Zinc, copper, and silver-doped acidified metal oxides

Abstract

Zinc-, copper -, and / or silver-doped metal oxide materials and related electrodes and electrochemical cells incorporating the zinc-, copper, or silver-doped metal oxide materials are described. The zinc-, copper-, or silver-doped metal oxide materials are useful in cathodes and electrochemical cells and can contribute improved performance and stability to the electrochemical cells incorporating the zinc-, copper-, or silver-doped metal oxide materials, particularly when incorporated as cathode additives in alkaline battery cells. In examples, the zinc-, copper, or silver-doped metal oxide materials are acidified metal oxide (AMO) particles or nanoparticles.

Description

Attorney Docket No. 009052-00234 (TNP0027-PCT) ZINC, COPPER, AND SILVER-DOPED ACIDIFIED METAL OXIDESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application No.63 / 739,250, filed on December 27, 2024, which is hereby incorporated by reference.FIELD

[0002] This invention is in the field of nanomaterials. This invention relates generally to acidified metal oxides doped with zinc, copper, and / or silver. Such materials may find use as additives in battery cathodes, such as in alkaline, lithium primary, and lithium-ion batteries.BACKGROUND

[0003] Various cathode active materials are used in conventional primary and secondary battery systems, such as lithium primary batteries, alkaline primary batteries, and lithium-ion secondary batteries. A variety of additives are combined with the cathode active materials, such as conductive additives like carbon or graphite, as well as binder materials. Some additives provide for enhancing electrical performance while other additives are used for structural integrity enhancement.SUMMARY

[0004] The present disclosure provides mixed-metal oxide materials, including zinc-, copper-, and / or silver-doped metal oxide materials and related electrodes and electrochemical cells incorporating the zinc-, copper-, or silver-doped mixed-metal oxide materials. The metal oxide materials are mixed-metal oxides in that they contain other metals besides zinc, copper, or silver and may, in some cases, be referred to as doped metal oxides, such as where the zinc, copper, or silver components corresponds to a dopant or minor metal oxide component as compared to the other metal oxide component s). Advantageously, the disclosed metal oxide materials are useful in cathodes and electrochemical cells and can contribute improved performance and stability to the electrochemical cells incorporating the metal oxide materials, particularly when incorporated as cathode additives in alkaline battery cells or lithium-ion cells. In examples, the zinc-, copper-, or silver-doped metal oxide materials are acidified metal oxide (AMO) particles or nanoparticles.

[0005] In one example, material disclosed herein may comprise a solid metal oxide nanomaterial including zinc, copper, or silver and at least one other metal oxide, the solid metaloxide nanomaterial having or characterized by a pH less than 7. In examples, the pH is measured when the solid metal oxide nanomaterial is dried and the dried solid oxide nanomaterial is suspended in an aqueous solution at 5 wt.%.

[0006] In one example, material disclosed herein may comprise a solid metal oxide nanomaterial having a composition MmOx / G, such as where M comprises zinc, copper, or silver and at least one other metal, O is oxygen, MmOxrepresents a metal oxide, m and x represent integer or non-integer relative molar amounts of M and O, respectively, G is at least one electron-withdrawing surface group, and “ / ” makes a distinction between the metal oxide and the electron- withdrawing surface group. In examples, m can range from 1 to 5 and x can range from 1 to 5.

[0007] In examples, material disclosed herein may comprise a solid metal oxide nanomaterial selected from the group consisting of zinc-doped aluminum oxide, zinc-doped titanium oxide, zinc-doped manganese oxide, zinc-doped iron oxide, zinc-doped zirconium oxide, zinc-doped indium oxide, zinc-doped tin oxide, zinc-doped antimony oxide, zinc-doped bismuth oxide, copper-doped aluminum oxide, copper-doped titanium oxide, copper-doped manganese oxide, copper-doped iron oxide, copper-doped zirconium oxide, copper-doped indium oxide, copper-doped tin oxide, copper-doped antimony oxide, copper-doped bismuth oxide, silver-doped aluminum oxide, silver-doped titanium oxide, silver-doped manganese oxide, silver-doped iron oxide, silver-doped zirconium oxide, silver-doped indium oxide, silver-doped tin oxide, silver-doped antimony oxide, or silver-doped bismuth oxide.

[0008] In one example, material disclosed herein may comprise a solid metal oxide nanomaterial comprising particles that are surface-functionalized, such as where a diameter of the particles is less than one micron, the particles comprise oxygen and a plurality of metals including at least one of zinc, copper, or silver, and the particles are surface functionalized with an electron withdrawing group. One or more additional metals may be selected from aluminum, titanium, manganese, iron, zirconium, indium, tin, antimony, or bismuth. Optionally, the solid metal oxide nanomaterial is surface functionalized with an electron withdrawing group that is not hydroxy or the solid metal oxide nanomaterial comprises a plurality of surface functional groups other than hydroxy. In examples, the solid metal oxide nanomaterial is surface functionalized with an electron withdrawing group selected from one or more of: Cl, CIO, CIO2, CIO3, CIO4, or hydrogenated forms thereof; Br, BrO, BrO2, BrOs, BrO4, or hydrogenated forms thereof; I or IO3; F; S, SO2, SO3, SO4, or hydrogenated forms thereof; N, NO, NO2, NO3, or hydrogenatedforms thereof; BO3or HBO3; CN, SCN, or OCN; or COO, CH3COO, CO3, HCO3, C2O4, C6H7O7, C2H5CO2, C3H7CO2, or C4H9CO2.

[0009] Optionally, the solid metal oxide nanomaterial comprises a matrix of oxygen and a plurality of metals including at least zinc, silver, or copper. In some examples, the plurality of metals includes one or more of zinc, copper, or silver and one or more of aluminum, titanium, manganese, iron, zirconium, indium, tin, antimony, or bismuth. Optionally, the plurality of metals includes lithium or sodium (e.g., zinc, copper, or silver and lithium or sodium and one or more of aluminum, titanium, manganese, iron, zirconium, indium, tin, antimony, or bismuth).

[0010] In some examples, the solid metal oxide nanomaterial comprises zinc oxide mixed with aluminum oxide, zinc oxide mixed with titanium oxide, zinc oxide mixed with manganese oxide, zinc oxide mixed with iron oxide, zinc oxide mixed with zirconium oxide, zinc oxide mixed with indium oxide, zinc oxide mixed with tin oxide, zinc oxide mixed with antimony oxide, zinc oxide mixed with bismuth oxide, copper oxide mixed with aluminum oxide, copper oxide mixed with titanium oxide, copper oxide mixed with manganese oxide, copper oxide mixed with iron oxide, copper oxide mixed with zirconium oxide, copper oxide mixed with indium oxide, copper oxide mixed with tin oxide, copper oxide mixed with antimony oxide, copper oxide mixed with bismuth oxide, silver oxide mixed with aluminum oxide, silver oxide mixed with titanium oxide, silver oxide mixed with manganese oxide, silver oxide mixed with iron oxide, silver oxide mixed with zirconium oxide, silver oxide mixed with indium oxide, silver oxide mixed with tin oxide, silver oxide mixed with antimony oxide, or silver oxide mixed with bismuth oxide.

[0011] In some examples, zinc, copper, or silver is a dopant in the solid metal oxide nanomaterial, such as comprising up to 10 wt.% of the solid metal oxide nanomaterial. In some examples, zinc, copper, or silver may comprise or correspond to a component of the solid metal oxide nanomaterial from 0.01 wt.% to 0.05 wt.%, from 0.05 wt.% to 0.1 wt.%, from 0.1 wt.% to 0.5 wt.%, from 0.5 wt.% to 1 wt.%, from 1 wt.% to 1.5 wt.%, from 1.5 wt.% to 2 wt.%, from 2 wt.% to 3 wt.%, from 3 wt.% to 4 wt.%, from 4 wt.% to 5 wt.%, from 5 wt.% to 6 wt.%, from 6 wt.% to 7 wt.%, from 7 wt.% to 8 wt.%, from 8 wt.% to 9 wt.%, or from 9 wt.% to 10 wt.%. Optionally, a mass ratio of zinc, copper, or silver to all other metals in the solid metal oxide nanomaterial is 0.001 to 0.1 (e g., 0.1 wt.% to 10 wt.% of all metals). Optionally, zinc, copper, or silver may be considered to be more than a dopant and may be present at more than 10 wt.%, such as up to 50 wt.%.

[0012] In some examples, the solid metal oxide nanomaterial has or is characterized by a pH less than 7 when suspended or re-suspended (e.g., after washing and drying), in water at 5 wt.%. Optionally, the solid metal oxide nanomaterial is characterized by a Hammet function Ho greater than -12. Optionally, the solid metal oxide nanomaterial has or is characterized by a pH of from 1 to 2, from 2 to 3, from 3 to 4, from 4 to 5, from 5 to 6, or from 6 to 7.

[0013] In some examples, the solid metal oxide nanomaterial comprises agglomerated particles or dispersed individual particles. Optionally, the solid metal oxide nanomaterial comprises particles having cross-sectional dimensions selected from 1 nm to 1000 nm, such as from 1 nm to 5 nm, from 5 nm to 10 nm, from 10 nm to 20 nm, from 20 nm to 50 nm, from 50 nm to 100 nm, from 100 nm to 150 nm, from 150 nm to 200 nm, from 200 nm to 250 nm, from 250 nm to 300 nm, from 300 nm to 350 nm, from 350 nm to 400 nm, from 400 nm to 450 nm, from 450 nm to 500 nm, from 500 nm to 600 nm, from 600 nm to 700 nm, from 700 nm to 800 nm, from 800 nm to 900 nm, or from 900 nm to 1000 nm. In some examples, the agglomerated particles have cross cross-sectional dimensions selected from 5 nm to 50 pm, such as from 5 nm to 10 nm, from 10 nm to 50 nm, from 50 nm to 100 nm, from 100 nm to 500 nm, from 500 nm to 1 pm, from 1 pm to 2 pm, from 2 pm to 5 pm, from 5 pm to 10 pm, from 10 nm to 20 pm, from 20 pm to 30 pm, from 30 pm to 40 pm, or from 40 pm to 50 pm.

[0014] Optionally, other material may be mixed with the solid metal oxide metal nanomaterial. For example, a carbonaceous material may be mixed with the solid metal oxide nanomaterial. In some examples, the carbonaceous material is present in a mixture in an amount from 0.1 wt.% to 30 wt.%. Optionally, the carbonaceous material is graphite, graphene, carbon black, Ketjenblack, Super P, a fullerene, or a combination of these. In some examples, the carbonaceous material functions as a conductivity enhancer or may serve to provide improved electrical conductivity compared to the mixture without the carbonaceous material.

[0015] In some examples, a cathode active material is mixed with the solid metal oxide nanomaterial. In some examples, the cathode active material is present in a mixture in an amount from 30 wt.% to 99.5 wt.%. Optionally, particles of the solid metal oxide nanomaterial are coated on surfaces of the particles of the cathode active material. In some examples, particles of the solid metal oxide nanomaterial are chemically bonded, mechanically fused, or otherwise bound to or associated with the surface of the cathode active material particles. In examples, the cathode active material is selected from a lithium intercalation cathode active material, a transition metal oxide, a polyanion compound, a lithium conversion cathode active material, or an alkaline cathode material. Optionally, the particles of the solid metal oxide nanomaterialprovide a partial coating on the particles of the cathode active material. In some examples, a coverage (e.g., a surface area coverage) of the particles of the cathode active material by the particles of the solid metal oxide nanomaterial is from 0.1% to 99.9%. Optionally, a weight ratio of the particles of the solid metal oxide nanomaterial to the particles of the cathode active material in a mixture is from 0.01% to 10%, such as from 0.01% to 0.05%, from 0.05% to 0.1%, from 0.1% to 0.5%, from 0.5% to 1.0%, from 1.0% to 1.5%, from 1.5% to 2.0%, from 2.0% to 2.5%, from 2.5% to 3.0%, from 3.0% to 3.5%, from 3.5% to 4.0%, from 4.0% to 4.5%, from 4.5% to 5.0%, from 5.0% to 5.5%, from 5.5% to 6.0%, from 6.0% to 6.5%, from 6.5% to 7.0%, from 7.0% to 7.5%, from 7.5% to 8.0%, from 8.0% to 8.5%, from 8.5% to 9.0%, from 9.0% to 9.5%, or from 9.5% to 10.0%.

[0016] The disclosed materials, including solid metal oxide nanomaterials or mixtures including solid metal oxide nanomaterials, may be used for various applications, such as battery applications. In some examples, an electrode (e.g., a cathode) may comprise a solid metal oxide nanomaterial or a mixture including the solid metal oxide nanomaterial. An electrode may optionally, further comprise one or more additives mixed with the material, such as a conductive material or a binder. In an electrode, the metal oxide nanomaterial may comprise or correspond to an amount from 0.1 wt.% to 20 wt.% and an active electrode material (e.g., cathode active material) may comprise or correspond to an amount from 80 wt.% to 99.9 wt.%. Optionally, an electrode active material may be or comprise a lithium intercalation cathode active material, a lithium conversion cathode active material, or an alkaline cathode active material. Specific example cathode active materials, such as for an alkaline battery, include a manganese oxide, a silver oxide, and / or a nickel oxide.

[0017] The electrode may be incorporated into a battery, such as with a counter electrode (e.g., an anode) and an electrolyte. In examples, the battery is an alkaline battery. In examples, a cathode of the battery comprises a cathode active material mixed with the solid metal oxide nanomaterial, such as a cathode active material comprising a manganese oxide, a silver oxide, and / or a nickel oxide, wherein the anode comprises zinc, copper, or silver. Example electrolytes, such as for an alkaline battery, include aqueous alkali metal hydroxides.

[0018] In examples, a cathode (e.g., a lithium primary cathode or a lithium-ion cathode) comprises a cathode active material mixed with a solid metal oxide nanomaterial, such as a cathode active material comprising a lithium intercalation cathode active material or a lithium conversion cathode active material. Optionally, the anode comprises lithium metal, a lithium intercalation anode active material, or a lithium conversion anode active material. Optionally,the electrolyte comprises a lithium salt and an organic solvent, a lithium polymer electrolyte material, or a lithium solid electrolyte material. In some examples, a lithium intercalation cathode active material comprises a transition metal oxide or a polyanion compound. In some examples, a lithium conversion cathode active material comprises a metal fluoride, a metal chloride, a metal iodide, iodine, a metal sulfide, sulfur, a metal selenide, selenium, or tellurium. In some examples, a lithium intercalation anode active material comprises graphite or lithium titanium oxide. In some examples, a lithium conversion anode active material comprises silicon, tin, germanium, gallium, zinc, cadmium, lead, phosphorus, antimony, or lithium oxide.

[0019] Optionally, the solid metal oxide nanomaterial may be present in a mixture of the solid metal oxide nanomaterial and a solvent. In some cases, such a mixture may be a suspension or dispersion, such as where the solid metal oxide nanomaterial may be mixed in or suspended throughout the solvent, such as in the form of a colloidal mixture. Use of suspensions and dispersions may be advantageous for allowing rapid incorporation into a slurry used for preparing an electrode, such as where the mixture, including the solid metal oxide nanomaterial and the solvent, is mixed with one or more of an electrode active material, a binder, a conductive additive, or additional solvent to ensure adequate mixing of the solid components (e.g., electrode active material, binder, conductive additive, solid metal oxide nanomaterial) in the slurry prior to deposition onto a current collector. In some examples, the mixture of the solid metal oxide nanomaterial and a solvent may include the solid metal oxide nanomaterial at any suitable weight percent, such as from about 1 wt.% to about 50 wt.%, e.g., from 1 wt.% to 5 wt.%, from 5 wt.% to 10 wt.%, from 10 wt.% to 15 wt.%, from 15 wt.% to 20 wt.%, from 20 wt.% to 25 wt.%, from 25 wt.% to 30 wt.%, from 30 wt.% to 35 wt.%, from 35 wt.% to 40 wt.%, from 40 wt.% to 45 wt.%, or from 45 wt.% to 50 wt.%. In some cases, however, the mixture may contain more than 50 wt.% of the solid metal oxide nanomaterial. Other components may be added to the mixture, such as a binder, a conductive additive, dispersants, stabilizers, or the like.

[0020] Without wishing to be bound by any particular theory, there can be discussion herein of beliefs or understandings of underlying principles relating to the invention. It is recognized that regardless of the ultimate correctness of any mechanistic explanation or hypothesis, an embodiment of the invention can nonetheless be operative and useful.BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG. 1 is a simplified cutaway view of an example battery cell.

[0022] FIG. 2 is another simplified cutaway view of an example battery cell with the electrolyte substantially contained by the separator or alternatively including a solid electrolyte.

[0023] FIG. 3 is a schematic of a battery comprising multiple cells.

[0024] FIG. 4 provides a schematic illustration of a metal oxide material.

[0025] FIG. 5 provides a schematic illustration of another metal oxide material.

[0026] FIG. 6 provides a schematic illustration of particles of a metal oxide material.

[0027] FIG. 7 provides a scanning electron micrograph image of a zinc-doped metal oxide material.

[0028] FIG. 8 provides discharge data for a variety of lithium primary cells at a discharge rate of 1C.

[0029] FIG. 9 provides an expanded view of a portion of FIG. 8.

[0030] FIG. 10 provides discharge data for a variety of lithium primary cells at a discharge rate of 5C.

[0031] FIG. 11 provides an expanded view of a portion of FIG. 10.

[0032] FIG. 12 provides cell performance data for lithium-ion secondary cells at different charge / discharge rates.DETAILED DESCRIPTION

[0033] This application provides acidified metal oxide materials, which may be useful as battery cathode materials or battery cathode additives, and related electrodes and electrochemical cells incorporating the acidified metal oxide materials. The acidified metal oxide materials generally correspond to mixed-metal acidified metal oxides, where at least one of the metals in the mixed-metal acidified metal oxides is zinc, copper, or silver. The mixed-metal acidified metal oxides including zinc, copper, or silver may be useful in a variety of battery systems, such as lithium, lithium-ion, or alkaline systems.

[0034] In general, the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references, and contexts known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the invention.

[0035] “Acidic” refers to substances or mixtures, as generally used in the scientific literature, having a pH of less than 7 in aqueous solution.

[0036] “Acidic oxide” refers, as generally used in the scientific literature, to binary compounds of oxygen with a nonmetallic element. An example is carbon dioxide, CO2. Theoxides of some metalloids (e.g., Si, Te, Po) also have weakly acidic properties in their pure molecular state.

[0037] “Acidified metal oxide”, “AMO”, or “AMO material” interchangeably refer to binary compounds of oxygen with a metallic element that has been synthesized to exhibit, modified to exhibit, or generally otherwise exhibits an acidity greater than that of its natural mineralogical state. In some examples, AMOs may also exhibit a Hammet function, Ho, greater than -12 (e.g., not superacidic). It will be appreciated that AMOs may be characterized by, have, or exhibit a pH or surface pH less than 7, such as when suspended in water (or resuspended in water after drying) at 5 wt. %. Optionally, AMOs may have or exhibit a pH or surface pH less than 6, less than 5, less than 4, less than 3, or less than 2. AMOs may also exhibit a particle size less than that of the natural mineralogical state. For example, AMOs may comprise nanomaterials, such as particles having at least one dimension less than 1 pm, less than 100 nm, less than 50 nm, less than 20 nm, less than 10 nm, or falling between 1 nm and 100 nm or between 1 nm and 1000 nm. In some examples, the particles may have average diameters less than or equal to 1000 nm, optionally in a range of 1 nm to 20 nm, 20 to 50 nm, 50 to 100 nm, 100 to 150 nm, 150 to 200 nm, 200 to 500 nm, or 500 to 1000 nm. In some examples, larger particles may be included in a distribution of particles of AMOs. Particles of AMOs may be dispersed individual particles or agglomerates (also referred to as aggregates) comprising multiple individual particles. Naturally occurring mineralogical forms do not fall within the scope of the inventive AMO material. A synthesized metal oxide, however, that is more acidic than its most abundant naturally occurring mineralogical form (of equivalent base stoichiometry), but not superacidic, may be characterized as an AMO material provided it satisfies certain other conditions discussed in this disclosure.

[0038] “Battery,” “battery cell,” “electrochemical cell,” “cell” and like terms are generally used herein interchangeably to refer to a device comprising a cathode, anode, and electrolyte between them to allow for electrical energy to be stored or discharged through the transfer of electrons and ions between the anode and the cathode. In some cases, a battery may refer to devices including a plurality of electrochemical cells and optionally supporting circuitry, but a device including a single electrochemical cell may still be referred to as a battery.

[0039] “Coated” or “ coating” refers herein to a distribution of the metal oxide nanoparticles on a surface of a cathode active material particle, such as where the metal oxide nanoparticles are not simply physically sitting on top of or adjacent to the cathode active material particles but are instead bonded (e.g., chemically bonded), fused (e.g., mechanically fused), or otherwisechemically associated with or bound to the cathode active material particle at a surface or interface. In various examples, a high-shear or high-energy mixing process may be used for bonding the metal oxide nanoparticles to the cathode active material particles, though other techniques may be used for generating a metal oxide nanoparticle coating on a cathode active material.

[0040] “Electron-withdrawing group” or “EWG” refers to an atom or molecular group that draws electron density towards itself. The strength of an EWG may be based upon its known behavior in chemical reactions. Halogens, for example, are known to be strong EWGs. Organic acid groups, such as acetate, are known to be weakly electron withdrawing.

[0041] “Hammet function” or “Hammet number” refers to an additional means of quantifying acidity besides pH and is typically useful in highly concentrated acid solutions and in superacids. A Hammet acidity function is generally defined by the following equation: Ho =PKBH+ + log([B] / [BH+]). On this scale, pure 18.4 molar H2SO4 has a Ho value of -12. The value Ho = -12 for pure sulfuric acid must not be interpreted as pH = -12, instead it means that the acid species present has a protonating ability equivalent to TbO at a fictitious (ideal) concentration of 1012mol / L, as measured by its ability to protonate weak bases. The Hammet acidity function avoids water in its equation. It is used herein to provide a quantitative means of distinguishing AMO material from superacids. The Hammet function can be correlated with colorimetric indicator tests and temperature programmed desorption results.

[0042] “Metal oxide” refers, as generally used in the scientific literature, to compounds of oxygen with one or more metallic elements. In examples, a metal oxide may be referred to as MO, where M ix a metal and O is oxygen, without specifying stoichiometry between the metal and oxygen. In some examples, a metal oxide may be referred to as MmOx, where m is the relative stoichiometry of the metal and x is the relative stoichiometry of oxygen. In examples, m may be from 1 to 5 and x may be from 1 to 5. Generally, oxygen will adopt a -2 oxidation state such that m relates to the number of metal atoms at the metal atom oxidation state to balance x atoms of oxygen and form a neutral metal oxide. Depending on their position in the periodic table, metal oxides range from weakly basic to amphoteric (showing both acidic and basic properties) in their pure molecular state. Weakly basic metal oxides are the oxides of lithium, sodium, magnesium, potassium, calcium, rubidium, strontium, indium, cesium, barium, and tellurium. Amphoteric oxides are those of beryllium, aluminum, gallium, germanium, astatine, tin, antimony, lead, and bismuth. These and other metal oxides may optionally be useful as AMO materials. The acidic character of a metal oxide may be modified from its naturalmineralogical form, such as by bonding one or more electron withdrawing groups (e.g., groups other than hydroxy) to surfaces of the metal oxide. In some examples, metal oxides may be binary metal oxides, such as where a single metal is present. In other examples, metal oxides may be mixed metal oxides, such as where multiple different metals are present, such that M represents two or more metals in the formula MmOx, and may be represented as MlmiM2m20x, where Ml and M2 are different metals and ml and m2 represent different stoichiometric fractions of metals Ml and M2, respectively.

[0043] “Metallic lithium” or ‘ “lithium metal” refers to lithium in its neutral atomic state (e.g., non-ionic state). The term metallic lithium is intended to distinguish over other forms of lithium including lithium ions and lithium compounds (e.g., lithium salts). The term metallic lithium may refer to neutral atomic lithium present in mixtures that comprise lithium atoms, such as mixtures of lithium and other elements, compounds, or substances. The term metallic lithium may refer to neutral atomic lithium present in lithium alloys, such as a metallic mixture including lithium and one or more other metals. The term metallic lithium may refer to neutral atomic lithium present in composite structures including lithium and one or more other materials.Electrodes comprising or including metallic lithium may include other materials besides lithium, but it will be appreciated that metallic lithium may correspond to an active material of such an electrode. In some cases, an anode in an electrochemical cell (e.g., a lithium primary cell) comprises metallic lithium.

[0044] “pH” refers, as generally used in the scientific literature, to a functional numeric scale that specifies the acidity or alkalinity of an aqueous solution. It is the negative of the logarithm of the concentration of the hydronium ion [FEO-]. As used herein, pH may be used to describe the relative acidity of particles suspended or dispersed in an aqueous solution.

[0045] “Surface functionalization” refers to the attachment of atoms or molecular groups to the surface of a material or particle. In some examples, AMO material may be surface functionalized by covalently bonding EWGs to the surface of the AMO material.

[0046] “Superacid” refers to substances that are more acidic than 100% H2SO4, having a Hammet function, Ho, less than -12.

[0047] Referring now to FIG. 1, a battery cell 100 is illustrated in a simplified cutaway view, here exemplified as a lithium-ion battery for convenience to discuss operation of the cell, but such example will be appreciated as being non-limiting and other battery cell chemistries will be understood to those of skill in the art (e.g., a lithium primary battery or an alkaline battery). The cell 100 may comprise a casing or container 102. In some examples, the casing 102 comprises apolymer or an alloy, such as a plastic film or stainless steel. The casing 102 physically, chemically, and electrically isolates the contents of the cell 100 from adjacent cells, from contamination, from the environment, and from damaging or being damaged by other components of the device into which the cell 100 is installed. In some examples, the casing 102 may include multiple components, optionally with an electrically insulating seal between different components. In some examples, the casing 102 may act, at least in part, as an external terminal or terminals for the cell 100. A full battery may contain a plurality of cells arranged in a series and / or parallel configuration, but optionally may include only a single cell. The battery may have a further casing or securement mechanism binding the plurality of cells together, as is known in the art. The arrangement and structure of battery cell 100 depicted in FIG. 1 is merely one example and is not intended to be limiting; other cell structures, components, and arrangements are possible.

[0048] The cell 100 comprises a cathode 104 and an anode 106. The contents of the cell 100 undergo a chemical reaction when a conduction path is provided between the cathode 104 and anode 106 that is external to the cell 100, such as by way of element 115. As a result of the chemical reaction, electrons are provided from the anode 106 and flow through element 115 (sometimes referred to as a load) to the cathode 104 via the circuit provided external to the cell. At a basic level, during discharge of the cell 100, the materials comprising the anode 106 are oxidized providing the electrons that flow through the circuit. The materials comprising the cathode 104, as recipient of the electrons given up by the anode 106, are reduced.

[0049] Within the cell 100, during discharge, working ions move from the cathode 104 to the anode 106, such as by way of an electrolyte 108. In the case of a lithium-ion or lithium primary battery, the working ion may be lithium (Li+), and the lithium ions move from the anode 106 to the cathode 104 during discharge. In the case of an alkaline battery, the working ion may be hydroxide ion (OH), and the hydroxide ions move, overall, from the cathode 104 to the anode 106 during discharge. In examples, any suitable electrolyte 108 for the specific battery chemistry may be used. For lithium-ion or lithium primary cells, the electrolyte may comprise a lithium salt in a nonaqueous solvent, such as a carbonate solvent. For an alkaline battery, the electrolyte may comprise an aqueous solution of potassium hydroxide, ammonium hydroxide, and / or sodium hydroxide.

[0050] A separator 110 may be employed to prevent contact between the electrodes 104, 106. The separator 110 may be a porous layer of material that is permeable to the working ions and the electrolyte 108 but not otherwise electrically conductive so as to prevent internal shortingof the cell 100. As is known in the art, the separator 110 may comprise glass fibers, paper, or may comprise a polymer, possibly with a semi-crystalline structure, or other solid-state electrolyte structure suitable for the particular chemistry of the cell 100. Additional components, such as current collectors, may also be included in the cell 100, but are not shown in FIG. 1.

[0051] Together the anode 104, cathode 106, electrolyte 108, and separator 110 form the completed cell 100. When the separator 110 is porous, the electrolyte 108 may flow into, or be contained by, the separator 110. Under normal operating conditions, the porosity or chemical makeup of the separator 110 allows for the working ion (e.g., Li+or OH) to flow between the electrodes 104, 106 via the electrolyte 108. In some examples, the separator 110 may not be present or may be combined with the electrolyte 108, such as in the form of a solid-state electrolyte.

[0052] Cells and batteries according to the present disclosure primarily include primary (e.g., single use) batteries, but secondary (e.g., rechargeable) batteries also fall within the scope of the disclosed cells and batteries. In the case of the cell 100 being a secondary cell (or part of a secondary battery) it should be understood that the cell 100 may be recharged either alone or as a component of a completed system wherein multiple cells are recharged simultaneously (and possibly in the same parallel or series circuit). It will be appreciated that most alkaline cells are constructed, marketed, or otherwise adopted as primary cells and that charging operations on such cells generally may not occur. FIG. 1 shows movement of lithium ions and electrons during both discharging and charging as the aspects provided herein are applicable to secondary cells, though primary cells are contemplated. Charging and the resultant movement of ions and electrons would generally not be desirable or applicable for primary cells.

[0053] A reverse voltage is applied to the cell 100 in order to effect charging. It should be understood that various schemes for effective recharging of batteries can be employed. The present disclosure is not intended to be limited to a particular charging methodology unless stated in the claims. During charging of cell 100, element 115 represents a voltage source that is applied between cathode 104 and anode 106 to provide electrons from cathode 105 to anode 106 and allow chemical reactions to take place.

[0054] It should be understood that FIG. 1 is not necessarily to scale. As shown in FIG. 2, in some applications, the separator 110 occupies most or all of the space between the electrodes 104, 106 and is in contact with the electrodes 104, 106. In such case, the electrolyte 108 is contained within the separator 110 (but may also intrude into the pores or surface of the anode or cathode). FIG. 2 can also depict the general structure where a solid-state electrolyte occupies thespace between the electrodes 104, 106. FIG. 2 is also not necessarily to scale. The actual geometry of a cell can be relatively thin and flat, such as in the form of pouches, canister type constructions, wound cells, button cells, coin cells, or others, including conventional cylindrical constructions with a pin-type current collectors, jelly roll construction with tabbed current collectors, etc. Cell construction techniques such as winding, bobbin, pin type assemblies or canister construction may be used.

[0055] Current collectors known in the art and other components (not shown) may also be relied upon to form a cell 100 into a commercially viable package. Although overall shape or geometry may vary, a cell or battery will normally, at some location or cross section, contain the electrodes 104, 106 separated rather than touching, and have the electrolyte 108 and / or separator 110 between them. Cells may also be constructed such that there are multiple layers of anodes and cathodes. Cells may be constructed such that two cathodes are on opposite sides of a single anode or vice versa.

[0056] A functional or operational battery intended for a specific purpose may comprise a plurality of cells arranged according to the needs of a particular application. An example of such a battery 300 is shown schematically in FIG. 3. Here the battery 300 comprises four cells 100 arranged in series to increase voltage, but various arrangements including series, parallel, or combination series and parallel can be used in any desired configuration.

[0057] A positive electrode terminal 306 may be accessible on the outside of a casing 302 of the battery 300. A negative electrode terminal 304 is also provided. The physical form factor of the electrode terminals 304, 306 may vary according to application. Various binders, glues, tapes and / or other securement mechanisms (not shown) may be employed within a battery casing 302 to stabilize the other components. Many batteries are operable and storable in any orientation. As discussed above, cells 100 may take on various different geometric shapes. Thus, FIG. 3 is not meant to represent any particular physical form factor of the battery 300.

[0058] The battery 300 may also comprise various adjunct circuitry 308, here shown as interposing the positive electrode terminal 306 and the cells 100 within the casing 302 of the battery 300, but any desired configuration can be used, such as where the adjunct circuitry 308 interposes the negative electrode terminal 304 and the cells 100 instead of, or in addition to, interposing the positive electrode terminal 306 and the cells 100. The adjunct circuitry 308 may be constructed so as to interface with any of the cathodes and anodes of the individual cells 100 within battery 300. The adjunct circuitry may include short circuit protection, overcharge protection, overheating shutdown, battery management, or other circuitry as is known in the artto protect, monitor, operate, balance, charge, etc. the battery 300, the cells 100, and / or any load attached to the battery 300. In some examples, the adjunct circuitry 308 may perform additional functions.

[0059] FIG. 4 provides a schematic illustration of an example metal oxide material 400, comprising atoms of oxygen 405, a first metal 410, and a second metal 415. Such metal oxide material 400 may correspond to the bulk of particles of an acidified metal oxide material as disclosed herein. In examples, the metal oxide material 400 may optionally include surface functionalization, such as where various groups (e.g., any one or more or any combination of Cl, CIO, CIO2, CIO3, C1O4, Br, BrO, BrO2, BrO3, BrO4, 1, IO3, F, S, SO2, SO3, SO4, N, NO, NO2, NO3, BO3 or HBO3, CN, SCN, OCN, COO, CH3COO, CO3, HCO3, C2O4, C6H7O7, C2H5CO2, C3H7CO2, or C4H9CO2) are present on the surface of particles of the metal oxide material 400 (e.g., as depicted in further detail in FIG. 6). In examples, the surface functional groups are distinguished and different from hydroxy groups (-OH), which may form naturally through interaction of oxygen atoms in the metal oxide with hydrogen atoms in the environment (e.g., via water). Surface functional groups are not illustrated in FIG. 4. Instead, FIG. 4 depicts a crystal structure or matrix of atoms of oxygen 405, first metal 410, and second metal 415 to illustrate that the metal oxide may include a distribution of atoms of first metal 410 and second metal 415 throughout the particles making up metal oxide material 400, along with atoms of oxygen 405. It will be appreciated that FIG. 4 does not represent any specific crystal structure but instead can correspond to any suitable crystal, polycrystal, or amorphous structure to show that both the first metal 410 and second metal 415 are mixed in the matrix of metal oxide material 400 instead of merely separated as individual domains of separate oxides of first metal 410 and second metal 415. It will be appreciated that the crystal structure or distribution of atoms in metal oxide material 400 may be dictated by the specific identity and relative amounts of oxygen 405, first metal 410, and second metal 415.

[0060] FIG. 5 provides a schematic illustration of an example metal oxide material 500, comprising atoms of oxygen 505, a first metal 510, and a second metal 515. Such metal oxide material 500 may correspond to the bulk of particles of an acidified metal oxide material as disclosed herein. In examples, the metal oxide material 500 may optionally include surface functionalization, such as where various groups (e.g., any one or more or any combination of Cl, CIO, CIO2, CIO3, C1O4, Br, BrO, BrO2, BrO3, BrO4, 1, IO3, F, S, SO2, SO3, SO4, N, NO, NO2, NO3, BO3 or HBO3, CN, SCN, OCN, COO, CH3COO, CO3, HCO3, C2O4, C6H7O7, C2H5CO2, C3H7CO2, or C4H9CO2) are present on the surface of particles of the metal oxide material 500(e.g., as depicted in further detail in FIG. 6). In examples, the surface functional groups are distinguished and different from hydroxy groups (-OH), which may form naturally through interaction of oxygen atoms in the metal oxide with hydrogen atoms in the environment (e.g., via water). Surface functional groups are not illustrated in FIG. 5. Instead, FIG. 5 depicts a crystal structure or matrix of atoms of oxygen 405, first metal 410, and second metal 415 to illustrate that the metal oxide may include separate metal oxide domains in the particle, such as where atoms of first metal 410 are separated from atoms of second metal 415. It will be appreciated that FIG. 5 does not represent any specific crystal structure but instead can correspond to any suitable crystal, polycrystal, or amorphous structure to show that both the first metal 510 and second metal 515 are arranged as separated individual domains of separate oxides of first metal 510 and second metal 515. It will be appreciated that the crystal structure or distribution of atoms in metal oxide material 500 may be dictated by the specific identity and / or relative amounts of oxygen 505, first metal 510, and second metal 515. Though mixed metal oxides are depicted in FIG. 4 and separate metal oxide domains are depicted in FIG. 5, examples may include structures where both mixed metal oxides and separate domains are present.[0061J As illustrated in FIG. 4 and FIG. 5, first metal 410 and second metal 415 or first metal 510 and second metal 515 each make up about half of the metal component of the respective metal oxide material 400, 500, by atom% or mol%. Such configuration is not intended to be limiting, and the first metal 410, 510 and second metal 415, 515 can each comprise any suitable amount of the metal oxide material 400, 500. Although atomic percent (atom %) or mole percent (mol%) is referred here, in practice weight percent (wt.%) may be used instead. In some examples the first metal 410, 510 and second metal 415, 515 each comprise 0.1 wt.% to 99.9 wt.% of the metals in the metal oxide material 400, 500. In some examples, additional metals may be present. Example compositional ranges for each metal component of metal oxide material 400, 500 may be from 0.1 wt.% to 1 wt.%, from 1 wt.% to 5 wt.%, from 5 wt.% to 10 wt.%, from 10 wt.% to 15 wt.%, from 15 wt.% to 20 wt.%, from 20 wt.% to 25 wt.%, from 25 wt.% to 30 wt.%, from 30 wt.% to 35 wt.%, from 35 wt.% to 40 wt.%, from 40 wt.% to 45 wt.%, from 45 wt.% to 50 wt.%, from 50 wt.% to 55 wt.%, from 55 wt.% to 60 wt.%, from 60 wt.% to 65 wt.%, from 65 wt.% to 70 wt.%, from 70 wt.% to 75 wt.%, from 75 wt.% to 80 wt.%, from 80 wt.% to 85 wt.%, from 85 wt.% to 90 wt.%, from 90 wt.% to 95 wt.%, from 95 wt.% to 99 wt.%, or from 99 wt.% to 99.9 wt.%. In some examples, first metal 410, 510 may be present as a minor component of metal oxide material 400, 500, such as in amounts of up to about 10 wt.% of all metals present in metal oxide material 400, 500 (e.g., from 0.01 wt.% to 0.5 wt.%, from 0.5 wt.%to 1.0 wt.%, from 1.0 wt.% to 1.5 wt.%, from 1.5 wt.% to 2.0 wt.%, from 2.0 wt.% to 2.5 wt.%, from 2.5 wt.% to 3.0 wt.%, from 3.0 wt.% to 3.5 wt.%, from 3.5 wt.% to 4.0 wt.%, from 4.0 wt.% to 4.5 wt.%, from 4.5 wt.% to 5.0 wt.%, from 5.0 wt.% to 5.5 wt.%, from 5.5 wt.% to 6.0 wt.%, from 6.0 wt.% to 6.5 wt.%, from 6.5 wt.% to 7.0 wt.%, from 7.0 wt.% to 7.5 wt.%, from 7.5 wt.% to 8.0 wt.%, from 8.0 wt.% to 8.5 wt.%, from 8.5 wt.% to 9.0 wt.%, from 9.0 wt.% to 9.5 wt.%, or from 9.5 wt.% to 10.0 wt.%). Suitable metals for first metal 410, 510 include one or more of zinc, copper, or silver (or a combination thereof). Suitable metals for second metal 415, 515 include, but are not limited to, one or more of aluminum, titanium, manganese, iron, zirconium, indium, tin, antimony, or bismuth (or a combination thereof).

[0062] FIG. 6 provides a schematic illustration of an individual particle 600 and agglomerated particles 650 of a metal oxide material, each including a matrix 605 of metal oxide, which may be the same as or different from metal oxide material 400 or metal oxide material 500. Here, each agglomerated particle 650 includes multiple individual particles. The bulk or matrix 605 of individual particle 600 and agglomerated particles 650 may include any suitable metal oxide materials as described herein, such as comprising oxygen and a plurality of metals (e.g., at least one of zinc, copper, or silver and at least one of aluminum, titanium, manganese, iron, zirconium, indium, tin, antimony, or bismuth). FIG. 6 also shows that individual particle 600 and agglomerated particles 650 can optionally include surface functional groups 620. The surface functional groups 620 here may represent electron withdrawing groups other than hyroxy (OH). Example functional groups include one or more of Cl, CIO, CIO2, CIO3, CIO4, or hydrogenated forms thereof; Br, BrO, BrO2, BrOs, BrO4, or hydrogenated forms thereof; I or IO; F; S, SO2, SO3, SO4, or hydrogenated forms thereof; N, NO, NO2, NO3, or hydrogenated forms thereof; PO3, PO4, or hydrogenated forms thereof; BO3 or HBO3; CN, SCN, or OCN; or COO, CH3COO, CO3, HCO3, C2O4, C6H7O7, C2H5CO2, C3H7CO2, or C4H9CO2.

[0063] Individual particle 600 and / or agglomerated particles 650 may be used in various applications described herein, such as for components of an electrode of an electrochemical cell (e.g., a cathode). In examples, the electrode may comprise particles 600, 650 in significant amounts (e.g., from 0.01 wt.% to 10 wt.%), as described herein. The particles 600, 650 may be mixed with other particles or components of the electrode, such as active material components, conductive additives, binders, etc. In some cases, the particles 600, 650 are coated onto particles of the active material.

[0064] Aspects of the invention may be further understood by the following non-limiting examples.EXAMPLE 1 : PREPARATION OF MIXED-METAL OXIDE MATERIALS

[0065] Metal oxide materials are generally prepared according to the techniques described in U.S. Patent Nos. 9,786,910, 10,553,861, 10,566,620, 10,978,704, 11,302,912, 11,581,536, 11,641,014,11,962,004, 11,973,224, 12,009,508, and 12,087,901, hereby incorporated by reference. For the mixed-metal oxides described herein, different reactants may be used. By way of example, the following general procedure is used. Initially, masses of a first metal salt and a second metal salt are dissolved in a solution of absolute ethanol and distilled water. The resulting solution is stirred to ensure good dissolution. The solution is acidified by the addition of a suitable aqueous acid, added dropwise, with the resulting solution stirred to ensure good dissolution. Suitable acids for preparation of the mixed-metal oxide materials include relatively strong acids, such as halide acids (e.g., HC1, HBr, HI), nitric acid, or sulfuric acid, or optionally relatively weak acids, such as acetic acid, optionally in combination with a strong acid. The solution is then basified by the addition of a suitable aqueous base, added dropwise, until the pH of the solution is about 8.5. Suitable aqueous bases include ammonium or alkali-metal hydroxides. The resulting suspension is then placed in a hot-water bath (~ 60° to 90° C) while under stirring. The suspended solid material is then collected and washed with distilled water and absolute ethanol. The washed suspension is dried at 100 °C for 1 hour in air and then annealed at 200 °C for 4 hours in air.

[0066] Several mixed-metal oxide materials were prepared, including mixed zinc oxide and iron oxide, mixed zinc oxide and tin oxide, mixed zinc oxide and manganese oxide, mixed copper oxide and tin oxide, and mixed copper oxide and manganese oxide. For preparing zinc oxide-containing materials, ZnCh was used, at least in part, as a reactant. For preparing copper oxide-containing materials, CuCh was used, at least in part, as a reactant. Other suitable salts are useful for preparing zinc oxide-, copper-oxide-, and silver oxide-containing materials, including suitable sulfate salts, chloride salts, bromide salts, nitrate salts, acetate salts, cyanide salts, etc. Additionally, other metals may be used for mixing with the zinc, copper, or silver besides iron, manganese, or tin, including aluminum, antimony, bismuth, titanium, zirconium, or indium.

[0067] Chemical analyses were conducted on some of the prepared metal oxide materials, showing that the zinc oxide-containing samples included zinc in amounts of about 0.7 wt.% to about 7 wt.%, and that the copper oxide-containing samples included copper in amounts of about 3 to about 4 wt.%.

[0068] Scanning electron micrograph (SEM) images of zinc oxide-containing metal oxide materials were obtained. An example SEM image is depicted in FIG. 7, showing individual andagglomerated metal oxide nanoparticles, with individual nanoparticles having dimensions smaller than 1 pm, and even smaller than 100 nm.

[0069] The prepared metal oxide materials were also evaluated for acidity. As an example, the acidity was measured by preparing a room-temperature aqueous suspension of the metal oxide materials at 5 wt.%. The pH of samples of the copper-containing metal oxide material were found to be in the range of about 3.7 to about 5. The pH of samples of the zinc-containing metal oxide material were found to be in the range of about 2.5 to 6.6.EXAMPLE 2: ALKALINE ELECTROCHEMICAL CELL TESTING

[0070] Alkaline electrochemical half cells (cathode limited) were prepared and tested for this Example. The cells were prepared using electrolytic manganese dioxide (EMD) as the cathode active material with a small amount (about 4 wt.%) of a conductive carbon (graphite). Test cells were prepared by including in the cathode up to about 2.5 wt.% of a mixed-metal oxide material (e.g., Zn-containing or Cu-containing) from Example 1 as an additive in place of some of the EMD, while control cells were prepared with no mixed metal oxide material, using only EMD and graphite. The cathodes are prepared by mixing the mixed-metal oxide material with the cathode active material and conductive carbon and pressing into pellets according to typical pellet pressing procedures. All cells were constructed using a zinc anode and a potassium hydroxide electrolyte. The test cells and control cells were subjected to an 85 mA / g discharge rate, either immediately or after aging for two weeks at elevated temperature (e.g., > 40 °C) to expedite aging. Specific capacities of each cell for discharging to 1.2 V, 1.0 V, or 0.8 V at a discharge rate of 85 mA / g were measured. The specific capacity results are summarized in Table 1. Overall, the Zn-containing and Cu-containing mixed-metal oxide additives were found to improve the specific capacity in both the fresh and aged cells, indicating the additives improve alkaline performance and shelf-stability.Table 1.EXAMPLE 3 : LITHIUM PRIMARY ELECTROCHEMICAL CELL TESTING

[0071] Lithium primary electrochemical cells were prepared and tested for this Example. The cells were prepared using electrolytic manganese dioxide (EMD) as the cathode active material with a small amount (about 2 wt.%) of a conductive carbon and a small amount (about 2 wt.%) of a binder. Test cells were prepared by including in the cathode up to about 10 wt.% of a mixed-metal oxide material (e.g., Zn-containing or Cu-containing) from Example 1 as an additive in place of some of the EMD, while control cells were prepared with no mixed-metal oxide material, using only EMD and the conductive carbon and binder. Cathode slurries are prepared by mixing the cathode active material, conductive carbon, binder, and mixed metal oxide material in the desired weight ratios with a solvent (e.g., N-methyl-2-pyrrolidone (NMP)) until a homogenous slurry is formed. All cathodes are constructed by tape casting the cathode slurry onto an aluminum foil current collector and allowing the solvent to evaporate. Cells are prepared by pairing the cathode with a lithium metal anode on a copper current collector, a LiCICh-based carbonate electrolyte, and a polypropylene separator, and assembling into coin cells. The cells were subjected to discharge at 1C and 5C. Voltage was monitored as a function of discharge capacity and the discharge profile of the test and control cells.

[0072] FIG. 8 provides the discharge profile of the test and control cells at 1C discharge and FIG. 9 provides an expanded view of the data from FIG. 8 in the range of 0.8 V to 1.2 V. The test cells both show improvements in total capacity in the range of 1.2 V to 0.8 V and lower. The cell including Cu-containing mixed-metal oxide material shows overall capacity improvements compared to the control cell starting from about 1.8 V, while the cell including Zn-containing mixed-metal oxide material shows overall capacity improvements from about 1.4 V.

[0073] FIG. 10 provides the discharge profile of the test and control cells at 5C discharge and FIG. 11 provides an expanded view of the data from FIG. 10 in the range of 0.8 V to 1.2 V. In these results, the cell including Zn-containing mixed-metal oxide material shows overall capacity improvements compared to the control cell starting from about 0.35 V, while the cell including Zn-containing mixed-metal oxide material shows overall capacity improvements from about 1.4 V.EXAMPLE 4: LITHIUM SECONDARY ELECTROCHEMICAL CELL TESTING

[0074] Lithium secondary electrochemical cells were prepared and tested for this Example. The cells were prepared using lithium nickel manganese cobalt oxide (NMC) as the cathode active material with a small amount (about 2 wt.%) of a conductive carbon and a small amount (about 2 wt.%) of a binder. Test cells were prepared by including in the cathode up to about 6 wt.% of a mixed-metal oxide material (e.g., Zn-containing or Cu-containing) from Example 1 as an additive in place of some of the NMC, while control cells were prepared with no mixed metal oxide material, using only NMC and the conductive carbon and binder. Cathode slurries are prepared by mixing the cathode active material, conductive carbon, binder, and mixed metal oxide material in the desired weight ratios with a solvent (e.g., N-methyl-2-pyrrolidone (NMP)) until a homogenous slurry is formed. All cathodes are constructed by tape casting the cathode slurry onto an aluminum foil current collector and allowing the solvent to evaporate. All cells were constructed by pairing the cathode with a graphite anode on a copper current collector, a LiPFe-based carbonate electrolyte, and a polypropylene separator, and assembling into coin cells prior to formation at C / 10. For rate performance evaluation, the cells were subjected to C / 2, 1C, 2C, 5C symmetric cycling, asymmetric cycling at 1C, 2C, 3C, 5C discharge with C / 3 charge, and asymmetric cycling at C / 3 discharge and 1C, 2C, 3C, 4C charge. FIG. 12 provides data showing the measured specific capacity for formation, symmetric cycling, and asymmetric (C / 3 charging) cycling. In general, the control was outperformed at the highest discharge rates by both the Zn-containing and the Cu-containing mixed-metal oxide material.REFERENCES

[0075] U.S. Patent No. 9,786,910, 10,553,861, 10,566,620, 10,978,704, 11,302,912, 11,581,536, 11,641,014, 11,962,004, 11,973,224, 12,009,508, and 12,087,901.

[0076] Absi et al., 2025, “Silver oxide nanoparticles: Synthesis and characterization by thermal treatment technique,” Physica B, 715, 417636, DOI: 10.1016 / j.physb.2025.417636

[0077] Ahmad et al., 2017, “Effect of (Mn-Co) co-doping on the structural, morphological, optical, photoluminescence and electrical properties of SnO2,” Journal of Alloys and Compounds, 720, 502-509, DOI: 10.1016 / j.jallcom.2017.05.293

[0078] Medhi et al., 2019, “Uniformly spherical and monodisperse antimony- and zinc-doped tin oxide nanoparticles for optical and electronic applications,” ACS Appl. Nano Mater., 2, 6554-6564, DOI: 10.1021 / acsanm.9b01474

[0079] Ramah et al., 2021, “Double hydrothermal synthesis of iron oxide / silver oxide nanocomposites with antibacterial activity,” J. Meeh. Beh. Mater., 30, 207-212, DOI:10.1515 / jmbm-2021-0021

[0080] Rao et al., 1970, “Electrical Conduction in Metal Oxides,” Phys. Stat. Sol. (a), 1(4), 597-652, DOI: 10.1002 / pssa.19700010402

[0081] Thangamani et al., 2021, “Hydrothermal synthesis of copper (II) oxide-nanoparticles with highly enhanced BTEX gas sensing performance using chemiresi stive sensor,” Chemosphere, 7, 130237, DOI: 10.1016 / j.chemosphere.2021.130237STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS

[0082] All references throughout this application, for example patent documents, including issued or granted patents or equivalents and patent application publications, and non-patent literature documents or other source material are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference.

[0083] All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art, in some cases as of their filing date, and it is intended that this information can be employed herein, if needed, to exclude (for example, to disclaim) specific embodiments that are in the prior art.

[0084] When a group of substituents is disclosed herein, it is understood that all individual members of those groups and all subgroups and classes that can be formed using the substituents are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. As used herein, “and / or” means that one, all, or any combination of items in a list separated by “and / or” are included in the list; for example “1, 2 and / or 3” is equivalent to “1, 2, 3, 1 and 2, 1 and 3, 2 and 3, or 1, 2, and 3”.

[0085] Every formulation or combination of components described or exemplified can be used to practice the invention, unless otherwise stated. Specific names of materials are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same material differently. It will be appreciated that methods, device elements, starting materials, and synthetic methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such methods, device elements, starting materials, and synthetic methods are intended to beincluded in this invention. Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure.

[0086] As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of’ excludes any element, step, or ingredient not specified in the claim element. As used herein, “consisting essentially of’ does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. Any recitation herein of the term “comprising”, particularly in a description of components of a composition, in a description of a method, or in a description of elements of a device, is understood to encompass those compositions, methods, or devices consisting essentially of and consisting of the recited components or elements, optionally in addition to other components or elements. The invention illustratively described herein suitably may be practiced in the absence of any element, elements, limitation, or limitations which is not specifically disclosed herein.

[0087] The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.

Claims

Attorney Docket No. 009052-00234 (TNP0027-PCT) WHAT IS CLAIMED IS:

1. A material comprising:a solid metal oxide nanomaterial including zinc, copper, or silver and at least one other metal oxide, the solid metal oxide nanomaterial having or characterized by a pH less than 7, the pH measured when the solid metal oxide nanomaterial is dried and the dried solid oxide nanomaterial is suspended in an aqueous solution at 5 wt.%; ora solid metal oxide nanomaterial having a composition MmOx / G, wherein M comprises zinc, copper, or silver and at least one other metal, wherein O is oxygen, wherein MmOx represents a metal oxide, wherein m and x represent relative molar amounts of M and O, respectively, wherein G is at least one electron-withdrawing surface group, and whereinmakes a distinction between the metal oxide and the electron-withdrawing surface group; or a solid metal oxide nanomaterial selected from the group consisting of zinc-doped aluminum oxide, zinc-doped titanium oxide, zinc-doped manganese oxide, zinc-doped iron oxide, zinc-doped zirconium oxide, zinc-doped indium oxide, zinc-doped tin oxide, zinc-doped antimony oxide, zinc-doped bismuth oxide, copper-doped aluminum oxide, copper-doped titanium oxide, copper-doped manganese oxide, copper-doped iron oxide, copper-doped zirconium oxide, copper-doped indium oxide, copper-doped tin oxide, copper-doped antimony oxide, copper-doped bismuth oxide, silver-doped aluminum oxide, silver-doped titanium oxide, silver-doped manganese oxide, silver-doped iron oxide, silver-doped zirconium oxide, silver-doped indium oxide, silver-doped tin oxide, silver-doped antimony oxide, or silver-doped bismuth oxide; ora solid metal oxide nanomaterial comprising particles that are surface-functionalized, wherein a diameter of the particles is less than one micron, wherein the particles comprise oxygen and a plurality of metals including at least one of zinc, copper, or silver, and wherein the particles are surface functionalized with an electron withdrawing group.

2. The material of claim 1, wherein the solid metal oxide nanomaterial is surface functionalized with an electron withdrawing group that is not hydroxy or wherein the solid metal oxide nanomaterial comprises a plurality of surface functional groups other than hydroxy.

3. The material of claim 1, wherein the solid metal oxide nanomaterial is surface functionalized with an electron withdrawing group selected from one or more of:Cl, CIO, CIO2, CIO3, CIO4, or hydrogenated forms thereof;Br, BrO, BrO2, BrOa, BrO4, or hydrogenated forms thereof;I or IO3;F;S, SO2, SO3, SO4, or hydrogenated forms thereof;N, NO, NO2, NO3, or hydrogenated forms thereof;BO3 or HBO3;CN, SCN, or OCN; orCOO, CH3COO, CO3, HCO3, C2O4, C6H7O7, C2H5CO2, C3H7CO2, or C4H9CO24. The material of claim 1, wherein the solid metal oxide nanomaterial comprises a matrix of oxygen and a plurality of metals including at least zinc, silver, or copper.

5. The material of claim 4, wherein the plurality of metals include one or more of zinc, copper, or silver and one or more of aluminum, titanium, manganese, iron, zirconium, indium, tin, antimony, or bismuth.

6. The material of claim 5, wherein the plurality of metals further includes lithium or sodium.

7. The material of claim 1, wherein the solid metal oxide nanomaterial comprises zinc oxide mixed with aluminum oxide, zinc oxide mixed with titanium oxide, zinc oxide mixed with manganese oxide, zinc oxide mixed with iron oxide, zinc oxide mixed with zirconium oxide, zinc oxide mixed with indium oxide, zinc oxide mixed with tin oxide, zinc oxide mixed with antimony oxide, zinc oxide mixed with bismuth oxide, copper oxide mixed with aluminum oxide, copper oxide mixed with titanium oxide, copper oxide mixed with manganese oxide, copper oxide mixed with iron oxide, copper oxide mixed with zirconium oxide, copper oxide mixed with indium oxide, copper oxide mixed with tin oxide, copper oxide mixed with antimony oxide, copper oxide mixed with bismuth oxide, silver oxide mixed with aluminum oxide, silver oxide mixed with titanium oxide, silver oxide mixed with manganese oxide, silver oxide mixed with iron oxide, silver oxide mixed with zirconium oxide, silver oxidemixed with indium oxide, silver oxide mixed with tin oxide, silver oxide mixed with antimony oxide, or silver oxide mixed with bismuth oxide.

8. The material of claim 1, wherein zinc, copper, or silver is a dopant in the solid metal oxide nanomaterial, comprising up to 10 wt.% of the solid metal oxide nanomaterial.

9. The material of claim 1, wherein a mass ratio of zinc, copper, or silver to all other metals in the solid metal oxide nanomaterial is 0.001 to 0.1.

10. The material of claim 1, wherein the solid metal oxide nanomaterial has or is characterized by a pH less than 7 when suspended or re-suspended, after washing and drying, in water at 5 wt.%.

11. The material of claim 1, wherein the solid metal oxide nanomaterial comprises agglomerated particles or dispersed individual particles.

12. The material of claim 1, wherein the solid metal oxide nanomaterial comprises particles having cross-sectional dimensions selected from 1 nm to 1000 nm.

13. The material of claim 1, further comprising a cathode active material mixed with the solid metal oxide nanomaterial.

14. The material of claim 13, wherein the cathode active material comprises particles, and wherein particles of the solid metal oxide nanomaterial is coated on surfaces of the particles of the cathode active material or wherein the particles of the solid metal oxide nanomaterial are chemically bonded, mechanically fused, or otherwise bound to or associated with the surface of the cathode active material particles.

15. The material of claim 13, wherein the cathode active material is selected from a lithium intercalation cathode active material, a transition metal oxide, a polyanion compound, a lithium conversion cathode active material, or an alkaline cathode material.

16. The material of claim 13, wherein a coverage of the particles of the cathode active material by the particles of the solid metal oxide nanomaterial is from 1% to 100%.

17. The material of claim 13, wherein a weight ratio of the particles of the solid metal oxide nanomaterial to the particles of the cathode active material is from 0.01% to 10%.

18. A cathode comprising the material of claim 1.

19. The cathode of claim 18, wherein the cathode further comprises one or more additives mixed with the material, the one or more additives selected from a conductive material and a binder, and a cathode active material mixed with the material, wherein the material corresponds to an amount from 0.1 wt.% to 20 wt.% of the cathode, and wherein the cathode active material corresponds to an amount from 80 wt.% to 99.9 wt.% of the cathode.

20. The cathode of claim 19, wherein the cathode active material comprises a lithium intercalation cathode active material, a lithium conversion cathode active material, or an alkaline cathode active material.

21. The cathode of claim 19, wherein the cathode active material comprises a manganese oxide, a silver oxide, and / or a nickel oxide.

22. A battery comprising:the cathode of claim 18;an anode; andan electrolyte positioned between the cathode and the anode.

23. The battery of claim 22, wherein the cathode comprises a cathode active material mixed with the solid metal oxide nanomaterial, wherein the cathode active material comprises a manganese oxide, a silver oxide, and / or a nickel oxide, wherein the anode comprises zinc, copper, or silver, and wherein the electrolyte comprises an alkali metal hydroxide.

24. The battery of claim 22, wherein the cathode comprises a cathode active material mixed with the solid metal oxide nanomaterial, wherein the cathode active material comprises a lithium intercalation cathode active material or a lithium conversion cathode active material, wherein the anode comprises lithium metal, a lithium intercalation anode active material, or a lithium conversion anode active material, and wherein the electrolyte comprises alithium salt and an organic solvent, a lithium polymer electrolyte material, or a lithium solid electrolyte material.

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