Patent Application
20240322221
The present application claims priority and the benefit of Korean Patent Application Nos. 10-2023-0039381, filed on Mar. 26, 2023, in the Korean Intellectual Property Office, and 10-2023-0135953, filed on Oct. 12, 2023, in the Korean Intellectual Property Office, the entire content of each of the two applications is incorporated herein by references.
According to one or more embodiments, the present disclosure provides an electrode structure containing a polymer electrolyte, a method of manufacturing the electrode structure, and lithium battery including the electrode structure.
Lithium secondary batteries are high-performance secondary batteries having some of the highest energy densities among related art secondary batteries, and may be utilized in one or more suitable fields such as electric vehicles.
As an anode of a lithium metal battery, a lithium metal thin film is utilized. If (e.g., when) the lithium metal thin film is utilized as an anode, the reactivity with a liquid electrolyte may be relatively high due to the high reactivity of lithium during charging and discharging. For example, side reactions between lithium metal and the electrolyte may create dendrites on the lithium metal surface, which may grow and (e.g., short circuit the electrodes to thereby) degrade the lifespan characteristics of the lithium metal battery.
Accordingly, if (e.g., when) dendrites are formed on the lithium metal thin film of the lithium anode, the lithium metal battery utilizing the lithium metal thin film may have reduced lifespan and stability. Thus, there is a need and/or desire to improve the design and method of preparing the lithium metal thin film utilized in lithium metal battery.
One or more aspects of embodiments are directed toward an electrode structure including a polymer electrolyte having improved durability and lifespan characteristics.
One or more aspects of embodiments are directed toward a lithium battery including the herein-described electrode structure.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the present disclosure.
According to one or more embodiments, an electrode structure includes an electrode current collector; and a polymer electrolyte provided on the electrode current collector, wherein the electrode current collector includes nickel (Ni), chromium (Cr), or zinc (Zn), the polymer electrolyte includes a cross-linked structure and a metal salt, the cross-linked structure including a repeating unit (A) including (e.g., derived from) a first polymer and a repeating unit (B) including (e.g., derived from) a second polymer, the first polymer includes a polymer containing a polar functional group, and the second polymer includes a polyurethane-based polymer.
According to one or more embodiments, a method of manufacturing (e.g., preparing) the electrode structure includes: preparing an electrode current collector; preparing a composition for providing a polymer electrolyte including a first polymer, a second polymer, a metal salt and an initiator; applying the composition for providing a polymer electrolyte onto the electrode current collector; and providing the polymer electrolyte on the electrode current collector to be coated with the composition for providing a polymer electrolyte, wherein the electrode current collector includes nickel (Ni), chromium (Cr) or zinc (Zn) the first polymer includes a polymer containing a polar functional group, and the second polymer includes a polyurethane-based polymer.
One or more embodiments provide a lithium battery including the herein-described electrode structure.
The preceding and other aspects, features, and advantages of certain embodiments of the present disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
Reference will now be made in more detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout, and duplicative descriptions thereof may not be provided. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described, by referring to the drawings, to explain aspects of the present description. As utilized herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” if (e.g., when) preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
Hereinafter, an electrode structure including a polymer electrolyte according to embodiments, a method of manufacturing the electrode structure, and a lithium battery including the electrode structure will be described in more detail. These embodiments are merely presented as examples to explain the present disclosure in more detail, and it will be apparent to those skilled in the art that the scope of the present disclosure is not limited by these embodiments.
Unless otherwise defined, all chemical, technical, and scientific terms utilized in this specification have the same meaning as commonly understood by a person skilled in the art to which the present disclosure pertains. In the event of a conflict, this specification including definitions will prevail.
Although methods and materials similar or equivalent to those described herein may be utilized in examples or evaluations of the present disclosure, suitable methods and materials are described herein. As utilized herein, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As utilized herein, the terms “comprise,” “comprising,” “comprises,” “include,” “includes,” “including,” “have,” “having,” and/or “has,” and/or the like if (e.g., when) utilized in this specification, may specify the presence of stated features, integers, steps, operations, elements, components, ingredients, materials, or combinations thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, ingredients, materials, or combinations thereof.
As utilized herein, the term “a combination thereof” may refer to a mixture or combination of one or more of the listed elements. As utilized herein, “/” may be interpreted as “and”, or as “or” depending on the context.
As utilized herein, the term “may” will be understood to refer to “one or more embodiments of the present disclosure,” some of which include the described element and some of which exclude that element and/or include an alternate element. Similarly, the term “and/or” may be meant to include any and all combinations of one or more items listed. As utilized herein, the term “or” may refer to “and/or”. In this specification, the expression “at least one type or kind”, “one or more types (kinds)”, or “one or more” in front of the components may refer to that the entire list of components may be supplemented, but may not refer to that the individual components of the preceding description may be not supplemented.
As used herein, singular forms such as “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As used herein, the terms “use,” “using,” and “used” may be considered synonymous with the terms “utilize,” “utilizing,” and “utilized,” respectively.
As used herein, expressions such as “at least one of,” “one of,” and “selected from,” if (e.g., when) preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. For example, the expressions “at least one of a to c,” “at least one of a, b or c,” and “at least one of a, b and/or c” may indicate only a, only b, only c, both (e.g., simultaneously) a and b, both (e.g., simultaneously) a and c, both (e.g., simultaneously) b and c, all of a, b, and c, or variations thereof.
In the drawings, the thicknesses of layers and regions may be exaggerated for clarity of description. Like drawing reference numerals are utilized for like elements through the specification. Throughout the specification, if (e.g., when) a component, such as a layer, a film, a region, or a plate, is described as being “above” or “on” another component, the component may be directly above the another component, or there may be yet another component therebetween. It will be understood that although the terms “first,” “second,” and/or the like may be utilized herein to describe one or more suitable elements, these elements should not be limited by these terms. These terms are only utilized to distinguish one element from another element.
Spatially relative terms, such as “beneath,” “below,” “lower,” “above,” “upper,” “bottom,” “top,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the drawings. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the drawings. For example, if the device in the drawings is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” or “over” the other elements or features. Thus, the term “below” may encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein should be interpreted accordingly.
In this context, “consisting essentially of” means that any additional components will not materially affect the chemical, physical, optical or electrical properties of the semiconductor film.
Further, in this specification, the phrase “on a plane,” or “plan view,” means viewing a target portion from the top, and the phrase “on a cross-section” means viewing a cross-section formed by vertically cutting a target portion from the side.
In present disclosure, “not include (or not including) a or any ‘component”, “exclude (or excluding) a or any ‘component”, “omit (or omitting) a or any ‘component”, “component’-free”, and/or the like refers to that the “component” not being added, selected or utilized as a component or compound in the element/composition, but the “component” of less than a suitable amount may still be included due to other impurities and/or external factors.
As utilized herein, the term “particle diameter” of a particle refers to an average particle diameter if (e.g., when) the particle is spherical, and for a particle that is non-spherical, said term refers to an average major axis length of the particle. The particle diameter of the particles may be measured by utilizing a particle size analyzer (PSA), a transmission electron microscopic (TEM) image, or a scanning electron microscopic (SEM) image. The “particle diameter’ of the particles refers to, for example, an average particle diameter. The average particle diameter may be, for example, a median particle diameter (D50). The median particle diameter D50 is a particle size corresponding to a 50% cumulative volume calculated from particles having a small particle size in a particle size distribution measured by, for example, a laser diffraction method. The average particle diameter and average major axis length of particles may be measured utilizing a scanning electron microscope. If (e.g., when) the size of the particles is measured utilizing a scanning electron microscope, the size of the particles is determined by the average value of 30 or more randomly extracted particles of 1 μm or more excluding differentials. Also, depending on context, when particles are spherical, “diameter” indicates a particle diameter or an average particle diameter, and when the particles are non-spherical, the “diameter” indicates a major axis length or an average major axis length.
As utilized herein, a “metal” refers to both (e.g., simultaneously) metals and metalloids such as silicon and germanium in an elemental or ionic state.
As utilized herein, an “alloy” refers to a mixture of two or more metals.
As utilized herein, a “cathode active material refers to a cathode material capable of undergoing lithiation and delithiation.
As utilized herein, an “anode active material” refers to an anode material capable of undergoing lithiation and delithiation.
As utilized herein, the terms “lithiation” and “to lithiate” refer to a process of adding lithium to a cathode active material or an anode active material.
As utilized herein, the terms “delithiation” and “to delithiate” refer to a process of removing lithium from a cathode active material or an anode active material.
As utilized herein, “charging” and “charge” refer to a process of providing electrochemical energy to a battery.
As utilized herein, “discharging” and “discharge” refer to a process of removing electrochemical energy from a battery.
As utilized herein, a “positive electrode” and a “cathode” refer to an electrode where electrochemical reduction and lithiation occur during a discharging process.
As utilized herein, a “negative electrode” and an “anode” refer to an electrode where electrochemical oxidation and delithiation occur during a discharging process.
A polymer electrolyte according to embodiments and a lithium battery including the same will be described in more detail with reference to the attached drawings.
Referring to
According to some embodiments, a surface of the electrode current collector 110 may include nickel (Ni), chromium (Cr) or zinc (Zn) and include no (e.g., may exclude) copper (Cu). In this case, in the preparing process of the electrode structure 10, the polymer electrolyte 120 may include no (e.g., may exclude) copper ion Cu2+). As a result, the polymerization or cross-linked reaction of the first polymer and the second polymer may be easily performed while an inhibitory effect of the polymerization reaction of the first polymer and the second polymer due to copper ions (Cu2+) may be effectively prevented or reduced.
According to some embodiments, the electrode current collector 110 may include a base film and a metal layer provided on at least one side (e.g., one side or both (e.g., opposite) sides of the base film. In some embodiments, the base film may include a metal or a polymer, and the metal in the base film may include indium (In), copper (Cu), magnesium (Mg), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof. The polymer in the base film may include polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), or a combination thereof. The metal layer may include nickel (Ni), chromium (Cr) or zinc (Zn). According to other embodiments, the electrode current collector 110 may include (e.g., be formed utilizing) nickel (Ni), chromium (Cr) or zinc (Zn).
In some embodiments, if (e.g., when) the base film includes a polymer, the polymer may be a thermoplastic polymer. Examples of the polymer may include polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), or a combination thereof. Due to the inclusion of a thermoplastic polymer in the base film, the base film may be melted in the event of a short circuit and thus may prevent or reduce a rapid increase in electric current. The base film may be, for example, an insulator.
In some embodiments, if (e.g., when) the base film includes a metal, the metal may include indium (In), copper (Cu), magnesium (Mg), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.
In some embodiments, the metal layer may include nickel (Ni), chromium (Cr), or zinc (Zn). In embodiments, the metal layer may include nickel (Ni), chromium (Cr), or zinc (Zn), and include no (e.g., may exclude) copper (Cu). The metal layer may be disconnected in the event of an overcurrent, thereby acting as an electrochemical fuse, and therefore providing a protection against short circuits. Limiting current and peak current may be controlled or selected by controlling of a thickness of the metal layer. The metal layer may be plated or deposited on the base film.
In some embodiments, as the thickness of the metal substrate layer decreases, the limiting current and/or peak current of the electrode current collector 110 may also decrease, and therefore, the lithium battery may have improved stability during a short circuit. A lead tab may be added on the metal layer for external connection. The lead tab may be welded to the metal layer or a metal layer/base film laminate by ultrasonic welding, laser welding, spot welding, and/or the like. As the base film and/or the metal substrate layer melt during welding, the metal layer may be electrically connected to the lead tab. To further secure the welding between the metal substrate layer and the lead tab, a metal chip may be further added between the metal layer and the lead tab. The metal chip may be a flake of the same material as the metal of the metal layer. For example, the metal chip may be a metal foil, a metal mesh, and/or the like. For example, the metal chip may be an aluminum foil, a copper foil, an SUS foil, and/or the like. By welding the lead tab after placing the metal chip on the metal layer, the lead tab may be welded to a metal chip/metal layer laminate or a metal chip/metal layer/base film laminate. As the base film, the metal layer, and/or the metal chip melt during welding, the metal layer or the metal layer/metal chip laminate may be electrically connected to the lead tab. A metal chip and/or a lead tab may be further added to a portion of the metal layer.
For example, the base film may have a thickness of about 1 micrometer (μm) to about 50 μm, about 1.5 μm to about 50 μm, about 1.5 μm to about 40 μm, or about 1 μm to about 30 μm. If (e.g., when) the base film has a thickness within the described range, a reduction in the weight of the electrode assembly may be more effectively achieved. For example, the base film may have a melting point of about 100° C. to about 300° C., about 100° C. to about 250° C., or about 100° C. to about 200° C. As the base film has a melting point within the described ranges, during the welding process of the lead tab, the base film may melt and be easily bonded to the lead tab. To improve the adhesion between the base film and the metal layer, a surface treatment such as the corona treatment may be performed on the base film. The metal layer may have a thickness of, for example, about 0.01 μm to about 3 μm, about 0.1 μm to about 3 μm, about 0.1 μm to about 2 μm, or about 0.1 μm to about 1 μm. If (e.g., when) the thickness of the metal layer falls within the described range, the stability of the anode may be secured while maintaining conductivity. The metal chip may have, for example, a thickness of about 2 μm to about 10 μm, about 2 μm to about 7 μm, or about 4 μm to about 6 μm. If (e.g., when) the thickness of the metal chip falls within the described range, the metal layer and the lead tab may be more easily connected. A weight of the electrode may be reduced and as a result, energy density may be improved because the electrode current collector 110 has such a structure.
For example, the electrode current collector 110 may be in the form selected from among a sheet, a foil, a film, a plate, a porous structure, a mesoporous structure, a through-hole-containing structure, a polygonal ring structure, a mesh structure, a foam structure, and a non-woven fabric structure, but is not limited thereto, and any form available in the art may be utilized.
For example, the electrode current collector 110 may have a reduced thickness compared to a comparable electrode current collector. Therefore, the electrode according to some embodiments of the present disclosure includes, for example, a thin film current collector, thereby being distinct from a comparable electrode including the thick current collector. In the electrode including the thin current collector, the electrode active material layer may have a relatively increased thickness because the electrode according to some embodiments of the present disclosure includes the thin current collector having the reduced thickness. In this regard, energy density of the lithium battery utilizing such an electrode may increase. The electrode current collector 110 may have a thickness of, for example, 15 μm or less, 14.5 μm or less, or 14 μm or less. The electrode current collector 110 may have a thickness of, for example, 0.1 μm or more and less than 15 μm, about 1 μm to about 14.5 μm, about 2 μm to about 14 μm, about 3 μm to about 14 μm, about 5 μm to about 14 μm, or about 10 μm to about 14 μm.
The polymer electrolyte 120 may include a cross-linked structure and a metal salt, the cross-linked structure including a repeating unit (A) including (e.g., derived from) the first polymer and a repeating unit (B) including (e.g., derived from) the second polymer. In this case, the metal salt may be provided inside the cross-linked structure.
For example, the cross-linked structure may be a structure in which the first polymer and the second polymer included in the polymer electrolyte 120 may be cross-linked, e.g., to thereby form a cross-linked network. For example, the first polymer may include a polymer including a polar functional group, and lithium ions may move along the polymer (of the first polymer) including the polar functional group in the polymer electrolyte 120. For example, the second polymer may be polyurethane-based and may impart elastic characteristics to the polymer electrolyte 120.
According to some embodiments, the polymer including the polar functional group included in the first polymer may contain polyethylene oxide, polyacrylonitrile, a polyvinylidene fluoride-hexafluoropropylene copolymer, or a (e.g., any) combination thereof.
According to some embodiments, the first polymer may further include at least one (e.g., one or more) terminal double bonds. For example, the first polymer may further include two or more terminal double bonds. For example, the one or more terminal double bonds may include an ally group, an acryl group, or a vinyl group. For example, the one or more terminal double bonds may include an acryl group. In embodiments, if (e.g., when) the first polymer further includes at least one terminal double bond, the first polymer, as a cross-linking agent, may easily form a cross-linked network between the first polymer and/or the second polymer. In this regard, the cross-linked structure including the repeating unit (A) derived from (e.g., including) the first polymer may have more improved durability.
According to some embodiments, the first polymer may include polyethylene oxide, polyacrylonitrile, a polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene glycol diacrylate, polyethylene glycol methyl ether acrylate, polymethyl methacrylate, polyethyl methacrylate, polycaprolactone, polyethylene carbonate, polypropylene carbonate, or a (e.g., any) combination thereof.
According to some embodiments, the second polymer may include polyurethane, urethane acrylate, urethane methacrylate, perfluoropolyether urethane acrylate, perfluoropolyether urethane methacrylate, or a (e.g., any) combination thereof.
According to some embodiments, an amount of the repeating unit (A) derived from the first polymer in the cross-linked structure may be about 50 wt % to about 90 wt % with respect to a total weight of the cross-linked structure, and an amount of the repeating unit (B) derived from the second polymer may be about 10 wt % to about 50 wt % with respect to the total weight of the cross-linked structure. For example, the amount of the repeating unit (A) derived from the first polymer in the cross-linked structure may be about 60 wt % to about 90 wt %, about 70 wt % to about 90 wt %, about 50 wt % to about 80 wt %, or about 60 wt % to about 80 wt % with respect to the total weight of the cross-linked structure. For example, the amount of the repeating unit (B) derived from the second polymer may be about 10 wt % to about 40 wt %, about 10 wt % to about 30 wt %, about 20 wt % to about 50 wt %, or about 20 wt % to about 30 wt % with respect to the total weight of the cross-linked structure.
The metal salt may include a metal salt having lithiophilicity. In embodiments, the metal salt having lithiophilicity may include a metal having lithiophilicity. For example, the metal salt includes the metal salt having lithiophilicity, and thus in the lithium metal including the electrode structure 10 containing the polymer electrolyte 120, lithium may be more uniformly electrodeposited due to the metal salt included in the polymer electrolyte 120 during charging and discharging. For example, metal ions included in the metal salt having lithiophilicity, and lithium ions may form an alloy during charging and discharging, and the formed alloy may act as a nucleation site, thereby inducing substantially uniform electrodeposition of lithium.
According to some embodiments, the metal salt may include gold (Au), silver (Ag), platinum (Pt), zinc (Zn), silicon (Si), and magnesium (Mg), or any combination thereof. In embodiments, the metal having lithiophilicity may include gold (Au), silver (Ag), platinum (Pt), zinc (Zn), silicon (Si), and magnesium (Mg), or a (e.g., any) combination thereof. For example, the metal salt may include silver (Ag). In embodiments, if (e.g., when) the metal salt includes silver (Ag), silver (Ag) and lithium may form an alloy of Li—Ag during charging and discharging, the formed Li—Ag alloy may act as a nucleation site and thus substantially uniform electrodeposition of lithium may be induced.
According to embodiments, the metal salt may include AgNO3, AuCl3, Mg(NO3)2, Zn(NO3)2, and/or the like
According to some embodiments, an amount of the metal salt may be about 1 part by weight to about 50 parts by weight with respect to 100 parts by weight of the cross-linked structure. For example, the amount of the metal salt may be about 1 part by weight to about 40 parts by weight, about 1 part by weight to about 30 parts by weight, about 1 part by weight to about 20 parts by weight, about 5 parts by weight to about 50 parts by weight, or about 5 parts by weight to about 20 parts by weight with respect to 100 parts by weight of the cross-linked structure.
The polymer electrolyte according to embodiments may further include a lithium salt. An amount of the lithium salt may be about 20 parts by weight to about 100 parts by weight with respect to 100 parts by weight of the cross-linked structure. In embodiments, if (e.g., when) the polymer electrolyte includes a lithium salt, the polymer electrolyte may be a polymer solid electrolyte including a lithium salt. For example, if (e.g., when) the polymer electrolyte includes a lithium salt and an organic solvent, the polymer electrolyte may be a polymer gel electrolyte including a liquid electrolyte containing a lithium salt.
The polymer solid electrolyte may include, for example, a lithium salt and the herein-described cross-linked structure. The polymer solid electrolyte may be, for example, a polymer electrolyte including no liquid electrolyte.
According to some embodiments, the polymer solid electrolyte may further include a third polymer in addition to the herein-described cross-linked structure. For example, the third polymer may be polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene (PVDF-HFP), a poly(styrene-b-ethylene oxide) block copolymer (PS-PEO), poly(styrene-butadiene), poly(styrene-isoprene-styrene), a poly(styrene-b-divinylbenzene) block copolymer, a poly(styrene-ethylene oxide-styrene) block copolymer, polystyrene sulfonate (PSS), polyvinyl fluoride (PVF), poly(methylmethacrylate) (PMMA), polyethylene glycol (PEG), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), polyethylenedioxythiophene (PEDOT), polypyrrole (PPY), polyacrylonitrile (PAN), polyaniline, polyacetylene, Nafion, Aquivion, Flemion, Gore, Aciplex, Morgane ADP, sulfonated poly(ether ether ketone) (SPEEK), sulfonated poly(arylene ether ketone ketone sulfone) (SPAEKKS), sulfonated poly(aryl ether ketone (SPAEK), poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI), poly(styrene sulfonate) (PSS), lithium 9,10-diphenylanthracene-2-sulfonate (DPASLi+), or a (e.g., any) combination thereof, but is not limited thereto, and any polymer electrolyte available in the art may be utilized.
For example, any lithium salt available in the art as a lithium salt may be utilized. The lithium salt may include LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2) wherein x and y are each 1 to 20, LiCl, LiI, and/or a mixture thereof.
According to some embodiments, the polymer electrolyte may further include a liquid electrolyte. For example, the polymer electrolyte may be a gel polymer electrolyte including the herein-described cross-linked structure and a liquid electrolyte. For example, the liquid electrolyte may be provided within the cross-linked network formed by the cross-linked structure.
According to some embodiments, the liquid electrolyte may include an organic solvent or an ionic liquid. For example, the liquid electrolyte may further include a lithium salt. For example, the liquid electrolyte may be an ionic liquid, an organic solvent, a mixture of a lithium salt and an organic solvent, a mixture of an ionic liquid and an organic solvent, and/or a mixture of a lithium salt, an ionic liquid, and an organic solvent.
According to some embodiments, for the organic solvent, any organic solvent available in the art may be utilized. Examples of the organic solvent may include, for example, propylene carbonate, ethylene carbonate, fluoroethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, dibutyl carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, diethylene glycol, dimethyl ether, and/or a mixture thereof.
For example, the ionic liquid refers to a salt that may be in a liquid state at room temperature or an ambient temperature molten salt, which has a melting point of room temperature or lower and is composed solely of ions. The ionic liquid may include, for example, at least one selected from among compounds including: a) at least one cation selected from among ammonium-based cation, pyrrolidinium-based cation, pyridinium-based cation, pyrimidine-based cation, imidazolium-based cation, piperidinium-based cation, pyrazolium-based cation, oxazolium-based cation, pyridazinium-based cation, phosphonium-based cation, sulfonium-based cation, triazolium-based cation, and a mixture thereof; and b) one or more selected from among BF4−, PF6−, AsF6−, SbF6−, AlCl4−, HSO4−, ClO4−, CH3SO3−, CF3CO2−, Cl−, Br−, I−, BF4-, SO42−, CF3SO3−, (FSO2)2N−, (C2F5SO2)2N−, (C2F5SO2)(CF3SO2)N−, and (CF3SO2)2N−.
For example, a gel polymer electrolyte may be formed by impregnating the polymer solid electrolyte with an electrolyte in the lithium battery. The gel polymer electrolyte may further include an inorganic particle.
According to some embodiments, the polymer electrolyte may further include a solid electrolyte.
The solid electrolyte may be an oxide-based solid electrolyte, a sulfide-based solid electrolyte, or a combination thereof.
The solid-state electrolyte may be, for example, an oxide-based solid-state electrolyte. The oxide-based solid electrolyte may be at least one selected from among Li1+x+yAlxTi2-xSiyP3-yO12 (0<x<2, 0≤y<3), BaTiO3, Pb(Zr,Ti)O3(PZT), Pb1-xLaxZr1-y TiyO3(PLZT)(O≤x<1, O≤y<1), PB(Mg3Nb2/3)O3—PbTiO3(PMN-PT), HfO2, SrTiO3, SnO2, CeO2, Na2O, MgO, NiO, CaO, BaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, SiO2, Li3PO4, LixTiy(PO4)3 (0<x<2, 0<y<3), LixAlyTiz(PO4)3 (0<x<2, 0<y<1, 0<z<3), Li1+x+y(Al, Ga)x(Ti, Ge)2-xSiyP3-yO12 (0≤x≤1 0≤y≤1), LixLayTiO3 (0<x<2, 0<y<3), Li2O, LiOH, Li2CO3, LiAlO2, Li2O—Al2O3—SiO2—P2O5—TiO2—GeO2, and Li3+xLa3M2O12 (M=Te, Nb, or Zr, and x may be an integer of 1 to 10). The solid-state electrolyte may be prepared by a sintering method and/or the like. For example, the oxide-based solid electrolyte may be a garnet-type or kind solid electrolyte selected from among Li7La3Zr2O12 (LLZO) and Li3+xLa3Zr2-aMaO12 (M-doped LLZO, M=Ga, W, Nb, Ta, or Al, and x is an integer of 1 to 10).
Examples of the sulfide-based solid electrolyte may include lithium sulfide, silicon sulfide, phosphorus sulfide, boron sulfide, or a (e.g., any) combination (e.g., one or more combinations) thereof. Sulfide-based solid electrolyte particles may include Li2S, P2S5, SiS2, GeS2, B2S3, or (e.g., any) a combination thereof. The sulfide-based solid electrolyte particles may be Li2S or P2S5. The sulfide-based solid electrolyte particles are suitable to have a higher lithium-ion conductivity than that of other inorganic compounds. For example, the sulfide-based solid electrolyte may include Li2S and P2S5. If (e.g., when) sulfide solid electrolyte materials constituting the sulfide-based solid electrolyte include Li2S—P2S5, a mixing molar ratio of Li2S and P2S5 may be, for example, in a range of about 50:50 to about 90:10. An inorganic solid electrolyte prepared by adding a material such as Li3PO4, halogen, a halogen compound, Li2+2xZn1?? xGeO4 (“LISICON”, 0≤x<1), Li3+yPO4-xNx (“LIPON”, 0<x<4 and 0<y<3), Li3.25Ge0.25P0.75S4 (“Thio-LISICON”), and Li2O—Al2O3—TiO2—P2O5 (“LATP”) to an inorganic solid electrolyte of Li2S—P2S5, SiS2, GeS2, B2S3, or a combination thereof, may be utilized as a sulfide solid electrolyte. Non-limiting examples of the sulfide solid electrolyte materials may include Li2S—P2S5; Li2S—P2S5—LiX (X=a halogen element); Li2S—P2S5—Li2O; Li2S—P2S5-Li2O—LiI; Li2S—SiS2; Li2S—SiS2—LiI; Li2S—SiS2—LiBr; Li2S—SiS2—LiCl; Li2S—SiS2—B2S3—LiI; Li2S—SiS2—P2S5—LiI; Li2S—B2S3; Li2S—P2S5—ZmSn (0<m<10, 0<n<10, Z═Ge, Zn, or Ga); Li2S—GeS2; Li2S—SiS2—Li3PO4; and/or Li2S—SiS2-LipMOq (0<p<10, 0<q<10, and M=P, Si, Ge, B, Al, Ga, or In). In this regard, the sulfide-based solid electrolyte material may be prepared by subjecting a starting material (e.g., Li2S, P2S5, and/or the like) of the sulfide-based solid electrolyte material to a treatment such as melt quenching, mechanical milling, and/or the like. In some embodiments, a calcination process may be performed following the described treatment. The sulfide-based solid electrolyte may be amorphous or crystalline or may be in a mixed state thereof.
According to some embodiments, the polymer electrolyte 120 may have a thickness of about 4 μm to about 20 μm.
According to some embodiments, the polymer electrolyte may be utilized as a polymer electrolyte of a lithium battery. For example, the lithium battery may be an anodeless (e.g., anode-free) lithium metal battery.
For example, the lithium battery may included in any (e.g., all) of a lithium-air battery, a lithium-ion battery, a lithium polymer battery, a lithium-sulfur battery, and/or the like, which utilize a lithium electrode.
The polymer electrolyte 120 according to embodiments may be utilized as a protective film or an electrolyte of the electrode current collector 110. The polymer electrolyte may have excellent or suitable interfacial characteristics and high lithium transfer constant, and thus lithium-ion conductivity may be excellent or suitable.
According to some embodiments, the electrode structure 10 may further include an interlayer provided between the electrode current collector 110 and the polymer electrolytes 120.
According to some embodiments, the interlayer may be directly provided on at least one (e.g., one side or both (e.g., opposite) sides of the electrode current collector 110. Therefore, no intervening layer may be provided between the electrode current collector 110 and the interlayer. The interlayer (not illustrated) is provided on one side or both (e.g., opposite) sides of the electrode current collector 110, and thus adhesion between the electrode current collector 110 and the polymer electrolyte 120 may be further improved.
The interlayer may have a thickness of, for example, 30% or less of the thickness of the anode current collector 110. The interlayer (not illustrated) may have a thickness of, for example, about 0.01% to about 30%, about 0.1% to about 30%, about 0.5% to about 30%, about 1% to about 25%, about 1% to about 20%, about 1% to about 15%, about 1% to about 10%, about 1% to about 5%, or about 1% to about 3%. The interlayer (not illustrated) may have a thickness of, for example, about 10 nm to about 5 μm, about 50 nm to about 5 μm, about 200 nm to about 4 μm, about 500 nm to about 3 μm, about 500 nm to about 2 μm, about 500 nm to about 1.5 μm, or about 700 nm to about 1.3 μm. If (e.g., when) the interlayer has a thickness in these ranges, adhesion between the electrode current collector 110 and the polymer electrolyte 120 may further increase, and an increase in interfacial resistance may be suppressed or reduced.
For example, the interlayer may include a binder. If (e.g., when) the interlayer includes a binder, adhesion between the electrode current collector 110 and the polymer electrolyte 120 may be further improved. The binder included in the interlayer may be, for example, a conductive binder or a non-conductive binder.
The conductive binder may be, for example, an ionically conductive binder, and/or an electronically conductive binder. The binder having both (e.g., simultaneously) ionically conductive and electronically conductive properties may be classified as both (e.g., simultaneously) an ionically (e.g., ion) conductive binder and an electronically (e.g., electron) conductive binder.
The ionically conductive binder may be, for example, polystyrene sulfonate (PSS), a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), poly(methylmethacrylate) (PMMA), polyethylene oxide (PEO), polyethylene glycol (PEG), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), polyethylene dioxythiophene (PEDOT), polypyrrole (PPY), polyacrylonitrile (PAN), polyaniline, and polyacetylene, and/or the like The ionically conductive binder may include a polar functional group. The ionically conductive binder including the polar functional group may be, for example, Nafion, Aquivion, Flemion, Gore, Aciphex, Morgane ADP, sulfonated poly(ether ether ketone (SPEEK), sulfonated poly(arylene ether ketone ketone sulfone (SPAEKKS), sulfonated poly(aryl ether ketone (SPAEK), poly[bis (benzimidazobenzisoquinolinones)] (SPBIBI), poly(styrene sulfonate) (PSS), lithium 9,10-diphenylanthracene-2-sulfonate (DPASLi+), and/or the like The electronically conductive binder may be, for example, polyacetylene, polythiophene, polypyrrole, poly(p-phenylene), poly(phenylenevinylene), poly(phenylenesulfide), polyaniline, and/or the like The interlayer may be, for example, a conductive layer including a conductive polymer.
The binder included in the interlayer may be, for example, a fluorine-based binder. The fluorine-based binder included in the interlayer may be, for example, a polyvinylidene fluoride (PVDF). The interlayer may be provided on the anode current collector 210, for example, by a dry method or a wet method. The interlayer may be, for example, a binding layer including a binder.
The interlayer may additionally include, for example, a carbonaceous conductive material. The interlayer may be, for example, a conductive layer because of inclusion of the carbonaceous conductive material. The interlayer may be, for example, a conductive layer including a binder and a carbonaceous conductive material.
The interlayer may be provided on the electrode current collector 110 in a dry manner for example, by a deposition such as CVD, or PVD. The interlayer may be provided on the electrode current collector 110 in a wet manner by a spin coating, a dip coating, and/or the like The interlayer may be provided on the electrode current collector 110, for example, by depositing, a carbonaceous conductive material on the electrode current collector 110. The dry-coated interlayer may be formed of a carbonaceous conductive material and include no binder. In other embodiments, the interlayer may be provided on the electrode current collector 110 by, for example, applying and drying a composition including the carbonaceous conductive material, a binder, and a solvent onto the surface of the anode current collector. The interlayer may be a multilayer structure including a single layered structure or a plurality of layers.
A method of preparing the electrode structure 10 according to embodiments will be described.
The method of preparing the electrode structure 10 according to embodiments includes: preparing an electrode current collector 110; preparing a composition for providing a polymer electrolyte including a first polymer, a second polymer, a metal salt, and an initiator; applying the composition for providing a polymer electrolyte onto the electrode current collector 110; and providing the electrode structure 10 including the polymer electrolyte 120 on the electrode current collector 110 coated with the composition for providing the polymer electrolyte. For example, the electrode current collector 110 may include nickel (Ni), chromium (Cr) or zinc (Zn), the first polymer may include a polymer containing a polar functional group, and the second polymer may include a polyurethane-based polymer.
For example, even though the composition for providing a polymer electrolyte including the metal salt is applied onto the electrode current collector 110, a radical scavenger (for example, Cu2+) may not be formed (e.g., may be excluded from) on the electrode current collector 110 because the current collector 110 includes nickel (Ni), chromium (Cr) or zinc (Zn). Therefore, the polymerization reaction of the first polymer and the second polymer included in the composition for providing the polymer electrolyte may be easily performed, thus the polymer electrolyte 120 may be more easily formed, adhesion between the polymer electrolyte 120 and the electrode current collector 110 may be further improved, and thus durability of the electrode current collector 110 may be further improved. The polymer electrolyte 120 includes a metal salt, and thus lithium may be more uniformly electrodeposited on the electrode current collector 110.
For example, the descriptions of the electrode collector 110, the first polymer, the second polymer, the metal salt, and the polymer electrolyte 120, may be referred to in the herein-described descriptions.
According to some embodiments, the composition for providing the polymer electrolyte may include the first polymer, the second polymer, the metal salt, and the initiator, and the polymer electrolyte may be formed from the composition for providing the polymer electrolyte. For example, the polymer electrolyte may be formed through the polymerization reaction of the first polymer and the second polymer included in the composition for providing the polymer electrolyte.
The polymerization reaction may be carried out by heating or irradiating light such as UV. Herein, heat and light may be applied to the lithium metal electrode as long as it does not have a negative effect. For example, the polymerization reaction may be processed by applying heat.
The polymerization reaction may be a copolymerization, cross-linking, or graft reaction.
If (e.g., when) the electrode current collector 110 is heated or irradiated with light such as UV to perform the polymerization reaction, heat or light may be applied electrode as long as it does not negatively affect the electrode current collector 110.
According to other embodiments, the polymerization reaction of the first polymer and the second polymer may be also performed by irradiating light at room temperature (25° C.). In the cross-linking reaction due to light irradiation, a photopolymerization initiator may be utilized. As the photopolymerization initiators, any compound as long as it is a compound that may form radicals by light such as ultraviolet rays may be utilized without limitation in composition. As the photopolymerization initiator, for example, at least one selected from the group consisting of 2-hydroxy-2-methylpropiophenone (HMPP), benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, benzyl dimethyl ketal, acyl phosphine, and α-aminoketone may be utilized. As the acyl phosphine, for example, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide may be utilized.
According to other embodiments, the polymerization reaction of the first polymer and the second polymer may be performed by heating the composition for providing the polymer electrolyte. In the cross-linking reaction by applying heat, a thermal initiator may be utilized. As the thermal initiator, any compound as long as capable of providing radicals by heat may be utilized without limitation in composition.
As the thermal initiator, at least one selected from the group consisting of a persulfate-based initiator, an azo-based initiator, a peroxide-based initiator, and ascorbic acid may be utilized. In embodiments, examples of the persulfate-based initiator may include sodium persulfate; Na2S2O8), potassium persulfate (K2S2O8), ammonium persulfate; (NH4)2S2O8), and/or the like, examples of the azo-based initiator may include 2, 2-azobis(2-amidinopropane) dihydrochloride, 2,2-azobis-(N, N-dimethylene)isobutyramidine dihydrochloride), 2-(carbamoylazo)isobutylonitril, 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 4,4-azobis-(4-cyanovaleric acid), and/or the like, and examples of the peroxide-based initiator may include t-butyl peroxide, dicumyl peroxide, and t-amyl peroxide, and/or the like.
According to some embodiments, in the providing of the polymer electrolyte on the electrode current collector, the composition for providing the polymer electrolyte, which is applied onto the electrode current collector, may be heated for about 1 hour to about 15 hours at about 60° C. to about 180° C. and may be vacuum dried. For example, the heating of the electrode current collector, on which the composition for providing the polymer electrolyte is applied, may be performed for about 1 hour to about 12 hours, about 1 hour to about 10 hours, about 2 hours to about 15 hours, about 4 hours to about 15 hours, or about 4 hours to about 12 hours. For example, the heating of the electrode current collector, on which the composition for providing the polymer electrolyte is applied, may be performed at about 80° C. to about 180° C., about 100° C. to about 180° C., about 60° C. to about 160° C., about 60° C. to about 140° C., or about 80° C. to about 140° C.
According to some embodiments, the composition for providing the polymer electrolyte may further include the herein-described lithium salt.
According to some embodiments, the composition for providing the polymer electrolyte may further include the herein-described organic solvent. For example, if (e.g., when) the composition for providing the polymer further includes the organic solvent, a gel polymer electrolyte including the organic solvent may be formed from the composition for providing the polymer. For example, the composition for providing the polymer may further include the herein-described liquid electrolyte.
The descriptions of the lithium salt, the organic solvent, and the liquid electrolyte may be referred to in the herein-described descriptions.
A lithium battery according to embodiments may include the herein-described electrode structure. Improved capacity and excellent or suitable lifespan characteristics at room temperature and high temperature may be concurrently (e.g., simultaneously) provided by including the herein-described electrode structure.
The lithium battery may be, for example, a lithium primary battery, a lithium secondary battery, a lithium-sulfur battery, a lithium-air battery, and/or the like, but is not limited thereto, and may be any lithium battery available in the art.
The lithium battery may be manufactured by the following example method, but embodiments of the present disclosure are not limited thereto and the method may be adjusted depending on required conditions.
Referring to
The lithium battery 100 according to embodiments may include the herein-described electrode structure 10. For example, the lithium battery 100 may include the herein-described electrode structure 10 and a cathode provided on the electrode structure 10.
According to some embodiments, the polymer electrolyte 120 included in the lithium battery 100 may be in a solid, liquid, or gel form.
The lithium battery 100 according to embodiments may include, as shown in
The lithium battery 100 according to embodiments may further include, as shown in
According to some embodiments, the lithium battery 100 including the herein-described electrode structure 10 may further include a protecting layer (not illustrated) provided between the anode and the polymer electrolyte.
Referring to
Referring to
According to some embodiments, the electrode current collector 110 included in the electrode structure 10 may be an anode current collector. For example, the electrode structure 10 may include an electrode current collector 110, which is the anode current collector, and a polymer electrolyte 120 provided on the electrode current structure 110.
According to some embodiments, the anode active material layer may be free on the anode current collector before charging and discharging. For example, the lithium metal layer may be free on the anode current collector before charging and discharging. For example, in the lithium battery in which the anode active material layer or the lithium metal layer is free on the anode current collector before charging and discharging, dendrite formation may be prevented or reduced and lifespan characteristics may be further improved.
The description of the anode current collector may be referred to in the description of the herein-described electrode current collector 110.
For example, the description of the polymer electrolyte 120 may be referred to in the description of the polymer electrolyte 120 included in the herein-described electrode structure 10.
According to other embodiments, the polymer electrolyte 120 may further include a non-woven fabric. The non-woven fabric may serve to support one or more selected from a lithium metal and a lithium alloy deposited during the charging process. In embodiments, the non-woven fabric may not be provided. For example, if (e.g., when) the anode current collector is a mesh type or kind, there is no need to utilize the non-woven fabric.
The non-woven fabric may have a porosity of about 10 volume % to about 90 volume %, for example, about 10 volume % to about 80 volume %, for example, about 10 volume % to about 50 volume %, or for example, about 25 volume % to about 50 volume %, and may have an average pore size of about 0.1 μm to about 10 μm, for example, about 0.01 μm to about 8 μm, or for example, about 0.1 μm to about 1.0 μm. The average pore size refers to a diameter if (e.g., when) the pore has a spherical shape, and for a pore that is non-spherical, the pore size refers to the major axis length of the pore.
According to some embodiments, the non-woven fabric may include at least one selected from among non-woven fabric selected from among cellulose, polyester (e.g., for example polyethylene terephthalate (PET)), polyetherimide, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyacetal, polycarbonate, polyimide, polyetherketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyethylenenaphthalene, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, nylon, and polyparaphenylenebenzobisoxazole.
Referring to
For example, as the lithium battery 100 is charged, lithium ions included in the polymer electrolyte 120 may be electrodeposited on the electrode current collector 110 to thereby generate the lithium metal layer 125. For example, as the lithium battery 100 is charged, the lithium metal layer 125 may be generated by electrodeposition, on the electrode current collector 110, a lithium alloy formed of lithium ions included in the polymer electrolyte 120 and metal ions of the metal salt included in the polymer electrolyte 120.
For example, the lithium metal layer 125 may include a lithium alloy and a lithium metal. For example, the lithium alloy included in the lithium metal layer 125 may weaken reactivity of the lithium metal, and thus a side reaction of the lithium metal layer 125 and the polymer electrolyte 120 may be effectively inhibited. The lithium alloy included in the lithium metal layer 125 may function as a nucleation site for lithium electrodeposition, and thus the lithium-ion may be more uniformly electrodeposited. The lithium metal layer 125 has excellent or suitable electrical conductivity, and thus the lithium battery 100 including the same may have decreased internal resistance. Therefore, the lithium battery 100 including the lithium metal layer 125 may have improved charging and discharging efficiency as well as lifespan characteristics.
According to some embodiments, the lithium metal layer 125 may include, for example, plated lithium or a lithium alloy. The lithium metal layer 125 may be a lithium electrodeposition layer. For example, the lithium alloy may be an alloy of lithium ions and metal ions included in the herein-described metal salt, and the metal ions may include the herein-described metal having lithiophilicity. In this case, the lithium alloy may be an alloy of lithium and the metal having lithiophilicity. For example, if (e.g., when) the metal having lithiophilicity is silver (Ag), the lithium alloy may include a Li—Ag alloy.
According to some embodiments, the lithium metal layer 125 may include no (e.g., may exclude) carbonaceous anode active material. Therefore, the lithium metal layer 125 may be formed of a metal-based anode active material.
For example, the lithium metal layer 125 may have a thickness of about 0.1 μm to about 100 μm, about 0.1 μm to about 80 μm, about 1 μm to about 80 μm, or about 10 μm to about 80 μm, but the thickness of the lithium metal layer is not necessarily limited in these ranges and may be adjusted depending on the type or kind, capacity, and/or the like of the lithium battery required. An excessive increase in the thickness of the lithium metal layer 125 may cause structural stability of the lithium battery to be reduced and a side reaction may increase. An excessively small thickness of the lithium metal layer 125 may cause energy density of the lithium metal battery to be reduced.
As shown in
Referring to
For example, the cathode current collector 140 may include indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.
According to some embodiments, the cathode current collector 140 may include aluminum (Al).
According to some embodiments, the cathode current collector 140 may include, for example, a base film and a metal layer provided on at least one (e.g., one side or both (e.g., opposite) sides of the base film. The base film may include, for example, a polymer. The polymer may be, for example, a thermoplastic polymer. Examples of the polymer may include polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), and/or a combination thereof. Due to inclusion of a thermoplastic polymer in the base film, the base film gets liquefied in the event of a short circuit and thus may prevent or reduce a rapid increase in electric current. The base film may be, for example, an insulator. For example, the metal layer may include indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), or an alloy thereof. The metal layer may be disconnected in the event of an overcurrent, thereby acting as an electrochemical fuse, and therefore may provide protection against a short circuit.
According to some embodiments, a limiting current and peak current may be adjusted by adjusting the thickness of the metal layer. The metal layer may be plated or deposited on the base film. If (e.g., when) the thickness of the metal layer decreases, the limiting current and/or peak current of the cathode current collector 140 may decrease, and therefore, the lithium battery may have improved stability during a short circuit. A lead tab may be added on the metal layer for external connection. The lead tab may be welded to the metal layer or a metal layer/base film laminate by ultrasonic welding, laser welding, spot welding, and/or the like. As the base film and/or the metal layer melt during welding, the metal layer may be electrically connected to the lead tab. To further secure the welding between the metal layer and the lead tab, a metal chip may be added between the metal layer and the lead tab. The metal chip may be a flake of the same material as the metal of the metal layer. For example, the metal chip may be a metal foil, a metal mesh, and/or the like. For example, the metal chip may be an aluminum foil, a copper foil, an SUS foil, and/or the like. By welding the lead tab after placing the metal chip on the metal layer, the lead tab may be welded to a metal chip/metal layer laminate or a metal chip/metal layer/base film laminate. As the base film, the metal layer, and/or the metal chip melt during welding, the metal layer or the metal layer/metal chip laminate may be electrically connected to the lead tab. A metal chip and/or a lead tab may be further added to a portion of the metal layer. The base film may have a thickness of about 1 μm to about 50 μm, about 1.5 μm to about 50 μm, about 1.5 μm to about 40 μm, or about 1 μm to about 30 μm. If (e.g., when) the thickness of the base film falls within the described ranges, a reduction of the weight of the cathode current collector may be more effectively achieved. For example, the base film may have a melting point of about 100° C. to about 300° C., about 100° C. to about 250° C., or about 100° C. to about 200° C. As the melting point of the base film falls within the described ranges, during the welding process of the lead tab, the base film may melt and be easily bonded to the lead tab. To improve adhesion between the base film and the metal layer, a surface treatment such as the corona treatment may be performed on the base film. The metal layer may have a thickness of, for example, about 0.01 μm to about 3 μm, about 0.1 μm to about 3 μm, about 0.1 μm to about 2 μm, or about 0.1 μm to about 1 μm. If (e.g., when) the thickness of the metal layer falls within these ranges, stability of the electrode assembly may be secured while maintaining conductivity. The metal chip may have a thickness of, for example, about 2 μm to about 10 μm, about 2 μm to about 7 μm, or about 4 μm to about 6 μm. As the thickness of the metal chip falls within these ranges, the connection between the metal layer and the lead tab may be more easily performed. As the cathode current collector 140 has such a structure, the weight of the electrode may be reduced and as a result, energy density may be improved.
The cathode active material layer 130 may include a cathode active material, a conductive material, and a binder.
For example, at least one among a composite oxide of lithium and a metal selected from cobalt, manganese, nickel, and a combination thereof may be utilized as the cathode active material. In some embodiments, examples of the cathode active material include a compound represented by at least one selected from among: LiaA1-bBbD2 (where, 0.90≤a≤1.8, and 0≤b≤0.5 are satisfied); LiaE1-bBbO2-cDc (where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05 are satisfied); LiE2-bB1bO4-cD1c (where, 0≤b≤0.5, 0≤c≤0.05 are satisfied); LiaNi1-b-cCObB1cD1α (where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤ 0.05, 0<α≤2 are satisfied); LiaNi1-b-cCobB1cO2-αF1α (where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2 are satisfied); LiaNi1-b-cCobB1cO2-αF1α (where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2 are satisfied); LiaNi1-b-cMnbB1cD1α (where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2 are satisfied); LiaNi1-b-cMnbB1cO2-αF1α (where, 0.90≤ a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2 are satisfied); LiaNi1-b-cMnbB1cO2-αF12 (where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2 are satisfied); LiaNibEcGdO2 (where, 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1 are satisfied); LiaNibCocMndGeO2 (where, 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1 are satisfied); LiaNiGbO2 (where, 0.90≤a≤1.8, 0.001≤b≤0.1 are satisfied); LiaCoGbO2 (where, 0.90≤a≤1.8, 0.001≤b≤0.1 are satisfied); LiaMnGbO2 (where, 0.90≤a≤1.8, 0.001≤b≤0.1 are satisfied); LiaMn2GbO4 (where, 0.90≤a≤1.8, 0.001≤b≤0.1 are satisfied); QO2; QS2; LiQS2; V2O5; LiV2O5; LiIO2; LiNiVO4; Li(3-f)J2(PO4)3 (0≤f≤2); Li(3-f)Fe2(PO4)3 (0≤ f≤2); and LiFePO4.
In the preceding formulas, A may be Ni, Co, Mn, or a combination thereof; B1 may be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Ga, Si, W, Mo, Cu, Zn, Ti, boron (B), a rare earth element, or a combination thereof; D1 may be O, F, S, P, or a combination thereof; E may be Co, Mn, or a combination thereof; F1 may be F, S, P, CI, Br, or a combination thereof; G may be Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; Q may be Ti, Mo, Mn, a combination thereof; I may be Cr, V, Fe, Sc, Y, or a combination thereof; and J may be V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
For example, the cathode active material may include a lithium transition metal oxide containing nickel and other transition metals. In the lithium transition metal oxide containing nickel and other transition metals, an amount of nickel may be 60 mol % or more, for example. 75 mol % or more, for example, 80 mol % or more, for example, 85 mol % or more, for example, 90 mol % or more with respect to the total number of moles of the transition metal.
For example, the lithium transition metal oxide may be a compound represented by Formula 3.
LiaNixCoyMzO2-bAb Formula 3
In Formula 3, 1.0≤a≤1.2, 0≤b≤0.2, 0.6≤x<1, 0≤y≤0.3, 0<z≤0.3, x+y+z=1, M is at least one selected from the group consisting of manganese (Mn), vanadium (V), magnesium (Mg), gallium (Ga), silicon (Si), tungsten (W), molybdenum (Mo), iron (Fe), chromium (Cr), copper (Cu), zinc (Zn), titanium (Ti), aluminum (Al), and boron (B).
A is F, S, CI, Br, or a combination thereof.
In Formula 3, for example 0.7≤x<1, 0<y≤0.3, 0<z≤0.3; 0.8≤x<1, 0<y≤0.3, 0<z≤0.3; 0.8≤x<1, 0<y≤0.2, 0<z≤0.2; 0.83≤x<0.97, 0<y≤0.15, 0<z≤0.15; or 0.85≤x<0.95, 0<y≤0.1, 0<z≤0.1.
For example, the lithium transition metal oxide may be at least one selected from among compounds represented by Formula 3-1 and Formula 3-2.
LiNixCoyMnzO2 Formula 3-1
LiNixCoyAlzO2 Formula 3-2
For example, the lithium transition metal oxide may be LiNi0.6Co0.2Mn0.2O2, LiNi0.88Co0.08Mn0.04O2, LiNi0.8Co0.15Mn0.05O2, LiNi0.8Co0.1Mn0.1O2, LiNi0.88Co0.1Mn0.02O2, LiNi0.8Co0.15Al0.05O2, LiNi0.8Co0.1Mn0.2O2, and/or LiNi0.88Co0.1Al0.02O2.
For example, materials having a coating layer on the surface of the lithium transition metal oxide may also be utilized, or a mixture of the lithium transition metal oxide and the lithium transition metal oxide having a coating layer may also be utilized.
For example, the coating layer may include an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element.
For example, the compound providing the coating layer may be amorphous or crystalline. The coating element included in the coating layer may be Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof. The coating layer formation process may be performed by any coating method (for example, spray coating, dipping, and/or the like) that does not adversely affect the properties of the cathode active material utilizing the coating elements on the lithium transition metal oxide, and a detailed description thereof will not be provided because these methods are well suitable to those skilled in the art.
Examples of conductive material may include carbon black, graphite fine particles and/or the like, but are not limited thereto, and any conductive material available in the art may be utilized.
As the binder, a vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene, and a mixture thereof, styrene butadiene rubber-based polymer, and/or the like may be utilized. However, embodiments are not limited thereto, and any material available as the binder in the art may be utilized.
The lithium battery according to embodiments may further include a separator.
According to some embodiments, examples of the separator may include polyethylene, polypropylene, polyvinylidene fluoride, or multilayer films thereof, and may include a polyethylene/polypropylene bi-layer separator, polyethylene/polypropylene/polyethylene tri-layer separator, and a polypropylene/polyethylene/polypropylene tri-layer separator.
According to some embodiments, a battery case including the lithium battery may have a cylindrical shape, a polygonal shape, a thin-film shape, and/or the like. For example, the lithium battery may be a large-sized thin-film shaped battery. The lithium battery may be a lithium-ion battery.
According to some embodiments, the lithium battery 100 may include, for example. a lithium-air battery, a lithium-sulfur battery, and/or the like.
According to some embodiments, the lithium battery 100 may have excellent or suitable lifespan characteristics and high rate characteristics and thus may be utilized in an electric vehicle (EV). For example, the lithium battery 100 may be utilized for hybrid vehicles such as plug-in hybrid electric vehicles (PHEVs). The lithium battery may be utilized in any field that requires a large amount of energy storage. For example, the lithium battery may be utilized in an electric bicycle, a power tool, and/or the like.
If (e.g., when) a plurality of the lithium battery 100 according to some embodiments are stacked, a gel type or kind electrolyte may be provided between the cathode and the liquid impermeable ion conductive composite film. The gel type or kind electrolyte may include, for example, a VDF-HFP copolymer, a lithium salt, and a solvent.
Referring to
For example, a polymer electrolyte including cathode 3, anode 2, and separator 4 is wound or folded to form a battery structure 7. The formed battery structure 7 may be accommodated in a battery case 5. A liquid electrolyte may be injected into the battery case 5 and sealed with a cap assembly 6 to complete the manufacture of the lithium battery 1. The battery case 5 may have a cylindrical shape, but is not necessarily limited thereto and may have a polygonal shape, a thin-film shape, and/or the like.
Referring to
For example, a polymer electrolyte including the separator 4 may be provided between the cathode 3 and the anode 2, and then the cathode 3, the anode 2, and the separator 4 may be wound or folded to thereby form a battery structure 7. The formed battery structure 7 may be accommodated in a battery case 5. An electrode tab 8, acting as an electrical path for inducing an electric current generated in the battery structure 7 to the outside, may be included. A liquid electrolyte may be injected into the battery case 5 and sealed to complete the manufacture of the lithium battery 1. The battery case 5 may have a polygonal shape, but is not necessarily limited thereto, for example, may also have a cylindrical shape, a thin-film shape, and/or the like.
Referring to
A pouch-type or kind lithium battery corresponds to lithium batteries in
The lithium battery may have excellent or suitable lifespan characteristics and high rate characteristics, which makes it suitable for utilize in, for example, electric vehicles (EVs). For example, the lithium battery may be utilized in hybrid vehicles, such as plug-in hybrid electric vehicles (PHEVs) and/or the like. Also, the lithium battery may be utilized in any field that requires a large amount of energy storage. For example, the lithium battery may be utilized in an electric bicycle, a power tool, and/or the like.
The lithium batteries may be stacked in plurality to form a battery module, and a plurality of battery modules may form a battery pack. Such a battery pack may be utilized in all types (kinds) of devices that require high capacity and high output. For example, the battery pack may be utilized in laptop computers, smartphones, electric vehicles, and/or the like The battery module may include, for example, a plurality of batteries and a frame holding the batteries. The battery pack may include, for example, a plurality of battery modules and a bus bar connecting the same. The battery module and/or the battery pack may further include a cooling device. The plurality of battery packs may be adjusted by a battery management system. The battery management system may include a battery pack and a battery control device connected to the battery pack.
Terms such as “substantially,” “about,” and “approximately” are used as relative terms and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art. They may be inclusive of the stated value and an acceptable range of deviation as determined by one of ordinary skill in the art, considering the limitations and error associated with measurement of that quantity. For example, “about” may refer to one or more standard deviations, or +30%, 20%, 10%, 5% of the stated value.
Numerical ranges disclosed herein include and are intended to disclose all subsumed sub-ranges of the same numerical precision. For example, a range of “1.0 to 10.0” includes all subranges having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Applicant therefore reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein.
The present disclosure will be described in more detail through Examples and Comparative Examples hereafter. However, Examples are provided to exemplify the present disclosure, and the scope of the present disclosure is not limited thereto.
A nickel current collector was prepared. 0.625 gram (g) of poly(ethylene glycol) diacrylate (PEGDA), 1.125 g of polyurethane, 1.17 g of lithium bis(trifluoromethanesulfonyl) imide (LiTFSI), 0.75 g of silver nitrate (AgNO3), and 0.002 g of t-amyl peroxide, which is a thermal initiator, were dissolved in 9.0 g of dimethylformamide (DMF) to prepare a composition for providing a polymer electrolyte. The composition for providing the polymer electrolyte was cast on the nickel current collector utilizing a doctor blade. Thereafter, the obtained polymer electrolyte (e.g., the polymer electrolyte layer) was cross-linked and dried in a vacuum oven at 110° C. for 6 hours or more to prepare an electrode structure.
A polymer electrolyte was prepared in substantially the same manner as in Example 1, except that the type or kind of electrode current collector and the type or kind and amount of metal salt were changed as shown in Table 1.
1H-NMR was measured for the polymer electrolytes and the compositions for providing a polymer electrolyte with a 600 megahertz (MHz) spectrometer, and a method of manufacturing a sample for NMR measurement is as follows.
0.03 g of the composition for providing a polymer electrolyte and 0.0004 g of the reference material (p-xylene) were added and dissolved in 1 milliliter (mL) of NMR solvent (dimethyl sulfoxide-d6 (DMSO-d6).
The polymer electrolytes prepared according to Preparation Examples 1 to 5 and Comparative Preparation Examples 1 and 2 were punched in a circular shape having a diameter of 16 millimeter (mm) and put in 1 mL of NMR solvent (DMSO-d6), and 0.0004 g of reference material (p-xylene) was added and dissolved.
Among the 1H-NMR measurement results, the area of hydrogen (e.g., a peak having a chemical shift value of 6.3 parts per million (ppm), B peak having a chemical shift value of 6.2 ppm, and C peak having a value of 5.9 ppm), corresponding to the acrylate group of PEGDA, was calculated with respect to 1000 parts of the area of p-Xylene, (e.g., the reference material described herein). The calculated results were listed in Table 2. Conversion was calculated according to Equation 1, and the calculated values were listed in Table 2.
Referring to Table 2, it may be confirmed that the polymer electrolytes according to Preparation Examples 1 to 5, when compared to Comparative Preparation Example 1, have excellent or suitable conversion. Based on these results, it can be confirmed that the polymer electrolytes prepared according to Preparation Examples 1 to 5 participate in the polymerization reaction without any unreacted polymer.
LiNi0.6Co0.2Al0.2O2, a conductive material (Super-P; Timcal Ltd.), a binder, and N-methylpyrrolidone were mixed to obtain a cathode composition. In the cathode composition, a mixed weight ratio of LiNi0.6Co0.2Al0.2O2, the conductive material, and the binder was 97.5:1.5:1.
The cathode composition was applied onto the aluminum foil (thickness: about 15 μm), and dried at about 110° C. to prepare a cathode.
The cathode obtained according to the described processes, a polyolefin-based separator, and a liquid electrolyte were stacked to be adjacent to the polymer electrolyte among (e.g., included in) the electrode structure according to Preparation Example 1 to prepare a lithium battery (pouch cell).
A lithium battery was manufactured in substantially the same manner as in Example 1, except that the type or kind of polymer electrolyte utilized was changed as shown in Table 3.
The lithium batteries (coin cells) manufactured according to Examples 1 to 5, and Comparative Examples 1 to 2 were each charged at a constant current of 0.1 C rate at 45° C. until the voltage reached 4.30 V (vs. Li) and then the charging was cut off at a current of 0.05 C rate while maintaining 4.30 V in a constant voltage mode. Subsequently, each battery was discharged at a constant current of 0.1 C rate until the battery voltage reached 3.6 V (vs. Li) during discharge (formation cycle, 1st cycle). Another charging and discharging process was performed 2 times to complete a formation process.
The lithium battery after the formation cycle was charged at 45° C. with a constant current of 0.2 C in a voltage range of about 3.6 V to about 4.3 V compared to lithium metal, and then the charging was cut off at a current of 0.05 C rate while maintaining 4.30 V in a constant voltage mode. Subsequently, a constant current discharge was performed at 0.5 C until a voltage reached a cut-off voltage of 3.6 V. The herein-described charging and discharging process was repeatedly performed a total of 200 times.
Throughout the charging and discharging cycles described, a rest period of 5 minutes was provided after each charging and discharging cycle. Herein, a capacity retention ratio at the 200th cycle is represented by Equation 2.
The capacity retention ratio and discharge capacity at 200th cycle were measured and the values were listed in Table 3.
Referring to Table 3, Examples 1 to 5 include electrode structures according to Preparation Examples 1 to 5, respectively, and compared to Comparative Examples 1 to 2, which include electrode structures according to Comparative Preparation Examples 1 and 2, respectively, capacity characteristics and capacity retention rate characteristics at 45° C. were excellent or suitable.
Hitherto, embodiments have been described with reference to the drawings and Examples, and it is understood that the present disclosure should not be limited to these embodiments, but one or more suitable changes, modifications, and other equivalent embodiments can be made by one ordinary skilled in the art. Therefore, the scope of protection of the present disclosure should be defined by the following claims and equivalents thereof.
The electrode structure according to one or more embodiments includes an electrode current collector and a polymer electrolyte provided on the electrode current collector, wherein the electrode current collector includes a nickel or chromium metal, the polymer electrolyte includes a metal salt, so that suppression of polymerization reactions during and/or for providing the polymer electrolyte, e.g., due to metal ions released from the electrode current collector, during the providing process of the polymer electrolyte may be prevented or reduced. Therefore, the durability and high-temperature stability of the electrode structure may be improved.
The electrode structure includes a polymer electrolyte containing a metal salt, and thus the metal salt may induce a substantially uniform electrodeposition of lithium. The electrode structure including such a polymer electrolyte may have improved lifespan characteristics.
A battery management system (BMS) device, and/or any other relevant devices or components according to embodiments of the present disclosure described herein may be implemented utilizing any suitable hardware, firmware (e.g., an application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, the various components of the device may be formed on one integrated circuit (IC) chip or on separate IC chips. Further, the various components of the device may be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on one substrate. Further, the various components of the device may be a process or thread, running on one or more processors, in one or more computing devices, executing computer program instructions and interacting with other system components for performing the various functionalities described herein. The computer program instructions are stored in a memory which may be implemented in a computing device using a standard memory device, such as, for example, a random access memory (RAM). The computer program instructions may also be stored in other non-transitory computer readable media such as, for example, a CD-ROM, flash drive, or the like. Also, a person of skill in the art should recognize that the functionality of various computing devices may be combined or integrated into a single computing device, or the functionality of a particular computing device may be distributed across one or more other computing devices without departing from the scope of the present disclosure.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the drawings, it will be understood by those of ordinary skill in the art that one or more suitable changes in form and details may be made therein without departing from the spirit and scope of the present disclosure as defined by the following claims and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0039381 | Mar 2023 | KR | national |
| 10-2023-0135953 | Oct 2023 | KR | national |
