Energy dense proton-insertion zinc-manganese dioxide batteries

Abstract

A rechargeable, proton-insertion battery can include a cathode, an anode, a separator, and an electrolyte. The cathode includes an active material that includes an additive. The additive can include compound(s) forms of elements such as titanium, nickel, bismuth, or combinations thereof. The anode can comprise one or more anode additives that can include insoluble hydroxides, zincates, oxides such as calcium hydroxide, calcium zincate, bismuth oxide, zinc oxide, or combinations thereof.

Description

ENERGY DENSE PROTON-INSERTION ZINC-MANGANESEDIOXIDE BATTERIESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority7to U.S. Provisional Application No. 63 / 557,997 filed on February726, 2024 and entitled, “ENERGY DENSE PROTON-INSERTION ZINCMANGANESE DIOXIDE BATTERIES”, the entire disclosure of which is incorporated herein by reference.STATEMENT OF FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] None.BACKGROUND

[0003] 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.

[0004] 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.SUMMARY

[0005] These and other features will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings and claims.

[0006] In some embodiments, a rechargeable, proton-insertion battery can include 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.

[0007] In some embodiments, a rechargeable, proton-insertion battery can include a cathode, wherein the cathode comprises an active material comprises one or more manganeseoxides, 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.

[0008] In some embodiments, 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.

[0009] In some embodiments, 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.BRIEF DESCRIPTION OF DRAWINGS

[0010] For a more complete understanding of the present disclosure and the advantages thereof, reference is now made to the following brief description, taken in connection with the accompanying drawings and detailed description, wherein like reference numerals represent like parts.

[0011] Figure 1 is a cross-sectional view of an embodiment of a battery in a prismatic arrangement.

[0012] Figure 2 depicts performance data of zinc|manganese dioxide cells, where manganese dioxide (cathode) is cycled at 40% utilization and zinc (anode) is cycled at 20% utilization of its theoretical capacity. 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.DETAILED DESCRIPTION

[0013] In this disclosure, the terms "‘negative electrode" and "anode" are both used to mean “negative electrode." Likewise, 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. Reference to the term “secondary battery” (e.g., “secondary battery,” “secondary’ electrochemical cell,” or “secondary’ cell”), refers to a cell or battery that can be recharged one or more times and reused. As used herein, a catholyte refers to an electrolyte solution in contact with the cathode without being in direct contact with the anode, and an “anolyte” refers to an electrolyte solution in contact with the anode without being in direct contact with the cathode.

[0014] In this disclosure, 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”.

[0015] In this disclosure, the term “and / or” can mean one or more of items in any combination in a list, such as “A and / or B” means “A, B, or the combination of A and B”.

[0016] 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. Disclosed herein are 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.

[0017] In this disclosure a stabilized and reversible manganese dioxide electrode is described for use in batteries. The starting manganese dioxide can include any of its polymorphs, which are used in a number of different battery’ chemistries. For example, 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.

[0018] Referring to Figure 1, 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. Referring to Figure1, the cathode current collector 1 and cathode material 2 are collectively called either the cathode or the positive electrode. Similarly, 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.

[0019] In some aspects, 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.

[0020] 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. In general, bimessite has a formula:(NaxCaYKz)(Mn4+,Mn3+)2O4 where X may have a value between 0 and about 0.4, or about 0.0001 and about 0.4, Y has a value between 0 and about 0. 15. or about 0.0001 and about 0. 15, and Z has a value between 0 and about 0. 15, or about 0.0001 and about 0. 15. In some embodiments, 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. As used herein, 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.

[0021] 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. However, 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 Mn3+, which is soluble in alkaline electrolyte. Incorporating additives that limitvolume expansion and limit Mn dissolution can help utilize >40% of the one electron capacity for long periods of time.

[0022] 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. 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.

[0023] In some aspects, the additives can be inserted into the sheet structure of the bimessite using a charging-discharging process. For example, the metallic element(s) can be inserted into the layered structure of the bimessite through an intercalation reaction or process. As used herein, 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).

[0024] In alkaline electrolyte, the manganese dioxide formed while reducing and oxidizing at any utilization of the theoretical 2ndelectron capacity7(e.g., about 617 milliampere- hours per gram (mAh / g)) 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. When zinc is used as the counter electrode or zinc ions are present in the electrolyte, there is a possibility of chalcophanite or zinc bimessite phase forming as well. Sometimes 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.

[0025] In some aspects, 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.%). Examples ofinorganic 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 yittia stabilized, bismuth-lead alloy, ammonium bismuth citrate, 2-napthol bismuth salt, duchloritri(o-tolyl)bismuth, dichlordiphenyl(p-tolyl)bismuth, and / or triphenylbismuth.

[0026] In some aspects, 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).

[0027] In some aspects, 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).

[0028] 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.

[0029] Additional materials can also be optionally used in the cathode material. The addition of 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. In some embodiments, 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. Nonlimiting examples of conductive carbon suitable for use in the present disclosure as a conductive additive include single walled carbon nanotubes, multi-walled carbon nanotubes, graphene, carbon blacks of various surface areas, any other suitable conductive carbon that specificallyhas relatively very high surface area and conductivity, or any combination thereof. In some embodiments, the conductive additive can comprise 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. Higher loadings of the electroactive material (e.g., manganese dioxide (MnCh)) in the cathode are. in some embodiments, desirable to increase the energy density. Other examples of conductive carbon 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. of Paris, France; carbon black sold under the trade designation ENASCO 150G, 210G, 250G, 260G, 350G, 150P, 250P; SUPER P, and SUPER P Li by Imerys S.A. of Paris, France, carbon black (examples include those sold under the trade designation Ketjenblack EC- 3001. Ketjenblack EC-600JD. and Ketjenblack EC-600JD powder by Ketjen of Charlotte, North Carolina, a subsidiary of Albemarle Corporation of Charlotte. North Carolina), acetylene black, carbon nanotubes (single or multi-walled), graphite sold under the trade designation ZENYATTA™ graphite by Zentek Ltd. of Thunder Bay, Ontario, Canada, and / or combinations thereof.

[0030] In some embodiments, the conductive additive (e.g., conductive carbon) 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. In some embodiments, 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. In some embodiments, 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%. In some embodiments, 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, and the conductive additive can be between about 1 and about 99 wt.% of the weight of the cathode material 2.

[0031] In some embodiments, 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. In some embodiments, the conductive metal component is a powder. In some aspects, the conductive metal component may not be electroactive. In some embodiments, the conductive component can be added as an oxide and / or salt. For example, the conductive component can be cobalt oxide, cobalt hydroxide, lead oxide, lead hydroxide, or a combination thereof. In some embodiments, 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 Mn3+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 Mn3+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.

[0032] In some embodiments, 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. In some embodiments, the dopants or additives can be present in thecathode material 2 in an amount between 0 to 30 wt.%, based on the total weight of the cathode material 2.

[0033] In some embodiments, 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. In some embodiments, 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. In some embodiments, 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. 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. This, however, does not rule out using TEFLON® or PTFE as a binder. In some embodiments, 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. In some embodiments, 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. Examples of suitable water-based hydrogels (e.g., water-soluble cellulose-based hydrogels) can include, but are not limited to, a methyl cellulose (MC), a carboxymethyl cellulose (CMC), a hydroypropyl cellulose (HPH), a hydroypropylmethyl cellulose (HPMC), a hydroxyethylmethyl cellulose (HEMC), a carboxymethylhydroxyethyl cellulose, a hydroxyethyl cellulose (HEC), or combinations thereof. Examples of crosslinking polymers (e.g., conductive polymers) include a polyvinyl alcohol, a poly vinylacetate, apolyaniline, a poly vinylpyrrolidone, a poly vinylidene fluoride, a polypyrrole, or combinations thereof. In some embodiments, 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.%, orabout 0.0001 - about 5 wt.%, PTFE to improve manufacturability'. In some embodiments, polyvinyl alcohol (PVA) can be used as a binder by itself.

[0034] In some aspects, 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 ACRYSOL™ 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). In addition to organic rheology modifiers, 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. In some aspects, the binders can serve as thickeners.

[0035] 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. In some embodiments, 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. In some embodiments, the current collector 1 can comprise a carbon felt, carbon foam, a conductive polymer mesh, a polymer (e.g., polypropylene, etc,), or any7combination 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. In some embodiments, 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.

[0036] The cathode material 2 can be pressed onto the cathode current collector 1 to form the cathode. For example, 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><106and 1.4*108Pascals). 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.

[0037] In some embodiments, 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 wt.% of a titanium-based additive, about 0.9 - about 10 wt.%, about 1.1 - about 9 wt.%, about 1.3 - about 8 wt.%, about 1.5 - about 7 wt.%, about 1.7 - about 6 wt.%, about 1.9 - about 5 wt.%, or about 2.1 - about 4 wt.% of metal oxide and hydroxide additives, and about 1 - about 5 wt.%, about 1.2 - about 4 wt.%, about 1.4 - about 3 wt.%. about 1.6 - about 2.8 wt.%, about 1.8 - about 2.5 wt.%, or about 2.0 - about 2.3 wt.% of a binder.

[0038] In some embodiments, 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.

[0039] In some embodiments, 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. In some embodiments, 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.

[0040] In some aspects, 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. In certain embodiments, 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. Furthermore, the anode active material can be further mixed with a rheological modifier, suchas laponite. In some embodiments, 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.

[0041] In some aspects, 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. In some embodiments, 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.

[0042] In some embodiments, the anode material 5 can comprise zinc, which can be present as elemental zinc and / or zinc oxide. In some embodiments, 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.

[0043] In some embodiments, the anode material 5 can comprise zinc oxide (ZnO), which can be formed into Zn by a charging step in-situ during battery operation. In some embodiments, 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. Although not wanting to be bound by theory, 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.

[0044] In some embodiments, 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. Although not wanting to be bound by theory, 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. In some embodiments, 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.

[0045] The anode material 5 may also comprise a binder. Generally, 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). which can be used as thickeners and strong binders, and have been cross-linked with good mechanical strength and with conductive polymers such as a polyvinyl alcohol, a polyvinylacetate, a polyaniline, a polyvinylpyrrolidone, a polyvinylidene fluoride and / or polypyrrole. 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. In some embodiments, 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.

[0046] In some aspects, 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. During fabrication of the anode, in some embodiments, 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.

[0047] In some embodiments, 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. In some embodiments, the anode material may have the form or architecture of a foil, a mesh, a perforated layer, a foam, a felt, and / or a powder. For example, the anode can comprise a metal foil electrode, a mesh electrode, and / or a perforated metal foil electrode.

[0048] In some embodiments, 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. For example, 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>< 106and about 1.4* 108Pascals). 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.

[0049] In some embodiments, 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. 1 to about 4 wt.%, about 0.3 to about 3 wt.%, about 0.5 to about 2.5 wt.%, about 0.7 to about 2 wt.%, or about 0.9 to about 1.5 wt.% of gassing inhibitors and conductive enhancers, about 0.1 to about 4 wt.%, about 0.3 to about 3 wt.%, about 0.5 to about 2.5 wt.%, about 0.7 to about 2 wt.%, or about 0.9 to about 1.5 wt.% of a rheological modifier, and about 0.1 to about 4 wt.%, about 0.3 to about 3 wt.%, about 0.5 to about 2.5 wt.%, about 0.7 to about 2 wt.%, or about 0.9 to about 1.5 wt.% of a binder.

[0050] In some embodiments, 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.

[0051] 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. As used herein, the phrase "‘hydrophilically modified7’ 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 about 20°. The polyolefin may be modified by, for example, the addition of an octylphenol ethoxylate sold under the trade designation TRITON X-100™ by Dow Inc. of Midland, MI, or oxygen plasma treatment. In some embodiment, the separator 9 may be a polymeric separator (e.g., a cellophane, a sintered polymer film, and / or a hydrophilically modified polyolefin). In some embodiments, 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. In some embodiments, 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. In some embodiments, 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. Alberta, 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. In some aspects when a gelled electrolyte is used, the gelled electrolyte can also serve as the separator.

[0052] An electrolyte (e.g. an alkaline hydroxide, such as NaOH, KOH. LiOH, or mixtures thereof) can be contained within the free spaces of the electrodes, the separator 93 and the housing 6. 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. For example, the battery 10 can comprise an electrolyte that can be gelled to form a semi-solid polymerized electrolyte. In some embodiments, the electrolyte can be an alkaline electrolyte. The alkaline electrolyte canbe 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.

[0053] In some embodiments, 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.%.

[0054] Once formed as a battery', 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. For example, the cell can be cycled between about -1 volt (V) vs Hg|HgO and about 0.3 V vs Hg|HgO. In some embodiments, the cell can be cycled between about -2 V vs Hg|HgO and about 1 V vs Hg|HgO. The bimessite phase formation can happen between the limits of about -2 V and about IV vs Hg|HgO. Generally, the layer formation reactions are seen between about -0.3 V and about 1 V vs Hg|HgO. Between about -0.3 V and about -2 V vs Hg|HgO, the layered phases of Mn(0H)2 are generally seen.

[0055] Within the production process, 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. Thus, 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.

[0056] Once constructed into a battery, the battery can be used as a primary or secondary battery. For example, the cell can be used as a secondary battery to power a load and be recharged one or more times.EXAMPLES

[0057] The embodiments having been generally7described, the following examples are given as particular embodiments of the disclosure and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims in any manner.EXAMPLE 1

[0058] 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]. 1% titanium diboride (TiB2). 16% graphite and 4% solution of Teflon. The cathode composition in the 2ndcell contained 75% Mn02, 4% Bi20s, 1% TiB2, 16% graphite and 4% solution of Teflon.

[0059] 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.

[0060] The cycle life of both cells is shown in Figure 2, where the percent utilization of the cathode is plotted against cycle number. The anode was cycled at 20% utilization in these cells. Both cells with Ni(0H)2 and Bi2O3 reached 300 cycles, where point of failure was detected.

[0061] 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. In the anode, 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.

[0062] Having described various systems and methods herein, certain embodiments can include, but are not limited to:

[0063] In a first aspect, 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.

[0064] 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).

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] A seventh aspect can include the battery of any one of the first to sixth aspects, wherein the active material is made into sheets and coatable on substrates or current collectors with binders such as a polytetrafluoroethylene, a carboxymethyl cellulose, a styrene butadiene rubber or a combination thereof.

[0070] 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.%. 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 wt.% of a titanium-based additive, about 0.9 - about 10 wt.%, about 1.1 - about 9 wt.%, about 1.3 - about 8 wt.%, about 1.5 - about 7 wt.%, about 1.7 - about 6 wt.%, about 1.9 - about 5 wt.%, or about 2.1 - about 4 wt.% of metal oxide and hydroxide additives, and about 1 - about 5wt.%, about 1.2 - about 4 wt.%, about 1.4 - about 3 wt.%, about 1.6 - about 2.8 wt.%, about 1.8 - about 2.5 wt.%, or about 2.0 - about 2.3 wt.% of a binder.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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. 1 to about 4 wt.%, about 0.3 to about 3 wt.%, about 0.5 to about 2.5 wt.%, about 0.7 to about 2 wt.%, or about 0.9 to about 1.5 wt.% of gassing inhibitors and conductive enhancers, about 0. 1 to about 4 wt.%, about 0.3 to about 3 wt.%, about 0.5 to about 2.5 wt.%, about 0.7 toabout 2 wt.%, or about 0.9 to about 1.5 wt.% of a rheological modifier, and about 0.1 to about 4 wt.%, about 0.3 to about 3 wt.%, about 0.5 to about 2.5 wt.%, about 0.7 to about 2 wt.%, or about 0.9 to about 1.5 wt.% of a binder.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.%.

[0086] In a twenty fourth aspect, 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.

[0087] In a twenty fifth aspect, 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.

[0088] In a twenty sixth aspect, 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.

[0089] The present systems and methods are best understood by reference to the detailed figure and description set forth herein. Embodiments are discussed below with reference to the Figures. However, those skilled in the art will readily appreciate that the detailed description given herein with respect to these figures is for explanatory' purposes as the systems and methods extend beyond these limited embodiments. For example, it should be appreciated that those skilled in the art will, in light of the teachings of the present description, recognize a multiplicity of alternate and suitable approaches, depending upon the needs of the particular application, to implement the functionality of any given detail described herein, beyond the particular implementation choices in the following embodiments described and shown. That is, there are numerous modifications and variations that are too numerous to be listed but that all fit within the scope of the present description. Also, singular words should be read as plural and vice versa and masculine as feminine and vice versa, where appropriate, and alternative embodiments do not necessarily imply that the two are mutually exclusive.

[0090] It is to be further understood that the present description is not limited to the particular methodology, compounds, materials, manufacturing techniques, uses, and applications, described herein, as these may vary. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present systems and methods. It must be noted that as used herein and in the appended claims (in this application, or any derived applications thereof), the singular forms "a," "an," and "the" include the plural reference unless the context clearly dictates otherwise. Thus, for example, a reference to "an element" is a reference to one or more elements and includes equivalents thereof known to those skilled in the art. All conjunctions used are to be understood in the most inclusive sense possible. Thus, the word "or" should be understood as having the definition of a logical "or" rather than that of a logical"exclusive or" unless the context clearly necessitates otherwise. Structures described herein are to be understood also to refer to functional equivalents of such structures. Language that may be construed to express approximation should be so understood unless the context clearly dictates otherwise.

[0091] Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this description belongs. Preferred methods, techniques, devices, and materials are described, although any methods, techniques, devices, or materials similar or equivalent to those described herein may be used in the practice or testing of the present systems and methods. Structures described herein are to be understood also to refer to functional equivalents of such structures.

[0092] From reading the present disclosure, other variations and modifications will be apparent to persons skilled in the art. Such variations and modifications may involve equivalent and other features which are already known in the art, and which may be used instead of or in addition to features already described herein.

[0093] Although claims may be formulated in this Application or of any further Application derived therefrom, to particular combinations of features, it should be understood that the scope of the disclosure also includes any novel feature or any novel combination of features disclosed herein either explicitly or implicitly or any generalization thereof, whether or not it relates to the same systems or methods as presently claimed in any claim and whether or not it mitigates any or all of the same technical problems as do the present systems and methods.

[0094] Features which are described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination. The Applicant hereby gives notice that new claims may be formulated to such features and / or combinations of such features during the prosecution of the present Application or of any further Application derived therefrom.

Claims

C 1 \1 VI>What is claimed is:

1. A battery comprising: 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 batten comprises a rechargeable, proton-insertion battery.

2. The battery of claim 1, wherein the cathode active material comprises one or more manganese oxides.

3. The battety of claim 1, wherein the cathode active material is further mixed with a conductive carbon and a binder, wherein the conductive carbon comprises a graphite, a carbon fiber, a carbon black, an acetylene black, single walled carbon nanotubes, multiwalled carbon nanotubes, nickel or copper coated carbon nanotubes, dispersions of single walled carbon nanotubes, dispersions of multi-walled carbon nanotubes, a graphene, a graphyne, a graphene oxide, or a combination thereof, and wherein the binder comprises a polytetrafluoroethylene, a carboxymethyl cellulose, a polyvinyl alcohol, or a combination thereof.

4. The battery' of claim 1, wherein the additive comprises one or more of titanium-based additives.

5. The battery of claim 1. wherein the additive comprises one or more of a metal oxide or a hydroxide.

6. The battery of claim 1, wherein the cathode active material is further mixed with a rheological modifier.

7. The batter ' of claim 1, wherein the cathode active material is made into sheets and coatable on substrates or current collectors with binders.

8. The batery of claim 1 , wherein a composition of the cathode is about 1 - about 94 wt. % of the cathode active material, about 4 - about 98 wt.% conductive carbon, about 0.1 - about 5 wt.% of a titanium-based additive, about 0.9 - about 10 wt.% of metal oxide and hydroxide additives, and about 1 - about 5 wt.% of a binder.

9. The batery of claim 1. 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.

10. The batery of claim 9, 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.

11. The batery of claim 1, wherein the anode comprises an anode active material comprising zinc, calcium zincate, zinc oxide, or a combination thereof.

12. The battery of claim 11, wherein the anode active material further comprises one or more complexation additives.

13. The battery' of claim 11, wherein the anode active material is mixed with gassing inhibitors and conductive enhancers.

14. The batery of 11 , wherein the anode active material is further mixed with a rheological modifier.

15. The batery of 11, wherein the anode active material is made into sheets and coated onto substrates or current collectors with binders.

16. The batery' of claim 1, wherein the anode comprises about 1 to about 92 wt.% of active materials, 0 to about 6 wt.% of calcium hydroxide, about 0. 1 to about 4 wt.% of gassing inhibitors and conductive enhancers, about 0.1 to about 4 wt.% of a rheological modifier, and about 0. 1 to about 4 wt.% of a binder.

17. The batery of claim 11, wherein the anode active material is coated onto a substrate or a cunent collector.

18. The batery of claim 17, wherein the anode 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.

19. The batery of claim 17, comprising pre-mixing an anode materials mix between about 1 to about 120 minutes of a coating process.

20. The batery' of claim 19, wherein the coating process further comprises a drying step preceding a calendaring step, wherein a drying temperature is between about 50 °C to about 350 °C.

21. The batery of claim 1, wherein the separator is cellophane, a polypropylene separator, polyvinyl alcohol, cross-linked polyvinyl alcohol, calcium hydroxide, polymer gelled electrolyte, layered double hydroxide (hydrotalcites, quintinite, fougerite or magnesium hydroxide), a sodium super ionic conductions conductor, a lithium super ionic conductor, or combinations thereof.

22. The batery' of claim 1, wherein the electrolyte is potassium hydroxide, lithium hydroxide, sodium hydroxide, or combinations thereof.

23. The batery of claim 1, wherein an electrolyte concentration is between about 1 to about 50 wt.%.

24. A rechargeable, proton-insertion batery comprising: 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; andan electrolyte.

25. A rechargeable, proton-insertion battery comprising: 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.

26. A battery formation process, comprising: combining 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, to form a cathode; combining a zinc material with an anode additive to form an anode, wherein the anode additive comprises an insoluble hydroxide, a zincate, or an oxide; disposing the cathode and the anode in a housing with a separator disposed between the anode and the cathode; and disposing an electrolyte in contact with the cathode, the anode, both to form a battery.

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