Patent Application
20240014397
This patent document relates to elastomer binder materials.
Conformal electronics are a new, emerging class of electronic devices that can conform to complex non-planar and deformable surfaces, such as living tissues like skin, textiles, robotics and others. Conformal electronic devices can include electric circuits and devices formed on flexible substrates that can be applied to and conform to a variety of surface geometries.
The techniques disclosed herein can be implemented in various embodiments to achieve chemical-resistant elastomer binders and flexible, printed, high-performance electrochemical systems based on said binders.
An aspect of the disclosed embodiments relates to a chemical-resistant flexible composite for electrochemical cells that includes a plurality of particles. The composite also includes a polymer comprising fluorine, wherein the polymer is an elastomer, wherein the polymer is configured to confine the plurality of particles within a structure formed by the polymer, and wherein the polymer and the plurality of particles form an elastic polymer-particle composite.
Another aspect of the disclosed embodiments relates to a printable ink for chemical-resistant flexible electronics components that includes a matrix including an organic solvent and a polymer comprising fluorine, wherein the polymer is dissolved in the organic solvent, and wherein the polymer is an elastomer. The ink also includes a plurality of particles contained within the matrix, wherein the organic solvent is capable of vaporizing from the matrix such that the printable ink forms an elastic polymer-particle composite upon removal of at least a part of the organic solvent from the printable ink, and wherein the polymer is configured to confine the plurality of particles within the formed composite.
Yet another aspect of the disclosed embodiments relates to a chemical-resistant flexible composite for electrochemical cells that includes a plurality of particles. The composite also includes a copolymer comprising atoms of a halogen element, wherein the copolymer is an elastomer, wherein the copolymer is configured to confine the plurality of particles within a structure formed by the copolymer, and wherein the copolymer and the plurality of particles form an elastic polymer-particle composite.
An aspect of the disclosed embodiments relates to a printable ink for chemical-resistant flexible electronics components that includes a matrix including an organic solvent and a copolymer comprising a halogen chemical element in its structure, wherein the copolymer is dissolved in the organic solvent, and wherein the copolymer is an elastomer. The printable ink also includes a plurality of particles contained within the matrix. The organic solvent of the printable ink is capable of vaporizing from the matrix such that the printable ink forms an elastic polymer-particle composite upon removal of at least a part of the organic solvent from the printable ink, and wherein the copolymer is configured to confine the plurality of particles within the formed composite.
Another aspect of the disclosed embodiments relates to a flexible battery that includes a composite material, comprising: a plurality of particles; and a polymer comprising fluorine, wherein the polymer is an elastomer, wherein the polymer is configured to confine the plurality of particles within a structure formed by the polymer, and wherein the polymer and the plurality of particles form an elastic polymer-particle composite.
Yet another aspect of the disclosed embodiments relates to a flexible battery that includes an anode comprising a first layer of a first elastic composite material including a plurality of Zn particles and a first fluorine-containing polymer confining the plurality of Zn particles within the first layer. The battery also includes a cathode comprising a second layer of a second elastic composite material including a plurality of AgO particles and a second fluorine-incorporating polymer confining the plurality of AgO particles within the second layer. The battery further includes a layer of a hydrogel electrolyte disposed between the anode and the cathode.
The subject matter described in this patent document can be implemented in specific ways that provide one or more of the following features.
The rise of flexible electronics calls for cost-effective and scalable (in their manufacturing) flexible batteries having good mechanical and electrochemical performance. Polymers that can be used in products that benefit from flexible electronics, e.g., such as batteries, fuel cells, enzymatic sensors, etc., should have both good chemical stability (e.g., under low-pH, high-pH, and/or high-salinity conditions) and a degree of mechanical flexibility and/or stretchability, and further, at the same time, should enable good electrochemical performance of the devices that incorporate such polymers. However, current flexible electronics devices often do not meet these requirements (and therefore risk premature failure) because they do not utilize materials capable of performing under the strenuous and extreme conditions the devices typically face in practical, real-world use. In particular, materials used in battery, fuel cell and/or biosensor applications can be exposed, e.g., to deleterious chemical species, high pH, and/or high temperatures. What is needed are specialized materials that can be used in flexible electronic devices and that can perform and last under such conditions.
Flexible electronics devices should possess a high degree of chemical stability. That stability can be provided using materials which are chemically stable in the range of possible device operating conditions. Furthermore, materials used, e.g., in wearable form-factor batteries to power flexible wearable electronics should enable the batteries to supply enough power and store sufficient energy for a prolonged wearable device operation. Current flexible film batteries can only hold 0.1-5 mAh/cm2, which is not enough for may practical applications. Limitations on advancing such flexible film batteries or other wearable power sources for flexible wearable electronic devices require suitable materials that possess a large propensity to resist chemical or mechanical degradation while allowing for sufficient energy storage.
Disclosed herein are compositions, materials, methods, and articles of manufacture and devices that pertain to chemical-resistant elastomer binders and flexible, printed, high-performance electrochemical systems based on said binders.
According to some embodiments of the disclosed technology, a chemical-resistant flexible composite material for providing a high chemical resilience against degradation for flexible electronics includes a polymer and a plurality of particles, in which the polymer includes fluorine and is an elastomer, and which the polymer is configured to confine the plurality of particles within a structure formed by the polymer, such that the polymer and confined plurality of particles form an elastic polymer-particle composite.). In various example embodiments, the polymer can be a copolymer.
In some implementations, for example, a chemical-resistant, flexible elastomer binder according to the disclosed technology can be used in printable, flexible batteries or supercapacitors with high areal energy density for wearable and flexible electronics, printable, flexible sensors, as well as printable, flexible fuel cells, solar cells, display panels requiring special operation environment including low pH, high pH, or high salinity. More generally, the disclosed binder materials can be used in any printed electrochemical and electronic systems, e.g., supercapacitors, electrochromic cells, sensors, circuit interconnections, thin-film or organic electrochemical transistors, touch screens, solar cells, etc.
In some example embodiments, fluorine-incorporating or chlorine-incorporating elastomeric copolymers (e.g., bipolymers, terpolymers or quaterpolymers, such as FKM/FPM fluorine rubber, or tetrafluoroethylene propylene (FEPM)) according to the disclosed technology are used as a binder that immobilizes particles in an elastic polymer-particle composite after an ink or a slurry containing the fluorine-incorporating (or the chlorine-incorporating) elastomeric copolymer according to the disclosed technology mixed with particles and an organic solvent has been cured (e.g., at an elevated temperature and/or over a certain amount of time. In this patent document, the term “fluorine-incorporating polymer” is used interchangeably with the term “fluorine-containing polymer,” the term or expression “polymer comprising fluorine” or “polymer including fluorine” or the like, the term “fluoropolymer,” or the term “fluoroelastomer.” Similarly, the term “chlorine-incorporating polymer” is used interchangeably with the term “chlorine-containing polymer,” the term or expression “polymer comprising chlorine” or “polymer including chlorine” or the like, the term “chloropolymer,” or the term “chloroelastomer.”
According to some example embodiments, copolymers (e.g., bipolymers, terpolymers or quaterpolymers) according to the disclosed technology can incorporate in their structure atoms of one or more types of halogen elements such as, e.g., fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), or tennessine (Ts). In some example embodiments, copolymers can be elastomers.
For example, a polymer according to the disclosed technology can be composed of a combination of ethylene fluorinated with 0-4 fluorine atoms and/or propylene fluorinated with 0-6 fluorine atoms with a different degree of cross-linking, polymer chain length, fluorination, or chlorination. For example, the polymer according to the disclosed technology can be a Dai-El, Viton, Tecnoflon, Fluorel, or Aflas. The monomers of the copolymer or terpolymer according to the disclosed technology can be any of: ethylene, vinylidene fluoride, tetrafluoro propylene, tetrafluoroethylene, hexafluoropropylene, ethylene tetrafluoroethylene, chlorotrifluoroethylene, perfluoro alkoxy alkane, or perfluoromethylvinylether. The polymer can be dissolved in organic solvents and mixed with various types of materials to form flexible high-pH, low-pH, or high salinity resistant composite (e.g., after the solvent has been evaporated at an elevated temperature). When mixed with particles such as, e.g., graphite, carbon black, zinc, silver, copper, bismuth, oxides of metals such as zinc oxide, silver (I) oxide, silver (I, III) oxide, bismuth (III) oxide, lead (II) oxide, titanium (IV) oxide, other solid organic material powders such as cellulose, methylcellulose, sucrose, or polymers such as polyvinyl alcohol, polyacrylic acid, polyethylene oxide, etc., the dissolved polymer and the particles form a printable or casting-compatible ink or slurry. After removing the solvent at, e.g., an elevated temperature (e.g., the one above 30 degrees Celsius), the resultant composite material is mechanically self-supporting (e.g., capable of maintaining its mechanical structure on its own), soft, flexible, stretchable, and porous. The printed/cast composite can be used as a sealant, encapsulation, current collectors, electrodes, electrode surface coating, separators, or a part of an electrolyte.
Devices fabricated with a composite material according to the technology disclosed in this patent document can be electrochemically active yet chemically stable without self-degradation. An electrode printed using an ink or a slurry containing a binder according to the disclosed technology can hold low impedance and can be very thick without affecting its electrochemical or electrical performance (e.g., after the ink or the slurry has been cured). The flexible composite materials according to the disclosed technology also offer a certain amount of mechanical resilience against bending, twisting, and stretching deformations. For example, flexible electronics produced using materials and techniques according to the disclosed technology (e.g., deposited as composites with elastomeric materials as binders, according to the disclosed technology) can be wrapped or be bent and can be shaped to fit to, e.g., curvilinear surfaces. For various conformal electrochemical systems, chemical stability of the materials according to the disclosed technology ensures device robustness and durability.
In some example embodiments according to the disclosed technology, a chemically-stable fluoroelastomer according to the disclosed technology can be dissolved, e.g., in a low molecular weight ketone (e.g. acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, acetophenone, benzophenone), and/or a low molecular weight ester (e.g., methyl formate, methyl acetate, ethyl acetate, ethyl propionate, isopropyl butyrate, and ethylbenzoate) and mixed with carbonaceous powder (e.g., graphite, carbon black, activated carbon, graphene, carbon nanotubes), metal powder in a form of, e.g., microparticles, nanoparticles, nanowires, nanorods or flakes (e.g., platinum, gold, silver, zinc, nickel, tin, iron, manganese, magnesium, aluminum, copper, bismuth, indium, lithium, sodium), metal oxides (e.g., zinc oxide, silver (I) oxide, silver (I,III) oxide, manganese (II) oxide, manganese (IV) oxide, bismuth (III) oxide, lead(II) oxide, lead (II, IV) oxide, titanium (IV) oxide, vanadium (III) oxide, vanadium (IV) oxide, vanadium (V) oxide, lithium (I) oxide, magnesium oxide, copper (I) oxide, copper (II) oxide, indium (III) oxide, tin (II) oxide, tin (IV) oxide, lead (II) oxide, iron (II) oxide, iron (III) oxide), metal salts (fluorides, chlorides, bromides, iodides, acetates, nitrates, sulfates, carbonates persulfates, permanganates, hydroxides, oxyhydroxides, sulfonates), saccharides and their derivatives (e.g., glucose, sucrose, cellulose, maltodextrin methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose), surfactants (e.g., sodium dodecyl sulfate, dodecyl benzene sodium sulfonate, Triton-X 100, Triton-X 114, Zonyl fluorosurfactants, Span 80, perfluorooctanesulfonate) or other polymers (e.g., polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polystyrene, polystyrene sulfonate, polymethacrylate, polystyrene block copolymers, polyethylene vinyl acetate, polyurethane, polyvinylidene fluoride, tetrafluoro ethylene, polyvinylpyrrolidone, polypropylene oxide) to form a polymer-particle (or polymer-powder) composite ink or slurry according to the disclosed technology. The ink can be deposited onto various substrates via different printing techniques as electrodes, separators, or part of an electrolyte, for example. The printed elements (e.g., electrodes) can be thereafter assembled into electrochemical cells for use in low-pH, high-pH, or high-salinity conditions.
In some example embodiments, the fluorine-containing or chlorine-containing polymer according to the disclosed technology can be dissolved in methyl isobutyl ketone (MIBK) and mixed with silver (I, III) oxide and carbon black to form a cathode ink, with zinc and bismuth oxide to form an anode ink, with titanium oxide and cellulose powder to form a separator ink, and with graphite and carbon black to form a conductive current collector ink. The inks can be printed layer-by-layer to form a silver-zinc battery according to the disclosed technology that can work with a high-pH electrolyte (e.g., the one with pH>10 or pH>14). The printed silver-zinc battery according to the disclosed technology is stable at such high pH and provides high areal capacity (e.g., >50 mAh/cm2) with low cell impedance for high current discharges.
According to various example embodiments, a polymer binder according to the disclosed technology can be used in printable, flexible high areal energy density batteries for wearable and flexible electronics. An elastomer polymer binder according to the disclosed technology can also be used in printable, flexible fuel cells that require special operating environments (e.g., low pH, high pH, or high salinity). The polymer can be also used in any printed electrochemical and/or electronic systems, such as sensors, batteries, supercapacitors, fuel cells, electrochromic cells, circuit interconnections, thin-film or organic electrochemical transistors, touch screens, solar cells, etc.
The ink or slurry formulated according to the disclosed technology can be deposited
on a substrate by various production processes, such as inkjet printing, screen-printing, stencil printing, dip coating, spray coating, drop casting, 3D printing, injection molding, stamping, transfer printing, water transfer printing, etc. The substrate can include a flexible polymer, a stretchable elastomer, various textiles, glasses, ceramics, metal, etc. The substrate can be structured, for example, in flat sheets or various curved surfaces. The ink or slurry deposited on the substrate can be cured, for example, by exposing it to an elevated temperature, or enhanced ventilation to remove excess solvent from it. The ink or the slurry can be also illuminated with ultraviolet or visible light or interacted with a peroxide or bisphenol curing agent. The thickness of the ink/slurry deposition can be controlled by controlling, for example, the time of deposition, viscosity of the ink or slurry, dilution of the ink or slurry, inclusion of additives, or thickness of stencils. Repeated deposition after curing can be implemented to deposit the composite material layer-by-layer, to obtain high areal loading for high areal capacity or high surface area. A calibration curve for an individual ink formulation according to the technology disclosed herein that determines thickness of a resulting deposited material layer can be established based on the deposition methods, deposition variables, and the number of deposition repetitions or cycles.
Non-limiting example embodiments and implementations of the chemical-resistant, flexible elastomer binder compositions, material products, methods and devices incorporating such therein are disclosed in this patent document. In particular, some examples of the disclosed technology are embodied in the following examples of a high-performance printed AgO—Zn rechargeable battery for flexible electronics.
In the following example implementations, example embodiments of printable, polymer-based AgO—Zn batteries are described that feature flexibility, rechargeability, high areal capacity, and low impedance. Using elastomeric substrate and binders according to the technology disclosed herein, the current collectors, electrodes, and separators can be printed (e.g., screen-printed) layer-by-layer and vacuum-sealed in a stacked configuration. The batteries according to the disclosed technology are customizable in sizes and capacities, with areal capacities as high as 54 mAh/cm2 for primary applications. The batteries were used, for example, to power a flexible E-ink display system that requires a high-current drain, and exhibited superior performance compared to commercial coin-cell batteries. Advanced micro computed tomography (micro-CT) and electrochemical impedance spectroscopy (EIS) were used to characterize a battery according to an example embodiment of the disclosed technology, whose mechanical stability was tested with repeated twisting and bending. The disclosed AgO—Zn batteries present a practical solution for powering a wide range of electronics and hold major implications for the future development of practical and high-performance flexible batteries.
Recent interest in multifunctional flexible electronics for applications in sensing, displays, and wireless communication advocates for the development of complementary flexible energy storage solutions. Despite the exponential growth in the wearable flexible electronics market, a need still exists for scalable, low-cost, and high-performance flexible battery technologies to provide practical energy storage solutions for the tens of millions of devices produced every year. Many existing flexible batteries rely on fabrication processes that are complex, low throughput, and high cost, and thus have limited practicality which hinders their lab-to-market transformation. Printed high-performance batteries according to the disclosed technology address the need for flexibility and scalability while maintaining low cost. Using low-cost thick-film fabrication technologies, flexible battery components according to the disclosed technology can be printed sheet-to-sheet or roll-to-roll using traditional, low-maintenance screen printing or doctor blade casting equipment, for example, thus realizing low-cost mass production of flexible batteries.
Among commercialized printed flexible batteries, aqueous zinc (Zn)-based conversion cells were successful in developing products with high throughput and low production cost. The Zn anode chemistry has been of special interest for the flexible battery market due to its low material cost, high theoretical capacity (820 mAh/g, 5854 mAh/L), good rechargeability, and safe chemistry. In addition, as Zn and the aqueous electrolyte can be readily handled in ambient environment, the equipment and production costs of Zn-based batteries are often considerably lower compared to lithium-ion batteries. However, commercial Zn-based printed flexible batteries are usually non-rechargeable and feature low capacity and high impedance, thus limiting their applications to low-power, disposable electronics only. Silver oxide-zinc (Ag2O—Zn) batteries have a rechargeable chemistry and can tolerate a high-current discharge. The redox reaction in such batteries relies on the dissolution of zinc ions (Zn2+) and silver ions (Ag+) in the alkaline electrolyte and their supersaturation-induced precipitation, which takes place rapidly while maintaining a stable voltage at 1.56 V, as shown in Equations 1-6.
(Dissolution) Zn(s)+4OH−(aq)⇄Zn(OH)42−(aq)+2e− (1)
(Relaxation) Zn(OH)42−(aq)⇄ZnO(s)+H2O+2OH−(aq) (2)
(Overall) Zn(s)+2OH−(aq)⇄ZnO+H2O+2e−E°=−1.22V vs. SHE (3)
(Dissolution) Ag+OH−⇄AgOH(aq)+e− (4)
(Relaxation) 2AgOH(aq)⇄Ag2O(s)+H2O (5)
(Overall) Ag2O(s)+H2O⇄2Ag(s)+2OH−(aq) E°=+0.34 V vs. SHE (6)
Most of these batteries rely solely on the use of the lower oxidation state of silver to obtain reversible redox reaction, while the higher oxidation state (AgO), with its redox reaction described in Equation 7, has been rarely utilized.
2AgO(s)+H2O+2e−⇄Ag2O(s)+H2O(l) E°=+0.60 V vs. SHE (7)
The previous underutilization of AgO can be attributed to its instability, namely, its lattice phase change when transitioning into Ag2O, which may result in irreversible shape changes that impede rechargeability, and its high charging potential responsible of possible electrode gassing due to oxygen evolution reaction. However, once these issues are addressed, it is possible to access a much higher theoretical cathode capacity (from 231 mAh/g for Ag2O to 432 mAh/g for AgO). So far, printed silver-zinc batteries reported in the literature still have low rechargeability (e.g., <50 cycles), limited capacity (e.g., <12 mAh/cm2 for primary cell, <3 mAh/cm2 for secondary cell), along with high internal resistance (e.g., ˜102Ω) that results in a large voltage drop during operation. Such limitations are hindering the adaptation of silver-zinc printed batteries in flexible electronics.
Herein, as shown by example embodiments and implementations, a new material and fabrication process for all-printed, flexible, and rechargeable AgO—Zn batteries with ultra-high areal capacity, low impedance, and good rechargeability as a practical energy storage solution for flexible electronics is presented.
The fabrication of a battery cell according to the disclosed technology relies on low-cost, high-throughput, layer-by-layer printing of formulated powder-elastomer (or particle-elastomer) composite inks according to the disclosed technology to form the current collectors, Zn anode, AgO cathode, and their corresponding separators. The battery adopts a low-footprint stacked configuration, with potassium hydroxide (KOH)-poly(vinyl alcohol) (PVA) hydrogel as a low impedance electrolyte sandwiched between the two fully printed electrodes. Using the thermoplastic styrene-ethyl-butylene-styrene block copolymer (SEBS) elastomer-based substrate, the assembled battery can be directly heat- and vacuum-sealed to preserve the electrolyte and ensure appropriate cell pressure during operation. This fabrication and assembly process can be applied to different cell sizes with adjustable areal capacity, allowing customizable battery form factors that are tailored for specific applications. Fully utilizing the higher oxidation state of the AgO, example as-printed cells according to the disclosed technology were able to reach a high areal capacity of >54 mAh/cm2 while maintaining a low internal resistance (e.g., ˜10Ω) for primary applications. Furthermore, utilizing an optimized cycling profile according to the disclosed technology, the printed cells were recharged for over 80 cycles, sustaining 0.2 C-1 C discharges without exhibiting significant capacity loss, while maintaining low impedance throughout each cycle. Moreover, the fabricated cells according to the disclosed technology displayed outstanding robustness against repeated bending and twisting deformations. To demonstrate their performance in powering typical flexible electronics, the fabricated thin-film batteries according to the technology disclosed herein were successfully implemented in a flexible E-ink display system with an integrated microcontroller unit (MCU) and Bluetooth (BT) modules that require pulsed high-current discharges. Leveraging low-cost scalable production process, polymer-based flexible architecture, and customized ink formulations, the all-printed AgO—Zn battery according to the disclosed technology, with its desirable mechanical and electrochemical performance, presents a practical solution for powering the next-generation flexible electronics, and sets a new benchmark for the further development of printable flexible batteries.
An example all-printed fabrication method of the flexible AgO—Zn battery according to the disclosed technology was designed based on the careful selection of elastomers for the substrate, sealing, and ink binders based on their mechanical properties, chemical stabilities, and processabilities. SEBS was selected as the substrate material for its good solvent processability, chemical stability under high pH, outstanding elasticity, as well as its appropriate melting point (˜200° C.), allowing it to be easily cast into films that are chemically stable, flexible, and heat-sealable to support and seal the battery. Screen-printing, a low-cost high-throughput thick-film technique was used for ink deposition, as it allows the efficient fabrication of the current collectors, electrodes, and separators into their preferred shapes and thicknesses. The screen-printing of the batteries according to an example embodiment of the disclosed technology relies on the customized formulation of 6 inks corresponding to the current collectors, electrodes, and the separators for both the anode and cathode. Conductive and flexible silver ink and carbon ink were printed as the anode and cathode current collectors, respectively. Both inks use SEBS as the elastomer binder and toluene as the solvent to allow the ink to firmly bond to the toluene-soluble SEBS substrate. The anode ink was composed of Zn particles with bismuth oxide (Bi2O3) as an additive to reduce dendrite formation and suppress H2 gassing, while the cathode ink was mainly composed of AgO powder with a small amount of lead oxide coating to enhance the electrochemical stability and carbon black added to enhance the electronic conductivity of the electrode. A chemically stable (e.g., high-pH, low-pH, and/or high-salinity stable), elastomeric fluorocopolymer was used as the binder for both electrodes for its solubility in lower ketones which is less prone to oxidation by the highly oxidative AgO. Cellulose powder was used to form the porous cathode separator to capture and reduce dissolved silver ions and prevent material crossover. In some embodiments, the cathode separator can be made of cellophane. A titanium dioxide (TiO2)-based ink was formulated for the anode separator, acting as a physical barrier to Zn dendrite growth. Lastly, a solid-phase polyvinyl alcohol (PVA) hydrogel crosslinked with potassium hydroxide (KOH) was prepared as the electrolyte, which complements the cell flexibility without the risk of leaking. Lithium hydroxide (LiOH) and calcium hydroxide (Ca(OH)2) were used as additives in the electrolyte to maintain electrolyte chemical stability and minimize zinc dissolution.
cell according to the disclosed technology: the (i) AgO electrode (cathode) 210, (ii) Zn electrode (anode) 220, (iii) cellulose separator 230, and (iv) TiO2 separator 240.
The printed electrodes and separators (
The loosely packed Zn anode according to some example embodiments of the disclosed technology includes large particles, with sizes in the range of 50 μm to 100 μm, which can reduce the surface passivation induced by the spontaneous reaction with the electrolyte. Energy Dispersive X-Ray Analysis (EDX) further shows the homogeneous coverage of the Bi2O3 and the fluoropolymer binders on the surfaces of the Zn particles (
In comparison, for example, the AgO electrode (cathode) uses 1-20 μm particles to produce a porous electrode, which was paired with a separator with similar particle sizes to capture the dissolved Ag species (
Overall, the porous electrodes grant easy permeation of the electrolyte, thus allowing the fabrication of cells with thicker electrodes to increase areal capacity. The conductivity of the PVA-based electrolyte (
The CV of the current collectors in the corresponding voltage window (
The ability of the cell design according to the disclosed technology to adapt to different cell sizes and areal loadings was evaluated. Cells with the same electrode thickness but different form factors, by varying the electrode designs, as well as the cells with the same form factors and different thicknesses by varying the number of layers of active material printed, were fabricated and discharged at a constant 1 mA current. As shown in
Beyond the application as a primary battery, the electrochemical performance of a flexible AgO—Zn battery according to an example embodiment of the disclosed technology as a secondary cell was also characterized. As a cell operating with conversion-type chemistry, it is crucial to avoid over-oxidation of the anode materials or over-reduction of the cathode material that would lead to irreversible particle shape change. A loss of capacity in this system is possible due to the increased thickness of the ZnO layer that passivates the anode surface, as well as the coarsening of the AgO/Ag2O particles leading to a decrease in cathode surface area. Such behavior can be effectively mitigated by accurately controlling the degree of charge and discharge to limit the occurrence of irreversible electrode shape changes. The optimized charge-discharge algorithm according to the disclosed technology was determined to cycle the cell between 40% and 90% of its maximum capacity, with larger ranges resulting in lower cycle life as shown in
Referring back to
Impedance measurements of the flexible batteries according to the disclosed technology showed relatively low impedances throughout cycling. The impedances of the batteries were either determined during cycling of the full-cell using direct current internal resistance (DCIR) method, or during cycling of the separated anode and cathode half-cells using a 3-electrode configuration with a Zn foil serving as the reference. The DCIR analysis offers a straightforward and simple way to gauge the change in the internal resistance of the battery. As shown in
Overall, the 3-electrode impedance results provide a deep insight into the reaction and possible routes in improving the battery's cycle-life and performance. These data indicate that the impedance of the AgO cathode is responsible for the majority of the cell impedance. Incorporation of additives can increase the cathode electrical conductivity to improve the performance in high-current applications. For the anode, the monitoring of ZnO formation via EIS can be paired with topological characterization methods to control the conversion of Zn electrodes towards extended cycle life.
Compared to coin-cell, cylindrical or prismatic cells, the printed flexible batteries according to the disclosed technology have the unique advantage of allowing bending, flexing, and twisting without causing their structural failure. To endow such mechanical resiliency, the printed AgO—Zn batteries according to the disclosed technology are composed of flexible and stretchable polymer-particle composite layers which use highly elastic binders. These flexibility and stretchability allow the layers of the battery to deform to release the inter-layer strain, thus allowing the battery to endure large deformation without delamination between its layers or build-up of fatigue, even when very thick electrodes are used. To test the performance of the batteries under severe strain, a 2-layer 1×5 cm2 cell (also referred to as battery) was fabricated according to an example embodiment of the disclosed technology and discharged at a current of 1 mA while undergoing repeated bending and twisting deformations. As illustrated in
To demonstrate performance of the batteries according to the disclosed technology powering typical flexible electronics, we designed a flexible E-ink display system controlled by an Arduino-type microcontroller unit with added Bluetooth (BT) communication module (
Flexible and high-performance thin-film AgO—Zn batteries according to the disclosed technology are based on rechargeable conversion chemistry. Using specially formulated ink with stretchable elastomeric binders and thermoplastic elastomeric substrates, the batteries according to the disclosed technology can be printed layer-by-layer using, e.g., low-cost, high-throughput screen-printing techniques and assembled with a heat and vacuum sealing processes, for example. To obtain a low device footprint while maintaining easy processability, printable and flexible separators and solid-phase KOH-PVA hydrogel were developed to allow a stacked sandwich configuration. Printable batteries according to the technology disclosed herein are compatible with various cell sizes and areal loading, leading to a high areal capacity of, e.g., 54 mAh/cm2 in connection to repeated multilayer printing for primary applications. The batteries are also rechargeable (e.g., upon implementing the capacity-controlled cycling algorithm described above), with high cycle life beyond 70 cycles with varying discharge C-rates without loss in capacity and coulombic efficiency. The batteries exhibited low impedance within each discharge-charge cycle, while maintaining low internal resistance throughout multiple cycles, suggesting stable and reversible electrode morphological change during electrode redox reactions. As a flexible energy storage unit for powering various flexible, wearable electronics, the performance of a battery according to an example embodiment of the disclosed technology was evaluated under rigorous mechanical testing, demonstrating that the battery offers remarkable resiliency against repeated large deformation bending and twisting cycles. The fabricated batteries were used in the powering of a customized flexible E-ink display system with BT connectivity and delivered an outstanding performance that surpassed commercial coin cells under the high-current pulsed discharge regime required by the electronics. The example implementations demonstrate the scalable fabrication of flexible thin-film AgO—Zn batteries with highly desirable electrochemical and mechanical performance and tremendous implications towards the development of novel energy storage devices for the powering of next-generation electronics.
Bi2O3, Ca(OH)2, KOH (pellets, ≥85%), LiOH, methyl isobutyl ketone (MIBK), toluene, cellulose (microcrystalline powder, 20 μm), Triton-X 114, Poly(ethylene oxide) (PEO) (MW 600,000), and PVA (MW=89000-98000, 99+% Hydrolyzed) were purchased from Sigma Aldrich (St. Louis, MO, USA). Zn, AgO, and TiO2 were obtained from Zpower LLC (Camarillo, CA, USA). The fluorocopolymer (GBR-6005, poly(vinylfluoride-co-2,3,3,3-tetrafluoropropylene)) was obtained from Daikin US Corporation (New York, NY, USA). SEBS (G1645) was obtained from Kraton (Houston, TX, USA). Graphite powder was purchased from Acros Organics (USA). Super-P carbon black was purchased from MTI Corporation (Richmond, CA, USA). All reagents were used without further purification.
The electrode resin was prepared by adding 5 g of the fluorine rubber in 10 g of MIBK solvent and left on a shake table until the mixture was homogeneous. The SEBS resin was prepared by adding 40 g of the SEBS into 100 mL of toluene and left on a shake table until the mixture was homogeneous.
The silver current collector ink was formulated by combining Ag flakes, SEBS resin, and toluene in 4:2:1 weight ratio and mixing in a planetary mixer (Flaktak Speedmixer™ DAC 150.1 FV) at 1800 rotations per minute (RPM) for 5 minutes. The carbon current collector ink was formulated by firstly mixing graphite, Super-P, and PTFE powder in 84:14:2 weight ratio with a set of pestle and mortar. The mixed powder was mixed with the SEBS resin and toluene in a 10:12:3 weight ratio using the mixer at 2250 RPM for 10 minutes to obtain a printable ink. The Zn anode ink was formulated by firstly mixing the Zn and Bi2O3 powders in a 9:1 ratio with a set of pestle and mortar until the Zn particles are evenly coated with the Bi2O3 powder. The evenly mixed powder was then mixed with the electrode resin and MIBK in a 20:4:1 weight ratio using the mixer at 1800 RPM for 5 minutes to obtain a printable ink. The AgO cathode ink was formulated by firstly mixing the AgO and Super-P powders in a 95:5 weight ratio using a set of pestle and mortar until homogeneous. The powder was then mixed with the electrode resin and MIBK in 5:5:2 weight ratio using the mixer at 2250 RPM for 5 minutes to obtain a printable ink.
The TiO2 separator ink was prepared by firstly mixing TiO2 and cellulose powder in a 2:1 ratio using a set of pestle and mortar. The mixed powder was then added with the SEBS resin, toluene and Triton-X in 50:55:75:3 weight ratio and mixed with the mixer at 2250 RPM for 10 minutes to obtain a printable ink. The cellulose separator ink was prepared by firstly mixing TiO2 and cellulose powder in a 26:9 ratio using a set of pestle and mortar. The mixed powder was then added with the electrode resin, MIBK in an 8:7:4 weight ratio and mixed with the mixer at 2250 RPM for 10 minutes to obtain a printable ink.
A resin with 40.8 wt % of SEBS dissolved in toluene was prepared and left on a linear shaker (Scilogex, SK-L180-E) overnight or until the mixture became transparent and homogeneous. Wax paper was used as the temporary casting substrate, and a film caster with the clearance of 1000 um was used to cast the SEBS resin onto the wax paper. The cast resin was firstly dried in the ambient environment for 1 h, followed by curing in a conventional oven at 80° C. for 1 h to remove the excess solvent. The transparent, uniform SEBS film, which can be readily peeled off from the wax paper after curing, was used as the substrate for subsequent battery printing.
Stencils for printing the current collectors, electrodes, and separators were designed using AutoCAD software (Autodesk, San Rafael, CA, USA) and produced by Metal Etch Services (San Marcos, CA), with dimensions of 12 in×12 in. The thickness of the stencils was designed to be 100 μm for the carbon and silver current collectors, 300 μm for the TiO2 separator and the Zn anode, and 500 μm for the cellulose separator and the AgO cathode. To print the anode, the silver ink was first printed onto the SEBS substrate and cured in a conventional oven at 80° C. for 10 minutes. The Zn ink was then printed onto the silver current collectors and cured at 80° C. for 30 minutes. The TiO2 ink was lastly printed onto the anode and cured at 80° C. for 10 minutes. To print the cathode, the carbon ink was firstly printed onto the SEBS substrate and cured at 80° C. for 10 minutes. PET sheets were cut using a computer-controlled cutting machine (Cricut Maker®, Cricut, Inc., South Jordan, UT, USA) into a mask exposing the printed carbon electrodes, and the masked carbon current collector was sputtered with ˜400 nm of Au and adhesion interlayer of Cr at a DC power of 100 W and 200 W, respectively, and an Ar gas flow rate of 16 SCCM using a Denton Discovery 635 Sputter System (Denton Discovery 635 Sputter System, Denton Vacuum, LLC, Moorestown, NJ, USA). The AgO ink was then printed onto the sputtered current collectors and cured at 50° C. for 60 minutes. Lastly, the cellulose ink was printed onto the cathode and cured at 50° C. for 60 minutes. To print multiple layers of electrodes or the separators, the stencil was offset by an additional 65 μm for each layer of AgO and 100 μm for each layer of Zn to compensate for the electrode thickness.
The hydrogel used in some example embodiments of the batteries according to the disclosed technology is synthesized by mixing the PVA solution and the hydroxide solution into a gel precursor and dried in a desiccator until the desired weight is reached. For synthesizing the 36.5% hydroxide gel used in some example embodiments, the following formulations were used. A hydroxide solution was prepared by dissolving 9.426 g KOH and 0.342 g LiOH into 50 mL deionized (DI) water. 0.5g Ca(OH)2 was then added into the solution and stirred in a closed container under room temperature for 1 hour to saturate the solution with Ca(OH)2, and the excess Ca(OH)2 was then removed from the solution. A PVA solution was prepared by dissolving 4.033 g PVA and 0.056 g PEO into 50 mL DI water heated to 90° C. The precursor solution was prepared by mixing the hydroxide solution and the PVA solution in the weight ratio of 13.677:10 and poured into a flat petri dish with the weight of 0.2 g/cm2. The precursor was left to dry in a vacuum desiccator until the weight decreased to 26.12% of precursor weight to obtain a soft, translucent hydrogel with its caustic material taking 36.5% of the sum of caustic material and the water content. Additional weight and conductivity information for different hydroxide concentrations can be found in Table 1. The hydrogel can be then cut into desired sizes and directly used or stored in a hydroxide solution with the same weight ratio of hydroxide without PVA. The storage solution for the 36.5% KOH-PVA gel was prepared similar to the hydroxide solution, where 10.777 g KOH, 0.391 g LiOH, and 0.5 g Ca(OH)2 were dissolved into 15 mL DI water and the excess Ca(OH)2 was removed.
Morphological analyses of the current collectors, separators, and active material electrodes were performed with SEM and micro-CT. SEM images were taken using a FEI Quanta FEG 250 instrument with an electron beam energy of 15 keV, a spot size of 3, and a dwell time of 10 μs. Micro-CT experiments were conducted using a ZEISS Xradia 510 Versa. For individual film analysis, micro-CT samples were prepared by punching 2 mm radii disks and stacking them in a PTFE cylindrical tube with alternating PTFE films to provide separation between neighboring film disks. For the Micro-CT of full and sealed cell bending, a 1×5 cm2 Zn—AgO battery was bent or rolled around a polyethylene (PE) cylindrical tube with a diameter of 1 cm.
For the micro-CT of active material electrodes, the heavier metals, such as Zn and Ag, warranted higher X-Ray energies than the printed polymer separator films. Accordingly, scans at 140 keV and a current of 71.26 μA were performed with high energy filters and a magnification of 4× on the Zn and AgO films with voxel sizes of 2.5 μm and 0.75 μm and exposure times of 2 s and 18 s, respectively. For the polymer separators, 80 keV scans with an 87.63 μA current were used with low energy filters at a magnification of 4× with voxel resolutions of 0.75 μm and 1.1 μm and exposure times of 8 s and 1 s for the printed anode and cathode separators, respectively. For scans of the full cell bending, a voltage of 140 keV and a current of 71.26 μA with a 4× magnification were performed with the following voxel resolutions and exposure times for the respective cases: 18.35 μm and 2 s for low resolution bending scan, 3.54 μm and 5 s for higher resolution bending scan, and 7.55μm and 2 s for rolled cell scan. For all micro-CT scans conducted, 1801 projections were taken for a full 360° rotation with beam hardening and center shift constants implemented during the data reconstruction. Post measurement imaging and analysis were performed by Amira-Avizo using the Despeckle, Deblur, Median Filter, Non-local Means Filter, Unsharp Mask, and Delineate modules for data sharpening and filtration provided by the software.
The 3-electrode half-cell CV characterization was performed on a cell according to an example embodiment of the disclosed technology assembled with the printed electrodes as the working electrode, a platinum foil as the counter electrode, Zn metal foil as the reference electrode, and 2 pieces of KOH-PVA hydrogel as the electrolyte. The 3-electrode full-cell CV characterization was performed between 1.35 V to 2 Von a cell according to an example embodiment of the disclosed technology assembled with an extra Zn metal foil as the reference electrode. The structures of both cells are illustrated in
The constant current complete discharge of a battery according to an example embodiment of the disclosed technology for primary applications was performed with the following procedure. Firstly, the assembled and vacuum-sealed battery was left idle for 1 hour to allow the electrolyte to fully permeate through the electrodes. Then, the battery was discharged using a battery test system (Landt Instruments CT2001A) at the desired current, until reaching the lower cut-off voltage of 1.35 V.
To enable the secondary application of the battery, cycling protocols were established that rely on the accurate control of the potential and DOD of the battery. To perform charge-discharge cycling on a fabricated battery, 50% of its maximum capacity, which was estimated by the low-current complete discharges, was first determined as the cyclable capacity and the basis to determine C-rates of the protocol. The battery was firstly discharged at the C-rate of 0.1C from 100% to 40% DOD. Then, the battery was recharged at the C-rate of 0.2C until reaching 2V, and then at 2V until reaching 90% DOD or C-rate of 0.05C. The battery could be then discharged and recharged at the desired C-rates between 1.35 V and 2 V, with the DOD maintained between 40% and 90% of its maximum value. Unless specified otherwise, all cycling data were performed using cells with 1×1 cm2 form factor with 2 layers of active electrode materials. Example cycling data for two cells with 8-layer electrode thickness connected in series is shown in
Electrochemical Impedance Spectroscopy (EIS) measurements were performed with a Biologic SP-150 in a 3-electrode configuration. The Zn—AgO three electrodes cell according to an example embodiment of the disclosed technology was fabricated with a Zn reference wire placed between an extra layer of hydrogel electrolyte and the original electrolyte layer, as, e.g., shown in
The impedances of the two half cells and the full cell were monitored in-situ during charging and discharging to analyze impedance changes most closely related to practical cycling conditions with a galvanostatic-EIS (GEIS) measurement. Accordingly, the DC base current was set to the current of the charging/discharging step, while the AC amplitude was set to 300 μA, approximately one-fifth of the cycling current. The frequency sweep was between 1 MHz and 1 Hz with 10 points per decade and an average of 8 measures per frequency. The cycling script implemented with GEIS is similar to that of the capacity-limited electrochemical cycling protocol, with the exception that the voltage limits applied were 1.95 V and 1.4 V vs. the reference instead of the anode for the charging and discharging respectfully. For each charge and discharge step, 10 GEIS was measured for 15 complete cycles, resulting in a total of 870 separate Nyquist plots (29 steps×10 measures×3 cell configurations). For analysis simplicity, only the 5th cycle's discharge and charge were analyzed.
Both half-cell Nyquist plots for the 5th cycle's discharge and charge steps were fitted to equivalent circuits using a slightly modified version of the Zfit function available as open-source code from Mathworks. Zfit utilizes another Mathworks open source code, fminsearchbnd, to minimize the error of simulated impedances with the experimental values by altering the impedance parameters (e.g., resistance values, constant phase element values, etc.) under realistic parameter boundary conditions. The use of this code allowed for streamline fitting of many successive Nyquist to provide insights in observable trends in the fitted parameters. Additional data of the EIS measurement can be found in
The ionic conductivity of the gel electrolyte was measured by a customized two-electrode (Stainless Steel 316L) conductivity cell with an inner impedance at 0.54Ω. The cell constant is frequently calibrated by using OAKTON standard conductivity solutions at 0.447, 1.5, 15, and 80 mS·cm−1 respectively. A constant thickness spacer was positioned between the two electrodes which ensure no distance changes during multiple-time measurements. The electrolytic conductivity value was obtained with a floating AC signal at a frequency determined by the phase angle minima given by Electrochemical Impedance Spectroscopy (EIS) using the following equation: σ=KR−Q, where R is the tested impedance (Ω), K is the cell constant (cm−1) and Q is the fitting parameter. All of data acquisition and output were done by LabView Software, which was also used to control an ESPEC BTX-475 programming temperature chamber to maintain the cell at a set temperature in 30 minutes intervals.
The bending deformation of the battery was conducted by bending a 1×5 cm2 battery around a cylinder with the diameter of 1 cm manually. The deformation was cycled between the bent and relaxed state at the rate of 1 s/cycle for 100 cycles. Similarly, the twisting deformation of the battery was performed manually at 1 s/cycle by fixing one end of the battery and twisting the other end 180° clockwise and counterclockwise for 100 cycles.
To demonstrate the battery's ability to power flexible electronics, a Waveshare 2.9-inch e-Paper flexible display was powered by two Zn—AgO batteries according to the disclosed technology in series. The display module was connected to an Adafruit Feather nRF52Bluefruit Low Energy (LE) chip and programmed using Arduino and C.
Several aspects of the present technology are set forth in the following examples. Although several aspects of the present technology are set forth in examples directed to compositions, composite materials, printable inks, flexible electronic devices or systems, and/or methods, any of these aspects of the present technology can similarly be set forth in examples directed to any of compositions, composite materials, printable inks, flexible electronic devices and/or systems, and/or methods in other embodiments described herein.
In some embodiments in accordance with the present technology (example 1), a chemical-resistant flexible composite for electrochemical cells includes a plurality of particles; and a polymer comprising fluorine, wherein the polymer is an elastomer, and wherein the polymer is configured to confine the plurality of particles within a structure formed by the polymer, wherein the polymer and the plurality of particles form an elastic polymer-particle composite.
Example 2 includes the composite of any of examples 1-24, wherein the polymer is a copolymer.
Example 3 includes the composite of example 2 or any of examples 1-24, wherein the copolymer is one of: a bipolymer, a terpolymer, or a quaterpolymer.
Example 4 includes the composite of example 2 or any of examples 1-24, wherein the copolymer comprises chlorine.
Example 5 includes the composite of example 2 or any of examples 1-24, wherein the copolymer comprises bromine.
Example 6 includes the composite of example 2 or any of examples 1-24, wherein the copolymer comprises iodine.
Example 7 includes the composite of any of examples 1-24, wherein the polymer is dissolvable in an organic solvent.
Example 8 includes the composite of any of examples 1-24, wherein the polymer is a copolymer including a combination of ethylene monomers fluorinated with between 0 and 4 fluorine atoms and/or propylene monomers fluorinated with between 0 and 6 fluorine atoms.
Example 9 includes the composite of any of examples 1-24, wherein monomers of the polymer include at least one of: vinylidene fluoride, tetrafluoropropylene, tetrafluoroethylene, hexafluoropropylene, ethylene tetrafluoroethylene, chlorotrifluoroethylene, perfluoro alkoxy alkane, or perfluoromethylvinylether.
Example 10 includes the composite of any of examples 1-24, wherein the plurality of particles includes at least one of: a carbonaceous material, a metal, a metal oxide, a metal salt, metal flakes, nanoparticles, nanowires, nanorods, nanotubes, a powder, a polymer, a surfactant, a saccharide, or a saccharide derivative.
Example 11 includes the composite of any of examples 1-24, wherein particles in the plurality of particles include a coating layer of a coating material.
Example 12 includes the composite of example 11 or any of examples 1-24, wherein the coating material includes at least one of: a carbonaceous material, a metal, a metal oxide, a metal salt, a polymer, a surfactant, a saccharide, or a saccharide derivative.
Example 13 includes the composite of any of examples 10 or 12 or any of examples 1-24, wherein the carbonaceous material is one of: carbon, graphite, carbon black, activated carbon, graphene, or carbon nanotubes.
Example 14 includes the composite of any of examples 10 or 12 or any of examples 1-24, wherein the metal is one of: platinum, gold, silver, zinc, nickel, tin, iron, manganese, magnesium, aluminum, copper, bismuth, indium, lithium, sodium, lead, or titanium.
Example 15 includes the composite of any of examples 10 or 12 or any of examples 1-24, wherein the metal oxide is one of: zinc oxide, silver (I) oxide, silver (I, III) oxide, manganese (II) oxide, manganese (IV) oxide, bismuth (III) oxide, lead (II) oxide, lead (II, IV) oxide, titanium (IV) oxide, vanadium (III) oxide, vanadium (IV) oxide, vanadium (V) oxide, lithium (I) oxide, magnesium oxide, copper (I) oxide, copper (II) oxide, indium (III) oxide, tin (II) oxide, tin (IV) oxide, lead (II) oxide, iron (II) oxide, or iron (III) oxide.
Example 16 includes the composite of any of examples 10 or 12 or any of examples 1-24, wherein the metal salt is one of: a fluoride, a chloride, a bromide, an iodide, an acetate, a nitrate, a sulfate, a carbonate persulfate, a permanganate, a hydroxide, an oxyhydroxide, or a sulfonate.
Example 17 includes the composite of any of examples 10 or 12 or any of examples 1-24, wherein the polymer is one of: polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polystyrene, polystyrene sulfonate, polymethacrylate, a polystyrene block copolymer, polyethylene vinyl acetate, polyurethane, polyvinylidene fluoride, tetrafluoro ethylene, polyvinylpyrrolidone, or polypropylene oxide.
Example 18 includes the composite of any of examples 10 or 12 or any of examples 1-24, wherein the surfactant is one of: sodium dodecyl sulfate, dodecyl benzene sodium sulfonate, or perfluorooctanesulfonate.
Example 19 includes the composite of any of examples 10 or 12 or any of examples 1-24, wherein the saccharide, or the saccharide derivative is one of: glucose, sucrose, cellulose, methylcellulose, maltodextrin methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, or carboxymethyl cellulose.
Example 20 includes the composite of any of examples 1-24, wherein a chemical resistance of the polymer includes a resistance to: a pH above 10, a pH below 4, or a salinity above 2M.
Example 21 includes the composite of any of examples 1-24, wherein a chemical resistance of the polymer includes a resistance to: a pH above 14, a pH below 1, or a salinity above 5M.
Example 22 includes the composite of any of examples 1-24, wherein the composite is structured to be mechanically self-supporting.
Example 23 includes the composite of any of examples 1-24, wherein the composite is included in an electrochemical and/or electronic device.
Example 24 includes the composite of any of examples 1-23, wherein the electrochemical and/or electronic device is one of: a fuel cell, a supercapacitor, an electrochromic cell, an electrochemical sensor, a circuit interconnector, a transistor, a battery, a solar cell, or a touch screen.
In some embodiments in accordance with the present technology (example 25), a printable ink for chemical-resistant flexible electronics components includes a matrix including an organic solvent and a polymer comprising fluorine, wherein the polymer is dissolved in the organic solvent, and wherein the polymer is an elastomer; and a plurality of particles contained within the matrix, wherein the organic solvent is capable of vaporizing from the matrix such that the printable ink forms an elastic polymer-particle composite upon removal of at least a part of the organic solvent from the printable ink, and wherein the polymer is configured to confine the plurality of particles within the formed composite.
Example 26 includes the printable ink of any of examples 25-47, wherein the polymer
is a copolymer.
Example 27 includes the printable ink of example 26 or any of examples 25-47, wherein the copolymer is one of: a bipolymer, a terpolymer or a quaterpolymer.
Example 28 includes the printable ink of example 26 or any of examples 25-47, wherein the copolymer comprises chlorine.
Example 29 includes the printable ink of example 26 or any of examples 25-47, wherein the copolymer comprises bromine.
Example 30 includes the printable ink of example 26 or any of examples 25-47, wherein the copolymer comprises iodine.
Example 31 includes the printable ink of any of examples 25-47, wherein the organic solvent includes a ketone.
Example 32 includes the printable ink of example 31 or any of examples 25-47, wherein the ketone is one of: acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, acetophenone, or benzophenone.
Example 33 includes the printable ink of any of examples 25-47, wherein the organic solvent includes an ester.
Example 34 includes the printable ink of example 33 or any of examples 25-47, wherein the ester is one of: methyl formate, methyl acetate, ethyl acetate, ethyl propionate, isopropyl butyrate, or ethyl benzoate.
Example 35 includes the printable ink of any of examples 25-47, wherein the polymer is a copolymer including a combination of ethylene monomers fluorinated with between 0 and 4 fluorine atoms and/or propylene monomers fluorinated with between 0 and 6 fluorine atoms.
Example 36 includes the printable ink of any of examples 25-47, wherein monomers of the polymer include at least one of: vinylidene fluoride, tetrafluoropropylene, tetrafluoroethylene, hexafluoropropylene, ethylene tetrafluoroethylene, chlorotrifluoroethylene, perfluoro alkoxy alkane, or perfluoromethylvinylether.
Example 37 includes the printable ink of any of examples 25-47, wherein the plurality of particles includes at least one of: a carbonaceous material, a metal, a metal oxide, a metal salt, metal flakes, nanoparticles, nanowires, nanorods, nanotubes, a powder, a polymer, a surfactant, a saccharide, or a saccharide derivative.
Example 38 includes the printable ink of any of examples 25-47, wherein the ink includes at least one of: a carbonaceous material, a metal, a metal oxide, a metal salt, a polymer, a surfactant, a saccharide, or a saccharide derivative.
Example 39 includes the printable ink of any of examples 37 or 38 or any of examples 25-47, wherein the carbonaceous material is one of: carbon, graphite, carbon black, activated carbon, graphene, or carbon nanotubes.
Example 40 includes the printable ink of any of examples 37 or 38 or any of examples 25-47, wherein the metal is one of: platinum, gold, silver, zinc, nickel, tin, iron, manganese, magnesium, aluminum, copper, bismuth, indium, lithium, sodium, lead, or titanium.
Example 41 includes the printable ink of any of examples 37 or 38 or any of examples 25-47, wherein the metal oxide is one of: zinc oxide, silver (I) oxide, silver (I, III) oxide, manganese (II) oxide, manganese (IV) oxide, bismuth (III) oxide, lead (II) oxide, lead (II, IV) oxide, titanium (IV) oxide, vanadium (III) oxide, vanadium (IV) oxide, vanadium (V) oxide, lithium (I) oxide, magnesium oxide, copper (I) oxide, copper (II) oxide, indium (III) oxide, tin (II) oxide, tin (IV) oxide, lead (II) oxide, iron (II) oxide, or iron (III) oxide.
Example 42 includes the printable ink of any of examples 37 or 38 or any of examples 25-47, wherein the metal salt is one of: a fluoride, a chloride, a bromide, an iodide, an acetate, a nitrate, a sulfate, a carbonate persulfate, a permanganate, a hydroxide, an oxyhydroxide, or a sulfonate.
Example 43 includes the printable ink of any of examples 37 or 38 or any of examples 25-47, wherein the polymer is one of: polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polystyrene, polystyrene sulfonate, polymethacrylate, a polystyrene block copolymer, polyethylene vinyl acetate, polyurethane, polyvinylidene fluoride, tetrafluoro ethylene, polyvinylpyrrolidone, or polypropylene oxide.
Example 44 includes the printable ink of any of examples 37 or 38 or any of examples 25-47, wherein the surfactant is one of: sodium dodecyl sulfate, dodecyl benzene sodium sulfonate, or perfluorooctanesulfonate.
Example 45 includes the printable ink of any of examples 37 or 38 or any of examples 25-47, wherein the saccharide, or the saccharide derivative is one of: glucose, sucrose, cellulose, methylcellulose, maltodextrin methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, or carboxymethyl cellulose.
Example 46 includes the printable ink of any of examples 25-47, wherein the ink is a printable or casting-compatible ink or slurry.
Example 47 includes the printable ink of example 46 or any of examples 25-46, wherein the ink is configured to be deposited via one of: inkjet printing, screen-printing, stencil printing, dip coating, spray coating, drop casting, 3D printing, injection molding, stamping, transfer printing, or water transfer printing.
In some embodiments in accordance with the present technology (example 48), a chemical-resistant flexible composite for electrochemical cells includes a plurality of particles; and a copolymer comprising atoms of a halogen element, wherein the copolymer is an elastomer, and wherein the copolymer is configured to confine the plurality of particles within a structure formed by the copolymer, wherein the copolymer and the plurality of particles form an elastic polymer-particle composite.
In some embodiments in accordance with the present technology (example 49), a printable ink for chemical-resistant flexible electronics components includes a matrix including an organic solvent and a copolymer comprising a halogen chemical element in its structure, wherein the copolymer is dissolved in the organic solvent, and wherein the copolymer is an elastomer; and a plurality of particles contained within the matrix, wherein the organic solvent is capable of vaporizing from the matrix such that the printable ink forms an elastic polymer-particle composite upon removal of at least a part of the organic solvent from the printable ink, and wherein the copolymer is configured to confine the plurality of particles within the formed composite.
In some embodiments in accordance with the present technology (example 50), a flexible battery includes a composite material, comprising: a plurality of particles; and a polymer comprising fluorine, wherein the polymer is an elastomer, wherein the polymer is configured to confine the plurality of particles within a structure formed by the polymer, and wherein the polymer and the plurality of particles form an elastic polymer-particle composite.
In some embodiments in accordance with the present technology (example 51), a flexible battery includes an anode, comprising a first layer of a first elastic composite material including a plurality of Zn particles and a first fluorine-containing polymer confining the plurality of Zn particles within the first layer; a cathode, comprising a second layer of a second elastic composite material including a plurality of AgO particles and a second fluorine-incorporating polymer confining the plurality of AgO particles within the second layer; and a layer of a hydrogel electrolyte disposed between the anode and the cathode.
Example 52 includes the battery of any of examples 51-58, wherein the first fluorine-containing polymer and the second fluorine-containing polymer are the same fluorine-containing polymer.
Example 53 includes the battery of any of examples 51-58, wherein the Zn particles are coated with a Bi2O3 powder.
Example 54 includes the battery of any of examples 51-58, comprising a layer of a first separator material disposed between the anode and the layer of the hydrogel electrolyte.
Example 55 includes the battery of any of example 54 or examples 51-58, wherein the first separator material includes TiO2.
Example 56 includes the battery of any of examples 51-58, comprising a layer of a second separator material disposed between the cathode and the layer of the hydrogel electrolyte.
Example 57 includes the battery of example 56 or any of examples 51-58, wherein the second separator material includes cellulose.
Example 58 includes the battery of any of examples 51-58, wherein the hydrogel is a potassium hydroxide-poly(vinyl alcohol) hydrogel (KOH-PVA hydrogel).
In some embodiments in accordance with the present technology (example P1), a high pH-resistant elastomer binder includes a plurality of particles; and a polymer comprising fluorine-incorporated elastomeric copolymers that immobilize at least some of the plurality of particles and form an elastic polymer-particle composite.
Example P2 includes the binder of example P1, wherein the polymer is dissolvable in an organic solvent and capable of mixing with various types of materials to form flexible high-pH resist composite.
Example P3 includes the binder of example P2, wherein the dissolved polymer and the particles form a printable or casting-compatible ink or slurry.
Example P4 includes the binder of any of the preceding or subsequent examples P1-P8, wherein the polymer includes one or more of polyvinyl alcohol, polyacrylic acid, or polyethylene oxide.
Example P5 includes the binder of any of the preceding or subsequent examples P1-P8, wherein the fluorine-incorporated elastomeric copolymers include a combination of ethylene fluorinated with 0-4 fluorine atoms or propylene fluorinated with 0-6 fluorine atoms with a different degree of cross-linking and fluorination.
Example P6 includes the binder of any of the preceding or subsequent examples P1-P8, wherein the plurality of particles include one or more of graphite, carbon black, zinc, silver, copper, bismuth, the oxide of metals such as zinc oxide, silver (I) oxide, silver (I, III) oxide, bismuth (III) oxide, lead (II) oxide, titanium (IV) oxide, or other solid organic material powders such as cellulose, methylcellulose, and/or sucrose.
Example P7 includes the binder of any of the preceding or subsequent examples P1-P8, wherein the binder is included in a printed electrochemical and/or electronic device.
Example P8 includes the binder of any of example P7 or any of the preceding or subsequent examples P1-P7, wherein the printed electrochemical and/or electronic device includes a supercapacitor, electrochromic cell, sensor, circuit interconnection, thin-film transistor, battery, or touch screen.
An aspect of the disclosed embodiments relates to a chemical-resistant flexible composite for electrochemical cells, comprising: a plurality of particles; and a polymer comprising fluorine, wherein the polymer is an elastomer, and wherein the polymer is configured to confine the plurality of particles within a structure formed by the polymer, wherein the polymer and the plurality of particles form an elastic polymer-particle composite.
In some example embodiments of the chemical-resistant flexible composite for electrochemical cells, the polymer is a copolymer. According to some example embodiments, the copolymer is one of: a bipolymer, a terpolymer, or a quaterpolymer. In certain example embodiments, the copolymer comprises chlorine. In an example embodiment, the copolymer comprises bromine. In another example embodiment, the copolymer comprises iodine. In yet another example embodiment, the polymer is dissolvable in an organic solvent. According to certain example embodiments, the polymer is a copolymer including a combination of ethylene monomers fluorinated with between 0 and 4 fluorine atoms and/or propylene monomers fluorinated with between 0 and 6 fluorine atoms. In some example embodiments, monomers of the polymer include at least one of: vinylidene fluoride, tetrafluoropropylene, tetrafluoroethylene, hexafluoropropylene, ethylene tetrafluoroethylene, chlorotrifluoroethylene, perfluoro alkoxy alkane, or perfluoromethylvinylether. According to some example embodiments, the plurality of particles includes at least one of: a carbonaceous material, a metal, a metal oxide, a metal salt, metal flakes, nanoparticles, nanowires, nanorods, nanotubes, a powder, a polymer, a surfactant, a saccharide, or a saccharide derivative. In certain example embodiments, particles in the plurality of particles include a coating layer of a coating material. In some example embodiments, the coating material includes at least one of: a carbonaceous material, a metal, a metal oxide, a metal salt, a polymer, a surfactant, a saccharide, or a saccharide derivative. According to certain example embodiments, the carbonaceous material is one of: carbon, graphite, carbon black, activated carbon, graphene, or carbon nanotubes. In some example embodiments, the metal is one of: platinum, gold, silver, zinc, nickel, tin, iron, manganese, magnesium, aluminum, copper, bismuth, indium, lithium, sodium, lead, or titanium. In certain example embodiments, the metal oxide is one of: zinc oxide, silver (I) oxide, silver (I, III) oxide, manganese (II) oxide, manganese (IV) oxide, bismuth (III) oxide, lead (II) oxide, lead (II, IV) oxide, titanium (IV) oxide, vanadium (III) oxide, vanadium (IV) oxide, vanadium (V) oxide, lithium (I) oxide, magnesium oxide, copper (I) oxide, copper (II) oxide, indium (III) oxide, tin (II) oxide, tin (IV) oxide, lead (II) oxide, iron (II) oxide, or iron (III) oxide. According to some example embodiments, the metal salt is one of: a fluoride, a chloride, a bromide, an iodide, an acetate, a nitrate, a sulfate, a carbonate persulfate, a permanganate, a hydroxide, an oxyhydroxide, or a sulfonate. In some example embodiments, the polymer is one of: polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polystyrene, polystyrene sulfonate, polymethacrylate, a polystyrene block copolymer, polyethylene vinyl acetate, polyurethane, polyvinylidene fluoride, tetrafluoro ethylene, polyvinylpyrrolidone, or polypropylene oxide. In certain example embodiments, the surfactant is one of: sodium dodecyl sulfate, dodecyl benzene sodium sulfonate, or perfluorooctanesulfonate. According to some example embodiments, the saccharide, or the saccharide derivative is one of: glucose, sucrose, cellulose, methylcellulose, maltodextrin methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, or carboxymethyl cellulose. In some example embodiments, a chemical resistance of the polymer includes a resistance to: a pH above 10, a pH below 4, or a salinity above 2M. In certain example embodiments, a chemical resistance of the polymer includes a resistance to: a pH above 14, a pH below 1, or a salinity above 5M. According to some example embodiments, the composite is structured to be mechanically self-supporting. In some example embodiments, the composite is included in an electrochemical and/or electronic device. In certain example embodiments, the electrochemical and/or electronic device is one of: a fuel cell, a supercapacitor, an electrochromic cell, an electrochemical sensor, a circuit interconnector, a transistor, a battery, a solar cell, or a touch screen.
Another aspect of the disclosed embodiments relates to a printable ink for chemical-resistant flexible electronics components, comprising: a matrix including an organic solvent and a polymer comprising fluorine, wherein the polymer is dissolved in the organic solvent, and wherein the polymer is an elastomer; and a plurality of particles contained within the matrix, wherein the organic solvent is capable of vaporizing from the matrix such that the printable ink forms an elastic polymer-particle composite upon removal of at least a part of the organic solvent from the printable ink, and wherein the polymer is configured to confine the plurality of particles within the formed composite.
In some example embodiments of the ink for chemical-resistant flexible electronics components, the polymer is a copolymer. According to some example embodiments, the copolymer is one of: a bipolymer, a terpolymer or a quaterpolymer. In an example embodiment, the copolymer comprises chlorine. In another example embodiment, the copolymer comprises bromine. In yet another example embodiment, the copolymer comprises iodine. In some example embodiments, the organic solvent includes a ketone. In certain example embodiments, the ketone is one of: acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, acetophenone, or benzophenone. According to some example embodiments, the organic solvent includes an ester. In some example embodiments, the ester is one of: methyl formate, methyl acetate, ethyl acetate, ethyl propionate, isopropyl butyrate, or ethyl benzoate. According to certain example embodiments, the polymer is a copolymer including a combination of ethylene monomers fluorinated with between 0 and 4 fluorine atoms and/or propylene monomers fluorinated with between 0 and 6 fluorine atoms. In some example embodiments, monomers of the polymer include at least one of: vinylidene fluoride, tetrafluoropropylene, tetrafluoroethylene, hexafluoropropylene, ethylene tetrafluoroethylene, chlorotrifluoroethylene, perfluoro alkoxy alkane, or perfluoromethylvinylether. According to some example embodiments, the plurality of particles includes at least one of: a carbonaceous material, a metal, a metal oxide, a metal salt, metal flakes, nanoparticles, nanowires, nanorods, nanotubes, a powder, a polymer, a surfactant, a saccharide, or a saccharide derivative. In some example embodiments, the ink includes at least one of: a carbonaceous material, a metal, a metal oxide, a metal salt, a polymer, a surfactant, a saccharide, or a saccharide derivative. In certain example embodiments, the carbonaceous material is one of: carbon, graphite, carbon black, activated carbon, graphene, or carbon nanotubes. According to certain example embodiments, the metal is one of: platinum, gold, silver, zinc, nickel, tin, iron, manganese, magnesium, aluminum, copper, bismuth, indium, lithium, sodium, lead, or titanium. In some example embodiments, the metal oxide is one of: zinc oxide, silver (I) oxide, silver (I, III) oxide, manganese (II) oxide, manganese (IV) oxide, bismuth (III) oxide, lead (II) oxide, lead (II, IV) oxide, titanium (IV) oxide, vanadium (III) oxide, vanadium (IV) oxide, vanadium (V) oxide, lithium (I) oxide, magnesium oxide, copper (I) oxide, copper (II) oxide, indium (III) oxide, tin (II) oxide, tin (IV) oxide, lead (II) oxide, iron (II) oxide, or iron (III) oxide. According to some example embodiments, the metal salt is one of: a fluoride, a chloride, a bromide, an iodide, an acetate, a nitrate, a sulfate, a carbonate persulfate, a permanganate, a hydroxide, an oxyhydroxide, or a sulfonate. In some example embodiments, the polymer is one of: polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polystyrene, polystyrene sulfonate, polymethacrylate, a polystyrene block copolymer, polyethylene vinyl acetate, polyurethane, polyvinylidene fluoride, tetrafluoro ethylene, polyvinylpyrrolidone, or polypropylene oxide. In certain example embodiments, the surfactant is one of: sodium dodecyl sulfate, dodecyl benzene sodium sulfonate, or perfluorooctanesulfonate. In some example embodiments, the saccharide, or the saccharide derivative is one of: glucose, sucrose, cellulose, methylcellulose, maltodextrin methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, or carboxymethyl cellulose. According to some example embodiments, the ink is a printable or casting-compatible ink or slurry. In some example embodiments, the ink is configured to be deposited via one of: inkjet printing, screen-printing, stencil printing, dip coating, spray coating, drop casting, 3D printing, injection molding, stamping, transfer printing, or water transfer printing.
Yet another aspect of the disclosed embodiments relates to a chemical-resistant flexible composite for electrochemical cells, comprising: a plurality of particles; and a copolymer comprising atoms of a halogen element, wherein the copolymer is an elastomer, and wherein the copolymer is configured to confine the plurality of particles within a structure formed by the copolymer, wherein the copolymer and the plurality of particles form an elastic polymer-particle composite.
An aspect of the disclosed embodiments relates to a printable ink for chemical-resistant flexible electronics components, comprising: a matrix including an organic solvent and a copolymer comprising a halogen chemical element in its structure, wherein the copolymer is dissolved in the organic solvent, and wherein the copolymer is an elastomer; and a plurality of particles contained within the matrix, wherein the organic solvent is capable of vaporizing from the matrix such that the printable ink forms an elastic polymer-particle composite upon removal of at least a part of the organic solvent from the printable ink, and wherein the copolymer is configured to confine the plurality of particles within the formed composite.
Another aspect of the disclosed embodiments relates to a flexible battery, comprising a composite material, comprising: a plurality of particles; and a polymer comprising fluorine, wherein the polymer is an elastomer, wherein the polymer is configured to confine the plurality of particles within a structure formed by the polymer, and wherein the polymer and the plurality of particles form an elastic polymer-particle composite.
Yet another aspect of the disclosed embodiments relates to a flexible battery, comprising: an anode, comprising a first layer of a first elastic composite material including a plurality of Zn particles and a first fluorine-containing polymer confining the plurality of Zn particles within the first layer; a cathode, comprising a second layer of a second elastic composite material including a plurality of AgO particles and a second fluorine-incorporating polymer confining the plurality of AgO particles within the second layer; and a layer of a hydrogel electrolyte disposed between the anode and the cathode.
In some example embodiments of the flexible battery, the first fluorine-containing polymer and the second fluorine-containing polymer are the same fluorine-containing polymer. According to some example embodiments, the Zn particles are coated with a Bi2O3 powder. In certain example embodiments, the flexible battery includes a layer of a first separator material disposed between the anode and the layer of the hydrogel electrolyte. In some example embodiments, the first separator material includes TiO2. According to certain example embodiments, the flexible battery includes a layer of a second separator material disposed between the cathode and the layer of the hydrogel electrolyte. In some example embodiments, the second separator material includes cellulose. According to some example embodiments, the hydrogel is a potassium hydroxide-poly(vinyl alcohol) hydrogel (KOH-PVA hydrogel).
Implementations of the subject matter and the functional operations described in this patent document can be implemented in various systems, digital electronic circuitry, or in computer software, firmware, or hardware, including the structures disclosed in this specification and their structural equivalents, or in combinations of one or more of them. Implementations of the subject matter described in this specification can be implemented as one or more computer program products, i.e., one or more modules of computer program instructions encoded on a tangible and non-transitory computer readable medium for execution by, or to control the operation of, data processing apparatus. The computer readable medium can be a machine-readable storage device, a machine-readable storage substrate, a memory device, a composition of matter effecting a machine-readable propagated signal, or a combination of one or more of them. The term “data processing unit” or “data processing apparatus” encompasses all apparatus, devices, and machines for processing data, including by way of example a programmable processor, a computer, or multiple processors or computers. The apparatus can include, in addition to hardware, code that creates an execution environment for the computer program in question, e.g., code that constitutes processor firmware, a protocol stack, a database management system, an operating system, or a combination of one or more of them.
A computer program (also known as a program, software, software application, script, or code) can be written in any form of programming language, including compiled or interpreted languages, and it can be deployed in any form, including as a stand-alone program or as a module, component, subroutine, or other unit suitable for use in a computing environment. A computer program does not necessarily correspond to a file in a file system. A program can be stored in a portion of a file that holds other programs or data (e.g., one or more scripts stored in a markup language document), in a single file dedicated to the program in question, or in multiple coordinated files (e.g., files that store one or more modules, sub programs, or portions of code). A computer program can be deployed to be executed on one computer or on multiple computers that are located at one site or distributed across multiple sites and interconnected by a communication network.
The processes and logic flows described in this specification can be performed by one or more programmable processors executing one or more computer programs to perform functions by operating on input data and generating output. The processes and logic flows can also be performed by, and apparatus can also be implemented as, special purpose logic circuitry, e.g., an FPGA (field programmable gate array) or an ASIC (application specific integrated circuit).
Processors suitable for the execution of a computer program include, by way of example, both general and special purpose microprocessors, and any one or more processors of any kind of digital computer. Generally, a processor will receive instructions and data from a read only memory or a random access memory or both. The essential elements of a computer are a processor for performing instructions and one or more memory devices for storing instructions and data. Generally, a computer will also include, or be operatively coupled to receive data from or transfer data to, or both, one or more mass storage devices for storing data, e.g., magnetic, magneto optical disks, or optical disks. However, a computer need not have such devices. Computer readable media suitable for storing computer program instructions and data include all forms of nonvolatile memory, media and memory devices, including by way of example semiconductor memory devices, e.g., EPROM, EEPROM, and flash memory devices. The processor and the memory can be supplemented by, or incorporated in, special purpose logic circuitry.
It is intended that the specification, together with the drawings, be considered exemplary only, where exemplary means an example. As used herein, the singular forms“a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Additionally, the use of “or” is intended to include “and/or”, unless the context clearly indicates otherwise.
While this patent document contains many specifics, these should not be construed as limitations on the scope of any invention or of what may be claimed, but rather as descriptions of features that may be specific to particular embodiments of particular inventions. Certain features that are described in this patent document in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a sub combination or variation of a subcombination.
Similarly, while operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. Moreover, the separation of various system components in the embodiments described in this patent document should not be understood as requiring such separation in all embodiments.
Only a few implementations and examples are described and other implementations, enhancements and variations can be made based on what is described and illustrated in this patent document.
This patent document claims priority to and the benefits of the U.S. Provisional Patent Application No. 63/066,609, titled “HIGH-pH RESISTANT ELASTOMER BINDER FOR FLEXIBLE ELECTRONICS,” filed on Aug. 17, 2020. The entire contents of the aforementioned patent application are incorporated by reference as part of the disclosure of this patent document.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2021/046179 | 8/16/2021 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63066609 | Aug 2020 | US |
