about 550 g/L, about 400 g/L to about 600 g/L, about 400 g/L to about 700 g/L, about 400 g/L to about 800 g/L, about 400 g/L to about 900 g/L, about 450 g/L to about 500 g/L, about 450 g/L to about 550 g/L, about 450 g/L to about 600 g/L, about 450 g/L to about 700 g/L, about 450 g/L to about 800 g/L, about 450 g/L to about 900 g/L, about 500 g/L to about 550 g/L, about 500 g/L to about 600 g/L, about 500 g/L to about 700 g/L, about 500 g/L to about 800 g/L, about 500 g/L to about 900 g/L, about 550 g/L to about 600 g/L, about 550 g/L to about 700 g/L, about 550 g/L to about 800 g/L, about 550 g/L to about 900 g/L, about 600 g/L to about 700 g/L, about 600 g/L to about 800 g/L, about 600 g/L to about 900 g/L, about 700 g/L to about 800 g/L, about 700 g/L to about 900 g/L, or about 800 g/L to about 900 g/L. In some embodiments, a concentration by volume of the hydroxide within the electrolyte is about 220 g/L, about 250 g/L, about 300 g/L, about 350 g/L, about 400 g/L, about 450 g/L, about 500 g/L, about 550 g/L, about 600 g/L, about 700 g/L, about 800 g/L, or about 900 g/L. In some embodiments, a concentration by volume of the hydroxide within the electrolyte is at least about 220 g/L, about 250 g/L, about 300 g/L, about 350 g/L, about 400 g/L, about 450 g/L, about 500 g/L, about 550 g/L, about 600 g/L, about 700 g/L, or about 800 g/L. In some embodiments, a concentration by volume of the hydroxide within the electrolyte is at most about 250 g/L, about 300 g/L, about 350 g/L, about 400 g/L, about 450 g/L, about 500 g/L, about 550 g/L, about 600 g/L, about 700 g/L, about 800 g/L, or about 900 g/L.
In some embodiments, a concentration by volume of the additive within the electrolyte is about 30 g/L to about 160 g/L. In some embodiments, a concentration by volume of the additive within the electrolyte is about 30 g/L to about 40 g/L, about 30 g/L to about 50 g/L, about 30 g/L to about 60 g/L, about 30 g/L to about 70 g/L, about 30 g/L to about 80 g/L, about 30 g/L to about 90 g/L, about 30 g/L to about 100 g/L, about 30 g/L to about 120 g/L, about 30 g/L to about 140 g/L, about 30 g/L to about 160 g/L, about 40 g/L to about 50 g/L, about 40 g/L to about 60 g/L, about 40 g/L to about 70 g/L, about 40 g/L to about 80 g/L, about 40 g/L to about 90 g/L, about 40 g/L to about 100 g/L, about 40 g/L to about 120 g/L, about 40 g/L to about 140 g/L, about 40 g/L to about 160 g/L, about 50 g/L to about 60 g/L, about 50 g/L to about 70 g/L, about 50 g/L to about 80 g/L, about 50 g/L to about 90 g/L, about 50 g/L to about 100 g/L, about 50 g/L to about 120 g/L, about 50 g/L to about 140 g/L, about 50 g/L to about 160 g/L, about 60 g/L to about 70 g/L, about 60 g/L to about 80 g/L, about 60 g/L to about 90 g/L, about 60 g/L to about 100 g/L, about 60 g/L to about 120 g/L, about 60 g/L to about 140 g/L, about 60 g/L to about 160 g/L, about 70 g/L to about 80 g/L, about 70 g/L to about 90 g/L, about 70 g/L to about 100 g/L, about 70 g/L to about 120 g/L, about 70 g/L to about 140 g/L, about 70 g/L to about 160 g/L, about 80 g/L to about 90 g/L, about 80 g/L to about 100 g/L, about 80 g/L to about 120 g/L, about 80 g/L to about 140 g/L, about 80 g/L to about 160 g/L, about 90 g/L to about 100 g/L, about 90 g/L to about 120 g/L, about 90 g/L to about 140 g/L, about 90 g/L to about 160 g/L, about 100 g/L to about 120 g/L, about 100 g/L to about 140 g/L, about 100 g/L to about 160 g/L, about 120 g/L to about 140 g/L, about 120 g/L to about 160 g/L, or about 140 g/L to about 160 g/L. In some embodiments, a concentration by volume of the additive within the electrolyte is about 30 g/L, about 40 g/L, about 50 g/L, about 60 g/L, about 70 g/L, about 80 g/L, about 90 g/L, about 100 g/L, about 120 g/L, about 140 g/L, or about 160 g/L. In some embodiments, a concentration by volume of the additive within the electrolyte is at least about 30 g/L, about 40 g/L, about 50 g/L, about 60 g/L, about 70 g/L, about 80 g/L, about 90 g/L, about 100 g/L, about 120 g/L, or about 140 g/L. In some embodiments, a concentration by volume of the additive within the electrolyte is at most about 40 g/L, about 50 g/L, about 60 g/L, about 70 g/L, about 80 g/L, about 90 g/L, about 100 g/L, about 120 g/L, about 140 g/L, or about 160 g/L.
In some embodiments, a concentration by volume of the stabilizer within the electrolyte is about 10 g/L to about 40 g/L. In some embodiments, a concentration by volume of the stabilizer within the electrolyte is about 10 g/L to about 12 g/L, about 10 g/L to about 14 g/L, about 10 g/L to about 16 g/L, about 10 g/L to about 18 g/L, about 10 g/L to about 20 g/L, about 10 g/L to about 24 g/L, about 10 g/L to about 28 g/L, about 10 g/L to about 32 g/L, about 10 g/L to about 36 g/L, about 10 g/L to about 40 g/L, about 12 g/L to about 14 g/L, about 12 g/L to about 16 g/L, about 12 g/L to about 18 g/L, about 12 g/L to about 20 g/L, about 12 g/L to about 24 g/L, about 12 g/L to about 28 g/L, about 12 g/L to about 32 g/L, about 12 g/L to about 36 g/L, about 12 g/L to about 40 g/L, about 14 g/L to about 16 g/L, about 14 g/L to about 18 g/L, about 14 g/L to about 20 g/L, about 14 g/L to about 24 g/L, about 14 g/L to about 28 g/L, about 14 g/L to about 32 g/L, about 14 g/L to about 36 g/L, about 14 g/L to about 40 g/L, about 16 g/L to about 18 g/L, about 16 g/L to about 20 g/L, about 16 g/L to about 24 g/L, about 16 g/L to about 28 g/L, about 16 g/L to about 32 g/L, about 16 g/L to about 36 g/L, about 16 g/L to about 40 g/L, about 18 g/L to about 20 g/L, about 18 g/L to about 24 g/L, about 18 g/L to about 28 g/L, about 18 g/L to about 32 g/L, about 18 g/L to about 36 g/L, about 18 g/L to about 40 g/L, about 20 g/L to about 24 g/L, about 20 g/L to about 28 g/L, about 20 g/L to about 32 g/L, about 20 g/L to about 36 g/L, about 20 g/L to about 40 g/L, about 24 g/L to about 28 g/L, about 24 g/L to about 32 g/L, about 24 g/L to about 36 g/L, about 24 g/L to about 40 g/L, about 28 g/L to about 32 g/L, about 28 g/L to about 36 g/L, about 28 g/L to about 40 g/L, about 32 g/L to about 36 g/L, about 32 g/L to about 40 g/L, or about 36 g/L to about 40 g/L. In some embodiments, a concentration by volume of the stabilizer within the electrolyte is about 10 g/L, about 12 g/L, about 14 g/L, about 16 g/L, about 18 g/L, about 20 g/L, about 24 g/L, about 28 g/L, about 32 g/L, about 36 g/L, or about 40 g/L. In some embodiments, a concentration by volume of the stabilizer within the electrolyte is at least about 10 g/L, about 12 g/L, about 14 g/L, about 16 g/L, about 18 g/L, about 20 g/L, about 24 g/L, about 28 g/L, about 32 g/L, or about 36 g/L. In some embodiments, a concentration by volume of the stabilizer within the electrolyte is at most about 12 g/L, about 14 g/L, about 16 g/L, about 18 g/L, about 20 g/L, about 24 g/L, about 28 g/L, about 32 g/L, about 36 g/L, or about 40 g/L.
Methods of Forming Electrodes
Provided herein are methods of forming an electrode. In some embodiments, the method comprises ambient pressure synthesis. In some embodiments, the methods herein are performed at ambient temperatures, ambient pressures, or both. In some embodiments, the low/ambient temperatures and pressures used by the methods herein enable the formation of electrodes at a large scales and reduced costs. In some embodiments, the methods herein do not comprise hydrothermal synthesis. In some embodiments, the methods herein are not performed in a dry room. In some embodiments, the methods herein are not performed in a clean room. In some embodiments, the electrodes made by the methods herein store energy through both redox reactions and ion adsorption.
In some embodiments, the method of forming the electrode comprises: forming a first dispersion comprising a three-dimensional carbon additive, a first precursor to trivalent ions, a precursor to divalent ions, and a first solvent; forming a second dispersion comprising a second solvent and a conductive additive; adding the second dispersion to the first dispersion to form a third dispersion; adding a reducing agent to the third dispersion; heating the third dispersion; cooling the third dispersion; centrifuging the third dispersion with a third solvent; drying the third dispersion; and depositing the dried third dispersion and a binder onto a current collector.
In some embodiments, heating the third dispersion comprises heating the third dispersion at a first temperature for a first time period, heating the third dispersion at a second temperature for a second time period, and heating the third dispersion at a third temperature for a third time period. In some embodiments, heating the third dispersion comprises heating the third dispersion in an autoclave. In some embodiments, forming the first dispersion occurs in a vessel that is at least partially enclosed. In some embodiments, autoclave comprises a Teflon®-lined stainless steel autoclave.
In some embodiments, at least one of the first temperature, the second temperature, and the third temperature are at ambient temperatures. In some embodiments, at least one of the first temperature, the second temperature, and the third temperature are within about 1° C., 2° C., 3° C., 4° C., 5° C., 6° C., 7° C., 8° C., 9° C., 10° C., 15° C., 20° C., or more, including increments therein of ambient temperatures. In some embodiments, the reduced proximity of at least one of the first temperature, the second temperature, and the third temperature to ambient temperatures improved production, efficiency, and scaling.
In some embodiments, at least one of the mixing of the three-dimensional carbon additive and the first solvent, the mixing of the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent, and the mixing of the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive, and the first solvent reduces a particle size of the components within the first dispersion. In some embodiments, at least one of the mixing of the three-dimensional carbon additive and the first solvent, the mixing of the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent, and the mixing of the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive, and the first solvent breaks down any agglomerations within the first dispersion. In some embodiments, mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent comprises mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent in two or more portions. In some embodiments, forming the first dispersion comprises: mixing the three-dimensional carbon additive and the first solvent, mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent, and mixing the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive, and the first solvent. In some embodiments, at least one of the reduced particle size and reduced agglomeration in the first dispersion enables regular consistent coating of a current collector to form the first electrode, the second electrode, or both.
In some embodiments, the conductive additive comprises a zero-dimensional carbon additive, a one-dimensional carbon additive, a two-dimensional carbon additive, a three-dimensional carbon additive, or any combination thereof. In some embodiments, the zero-dimensional carbon additive comprises carbon black, acetylene black, or both. In some embodiments, the one-dimensional carbon additive comprises a carbon fiber, an activated carbon fiber, a carbon nanotube, an activated carbon nanotube, a carbon nanoplatelet, an activated carbon nanoplatelet, a carbon nanoribbon, an activated carbon nanoribbon, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a nanosheet, a microsheet, a platelet, or any combination thereof.
In some embodiments, the electrode formed by the methods herein is solid. In some embodiments, the electrode formed by the methods herein is semi-solid. In some embodiments, the electrode formed by the methods herein is not a hydrogel. In some embodiments, the low concentration of the two-dimensional carbon additive used in the methods herein forms an electrode that is solid or semi-solid, while maintaining the superior electrochemical properties of the electrode. In some embodiments, the low concentration of the two-dimensional carbon additive used in the methods herein forms an electrode that is not a hydrogel, while maintaining the superior electrochemical properties of the electrode. In some embodiments, solid, non-hydrogel, electrodes are more easily manufactured and formed into large area battery electrodes on high scales and at reduced costs. As such, the specific method steps and components herein enable the low-cost, high-scale production of electrodes with increased energy storage capabilities.
In some embodiments, the conductive additive comprises a two-dimensional carbon additive comprising one or more graphene oxide (GO) sheets. In some embodiments, the reducing agent reduces the GO sheet to form a graphene sheet. In some embodiments, the GO sheet provides a surface for LDH growth. In some embodiments, the methods herein form an electrode wherein the LDH coupled is to the graphene sheet. In some embodiments, the methods herein form an LDH bonded to the graphene sheet. In some embodiments, the LDH bonded to the graphene sheet is an LDH-graphene composite.
In some embodiments, the reducing agent is any chemical that hydrolyzes at a temperature at or above the first temperature. In some embodiments, heating the third dispersion to the first temperature hydrolyzes the reducing agent, which hydrolyzes the third dispersion. In some embodiments, the hydrolyzation of the third dispersion maintains a pH of the third dispersion. In some embodiments, hydrolyzation of the third dispersion maintains the pH of the third dispersion in the alkaline region. In some embodiments, a pH of the third dispersion in the alkaline region enables the formation of the LDH. In some embodiments, hydrolyzation of the third dispersion enables co-deposition of the M(II) and M(III) cations on the GO sheet with increased homogeneity. In some embodiments, during hydrolyzation, the zinc and bismuth ions co-precipitate out of the solution, forming the LDH. Furthermore, in some embodiments the hydrolyzing of the GO also changes the morphology of the LDH/rGO and improves the electrochemical performances of the composite material. Furthermore, in some embodiments the hydrolyzing of the GO changes the morphology of the LDH/rGO to form nanoplatelets.
In some embodiments, centrifuging the third dispersion with a third solvent comprises: centrifuging the third dispersion with a primary third solvent for one or more periods of time; decanting a supernatant from the third dispersion; centrifuging the third dispersion with a secondary third solvent for one or more periods of time; and decanting the supernatant from the third dispersion. In some embodiments, centrifuging the third dispersion with the primary third solvent for one or more periods of time comprises centrifuging the third dispersion with the primary third solvent for three periods of about three minutes each. In some embodiments, centrifuging the third dispersion with the secondary third solvent for one or more periods of time comprises centrifuging the third dispersion with the secondary third solvent for two periods of about three minutes each. In some embodiments, the primary third solvent comprises water, N-methyl-2-pyrrolidone, acetone, ethanol, isopropanol, or any combination thereof. In some embodiments, the secondary third solvent comprises water, N-methyl-2-pyrrolidone, acetone, ethanol, isopropanol, or any combination thereof.
In some embodiments, depositing the third dispersion onto the current collector comprises roll coating, slot die coating, film coating, doctor blade coating, or any combination thereof. In some embodiments, depositing the third dispersion onto the current collector comprises applying a consistent coating thickness to achieve a target loading mass of active electrode materials per unit area.
In some embodiments, the method further comprises cutting the third dispersion applied on the current collector. In some embodiments, the method further comprises adding one or more metal tabs to an edge of the current collector. In some embodiments, adding the one or more metal tabs to the edge of the current collector comprises ultrasonic welding.
In some embodiments, per
In some embodiments, the three-dimensional carbon additive comprises graphite, carbon foam, activated carbon, graphene foam, carbon aerogel, graphene aerogel, porous carbon, a buckminsterfullerene, an interconnected corrugated carbon-based network, or any combination thereof. In some embodiments, the first precursor to trivalent ions comprises a metal salt. In some embodiments, the first precursor to trivalent ions comprises aluminum nitrate, aluminum acetate, aluminum chloride, aluminum sulfate, aluminum carbonate, aluminum bromide, bismuth nitrate, bismuth acetate, bismuth chloride, bismuth sulfate, bismuth carbonate, bismuth bromide, chromium nitrate, chromium acetate, chromium chloride, chromium sulfate, chromium carbonate, chromium bromide, iron nitrate, iron acetate, iron chloride, iron sulfate, iron carbonate, iron bromide, or any combination thereof. In some embodiments, the first precursor to trivalent ions comprises a powder, a liquid, a paste, a gel, a dispersion, or any combination thereof. In some embodiments, the precursor to divalent ions comprises a metal salt. In some embodiments, the precursor to divalent ions comprises zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride, zinc bromide, barium nitrate, barium sulfate, barium carbonate, barium chloride, barium bromide, cadmium nitrate, cadmium sulfate, cadmium carbonate, cadmium chloride, cadmium bromide, calcium nitrate, calcium sulfate, calcium carbonate, calcium chloride, calcium bromide, cobalt nitrate, cobalt sulfate, cobalt carbonate, cobalt chloride, cobalt bromide, copper nitrate, copper sulfate, copper carbonate, copper chloride, copper bromide, iron nitrate, iron sulfate, iron carbonate, iron chloride, iron bromide, lead nitrate, lead sulfate, lead carbonate, lead chloride, lead bromide, magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium chloride, magnesium bromide, mercury nitrate, mercury sulfate, mercury carbonate, mercury chloride, mercury bromide, nickel nitrate, nickel sulfate, nickel carbonate, nickel chloride, nickel bromide, strontium nitrate, strontium sulfate, strontium carbonate, strontium chloride, strontium bromide, tin nitrate, tin sulfate, tin carbonate, tin chloride, tin bromide, or any combination thereof. In some embodiments, the zero-dimensional carbon additive comprises carbon black, acetylene black, or both. In some embodiments, the one-dimensional carbon additive comprises a carbon fiber, an activated carbon fiber, a carbon nanotube, an activated carbon nanotube, a carbon nanoplatelet, an activated carbon nanoplatelet, a carbon nanoribbon, an activated carbon nanoribbon, or any combination thereof. In some embodiments, the two-dimensional carbon additive comprises a graphene sheet, an activated graphene sheet, a reduced graphene sheet, a holey graphene sheet, a graphene oxide sheet, an activated graphene oxide sheet, a reduced graphene oxide sheet, a holey graphene oxide sheet, a reduced holey graphene oxide sheet, or any combination thereof. In some embodiments, the three-dimensional carbon additive comprises graphite, carbon foam, activated carbon, graphene foam, carbon aerogel, graphene aerogel, porous carbon, a buckminsterfullerene, an interconnected corrugated carbon-based network, or any combination thereof. In some embodiments, at least one of the first current collector and the second current collector comprises a foam, a foil, a mesh, an aerogel, or any combination thereof. In some embodiments, at least one of the first current collector and the second current collector comprises a copper-based current collector, a nickel-based current collector, a zinc-based current collector, a graphite-based current collector, a stainless steel-based current collector, a brass-based current collector, a bronze-based current collector, or any combination thereof. In some embodiments, the reducing agent comprises urea. In some embodiments, the binder comprises a polymeric binder. In some embodiments, the polymeric binder comprises polyvinylidene fluoride, carboxymethyl cellulose, polyacrylic acid, polyethylene glycol, alginic acid (sodium alginate), polypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene), a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer (Nafion®), polytetrafluoroethylene (Teflon®), polydopamine, polyvinylpyrrolidone, polyacrylonitrile, carbonyl β-cyclodextrin, or any combination thereof.
In some embodiments, a concentration by mass of the three-dimensional carbon additive within the third dispersion is about 1% to about 5%. In some embodiments, a concentration by mass of the three-dimensional carbon additive within the third dispersion is about 1% to about 1.5%, about 1% to about 2%, about 1% to about 2.5%, about 1% to about 3%, about 1% to about 3.5%, about 1% to about 4%, about 1% to about 4.5%, about 1% to about 5%, about 1.5% to about 2%, about 1.5% to about 2.5%, about 1.5% to about 3%, about 1.5% to about 3.5%, about 1.5% to about 4%, about 1.5% to about 4.5%, about 1.5% to about 5%, about 2% to about 2.5%, about 2% to about 3%, about 2% to about 3.5%, about 2% to about 4%, about 2% to about 4.5%, about 2% to about 5%, about 2.5% to about 3%, about 2.5% to about 3.5%, about 2.5% to about 4%, about 2.5% to about 4.5%, about 2.5% to about 5%, about 3% to about 3.5%, about 3% to about 4%, about 3% to about 4.5%, about 3% to about 5%, about 3.5% to about 4%, about 3.5% to about 4.5%, about 3.5% to about 5%, about 4% to about 4.5%, about 4% to about 5%, or about 4.5% to about 5%. In some embodiments, a concentration by mass of the three-dimensional carbon additive within the third dispersion is about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%. In some embodiments, a concentration by mass of the three-dimensional carbon additive within the third dispersion is at least about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, or about 4.5%. In some embodiments, a concentration by mass of the three-dimensional carbon additive within the third dispersion is at most about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%.
In some embodiments, a concentration by mass of the first precursor to trivalent ions within the third dispersion is about 5% to about 20%. In some embodiments, a concentration by mass of the first precursor to trivalent ions within the third dispersion is about 5% to about 6%, about 5% to about 7%, about 5% to about 8%, about 5% to about 9%, about 5% to about 10%, about 5% to about 12%, about 5% to about 14%, about 5% to about 16%, about 5% to about 18%, about 5% to about 20%, about 6% to about 7%, about 6% to about 8%, about 6% to about 9%, about 6% to about 10%, about 6% to about 12%, about 6% to about 14%, about 6% to about 16%, about 6% to about 18%, about 6% to about 20%, about 7% to about 8%, about 7% to about 9%, about 7% to about 10%, about 7% to about 12%, about 7% to about 14%, about 7% to about 16%, about 7% to about 18%, about 7% to about 20%, about 8% to about 9%, about 8% to about 10%, about 8% to about 12%, about 8% to about 14%, about 8% to about 16%, about 8% to about 18%, about 8% to about 20%, about 9% to about 10%, about 9% to about 12%, about 9% to about 14%, about 9% to about 16%, about 9% to about 18%, about 9% to about 20%, about 10% to about 12%, about 10% to about 14%, about 10% to about 16%, about 10% to about 18%, about 10% to about 20%, about 12% to about 14%, about 12% to about 16%, about 12% to about 18%, about 12% to about 20%, about 14% to about 16%, about 14% to about 18%, about 14% to about 20%, about 16% to about 18%, about 16% to about 20%, or about 18% to about 20%. In some embodiments, a concentration by mass of the first precursor to trivalent ions within the third dispersion is about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 12%, about 14%, about 16%, about 18%, or about 20%. In some embodiments, a concentration by mass of the first precursor to trivalent ions within the third dispersion is at least about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 12%, about 14%, about 16%, or about 18%. In some embodiments, a concentration by mass of the first precursor to trivalent ions within the third dispersion is at most about 6%, about 7%, about 8%, about 9%, about 10%, about 12%, about 14%, about 16%, about 18%, or about 20%.
In some embodiments, a concentration by mass of the precursor to divalent ions within the third dispersion is about 12% to about 48%. In some embodiments, a concentration by mass of the precursor to divalent ions within the third dispersion is about 12% to about 16%, about 12% to about 20%, about 12% to about 24%, about 12% to about 28%, about 12% to about 32%, about 12% to about 36%, about 12% to about 40%, about 12% to about 44%, about 12% to about 48%, about 16% to about 20%, about 16% to about 24%, about 16% to about 28%, about 16% to about 32%, about 16% to about 36%, about 16% to about 40%, about 16% to about 44%, about 16% to about 48%, about 20% to about 24%, about 20% to about 28%, about 20% to about 32%, about 20% to about 36%, about 20% to about 40%, about 20% to about 44%, about 20% to about 48%, about 24% to about 28%, about 24% to about 32%, about 24% to about 36%, about 24% to about 40%, about 24% to about 44%, about 24% to about 48%, about 28% to about 32%, about 28% to about 36%, about 28% to about 40%, about 28% to about 44%, about 28% to about 48%, about 32% to about 36%, about 32% to about 40%, about 32% to about 44%, about 32% to about 48%, about 36% to about 40%, about 36% to about 44%, about 36% to about 48%, about 40% to about 44%, about 40% to about 48%, or about 44% to about 48%. In some embodiments, a concentration by mass of the precursor to divalent ions within the third dispersion is about 12%, about 16%, about 20%, about 24%, about 28%, about 32%, about 36%, about 40%, about 44%, or about 48%. In some embodiments, a concentration by mass of the precursor to divalent ions within the third dispersion is at least about 12%, about 16%, about 20%, about 24%, about 28%, about 32%, about 36%, about 40%, or about 44%. In some embodiments, a concentration by mass of the precursor to divalent ions within the third dispersion is at most about 16%, about 20%, about 24%, about 28%, about 32%, about 36%, about 40%, about 44%, or about 48%.
In some embodiments, a concentration by mass of the conductive additive within the third dispersion is about 1% to about 5%. In some embodiments, a concentration by mass of the conductive additive within the third dispersion is about 1% to about 1.5%, about 1% to about 2%, about 1% to about 2.5%, about 1% to about 3%, about 1% to about 3.5%, about 1% to about 4%, about 1% to about 4.5%, about 1% to about 5%, about 1.5% to about 2%, about 1.5% to about 2.5%, about 1.5% to about 3%, about 1.5% to about 3.5%, about 1.5% to about 4%, about 1.5% to about 4.5%, about 1.5% to about 5%, about 2% to about 2.5%, about 2% to about 3%, about 2% to about 3.5%, about 2% to about 4%, about 2% to about 4.5%, about 2% to about 5%, about 2.5% to about 3%, about 2.5% to about 3.5%, about 2.5% to about 4%, about 2.5% to about 4.5%, about 2.5% to about 5%, about 3% to about 3.5%, about 3% to about 4%, about 3% to about 4.5%, about 3% to about 5%, about 3.5% to about 4%, about 3.5% to about 4.5%, about 3.5% to about 5%, about 4% to about 4.5%, about 4% to about 5%, or about 4.5% to about 5%. In some embodiments, a concentration by mass of the conductive additive within the third dispersion is about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%. In some embodiments, a concentration by mass of the conductive additive within the third dispersion is at least about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, or about 4.5%. In some embodiments, a concentration by mass of the conductive additive within the third dispersion is at most about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5%.
In some embodiments, a concentration by mass of the reducing agent within the third dispersion is about 9% to about 36%. In some embodiments, a concentration by mass of the reducing agent within the third dispersion is about 9% to about 10%, about 9% to about 12%, about 9% to about 14%, about 9% to about 16%, about 9% to about 18%, about 9% to about 20%, about 9% to about 24%, about 9% to about 28%, about 9% to about 32%, about 9% to about 36%, about 10% to about 12%, about 10% to about 14%, about 10% to about 16%, about 10% to about 18%, about 10% to about 20%, about 10% to about 24%, about 10% to about 28%, about 10% to about 32%, about 10% to about 36%, about 12% to about 14%, about 12% to about 16%, about 12% to about 18%, about 12% to about 20%, about 12% to about 24%, about 12% to about 28%, about 12% to about 32%, about 12% to about 36%, about 14% to about 16%, about 14% to about 18%, about 14% to about 20%, about 14% to about 24%, about 14% to about 28%, about 14% to about 32%, about 14% to about 36%, about 16% to about 18%, about 16% to about 20%, about 16% to about 24%, about 16% to about 28%, about 16% to about 32%, about 16% to about 36%, about 18% to about 20%, about 18% to about 24%, about 18% to about 28%, about 18% to about 32%, about 18% to about 36%, about 20% to about 24%, about 20% to about 28%, about 20% to about 32%, about 20% to about 36%, about 24% to about 28%, about 24% to about 32%, about 24% to about 36%, about 28% to about 32%, about 28% to about 36%, or about 32% to about 36%. In some embodiments, a concentration by mass of the reducing agent within the third dispersion is about 9%, about 10%, about 12%, about 14%, about 16%, about 18%, about 20%, about 24%, about 28%, about 32%, or about 36%. In some embodiments, a concentration by mass of the reducing agent within the third dispersion is at least about 9%, about 10%, about 12%, about 14%, about 16%, about 18%, about 20%, about 24%, about 28%, or about 32%. In some embodiments, a concentration by mass of the reducing agent within the third dispersion is at most about 10%, about 12%, about 14%, about 16%, about 18%, about 20%, about 24%, about 28%, about 32%, or about 36%.
In some embodiments, a concentration by mass of the binder within the electrode is about 1% to about 50%. In some embodiments, a concentration by mass of the binder within the electrode is about 1% to about 5%, about 1% to about 10%, about 1% to about 15%, about 1% to about 20%, about 1% to about 25%, about 1% to about 30%, about 1% to about 35%, about 1% to about 40%, about 1% to about 45%, about 1% to about 50%, about 5% to about 10%, about 5% to about 15%, about 5% to about 20%, about 5% to about 25%, about 5% to about 30%, about 5% to about 35%, about 5% to about 40%, about 5% to about 45%, about 5% to about 50%, about 10% to about 15%, about 10% to about 20%, about 10% to about 25%, about 10% to about 30%, about 10% to about 35%, about 10% to about 40%, about 10% to about 45%, about 10% to about 50%, about 15% to about 20%, about 15% to about 25%, about 15% to about 30%, about 15% to about 35%, about 15% to about 40%, about 15% to about 45%, about 15% to about 50%, about 20% to about 25%, about 20% to about 30%, about 20% to about 35%, about 20% to about 40%, about 20% to about 45%, about 20% to about 50%, about 25% to about 30%, about 25% to about 35%, about 25% to about 40%, about 25% to about 45%, about 25% to about 50%, about 30% to about 35%, about 30% to about 40%, about 30% to about 45%, about 30% to about 50%, about 35% to about 40%, about 35% to about 45%, about 35% to about 50%, about 40% to about 45%, about 40% to about 50%, or about 45% to about 50%. In some embodiments, a concentration by mass of the binder within the electrode is about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, or about 50%. In some embodiments, a concentration by mass of the binder within the electrode is at least about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, or about 45%. In some embodiments, a concentration by mass of the binder within the electrode is at most about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, or about 50%.
In some embodiments, the first solvent comprises water, N-methyl-2-pyrrolidone, acetone, ethanol, isopropanol, or any combination thereof. In some embodiments, the second solvent comprises water, N-methyl-2-pyrrolidone, acetone, ethanol, isopropanol, or any combination thereof. In some embodiments, the third solvent comprises water, N-methyl-2-pyrrolidone, acetone, ethanol, isopropanol, or any combination thereof.
In some embodiments, the first dispersion further comprises a second precursor to trivalent ions. In some embodiments, the second precursor to trivalent ions comprises a metal salt. In some embodiments, the second precursor to trivalent ions comprises aluminum nitrate, aluminum acetate, aluminum chloride, aluminum sulfate, aluminum carbonate, aluminum bromide, bismuth nitrate, bismuth acetate, bismuth chloride, bismuth sulfate, bismuth carbonate, bismuth bromide, chromium nitrate, chromium acetate, chromium chloride, chromium sulfate, chromium carbonate, chromium bromide, iron nitrate, iron acetate, iron chloride, iron sulfate, iron carbonate, iron bromide, or any combination thereof. In some embodiments, the first dispersion does not comprise the second precursor to trivalent ions.
In some embodiments, a concentration by mass of the second precursor to trivalent ions within the third dispersion is about 4% to about 16%. In some embodiments, a concentration by mass of the second precursor to trivalent ions within the third dispersion is about 4% to about 5%, about 4% to about 6%, about 4% to about 7%, about 4% to about 8%, about 4% to about 9%, about 4% to about 10%, about 4% to about 11%, about 4% to about 12%, about 4% to about 13%, about 4% to about 14%, about 4% to about 16%, about 5% to about 6%, about 5% to about 7%, about 5% to about 8%, about 5% to about 9%, about 5% to about 10%, about 5% to about 11%, about 5% to about 12%, about 5% to about 13%, about 5% to about 14%, about 5% to about 16%, about 6% to about 7%, about 6% to about 8%, about 6% to about 9%, about 6% to about 10%, about 6% to about 11%, about 6% to about 12%, about 6% to about 13%, about 6% to about 14%, about 6% to about 16%, about 7% to about 8%, about 7% to about 9%, about 7% to about 10%, about 7% to about 11%, about 7% to about 12%, about 7% to about 13%, about 7% to about 14%, about 7% to about 16%, about 8% to about 9%, about 8% to about 10%, about 8% to about 11%, about 8% to about 12%, about 8% to about 13%, about 8% to about 14%, about 8% to about 16%, about 9% to about 10%, about 9% to about 11%, about 9% to about 12%, about 9% to about 13%, about 9% to about 14%, about 9% to about 16%, about 10% to about 11%, about 10% to about 12%, about 10% to about 13%, about 10% to about 14%, about 10% to about 16%, about 11% to about 12%, about 11% to about 13%, about 11% to about 14%, about 11% to about 16%, about 12% to about 13%, about 12% to about 14%, about 12% to about 16%, about 13% to about 14%, about 13% to about 16%, or about 14% to about 16%. In some embodiments, a concentration by mass of the second precursor to trivalent ions within the third dispersion is about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 16%. In some embodiments, a concentration by mass of the second precursor to trivalent ions within the third dispersion is at least about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, or about 14%. In some embodiments, a concentration by mass of the second precursor to trivalent ions within the third dispersion is at most about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 16%.
In some embodiments, mixing the three-dimensional carbon additive and the first solvent occurs over a period of time of about 5 minutes to about 20 minutes. In some embodiments, mixing the three-dimensional carbon additive and the first solvent occurs over a period of time of about 5 minutes to about 6 minutes, about 5 minutes to about 7 minutes, about 5 minutes to about 8 minutes, about 5 minutes to about 9 minutes, about 5 minutes to about 10 minutes, about 5 minutes to about 12 minutes, about 5 minutes to about 14 minutes, about 5 minutes to about 16 minutes, about 5 minutes to about 18 minutes, about 5 minutes to about 20 minutes, about 6 minutes to about 7 minutes, about 6 minutes to about 8 minutes, about 6 minutes to about 9 minutes, about 6 minutes to about 10 minutes, about 6 minutes to about 12 minutes, about 6 minutes to about 14 minutes, about 6 minutes to about 16 minutes, about 6 minutes to about 18 minutes, about 6 minutes to about 20 minutes, about 7 minutes to about 8 minutes, about 7 minutes to about 9 minutes, about 7 minutes to about 10 minutes, about 7 minutes to about 12 minutes, about 7 minutes to about 14 minutes, about 7 minutes to about 16 minutes, about 7 minutes to about 18 minutes, about 7 minutes to about 20 minutes, about 8 minutes to about 9 minutes, about 8 minutes to about 10 minutes, about 8 minutes to about 12 minutes, about 8 minutes to about 14 minutes, about 8 minutes to about 16 minutes, about 8 minutes to about 18 minutes, about 8 minutes to about 20 minutes, about 9 minutes to about 10 minutes, about 9 minutes to about 12 minutes, about 9 minutes to about 14 minutes, about 9 minutes to about 16 minutes, about 9 minutes to about 18 minutes, about 9 minutes to about 20 minutes, about 10 minutes to about 12 minutes, about 10 minutes to about 14 minutes, about 10 minutes to about 16 minutes, about 10 minutes to about 18 minutes, about 10 minutes to about 20 minutes, about 12 minutes to about 14 minutes, about 12 minutes to about 16 minutes, about 12 minutes to about 18 minutes, about 12 minutes to about 20 minutes, about 14 minutes to about 16 minutes, about 14 minutes to about 18 minutes, about 14 minutes to about 20 minutes, about 16 minutes to about 18 minutes, about 16 minutes to about 20 minutes, or about 18 minutes to about 20 minutes. In some embodiments, mixing the three-dimensional carbon additive and the first solvent occurs over a period of time of about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, about 10 minutes, about 12 minutes, about 14 minutes, about 16 minutes, about 18 minutes, or about 20 minutes. In some embodiments, mixing the three-dimensional carbon additive and the first solvent occurs over a period of time of at least about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, about 10 minutes, about 12 minutes, about 14 minutes, about 16 minutes, or about 18 minutes. In some embodiments, mixing the three-dimensional carbon additive and the first solvent occurs over a period of time of at most about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, about 10 minutes, about 12 minutes, about 14 minutes, about 16 minutes, about 18 minutes, or about 20 minutes.
In some embodiments, mixing the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive, and the first solvent occurs over a period of time of about 1 minute to about 10 minutes. In some embodiments, mixing the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive and the first solvent occurs over a period of time of about 1 minute to about 2 minutes, about 1 minute to about 3 minutes, about 1 minute to about 4 minutes, about 1 minute to about 5 minutes, about 1 minute to about 6 minutes, about 1 minute to about 7 minutes, about 1 minute to about 8 minutes, about 1 minute to about 9 minutes, about 1 minute to about 10 minutes, about 2 minutes to about 3 minutes, about 2 minutes to about 4 minutes, about 2 minutes to about 5 minutes, about 2 minutes to about 6 minutes, about 2 minutes to about 7 minutes, about 2 minutes to about 8 minutes, about 2 minutes to about 9 minutes, about 2 minutes to about 10 minutes, about 3 minutes to about 4 minutes, about 3 minutes to about 5 minutes, about 3 minutes to about 6 minutes, about 3 minutes to about 7 minutes, about 3 minutes to about 8 minutes, about 3 minutes to about 9 minutes, about 3 minutes to about 10 minutes, about 4 minutes to about 5 minutes, about 4 minutes to about 6 minutes, about 4 minutes to about 7 minutes, about 4 minutes to about 8 minutes, about 4 minutes to about 9 minutes, about 4 minutes to about 10 minutes, about 5 minutes to about 6 minutes, about 5 minutes to about 7 minutes, about 5 minutes to about 8 minutes, about 5 minutes to about 9 minutes, about 5 minutes to about 10 minutes, about 6 minutes to about 7 minutes, about 6 minutes to about 8 minutes, about 6 minutes to about 9 minutes, about 6 minutes to about 10 minutes, about 7 minutes to about 8 minutes, about 7 minutes to about 9 minutes, about 7 minutes to about 10 minutes, about 8 minutes to about 9 minutes, about 8 minutes to about 10 minutes, or about 9 minutes to about 10 minutes. In some embodiments, mixing the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive and the first solvent occurs over a period of time of about 1 minute, about 2 minutes, about 3 minutes, about 4 minutes, about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, or about 10 minutes. In some embodiments, mixing the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive, and the first solvent occurs over a period of time of at least about 1 minute, about 2 minutes, about 3 minutes, about 4 minutes, about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, or about 9 minutes. In some embodiments, mixing the precursor to divalent ions into the first precursor to trivalent ions, the three-dimensional carbon additive, and the first solvent occurs over a period of time of at most about 2 minutes, about 3 minutes, about 4 minutes, about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, or about 10 minutes.
In some embodiments, mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent occurs over a period of time of about 5 minutes to about 20 minutes. In some embodiments, mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent occurs over a period of time of about 5 minutes to about 6 minutes, about 5 minutes to about 7 minutes, about 5 minutes to about 8 minutes, about 5 minutes to about 9 minutes, about 5 minutes to about 10 minutes, about 5 minutes to about 12 minutes, about 5 minutes to about 14 minutes, about 5 minutes to about 16 minutes, about 5 minutes to about 18 minutes, about 5 minutes to about 20 minutes, about 6 minutes to about 7 minutes, about 6 minutes to about 8 minutes, about 6 minutes to about 9 minutes, about 6 minutes to about 10 minutes, about 6 minutes to about 12 minutes, about 6 minutes to about 14 minutes, about 6 minutes to about 16 minutes, about 6 minutes to about 18 minutes, about 6 minutes to about 20 minutes, about 7 minutes to about 8 minutes, about 7 minutes to about 9 minutes, about 7 minutes to about 10 minutes, about 7 minutes to about 12 minutes, about 7 minutes to about 14 minutes, about 7 minutes to about 16 minutes, about 7 minutes to about 18 minutes, about 7 minutes to about 20 minutes, about 8 minutes to about 9 minutes, about 8 minutes to about 10 minutes, about 8 minutes to about 12 minutes, about 8 minutes to about 14 minutes, about 8 minutes to about 16 minutes, about 8 minutes to about 18 minutes, about 8 minutes to about 20 minutes, about 9 minutes to about 10 minutes, about 9 minutes to about 12 minutes, about 9 minutes to about 14 minutes, about 9 minutes to about 16 minutes, about 9 minutes to about 18 minutes, about 9 minutes to about 20 minutes, about 10 minutes to about 12 minutes, about 10 minutes to about 14 minutes, about 10 minutes to about 16 minutes, about 10 minutes to about 18 minutes, about 10 minutes to about 20 minutes, about 12 minutes to about 14 minutes, about 12 minutes to about 16 minutes, about 12 minutes to about 18 minutes, about 12 minutes to about 20 minutes, about 14 minutes to about 16 minutes, about 14 minutes to about 18 minutes, about 14 minutes to about 20 minutes, about 16 minutes to about 18 minutes, about 16 minutes to about 20 minutes, or about 18 minutes to about 20 minutes. In some embodiments, mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent occurs over a period of time of about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, about 10 minutes, about 12 minutes, about 14 minutes, about 16 minutes, about 18 minutes, or about 20 minutes. In some embodiments, mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent occurs over a period of time of at least about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, about 10 minutes, about 12 minutes, about 14 minutes, about 16 minutes, or about 18 minutes. In some embodiments, mixing the first precursor to trivalent ions into the three-dimensional carbon additive and the first solvent occurs over a period of time of at most about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, about 10 minutes, about 12 minutes, about 14 minutes, about 16 minutes, about 18 minutes, or about 20 minutes.
In some embodiments, the first temperature is about 10° C. to about 50° C. In some embodiments, the first temperature is about 10° C. to about 15° C., about 10° C. to about 20° C., about 10° C. to about 25° C., about 10° C. to about 30° C., about 10° C. to about 35° C., about 10° C. to about 40° C., about 10° C. to about 45° C., about 10° C. to about 50° C., about 15° C. to about 20° C., about 15° C. to about 25° C., about 15° C. to about 30° C., about 15° C. to about 35° C., about 15° C. to about 40° C., about 15° C. to about 45° C., about 15° C. to about 50° C., about 20° C. to about 25° C., about 20° C. to about 30° C., about 20° C. to about 35° C., about 20° C. to about 40° C., about 20° C. to about 45° C., about 20° C. to about 50° C., about 25° C. to about 30° C., about 25° C. to about 35° C., about 25° C. to about 40° C., about 25° C. to about 45° C., about 25° C. to about 50° C., about 30° C. to about 35° C., about 30° C. to about 40° C., about 30° C. to about 45° C., about 30° C. to about 50° C., about 35° C. to about 40° C., about 35° C. to about 45° C., about 35° C. to about 50° C., about 40° C. to about 45° C., about 40° C. to about 50° C., or about 45° C. to about 50° C. In some embodiments, the first temperature is about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C. In some embodiments, the first temperature is at least about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., or about 45° C. In some embodiments, the first temperature is at most about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C.
In some embodiments, the second temperature is about 10° C. to about 50° C. In some embodiments, the second temperature is about 10° C. to about 15° C., about 10° C. to about 20° C., about 10° C. to about 25° C., about 10° C. to about 30° C., about 10° C. to about 35° C., about 10° C. to about 40° C., about 10° C. to about 45° C., about 10° C. to about 50° C., about 15° C. to about 20° C., about 15° C. to about 25° C., about 15° C. to about 30° C., about 15° C. to about 35° C., about 15° C. to about 40° C., about 15° C. to about 45° C., about 15° C. to about 50° C., about 20° C. to about 25° C., about 20° C. to about 30° C., about 20° C. to about 35° C., about 20° C. to about 40° C., about 20° C. to about 45° C., about 20° C. to about 50° C., about 25° C. to about 30° C., about 25° C. to about 35° C., about 25° C. to about 40° C., about 25° C. to about 45° C., about 25° C. to about 50° C., about 30° C. to about 35° C., about 30° C. to about 40° C., about 30° C. to about 45° C., about 30° C. to about 50° C., about 35° C. to about 40° C., about 35° C. to about 45° C., about 35° C. to about 50° C., about 40° C. to about 45° C., about 40° C. to about 50° C., or about 45° C. to about 50° C. In some embodiments, the second temperature is about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C. In some embodiments, the second temperature is at least about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., or about 45° C. In some embodiments, the second temperature is at most about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C.
In some embodiments, the third temperature is about 90° C. to about 360° C. In some embodiments, the third temperature is about 90° C. to about 120° C., about 90° C. to about 150° C., about 90° C. to about 180° C., about 90° C. to about 210° C., about 90° C. to about 250° C., about 90° C. to about 290° C., about 90° C. to about 330° C., about 90° C. to about 360° C., about 120° C. to about 150° C., about 120° C. to about 180° C., about 120° C. to about 210° C., about 120° C. to about 250° C., about 120° C. to about 290° C., about 120° C. to about 330° C., about 120° C. to about 360° C., about 150° C. to about 180° C., about 150° C. to about 210° C., about 150° C. to about 250° C., about 150° C. to about 290° C., about 150° C. to about 330° C., about 150° C. to about 360° C., about 180° C. to about 210° C., about 180° C. to about 250° C., about 180° C. to about 290° C., about 180° C. to about 330° C., about 180° C. to about 360° C., about 210° C. to about 250° C., about 210° C. to about 290° C., about 210° C. to about 330° C., about 210° C. to about 360° C., about 250° C. to about 290° C., about 250° C. to about 330° C., about 250° C. to about 360° C., about 290° C. to about 330° C., about 290° C. to about 360° C., or about 330° C. to about 360° C. In some embodiments, the third temperature is about 90° C., about 120° C., about 150° C., about 180° C., about 210° C., about 250° C., about 290° C., about 330° C., or about 360° C. In some embodiments, the third temperature is at least about 90° C., about 120° C., about 150° C., about 180° C., about 210° C., about 250° C., about 290° C., or about 330° C. In some embodiments, the third temperature is at most about 120° C., about 150° C., about 180° C., about 210° C., about 250° C., about 290° C., about 330° C., or about 360° C.
In some embodiments, the first time period is about 15 minutes to about 60 minutes. In some embodiments, the first time period is about 15 minutes to about 20 minutes, about 15 minutes to about 25 minutes, about 15 minutes to about 30 minutes, about 15 minutes to about 35 minutes, about 15 minutes to about 40 minutes, about 15 minutes to about 45 minutes, about 15 minutes to about 50 minutes, about 15 minutes to about 55 minutes, about 15 minutes to about 60 minutes, about 20 minutes to about 25 minutes, about 20 minutes to about 30 minutes, about 20 minutes to about 35 minutes, about 20 minutes to about 40 minutes, about 20 minutes to about 45 minutes, about 20 minutes to about 50 minutes, about 20 minutes to about 55 minutes, about 20 minutes to about 60 minutes, about 25 minutes to about 30 minutes, about 25 minutes to about 35 minutes, about 25 minutes to about 40 minutes, about 25 minutes to about 45 minutes, about 25 minutes to about 50 minutes, about 25 minutes to about 55 minutes, about 25 minutes to about 60 minutes, about 30 minutes to about 35 minutes, about 30 minutes to about 40 minutes, about 30 minutes to about 45 minutes, about 30 minutes to about 50 minutes, about 30 minutes to about 55 minutes, about 30 minutes to about 60 minutes, about 35 minutes to about 40 minutes, about 35 minutes to about 45 minutes, about 35 minutes to about 50 minutes, about 35 minutes to about 55 minutes, about 35 minutes to about 60 minutes, about 40 minutes to about 45 minutes, about 40 minutes to about 50 minutes, about 40 minutes to about 55 minutes, about 40 minutes to about 60 minutes, about 45 minutes to about 50 minutes, about 45 minutes to about 55 minutes, about 45 minutes to about 60 minutes, about 50 minutes to about 55 minutes, about 50 minutes to about 60 minutes, or about 55 minutes to about 60 minutes. In some embodiments, the first time period is about 15 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, about 55 minutes, or about 60 minutes. In some embodiments, the first time period is at least about 15 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, or about 55 minutes. In some embodiments, the first time period is at most about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, about 55 minutes, or about 60 minutes.
In some embodiments, the second time period is about 600 minutes to about 2,400 minutes. In some embodiments, the second time period is about 600 minutes to about 800 minutes, about 600 minutes to about 1,000 minutes, about 600 minutes to about 1,200 minutes, about 600 minutes to about 1,400 minutes, about 600 minutes to about 1,600 minutes, about 600 minutes to about 1,800 minutes, about 600 minutes to about 2,000 minutes, about 600 minutes to about 2,200 minutes, about 600 minutes to about 2,400 minutes, about 800 minutes to about 1,000 minutes, about 800 minutes to about 1,200 minutes, about 800 minutes to about 1,400 minutes, about 800 minutes to about 1,600 minutes, about 800 minutes to about 1,800 minutes, about 800 minutes to about 2,000 minutes, about 800 minutes to about 2,200 minutes, about 800 minutes to about 2,400 minutes, about 1,000 minutes to about 1,200 minutes, about 1,000 minutes to about 1,400 minutes, about 1,000 minutes to about 1,600 minutes, about 1,000 minutes to about 1,800 minutes, about 1,000 minutes to about 2,000 minutes, about 1,000 minutes to about 2,200 minutes, about 1,000 minutes to about 2,400 minutes, about 1,200 minutes to about 1,400 minutes, about 1,200 minutes to about 1,600 minutes, about 1,200 minutes to about 1,800 minutes, about 1,200 minutes to about 2,000 minutes, about 1,200 minutes to about 2,200 minutes, about 1,200 minutes to about 2,400 minutes, about 1,400 minutes to about 1,600 minutes, about 1,400 minutes to about 1,800 minutes, about 1,400 minutes to about 2,000 minutes, about 1,400 minutes to about 2,200 minutes, about 1,400 minutes to about 2,400 minutes, about 1,600 minutes to about 1,800 minutes, about 1,600 minutes to about 2,000 minutes, about 1,600 minutes to about 2,200 minutes, about 1,600 minutes to about 2,400 minutes, about 1,800 minutes to about 2,000 minutes, about 1,800 minutes to about 2,200 minutes, about 1,800 minutes to about 2,400 minutes, about 2,000 minutes to about 2,200 minutes, about 2,000 minutes to about 2,400 minutes, or about 2,200 minutes to about 2,400 minutes. In some embodiments, the second time period is about 600 minutes, about 800 minutes, about 1,000 minutes, about 1,200 minutes, about 1,400 minutes, about 1,600 minutes, about 1,800 minutes, about 2,000 minutes, about 2,200 minutes, or about 2,400 minutes. In some embodiments, the second time period is at least about 600 minutes, about 800 minutes, about 1,000 minutes, about 1,200 minutes, about 1,400 minutes, about 1,600 minutes, about 1,800 minutes, about 2,000 minutes, or about 2,200 minutes. In some embodiments, the second time period is at most about 800 minutes, about 1,000 minutes, about 1,200 minutes, about 1,400 minutes, about 1,600 minutes, about 1,800 minutes, about 2,000 minutes, about 2,200 minutes, or about 2,400 minutes.
In some embodiments, the third time period is about 15 minutes to about 60 minutes. In some embodiments, the third time period is about 15 minutes to about 20 minutes, about 15 minutes to about 25 minutes, about 15 minutes to about 30 minutes, about 15 minutes to about 35 minutes, about 15 minutes to about 40 minutes, about 15 minutes to about 45 minutes, about 15 minutes to about 50 minutes, about 15 minutes to about 55 minutes, about 15 minutes to about 60 minutes, about 20 minutes to about 25 minutes, about 20 minutes to about 30 minutes, about 20 minutes to about 35 minutes, about 20 minutes to about 40 minutes, about 20 minutes to about 45 minutes, about 20 minutes to about 50 minutes, about 20 minutes to about 55 minutes, about 20 minutes to about 60 minutes, about 25 minutes to about 30 minutes, about 25 minutes to about 35 minutes, about 25 minutes to about 40 minutes, about 25 minutes to about 45 minutes, about 25 minutes to about 50 minutes, about 25 minutes to about 55 minutes, about 25 minutes to about 60 minutes, about 30 minutes to about 35 minutes, about 30 minutes to about 40 minutes, about 30 minutes to about 45 minutes, about 30 minutes to about 50 minutes, about 30 minutes to about 55 minutes, about 30 minutes to about 60 minutes, about 35 minutes to about 40 minutes, about 35 minutes to about 45 minutes, about 35 minutes to about 50 minutes, about 35 minutes to about 55 minutes, about 35 minutes to about 60 minutes, about 40 minutes to about 45 minutes, about 40 minutes to about 50 minutes, about 40 minutes to about 55 minutes, about 40 minutes to about 60 minutes, about 45 minutes to about 50 minutes, about 45 minutes to about 55 minutes, about 45 minutes to about 60 minutes, about 50 minutes to about 55 minutes, about 50 minutes to about 60 minutes, or about 55 minutes to about 60 minutes. In some embodiments, the third time period is about 15 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, about 55 minutes, or about 60 minutes. In some embodiments, the third time period is at least about 15 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, or about 55 minutes. In some embodiments, the third time period is at most about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, about 55 minutes, or about 60 minutes.
In some embodiments, cooling the third dispersion comprises cooling the third dispersion at a temperature of about −200° C. to about −60° C. In some embodiments, cooling the third dispersion comprises cooling the third dispersion at a temperature of about −60° C. to about −70° C., about −60° C. to about −80° C., about −60° C. to about −100° C., about −60° C. to about −120° C., about −60° C. to about −140° C., about −60° C. to about −160° C., about −60° C. to about −180° C., about −60° C. to about −200° C., about −70° C. to about −80° C., about −70° C. to about −100° C., about −70° C. to about −120° C., about −70° C. to about −140° C., about −70° C. to about −160° C., about −70° C. to about −180° C., about −70° C. to about −200° C., about −80° C. to about −100° C., about −80° C. to about −120° C., about −80° C. to about −140° C., about −80° C. to about −160° C., about −80° C. to about −180° C., about −80° C. to about −200° C., about −100° C. to about −120° C., about −100° C. to about −140° C., about −100° C. to about −160° C., about −100° C. to about −180° C., about −100° C. to about −200° C., about −120° C. to about −140° C., about −120° C. to about −160° C., about −120° C. to about −180° C., about −120° C. to about −200° C., about −140° C. to about −160° C., about −140° C. to about −180° C., about −140° C. to about −200° C., about −160° C. to about −180° C., about −160° C. to about −200° C., or about −180° C. to about −200° C. In some embodiments, cooling the third dispersion comprises cooling the third dispersion at a temperature of about −60° C., about −70° C., about −80° C., about −100° C., about −120° C., about −140° C., about −160° C., about −180° C., or about −200° C. In some embodiments, cooling the third dispersion comprises cooling the third dispersion at a temperature of at least about −60° C., about −70° C., about −80° C., about −100° C., about −120° C., about −140° C., about −160° C., or about −180° C. In some embodiments, cooling the third dispersion comprises cooling the third dispersion at a temperature of at most about −70° C., about −80° C., about −100° C., about −120° C., about −140° C., about −160° C., about −180° C., or about −200° C.
In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature of about 25° C. to about 100° C. In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature of about 25° C. to about 30° C., about 25° C. to about 35° C., about 25° C. to about 40° C., about 25° C. to about 45° C., about 25° C. to about 50° C., about 25° C. to about 55° C., about 25° C. to about 60° C., about 25° C. to about 70° C., about 25° C. to about 80° C., about 25° C. to about 90° C., about 25° C. to about 100° C., about 30° C. to about 35° C., about 30° C. to about 40° C., about 30° C. to about 45° C., about 30° C. to about 50° C., about 30° C. to about 55° C., about 30° C. to about 60° C., about 30° C. to about 70° C., about 30° C. to about 80° C., about 30° C. to about 90° C., about 30° C. to about 100° C., about 35° C. to about 40° C., about 35° C. to about 45° C., about 35° C. to about 50° C., about 35° C. to about 55° C., about 35° C. to about 60° C., about 35° C. to about 70° C., about 35° C. to about 80° C., about 35° C. to about 90° C., about 35° C. to about 100° C., about 40° C. to about 45° C., about 40° C. to about 50° C., about 40° C. to about 55° C., about 40° C. to about 60° C., about 40° C. to about 70° C., about 40° C. to about 80° C., about 40° C. to about 90° C., about 40° C. to about 100° C., about 45° C. to about 50° C., about 45° C. to about 55° C., about 45° C. to about 60° C., about 45° C. to about 70° C., about 45° C. to about 80° C., about 45° C. to about 90° C., about 45° C. to about 100° C., about 50° C. to about 55° C., about 50° C. to about 60° C., about 50° C. to about 70° C., about 50° C. to about 80° C., about 50° C. to about 90° C., about 50° C. to about 100° C., about 55° C. to about 60° C., about 55° C. to about 70° C., about 55° C. to about 80° C., about 55° C. to about 90° C., about 55° C. to about 100° C., about 60° C. to about 70° C., about 60° C. to about 80° C., about 60° C. to about 90° C., about 60° C. to about 100° C., about 70° C. to about 80° C., about 70° C. to about 90° C., about 70° C. to about 100° C., about 80° C. to about 90° C., about 80° C. to about 100° C., or about 90° C. to about 100° C. In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature of about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., about 50° C., about 55° C., about 60° C., about 70° C., about 80° C., about 90° C., or about 100° C. In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature of at least about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., about 50° C., about 55° C., about 60° C., about 70° C., about 80° C., or about 90° C. In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature of at most about 30° C., about 35° C., about 40° C., about 45° C., about 50° C., about 55° C., about 60° C., about 70° C., about 80° C., about 90° C., or about 100° C.
In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature for a period of time of about 10 minutes to about 60 minutes. In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature for a period of time of about 10 minutes to about 15 minutes, about 10 minutes to about 20 minutes, about 10 minutes to about 25 minutes, about 10 minutes to about 30 minutes, about 10 minutes to about 35 minutes, about 10 minutes to about 40 minutes, about 10 minutes to about 45 minutes, about 10 minutes to about 50 minutes, about 10 minutes to about 55 minutes, about 10 minutes to about 60 minutes, about 15 minutes to about 20 minutes, about 15 minutes to about 25 minutes, about 15 minutes to about 30 minutes, about 15 minutes to about 35 minutes, about 15 minutes to about 40 minutes, about 15 minutes to about 45 minutes, about 15 minutes to about 50 minutes, about 15 minutes to about 55 minutes, about 15 minutes to about 60 minutes, about 20 minutes to about 25 minutes, about 20 minutes to about 30 minutes, about 20 minutes to about 35 minutes, about 20 minutes to about 40 minutes, about 20 minutes to about 45 minutes, about 20 minutes to about 50 minutes, about 20 minutes to about 55 minutes, about 20 minutes to about 60 minutes, about 25 minutes to about 30 minutes, about 25 minutes to about 35 minutes, about 25 minutes to about 40 minutes, about 25 minutes to about 45 minutes, about 25 minutes to about 50 minutes, about 25 minutes to about 55 minutes, about 25 minutes to about 60 minutes, about 30 minutes to about 35 minutes, about 30 minutes to about 40 minutes, about 30 minutes to about 45 minutes, about 30 minutes to about 50 minutes, about 30 minutes to about 55 minutes, about 30 minutes to about 60 minutes, about 35 minutes to about 40 minutes, about 35 minutes to about 45 minutes, about 35 minutes to about 50 minutes, about 35 minutes to about 55 minutes, about 35 minutes to about 60 minutes, about 40 minutes to about 45 minutes, about 40 minutes to about 50 minutes, about 40 minutes to about 55 minutes, about 40 minutes to about 60 minutes, about 45 minutes to about 50 minutes, about 45 minutes to about 55 minutes, about 45 minutes to about 60 minutes, about 50 minutes to about 55 minutes, about 50 minutes to about 60 minutes, or about 55 minutes to about 60 minutes. In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature for a period of time of about 10 minutes, about 15 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, about 55 minutes, or about 60 minutes. In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature for a period of time of at least about 10 minutes, about 15 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, or about 55 minutes. In some embodiments, drying the third dispersion comprises drying the third dispersion at a temperature for a period of time of at most about 15 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, about 55 minutes, or about 60 minutes.
In another embodiment the method of forming an electrode comprises forming a first dispersion comprising a first quantity of a reducing agent, a first precursor to trivalent ions, a precursor to divalent ions, a first solvent, and a conductive additive comprising at least one of a zero-dimensional carbon additive, a one-dimensional carbon additive, a two-dimensional carbon additive, or a three-dimensional carbon additive; heating the first dispersion while adding a second quantity of the reducing agent to the first dispersion; cooling the first dispersion; filtering the first dispersion; rinsing the first dispersion; drying the first dispersion; and depositing the dried first dispersion and a binder onto a current collector. In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs while stirring the first dispersion. In some embodiments, heating the first dispersion occurs at a temperature that is close to the ambient temperature for improved production efficiency and scaling. In some embodiments, the first dispersion is cooled to room temperature. In some embodiments, the method further comprises breaking up the rinsed first dispersion before the drying of the first dispersion. In some embodiments, a pH of the first dispersion before the addition of the second quantity of the reducing agent is below a pH required to precipitate the LDH out of the first dispersion. In some embodiments, at least one of the reducing agent, the first precursor to trivalent ions, the precursor to divalent ions, and the conductive additive are dispersed in the first solvent before the formation of the first dispersion. In some embodiments, the drying of the first dispersion occurs in an oven.
In some embodiments, adding a second quantity of the reducing agent to the first dispersion occurs over a period of time of about 8 hours to about 40 hours. In some embodiments, adding a second quantity of the reducing agent to the first dispersion occurs over a period of time of about 8 hours to about 12 hours, about 8 hours to about 16 hours, about 8 hours to about 20 hours, about 8 hours to about 24 hours, about 8 hours to about 28 hours, about 8 hours to about 32 hours, about 8 hours to about 36 hours, about 8 hours to about 40 hours, about 12 hours to about 16 hours, about 12 hours to about 20 hours, about 12 hours to about 24 hours, about 12 hours to about 28 hours, about 12 hours to about 32 hours, about 12 hours to about 36 hours, about 12 hours to about 40 hours, about 16 hours to about 20 hours, about 16 hours to about 24 hours, about 16 hours to about 28 hours, about 16 hours to about 32 hours, about 16 hours to about 36 hours, about 16 hours to about 40 hours, about 20 hours to about 24 hours, about 20 hours to about 28 hours, about 20 hours to about 32 hours, about 20 hours to about 36 hours, about 20 hours to about 40 hours, about 24 hours to about 28 hours, about 24 hours to about 32 hours, about 24 hours to about 36 hours, about 24 hours to about 40 hours, about 28 hours to about 32 hours, about 28 hours to about 36 hours, about 28 hours to about 40 hours, about 32 hours to about 36 hours, about 32 hours to about 40 hours, or about 36 hours to about 40 hours. In some embodiments, adding a second quantity of the reducing agent to the first dispersion occurs over a period of time of about 8 hours, about 12 hours, about 16 hours, about 20 hours, about 24 hours, about 28 hours, about 32 hours, about 36 hours, or about 40 hours. In some embodiments, adding a second quantity of the reducing agent to the first dispersion occurs over a period of time of at least about 8 hours, about 12 hours, about 16 hours, about 20 hours, about 24 hours, about 28 hours, about 32 hours, or about 36 hours. In some embodiments, adding a second quantity of the reducing agent to the first dispersion occurs over a period of time of at most about 12 hours, about 16 hours, about 20 hours, about 24 hours, about 28 hours, about 32 hours, about 36 hours, or about 40 hours.
In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a pH of about 7 to about 9. In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a pH of about 7 to about 7.25, about 7 to about 7.5, about 7 to about 7.75, about 7 to about 8, about 7 to about 8.25, about 7 to about 8.5, about 7 to about 8.75, about 7 to about 9, about 7.25 to about 7.5, about 7.25 to about 7.75, about 7.25 to about 8, about 7.25 to about 8.25, about 7.25 to about 8.5, about 7.25 to about 8.75, about 7.25 to about 9, about 7.5 to about 7.75, about 7.5 to about 8, about 7.5 to about 8.25, about 7.5 to about 8.5, about 7.5 to about 8.75, about 7.5 to about 9, about 7.75 to about 8, about 7.75 to about 8.25, about 7.75 to about 8.5, about 7.75 to about 8.75, about 7.75 to about 9, about 8 to about 8.25, about 8 to about 8.5, about 8 to about 8.75, about 8 to about 9, about 8.25 to about 8.5, about 8.25 to about 8.75, about 8.25 to about 9, about 8.5 to about 8.75, about 8.5 to about 9, or about 8.75 to about 9. In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a pH of about 7, about 7.25, about 7.5, about 7.75, about 8, about 8.25, about 8.5, about 8.75, or about 9. In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a pH of at least about 7, about 7.25, about 7.5, about 7.75, about 8, about 8.25, about 8.5, or about 8.75. In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a pH of at most about 7.25, about 7.5, about 7.75, about 8, about 8.25, about 8.5, about 8.75, or about 9.
In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a temperature of about 80° C. to about 120° C. In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a temperature of about 80° C. to about 85° C., about 80° C. to about 90° C., about 80° C. to about 95° C., about 80° C. to about 100° C., about 80° C. to about 105° C., about 80° C. to about 110° C., about 80° C. to about 115° C., about 80° C. to about 120° C., about 85° C. to about 90° C., about 85° C. to about 95° C., about 85° C. to about 100° C., about 85° C. to about 105° C., about 85° C. to about 110° C., about 85° C. to about 115° C., about 85° C. to about 120° C., about 90° C. to about 95° C., about 90° C. to about 100° C., about 90° C. to about 105° C., about 90° C. to about 110° C., about 90° C. to about 115° C., about 90° C. to about 120° C., about 95° C. to about 100° C., about 95° C. to about 105° C., about 95° C. to about 110° C., about 95° C. to about 115° C., about 95° C. to about 120° C., about 100° C. to about 105° C., about 100° C. to about 110° C., about 100° C. to about 115° C., about 100° C. to about 120° C., about 105° C. to about 110° C., about 105° C. to about 115° C., about 105° C. to about 120° C., about 110° C. to about 115° C., about 110° C. to about 120° C., or about 115° C. to about 120° C. In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a temperature of about 80° C., about 85° C., about 90° C., about 95° C., about 100° C., about 105° C., about 110° C., about 115° C., or about 120° C. In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a temperature of at least about 80° C., about 85° C., about 90° C., about 95° C., about 100° C., about 105° C., about 110° C., or about 115° C. In some embodiments, heating the first dispersion while adding the second quantity of the reducing agent to the first dispersion occurs until the first dispersion has a temperature of at most about 85° C., about 90° C., about 95° C., about 100° C., about 105° C., about 110° C., about 115° C., or about 120° C.
In some embodiments, the first dispersion is dried at a temperature of about 50° C. to about 90° C. In some embodiments, the first dispersion is dried at a temperature of about 50° C. to about 55° C., about 50° C. to about 60° C., about 50° C. to about 65° C., about 50° C. to about 70° C., about 50° C. to about 78° C., about 50° C. to about 80° C., about 50° C. to about 85° C., about 50° C. to about 90° C., about 55° C. to about 60° C., about 55° C. to about 65° C., about 55° C. to about 70° C., about 55° C. to about 78° C., about 55° C. to about 80° C., about 55° C. to about 85° C., about 55° C. to about 90° C., about 60° C. to about 65° C., about 60° C. to about 70° C., about 60° C. to about 78° C., about 60° C. to about 80° C., about 60° C. to about 85° C., about 60° C. to about 90° C., about 65° C. to about 70° C., about 65° C. to about 78° C., about 65° C. to about 80° C., about 65° C. to about 85° C., about 65° C. to about 90° C., about 70° C. to about 78° C., about 70° C. to about 80° C., about 70° C. to about 85° C., about 70° C. to about 90° C., about 78° C. to about 80° C., about 78° C. to about 85° C., about 78° C. to about 90° C., about 80° C. to about 85° C., about 80° C. to about 90° C., or about 85° C. to about 90° C. In some embodiments, the first dispersion is dried at a temperature of about 50° C., about 55° C., about 60° C., about 65° C., about 70° C., about 78° C., about 80° C., about 85° C., or about 90° C. In some embodiments, the first dispersion is dried at a temperature of at least about 50° C., about 55° C., about 60° C., about 65° C., about 70° C., about 78° C., about 80° C., or about 85° C. In some embodiments, the first dispersion is dried at a temperature of at most about 55° C., about 60° C., about 65° C., about 70° C., about 78° C., about 80° C., about 85° C., or about 90° C.
Pouch Cells and Methods of Manufacture
Another aspect provided herein is a method of forming an energy storage device. In some embodiments, the method comprises: forming a first electrode and forming a second electrode; and stacking the first electrode, a separator, and the second electrode to form a pouch cell. In some embodiments, the method is not performed in a dry room or a clean room. Another aspect provided herein is a method of forming a cylindrical energy storage device, the method comprising: forming a first electrode and forming a second electrode; stacking the first electrode, a separator, and the second electrode; wrapping the first electrode, the separator, and the second electrode into a spiral and inserting the spiral in a casing to form a cylindrical cell. Another aspect provided herein is a method of forming a button cell energy storage device, the method comprising: forming a first electrode and forming a second electrode; stacking the first electrode, a separator, and the second electrode; inserting the stacked first electrode, the separator, and the second electrode in a casing to form a button cell.
In some embodiments, the separator has a thickness of about 10 microns to about 80 microns. In one example the separator is a TF 3040 separator. In some embodiments, the separator prevents contact between the first electrode and the second electrode. In some embodiments, the separator absorbs and maintains at least a portion of the electrolyte.
In some embodiments, the method further comprises sealing the pouch cell. In some embodiments, sealing the pouch cell is performed by a heat sealer, a vacuum sealer, or any combination thereof. In some embodiments, the sealing the pouch cell prevents leakage of the electrolyte within. In some embodiments, the method further comprises adding an electrolyte to the pouch cell. In some embodiments, the method further comprises adding an electrolyte to the pouch cell through a hole in the pouch cell. In some embodiments, the electrolyte is a solid electrolyte, a liquid electrolyte, a gel electrolyte, or any combination thereof.
In some embodiments, the method further comprises performing a formation cycle of the pouch cell. In some embodiments, the formation cycle is performed in open air, at ambient temperature, or both. In some embodiments, the formation cycle comprises charging and discharging the pouch cell. In some embodiments, the formation cycle comprises charging and discharging the pouch cell 1, 2, 3, 4, or more times. In some embodiments during the formation cycle, the electrolyte releases a gas during the charging and discharging cycles. As such, in some embodiments, the method further comprises degassing the pouch cell. In some embodiments, the method further comprises sealing the pouch cell. In some embodiments, the method further comprises allowing the pouch cell to rest.
In some embodiments, the method further comprises cutting the pouch cell, degassing the pouch cell, and resealing the pouch cell.
In some embodiments, the method further comprises allowing the pouch cell to rest for a period of time of about 1 minute to about 10 minutes. In some embodiments, the method further comprises allowing the pouch cell to rest for a period of time of about 1 minute to about 2 minutes, about 1 minute to about 3 minutes, about 1 minute to about 4 minutes, about 1 minute to about 5 minutes, about 1 minute to about 6 minutes, about 1 minute to about 7 minutes, about 1 minute to about 8 minutes, about 1 minute to about 9 minutes, about 1 minute to about 10 minutes, about 2 minutes to about 3 minutes, about 2 minutes to about 4 minutes, about 2 minutes to about 5 minutes, about 2 minutes to about 6 minutes, about 2 minutes to about 7 minutes, about 2 minutes to about 8 minutes, about 2 minutes to about 9 minutes, about 2 minutes to about 10 minutes, about 3 minutes to about 4 minutes, about 3 minutes to about 5 minutes, about 3 minutes to about 6 minutes, about 3 minutes to about 7 minutes, about 3 minutes to about 8 minutes, about 3 minutes to about 9 minutes, about 3 minutes to about 10 minutes, about 4 minutes to about 5 minutes, about 4 minutes to about 6 minutes, about 4 minutes to about 7 minutes, about 4 minutes to about 8 minutes, about 4 minutes to about 9 minutes, about 4 minutes to about 10 minutes, about 5 minutes to about 6 minutes, about 5 minutes to about 7 minutes, about 5 minutes to about 8 minutes, about 5 minutes to about 9 minutes, about 5 minutes to about 10 minutes, about 6 minutes to about 7 minutes, about 6 minutes to about 8 minutes, about 6 minutes to about 9 minutes, about 6 minutes to about 10 minutes, about 7 minutes to about 8 minutes, about 7 minutes to about 9 minutes, about 7 minutes to about 10 minutes, about 8 minutes to about 9 minutes, about 8 minutes to about 10 minutes, or about 9 minutes to about 10 minutes. In some embodiments, the method further comprises allowing the pouch cell to rest for a period of time of about 1 minute, about 2 minutes, about 3 minutes, about 4 minutes, about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, or about 10 minutes. In some embodiments, the method further comprises allowing the pouch cell to rest for a period of time of at least about 1 minute, about 2 minutes, about 3 minutes, about 4 minutes, about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, or about 9 minutes. In some embodiments, the method further comprises allowing the pouch cell to rest for a period of time of at most about 2 minutes, about 3 minutes, about 4 minutes, about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, or about 10 minutes.
Charge and Discharge Circuits
An electric circuit switch has been designed to switch between serial and parallel connections for multiple energy storage devices, for example, three energy storage devices. In some embodiments, the batteries are designed to be charged in parallel to minimize the charging and times and improve charging characteristics. Once the battery pack is charged, a switch can be switched from three-cells-in-parallel to three-cells-in-series for powering a recent-generation cellular telephone.
The circuit switch can be made of two dual-pole double-throw toggle switches, three energy storage devices, and a number of wires, as shown in
In some embodiments, the energy storage devices herein have a nominal operating voltage of about 1.73 V. Thus, per
As such,
In some embodiments, the first switch 3006 and the second switch 3007 are sequentially toggled to enable the connection of the primary first portion of the circuit 3006A and the primary second portion of the circuit 3007A and to disable the secondary first portion of the circuit 3006B and the secondary second portion of the circuit 3007B. In some embodiments, the first switch 3006 and the second switch 3007 are sequentially toggled to disable the connection of the primary first portion of the circuit 3006A and the primary second portion of the circuit 3007A and to enable the secondary first portion of the circuit 3006B and the secondary second portion of the circuit 3007B. In some embodiments, the second switch 3007 and the first switch 3006 are sequentially toggled to enable the connection of the primary first portion of the circuit 3006A and the primary second portion of the circuit 3007A and to disable the secondary first portion of the circuit 3006B and the secondary second portion of the circuit 3007B. In some embodiments, the second switch 3007 and the first switch 3006 are sequentially toggled to disable the connection of the primary first portion of the circuit 3006A and the primary second portion of the circuit 3007A and to enable the secondary first portion of the circuit 3006B and the secondary second portion of the circuit 3007B.
As such, during discharge, per
As such, during charging, per
Characterization of the Energy Storage Devices
The SEM images of the Zn—Bi LDH of
The Ni—Co LDH was hydrothermally grown directly on nickel foam substrates, and the resulting electrodes can be used as positive electrodes.
The images of
The charge capacity of three energy storage device types are compared per
To compare the fast-charging capability of three different energy storage systems (lithium-ion polymer battery, supercapacitor, and the energy storage device of the present disclosure), all three energy storage devices were charged for 10 minutes, whereas the lithium-ion polymer was charged at two different rates. In terms of relative charge capacity, at 0.5C, the lithium-ion polymer reached about 8% of its rated capacity; at 1C, it was charged to about 17%. The supercapacitor was fully charged (100%) after 10 minutes of charging. The energy storage device was charged to about 45% its rated capacity. However, if the absolute capacity after 10 minutes of charging is compared, the supercapacitor, due to its small capacity, only stored 10.4 mAh of charge. The lithium-ion polymer stored 16.6 and 33.3 mAh at 0.5C and 1C rates, respectively. In comparison, the energy storage device was able to store 90 mAh during the 10 minutes of charging, a much higher capacity than that of the supercapacitor and the lithium-ion polymer battery.
The equivalent series resistance (ESR) of the lithium-ion polymer batteries and supercapacitors of similar electrode area is about 236.6 mOhm and about 24.1 mOhm, respectively. The energy storage device of the same electrode area exhibits an ESR of about 30.2 mOhm, much closer to that of the supercapacitor than that of the lithium-ion polymer battery. These results corroborate the claim that the energy storage device combines the high capacity of the lithium-ion polymer battery and the lower ESR of the supercapacitor, as shown in
An example of a charging profile of an energy storage device described herein and a typical discharging profile are shown in
The Ragone plot of
The plot of
Energy Storage Device Performance
The high energy densities and power densities exhibited by the storage devices herein were unexpectedly high given the composition by mass, by volume, or both of the graphene sheet of below about 10%. The concentration by mass, by volume, or both of the graphene sheet of below about 10% enables the graphene to serve as a substrate for LDH growth but does not form a complete matrix that limits the density of the LDH-graphene composite.
Furthermore, the ratio by mass or volume between the of the conductive additive, such as the high surface area carbon materials, and the LDH can be tuned to alter and improve performance of the electrodes and energy storage devices. In some embodiments, increasing the amount of the conductive additive improves the rate capability of the energy storage device for high power applications. In some embodiments, increasing the amount of LDH increases the specific capacity for high energy density applications.
Energy storage devices with a higher gravimetric energy densities and volumetric energy densities store a greater amount of energy and power an electronic device for a greater amount of time. Gravimetric energy density is measured in units of energy/mass (e.g., watt-hours per kilogram [Wh/kg]). Volumetric energy density is measured in units of energy/volume (e.g., watt-hours per liter [Wh/L]). In some embodiments, the gravimetric energy density of an energy storage device is measured as a gravimetric energy density of an entire cell including non-active materials. In some embodiments, the gravimetric energy density of an energy storage device is measured as a gravimetric energy density of only active materials. Alternatively, in some embodiments, the gravimetric energy density of an energy storage device is measured by any standard means. In some embodiments, the volumetric energy density of an energy storage device is measured as a volumetric energy density of an entire cell including non-active materials. In some embodiments, the volumetric energy density of an energy storage device is measured as a volumetric energy density of only active materials. Alternatively, in some embodiments, the volumetric energy density of an energy storage device is measured by any standard means.
Energy storage devices with a higher gravimetric power densities and volumetric power densities recharge faster. Gravimetric power density is measured in units of power/mass (e.g., watts per kilogram [W/kg]). Volumetric power density is measured in units of power/volume (e.g., watts per liter [W/L]). In some embodiments, the gravimetric power density of an energy storage device is measured as a gravimetric power density of an entire cell including non-active materials. In some embodiments, the gravimetric power density of an energy storage device is measured as a gravimetric power density of only active materials. Alternatively, in some embodiments, the gravimetric power density of an energy storage device is measured by any standard means. In some embodiments, the volumetric power density of an energy storage device is measured as a volumetric power density of an entire cell including non-active materials. In some embodiments, the volumetric power density of an energy storage device is measured as a volumetric power density of only active materials. Alternatively, in some embodiments, the volumetric power density of an energy storage device is measured by any standard means.
In some embodiments, the energy storage devices herein have an internal resistance of less than the internal resistance of a commercially available LIPO battery by a factor of 2, 3, 4, 5, 6, 7, 8, 9, 10, or more. In some embodiments, due to their low internal resistance, the energy storage devices herein can be charged at higher currents and at faster charging rates than commercially available LIPO batteries. While the internal resistance of commercial LIPO batteries limits their charge rates to 1C, the low internal resistance of the energy storage devices herein enables charge rates of at least about 1.5C, 2C, 3C, 4C, 5C, 6C, 7C, 8C, 9C, 10C, or more, including increments therein. In some instances, the energy storage devices disclosed herein can be charged at a charge rate above 1C. By contrast, commercial LIPO batteries have a higher internal resistance that prevents them from being safely charged at above 1C.
In some embodiments, the energy storage device has a charge rate of about 1C to about 10C. In some embodiments, the energy storage device has a charge rate of about 1C to about 2C, about 1C to about 3C, about 1C to about 4C, about 1C to about 5C, about 1C to about 6C, about 1C to about 7C, about 1C to about 8C, about 1C to about 9C, about 1C to about 10C, about 2C to about 3C, about 2C to about 4C, about 2C to about 5C, about 2C to about 6C, about 2C to about 7C, about 2C to about 8C, about 2C to about 9C, about 2C to about 10C, about 3C to about 4C, about 3C to about 5C, about 3C to about 6C, about 3C to about 7C, about 3C to about 8C, about 3C to about 9C, about 3C to about 10C, about 4C to about 5C, about 4C to about 6C, about 4C to about 7C, about 4C to about 8C, about 4C to about 9C, about 4C to about 10C, about 5C to about 6C, about 5C to about 7C, about 5C to about 8C, about 5C to about 9C, about 5C to about 10C, about 6C to about 7C, about 6C to about 8C, about 6C to about 9C, about 6C to about 10C, about 7C to about 8C, about 7C to about 9C, about 7C to about 10C, about 8C to about 9C, about 8C to about 10C, or about 9C to about 10C. In some embodiments, the energy storage device has a charge rate of about 1C, about 2C, about 3C, about 4C, about 5C, about 6C, about 7C, about 8C, about 9C, or about 10C. In some embodiments, the energy storage device has a charge rate of at least about 1C, about 2C, about 3C, about 4C, about 5C, about 6C, about 7C, about 8C, or about 9C. In some embodiments, the energy storage device has a charge rate of at most about 2C, about 3C, about 4C, about 5C, about 6C, about 7C, about 8C, about 9C, or about 10C.
In some embodiments, the energy storage device has an internal resistance of about 12 milliohms to about 38 milliohms. In some embodiments, the energy storage device has an internal resistance of about 12 milliohms to about 14 milliohms, about 12 milliohms to about 16 milliohms, about 12 milliohms to about 18 milliohms, about 12 milliohms to about 20 milliohms, about 12 milliohms to about 22 milliohms, about 12 milliohms to about 24 milliohms, about 12 milliohms to about 26 milliohms, about 12 milliohms to about 28 milliohms, about 12 milliohms to about 30 milliohms, about 12 milliohms to about 34 milliohms, about 12 milliohms to about 38 milliohms, about 14 milliohms to about 16 milliohms, about 14 milliohms to about 18 milliohms, about 14 milliohms to about 20 milliohms, about 14 milliohms to about 22 milliohms, about 14 milliohms to about 24 milliohms, about 14 milliohms to about 26 milliohms, about 14 milliohms to about 28 milliohms, about 14 milliohms to about 30 milliohms, about 14 milliohms to about 34 milliohms, about 14 milliohms to about 38 milliohms, about 16 milliohms to about 18 milliohms, about 16 milliohms to about 20 milliohms, about 16 milliohms to about 22 milliohms, about 16 milliohms to about 24 milliohms, about 16 milliohms to about 26 milliohms, about 16 milliohms to about 28 milliohms, about 16 milliohms to about 30 milliohms, about 16 milliohms to about 34 milliohms, about 16 milliohms to about 38 milliohms, about 18 milliohms to about 20 milliohms, about 18 milliohms to about 22 milliohms, about 18 milliohms to about 24 milliohms, about 18 milliohms to about 26 milliohms, about 18 milliohms to about 28 milliohms, about 18 milliohms to about 30 milliohms, about 18 milliohms to about 34 milliohms, about 18 milliohms to about 38 milliohms, about 20 milliohms to about 22 milliohms, about 20 milliohms to about 24 milliohms, about 20 milliohms to about 26 milliohms, about 20 milliohms to about 28 milliohms, about 20 milliohms to about 30 milliohms, about 20 milliohms to about 34 milliohms, about 20 milliohms to about 38 milliohms, about 22 milliohms to about 24 milliohms, about 22 milliohms to about 26 milliohms, about 22 milliohms to about 28 milliohms, about 22 milliohms to about 30 milliohms, about 22 milliohms to about 34 milliohms, about 22 milliohms to about 38 milliohms, about 24 milliohms to about 26 milliohms, about 24 milliohms to about 28 milliohms, about 24 milliohms to about 30 milliohms, about 24 milliohms to about 34 milliohms, about 24 milliohms to about 38 milliohms, about 26 milliohms to about 28 milliohms, about 26 milliohms to about 30 milliohms, about 26 milliohms to about 34 milliohms, about 26 milliohms to about 38 milliohms, about 28 milliohms to about 30 milliohms, about 28 milliohms to about 34 milliohms, about 28 milliohms to about 38 milliohms, about 30 milliohms to about 34 milliohms, about 30 milliohms to about 38 milliohms, or about 34 milliohms to about 38 milliohms. In some embodiments, the energy storage device has an internal resistance of about 12 milliohms, about 14 milliohms, about 16 milliohms, about 18 milliohms, about 20 milliohms, about 22 milliohms, about 24 milliohms, about 26 milliohms, about 28 milliohms, about 30 milliohms, about 34 milliohms, or about 38 milliohms. In some embodiments, the energy storage device has an internal resistance of at least about 12 milliohms, about 14 milliohms, about 16 milliohms, about 18 milliohms, about 20 milliohms, about 22 milliohms, about 24 milliohms, about 26 milliohms, about 28 milliohms, about 30 milliohms, or about 34 milliohms. In some embodiments, the energy storage device has an internal resistance of at most about 14 milliohms, about 16 milliohms, about 18 milliohms, about 20 milliohms, about 22 milliohms, about 24 milliohms, about 26 milliohms, about 28 milliohms, about 30 milliohms, about 34 milliohms, or about 38 milliohms.
In some embodiments, the energy storage device has a gravimetric energy density of about 200 Wh/kg to about 800 Wh/kg. In some embodiments, the energy storage device has a gravimetric energy density of about 200 Wh/kg to about 250 Wh/kg, about 200 Wh/kg to about 300 Wh/kg, about 200 Wh/kg to about 350 Wh/kg, about 200 Wh/kg to about 400 Wh/kg, about 200 Wh/kg to about 450 Wh/kg, about 200 Wh/kg to about 500 Wh/kg, about 200 Wh/kg to about 550 Wh/kg, about 200 Wh/kg to about 600 Wh/kg, about 200 Wh/kg to about 650 Wh/kg, about 200 Wh/kg to about 700 Wh/kg, about 200 Wh/kg to about 800 Wh/kg, about 250 Wh/kg to about 300 Wh/kg, about 250 Wh/kg to about 350 Wh/kg, about 250 Wh/kg to about 400 Wh/kg, about 250 Wh/kg to about 450 Wh/kg, about 250 Wh/kg to about 500 Wh/kg, about 250 Wh/kg to about 550 Wh/kg, about 250 Wh/kg to about 600 Wh/kg, about 250 Wh/kg to about 650 Wh/kg, about 250 Wh/kg to about 700 Wh/kg, about 250 Wh/kg to about 800 Wh/kg, about 300 Wh/kg to about 350 Wh/kg, about 300 Wh/kg to about 400 Wh/kg, about 300 Wh/kg to about 450 Wh/kg, about 300 Wh/kg to about 500 Wh/kg, about 300 Wh/kg to about 550 Wh/kg, about 300 Wh/kg to about 600 Wh/kg, about 300 Wh/kg to about 650 Wh/kg, about 300 Wh/kg to about 700 Wh/kg, about 300 Wh/kg to about 800 Wh/kg, about 350 Wh/kg to about 400 Wh/kg, about 350 Wh/kg to about 450 Wh/kg, about 350 Wh/kg to about 500 Wh/kg, about 350 Wh/kg to about 550 Wh/kg, about 350 Wh/kg to about 600 Wh/kg, about 350 Wh/kg to about 650 Wh/kg, about 350 Wh/kg to about 700 Wh/kg, about 350 Wh/kg to about 800 Wh/kg, about 400 Wh/kg to about 450 Wh/kg, about 400 Wh/kg to about 500 Wh/kg, about 400 Wh/kg to about 550 Wh/kg, about 400 Wh/kg to about 600 Wh/kg, about 400 Wh/kg to about 650 Wh/kg, about 400 Wh/kg to about 700 Wh/kg, about 400 Wh/kg to about 800 Wh/kg, about 450 Wh/kg to about 500 Wh/kg, about 450 Wh/kg to about 550 Wh/kg, about 450 Wh/kg to about 600 Wh/kg, about 450 Wh/kg to about 650 Wh/kg, about 450 Wh/kg to about 700 Wh/kg, about 450 Wh/kg to about 800 Wh/kg, about 500 Wh/kg to about 550 Wh/kg, about 500 Wh/kg to about 600 Wh/kg, about 500 Wh/kg to about 650 Wh/kg, about 500 Wh/kg to about 700 Wh/kg, about 500 Wh/kg to about 800 Wh/kg, about 550 Wh/kg to about 600 Wh/kg, about 550 Wh/kg to about 650 Wh/kg, about 550 Wh/kg to about 700 Wh/kg, about 550 Wh/kg to about 800 Wh/kg, about 600 Wh/kg to about 650 Wh/kg, about 600 Wh/kg to about 700 Wh/kg, about 600 Wh/kg to about 800 Wh/kg, about 650 Wh/kg to about 700 Wh/kg, about 650 Wh/kg to about 800 Wh/kg, or about 700 Wh/kg to about 800 Wh/kg. In some embodiments, the energy storage device has a gravimetric energy density of about 200 Wh/kg, about 250 Wh/kg, about 300 Wh/kg, about 350 Wh/kg, about 400 Wh/kg, about 450 Wh/kg, about 500 Wh/kg, about 550 Wh/kg, about 600 Wh/kg, about 650 Wh/kg, about 700 Wh/kg, or about 800 Wh/kg. In some embodiments, the energy storage device has a gravimetric energy density of at least about 200 Wh/kg, about 250 Wh/kg, about 300 Wh/kg, about 350 Wh/kg, about 400 Wh/kg, about 450 Wh/kg, about 500 Wh/kg, about 550 Wh/kg, about 600 Wh/kg, about 650 Wh/kg, or about 700 Wh/kg. In some embodiments, the energy storage device has a gravimetric energy density of at most about 250 Wh/kg, about 300 Wh/kg, about 350 Wh/kg, about 400 Wh/kg, about 450 Wh/kg, about 500 Wh/kg, about 550 Wh/kg, about 600 Wh/kg, about 650 Wh/kg, about 700 Wh/kg, or about 800 Wh/kg.
In some embodiments, the energy storage device has a volumetric energy density of about 400 Wh/L to about 1,600 Wh/L. In some embodiments, the energy storage device has a volumetric energy density of about 400 Wh/L to about 500 Wh/L, about 400 Wh/L to about 600 Wh/L, about 400 Wh/L to about 700 Wh/L, about 400 Wh/L to about 800 Wh/L, about 400 Wh/L to about 900 Wh/L, about 400 Wh/L to about 1,000 Wh/L, about 400 Wh/L to about 1,100 Wh/L, about 400 Wh/L to about 1,200 Wh/L, about 400 Wh/L to about 1,300 Wh/L, about 400 Wh/L to about 1,400 Wh/L, about 400 Wh/L to about 1,600 Wh/L, about 500 Wh/L to about 600 Wh/L, about 500 Wh/L to about 700 Wh/L, about 500 Wh/L to about 800 Wh/L, about 500 Wh/L to about 900 Wh/L, about 500 Wh/L to about 1,000 Wh/L, about 500 Wh/L to about 1,100 Wh/L, about 500 Wh/L to about 1,200 Wh/L, about 500 Wh/L to about 1,300 Wh/L, about 500 Wh/L to about 1,400 Wh/L, about 500 Wh/L to about 1,600 Wh/L, about 600 Wh/L to about 700 Wh/L, about 600 Wh/L to about 800 Wh/L, about 600 Wh/L to about 900 Wh/L, about 600 Wh/L to about 1,000 Wh/L, about 600 Wh/L to about 1,100 Wh/L, about 600 Wh/L to about 1,200 Wh/L, about 600 Wh/L to about 1,300 Wh/L, about 600 Wh/L to about 1,400 Wh/L, about 600 Wh/L to about 1,600 Wh/L, about 700 Wh/L to about 800 Wh/L, about 700 Wh/L to about 900 Wh/L, about 700 Wh/L to about 1,000 Wh/L, about 700 Wh/L to about 1,100 Wh/L, about 700 Wh/L to about 1,200 Wh/L, about 700 Wh/L to about 1,300 Wh/L, about 700 Wh/L to about 1,400 Wh/L, about 700 Wh/L to about 1,600 Wh/L, about 800 Wh/L to about 900 Wh/L, about 800 Wh/L to about 1,000 Wh/L, about 800 Wh/L to about 1,100 Wh/L, about 800 Wh/L to about 1,200 Wh/L, about 800 Wh/L to about 1,300 Wh/L, about 800 Wh/L to about 1,400 Wh/L, about 800 Wh/L to about 1,600 Wh/L, about 900 Wh/L to about 1,000 Wh/L, about 900 Wh/L to about 1,100 Wh/L, about 900 Wh/L to about 1,200 Wh/L, about 900 Wh/L to about 1,300 Wh/L, about 900 Wh/L to about 1,400 Wh/L, about 900 Wh/L to about 1,600 Wh/L, about 1,000 Wh/L to about 1,100 Wh/L, about 1,000 Wh/L to about 1,200 Wh/L, about 1,000 Wh/L to about 1,300 Wh/L, about 1,000 Wh/L to about 1,400 Wh/L, about 1,000 Wh/L to about 1,600 Wh/L, about 1,100 Wh/L to about 1,200 Wh/L, about 1,100 Wh/L to about 1,300 Wh/L, about 1,100 Wh/L to about 1,400 Wh/L, about 1,100 Wh/L to about 1,600 Wh/L, about 1,200 Wh/L to about 1,300 Wh/L, about 1,200 Wh/L to about 1,400 Wh/L, about 1,200 Wh/L to about 1,600 Wh/L, about 1,300 Wh/L to about 1,400 Wh/L, about 1,300 Wh/L to about 1,600 Wh/L, or about 1,400 Wh/L to about 1,600 Wh/L. In some embodiments, the energy storage device has a volumetric energy density of about 400 Wh/L, about 500 Wh/L, about 600 Wh/L, about 700 Wh/L, about 800 Wh/L, about 900 Wh/L, about 1,000 Wh/L, about 1,100 Wh/L, about 1,200 Wh/L, about 1,300 Wh/L, about 1,400 Wh/L, or about 1,600 Wh/L. In some embodiments, the energy storage device has a volumetric energy density of at least about 400 Wh/L, about 500 Wh/L, about 600 Wh/L, about 700 Wh/L, about 800 Wh/L, about 900 Wh/L, about 1,000 Wh/L, about 1,100 Wh/L, about 1,200 Wh/L, about 1,300 Wh/L, or about 1,400 Wh/L. In some embodiments, the energy storage device has a volumetric energy density of at most about 500 Wh/L, about 600 Wh/L, about 700 Wh/L, about 800 Wh/L, about 900 Wh/L, about 1,000 Wh/L, about 1,100 Wh/L, about 1,200 Wh/L, about 1,300 Wh/L, about 1,400 Wh/L, or about 1,600 Wh/L.
In some embodiments, the energy storage device has a gravimetric power density of about 2.5 kW/kg to about 12 kW/kg. In some embodiments, gravimetric power density is a measurement of power stored measured in units of power/mass (e.g., watt-hours per kilogram [W/kg]). In some embodiments, the gravimetric power density of a power storage device is measured as a power density of an entire cell (including non-active materials), or as a power density of only the active materials. In some embodiments, the energy storage device has a gravimetric power density of about 2.5 kW/kg to about 5 kW/kg, about 2.5 kW/kg to about 6 kW/kg, about 2.5 kW/kg to about 7 kW/kg, about 2.5 kW/kg to about 8 kW/kg, about 2.5 kW/kg to about 9 kW/kg, about 2.5 kW/kg to about 10 kW/kg, about 2.5 kW/kg to about 11 kW/kg, about 2.5 kW/kg to about 12 kW/kg, about 5 kW/kg to about 6 kW/kg, about 5 kW/kg to about 7 kW/kg, about 5 kW/kg to about 8 kW/kg, about 5 kW/kg to about 9 kW/kg, about 5 kW/kg to about 10 kW/kg, about 5 kW/kg to about 11 kW/kg, about 5 kW/kg to about 12 kW/kg, about 6 kW/kg to about 7 kW/kg, about 6 kW/kg to about 8 kW/kg, about 6 kW/kg to about 9 kW/kg, about 6 kW/kg to about 10 kW/kg, about 6 kW/kg to about 11 kW/kg, about 6 kW/kg to about 12 kW/kg, about 7 kW/kg to about 8 kW/kg, about 7 kW/kg to about 9 kW/kg, about 7 kW/kg to about 10 kW/kg, about 7 kW/kg to about 11 kW/kg, about 7 kW/kg to about 12 kW/kg, about 8 kW/kg to about 9 kW/kg, about 8 kW/kg to about 10 kW/kg, about 8 kW/kg to about 11 kW/kg, about 8 kW/kg to about 12 kW/kg, about 9 kW/kg to about 10 kW/kg, about 9 kW/kg to about 11 kW/kg, about 9 kW/kg to about 12 kW/kg, about 10 kW/kg to about 11 kW/kg, about 10 kW/kg to about 12 kW/kg, or about 11 kW/kg to about 12 kW/kg. In some embodiments, the energy storage device has a gravimetric power density of about 2.5 kW/kg, about 5 kW/kg, about 6 kW/kg, about 7 kW/kg, about 8 kW/kg, about 9 kW/kg, about 10 kW/kg, about 11 kW/kg, or about 12 kW/kg. In some embodiments, the energy storage device has a gravimetric power density of at least about 2.5 kW/kg, about 5 kW/kg, about 6 kW/kg, about 7 kW/kg, about 8 kW/kg, about 9 kW/kg, about 10 kW/kg, or about 11 kW/kg. In some embodiments, the energy storage device has a gravimetric power density of at most about 5 kW/kg, about 6 kW/kg, about 7 kW/kg, about 8 kW/kg, about 9 kW/kg, about 10 kW/kg, about 11 kW/kg, or about 12 kW/kg.
In some embodiments, the energy storage device has an internal resistance of about 1 mOhm to about 60 mOhm. In some embodiments, the energy storage device has an internal resistance of about 1 mOhm to about 2 mOhm, about 1 mOhm to about 5 mOhm, about 1 mOhm to about 10 mOhm, about 1 mOhm to about 20 mOhm, about 1 mOhm to about 30 mOhm, about 1 mOhm to about 40 mOhm, about 1 mOhm to about 50 mOhm, about 1 mOhm to about 60 mOhm, about 2 mOhm to about 5 mOhm, about 2 mOhm to about 10 mOhm, about 2 mOhm to about 20 mOhm, about 2 mOhm to about 30 mOhm, about 2 mOhm to about 40 mOhm, about 2 mOhm to about 50 mOhm, about 2 mOhm to about 60 mOhm, about 5 mOhm to about 10 mOhm, about 5 mOhm to about 20 mOhm, about 5 mOhm to about 30 mOhm, about 5 mOhm to about 40 mOhm, about 5 mOhm to about 50 mOhm, about 5 mOhm to about 60 mOhm, about 10 mOhm to about 20 mOhm, about 10 mOhm to about 30 mOhm, about 10 mOhm to about 40 mOhm, about 10 mOhm to about 50 mOhm, about 10 mOhm to about 60 mOhm, about 20 mOhm to about 30 mOhm, about 20 mOhm to about 40 mOhm, about 20 mOhm to about 50 mOhm, about 20 mOhm to about 60 mOhm, about 30 mOhm to about 40 mOhm, about 30 mOhm to about 50 mOhm, about 30 mOhm to about 60 mOhm, about 40 mOhm to about 50 mOhm, about 40 mOhm to about 60 mOhm, or about 50 mOhm to about 60 mOhm. In some embodiments, the energy storage device has an internal resistance of about 1 mOhm, about 2 mOhm, about 5 mOhm, about 10 mOhm, about 20 mOhm, about 30 mOhm, about 40 mOhm, about 50 mOhm, or about 60 mOhm. In some embodiments, the energy storage device has an internal resistance of at least about 1 mOhm, about 2 mOhm, about 5 mOhm, about 10 mOhm, about 20 mOhm, about 30 mOhm, about 40 mOhm, or about 50 mOhm. In some embodiments, the energy storage device has an internal resistance of at most about 2 mOhm, about 5 mOhm, about 10 mOhm, about 20 mOhm, about 30 mOhm, about 40 mOhm, about 50 mOhm, or about 60 mOhm.
In some embodiments, the energy storage device has a charge capacity percentage after about 10 minutes of about 23% to about 90%. In some embodiments, the energy storage device has a charge capacity percentage after about 10 minutes of about 23% to about 25%, about 23% to about 30%, about 23% to about 35%, about 23% to about 40%, about 23% to about 45%, about 23% to about 50%, about 23% to about 55%, about 23% to about 60%, about 23% to about 70%, about 23% to about 80%, about 23% to about 90%, about 25% to about 30%, about 25% to about 35%, about 25% to about 40%, about 25% to about 45%, about 25% to about 50%, about 25% to about 55%, about 25% to about 60%, about 25% to about 70%, about 25% to about 80%, about 25% to about 90%, about 30% to about 35%, about 30% to about 40%, about 30% to about 45%, about 30% to about 50%, about 30% to about 55%, about 30% to about 60%, about 30% to about 70%, about 30% to about 80%, about 30% to about 90%, about 35% to about 40%, about 35% to about 45%, about 35% to about 50%, about 35% to about 55%, about 35% to about 60%, about 35% to about 70%, about 35% to about 80%, about 35% to about 90%, about 40% to about 45%, about 40% to about 50%, about 40% to about 55%, about 40% to about 60%, about 40% to about 70%, about 40% to about 80%, about 40% to about 90%, about 45% to about 50%, about 45% to about 55%, about 45% to about 60%, about 45% to about 70%, about 45% to about 80%, about 45% to about 90%, about 50% to about 55%, about 50% to about 60%, about 50% to about 70%, about 50% to about 80%, about 50% to about 90%, about 55% to about 60%, about 55% to about 70%, about 55% to about 80%, about 55% to about 90%, about 60% to about 70%, about 60% to about 80%, about 60% to about 90%, about 70% to about 80%, about 70% to about 90%, or about 80% to about 90%. In some embodiments, the energy storage device has a charge capacity percentage after about 10 minutes of about 23%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 70%, about 80%, or about 90%. In some embodiments, the energy storage device has a charge capacity percentage after about 10 minutes of at least about 23%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 70%, or about 80%. In some embodiments, the energy storage device has a charge capacity percentage after about 10 minutes of at most about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 70%, about 80%, or about 90%.
In some embodiments, the energy storage device has a charge capacity of about 45 mAh to about 5,000 mAh. In some embodiments, the energy storage device has a charge capacity of about 45 mAh to about 100 mAh, about 45 mAh to about 250 mAh, about 45 mAh to about 500 mAh, about 45 mAh to about 750 mAh, about 45 mAh to about 1,000 mAh, about 45 mAh to about 2,000 mAh, about 45 mAh to about 3,000 mAh, about 45 mAh to about 4,000 mAh, about 45 mAh to about 5,000 mAh, about 100 mAh to about 250 mAh, about 100 mAh to about 500 mAh, about 100 mAh to about 750 mAh, about 100 mAh to about 1,000 mAh, about 100 mAh to about 2,000 mAh, about 100 mAh to about 3,000 mAh, about 100 mAh to about 4,000 mAh, about 100 mAh to about 5,000 mAh, about 250 mAh to about 500 mAh, about 250 mAh to about 750 mAh, about 250 mAh to about 1,000 mAh, about 250 mAh to about 2,000 mAh, about 250 mAh to about 3,000 mAh, about 250 mAh to about 4,000 mAh, about 250 mAh to about 5,000 mAh, about 500 mAh to about 750 mAh, about 500 mAh to about 1,000 mAh, about 500 mAh to about 2,000 mAh, about 500 mAh to about 3,000 mAh, about 500 mAh to about 4,000 mAh, about 500 mAh to about 5,000 mAh, about 750 mAh to about 1,000 mAh, about 750 mAh to about 2,000 mAh, about 750 mAh to about 3,000 mAh, about 750 mAh to about 4,000 mAh, about 750 mAh to about 5,000 mAh, about 1,000 mAh to about 2,000 mAh, about 1,000 mAh to about 3,000 mAh, about 1,000 mAh to about 4,000 mAh, about 1,000 mAh to about 5,000 mAh, about 2,000 mAh to about 3,000 mAh, about 2,000 mAh to about 4,000 mAh, about 2,000 mAh to about 5,000 mAh, about 3,000 mAh to about 4,000 mAh, about 3,000 mAh to about 5,000 mAh, or about 4,000 mAh to about 5,000 mAh. In some embodiments, the energy storage device has a charge capacity of about 45 mAh, about 100 mAh, about 250 mAh, about 500 mAh, about 750 mAh, about 1,000 mAh, about 2,000 mAh, about 3,000 mAh, about 4,000 mAh, or about 5,000 mAh. In some embodiments, the energy storage device has a charge capacity of at least about 45 mAh, about 100 mAh, about 250 mAh, about 500 mAh, about 750 mAh, about 1,000 mAh, about 2,000 mAh, about 3,000 mAh, or about 4,000 mAh. In some embodiments, the energy storage device has a charge capacity of at most about 100 mAh, about 250 mAh, about 500 mAh, about 750 mAh, about 1,000 mAh, about 2,000 mAh, about 3,000 mAh, about 4,000 mAh, or about 5,000 mAh.
Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
As used herein, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Any reference to “or” herein is intended to encompass “and/or” unless otherwise stated.
As used herein, the term “about” refers to an amount that is near the stated amount by 10%, 5%, or 1%, including increments therein.
As used herein, the term “about” in reference to a percentage refers to an amount that is greater than or less than the stated percentage by 10%, 5%, or 1%, including increments therein.
As used herein, the phrases “at least one”, “one or more”, and “and/or” are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions “at least one of A, B and C”, “at least one of A, B, or C”, “one or more of A, B, and C”, “one or more of A, B, or C”, and “A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B, and C together.
As used herein, the term “atomic ratio” refers to a measure of the ratio of atoms of one kind to another kind.
As used herein, the term “active material specific” refers to a property based solely on the active materials of the electrode or the energy storage device, not including any casing materials.
As used herein, the term “aspect ratio” refers to a ratio between a width and a thickness, a ratio between a length and a thickness or both.
As used herein, the term “cell specific” refers to a property based on the entirety of an electrode or energy storage device, including any casing materials.
As used herein, the term “charge capacity” refers to a value equal to the amount of time required to charge an energy storage device multiplied by the number of amperes (current) required to charge the energy storage device in the time required to charge the energy storage device. In some embodiments, charge capacity is measured in milliampere-hours (mAh).
As used herein, the term “charge capacity percentage” refers to a percentage of a charge of an energy storage device at a certain charge rate and after a certain amount of time. In some embodiments, 200 mAh is represented as a 100% state of charge, whereas 0 mAh is equivalent to 0% state of charge.
As used herein, the term “charge-discharge lifetime” refers to the number of charge and discharge cycles at which the rated capacity of an energy storage reduces by about 80%.
As used herein, the term “charge rate” and “discharge rate” refer to a measure of the rate at which a battery is charged or discharged relative to its capacity defined as the charge or discharge current divided by the capacity of an energy storage device to store an electrical charge.
As used herein, the term “clean room” refers to an area designed to maintain extremely low levels of particulates, such as dust, airborne organisms, or vaporized particles. In some embodiments, the clean room has a class of ISO 1, ISO 2, ISO 3, ISO 4, ISO 5, ISO 6, ISO 7, ISO 8, or ISO 9.
As used herein, the term “dry room” refers to an area designed to maintain temperatures from +20° C. to +40° C., humidities to less than 1%, supply air dew points of at least −60° C., or any combination thereof.
As used herein, the term “equivalent series resistance,” (ESR) refers to an approximation of the resistance of an energy storage device as a combination of ideal capacitors and inductors in series with a resistor. ESR is generally measured in ohms at a frequency of about 120 Hz to about 100 kHz.
As used herein, the term “freeze-drying,” also known as lyophilisation, lyophilization, or cryodesiccation, refers to a dehydration process of freezing the material and reducing the surrounding pressure to allow a frozen fluid in the material to sublime directly from the solid phase to the gas phase.
As used herein, the term “gravimetric energy density” refers to a measurement of energy stored measured in units of energy/mass (e.g., watt-hours per kilogram). In some embodiments, the gravimetric energy density of an energy storage device is measured as an energy density of an entire cell (including non-active materials) or as an energy density of only the active materials.
As used herein, the term “gravimetric power density” refers to a measurement of power stored measured in units of power/mass (e.g., watts per kilogram). In some embodiments, the gravimetric power density of a power storage device is measured as a power density of an entire cell (including non-active materials) or as a power density of only the active materials.
As used herein, the term “volumetric energy density” refers to a measurement of energy stored measured in units of energy/volume (e.g., watt-hours per liter). In some embodiments, the volumetric energy density of an energy storage device is measured as an energy density of an entire cell (including non-active materials) or as an energy density of only the active materials.
As used herein, the term “volumetric power density” refers to a measurement of power stored measured in units of power/volume (e.g., watts per liter). In some embodiments, the volumetric power density of a power storage device is measured as a power density of an entire cell (including non-active materials) or as a power density of only the active materials.
As used herein, the term “internal resistance” or “internal impedance” refers to a difference between a measured voltage output and a no-load voltage of an energy storage device.
As used herein, the term “interconnected corrugated carbon-based network” or “ICCN” refers to a conjugated carbon network comprising a plurality of expanded and interconnected carbon layers comprising one or more corrugated carbon sheets that are one atom thick. For example, an ICCN can include multiple corrugated carbon sheets in which each carbon sheet is one atom thick.
As used herein, the term “lamellar” refers to a form of a thin plate or sheet.
As used herein, the term “length” refers to an average length, a maximum length, or a minimum length.
As used herein, the term “nanogranulars” refers to a nanoscale granule.
As used herein, the term “thickness” refers to an average thickness, a maximum thickness, or a minimum thickness.
As used herein, the term “ratio” refers to a quantitative relation between two quantities of substances, wherein the quantitative relation can be based on mass, volume, or both.
As used herein, the term “supernatant” refers to a liquid that lies above a sediment or precipitate.
As used herein, the term “width” refers to an average width, a maximum width, or a minimum width.
As used herein, the term “3D” refers to three-dimensional.
As used herein, the term “GO” refers to graphene oxide.
As used herein, the term “rGO” refers to reduced graphene oxide.
As used herein, the term “GA” refers to a graphene aerogel.
As used herein, the term “3DGA” refers to a three-dimensional graphene aerogel.
As used herein, the term “LDH” refers to layered double hydroxide. In some embodiments, an LDH is a class of ionic solids characterized by a layered structure with the generic layer sequence [AcBZAcB]n, where c represents layers of metal cations, A and B are layers of hydroxide (HO−) anions, and Z represents layers of other anions and neutral molecules.
Method of Forming Electrodes
In one example, an electrode of the current disclosure is formed by the following steps:
The present disclosure relates to a composition for an anode of a hybrid battery that can store more charge and, importantly, is compatible with current fabrication process protocols used in the production of lithium-ion polymer batteries.
A prototype 200 milliampere-hour (mAh) energy storage device was used as a power source for a recent-generation cellular telephone, and the results were compared with a similarly sized lithium-ion polymer battery and a carbon supercapacitor. In one example, the fast-charging capability of energy storage devices was demonstrated as follows: The energy storage device was pre-charged and used to run a recent-generation cellular telephones. The functionality of the energy storage device was demonstrated by making a phone call and by watching a video on YouTube. Additionally, the fast-charging capability of the energy storage device was demonstrated by starting from a fully discharged state of charge of around zero, as confirmed by open circuit voltage and milliampere-hour measurements. During charging of the prototype energy device herein, the capacity (milliampere-hours) was monitored on a battery analyzer. The capacity is an indication of the state of charge of a battery, with for example 200 mAh being 100% state of charge (fully charged) and 0 mAh being equivalent to 0% state of charge. The performance of prototype energy storage device was compared with a commercial-grade lithium-ion polymer battery with similar capacity (about 200 mAh) and with a supercapacitor of similar size.
After charging the three energy storage devices for 5 to 10 minutes, the prototype energy storage device ran the recent-generation cellular telephone for over 18 minutes, whereas the lithium-ion polymer battery and the supercapacitor could only run the recent-generation cellular telephone for a few seconds. While, in some embodiments, the supercapacitor demonstrated the fastest charging times, corresponding to a higher power density, the supercapacitor was only capable of running the recent-generation cellular phone for a fraction of a minute. The commercial-grade lithium-ion polymer battery, on the other hand, which is limited by slow chemical reactions, charged slowly. By contrast, the prototype energy storage device of the present disclosure recharged quickly while at the same time providing enough current to run the cellular phone for a longer period. This outstanding performance demonstrates the high energy density and fast-charging capabilities of the energy storage devices disclosed herein.
Charge Capacity
To compare the fast-charging capability of three different energy storage systems (lithium-ion polymer battery, supercapacitor, and a prototype energy storage device per the disclosure herein), all three were charged for 10 minutes; the lithium-ion polymer was charged at two different rates. In terms of relative charge capacity, at 0.5C, the lithium-ion polymer reached about 8% of its rated capacity at 1C, it was charged to about 17%. The supercapacitor was fully charged (100%) after 10 minutes of charging. The energy storage device was charged to about 45% of its rated capacity. However, if the absolute capacity after 10 minutes of charging is compared, the supercapacitor, due to its small capacity, only stored 10.4 mAh of charge. The lithium-ion polymer stored 16.6 and 33.3 mAh at 0.5C and 1C rates, respectively. In comparison, the energy storage device was able to store 90 mAh during the 10 minutes of charging, a much higher capacity than that of the supercapacitor and the lithium-ion polymer battery.
While preferred embodiments of the present disclosure have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the disclosure. It should be understood that various alternatives to the embodiments of the disclosure described herein may be employed in practicing the disclosure.
This application claims the benefit of U.S. Provisional Application No. 62/906,844, filed Sep. 27, 2019, which is hereby incorporated herein by reference in its entirety.
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| Number | Date | Country | |
|---|---|---|---|
| 62906844 | Sep 2019 | US |
