Monolithic electrode assembly having three-dimensional channels usable with ion exchange material - Patent Application 20070122997

Abstract

The rechargeable battery cell can include an electrode having a plurality of three-dimensional channels defined therethrough, at least 90% of the three-dimensional channels having pores between 50 nanometers and 400 microns in size. An ion exchange material can be disposed to define an interface with at least a portion of the electrode. In some embodiments, the electrode includes a zinc (Zn)-containing anode and a cathode including at least one of nickel hydroxide (Ni(OH)2), nickel oxyhydroxide (NiOOH), manganese dioxide (MnO2), copper oxide, and bismuth oxide.

Description

[Technical Field]

[0001] (Related Applications) This application claims the benefit of U.S. Provisional Application No. 63 / 413,086, filed October 4, 2022, which is incorporated herein by reference in its entirety for all purposes.

[0002] (Technical field) The present disclosure relates generally to the field of batteries and battery components. More specifically, the present application relates to batteries or cells including ion exchange materials and electrodes having three-dimensional channels. [Background technology]

[0003] There is an increasing demand for high-energy density, low-cost rechargeable battery systems for portable devices, electric vehicles, grid storage, and other applications. Recently, lithium-ion batteries have emerged as a popular technology of choice for many energy storage applications. Unfortunately, the limited availability of key metals, high energy costs, and safety risks associated with lithium-ion technology limit the widespread adoption of batteries in many applications.

[0004] As an alternative, Zn-based batteries using aqueous electrolytes have been used, which have many potential applications due to their low cost and relative safety. Summary of the Invention

[0005] In one embodiment, a rechargeable battery cell includes an electrode incorporating three-dimensional channels and formed from a zinc-containing material. Additionally, an ion exchange material is disposed to define an interface in contact with at least a portion of the electrode. Providing the interface can include fully or partially embedding the electrode in the ion exchange material, or alternatively, surrounding the electrode or individual portions of the electrode with a thin film of ion exchange material. In one embodiment, the electrode can be a highly porous, monolithic, sponge-like structure having pore sizes ranging from 50 nm to 400 microns. The electrode can be coated with the ion exchange material or disposed in partial contact with the ion exchange material.

[0006] In some embodiments, the ion exchange material can comprise either an anion exchange material or a cation exchange material. The ion exchange material can comprise a polymeric material having attached charged functional groups.

[0007] In some embodiments, a liquid alkaline electrolyte contacts the electrodes to enable ion transport. Optionally, the electrolyte may incorporate at least an ion exchange material.

[0008] In one embodiment, a rechargeable battery cell can include electrodes in contact with or containing embedded ion exchange material.

[0009] In one embodiment, a method for manufacturing a rechargeable battery cell can include fusing a plurality of particles into a monolithic electrode having a plurality of three-dimensional channels defined therethrough, at least 90% of the three-dimensional channels having pores between 50 nanometers and 400 microns in size, and contacting the monolithic electrode with an ion exchange material. In some embodiments, the manufacturing can include contacting the monolithic electrode with the ion exchange material and contacting the monolithic electrode with a liquid electrolyte that is drawn by capillary forces into the three-dimensional channels defined therethrough.

[0010] In some embodiments, fabrication can include assembling a monolithic electrode with a liquid-phase polymer membrane solution that is drawn by capillary forces into a three-dimensional channel defined therethrough. After drying, the deposited polymer layer becomes the ion-exchange membrane coating of the sponge electrode.

[0011] In some embodiments, the current collector of the sponge electrode includes, but is not limited to, at least one of a metal conductive mesh, wire, or foil that is placed within the electrode body prior to high temperature fusing.

[0012] Non-limiting and non-exhaustive embodiments of the present disclosure are described with reference to the following figures, in which like reference numerals refer to like parts throughout the various views unless otherwise specified. [Brief explanation of the drawings]

[0013] [Figure 1] 1 shows a battery including an ion exchange material in contact with an electrode material. DETAILED DESCRIPTION OF THE INVENTION

[0014] (Detailed Description of the Invention) This disclosure relates in part to battery cells with improved cycle life and electrical performance during use. For example, the cells may exhibit higher battery discharge voltages, higher discharge capacities, lower internal resistance, and high-rate discharge capabilities. In some embodiments, the disclosed battery cells have long cycle lives at high-rate discharge currents.

[0015] 1 shows a rechargeable battery cell system 100 that includes a case 102 that encloses various battery components. The battery components can include current collectors 110 and 112 that facilitate charging and discharging the battery cell system 100. Other components include electrode materials 120 and 122 that contact the current collectors 110 and 112, respectively. The current collectors 110 and 112 can be fully (as shown) or partially embedded in the electrode material 120 or 122. In some embodiments, the current collectors can be attached to one or more surfaces of either or both of the electrode materials 120 or 122.

[0016] In one embodiment, the electrode material can include multiple interconnected three-dimensional channels that form a highly porous, monolithic, sponge-like structure with pore sizes ranging from 50 nm to 400 microns. Alternatively or additionally, the electrode can be fabricated as a metal foam, a three-dimensional lattice network, with internal voids connected to external pores, or a "tangled" or disordered channel structure. In some embodiments, the three-dimensional channels can have a regular or ordered layout. Advantageously, in some embodiments, the combination of a fully metal sponge network with an embedded current collector and numerous interconnected three-dimensional channels or voids provides an ideal electronic environment that enhances electrode functionality, including improved current distribution, mitigated dendrite formation, and access to the electrolyte. Furthermore, in some embodiments, the combination of a Zn conductive network, current collector, and three-dimensional channels or voids with pore sizes ranging from 50 nm to 200 microns results in very strong capillary action. Rather than requiring prolonged immersion or the use of a vacuum system to draw the electrolyte and / or ionic liquid material into the three-dimensional channels, the liquid electrolyte is drawn into the electrodes by capillary forces.

[0017] The electrode materials 120 and 122 may be separated from each other by a separator 130 that only allows the flow of ions between the materials. The rechargeable battery cell system 100 may include an anode, a cathode, an ion exchange material, and other materials and components, as described below.

[0018] (electrode) The electrode material can include a solid, interconnected pore structure, including, but not limited to, multiple interconnected three-dimensional channels within the electrode material that form a highly porous, rigid, monolithic, and / or sponge-like structure. In some embodiments, all or a portion of the electrode can be formed as a thin film or a structured pattern, such as pillars, needles, grooves, or slots. In some embodiments, the electrode can be a loosely arranged material, a tightly bonded structure, or a sintered structure. In one embodiment, the electrode can be formed from particles provided in various forms, such as powders, granules, pellets, or nanomaterials. In certain embodiments, the average size (diameter or longest dimension) of the particles is between about 0.1 μm and 300 μm, and in certain embodiments, between about 1 μm and 100 μm. In some embodiments, relatively uniform particle sizes can be used, while in other embodiments, non-uniformly sized materials can be used. Particles can be treated to increase the effective surface area. In some embodiments, the particles can be treated by heating, melting, fusing, or sintering the particles to bond them together. In other embodiments, an additional binder may be used to hold the particles together.

[0019] (current collector) At least a portion of the electrode material may be embedded in or disposed in contact with a current collector. The current collector serves to supply current so that it can be consumed in the electrode reaction during charging and to collect the current generated during discharge. The current collector is typically formed from a material that has high electrical conductivity and is inert to the electrochemical cell reaction. The current collector may be formed in the form of a plate, foil, mesh, porous sponge, punched or slit metal, or expanded metal.

[0020] Current collector materials include Ni, Ti, Cu, Al, Pt, V, Au, Zn, and alloys of two or more of these metals, such as stainless steel. In other embodiments, graphite cloth, copper sheet, or meshed slotted woven brass can be used.

[0021] (anode material) Anode materials for the electrodes include a wide range of materials, including zinc, aluminum, magnesium, iron, lithium, and other metals in pure oxide or salt form, or combinations thereof. In some embodiments, relatively pure Zn, ZnO, or a mixture of Zn and ZnO can be used. For rechargeable zinc negative electrodes, the electrochemically active material can be made from zinc oxide powder or a mixture of zinc and zinc oxide powder. Zinc oxide can be dissolved in an alkaline electrolyte to form zincate (Zn(OH)4 2- ) can be formed. Zinc oxide or zincate is reduced to zinc metal during the charging process.

[0022] More broadly, the anode material can include:

[0023] Any metal M, metal oxide MOx, or metal salt having a redox potential E0 lower than the redox potential of the cathode material.

[0024] Any metal oxide MOx having a standard potential E0 lower than the redox potential of the cathode material.

[0025] Any alloy, mixed oxide, or mixed salt of any metal M, M, M, M, Mn having an E0 lower than that of the cathode material.

[0026] Any polymer that can incorporate anions into its structure and has a redox potential E0 lower than that of the cathode material.

[0027] Any mixture of one or more of the above types of materials.

[0028] (cathode material) As a cathode material for the electrode, Fe 6+ , Mn 7+ The range of materials includes metals or metal-containing compounds such as nickel hydroxide Ni(OH)2, nickel oxyhydroxide NiOOH, manganese dioxide MnO2, copper oxide, bismuth oxide, or any combination thereof.

[0029] More broadly, the cathode material can include:

[0030] Any metal M having a redox potential E0 greater than the redox potential of the anode material.

[0031] Any metal oxide MOx with a redox potential E0 greater than the redox potential of the anode material.

[0032] Any alloy of metal Mm1M2...Mn having an E0 greater than that of the anode material.

[0033] Any metal fluoride MFn that has a redox potential greater than that of the anode material.

[0034] Any alloy MM1M2...MnOxFm where n is 2 or greater and m is 0 or greater.

[0035] Any polymer that can incorporate anions into its structure and has a redox potential E0 greater than the redox potential of the anode material.

[0036] CFx fluorocarbons where x is between 0 and 2.

[0037] Unstable salts that are not stable in aqueous electrolyte solutions, including but not limited to FeVI (iron hexavalent) based battery systems.

[0038] Any mixture of one or more of the above types of materials.

[0039] (additives and binders) Various additives can be used to improve the electrochemical, electrical, or mechanical properties of electrodes. For example, electrochemical performance can be improved by adding cathode materials containing nickel, nickel hydroxide, nickel oxyhydroxide, or nickel oxide. These cathode materials can incorporate or be coated with small amounts of cobalt oxide, strontium hydroxide (Sr(OH)2), barium oxide (BaO), calcium hydroxide (Ca(OH)2), Fe3O4, calcium fluoride (CaF2), or yttrium oxide (YO3) to improve battery cell performance. As another example, electrodes can include oxides such as bismuth oxide, indium oxide, and / or aluminum oxide. Bismuth oxide and indium oxide may interact with zinc and reduce gassing at the electrode. Bismuth oxide can be provided at a concentration of approximately 1 to 10% by weight of the dry anode formulation. Indium oxide may be present at a concentration of approximately 0.05 to 1% by weight of the dry anode formulation. Aluminum oxide may be provided at a concentration of about 1-5% by weight of the dry negative electrode formulation.

[0040] In certain embodiments, one or more additives may be included to improve the corrosion resistance of the zinc electrode material. Specific examples of anions that may be included to reduce the solubility of zinc in the electrolyte include phosphate, fluoride, borate, zincate, silicate, or stearate. Generally, these anions may be present in the electrode at a concentration of up to about 10% by weight of the dry electrode formulation.

[0041] Additives that improve electrical properties such as conductivity can also be added. For example, various carbonaceous materials can be used as electrode additives, including powdered or fibrous carbon such as graphite, coke, ketjen black, and acetylene black. Carbonaceous nanomaterials such as single-walled or multi-walled carbon nanotubes, carbon nanofibers, multi-walled carbon nanoparticles, carbon nanowhiskers, or carbon nanorods can also be used.

[0042] The additives may be provided as chemically homogeneous components in a mixture or solution, co-precipitated, or coated onto particles.

[0043] In one embodiment, the addition of a binder can improve the mechanical properties, increase the mechanical strength of the electrode, and reduce bending and cracking of the electrode. Examples of binders include polymeric materials such as polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polyisobutylene (PIB), polyvinyl alcohol (PVA), polyacrylic acid, polyvinyl acetate, carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), polyethylene oxide (PEO), polybutylene terephthalate (PBT), or silicone-based elastomers such as polyamide, polyvinylidene fluoride (PVDF), polydimethylsiloxane (PDMS), or rubber materials such as natural rubber (NR), ethylene propylene rubber (EPM), and ethylene propylene diene.

[0044] (ion exchange material) Ion exchange materials are generally selective for the transport of either cations or anions. Anion-selective ion exchange materials can be used alone, cation-selective ion exchange materials can be used alone, or they can be used in combination with each other. In one embodiment, the ion exchange material can be an organic or polymeric material having attached strong acidic groups, such as sodium polystyrene sulfonate or sulfonic acids, including polyAMPS. Alternatively, the ion exchange material can be an organic or polymeric material having attached strong basic groups, such as quaternary amino groups containing trimethylammonium groups (e.g., polyAPTAC). In another embodiment, the ion exchange material can be an organic or polymeric material having attached weakly acidic groups, including carboxylic acid groups. Alternatively, the ion exchange material can be an organic or polymeric material having attached weakly basic groups, typically characterized by primary, secondary, and / or tertiary amino groups (e.g., polyethyleneamine).

[0045] The ion exchange can be provided to interact with the electrode material as a fully or partially embedded polymer, particle mixture, membrane or film, microparticles or beads, or coating. Only the anode, only the cathode, or both the anode and cathode can be configured to interact with the ion exchange material, which can be the same or different materials for each electrode.

[0046] (electrolyte) An electrolyte is used to maintain high ionic conductivity between the electrodes. The electrolyte can be aqueous-based, solvent-based, a solid polymer, or an ionic liquid. In some embodiments, the electrolyte can be semi-solid or gelled. Gelling agents can include polymers that absorb the liquid of the electrolyte solution and swell. Such polymers include polyethylene oxide, polyvinyl alcohol, and polyacrylamide.

[0047] In another embodiment, the electrolyte can be a solid electrolyte. In another embodiment, the electrolyte can be formed as a solid material that has absorbed water, for example, KOH exposed to moist air.

[0048] In another embodiment, the electrolyte may be formed from an ion exchange material, such as those described above in the "Ion Exchange Material" section.

[0049] In one embodiment, an aqueous alkaline electrolyte may be used, including alkalis such as potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, or inorganic salts such as zinc bromide.

[0050] (separator) The separator may be replaced with (or used in combination with) an ion exchange membrane or film. Conventional porous polymer separators or ion exchange separators can be provided as polymer membranes or films. Typically, the separator is disposed between the anode and cathode and serves to prevent electrical short circuits between the anode and cathode. Furthermore, the separator can also serve to retain the electrolyte, particularly in battery systems using different cathode and anode electrolyte solutions. Separators are generally required to have a porous structure or a structure with numerous perforations that allows ions to pass through while being chemically stable to the electrolyte solution. In some embodiments, one or more separators can be formed by coating the electrodes or particles that make up the electrodes. Separators can be formed from a nonwoven fabric or membrane with a microporous structure made of glass, polypropylene, polyethylene, resin, or polyamide. Alternatively, the separators can be formed from a metal oxide film or a resin film combined with a metal oxide, each having multiple perforations.

[0051] (process) In one embodiment, a dry mixing process can be performed, in which various anode and cathode materials, as well as additives and binders, are dry mixed together. Optional processing steps, such as heating, fusing, compressing, and melting the ion exchange material, can be performed before the mixture is placed in the battery case. In other embodiments, optional processing steps, such as heating, fusing, compressing, and melting the ion exchange material, can be performed after the mixture is placed in the battery case. A liquid electrolyte can be added before sealing the battery case.

[0052] According to other embodiments, a wet mixing process may be used instead, in which one or more solvents are added at the beginning or during the mixing process, or alternatively, one or more components may be used in the form of a dispersion or suspension. The solvent may be removed after the mixing process or at a later stage in the manufacturing process.

[0053] In other embodiments, various individual components may be manufactured using different methods. For example, some electrodes may be manufactured using a dry blending process, while portions of the electrodes may be manufactured using a wet process. According to yet other embodiments, it is possible to combine both dry and wet processes for different components. In still other embodiments, the electrodes may be formed into a monolithic block with three-dimensional channels or pores therethrough by particle sintering, drilling or subtractive manufacturing, additive manufacturing, chemical fusion, or the use of additional adhesives, epoxies, or binders.

[0054] (Battery and cell design) The battery cells of the present invention can have a variety of shapes and sizes. For example, coin-shaped, prismatic, pouch-shaped, or cylindrical cells can be used. Cylindrical cells of the present invention can have the diameter and length of conventional AAA, AA, A, C, or D cells. Depending on the application, custom cell designs can be used. For example, prismatic cell designs can be used for portable or vehicle applications, as well as various larger format cells used in various non-portable applications. Battery packs can be custom designed for specific tools or applications. Battery packs can include one or more battery cells and appropriate cases, contacts, and conductive wires to enable reliable charging and discharging in electrical devices. In some embodiments, electrodes can be sized to precisely fit within the case of conventional AAA, AA, A, C, or D cells, or other known or custom cell sizes. This involves fabricating and placing a monolithic anode containing zinc or zinc oxide and sized to precisely match the case. This includes, for example, bobbin-type AA cells. [Example]

[0055] [Example 1] In embodiments, zinc or zinc-containing materials can be formed into an electrode (in this case, an anode) with a plurality of three-dimensional channels that form a sponge-like structure. Suitable fabrication techniques are described in U.S. Pat. No. 9,802,254 (Rolison et al., Assignee: United States, Represented by the Secretary of the Navy), the disclosure of which is specifically incorporated herein by reference. In one embodiment, a zinc sponge-like structure that can function as an electrode can be formed by the following steps: forming an emulsion having zinc powder and a liquid phase; drying the emulsion to form a sponge; sintering the sponge in an inert atmosphere to form a sintered sponge; heating the sintered sponge in an oxidizing atmosphere to form an oxide sponge with zinc oxide on the surface of the oxide sponge; and heating the oxide sponge in an inert atmosphere at a temperature above the melting point of zinc.

[0056] In some embodiments, the zinc sponge-like structure comprises two co-continuous interpenetrating networks: one solid and containing zinc, and the other void. A porous zinc structure is provided, which may be in the form commonly referred to as a sponge. The zinc network may contain zinc both on the surface and in the interior of the network. That is, it may be entirely pure or nearly pure zinc, rather than a zinc-free porous substrate coated with zinc. The zinc network may also contain zinc oxide and / or zinc oxyhydroxide, which form on the surface when the electrode is discharged in the cell. The zinc network is a three-dimensional, fused, monolithic structure. An electrolyte containing an ion-exchange material can be introduced into this zinc sponge-like structure. Alternatively or additionally, the ion-exchange material may include a polymer, which can be used to define an interface with the zinc sponge-like structure.

[0057] In the foregoing description, reference is made to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration specific exemplary embodiments in which the disclosure may be practiced. These embodiments have been described in sufficient detail to enable those skilled in the art to practice the concepts disclosed herein, and it will be understood that modifications may be made to the various disclosed embodiments and other embodiments may be utilized without departing from the scope of the present disclosure. Accordingly, the foregoing detailed description is not to be construed in a limiting sense.

[0058] When the term "one embodiment," "an embodiment," "one example," or "an example" is used throughout this specification, it means that a particular feature, structure, or characteristic described in connection with that embodiment or example is included in at least one embodiment of the present disclosure. Thus, the appearances of the phrases "in one embodiment," "in an embodiment," "one example," or "example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, particular features, structures, databases, or characteristics may be combined in any suitable combinations and / or subcombinations in one or more embodiments or examples. Additionally, it should be understood that the figures provided herein are for illustrative purposes for persons skilled in the art, and that the drawings are not necessarily drawn to scale.

[0059] Numerous modifications and other embodiments of the invention will come to mind to one skilled in the art having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. It is understood, therefore, that the invention is not limited to the specific embodiments disclosed, and modifications and embodiments are intended to be included within the scope of the appended claims. It is also understood that other embodiments of the invention can be practiced in the absence of elements / steps not specifically disclosed herein.

Claims

1. A rechargeable battery cell, an electrode having a plurality of three-dimensional channels defined therethrough, at least 90% of the three-dimensional channels having pores sized between 50 nanometers and 400 microns; an ion exchange material disposed to define an interface with at least a portion of the electrode; including a rechargeable battery cell.

2. 10. The rechargeable battery cell of claim 1, wherein the electrode further comprises a zinc (Zn)-containing anode.

3. The electrode is made of nickel hydroxide (Ni(OH) ２ ), nickel oxyhydroxide (NiOOH), manganese dioxide (MnO ２ 10. The rechargeable battery cell of claim 1, wherein the cathode comprises at least one of copper oxide, copper oxide, and bismuth oxide.

4. 10. The rechargeable battery cell of claim 1, wherein the electrode has a monolithic structure.

5. 10. The rechargeable battery cell of claim 1, wherein the electrodes have a pore volume greater than 50%.

6. 10. The rechargeable battery cell of claim 1, wherein the three-dimensional channel has a branched sponge-like pore structure.

7. 10. The rechargeable battery cell of claim 1, wherein the ion exchange material further comprises an anion exchange material.

8. 10. The rechargeable battery cell of claim 1, wherein the ion exchange material further comprises a polymer material.

9. 10. The rechargeable battery cell of claim 1, wherein the ion exchange material further comprises a polymeric material having positively charged functional groups attached thereto.

10. 10. The rechargeable battery cell of claim 1, further comprising a liquid alkaline electrolyte.

11. 10. The rechargeable battery cell of claim 1, further comprising an electrolyte having at least an ion exchange material incorporated therein.

12. 10. The rechargeable battery cell of claim 1, further comprising an electrolyte that is a liquid, solid, or gel.

13. 10. The rechargeable battery cell of claim 1, further comprising an electrolyte that is a hygroscopic solid material that has absorbed water, selected from the list including KOH, NaOH, LiOH, or any combination thereof.

14. 10. The rechargeable battery cell of claim 1, further comprising a current collector at least partially embedded within the electrode.

15. 10. The rechargeable battery cell of claim 1, further comprising a current collector disposed in contact with the electrode and formed from at least one of Sn, Cu, Fe, stainless steel, Ni, and Co.

16. A method for manufacturing a rechargeable battery cell, comprising: Fusing a plurality of particles into a monolithic electrode, the electrode having a plurality of three-dimensional channels defined therethrough, at least 90% of the three-dimensional channels having pores between 50 nanometers and 400 microns in size; contacting the monolithic electrode with an ion exchange material; A method for manufacturing a rechargeable battery cell, comprising:

17. 17. The method of claim 16, wherein contacting the monolithic electrode with the ion exchange material further comprises at least one of melting, softening, depositing from the melt, laminating, and applying pressure.

18. 17. The method of claim 16, further comprising contacting the monolithic electrode with a liquid electrolyte, the liquid electrolyte being capable of being drawn by capillary forces into the three-dimensional channel defined therethrough.

19. 17. The method of claim 16, further comprising placing a monolithic anode comprising zinc (Zn) within the case, the monolithic anode being sized to precisely match the case.

20. 17. The method for manufacturing a rechargeable battery cell of claim 16, further comprising assembling the monolithic electrode with a liquid-phase polymer membrane solution, the solution being drawn by capillary forces into the three-dimensional channels defined therethrough, and drying the deposited polymer layer to form an ion exchange membrane coating on the monolithic electrode.

21. 17. The method of claim 16, further comprising embedding at least one of a metal conductive mesh, wire, and foil inside the monolithic electrode before high temperature fusion.

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