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WO2025184200A1 - Batteries zinc-dioxyde de manganèse à insertion de protons denses en énergie - Google Patents

Batteries zinc-dioxyde de manganèse à insertion de protons denses en énergie

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Publication number
WO2025184200A1
WO2025184200A1 PCT/US2025/017376 US2025017376W WO2025184200A1 WO 2025184200 A1 WO2025184200 A1 WO 2025184200A1 US 2025017376 W US2025017376 W US 2025017376W WO 2025184200 A1 WO2025184200 A1 WO 2025184200A1
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WIPO (PCT)
Prior art keywords
anode
cathode
active material
battery
batery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/017376
Other languages
English (en)
Inventor
Gautam G. YADAV
Jinchao Huang
Meir WEINER
Shinju YANG
Brendan HAWKINS
Kristen VITALE
Sanbir RAHMAN
Kevin Keane
Patrick Yang
Xia WEI
Alexander Couzis
Michael NYCE
Sanjoy Banerjee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Urban Electric Power Inc
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Urban Electric Power Inc
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Publication date
Application filed by Urban Electric Power Inc filed Critical Urban Electric Power Inc
Publication of WO2025184200A1 publication Critical patent/WO2025184200A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Manganese dioxide is a material used in many applications, and is mostly used in battery applications, such as lithium-ion and alkaline batteries. In organic electrolyte, ionic liquids and alkaline electrolyte, manganese dioxide exhibits a range of chemical reactions. For example, in alkaline electrolyte, manganese dioxides and its polymorphs undergo solid state proton insertion and dissolution-precipitation reactions. However, these reactions result in hausmannite and other inactive phase formation that kill the reversibility' of the manganese dioxide electrode.
  • Zinc is another material used in batteries. In alkaline electrolyte, it undergoes a direct dissolution-precipitation reaction. However, in delivering its theoretical capacity (820mAh/g) it undergoes side-reactions such as shape change (zinc redistribution due to dissolution-precipitation), passivation and dendrite formation that affect its long-term reversibility.
  • a rechargeable, proton-insertion battery can include a cathode, wherein the cathode comprises an active material comprises one or more manganese oxides, and at least one additive comprising one or more of titanium-based additives, one or more metal oxides, one or more hydroxides, or a combination thereof; an anode; a separator; and an electrolyte.
  • a rechargeable, proton-insertion battery can include a cathode, wherein the cathode comprises an active material comprises one or more manganese oxides, and at least one additive comprising a titanium compound, a nickel hydroxide, or a combination thereof, and wherein the cathode active material is further mixed with a conductive carbon comprising a graphite and a binder comprising a polytetrafluoroethylene; an anode, wherein the anode comprises an anode active material comprising zinc; a separator; and an electrolyte.
  • a coating process comprises: pre-mixing an anode materials mix between about 1 to about 120 minutes; drying at a temperature of between about 50 °C to about 350 °C; and calendaring the dried anode materials mix.
  • FIG. 2 depicts performance data of zinc
  • the performance data is depicted of two cells with different additives - nickel hydroxide [Ni(OH)2] and bismuth oxide (B12O3)- in the cathode.
  • the zinc formulation contains zinc oxide, calcium hydroxide, and bismuth oxide as the additives for each cell.
  • the terms “‘negative electrode” and “anode” are both used to mean “negative electrode.”
  • the terms “positive electrode” and “cathode” are both used to mean “positive electrode.”
  • Reference to an “electrode” alone can refer to the anode, cathode, or both.
  • Reference to the term “primary battery” e.g., “primary battery,” “primary electrochemical cell.” or “primary cell”, refers to a cell or battery’ that after a single discharge is disposed of and replaced.
  • the term “about” can mean approximately, and may be quantified as within one standard deviation of the measured value or within plus or minus 10%, 5%, or even 1% of the value modified by “about”.
  • Zinc (Zn)-manganese dioxide (MnCh) batteries suffer from rechargeability' issues in the proton-insertion one electron region because of volume expansion, lattice dilation and deleterious side-reactions from the Zn and MnCh electrodes.
  • additives used in the Zn and MnCh electrodes that addresses the aforementioned problems.
  • Titanium- based additives such as titanium dioxide, titanium nitride and titanium diboride, nickel hydroxide and bismuth oxide when added to the MnCh cathode and calcium hy droxide, calcium zincate, bismuth oxide and zinc oxide when added to the Zn anode are found to increase the energy density by increasing the utilization in the proton-insertion range and cycle life.
  • the starting manganese dioxide can include any of its polymorphs, which are used in a number of different battery’ chemistries.
  • the manganese dioxide can be S-MnCh, Z-MnCh. a-MnCh. P-MnCh, e-MnCh, and/or y-MnCh. electrolytic manganese dioxide, pyrolusite, ramsdellite, hollandite, romanechite, todorokite, lithiophorite, chalcophanite, sodium or potassium rich bimessite, cryptomelane, buserite, a combination or an intermediate phase of manganese dioxide.
  • the spinel variations of manganese dioxide can also be stable and reversible by the application of the disclosed methods.
  • a battery’ 10 has a housing 6, a cathode current collector 1, a cathode material 2, a separator 3, an anode current collector 4, and an anode material 5.
  • Figure 2 shows a prismatic battery arrangement. In another embodiment, the battery is a cylindrical battery. An electrolyte is dispersed in an open space throughout battery 10.
  • the cathode current collector 1 and cathode material 2 are collectively called either the cathode or the positive electrode.
  • the anode current collector 4 and anode material 5 can collectively be called either the anode or the negative electrode.
  • the housing 6 can generally be sealed, except that a vent may be present to prevent over-pressurization.
  • the cathode can comprise manganese dioxide as the electroactive active material.
  • the cathode can comprise between about 1 wt.% and about 95 wt.% active material, alternatively between about 1 wt.% and about 90 wt.% active material, or alternatively between about 50 wt.% and about 90 wt.% active material.
  • Bimessite or 5 phase of manganese dioxide can be used as the main electroactive component of the cathode. However, other phases or polymorphs could also be present at the same time or by itself.
  • the hydroxide forms of manganese and water intercalated structures of manganese dioxide can also be stabilized by the use of this method.
  • bimessite has a formula:
  • the bimessite may not have one or more of the sodium, calcium, or potassium ions present.
  • the structure of bimessite consists of a sheet-like structure with layers of MnOe octahedra formed as sheets. Layers of water can be present between the manganese dioxide sheets, though some or all of the water can be replaced by one or more other elements or compounds.
  • an electroactive material is one that participate in reactions within the cathode or anode to generate a voltage and current from the resulting battery'.
  • Other elements or additives may be present that may not participate in reactions (but may aid in the stabilization of various electroactive materials) under the conditions present, and such materials are considered non-electroactive materials.
  • Electrolytic manganese dioxide (EMD) or /-MnO2 can also be used as the main electroactive component of the cathode.
  • EMD has a defect in its crystal structure as it is composed of two other polymorphs, which are ramsdellite and pyrolusite.
  • the tunneled EMD structure allows for protons to be inserted and extracted during the charge and discharge operation of the cathode in the first electron region.
  • accessing greater than about 40% of the EMD’s capacity or inserting protons in its crystal structure results in the breakdown due to volume expansion and other side-reactions such as loss of Mn ions in the electrolyte due to formation of Mn 3+ , which is soluble in alkaline electrolyte.
  • Incorporating additives that limit volume expansion and limit Mn dissolution can help utilize >40% of the one electron capacity for long periods of time.
  • the method involves the single use or a combination use of metallic forms or compound forms of elements such as titanium, nickel, and bismuth in the cathode, and insoluble hydroxides, zincates, oxides such as calcium hydroxide, calcium zincate, bismuth oxide and zinc oxide in the anode.
  • metallic forms or compound forms of elements such as titanium, nickel, and bismuth in the cathode, and insoluble hydroxides, zincates, oxides such as calcium hydroxide, calcium zincate, bismuth oxide and zinc oxide in the anode.
  • These components can be used alone or in combination with other additives such as bismuth, copper, tin. lead, silver, cobalt, nickel, magnesium, aluminum, potassium, lithium, gold, antimony, iron and/or zinc.
  • An advantage that is realized by use of these components is the reversibility of the manganese dioxide material.
  • the additives can be inserted into the sheet structure of the bimessite using a charging-discharging process.
  • the metallic element(s) can be inserted into the layered structure of the bimessite through an intercalation reaction or process.
  • an element incorporated into the layered manganese dioxide structure refers to the presence of atoms, ions, or compounds incorporated into the sheet-like layers of the bimessite (e.g., between the manganese dioxide sheet layers and/or complexed with the manganese dioxide sheet layers or any intervening layers).
  • the manganese dioxide formed while reducing and oxidizing at any utilization of the theoretical 2 nd electron capacity 7 results in the layered or layered-like phase formation of manganese dioxide.
  • a number of different polymorphs of manganese dioxide exhibit layered characteristics. Bimessite, cryptomelane, buserite, lithiophorite, chalcophanite, etc. all exhibit layered characteristics. If lithium hydroxide is used, then lithiated manganese dioxide or lithiophorite can be formed.
  • the layered phases can interchange between the spinel phases as well and form compounds such as M Ch, ZnMmO-i. LiM Ch, AlMmC , CuMmCh, and/or MgMmC .
  • the complexity' of the manganese dioxide phase results in a number of polymorphs existing at any given time.
  • the use of the term bimessite herein encompasses all the layered phases that could be present and also its interchangeability with the spinel phases.
  • the one or more additives used in the cathode can comprise a bismuth compound.
  • the bismuth compound can be included into the manganese dioxide in the mixture as an inorganic or organic salt of bismuth (oxidation states 5, 4, 3, 2, or 1), as a bismuth oxide, or as bismuth metal (i.e. elemental bismuth).
  • the bismuth compound can be present at a concentration between about 1 - about 20 weight percent (wt.%).
  • inorganic bismuth compounds include bismuth chloride, bismuth bromide, bismuth fluoride, bismuth iodide, bismuth sulfate, bismuth nitrate, bismuth trichloride, bismuth citrate, bismuth telluride, bismuth selenide, bismuth subsalicylate, bismuth neodecanoate, bismuth carbonate, bismuth subgallate, bismuth strontium calcium copper oxide, bismuth acetate, bismuth trifluoromethanesulfonate, bismuth nitrate oxide, bismuth gallate hydrate, bismuth phosphate, bismuth cobalt zinc oxide, bismuth sulphite agar, bismuth oxychloride, bismuth aluminate hydrate, bismuth tungsten oxide, bismuth lead strontium calcium copper oxide, bismuth antimonide, bismuth antimony telluride, bismuth oxide
  • the one or more additives used in the cathode can comprise a titanium compound.
  • the titanium compound can be included into the manganese dioxide in the mixture as an inorganic or organic salt of titanium (oxidation states 2, 3, or 4), a titanium oxide, titanium dioxide, titanium nitride, titanium boride (e.g., titanium diboride), and/or as titanium metal (i.e. elemental titanium).
  • the one or more additives used in the cathode can comprise a compound comprising nickel.
  • the nickel compound can be included into the manganese dioxide in the mixture as an inorganic or organic salt of nickel, a nickel hydroxide, nickel oxide, and/or as nickel metal (i.e. elemental nickel).
  • the additives that are added to the manganese dioxide cathode active material to aid in reversibility can be in powder form or metallic form.
  • Metallic powders can also be used.
  • a way of incorporating the metallic forms of the additives can include the use of metallic substrates, wires, mesh, or any combination thereof. Binder may or may not be used when making the manganese dioxide electrode.
  • Additional materials can also be optionally used in the cathode material.
  • a conductive additive such as conductive carbon enables high loadings of an electroactive material (e g., manganese dioxide (MnCh)) in the cathode material, resulting in high volumetric and gravimetric energy density.
  • the conductive additive can be present in the cathode material 2 in an amount of about I - about 90 wt.%. alternatively about 1 - about 50 wt.%, alternatively about 10 - about 50 wt .%, or alternatively about 1 - about 30 wt.%, based on the total weight of the cathode material 2.
  • conductive carbon examples include natural and synthetic graphite materials sold under the trade designation TIMREX Primary Synthetic Graphite (all types), TIMREX Natural Flake Graphite (all types), TIMREX MB, MK. MX, KC, B, LB Grades (examples, KS15, KS44, KC44, MB 15, MB25, MK15. MK25. MK44. MX15. MX25. BNB90, LB family) and TIMREX Dispersions by Imerys S.A.
  • the conductive additive e.g., conductive carbon
  • the conductive additive can have a particle size range from about 1 to about 50 microns, or between about 2 and about 30 microns, or between about 5 and about 15 microns.
  • the conductive additive can include expanded graphite having a particle size range from about 10 to about 50 microns, or from about 20 to about 30 microns.
  • Carbon fibers and nanotubes can have varying aspect ratios where their diameters can be in the tens to hundreds of nanometers.
  • the mass ratio of graphite to the conductive additive can range from about 5:1 to about 50: 1, or from about 7:1 to about 28: 1.
  • the total conductive additive mass percentage (e.g., total carbon mass percentage) in the cathode material 2 can range from about 1% to about 99%. alternatively from about 5% to about 99%. alternatively from about 1% to about 90%. alternatively from about 1% to about 50%, alternatively from about 5% to about 99%, alternatively from about 10% to about 80%, or alternatively from about 10% to about 50%.
  • the electroactive component in the cathode material 2 can be between about 1 and about 99 wt.% of the weight of the cathode material 2
  • the conductive additive can be between about 1 and about 99 wt.% of the weight of the cathode material 2.
  • the cathode material 2 can also comprise a conductive component.
  • the addition of a conductive component such as metal additives to the cathode material 2 may be accomplished by addition of one or more metal powders to the cathode material 2.
  • the conductive metal component can be present in a concentration of between about 0-30 wt.% in the cathode material 2.
  • the conductive metal component may be, for example, nickel, copper, silver, gold, tin, cobalt, antimony, brass, bronze, aluminum, calcium, iron, and/or platinum.
  • the conductive metal component is a powder.
  • the conductive metal component may not be electroactive.
  • the conductive component can be added as an oxide and/or salt.
  • the conductive component can be cobalt oxide, cobalt hydroxide, lead oxide, lead hydroxide, or a combination thereof.
  • a second conductive metal component is added to act as a supportive conductive backbone for the first and second electron reactions to take place.
  • the second electron reaction has a dissolution-precipitation reaction where Mn 3+ ions become soluble in the electrolyte and precipitate out on the materials such as graphite resulting in an electrochemical reaction and the formation of manganese hydroxide [Mn(0H)2] which is non-conductive. This ultimately results in a capacity fade in subsequent cycles.
  • Suitable conductive components that can help to reduce the solubility of the manganese ions include transition metals such as Ni, Co, Fe, Ti and metals such as Ag, Au, Al, and/or Ca. Oxides and salts of such metals are also suitable. Transition metals such as Co can also help in reducing the solubility of Mn 3+ ions.
  • Such conductive metal components may be incorporated into the electrode by chemical means or by physical means (e.g. ball milling, mortar and pestle, and/or a Spex mixture).
  • An example of such an electrode can comprise about 5 - about 95% bimessite, about 5 - about 95% conductive carbon, 0 - about 50%, or about 0.0001 % - about 50%, conductive component (e.g., a conductive metal), and about 1 - about 10% binder, based on the total weight of the electrode.
  • conductive component e.g., a conductive metal
  • dopants or additives can be added to the cathode material 2, to enhance rechargeability and performance.
  • the additives can be in the form of powders mixed with the electroactive material or in the form of metallic substrates onto which the electroactive and conductive carbon can be pasted thereon.
  • Nonlimiting examples of additives suitable for use in the electrode materials of this disclosure include bismuth, bismuth oxide, copper oxide, copper, indium, indium hydroxide, indium oxide, aluminum, aluminum oxide, nickel, nickel hydroxide, nickel oxide, silver, silver oxide, cobalt, cobalt oxide, cobalt hydroxide, lead, lead oxide, lead dioxide, quinones, salts thereof, derivatives thereof, or any combination thereof.
  • the dopants or additives can be present in the cathode material 2 in an amount between 0 to 30 wt.%, based on the total weight of the cathode material 2.
  • a binder can be used with the cathode material 2.
  • the binder can be present in a concentration of between about 0 - about 10 wt.%, or alternatively between about 1 - about 5 wt.% by weight of the cathode material.
  • the binder comprises water-soluble cellulose-based hydrogels, which can be used as thickeners and strong binders, and have been cross-linked with good mechanical strength and with conductive polymers.
  • the binder may also be a cellulose film sold as cellophane.
  • the binders can be made by physically cross-linking the water-soluble cellulose-based hydrogels with a polymer through repeated cooling and thawing cycles.
  • the binder can comprise aO - about 10 wt.%, or about 0.0001 - about 10 wt.%, carboxymethyl cellulose (CMC) solution cross-linked with a 0 - about 10 wt.%, or about 0.0001 - about 10 wt.%, polyvinyl alcohol (PVA) on an equal volume basis.
  • CMC carboxymethyl cellulose
  • PVA polyvinyl alcohol
  • the binder compared to the traditionally-used polytetrafluoroethy lene (PTFE) sold under the trade designation TEFLON® by The Chemours Company of Wilmington, DE, shows superior performance.
  • TEFLON® or PTFE is a very resistive material, but its use in the industry has been widespread due to its good rollable properties.
  • TEFLON® can be used as a binder.
  • Mixtures of TEFLON® or PTFE with the aqueous binder and some conductive carbon can be used to create rollable binders.
  • Using the aqueous-based binder can help in achieving a significant fraction of the two-electron capacity with minimal capacity loss over many cycles.
  • the binder can be waterbased, have superior water retention capabilities, adhesion properties, and help to maintain the conductivity relative to an identical cathode using a PTFE binder instead.
  • crosslinking polymers examples include a polyvinyl alcohol, a poly vinylacetate, apolyaniline, a poly vinylpyrrolidone, a poly vinylidene fluoride, a polypyrrole, or combinations thereof.
  • a 0 - about 10 wt.%, or about 0.0001 - about 10 wt.%, solution of water-cased cellulose hydrogen can be crosslinked with a 0 - about 10 wt.%, or about 0.0001 - about 10 wt.%, solution of crosslinking polymers by. for example, repeated freeze/thaw cycles, radiation treatment, and/or chemical agents (e.g., epichlorohydrin).
  • the aqueous binder may be mixed with a 0 - about 5 wt.%, or about 0.0001 - about 5 wt.%, PTFE to improve manufacturability'.
  • PTFE polyvinyl alcohol
  • PVA polyvinyl alcohol
  • one or more thickeners or rheological modifiers can be included in the cathode active material.
  • Thickeners and/or rheology modifiers may be present in the cathode active material in an amount ranging from a 0 - about 10 wt.%, or about 0.0001 - about 10 wt.%. or between about 1 - about 5 wt.%.
  • the thickeners may be any suitable water soluble thickeners, and can be used to prevent or reduce any settling of powdery' materials, while providing a desired slurry viscosity for a casting process.
  • Useful thickeners can include, but are not limited to, a poly aery lie acid sold under the trade designation of ACRYSOLTM from a series of products from Dow Inc. of Midland, Michigan; partially neutralized poly (acry lic acid) or a poly (methacrylic acid) carbomer sold under the trade designation CARBOPOL® by Lubrizol Corporation of Cleveland, Ohio; and a carboxylated alkyl cellulose, such as a carboxylated methyl cellulose (CMC).
  • CMC carboxylated methyl cellulose
  • inorganic rheology modifiers can also be used alone or in combination.
  • Useful inorganic rheology modifiers include, but are not limited to, inorganic rheology modifiers including but not limited to natural clays such as montmorillonite and bentonite, manmade clays such as laponite, and others such as silica, and talc.
  • the binders can serve as thickeners.
  • the cathode material 2 can be formed on a cathode current collector 1 formed from a conductive material that serves as an electrical connection between the cathode material and an external electrical connection or connections.
  • the cathode current collector 1 can be, for example, carbon, lead, zinc, nickel, steel (e.g., stainless steel, etc.), nickel-coated steel, nickel plated copper, tin-coated steel, copper plated nickel, silver coated copper, copper, magnesium, aluminum, indium, tin, iron, platinum, silver, gold, titanium, bismuth, half nickel and half copper, or any combination thereof.
  • the current collector 1 can comprise a carbon felt, carbon foam, a conductive polymer mesh, a polymer (e.g., polypropylene, etc,), or any 7 combination thereof.
  • the cathode current collector may be formed into a mesh (e.g., an expanded mesh, and/or woven mesh), a perforated metal, a foam, a foil, a felt, a fibrous architecture, a porous block architecture, a perforated foil, a wire screen, a wrapped assembly, or any combination thereof.
  • the cunent collector can be formed into or form a part of a pocket assembly, where the pocket can hold the cathode material 2 within the current collector 1.
  • a tab (e.g., a portion of the cathode current collector 1 extending outside of the cathode material 2 as shown at the top of the cathode currently collector 1 in Figure 1) can be coupled to the cunent collector to provide an electrical connection between an external source and the cunent collector.
  • the cathode material 2 can be pressed onto the cathode current collector 1 to form the cathode.
  • the cathode material 2 can be adhered to the cathode current collector 1 by pressing at, for example, a pressure between about 1,000 pounds per square inch (psi) and about 20,000 psi (between 6.9> ⁇ 10 6 and 1.4*10 8 Pascals).
  • the cathode material 2 may be adhered to the cathode current collector 1 as a paste.
  • the resulting cathode can have a thickness of between about 0. 1 mm to about 5 mm.
  • the cathode composition can be about 1 - about 94 wt.%. about 2 - about 92 wt.%, about 4 - about 90 wt.%, about 6 - about 88 wt.%, about 8 - about 86 wt.%, or about 10 - about 84 wt.% of the active material, about 4 - about 98 wt.%, about 6 - about 96 wt.%, about 8 - about 94 wt.%, about 10 - about 92 wt.%, about 12 - about 90 wt.%, or about 14 - about 88 wt.% conductive carbon, about 0.1 - about 5 wt.%, about 0.3 - about 4 wt.%, about 0.5 - about 3 wt.%, about 0.7 - about 2 wt.%, about 0.9 - about 1.7 wt.%, or about 1.1 - about 1.5
  • the anode material 5 can comprise an electroactive material, which can be Zn.
  • Zn can exist in powder form or as a metallic structure in the anode material 5.
  • the Zn powder can be of varying sizes ranging from nanometers to microns.
  • the Zn metallic structure can be a foil, a mesh, a perforated foil, a foam, a sponge-type, or any combination thereof.
  • the anode may comprise Zn metal (about 100 wt.%) or Zn powder of various morphologies (e.g., a sphere, a fiber, a wire, a tube, a sheet, or any combination thereof) and/or sizes.
  • the anode material 5 can comprise about 1 - about 99 wt.% Zn powder, a 0 - about 99 wt.%, or about 0.0001 wt.% - about 99 wt.%, zinc oxide (ZnO), and the remaining wt.% (the balance) as binder.
  • an anode includes an anode active material, having zinc, calcium zincate, zinc oxide, or a combination thereof.
  • the anode active material can further include one or more complexation additives, such as calcium hydroxide.
  • the anode active material can be mixed with gassing inhibitors and conductive enhancers, such as bismuth oxide, indium oxide, titanium nitride, polyethylene glycol or combinations thereof.
  • the anode active material can be further mixed with a rheological modifier, such as laponite.
  • the anode active material can be made into sheets and coated onto substrates or current collectors with binders, such as a polytetrafluoroethylene, a carboxymethyl cellulose, a styrene butadiene rubber or a combination thereof. Sometimes, the anode active material is coated onto substrates or current collectors.
  • binders such as a polytetrafluoroethylene, a carboxymethyl cellulose, a styrene butadiene rubber or a combination thereof.
  • the anode active material is coated onto substrates or current collectors.
  • one or more additives can be added to the anode material.
  • examples can include hydroxides (e.g., calcium hydroxide), zincates (e.g., calcium zincate), and/or oxides such as bismuth oxide or zinc oxide can be used to increase the energy density by increasing the utilization in the proton-insertion range and cycle life.
  • conductive, gas inhibitor and complexing additives such as copper (Cu), indium, indium oxide, bismuth, bismuth oxide, aluminum, aluminum oxide, aluminum hydroxide and/or calcium hydroxide can be added in 1-20 wt.% in place of the ZnO.
  • the anode material 5 can comprise zinc, which can be present as elemental zinc and/or zinc oxide.
  • the Zn anode mixture comprises Zn, zinc oxide (ZnO), the additive, an electronically conductive material, and/or a binder.
  • the Zn may be present in the anode material 5 in an amount of from about 50 wt.% to about 90 wt.%. alternatively from about 60 wt.% to about 80 wt.%. or alternatively from about 65 wt.% to about 75 wt.%, based on the total weight of the anode material.
  • Additional elements that can be in the anode in addition to the zinc or in place of the zinc include, but are not limited to, lithium, aluminum, magnesium, iron, cadmium and a combination thereof, where each element can be present in amounts that are the same or similar to that of the zinc described herein.
  • the anode material 5 can comprise zinc oxide (ZnO), which can be formed into Zn by a charging step in-situ during battery operation.
  • ZnO zinc oxide
  • the anode material 5 can comprise ZnO in an amount of from about 5 wt.% to about 20 wt.%, alternatively from about 5 wt.% to about 15 wt.%, or alternatively from about 5 wt.% to about 10 wt.%, based on the total weight of anode material.
  • the purpose of the ZnO in the anode mixture is to provide a source of Zn during the recharging steps, and the zinc present can be converted between zinc and zinc oxide during charging and discharging phases.
  • an electrically conductive material may be optionally present in the anode material in an amount of from about 5 wt.% to about 20 wt.%, alternatively from about 5 wt.% to about 15 wt.%. or alternatively from about 5 wt.% to about 10 wt.%, based on the total weight of the anode material.
  • the electrically conductive material can be used in the anode mixture as a conducting agent, e.g., to enhance the overall electric conductivity of the anode mixture.
  • Non-limiting examples of electrically conductive material suitable for use can include any of the conductive carbons described herein such as carbon, graphite, graphite powder, graphite powder flakes, graphite powder spheroids, carbon black, activated carbon, conductive carbon, amorphous carbon, glassy carbon, or combinations thereof.
  • the conductive material can also comprise any of the conductive carbon materials described with respect to the cathode material including, but not limited to, acetylene black, single walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphyne, or any combinations thereof.
  • the electrically conductive material used in the anode mixture can comprise a metallic conductive powder, wherein the metallic conductive powder comprises copper, bismuth, indium, nickel, silver, tin, or any combination thereof.
  • the anode material 5 may also comprise a binder.
  • a binder functions to hold the electroactive material particles together and in contact with the current collector.
  • the binder can be present in a concentration of a 0 - about 10 wt.%, or about 0.0001 - about 10 wt.%.
  • the binders in the anode material 5 can also comprise any of the binders described herein with respect to the cathode material.
  • the binders may comprise water-soluble cellulose- based hydrogels such as a methyl cellulose (MC), a carboxymethyl cellulose (CMC), a hydroypropyl cellulose (HPH), a hydroy propylmethyl cellulose (HPMC), ahydroxethylmethyl cellulose (HEMC), a carboxymethylhydroxyethyl cellulose and/or a hydroxyethyl cellulose (HEC).
  • MC methyl cellulose
  • CMC carboxymethyl cellulose
  • HPH hydroypropyl cellulose
  • HPMC hydroy propylmethyl cellulose
  • HEMC ahydroxethylmethyl cellulose
  • HEC hydroxyethyl cellulose
  • the binder may also be a cellulose film sold as cellophane.
  • the binder may also be PTFE. which is a very resistive material, but its use in the industry has been widespread due to its good rollable properties.
  • the binder may be present in the anode material in an amount of from about 2 wt.% to about 10 wt.%, alternatively from about 2 wt.% to about 7 wt.%, or alternatively from about 4 wt.% to about 6 wt.%, based on the total weight of the anode material.
  • one or more thickeners or rheological modifiers can be included in the anode active material.
  • Suitable thickeners for the anode can include any of those described herein, including the binders.
  • a coating process can pre-mix the anode materials mix between about 1 to about 120 minutes, and optionally require drying preceding calendaring, wherein the drying temperature can be between about 50 °C to about 350 °C.
  • the anode material 5 can be used by itself without a separate anode current collector 4, although a tab or other electrical connection can still be provided to the anode material 5.
  • the anode can comprise an optional anode current collector 4.
  • the anode current collector 4 can be used with an anode, including any of those described with respect to the cathode.
  • the anode material 5 can be pressed onto the anode current collector 4 to form the anode.
  • the anode material 5 can be adhered to the anode current collector 4 by pressing at, for example, a pressure between about 1,000 psi and about 20,000 psi (between about 6.9> ⁇ 10 6 and about 1.4* 10 8 Pascals).
  • the anode material 5 may be adhered to the anode current collector 4 as a paste.
  • a tab of the anode current collector 4, when present, can extend outside of the device to form the current collector tab.
  • the resulting anode can have a thickness of between about 0. 1 mm to about 5 mm.
  • the anode comprises about 1 to about 92 wt.%, about 2 to about 90 wt.%, about 3 to about 85 wt.%, about 5 to about 80 wt.%, about 10 to about 75 wt.%, or about 20 to about 60 wt.% of active materials, about 0 to about 6 wt.%, about 0.0001 to about 6 wt.%, about 1 to about 5 wt.%, about 2 to about 4 wt.%, or about 2.5 to about 3.5 wt.% of calcium hydroxide, about 0.
  • a separator 3 e.g., as shown in Figure 1 and/or buffer layer can be disposed betw een the anode and the cathode when the electrodes are constructed into the battery.
  • the separator e.g. separator 3 clearly demarcates the cathode from the anode. While shown as being disposed between the anode and the cathode, the separator 3 can be used to wrap one or more of the anode and/or the cathode, or alternatively one or more anodes and/or cathodes if multiple anodes and cathodes are present.
  • the separator 3 may comprise one or more layers. For example, when the separator is used, between 1 to 5 layers of the separator can be applied between adjacent electrodes.
  • the separator can be formed from a suitable material such as a nylon, a polyester, a polyethylene, a polypropylene, a poly (tetrafluoroethylene) (PTFE), a poly (vinyl chloride) (PVC), a polyvinyl alcohol, a cross-linked polyvinyl alcohol, a cellulose, or any combination thereof.
  • Suitable layers and separator forms can include, but are not limited to, a polymeric separator layer such as a sintered polymer film membrane, a polyolefin membrane, a polyolefin nonwoven membrane, a cellulose membrane, a cellophane, a battery-grade cellophane, a hydrophilically modified polyolefin membrane, or combinations thereof.
  • a polymeric separator layer such as a sintered polymer film membrane, a polyolefin membrane, a polyolefin nonwoven membrane, a cellulose membrane, a cellophane, a battery-grade cellophane, a hydrophilically modified polyolefin membrane, or combinations thereof.
  • the phrase “‘hydrophilically modified 7 ’ refers to a material whose contact angle with water is less than about 45°. In some other embodiments, the contact angle with water of the material used in the separator is less than about 30°. In yet other embodiments, the contact angle with water of the material used in the separator is less than
  • the polyolefin may be modified by, for example, the addition of an octylphenol ethoxylate sold under the trade designation TRITON X-100TM by Dow Inc. of Midland, MI, or oxygen plasma treatment.
  • the separator 9 may be a polymeric separator (e.g., a cellophane, a sintered polymer film, and/or a hydrophilically modified polyolefin).
  • the separator 3 can comprise a polypropylene separator sold under the trade designation CELGARD® brand microporous separator by Celgard. LLC, a subsidiary of Polypore International, both of Charlotte, NC.
  • the separator 3 can comprise a polyolefin nonwoven membrane sold under the trade designation FS 2192 SG membrane commercially available from Scinor Water America. LLC of New York, New York or Freudenberg. Germany.
  • the separator can comprise a lithium super ionic conductor sold under the trade designation LISICON® of NEI Corporation of Somerset, New Jersey, sodium super ionic conductors sold under the trade designation NASICON by Enlighten Innovations Inc. of Calgary.
  • a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer sold under the trade designation NAFION® by The Chemours Company of Wilmington, DE a bipolar membrane, a water electrolysis membrane, a composite of polyvinyl alcohol and graphene oxide, a polyvinyl alcohol, a crosslinked polyvinyl alcohol, and/or a combination thereof.
  • the gelled electrolyte can also serve as the separator.
  • An electrolyte e.g. an alkaline hydroxide, such as NaOH, KOH. LiOH, or mixtures thereof
  • the electrolyte may have a concentration of between about 5% and about 50% w/w.
  • the electrolyte can be in the form of a liquid and/or gel.
  • the battery 10 can comprise an electrolyte that can be gelled to form a semi-solid polymerized electrolyte.
  • the electrolyte can be an alkaline electrolyte.
  • the alkaline electrolyte can be ahydroxide such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, cesium hydroxide, or any combination thereof.
  • the resulting electrolyte can have a pH greater than about 7, for example between about 7 and about 15.1. In some embodiments, the pH of the electrolyte can be greater than or equal to about 10 and less than or equal to about 15.13.
  • the electrolyte is potassium hydroxide, lithium hydroxide, sodium hydroxide, or combinations thereof, and the electrolyte concentration is between about 1 to about 50 wt.%, about 5 to about 45 wt.%, about 10 to about 40 wt.%, about 15 to about 35 wt.%, about 20 to about 30 wt.%, or about 23 to about 27 wt.%.
  • the manganese dioxide having the metallic elements or compounds mixed therein and/or the anode material having the additives mixed therein can be optionally cycled to incorporate the additives into the respective cathode and anode materials.
  • the cell can be cycled between about -1 volt (V) vs Hg
  • the cell can be cycled between about -2 V vs Hg
  • the bimessite phase formation can happen between the limits of about -2 V and about IV vs Hg
  • the layer formation reactions are seen between about -0.3 V and about 1 V vs Hg
  • the metallic elements being incorporated into the manganese dioxide structure should be electrochemically active within the range of potentials at which the manganese dioxide is being cycled in order to assist with the inclusion of the elements in the cry stal structure.
  • the anode material as well as the range of potentials cycled through can both be selected to allow for a desired element or combination of elements or compounds to be incorporated into the manganese dioxide structure.
  • the battery can be used as a primary or secondary battery.
  • the cell can be used as a secondary battery to power a load and be recharged one or more times.
  • EXAMPLE 1 In a first example, two cells containing zinc and manganese dioxide (MnCh) were made and cycled in the proton-insertion reaction.
  • the zinc anode in both cells contained zinc (Zn) powder, zinc oxide (ZnO) powder, calcium hydroxide [Ca(OH)2] powder, bismuth oxide (BuCh) and solution of Teflon, polyethylene glycol (PEG) and laponite.
  • the weight constituents were 76% Zn, 16% ZnO, 5% Ca(OH)2, 2% Bi20s and 1% solution of Teflon, PEG and Laponite.
  • the cathode composition in 1 cell contained 75% Mn02, 4% nickel hydroxide [Ni(0H)2].
  • TiB2 titanium diboride
  • TiB2 16% graphite
  • Teflon 4% solution of Teflon.
  • the cathode composition in the 2 nd cell contained 75% Mn02, 4% Bi20s, 1% TiB2, 16% graphite and 4% solution of Teflon.
  • the cells made were in prismatic form factor.
  • the size of the electrodes were 3 inches in width and 6 inches in length.
  • the cathode was coated onto nickel-plated cold rolled steel and the anode was coated onto copper mesh.
  • Polyvinyl alcohol (PVA) was used as the separator.
  • the electrolyte used in both cells was 25wt.% potassium hydroxide (KOH) with 1% zinc oxide dissolved into the solution. Both cells were cycled at 8-hours charge and discharge between voltage limits of 2V and 0.8V. The charge was continued till 5 to 10% additional capacity was added at the same rate.
  • the high cycle life of these cells were enabled by the additives used in the cathode and anode.
  • the TiB2 additive in the cathode as used to increase conductivity, while the Bi2Ch helps to prevent spinel formation through its complexation reactions.
  • the Ni(0H)2 prevents overcharging of the cathode and prevent oxygen gas formation.
  • the ZnO and Ca(OH)2 react to form calcium zincate, which helps in preventing shape change.
  • the B12O3 in the anode helps to reduce hydrogen gas formation.
  • certain embodiments can include, but are not limited to:
  • a battery comprises a cathode, wherein the cathode comprises an active material, and wherein the cathode active material comprises an additive; an anode; a separator; and an electrolyte, wherein the battery comprises a rechargeable, proton-insertion battery.
  • a second aspect can include the battery of the first aspect, wherein the active material comprises one or more manganese oxides (e.g., 8-MnCh, Z-MnCh. a-MnCh. tyMnCh. e-MnCh. y-MnCh).
  • a third aspect can include the battery of the first or second aspect, wherein the cathode active material is further mixed with a conductive carbon and a binder, wherein the conductive carbon comprises graphite, carbon fiber, carbon black, acetylene black, single walled carbon nanotubes, multi-walled carbon nanotubes, nickel or copper coated carbon nanotubes, dispersions of single walled carbon nanotubes, dispersions of multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, or a combination thereof, and wherein the binder comprises A polytetrafluoroethylene, carboxymethyl cellulose, polyvinyl alcohol, or a combination thereof.
  • a fourth aspect can include the battery of any one of the first to third aspects, wherein the additive comprises one or more of titanium-based additives such as titanium dioxide, titanium nitride, titanium diboride, barium titanate or a combination thereof.
  • titanium-based additives such as titanium dioxide, titanium nitride, titanium diboride, barium titanate or a combination thereof.
  • a fifth aspect can include the battery of any one of the first to fourth aspects, wherein the additive comprises one or more of a metal oxide or a hydroxide such as bismuth oxide and nickel hydroxide.
  • a sixth aspect can include the battery of any one of the first to fifth aspects, wherein the active material is further mixed with a rheological modifier such as laponite.
  • An eighth aspect can include the battery of any one of the first to seventh aspects, wherein the cathode composition is about 1 - about 94 wt.%, about 2 - about 92 wt.%, about 4 - about 90 wt.%, about 6 - about 88 wt.%, about 8 - about 86 wt.%, or about 10 - about 84 wt.% of the active material, about 4 - about 98 wt.%, about 6 - about 96 wt.%, about 8 - about 94 wt.%, about 10 - about 92 wt.%, about 12 - about 90 wt.%, or about 14 - about 88 wt.% conductive carbon, about 0.1 - about 5 wt.%.
  • a ninth aspect can include the battery of any one of the first to eighth aspects, wherein the cathode active material is pressed onto a substrate or current collector comprising carbon, lead, zinc, stainless steel, copper, nickel, silver, bismuth, titanium, magnesium, aluminum, indium, tin. gold, polypropylene, cold rolled steel, or a combination thereof.
  • a tenth aspect can include the battery of the ninth aspect, wherein the substrate or the current collector is a mesh, a foil, a perforated foil, a foam, a felt, a fibrous substrate, a porous block architecture, or a combination thereof.
  • An eleventh aspect can include the battery' of any one of the first to tenth aspects, wherein the anode comprises an anode active material comprising zinc, calcium zincate, zinc oxide, or a combination thereof.
  • a twelfth aspect can include the battery' of any one of the first to eleventh aspects, wherein the anode active material further comprises one or more complexation additives such as calcium hydroxide.
  • a thirteenth aspect can include the battery of any one of the first, eleventh, or twelfth aspects, wherein the anode active material is mixed with gassing inhibitors and conductive enhancers such as bismuth oxide, indium oxide, titanium nitride, polyethylene glycol or combinations thereof.
  • gassing inhibitors and conductive enhancers such as bismuth oxide, indium oxide, titanium nitride, polyethylene glycol or combinations thereof.
  • a fourteenth aspect can include the battery of any one of the first to thirteenth aspects, wherein the anode active material is further mixed with a rheological modifier such as laponite.
  • a fifteenth aspect can include the battery of any one of the first to fourteenth aspects, wherein the anode active material is made into sheets and coated onto substrates or current collectors with binders such as a polytetrafluoroethylene, a carboxymethyl cellulose, a styrene butadiene rubber or a combination thereof.
  • binders such as a polytetrafluoroethylene, a carboxymethyl cellulose, a styrene butadiene rubber or a combination thereof.
  • a sixteenth aspect can include the battery' of any one of the first to fifteenth aspects, wherein the anode comprises about 1 to about 92 wt.%, about 2 to about 90 wt.%, about 3 to about 85 wt.%. about 5 to about 80 wt.%. about 10 to about 75 wt.%, or about 20 to about 60 wt.% of active materials, about 0 to about 6 wt.%, about 0.0001 to about 6 wt.%, about 1 to about 5 wt.%, about 2 to about 4 wt.%, or about 2.5 to about 3.5 wt.% of calcium hydroxide, about 0.
  • a seventeenth aspect can include the batten of any one of the first to sixteenth aspects, wherein the anode active material is coated onto substrates or current collectors such as copper, zinc, aluminum, bismuth, indium, tin, titanium, a stainless steel, a cold rolled steel or a combination thereof.
  • substrates or current collectors such as copper, zinc, aluminum, bismuth, indium, tin, titanium, a stainless steel, a cold rolled steel or a combination thereof.
  • An eighteenth aspect can include the battery of any one of the first to seventeenth aspects, wherein the anode substrate or current collector is a mesh, a foil, a perforated foil, a foam, a felt, a fibrous substrate, a porous block architecture, or a combination thereof.
  • a nineteenth aspect can include the battery of any one of the first to eighteenth aspects, wherein the coating process could require a pre-mixing step of the anode materials mix between about 1 to about 120 minutes of a coating process.
  • a twentieth aspect can include the battery of any one of the first to nineteenth aspects, wherein the coating process could require a drying step preceding the calendaring step, wherein a drying temperature is between about 50 °C to about 350 °C.
  • a twenty first aspect can include the battery of any one of the first to twentieth aspects, wherein the separator is a cellophane, a Celgard, a polyvinyl alcohol, a cross-linked polyvinyl alcohol, calcium hydroxide, a polymer gelled electrolyte, a layered double hydroxide (hydrotalcites, a quintinite, a fougerite or magnesium hydroxide), a sodium super ionic conductor, a lithium super ionic conductor, or combinations thereof.
  • the separator is a cellophane, a Celgard, a polyvinyl alcohol, a cross-linked polyvinyl alcohol, calcium hydroxide, a polymer gelled electrolyte, a layered double hydroxide (hydrotalcites, a quintinite, a fougerite or magnesium hydroxide), a sodium super ionic conductor, a lithium super ionic conductor, or combinations thereof.
  • a twenty second aspect can include the battery' of any one of the first to twenty first aspects, wherein the electrolyte is potassium hydroxide, lithium hydroxide, sodium hydroxide, or combinations thereof.
  • a twenty third aspect can include the battery of any one of the first to twenty second aspects, wherein the electrolyte concentration is between about 1 to about 50 wt.%, about 5 to about 45 wt.%, about 10 to about 40 wt.%, about 15 to about 35 wt.%, about 20 to about 30 wt.%. or about 23 to about 27 wt.%.
  • a rechargeable, proton-insertion battery' can include a cathode, wherein the cathode comprises an active material comprises one or more manganese oxides, and at least one additive comprising one or more of titanium-based additives, one or more metal oxides, one or more hydroxides, or a combination thereof; an anode; a separator; and an electrolyte.
  • a rechargeable, proton-insertion battery can include a cathode, wherein the cathode comprises an active material comprises one or more manganese oxides, and at least one additive comprising a titanium compound, a nickel hydroxide, or a combination thereof, and wherein the cathode active material is further mixed with a conductive carbon comprising a graphite and a binder comprising a polytetrafluoroethylene; an anode, wherein the anode comprises an anode active material comprising zinc; a separator; and an electrolyte.
  • a coating process comprises: pre-mixing an anode materials mix between about 1 to about 120 minutes; drying at a temperature of between about 50 °C to about 350 °C; and calendaring the dried anode materials mix.

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Abstract

L'invention concerne une batterie rechargeable à insertion de protons qui peut comprendre une cathode, une anode, un séparateur et un électrolyte. La cathode comprend un matériau actif qui comprend un additif. L'additif peut comprendre un ou plusieurs composés d'éléments tels que le titane, le nickel, le bismuth, ou des combinaisons de ceux-ci. L'anode peut comprendre un ou plusieurs additifs d'anode qui peuvent comprendre des hydroxydes insolubles, des zincates, des oxydes tels que l'hydroxyde de calcium, le zincate de calcium, l'oxyde de bismuth, l'oxyde de zinc, ou des combinaisons de ceux-ci.
PCT/US2025/017376 2024-02-26 2025-02-26 Batteries zinc-dioxyde de manganèse à insertion de protons denses en énergie Pending WO2025184200A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060046135A1 (en) * 2004-08-27 2006-03-02 Weiwei Huang Alkaline battery with MnO2/NiOOH active material
US20170301960A1 (en) * 2016-03-14 2017-10-19 Urban Electric Power Inc Secondary cell with high recharging efficiency and long term stability
US20230344014A1 (en) * 2020-04-13 2023-10-26 Urban Electric Power Inc. Metal-free high voltage battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060046135A1 (en) * 2004-08-27 2006-03-02 Weiwei Huang Alkaline battery with MnO2/NiOOH active material
US20170301960A1 (en) * 2016-03-14 2017-10-19 Urban Electric Power Inc Secondary cell with high recharging efficiency and long term stability
US20230344014A1 (en) * 2020-04-13 2023-10-26 Urban Electric Power Inc. Metal-free high voltage battery

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