High capacity batteries and components thereof

Abstract

This article describes a high-capacity electrochemical unit comprising a first electrode containing a metal oxide (e.g., an acidified metal oxide ("AMO") material) and a second electrode containing lithium metal, wherein the metal oxide is present in the first electrode at less than 80% by weight. Methods for preparing the electrode containing the metal oxide and methods for preparing the electrochemical unit are also disclosed.

Description

Technical Field

[0001] This disclosure relates to the field of materials and power devices (e.g., but not limited to) that can be used for chemical energy storage. More specifically, this disclosure relates to battery cells having cathodes and / or anodes comprising acidified metal oxide ("AMO") nanomaterials. Prior Technology

[0002] Metal oxides are compounds in which oxygen is bonded to a metal, possessing the general formula MmOx. They are found in nature but can also be synthesized artificially. In the synthesis of metal oxides, synthetic methods can have a wide range of effects on surface properties, including their acid / base characteristics. Changes in surface properties can alter the properties of the oxide, thereby affecting properties such as its catalytic activity and electron mobility. However, the mechanisms by which surface controls reactivity are not always fully characterized or understood. For example, in photocatalysis, it is believed that surface hydroxyl groups promote electron transfer from the conduction band to chemisorbed oxygen molecules. Despite the importance of surface properties, literature on metal oxides (both scientific papers and patents) primarily focuses on creating novel nanoscale metal oxide crystal forms for improved energy storage and power applications. Surface properties of metal oxides have been neglected, and, apart from literature on chemical catalysis, there is very little innovation regarding controlling or altering the surface of known metal oxides to achieve performance targets. Chemical catalysis literature primarily focuses on creating "superacids" typically used in large-scale reactions (such as hydrocarbon cracking), meaning acids with an acidity greater than pure sulfuric acid (18.4 MH₂SO₄). Superacidity cannot be measured on the traditional pH scale but is quantified using Hammett values. The Hammett value (H₀) can be considered as extending the pH scale to negative numbers below 0. The H₀ of pure sulfuric acid is -12. However, there are many reaction systems and applications where excessive acidity is too strong for it. For example, excessive acidity can degrade system components or catalyze undesirable side reactions. However, in such applications, acidity can still be useful to provide enhanced reactivity and rate characteristics or improved electron mobility. Battery literature teaches that acidic groups are harmful in batteries, as they can corrode metal current collectors and the casing, and cause deterioration of other electrode components. Furthermore, prior art teaches that active catalytic electrode surfaces lead to electrolyte decomposition, which can cause gas generation within the cell and ultimately result in cell failure. The industry needs to improve batteries and related components. Summary of the Invention

[0003] This application describes a high-capacity electrochemical unit comprising an electrode containing a metal oxide. It further discloses techniques for preparing the metal oxide and the electrochemical unit containing the metal oxide. Where appropriate, the disclosed metal oxide is used in combination with a conductive material to form the electrode. The formed electrode can be used together with lithium metal and conventional lithium-ion electrodes as corresponding counter electrodes. Where appropriate, the disclosed metal oxide is used in combination with acidic substances to enhance its performance. Electrochemical cells incorporating electrodes including metal oxides advantageously exhibit extremely high capacities, such as up to 15000 mAh / g metal oxide. Such high capacities can be achieved, for example, by using layered electrode constructions with low active material (i.e., metal oxide) loadings, such as less than 80% by weight of active material. This contrasts with conventional electrochemical cell techniques, which attempt to maximize the loading of active material, often exceeding approximately 80% by weight, for example, 90%, 95%, or 99%. While high active material loadings can be used to increase capacity in conventional electrochemical cell techniques, the inventors of this application have discovered that reducing the active material loading actually allows for even higher cell capacities. This capacity increase can be achieved, at least in part, by increasing the absorption of shuttle ions (i.e., lithium ions), as additional physical volume is obtained when the active material loading is lower. Alternatively or otherwise, this capacity increase can be achieved at least in part by increasing the number of active sites for the absorption of shuttle ions and by reducing the blockage of active sites through additional material mass. [] The disclosed electrochemical unit may be a metal oxide in the form of an acidified metal oxide (“AMO”) material, as appropriate. Available AMOs include those in the form of nanomaterials (e.g., nanoparticles), which may be monodisperse or substantially monodisperse and have a particle size (e.g., less than 100 nm). When suspended in water at a specific concentration (e.g., 5 wt.%) or dried and resuspended in water, the disclosed AMO exhibits a low pH, e.g., less than 7 (e.g., between 0 and 7), and further exhibits a Hammett function H₂O greater than -12 (i.e., non-superacid) at least on the surface of the AMO. The surface of the metal oxide can be functionalized, for example, by means of an acid or other electron-withdrawing substance. Synthesis and surface functionalization can be accomplished using a "single-pot" hydrothermal method, in which the surface of the metal oxide is functionalized as it is synthesized from a suitable precursor. In some embodiments, this single-pot method does not require any additional acidification steps beyond those steps necessary for the synthesis of the metal oxide itself, and produces a metal oxide with a desired surface acidity (but not a superacid). Depending on the circumstances, surface functionalization can be achieved using individual or combined strong electron-withdrawing groups ("EWGs") (e.g., SO₄, PO₄, or halogens (Br, Cl, etc.)). Surface functionalization can also be achieved using EWGs weaker than SO₄, PO₄, or halogens. For example, the synthesized metal oxides can be surface functionalized using acetate (CH₃COO), oxalate (C₂O₄), and citrate (C₆H₅O₇) groups. Although conventional knowledge holds that acidic substances are undesirable in batteries because they can attack metal current collectors and the casing and cause degradation of other electrode components, and that active catalytic electrode surfaces can lead to electrolyte decomposition, gas generation within the cell, and ultimately cell failure, the inventors have discovered that acidic substances and components are advantageous in batteries where metal oxide materials (e.g., AMO nanomaterials) are used in the battery electrodes. For example, the combination or use of metal oxides with acidic substances can enhance the performance of the resulting materials, systems, or devices, resulting in improved capacity, cycle characteristics, and device lifespan. As an example, batteries employing a combination of metal oxides and acidic electrolytes or electrolytes containing acidic substances as described herein exhibit substantial capacity gains, such as up to 100 mAh / g, or significantly greater than similar batteries using non-acidified electrolytes or electrolytes lacking acidic substances. In some embodiments, capacity improvements between 50 mAh / g and 300 mAh / g can be achieved. Furthermore, batteries using acidified electrolytes or electrolytes containing acidic substances can achieve absolute capacities of up to 1000 mAh / g or higher. Moreover, battery cycle life can be improved by using acidic electrolytes or electrolytes containing acidic substances, for example, in this case, extending the battery cycle life by up to 100 or more charge-discharge cycles. High-capacity batteries and electrochemical units are disclosed in this study. The example capacities of the batteries and units described herein include, for example, primary capacities between 2000 mAh / g metal oxide and 15000 mAh / g metal oxide, such as between 2500 mAh / g metal oxide and 15000 mAh / g metal oxide, and between 3000 mAh / g metal oxide and 15000 mAh / g metal oxide. It can also achieve intermediate and specific capacity ranges, including (for example) from metal oxides of about 3500 mAh / g, 4000 mAh / g, 4500 mAh / g, 5000 mAh / g, 5500 mAh / g, 6000 mAh / g, 6500 mAh / g or 7000 mAh / g to about 10000 mAh / g, 10500 mAh / g, 11000 mAh / g, 11500 mAh / g, 12000 mAh / g, 12500 mAh / g, 13000 mAh / g, 13500 mAh / g, 14000 mAh / g or and 14500 mAh / g. When used as a secondary unit, the instance capacity includes, for example, a secondary capacity between 1000 mAh / g metal oxide and 5000 mAh / g metal oxide, or an intermediate range or specific value between such values, such as from about 1500 mAh / g, 2000 mAh / g, or 2500 mAh / g metal oxide to about 3000 mAh / g, 3500 mAh / g, 4000 mAh / g, or 4500 mAh / g metal oxide. An example high-capacity battery cell includes a first electrode, such as a first electrode comprising a metal oxide (and possibly an AMO nanomaterial), a conductive material, and a binder; a second electrode, such as a second electrode comprising lithium metal; and an electrolyte positioned between the first electrode and the second electrode. Where appropriate, the metal oxide constitutes less than 80% by weight of the first electrode. The example electrolyte includes metal salts dissolved in a solvent, solid electrolytes, and gel electrolytes. Where appropriate, a separator is positioned between the first electrode and the second electrode. Depending on the application, the first electrode may include a layered structure comprising a first set of layers containing a conductive material and a second set of layers containing a metal oxide (e.g., acidified metal oxide (AMO) nanomaterial). However, the use of a layered structure is optional. In some embodiments, the first electrode may not exhibit a layered construction. Depending on the application, the first and second sets of layers may be provided in an alternating configuration. Depending on the application, the first and second sets of layers may independently comprise a layer between 1 and 20. Depending on the application, the first and second sets of layers may independently have the following thicknesses: between 1 µm and 50 µm, between 2 µm and 25 µm, between 3 µm and 20 µm, between 4 µm and 15 µm, or between 5 µm and 10 µm. Depending on the application, the metal oxide may comprise a second layer comprising between 5% and 90% by weight, for example, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, or 90% by weight. Depending on the application, the conductive material and the adhesive may each independently comprise a first layer comprising between 5% and 90% by weight, for example, 25% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, or 90% by weight. The first electrode may contain the following amounts of metal oxide: up to 95% by weight, up to 80% by weight, up to 70% by weight, between 1% and 50% by weight, between 1% and 33% by weight, between 1% and 25% by weight, between 55% and 70% by weight, between 20% and 35% by weight, or between 5% and 15% by weight. Specific examples of the percentage by weight of metal oxide in the first electrode include 1%, 5%, 11%, 12%, 13%, 14%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 60%, 61%, 62%, 63%, 64%, and 65%. Depending on the situation, conductive material and binder each independently constitute the remaining majority of the first electrode. For example, the conductive material and the binder each independently constitute between 10% and 74% by weight of the first electrode. Depending on the situation, the conductive material and the binder together constitute between 20% and 90% by weight of the first electrode. Depending on the situation, AMO nanomaterials are added as a dopant of 1-10% by weight to conventional lithium-ion electrodes, such as graphite, lithium cobalt oxide, etc. Various materials can be used for the electrodes described herein. Examples of metal oxides include (but are not limited to) lithium oxides, aluminum oxide, titanium oxide, manganese oxide, iron oxide, zirconium oxide, indium oxide, tin oxide, antimony oxide, bismuth oxide, or any combination thereof. Where appropriate, the oxide is in the form of AMO. As described herein, the metal oxide may contain one or more electron-withdrawing groups selected from Cl, Br, BO₃, SO₄, PO₄, NO₃, CH₃COO, C₂O₄, C₂H₂O₄, C₆H₈O₇ or C₆H₅O₇ and / or functionalized thereon. Examples of conductive materials include one or more of the following: graphite, conductive carbon, carbon black, Ketjenblack, or conductive polymers (e.g., poly(3,4-epethyldioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composites, polyaniline (PANI), or polypyrrole (PPY)). In some embodiments, an electrode comprising AMO nanomaterial is used in combination with other electrodes to form a unit. For example, the second electrode of this unit may comprise graphite, lithium metal, sodium metal, lithium cobalt oxide, lithium titanate, lithium manganese oxide, lithium nickel manganese cobalt oxide (NMC), lithium iron phosphate, lithium nickel cobalt aluminum oxide (NCA), AMO nanomaterial, or any combination thereof. In a specific embodiment, the first electrode comprises AMO of SnO2, and the second electrode comprises lithium metal. The electrode and electrochemical cell construction described herein achieves high capacity for both the primary cell (in its assembled state) and the secondary cell. Examples of primary capacities range from 3000 mAh / g AMO nanomaterials to 15000 mAh / g metal oxides. Examples of secondary capacities range from 1000 mAh / g metal oxides to 5000 mAh / g metal oxides. The cells disclosed herein exhibit a lifespan of 100 to 5000 charge-discharge cycles without failure, for example, 100-1000 charge-discharge cycles. Upon assembly, the disclosed cells exhibit an open-circuit voltage between 2 V and 4 V. The disclosed cells are recharged to a potential difference between the first and second electrodes between 1.0 V and 3.2 V; this recharge can occur after the cell is fully discharged (i.e., to 0 V) ​​or partially discharged (i.e., to a voltage greater than 0 V). In one specific embodiment, the high-capacity battery cell includes a first electrode comprising an acidified metal oxide (AMO) nanomaterial, a conductive material, and an adhesive; a second electrode; and an electrolyte positioned between the first electrode and the second electrode, wherein the AMO nanomaterial constitutes 5-15% by weight, 20-35% by weight, or 55-70% by weight of the first electrode, wherein the AMO nanomaterial comprises 0-15% by weight of iron oxide and 85-100% by weight of tin oxide, wherein the AMO nanomaterial comprises one or more electron-withdrawing groups and / or is functionalized thereon, wherein the conductive material comprises one or more of graphite, conductive carbon, carbon black, Ketjen black, and conductive polymers (e.g., poly(3,4-epoxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composite, polyaniline (PANI), or polypyrrole (PPY)), and wherein the second electrode comprises or includes lithium metal. This high-capacity battery cell, after assembly, exhibits a primary capacity between 3000 mAh / g and 15000 mAh / g of AMO nanomaterials, a secondary capacity between 1000 mAh / g and 5000 mAh / g of AMO nanomaterials, a lifespan of 100 to 1000 charge-discharge cycles without failure, and an open-circuit voltage between 2 V and 4 V after assembly. Depending on the configuration, the first electrode comprises a layered structure including a first layer containing conductive material and a second layer containing AMO nanomaterials. For example, the first and second layers are provided in an alternating configuration, wherein the first layer contains between 1 and 20 layers and the second layer contains between 1 and 20 layers, wherein the first and second layers independently have a thickness between 1 µm and 50 µm, and wherein the AMO nanomaterials constitute between 5% and 70% by weight of the second layer. In another embodiment, a method for fabricating electrodes and high-capacity battery cells is disclosed. Wherein, the method for fabricating electrodes or high-capacity battery cells includes preparing a metal oxide, such as an acidified metal oxide (AMO) nanomaterial; forming a slurry using the metal oxide, a conductive material, a binder, and a solvent; depositing a layer of the slurry onto a current collector; and evaporating at least a portion of the solvent to form an electrode comprising the AMO nanomaterial. Wherein, an electrolyte system is positioned between the electrode and a second electrode. Wherein, firstly, a slurry comprising a conductive material, a binder, and a solvent is deposited onto the current collector, and the solvent is evaporated to form a conductive coating on the current collector, after which an electrode layer is formed on the conductive coating. Various techniques can be used to prepare metal oxides. Depending on the application, the preparation of metal oxides may involve forming a solution containing a metal salt, ethanol, and water; acidifying the solution by adding an acid; alkalizing the solution by adding an aqueous alkaline solution; collecting a precipitate from the solution; washing the precipitate; and drying the precipitate. Depending on the application, electrode fabrication may further include depositing another conductive layer on the electrode layer, such as a conductive layer comprising a second conductive material. Depending on the application, depositing the conductive layer may include forming a conductive slurry using the second conductive material, a second binder, and a second solvent; depositing the conductive slurry layer on the electrode layer; and evaporating at least a portion of the second solvent to form the conductive layer. Depending on the application, electrode fabrication may include forming 1-20 additional conductive layers comprising conductive material and 1-20 additional electrode layers comprising metal oxide. For example, the electrode may comprise a layered structure comprising a first set of layers comprising a second conductive material and a second set of layers comprising metal oxide, for example, wherein the first set of layers and the second set of layers are provided in an alternating configuration. Example layers include those independently having a thickness between 1 µm and 50 µm. Example layers include those comprising those comprising between 10 wt% and 90 wt% metal oxide. Example layers include those independently comprising between 5 wt% and 85 wt% conductive material and / or binder. The metal oxide content of the electrode formed by this method can be up to 80% by weight. The conductive material and / or binder content of the electrode formed by this method can be between 10% by weight and 70% by weight of the electrode. Alternatively, batteries or electrochemical units that include electrodes that are acidic themselves or contain acidic substances (e.g., organic acids) can also be beneficial, again contrary to conventional teachings in battery technology. For example, batteries incorporating acidic electrodes or acidic substances within the electrodes can enhance performance and produce improved capacity, cycle characteristics, and lifespan, especially when used with electrodes that include metal oxides (e.g., AMO nanomaterials). Capacity gains of up to 100 mAh / g or greater can be achieved. Battery cycle life can also be improved by using acidic electrodes or electrodes containing acidic substances, for example, extending the battery cycle life by up to 100 or more cycles. As an example, acidic electrodes or electrodes containing acidic substances can exhibit a pH of less than 7 (but not superacids), for example, when the electrode components are suspended in water at 5 wt.% (or dried and resuspended in water). As another example, batteries where the electrodes are formed using a slurry can also be beneficial and contrary to conventional teachings in battery technology. As illustrated herein, AMO nanomaterials can be formed as battery electrodes by, where appropriate, the following: First, a slurry of AMO nanomaterials and one or more binder compounds, solvents, additives (e.g., conductive or acidic additives) and / or other wet-processed materials is formed. The slurry can be deposited onto a conductive material or current collector to form the electrode. This slurry and / or solvent may be acidic or contain acidic substances, and again, this improves the capacity, cycle characteristics, and lifespan of the resulting battery. Where appropriate, all or part of the solvent can be evaporated, leaving the AMO nanomaterials, binders, additives, etc. When suspended in water (e.g., 5 wt.%) (or dried and resuspended in water), the resulting material may exhibit its own acidity, for example, having a pH less than 7 (but not a superacid). As explained above, acidic substances may be included as additives in any component of the battery, such as electrodes or electrolytes. Batteries containing metal oxides may include an electrolyte positioned between the electrodes, wherein the acidic substance is dissolved in a solvent. This electrolyte may also be referred to herein as an acidified electrolyte. The electrolyte may include one or more lithium salts dissolved in a solvent, such as LiPF6, LiAsF6, LiClO4, LiBF4, LiCF3SO3, and combinations thereof. It should be understood that the electrolyte may not only be positioned in the space separating the electrodes (i.e., between the electrodes), but may also penetrate or enter the pores of the electrodes and / or penetrate or enter the pores of any material or structure (e.g., separators) positioned between the electrodes, as appropriate. Examples of acidic substances that can be used with the metal oxides, electrodes, and electrolytes described herein include (but are not limited to) organic acids, such as carboxylic acids. Examples of acidic substances include those exhibiting pKa values ​​between -10 and 7, between -5 and 6, between 1 and 6, between 1.2 and 5.6, or about 4 in water. Specific examples of organic acids include (for example) oxalic acid, carbonic acid, citric acid, maleic acid, methylmalonic acid, formic acid, glutaric acid, succinic acid, methylsuccinic acid, methylenesuccinic acid, citralic acid, acetic acid, and benzoic acid. Examples of organic acids include dicarboxylic acids, such as those having the formula... In these, R refers to substituted or unsubstituted C1-C20 hydrocarbons, such as substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aromatic or heteroaromatic groups, substituted or unsubstituted amines, etc. Examples of organic acids also include those having the formula... Among them, L refers to substituted or unsubstituted C1-C20 divalent hydrocarbons, such as substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted amines, etc. Organic acids may include organic acid anhydrides, such as those having the formula... R1 and R2 are independently substituted or unsubstituted C1-C20 hydrocarbons, such as substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aromatic or heteroaromatic groups, substituted or unsubstituted amines, etc. Depending on the circumstances, R1 and R2 may form a ring. Examples of organic acid anhydrides include any anhydride of the organic acids mentioned above. Specific organic acid anhydrides include (but are not limited to) glutaric anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, and itconic anhydride. The usable concentrations of acidic substances in one or both of the electrolyte and AMO electrode include 0 wt.% to 10 wt.%, 0.01 wt.% to 10 wt.%, 0.1 wt.% to 10 wt.%, 1 wt.% to 5 wt.%, or 3 wt.% to 5 wt.%. Suitable solvents include, for example, those used in lithium-ion battery systems, such as ethyl carbonate, butyl carbonate, propyl carbonate, vinyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, fluoroethyl carbonate, and mixtures thereof. Those skilled in the art will recognize other suitable solvents. Where appropriate, when acidic substances and metal salts are dissolved in a solvent to form an electrolyte, the electrolyte itself exhibits acidic conditions (i.e., pH less than 7). Examples of adhesives that can be used in the batteries, cells, and electrodes described herein include styrene-butadiene copolymer (SBR), polyvinyl difluoride (PVDF), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), acrylonitrile, polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyamide-imide (PAI), and any combination thereof. Conductive polymers may be used as adhesives, depending on the application. Other example additives that can be used with the metal oxides and electrodes described herein include (but are not limited to) conductive additives. Examples of conductive additives include graphite, conductive carbon, carbon black, Ketjen black, and conductive polymers (e.g., poly(3,4-epoxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS complexes, polyaniline (PANI), and polypyrrole (PPY)). Conductive additives may be present in (e.g.) electrodes at any suitable concentration (e.g., at a weight percentage greater than 0 and up to 35 wt.%, 40 wt.%, or more). Depending on the application, conductive additives are present in the electrodes in the following ranges: 1 wt.% to 95 wt.%, 1 wt.% to 35 wt.%, 1 wt.% to 25 wt.%, 5 wt.% to 40 wt.%, 10 wt.% to 40 wt.%, 15 wt.% to 40 wt.%, 20 wt.% to 40 wt.%, 25 wt.% to 40 wt.%, 30 wt.% to 40 wt.%, 35 wt.% to 40 wt.%, 40 wt.% to 45 wt.%, 40 wt.% to 50 wt.%, 40 wt.% to 55 wt.%, 40 wt.% to 60 wt.%, 40 wt.% to 65 wt.%, 40 wt.% to 70 wt.%. wt.%, 40 wt.% to 75 wt.%, 40 wt.% to 80 wt.%, 40 wt.% to 85 wt.%, 40 wt.% to 90 wt.% or 40 wt.% to 95 wt.%. This article also describes methods for fabricating batteries. Example methods for fabricating batteries include preparing a metal oxide, such as AMO nanomaterials; forming a first electrode of the metal oxide or a first electrode containing the metal oxide; forming an electrolyte by dissolving one or more metal salts in a solvent; and positioning the electrolyte between the first electrode and a second electrode. Another example method for fabricating a battery includes preparing a metal oxide, such as AMO nanomaterials; forming a first electrode of the metal oxide and one or more metal salts or a first electrode containing the metal oxide and one or more metal salts; and positioning the electrolyte between the first electrode and a second electrode. This document also discloses electrolytes for use in batteries. For example, the disclosed electrolytes can be used in batteries comprising a first electrode and a second electrode, such as a first electrode comprising an acidified metal oxide (AMO) nanomaterial. The example electrolyte comprises a solvent and one or more metal salts dissolved in that solvent. Where appropriate, an acidic substance is dissolved in the solvent, for example, an acidic substance different from the one or more metal salts. As described above, a variety of acidic substances can be used in the disclosed electrolytes, such as acidic substances containing organic acids and / or organic anhydrides. Examples of organic acids include (but are not limited to) oxalic acid, acetic acid, citric acid, maleic acid, methylmalonic acid, glutaric acid, succinic acid, methylsuccinic acid, methylenesuccinic acid, citralic acid, or any combination thereof. Examples of organic anhydrides include (but are not limited to) glutaric anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, itconic anhydride, or any combination thereof. Examples of other acidic substances are described above. Usable acidic substances include (but are not limited to) substances exhibiting pKa values ​​between -10 and 7, between -5 and 6, between 1 and 6, between 1.2 and 5.6, or approximately 4. Acidic substances may be present in the electrolyte at any suitable concentration, for example, 0.01 wt.% to 10 wt.%, 0.1 wt.% to 10 wt.%, 1 wt.% to 5 wt.%, or 3 wt.% to 5 wt.%. It should be understood that lithium metal salts such as LiPF6, LiAsF6, LiClO4, LiBF4, and LiCF3SO3 are usable components of the acidified electrolytes disclosed herein. Example solvents include (but are not limited to) ethyl carbonate, butyl carbonate, propyl carbonate, vinyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethyl fluorocarbonate, and mixtures thereof. These example solvents can be used in metal-ion batteries, such as lithium-ion batteries. The above and other features and embodiments will become clearer with reference to the following description, the scope of the patent application, and the accompanying drawings. For example, further details of the disclosed battery and the method of manufacturing the battery are set forth in the detailed description below. Simple Explanation of the Diagram

[0004] Figure 1 is a simplified cross-sectional view of an example lithium-ion battery cell. Figure 2 is another simplified cross-sectional view of a lithium-ion battery cell in which the electrolyte is essentially contained by a separator. Figure 3 is a schematic diagram of a lithium-ion battery containing multiple cells. Figure 4 provides a graph showing the difference in cyclic voltammetry between AMO tin prepared by the method disclosed herein and commercially available non-AMO tin when compared with Li cycling. Figure 5 provides a graph showing the difference in total reflectance between AMO tin oxide and commercially available non-AMO tin oxide. Figure 6 provides X-ray photoelectron spectroscopy (XPS) data showing the endogenous surface functionalization resulting from the synthesis method disclosed herein. The values ​​shown are atomic concentrations expressed as percentages. The rightmost row and column show the corresponding pH values ​​of the synthesized nanoparticles when dispersed at 5 wt% in an aqueous solution. Figure 7 provides electron micrographs showing the morphological differences between AMO nanoparticles synthesized under the same conditions, except for the use of different functional groups. Figure 8 provides electron micrographs showing the morphological differences of AMO nanoparticles synthesized under the same conditions, except for two different total reaction times. Figure 9 provides representative half-cell data, showing the behavioral differences between spherical and elongated (needle-shaped or rod-shaped) AMOs relative to lithium cycling. Figure 10 shows the X-ray photoelectron spectroscopy analysis of the surface of AMO nanoparticles synthesized using both strong (phosphorus-containing) and weak (acetate) electron-withdrawing groups, which shows that the atomic concentration of phosphorus is greater than the atomic concentration of bonds associated with acetate groups. Figure 11A provides data showing the visible light-active degradation data of different AMOs. Figure 11B provides data showing the UV-active degradation data of different AMOs. Figure 12 provides data comparing two AMOs, one with higher capacity for primary (disposable) battery applications and the other with higher cyclability for secondary (rechargeable) battery applications. Figure 13 provides charging and discharging capacity data and columbic efficiency data. This diagram illustrates that AMO can enhance battery performance without degrading battery components or generating gas. Figure 14 shows the capacity and cycling data of AMO in standard, acidified, and alkaline electrolyte systems. Figure 15 shows the capacity and cycle data of AMO and the same AMO after acidification was removed by solvent washing. Figure 16 provides data showing the changes in temperature and voltage over time as the battery cell undergoes a nail penetration test. Figure 17A provides data showing the changes in temperature and voltage over time as the battery cell undergoes an overcharge test. Figure 17B provides an expanded view of the data from approximately the first 1400 seconds shown in Figure 17A. Figure 18 provides a schematic diagram of an example battery cathode. Figure 19 provides data showing how the cell capacity changes with the number of charge-discharge cycles achieved during cell cycling. Figure 20 provides data showing how the cell voltage changes over time with multiple charge-discharge cycles during cell cycling. Figure 21 shows a photograph of the components of the bag cell after 103 charge-discharge cycles. Figure 22 provides the following data: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 23 provides electron micrographs of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. [] Figure 24 provides electron micrographs of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. [] Figure 25 provides electron micrographs of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 26 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 27 provides the following data: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 28 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 29 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 30 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 31 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 32 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 33 provides electron micrographs of the synthesized material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes of the synthesized material. Figure 34 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 35 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 36 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 37 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 38 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 39 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 40 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 41 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 42 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 43 provides the following data: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 44 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 45 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 46 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 47 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 48 provides an electron micrograph of the AMO material and includes the following data: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 49 provides data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 50 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 51 provides an electron micrograph of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Figure 52 provides electron micrographs of the AMO material and data including: a graph of the measured capacity versus the number of cycles and a graph of the voltage versus time during the cycling of a battery cell containing electrodes with AMO material. Implementation

[0005] Cross-reference to related applications This application claims the interest and priority of the following U.S. provisional applications: 62 / 483,789, filed April 10, 2017; 62 / 507,655, filed May 17, 2017; 62 / 507,658, filed May 17, 2017; 62 / 507,659, filed May 17, 2017; 62 / 507,660, filed May 17, 2017; 62 / 507,662, filed May 17, 2017; and 62 / 651,002, filed March 30, 2018, which are incorporated herein by reference in their entirety for all purposes. This application also incorporates, by reference, U.S. Provisional Applications 62 / 256,065 and 62 / 256,059, both filed November 16, 2015; U.S. Provisional Application 62 / 422,483, filed November 15, 2016; U.S. Non-Provisional Application 15 / 352,388, filed November 15, 2016; U.S. Patent 9,786,910; and U.S. Non-Provisional Application 15 / 814,094, filed November 15, 2017. For the purposes of this disclosure, the following terms shall have the following meanings: [Acidic oxides] - This term is commonly used in scientific literature to refer to binary compounds of oxygen and nonmetallic elements. An example is carbon dioxide (CO2). Some metalloid oxides (such as Si, Te, and Po) also exhibit weak acid properties in their pure molecular state. [Acidified metal oxides] [(] [「] [AMO] [」] [)] [、] [AMO] [Nanomaterials or] [AMO] [Materials] - This term is used herein to refer to binary compounds of oxygen and a metallic element that has been synthesized or modified to have an acidity greater than that of its native mineralogical state and a Hammett function H0 greater than -12 (i.e., not a superacid). It should be understood that the surface pH of AMO can be less than 7, for example, when suspended in water at 5 wt.% (or resuspended in water after drying). Depending on the case, AMO can exhibit a surface pH less than 6, less than 5, less than 4, or less than 3. The average particle size of the AMO disclosed herein is also smaller than the average particle size of its native mineralogical state. For example, AMO may comprise nanomaterials, such as particles having at least one dimension less than 100 nm, less than 20 nm, less than 10 nm, or between 1 nm and 100 nm. Native mineralogical forms are not within the scope of the AMO materials of this invention. However, synthetic metal oxides that are more acidic than their most abundant natural mineralogical forms (with equivalent stoichiometry) but are not superacids are within the scope of this disclosure and can be considered AMO materials, provided that they meet certain other conditions discussed in this disclosure. [Acidity] - This term is commonly used in scientific literature to refer to compounds with a pH less than 7 in aqueous solution. Electron-withdrawing groups ("EWGs") are atomic or molecular groups that attract electrons towards themselves. The strength of an EWG is based on its known behavior in chemical reactions. For example, halogens are known to be strong EWGs. Organic acid groups (such as acetates) are known to be weak electron-withdrawing groups. The Hammett function is another way to quantify acidity in highly concentrated acid solutions and in superacids. Acidity is defined by the following equation: H0 = pKBH++ log([B] / [BH+]). On this scale, the H0 value of pure 18.4 moles of H2SO4 is -12. The value of H0 = -12 for pure sulfuric acid should not be interpreted as pH = -12; rather, it means that the acid present has a protonating ability equivalent to H3O+ at a hypothetical (ideal) concentration of 1012 mol / L, as measured by its ability to protonate weak bases. Water is avoided in the Hammett acidity function equation. It is used in this paper to provide a quantitative method for distinguishing AMO materials from superacids. The Hammett function can be correlated with colorimetric indicator tests and programmed temperature-controlled desorption results. [Metal oxides] - This term is commonly used in scientific literature to refer to binary compounds of oxygen and a metallic element. Depending on their position in the periodic table, metal oxides in their pure molecular state range from weakly basic to amphoteric (exhibiting both acidic and basic properties). Weakly basic metal oxides include oxides of the following: lithium, sodium, magnesium, potassium, calcium, rubidium, strontium, indium, cesium, barium, and tellurium. Amphoteric oxides include oxides of the following: beryllium, aluminum, gallium, germanium, arsenic, tin, antimony, lead, and bismuth. These and other metal oxides may be used as AMO materials, depending on the application. [Lithium Metal] - This term refers to lithium in its neutral atomic state (i.e., non-ionic state). The term lithium metal is intended to distinguish it from other forms of lithium (including lithium ions and lithium compounds). The term lithium metal may refer to neutral lithium atoms present in mixtures containing lithium atoms (e.g., mixtures of lithium and other elements, compounds, or substances). The term lithium metal may refer to neutral lithium atoms present in lithium alloys (e.g., mixtures of metals including lithium and one or more other metals). The term lithium metal may refer to neutral lithium atoms present in composite structures including lithium and one or more other materials. Electrodes containing or including lithium metal may include materials other than lithium, but it should be understood that lithium metal may correspond to the active material of such an electrode. In some cases, the anode in an electrochemical unit contains lithium metal. [] [Monodisperse] - characterized by particles of uniform size that are substantially separated from each other and do not aggregate into larger grains. Monodisperse particles may have a uniform size distribution, for example, at least 90% of the particle size distribution is within 5% of the median particle size. [pH] - A functional numerical scale commonly used in scientific literature to specify the acidity or alkalinity of aqueous solutions. It is the negative logarithm of the concentration of halogen ions [H₃O⁺]. As used herein, pH can be used to describe the relative acidity of nanoparticles suspended in aqueous solutions. [Surface Functionalization] - Attaching small atoms or molecular groups to the surface of a material. In this embodiment, the AMO material can be surface functionalized by covalently bonding EWG to the surface of the AMO material. [Superacid] - A substance with an acidity greater than 100% H 2SO 4 and a Hammett function H 0 less than -12. This article describes high-capacity electrochemical units and unit components, such as electrodes used in such units. The disclosed electrochemical units and electrodes comprise acidified metal oxide (“AMO”) nanomaterials and exhibit high capacity. In embodiments, the AMO nanomaterials are provided in the electrode at a relatively low loading (wt%), for example, less than 30% by weight, wherein the majority of the remaining portion of the electrode comprises conductive material and binder. Even with such a low loading, capacities greater than 10,000 mAh / g of AMO nanomaterials have been observed. The electrodes can be provided in layered or non-layered configurations. Example layered configurations include a single layer comprising AMO nanomaterials and a layer with a low loading or no AMO. However, layering of the electrode is entirely optional, and high capacity has been observed in both layered and non-layered electrodes. Referring now to Figure 1, lithium battery cell

[0100] The illustration is provided using a simplified sectional view. Unit

[0100] May include a housing or container.

[0102] In some embodiments, the housing

[0102] It is a polymer or alloy. Shell

[0102] The unit The contents of

[0100] are chemically and electrically isolated from adjacent units, preventing contamination and damage to the units.

[0100] Other components of the device installed therein may be protected from damage. A full battery may contain a plurality of cells configured in series and / or parallel configurations, but may include only a single cell as appropriate. The battery may have another housing or fixing mechanism for combining a plurality of cells together, as is known in the art. unit

[0100] Provide cathode

[0104] and anode

[0106] When in unit

[0100] outside the cathode

[0104] with anode

[0106] Provide conduction paths (e.g., between elements)

[0115] When ), unit The contents of

[0100] undergo a chemical reaction. As a result of the chemical reaction, at the anode...

[0106] Electrons are provided at the location and flow through element 115 (sometimes referred to as a load) to the cathode via circuitry provided outside the unit.

[0104] . At the base level, in the unit During the discharge of

[0100] , the anode is formed The material

[0106] is oxidized to provide electrons flowing through the circuit. As the anode...

[0106] The cathode is formed by the acceptor of the given electron. The material of

[0104] has been restored. In unit

[0100] Inside, during discharge, metal cations from the anode

[0106] Passing through electrolyte

[0108] Move to cathode

[0104] . In the case of lithium-based batteries, the metal cation can be lithium cation (Li+). Electrolyte

[0108] The electrolyte may be a liquid electrolyte, such as a lithium salt in an organic solvent (e.g., LiClO4 in ethyl carbonate). Other lithium-based electrolyte / solvent combinations may be used as known in the art. In some cases, the electrolyte...

[0108] It may be a solid electrolyte, such as a lithium salt in polyethylene oxide. Where appropriate, the electrolyte may comprise a polymeric electrolyte. Examples of electrolytes include those set forth in U.S. Patent Application Publication 2017 / 0069931, which is incorporated herein by reference. Partitions can be used

[0110] To prevent electrodes

[0104] 、

[0106] Contact between them. Partition.

[0110] Can be permeable to lithium ions and electrolytes

[0108] However, a porous layer of material that is otherwise non-conductive is used to prevent the unit

[0100] internal short circuit. As is known in the industry, partition

[0110] May contain glass fibers or polymers, possibly having a semi-crystalline structure. Other components (e.g., current collectors) may also be included in unit 100, but are not shown in FIG1. cathode

[0104] Anode

[0106] Electrolytes

[0108] and partition

[0110] Together they form a complete unit

[0100] . Due to the partition

[0110] It is porous, therefore the electrolyte

[0108] Can flow to the partition

[0110] or by a partition

[0110] Included. Under normal operating conditions, the partition...

[0110] Porosity-allowing ions (Li+) in the electrode

[0104] 、

[0106] between via electrolyte

[0108] Flow. As is known in the art, the baffle can be constructed to melt and close the internal pore structure to shut down the unit in the event of exposure to excessive heat or runaway exothermic reaction. Most lithium-based cells are so-called secondary batteries. They can be discharged and recharged multiple times before the chemical or structural integrity of the cell falls below acceptable limits. Cells and batteries according to this disclosure are considered both primary (e.g., single-use) and secondary batteries. In unit

[0100] In the case of a secondary unit (or part of a secondary battery), it should be understood that the unit

[0100] It can be recharged individually or as a component of a complete system in which multiple units are recharged simultaneously (and possibly in the same parallel or series circuit). Apply reverse voltage to the cell

[0100] To achieve charging. It should be understood that various methods can be used to effectively recharge the lithium battery. Constant current, variable current, constant voltage, variable voltage, partial duty cycle, etc., can be used. Unless otherwise specified in the technical solution, this disclosure is not intended to limit to a particular charging method. In the unit During the charging period of

[0100] , the component

[0115] indicates that it is applied to the cathode

[0104] with anode

[0106] A voltage source between them, so as to draw electrons from the cathode

[0105] Provided to the anode

[0106] And allow chemical reactions to occur. Lithium ions shuttle from the cathode 104 to the anode 106 through the electrolyte 108 and the separator 110. [] As an example, cathode

[0104] or anode

[0106] The AMO material disclosed herein may be included independently. For the use of an AMO material as the cathode, the anode may correspond to lithium metal or a lithium-intercalating material, such as graphite. Depending on the application, the electrolyte...

[0108] May include acidic substances, such as those dissolved in organic solvents containing lithium salts. Except in electrolytes

[0108] In addition to or alternatively, an acidic substance is used in the electrode (i.e., the cathode).

[0104] or anode

[0106] ) May include AMO and acidic substances as appropriate. Oxalic acid is an example of an acidic substance. Without being bound by any particular theory, it is believed that the presence of acidic substances in the cathode 104 or anode 106 and / or electrolyte 108 improves the surface affinity of the AMO material for lithium ions, thereby improving its ability to absorb lithium ions during discharge and resulting in an overall improved capacity compared to similar units lacking acidic substances or having alkaline electrodes or electrolytes (i.e., including alkaline substances). Alternatively, the presence of acidic substances may allow for additional active sites for lithium absorption in the cathode 104. It should be understood that Figure 1 is not to scale. As shown in Figure 2, in most applications, the partition...

[0110] Occupying electrode

[0104] 、

[0106] most or all of the space between and the electrode

[0104] 、

[0106] Contact. In this case, the electrolyte...

[0108] Included in the partition

[0110] Inside (but may also penetrate into the holes or surfaces of the anode or cathode). Figure 2 is not necessarily to scale. The actual geometry of the unit can range from relatively thin and flat bags to can-shaped constructions, button units, and others. Unit construction techniques such as windings or spools or pin assemblies can be used. Alternatively, known current collectors and other components (not shown) in the industry can be used to connect the unit.

[0100] This is formed into a commercially viable package. Although the overall shape or geometry may vary, the cell or battery will typically contain spaced-out, non-contact electrodes at some location or cross-section.

[0104] 、

[0106] and there is an electrolyte therebetween.

[0108] and possibly a partition

[0110] . The unit may also be constructed such that multiple anodes and cathodes exist. The unit may be constructed such that two cathodes are on opposite sides of a single anode or vice versa. A battery intended for a specific purpose or operation may comprise a plurality of units configured according to the needs of a particular application. An example of such a battery is schematically shown in Figure 3. Here, the battery...

[0300] Lithium cells with four series configuration

[0100] To increase the voltage. By providing four units in parallel with the stack shown. The additional stacking of

[0100] can increase capacity at this voltage. Different voltages can be achieved by changing the series configuration of the cells. The quantity of

[0100] is used to achieve this. positive electrode

[0306] Accessible battery

[0300] Casing

[0302] On the outer side. A negative electrode is also provided.

[0304] .electrode

[0304] 、 The physical shape factor of

[0306] can vary depending on the application. It can be found in the battery casing.

[0302] Various adhesives, water, tapes, and / or other fixing mechanisms (not shown) are used internally to stabilize other components. Lithium-based batteries are generally operable, rechargeable, and can be stored in any orientation (if it is a secondary cell). As discussed above, the cell

[0100] Various different geometric shapes can be presented. Therefore, Figure 3 is not intended to represent a battery.

[0300] any specific physical shape factor. Battery

[0300] May also include a positive electrode

[0306] With battery

[0300] Casing

[0302] Lithium unit inside Various additional circuits between

[0100]

[0308] In other embodiments, additional circuitry is placed on the negative electrode.

[0304] with lithium unit

[0100] between, rather than at the positive electrode

[0306] with lithium unit

[0100] between, or separately placed on the positive electrode

[0306] with lithium unit Between

[0100] . Additional circuitry

[0308] May include short-circuit protection, overcharge protection, overheat shutdown and other circuits as known in the art to protect the battery.

[0300] , Unit

[0100] and / or attached to the battery

[0300] Any load. Select for cathode

[0104] Anode

[0106] and the composition of the electrolyte material for the unit

[0100] and unit

[0100] The performance of the battery to which it is formed is of paramount importance. In this regard, various examples of AMOs and methods of their production are provided in the context of this disclosure. These AMOs are suitable for forming anodes or cathodes in half-cells, cells, and batteries. The AMOs of this disclosure are otherwise compatible with known lithium cell technologies, including existing anode and cathode compositions, electrolyte formulations, and separator compositions. In the context of this disclosure, various examples of AMOs, methods of their production, and uses are provided. These AMOs are suitable for forming cathodes or anodes in half-cells, cells, and batteries. The disclosed AMOs are also compatible with conventional lithium-ion battery technologies, including existing anode compositions, cathode compositions, electrolyte formulations, and separator compositions. It should be understood that the electronegativity of the material selected for the anode 106 of the cell or battery used in this disclosure may be less than that of the cathode material to suitably complement the cathode material. In one specific embodiment, the disclosed AMO can be used as a cathode in a cell having a lithium metal anode. [] In various embodiments of this disclosure, the cathode

[0104] An AMO material comprising a surface having an acidic but not superacidic nature. This directly contrasts with previously known materials used as cathodes (e.g., lithium cobalt or lithium manganese materials). The AMO material and its production method disclosed herein are described below. In other embodiments, the anode...

[0106] The AMO material disclosed herein includes a surface that is acidic but not superacidic. Ideally, the surface of a metal oxide is an array of metal and oxygen centers, ordered according to the oxide's crystal structure. In reality, however, this array is imperfect, prone to vacancies, distortions, and surface adhesion effects. Nevertheless, any exposed metal center is cationic (positively charged) and electron-accepting, thus functioning as a Lewis acid site by definition. Oxygen centers are anionic (negatively charged) and act as Lewis base sites, donating electrons. This allows the metal oxide surface to exhibit an amphoteric behavior. Under normal atmospheric conditions, water vapor will be adsorbed onto the surface of metal oxides either through molecular (hydration) or dissociation (hydroxylation). OH- and H+ ions can also adsorb onto the oxide surface. Negatively charged hydroxyl groups will attach to the metal cation (Lewis acid, electron-withdrawing) center, and H+ ions will attach to the oxygen anion (Lewis base, electron-donating) center. Both types of adsorption result in the presence of the same functional group, the hydroxyl group, on the metal oxide surface. These surface hydroxyl groups can function as Brønsted acids or bases because these groups can either donate or accept protons. The tendency of an individual hydroxyl group to act as a proton donor or acceptor is influenced by the coordination of the metal cation or oxygen anion to which it is attached. Defects on the surface of a metal oxide (such as oxygen vacancies or coordination of surface groups with other chemicals) mean that all cations and anions are not equally coordinated. The number and strength of acid-base sites will vary. When this is extensively "summed" across the surface of an oxide, it can give the surface an overall acidic or basic character. The quantity and intensity of Lewis acid and base sites (derived from exposed metal cations and oxygen anions, respectively) and Boucher acid and base sites (derived from surface hydroxyl groups) greatly enhance the utility and functionality of metal oxides in both chemical reactions and device applications. These sites are strong contributors to the chemical reactivity of metal oxides. They can serve as anchor sites for other chemical groups and even other metal oxides. Furthermore, they can influence surface charge, hydrophilicity, and biocompatibility. One way to modify the surface of a metal oxide is by attaching small chemical groups or electron-withdrawing groups ("EWGs") in a process called surface functionalization. EWGs induce polarization of the hydroxyl bonds and promote the dissociation of hydrogen. For example, a stronger EWG should produce more polarized bonds and therefore more acidic protons. It should be understood that usable EWGs include groups other than hydroxides. The acidity of Lewis sites can be increased by induced polarization, which helps to donate electrons to the sites. When the compound thus prepared is placed in water, the acidic protons will dissociate and lower the pH measurement in the water. While there may be some inaccuracies when using solid acid / base systems instead of liquid systems, conventional pH measurement methods using titration, pH test strips, and pH probes can be used to assess the acidity of metal oxides dispersed in aqueous solutions. These measurements can be supplemented by techniques including (but not limited to) colorimetric indicators, infrared spectroscopy, and programmed temperature-controlled desorption data to establish the acidification properties of the metal oxide surface. Surface functional groups can be examined using standard analytical techniques including (but not limited to) X-ray photoelectron spectroscopy. Surface functionalization can be performed post-synthesis, including (but not limited to) exposing the metal oxide to an acidic solution or vapor containing the desired functional group. It can also be performed via solid-state methods, wherein the metal oxide is ground together with and / or with a solid mixture containing the desired functional group. However, all such methods require one or more additional surface functionalization steps in addition to those steps necessary for the synthesis of the metal oxide itself. The synthesis and surface functionalization of AMO materials can be accomplished using a single-pot hydrothermal synthesis method or an equivalent, in which the surface of the metal oxide is functionalized as it is synthesized from a suitable precursor. The precursor salt containing EWG is dissolved and the resulting solution is acidified using an acid containing a second EWG. This acidified solution is then alkalized, heated, and washed. A drying step yields solid AMO material. For example, an example of AMO (tin oxide) synthesized using the following single-pot method with simultaneous surface functionalization: 1. First, dissolve 7 g (7 g) of tin(II) chloride dihydrate (SnCl 22H 2O) in a solution of 35 mL anhydrous ethanol and 77 mL distilled water. 2. Stir the resulting solution for 30 minutes. 3. Acidify the solution by adding (dropwise) 7 mL of 1.2 M HCl and stirring the resulting solution for 15 minutes. 4. Alkalize the solution by adding (dropwise) 1 M alkaline aqueous solution until the pH of the solution is about 8.5. 5. Then place the resulting opaque white suspension in a hot water bath (approximately 60°C to 90°C) for at least 2 hours while stirring. 6. Then wash the suspension with distilled water and anhydrous ethanol. 7. The washed suspension is dried in air at 100°C for 1 hour, and then annealed in air at 200°C for 4 hours. This method produces tin AMO with a chlorinated surface functionalization, which, when resuspended and measured in aqueous solution at 5 wt.% at room temperature, has a pH of approximately 2. By definition, its Hammett function H0 is greater than -12. Although open systems such as flasks are described here, closed systems such as autoclaves can also be used. Several AMOs have been synthesized using the single-pot method described above. Table 1 below lists the precursors and acids used, where Ac represents an acetate group with the chemical formula C2H3O2 or CH3COO. In some cases, dopants are also used. precursor dopant acid SnAc CH 3COOH SnAc H₂SO₄ SnAc HNO 3 SnAc H 3PO 4 SnAc C 6H 8O 7 SnAc C 2H 2O 4 SnAc FeAc HCl SnAc FeAc H 2SO 4 SnAc FeAc HNO 3 SnAc FeAc C 2H 2O 4 SnAc FeAc H 3PO 4 SnAc FeAc C 6H 8O 7 SnAc HBr SnAc H 3BO 3 SnSO MnCl H 2SO 4 SnCl MnCl HCl SnCl FeCl 3& AlCl 3 HCl FeCl 3 SnCl HCl Fe(NO 3) 3 HNO 3 BiCl HCl Zr(SO₄)₂ H₂SO₄ TiOSO 4 H₂SO₄ Sb₂(SO₄)₃ H₂SO₄ In(Cl) 3 HCl In 2(SO4)3 H₂SO₄ In(III)Br HBr InCl 3 HCl LiAc & FeCl3 SnCl 2 HCl In some embodiments, the electron-withdrawing group has a carbon chain length of 6 or less and / or an atomic mass of 200 AMU or less. In some embodiments, the electron-withdrawing group has a carbon chain length of 8 or less or 10 or less and / or an atomic mass of 500 AMU or less. It should be understood that the parameters of this method can be varied. These parameters include (but are not limited to) the type and concentration of reagents, the type and concentration of acids and bases, reaction time, temperature and pressure, stirring rate and time, the number and type of washing steps, the time and temperature of drying and calcination, and gas exposure during drying and calcination. These parameters can be varied individually or in any combination, depending on the experimental design method used. Furthermore, other methods for synthesizing metal oxides (e.g., spray pyrolysis, vapor phase growth, electrodeposition, solid-state methods, and hydrothermal or solvothermal processes) can be used to achieve the same or similar results as the method disclosed herein. A variety of annealing conditions can be used to prepare AMO nanomaterials. Example annealing temperatures can be below 300°C, for example, from 100°C to 300°C. Example annealing times can range from about 1 hour to about 8 hours or longer. Annealing can occur under a variety of atmospheric conditions. For example, annealing can occur in air at atmospheric pressure. Annealing can occur under pressurized (above atmospheric pressure) or depressurized (below atmospheric pressure or in a vacuum) conditions. Annealing can alternatively occur in a controlled atmosphere, such as in the presence of an inert gas (e.g., nitrogen, helium, or argon) or in the presence of an oxidizing gas (e.g., oxygen or water). Various drying conditions can be used to prepare AMO nanomaterials. Example drying temperatures range from 50°C to 150°C. Example drying times range from approximately 0.5 hours to approximately 8 hours or longer. Drying can occur under various atmospheric conditions. For example, drying can occur in air at atmospheric pressure. Drying can occur under pressurized (above atmospheric pressure) or depressurized (below atmospheric pressure or in a vacuum) conditions. Drying can alternatively occur in a controlled atmosphere, such as in the presence of an inert gas (e.g., nitrogen, helium, or argon) or in the presence of an oxidizing gas (e.g., oxygen or water). [] The performance characteristics of AMO nanomaterials differ from those of non-acidified metal oxide nanoparticles. As an example, Figure 4 shows the difference in cyclic voltammetry (CV) between AMO tin prepared by a single-pot method and commercially available non-AMO tin when cycling with lithium metal. For instance, surface-functionalized AMO materials exhibit superior reversibility compared to non-AMO materials. The presence of unique peaks in the CV of AMO materials indicates multiple electron transfer steps occurring during charge / discharge. For example, peaks at higher voltages may indicate direct oxidation / reduction of the AMO material, while peaks at lower voltages may be due to changes in the material structure of the AMO material (i.e., alloying). As another example, Figure 5 shows that the total reflectance of AMO tin oxide differs from that of commercially available non-AMO tin oxide. This data indicates that, in addition to being used as an anode or cathode according to this disclosure, AMO has a lower band gap and therefore more desirable properties as a component of photovoltaic systems. AMO materials can be represented by the following formula, depending on the situation. M mO x / G Where M mO x is a metal oxide, m is at least 1 and not more than 5, x is at least 1 and not more than 21; G is at least one EWG that is not a hydroxide; and " / " distinguishes metal oxides from EWG, indicating that there is no fixed mathematical relationship or ratio between the two. G can represent a single type of EWG, or more than one type of EWG. Examples of AMO are acidified tin oxide (SnxOy), acidified titanium dioxide (TiaOb), acidified iron oxide (FecOd), and acidified zirconium oxide (ZreOf). Preferred electron-withdrawing groups ("EWG") are Cl, Br, BO3, SO4, PO4, NO3, and CH3COO. Regardless of the specific metal or EWG, according to this disclosure, AMO materials, when suspended at 5 wt.% in aqueous solution, are acidic but not superacidic, producing at least a pH less than 7 and a Hammett function H0 greater than -12 on their surface. AMO materials can be crystalline or amorphous (or a combination thereof) and can be used alone or as a combination of each other, with unoxidized metal oxides, or with other additives, binders, or conductive agents known in the art. In other words, electrodes prepared to utilize the AMO disclosed herein may or may not contain other materials. In one embodiment, AMO can be laminated on a conductive material to form a cathode.

[0104] . In some embodiments, AMO material is added to conductive additive materials (e.g., graphite, carbon black, or conductive carbon (or equivalents thereof)) in the range of 5 wt.% to 90 wt.%, while conductive additives and / or binder materials may be present in the range of 10 wt.% to 95%. Depending on the situation, AMO is added at 10 wt.%, 33 wt.%, 50 wt.%, or 80 wt.%. To maximize the total surface area and the amount of active sites available for the reactive material, AMOs can exist in the form of nanoparticles (i.e., smaller than 1 micrometer) and be substantially monodisperse. Depending on the application, the nanoparticle size may be less than 100 nm, and can be even smaller, for example, less than 20 nm or 10 nm. It should be understood that nanoparticles with sizes ranging from 1 nm to 100 nm or 1000 nm can be used in certain AMOs. Mixed metal AMOs, which contain another metal or metal oxide in addition to simple or binary oxides, can be used to form the anodes and cathodes of half-cells, electrochemical cells, and batteries. These mixed metal AMOs can be represented by the following formula. M mN nO x / G and M mN nR rO x / G The M series metals have m at least 1 and no more than 5; the N series metals have n greater than 0 and no more than 5; the R series metals have r greater than 0 and no more than 5; the O series metals have a total oxygen content associated with all metals and x at least 1 and no more than 21; " / " distinguishes metal oxides from EWGs, indicating that there is no fixed mathematical relationship or ratio between the two; and G series metals are at least one type of EWG that is not a hydroxide. G can represent a single type of EWG or more than one type of EWG. Some prior art involves mixing metal oxide systems, with zeolite systems being the most prominent example, exhibiting strong acidity even if each simple oxide does not exhibit strong acidity. The preferred embodiments of the mixed metal AMOs disclosed herein differ from these systems because any embodiment must include at least one acidic (but not superacidic) AMO in the form of a simple M mO x / G. Example mixed metal and metal oxide systems include Sn xFe cO y+d and Sn xTi aO y+b, where y+d and y+b can be integer or non-integer values. Depending on the circumstances, mixed metal AMO materials are produced via a modified single-pot method: the synthesis begins with two metal precursor salts instead of one in any proportion. For example, step 1 of the single-pot method described above can be modified as follows: first, 3.8 g of tin(II) chloride dihydrate (SnCl₂2H₂O) and 0.2 g of lithium chloride (LiCl) are dissolved in a solution of 20 mL anhydrous ethanol and 44 mL distilled water. The three metal precursor salts shown in Table 1 can be used in any proportion, for example, as appropriate. The metal precursor salts may have the same or different anionic groups, depending on the desired product. The metal precursor salts may be introduced at different points in the synthesis. The metal precursor salts may be introduced as solids or in a solvent. In some embodiments, a first metal precursor salt may be used in the primary structure of the resulting AMO (i.e., in a larger proportion), and a second (and, if applicable, a third) metal precursor salt may be added as a dopant or as a secondary component for the resulting AMO. Seven useful findings were obtained from experiments using the single-pot method. First, in all cases, both surface functionalization and acidity were endogenously generated (see Figure 6), rather than generated post-synthesis. Unlike prior art surface functionalization methods, the single-pot method does not require any additional steps for surface functionalization other than those required for the synthesis of the metal oxide itself, and it does not use organic compounds containing hydroxyl groups or hydrogen peroxide. Second, this method can be widely extended to a broad range of metal oxides and EWGs. Using the method disclosed herein, metal oxides of iron, tin, antimony, bismuth, titanium, zirconium, manganese, and indium have been synthesized and simultaneously surface-functionalized with chlorides, sulfates, acetates, nitrates, phosphates, citrates, oxalates, borates, and bromides. Mixed metal AMOs of tin and iron, tin and manganese, tin and manganese and iron, tin and titanium, indium and tin, antimony and tin, aluminum and tin, lithium and iron, and lithium and tin have also been synthesized. Furthermore, surface functionalization can be performed using EWGs with surfaces weaker than halogens and SO₄, but still producing acidic but not ultra-acidic surfaces. For example, this method has also been used to synthesize AMOs surface-functionalized with acetates (CH₃COO), oxalates (C₂O₄), and citrates (C₆H₅O₇). Several examples are described below. Third, there is a synergistic relationship between EWGs and other properties of nanoparticles (e.g., size, morphology (e.g., plate-like, spherical, needle-like, or rod-like), oxidation state, and crystallinity (amorphous, crystalline, or mixtures thereof)). For example, morphological differences can occur between AMO nanoparticles synthesized under the same conditions, except for the use of different EWGs for surface functionalization, as illustrated in Figure 7, which provides electron micrographs of two AMOs produced using different EWGs. Surface functionalization can act as a "pin" for nanoparticle size, thereby stopping their growth. Depending on the precise synthesis conditions, this pinning can occur in only one dimension or in more than one dimension of the nanoparticle. Fourth, the properties of AMOs are extremely sensitive to synthetic conditions and procedures. For example, when synthesized under the same conditions except for two different total reaction times, the morphology and properties of AMO nanoparticles can differ. For instance, Figure 8 provides electron micrographs of two AMOs with different total reaction times, and Figure 9 provides a graph of capacity (mAh / g) versus cycle number, showing a comparison of the cycling characteristics of two AMOs with different morphologies and different total reaction times. Experimental design methods can be used to determine the optimal or best synthetic conditions and procedures to produce the desired properties or property sets. Fifth, both the anions present in the precursor salt and the anions present in the acid contribute to the surface functionalization of AMO. In one embodiment, a tin chloride precursor and hydrochloric acid are used in the synthesis of tin AMO. The properties of these particles differ from those in embodiments using a tin chloride precursor and sulfuric acid, or from embodiments using a tin sulfate precursor and hydrochloric acid. For some embodiments, matching the precursor anion and the acid anion may be advantageous. Sixth, when using a precursor with weak EWG and an acid with strong EWG, or vice versa, the strongly pulling anion will dominate surface functionalization. This opens up a wider range of synthetic possibilities, allowing functionalization using ions that are not readily available in either the precursor salt or the acid. It also allows for mixed functionalization using both strong and weak EWG. In one example, tin AMO was synthesized using a tin acetate precursor and phosphoric acid. X-ray photoelectron spectroscopy analysis of the surface showed that the atomic concentration of phosphorus was greater than that associated with the acetate groups (see Figure 10). Seventh, although the disclosed method is a general procedure for synthesizing AMO, the synthesis procedure and conditions can be adapted to produce sizes, morphologies, oxidation states, and crystal states desired for different applications. As an example, catalytic applications may desire AMO materials that are more active under visible light or more active under ultraviolet light. Figure 11A shows the visible light exposure degradation time of methylene blue when exposed to two different AMO materials. Figure 11B shows the ultraviolet light exposure degradation time of methylene blue when exposed to four different AMO materials. In another example, AMO materials can be used as battery electrodes. Primary (disposable) battery applications can expect AMOs that produce the highest capacity characteristics, while secondary (rechargeable) battery applications can expect the same AMOs but with the highest cycle performance characteristics. Figure 12 compares the cycleability of two different batteries constructed from AMO materials (including chlorinated AMO and sulfur-containing AMO). AMO materials can enhance battery performance without degrading battery components or generating gases (see Figure 13). This is exactly the opposite of what prior art has taught. [] Figure 13 shows the charge-discharge cycleability of a battery with a lithium metal cell constructed using an AMO nanomaterial electrode. It exhibits a cycle life of up to 900 charge-discharge cycles while maintaining usable capacity and exceptional coulombic efficiency. This long cycle life is exceptional, especially for a lithium metal reference electrode, as lithium metal is known to grow dendritic crystals even during low cycle counts, which can expand and lead to dangerous and catastrophic failures of the battery cell. According to this disclosure, the complete unit includes the anode of the disclosed AMO.

[0106] Can be used with known electrolytes

[0108] and a cathode comprising a known material (e.g., lithium cobalt oxide (LiCoO2)).

[0104] Used together. Forms a partition. The material of

[0110] can also be extracted from those currently known in the industry. The complete unit contains the cathode of the disclosed AMO.

[0104] Can be used with known electrolytes

[0108] and an anode comprising a known material (e.g., carbon-supported copper foil).

[0106] Together, they exhibit a negative charge less than that of the AMO disclosed herein. Other anode materials such as lithium metal, sodium metal, magnesium metal, or other composite materials containing one or more of these metals may also be used. In some embodiments, the anode

[0106] May be composed of lithium or substantially of lithium. Includes a separator.

[0110] and electrolytes

[0108] The material can be obtained from those currently known in the industry as discussed above. Various layering and other enhancement technologies known in the industry can be deployed to accommodate units.

[0100] Maximizing the capacity of lithium-ion batteries supplied. It should also be understood that, based on the AMO cathode according to this disclosure...

[0104] The battery can be deployed as a secondary (e.g., rechargeable) battery, but can also be used as a primary battery. Although the AMO anode of this disclosure is suitable for reversible battery chemistry, the cells or batteries constructed as described herein can be satisfactorily deployed as primary cells or batteries. In some contexts, the term "formation" is used to refer to the initial charging or discharging of a battery at a manufacturing facility before the battery is usable. Formation processes can typically be quite slow and may require multiple charge-discharge cycles to transform the in-process active materials into a form more suitable for cell cycling. These transformations may incorporate changes in the structure, morphology, crystallinity, and / or stoichiometry of the active materials. In contrast, in some embodiments, the cells and batteries constructed according to this disclosure do not require initial formation and are therefore ready to be used as primary cells or batteries upon assembly. In other cases, limited or rapid formation may be employed. Furthermore, by deploying the cells and batteries of this disclosure as primary cells not intended for recharging, some inherent safety issues of lithium-ion battery chemistry are mitigated, as safety issues are known in the industry to occur more frequently during battery cycling. However, after the initial discharge, the cells and batteries disclosed herein are suitable, depending on the circumstances, for use as secondary battery systems capable of undergoing multiple (e.g., up to tens, hundreds, or even thousands) charge-discharge cycles. In some embodiments, cathode

[0104] Contains tin oxide (SnO2) nanoparticles not acidified according to the AMO described above. Known electrolytes

[0108] , Anode

[0106] and partition

[0110] Or, as otherwise described in this disclosure, may be used in conjunction with these embodiments. It should be understood that various battery structures are possible using the AMO materials disclosed herein. For example, a battery may include a first electrode containing AMO nanomaterials, a second electrode, and an electrolyte positioned between the first and second electrodes. As an example, in a lithium-ion battery, the first electrode may operate as either a cathode or an anode. For example, when operating as a cathode, the second electrode may correspond to lithium metal, graphite, or another anode material. As another example, when operating as an anode, the second electrode may correspond to LiCoO₂, LiMn₂O₄, LiNiO₂, or another cathode material. Materials that can be used for the second electrode include (but are not limited to) graphite, lithium metal, sodium metal, lithium cobalt oxide, lithium titanate, lithium manganese oxide, lithium nickel manganese cobalt oxide (NMC), lithium iron phosphate, lithium nickel cobalt aluminum oxide (NCA), or any combination thereof. It should be understood that the AMO materials disclosed herein can also be added as dopants to conventional lithium-ion cell anodes and / or cathodes, for example, in amounts between 0.01 wt.% and 10 wt.%, or, for example, in amounts of about 1 wt.%, 5 wt.%, or 10 wt.% of AMO material in the electrode. The disclosed AMO materials provide an impressive capacity for storing lithium atoms, and by adding these materials to conventional lithium-ion cell electrodes, this capability is provided to the composites. As a specific example, the electrode comprises LiCoO₂ and AMO. As another example, the electrode comprises a carbonaceous material (e.g., graphite) and AMO. Advantageously, AMO materials can be used in conjunction with acidic components, such as binders, acidic electrolytes, or acidic electrolyte additives, depending on the application. This can be in the case of anodes, cathodes, half-cells, complete cells, integrated cells, or other components. The inventors have surprisingly discovered that including acidic components and / or acidic substances (e.g., organic acids or organic anhydrides) in batteries containing AMO materials increases capacity compared to batteries that do not contain acidic substances. Furthermore, prior art teaches against the use of acidic substances because such substances can degrade the metal current collector and casing and cause deterioration of other electrode components. Figure 14 shows comparative cycling characteristics data for AMO-based batteries formed from the same materials and structures, except that one has a standard electrolyte, one has an alkaline electrolyte, and one has an acidified electrolyte. These batteries are constructed as follows: all cathodes comprise the same AMO material; all anodes are lithium metal; the standard electrolyte is a 1:1:1 mixture of 1 M LiPF6 dimethyl carbonate, diethyl carbonate, and ethyl carbonate; the acidified electrolyte is a standard electrolyte containing 3 wt.% succinic anhydride; and the alkaline electrolyte is a standard electrolyte containing 3 wt.% dimethylacetamide. All batteries were cycled at the same discharge rate. As explained, the battery with the acidified electrolyte system exhibits the best cycling performance, maintaining the highest capacity within the maximum number of cycles. Figure 15 provides additional comparative cycling characteristics data for two different batteries with the same battery construction, including an acidified electrolyte, except that the AMO material in one battery was de-acidified by solvent washing. These batteries comprise the following constructions: a cathode comprising AMO material; an electrolyte consisting of a 1:1:1 mixture of dimethylene carbonate, diethyl carbonate, and ethyl carbonate containing 1 M LiPF6 and 3 wt.% succinic anhydride; and an anode of lithium metal. The batteries were cycled at the same discharge rate. The battery with the acidified AMO material exhibited a higher capacity retention relative to the number of cycles, indicating that the acidified surface of the AMO can interact with the acidified electrolyte, thereby providing enhanced performance. Several acidic electrolytes have been developed and / or tested, and the unit chemistry operations described herein have been found to be advantageously utilized. Currently, lithium batteries are considered to pose safety risks in certain situations. For example, airline regulations currently require lithium batteries to be partially discharged before transport in cargo holds. Fires have been reported in devices using lithium batteries due to runaway exothermic reactions. Furthermore, lithium fires can be difficult to extinguish using widely deployed fire suppression systems and devices. For these reasons, many commercially available battery cells use lithium compounds instead of metallic lithium. However, using lithium-containing compounds instead of lithium metal in the anode limits the amount of lithium available for the reaction and incorporated into the cathode during discharge, thus limiting the capacity of such cells. However, the AMO material disclosed in this invention not only exhibits greater lithium absorption during discharge but also enhanced safety characteristics. For example, when battery cells containing AMO material in both the cathode and lithium metal electrodes undergo safety tests (e.g., nail penetration tests, short-circuit tests, and overvoltage tests), the cells perform well and appear to pose no unacceptable risk of fire or explosion. Several units were constructed, with the cathode comprising SnO₂AMO and the anode comprising conductive carbon black (Ketjen Black), polyvinyl difluoride (PVDF), and polyarylamide (PAA) in a volume ratio of 63 / 10 / 26.1 / 0.9. The double-sided layer of this composition was prepared at 4 mg / cm² per side. Six of these layers constituted the cathode. The prepared cathode was 9 cm × 4 cm in size. A 25 µm thick polypropylene layer, obtained from Targray Technology International, Inc., was used as a separator. The separator was 9.4 cm × 4.4 cm in size. The electrolyte was prepared from 1 M LiPF₆ in a solvent of ethyl acetate (EC), diethyl carbonate (DEC), and dimethyl carbonate (DMC) in a 1:1:1 volume ratio. The anode was a 50 µm thick lithium metal layer with dimensions of 9.2 cm × 4.2 cm. Before safety testing, the two constructed cells were discharged, and the actual capacity was found to be 1.7 Ah and the specific capacity was 1575 mAh / g SnO 2. Figure 16 provides temperature and voltage data for the unit constructed as described above and subjected to the nail penetration test. The test was conducted at room temperature and no events (such as fire) were observed. Temperature and voltage remained stable. Figure 17A provides temperature and voltage data for the cell constructed as described above and subjected to the overcharge test. A current of 1 A was applied. Apart from some gas generation from the cell, no adverse events were observed during the test period. Figure 17B provides a breakdown of the overcharge test results from Figure 17A at the start of the test. Examples of electrochemical units constructed using AMO material as the cathode and lithium as the electrode have been tested and successfully withstood up to 900 or more charge-discharge cycles without catastrophic or destructive failure. Alternatively, examples of electrochemical units constructed using AMO material as the cathode and lithium as the electrode have been tested and successfully withstood up to 900 or more charge-discharge cycles while remaining charged and maintaining usable capacity. Without wishing to be limited by any particular theory, the enhanced safety provided by using AMO-based cathode materials in lithium cells stems from the ability of AMO materials to passivate lithium metal and prevent dendritic crystal formation. The inventors have observed that, during cycling, lithium metal anodes do not appear to grow or otherwise form dendritic crystals, but lithium anodes exhibit a softer and less crystalline appearance. In some embodiments, lithium anodes may be passivated, for example, by cycling as a component of an electrochemical cell as described herein, and then removing them from the electrochemical cell and using them as electrodes in new electrochemical cells with different cathodes. Furthermore, the cells constructed according to this disclosure utilize low operating voltages (e.g., between 1 and 2 volts), which contrasts with the typical voltages of lithium or lithium-ion battery cells, which typically operate at approximately 3–4.2 volts. This difference in operating voltage partially explains the safety of the disclosed cells. Referring now to Figure 18, a cathode of the form disclosed herein is provided.

[1800] Schematic illustration. Figure 18 is not to scale. Cathode.

[1800] Contains approximately 33.3% SnO2 in the form of AMO. AMO is prepared according to the method described herein. For the formation of the carbon layer...

[1804] A slurry of Ketjen Black EC-300J (SA: approximately 800 m² / g) was prepared using NMP solvent and coated onto a 10 µm thick copper foil.

[1802] The top layer is used as a current collector. The slurry composition is 80% by weight Ketjen black and 20% by weight PVDF. The coated belt is dried in a vacuum oven at 100°C. To form a carbon / SnO2 electrode layer

[1806] A mixture of AMO SnO2, Ketjen black, and PVDF (33.3% by weight each) was prepared, and a slurry was formed by adding NMP solvent. The slurry was then coated onto a copper foil coated with Ketjen black.

[1802] 、

[1804] ) on a portion of the strip. The resulting strip was dried in a vacuum oven at 100°C (overnight) and calendered at room temperature. The thickness of the strip was measured using a micrometer in the SnO 2 / Ketjen black coated area and the Ketjen black coated area only. The thickness of the Ketjen black layer 1804 was found to be approximately 8 µm, while the layer containing SnO 2AMO was found.

[1806] is approximately 2 µm thick. The foil layer is approximately 10 µm thick, thereby providing a cathode of approximately 18-20 µm.

[1800] Total thickness. The calendered strip is stamped into a disk from both the Ketjenblack-coated area and the SnO2 / Ketjenblack-coated area. The total mass of the electrode layer is obtained by subtracting the mass of the Ketjenblack-coated disk from the SnO2 / Ketjenblack-coated disk. In the case of one tested cell type, the total mass of the electrode material is 0.0005 g (after subtracting the equivalent mass of the Ketjenblack-coated disk), thus providing approximately 0.000167 g (33.3% of the total mass) of total active material (SnO2). cathode

[1800] Useful forms include a layered structure of a carbonaceous layer and an AMO-containing layer, the use of Ketjen Black high-surface-area conductive carbon in both layers, an active material content of 33% in the AMO-containing layer, the thickness of the AMO-containing layer, the use of PVDF as an adhesive, and the use of copper foil as a current collector. Each of these forms may vary as appropriate. For example, carbon other than Ketjen black can be used. It should be understood that AMO materials used as active materials have extremely small particle sizes, for example, approximately 1-100 nm (e.g., 2-5 nm), and a narrow size distribution. Although graphite can be used as carbon for the cathodes disclosed herein, Ketjen black has a particle size closer to that of AMO than commercially available graphite and some other conductive carbons. Ketjen black particles can be, for example, approximately 30-300 nm in size, and their distribution is wider than that of AMO particles. In contrast, graphite particles tend to have larger sizes, for example, approximately 100 µm. This close similarity in size allows for greater uniformity of the mixture of Ketjen black and AMO on a local scale, and results in more complete or better mixing and contact between carbon and AMO particles. As another example, the number of carbonaceous material layers and AMO-containing layers can be varied to form the electrode. In the example described above, the electrode comprises a carbonaceous material layer and an AMO-containing layer. Additional carbonaceous material layers may be included, as appropriate. Additional AMO-containing layers may be included, as appropriate. Advantageously, the carbonaceous material layer can be placed directly on the AMO-containing layer, followed by another carbonaceous material layer, followed by another AMO-containing layer, and so on. Examples of any number of layer pairs, such as 1-20 layer pairs, are contemplated in the electrode. Additionally, acidic substances may be incorporated into the electrode and / or electrode layers, as described above, and may be mixed with the carbonaceous material, AMO, and / or binder. However, in some embodiments, different layers are not used in the AMO-containing electrode, and the electrode may comprise AMO, carbonaceous material, and one or more binders (e.g., PVDF, PAA, etc.) in a single hybrid structure, having a composition similar to the overall structure of the layered electrode described above. For example, the electrode may comprise a separate carbonaceous layer (0% AMO) and an AMO-containing layer (e.g., 33% AMO) to provide an overall composition of approximately 21% AMO. Alternatively, the electrode may comprise a single structure containing a mixture of 21% AMO and carbonaceous material (and binder). Depending on the situation, the single hybrid electrode structure may be assembled into multiple layers, each having the common composition of the hybrid structure. As another example, the percentage of active material can vary. For instance, in the multilayer electrode described above, the carbonaceous layer does not contain AMO, while the AMO-containing layer contains approximately 33% AMO. When considered as a whole, the total AMO content of this composition of layers can reach approximately 21% by weight. However, the AMO-containing layer and / or the electrode as a whole may include between 1% and 90% by weight of AMO, depending on the configuration. In some embodiments, a high AMO fraction may be useful, for example, 50% by weight or more of AMO. In other embodiments, a low AMO loading can be useful, for example, 35% by weight or less of AMO. Contrary to conventional thinking, which typically maintains a high amount of active material in the electrode (e.g., 80% by weight or higher) to maximize the capacity and specific capacity of the cells incorporated into the electrode, the inventors have found that a lower AMO loading advantageously allows for the production of batteries with higher overall capacity and higher specific capacity. Not wishing to be limited by any theory, the high capacity of the cells incorporating AMO material can be achieved through the specific affinity of the AMO material for lithium atoms. The incredible amount of lithium atoms that electrodes incorporating AMO material can store can lead to the need for additional space to accommodate the absorbed lithium. This additional space for lithium atoms can be achieved by incorporating a lower percentage of active material. In fact, a total electrode or electrode layer with a percentage as low as 15% or 20% AMO active material can exhibit even higher capacity and specific capacity than electrodes with a significantly higher AMO active material loading. In addition, conductive carbon can be activated by the presence of AMO materials and can provide additional active sites for lithium absorption during charging and / or discharging. Due to its incredible affinity for lithium atoms, AMO can be added to conventional lithium cell electrodes or lithium-ion electrodes in some embodiments. In this way, conventional electrodes can have advantageously improved lithiation capacity with little or no change to the electrochemistry of the cell. In some instances, AMO can be added to conventional lithium cell electrodes or lithium-ion electrodes in amounts up to 5%. As another example, the thickness of the electrode layer containing AMO can be varied to, for example, improve performance or modify other properties of the electrode, such as the active material loading (i.e., AMO weight %). For example, the thickness of the carbonaceous layer of the electrode can be 0.5 µm to 50 µm, 1.0 µm to 20 µm, or 1.5 µm to 10 µm. For other examples, the thickness of the AMO-containing layer of the electrode can be 0.1 µm to 20 µm, 1 µm to 15 µm, or 5 µm to 10 µm. Values ​​or electrodes outside these ranges of electrode thickness can be used, for example, electrodes with thicknesses of up to 5 µm, 10 µm, 15 µm, 20 µm, 25 µm, 30 µm, 35 µm, 40 µm, 45 µm, or 50 µm. However, the inventors have discovered that, for some embodiments, as described above, different carbonaceous materials and AMO-containing layers are not required, and the electrode may include one or more AMO-containing layers or structures as appropriate. As another example, the amount and type of binder included in the electrode can be varied to achieve specific results. In some embodiments, a larger amount of binder may be included in the electrode or electrode layer. For example, the binder may be present in the electrode or electrode layer in an amount from 10% to 50% by weight or in a similar amount to that of carbonaceous materials. The inventors have found that incorporating a higher amount of binder, or an amount comparable to that of conductive carbon, can be advantageous for forming a high-quality electrode with usable structure and capacity characteristics. In some embodiments, conductive carbon itself may be difficult to form a compacted structure, and by incorporating a large amount of binder, the ability to form usable carbonaceous materials and AMO-containing layers and / or electrodes can be improved. As another example, various current collector configurations can be used. As described above, copper film current collectors can be used. Other metals can be used alternatively, including aluminum, stainless steel, brass, titanium, etc. Furthermore, multiple current collectors can be used, for example, in configurations where an AMO layer and / or a carbon layer can be positioned between multiple current collectors. It should be understood that different current collectors can be used at the anode and cathode. Additionally, the current collector does not need to contain a film and can instead be constructed as a sieve, grid, needle, or other structure with any suitable thickness or size. In some embodiments, the current collector can also be used for temperature control and can serve as a heat sink or heat carrier for removing excess heat from the active material of the cell. Coin-shaped battery cells were constructed and tested through repeated discharge-charge cycles. The cathode system containing SnO₂AMO was assembled as described above using a glass separator, an electrolyte of 1 M LiPF₆ in a 1:1:1 DEC / EC / DMC mixture, and a lithium metal anode. The cells were discharged at a rate of C / 10 from their assembled open-circuit voltage of 3.19 V to 0.01 V. The cells were then charged at a rate of C / 10 from 0.01 V to 1.5 V. After this, the cells were cycled at a rate of C / 5 from 1.5 V to 0.01 V and from 0.01 V to 1.5 V. While the voltages and charging rates described here are merely examples, it should be understood that other charging and discharging rates and voltages can be used. The cells were cycled at least 111 times, and the discharge capacity (mAh / g SnO₂AMO) was tabulated. Table 2 below shows the discharge and charge capacities for each cycle. Loop count Discharge capacity (mAh / g) Charging capacity (mAh / g) 1 10831.3 2662.62 2 2973.84 2421.68 3 2501.03 2222.64 4 2355.08 2174.04 5 2291.47 2139.19 6 2247.67 2111.76 7 2209.57 2087.83 8 2177.03 2065.89 9 2149.24 2047.6 10 2125.59 2030.36 11 2101.69 2013.46 12 2080.69 1997.5 13 2059.89 1981.24 14 2040.17 1966.72 15 2024.28 1953.37 16 2008.84 1942.08 17 1993.69 1929.4 18 1979.04 1917.43 19 1966.44 1908.6 20 1954.92 1898.9 21 1944.97 1891.23 22 1932.27 1880.72 23 1923.78 1874 24 1914.11 1866.1 25 1907.46 1860.21 26 1900.79 1855.01 27 1894.65 1850.32 28 1887.68 1844.6 29 1882.79 1840.91 30 1878.46 1837.21 31 1874.54 1835.35 32 1871.02 1831.98 33 1866.44 1827.26 34 1859.54 1822.82 35 1856.67 1821.53 36 1853.59 1819.6 37 1851.17 1816.69 38 1845.09 1812.14 39 1842.39 1810.32 40 1839.15 1807.1 41 1834.77 1803.97 42 1832.3 1802.13 43 1831.14 1801.41 44 1827.02 1797.32 45 1823.93 1795.17 46 1821.4 1793.15 47 1819.93 1792.26 48 1816.56 1788.62 49 1812.84 1785.92 50 1810.85 1783.93 51 1810.51 1783.87 52 1808.01 1781.22 53 1806.87 1780.98 54 1805.13 1779.63 55 1802.45 1777.16 56 1800.05 1775.29 57 1797.44 1773.06 58 1795.54 1771.9 59 1795.6 1771.34 60 1794.76 1770.37 61 1790.56 1767.23 62 1789.1 1765.94 63 1788.29 1765.07 64 1787.27 1764.56 65 1785.98 1762.92 66 1782.61 1760.38 67 1781.7 1758.88 68 1780.37 1757.5 69 1778.51 1756.19 70 1778.82 1756.4 71 1776.88 1754.59 72 1774.77 1753.22 73 1774.01 1752.07 74 1770.46 1749.82 75 1769.2 1748.57 76 1769.38 1748.77 77 1768.13 1747 78 1765.94 1745.88 79 1764.59 1744.82 80 1765.92 1746.01 81 1764.93 1745.57 82 1764.43 1744.88 83 1760.3 1741 84 1756.14 1737.34 85 1754.61 1736.06 86 1755.47 1736.32 87 1755.64 1736.73 88 1753.54 1735.07 89 1752.19 1734.21 90 1751.97 1733.89 91 1749.7 1731.48 92 1744.48 1726.11 93 1738.48 1721.23 94 1741.88 1723.88 95 1738.25 1719.81 96 1740.77 1722.4 97 1742.32 1723.85 98 1742.52 1723.86 99 1743.26 1724.59 100 1743.17 1723.9 101 1740.72 1722.31 102 1739.06 1721.01 103 1738.7 1720.81 104 1738.64 1721.39 105 1738.72 1720.88 106 1736.25 1717.86 107 1733.64 1716.71 108 1730.86 1714.26 109 1728.66 1712.09 110 1725.84 1710.23 111 1726.15 1709.76 Table 2. Discharge and Charge Capacity Figure 19 provides data showing the variation of the cell cycle with the observed charge capacity (CC) and discharge capacity (DC) (in mAh / g SnO2AMO). As shown in Table 2 and Figure 19, an extremely high initial discharge capacity of 10,831 mAh / g is observed. This initial discharge capacity includes the irreversible lithiation capacity within the cell. The reversible delithiation capacity starts at 2,662 mAh / g, as reflected in Table 2. It should be understood that this very high initial lithiation capacity can be obtained in any system where the self-assembled cell is deployed for first-time use. Figure 20 provides a voltage-time graph during the cycling of the cell constructed as described above. [] It should also be understood that the initial discharge occurs from an open-circuit voltage of approximately 3.2 volts to approximately 0.01 V, while charge and discharge cycles occur between 0.01 V and 1.5 V. Depending on the circumstances, charge and discharge cycles can occur at higher upper limits, such as 2.0 V, 2.5 V, 3.0 V, or 3.2 V. By cycling at higher voltage upper limits, although still below the assembly open-circuit voltage, the amount of capacity identified above as irreversible can be retained as reversible capacity. This unusual capacity also foreshadows a new type of "hybrid" battery system characterized by an extremely long first discharge cycle with high initial lithiation capacity, followed by shorter but reversible cycles with lower delithiation capacity. Such a system is not currently available on the market. The capacity revealed by the preliminary tests translates to an energy density of 12,584 Whr / kg SnO2, depending on the voltage range selected for cycling. This is an energy density comparable to gasoline (12,889 Whr / kg), and to the best of the inventors' knowledge, it is the highest energy density achieved to date with any battery material. Figure 21 provides an image of the pouch cell constructed as described above, disassembled after 103 cycles. The clear and intact separators indicate that lithium plating did not occur and could not be a source of the excess capacity exhibited by the cell. The cathode containing AMO SnO2 (appearing black on the copper current collector) is intact, still well attached to the current collector, and has not undergone mechanical degradation. This anomalous capacity measurement directly contrasts with the teachings of the scientific literature, which asserts that even capacities as high as approximately 1000 mAh / g in oxide materials lead to unavoidable volume changes and subsequent mechanical failure of the electrodes. In contrast, the embodiment disclosed herein exhibits a capacity 10 times greater than this without significant volume changes or associated mechanical structural alterations. Furthermore, not wishing to be limited by any theory, the inventors believe that the disclosed structure of the cell with an incredible lithiation capacity, comprising a lithium metal anode and an AMO-containing cathode, allows for such high capacity, partly due to the low content of the active material (AMO) in the cathode, for example, between 10% and 30% by weight. This low active material loading provides sufficient space for the absorption and storage of large amounts of lithium atoms in the cathode during discharge. An optimal loading of approximately 20-25% can be considered the transition point, where lower loadings do not provide sufficient active material or active sites for reaction and lithium atom absorption, while higher loadings may not provide a suitable volume for lithium atom absorption. The specific energy density of the AMO-based electrochemical cells described herein is novel and impossible according to scientific literature. Such results are possible here because they are achieved through novel mechanisms beyond those currently taught or understood by those skilled in the art, leading to the possibility of achieving capacities even higher than those described herein. This new availability of energy density inevitably leads to other electrodes and cells, which may manifest as unusual shapes and sizes, new electrolyte systems, separators, and current collectors. The electrodes, cells, and cells described and claimed should not be considered limited to auxiliary components currently available on the open market or disclosed herein or in the literature. Rather, it should be understood that the electrodes, cells, and cells described and claimed can take any suitable shape, size, or configuration, incorporate any suitable electrolyte, current collector, or separator, and employ any suitable discharge and / or charge distribution. [] The invention can be further understood by referring to the following non-limiting examples illustrating the formation of electrodes for electrochemical cells, comprising a first electrode containing a metal oxide (i.e., AMO) and a second electrode containing lithium metal. The first electrode is constructed to comprise 80% by weight of the metal oxide, consistent with conventional practices in the battery industry for forming electrochemical cells. As explained above, the capacity of such electrochemical cells can be significantly improved by reducing the amount of metal oxide in the first electrode to at least 80% by weight (e.g., 5-15%, 20-35%, or 55-70%). The following examples illustrate exemplary chemistry that can be optimized by constructing electrochemical cells with a smaller percentage of metal oxide by weight. Example 1: Tin oxide AMO functionalized with acetate / chloride. Tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, gray material and formed into electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 22 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 2: Tin oxide AMO functionalized with acetate / sulfate. Tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by adding sulfuric acid (H2SO4). The resulting AMO nanomaterial was a gray sheet-like material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 23 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 3: Tin oxide AMO functionalized with acetate / nitrate. Tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by adding nitric acid (HNO3). The resulting AMO nanomaterial was a gray sheet-like material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 24 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 4: Tin oxide AMO functionalized with acetate / phosphate. Tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by adding phosphoric acid (H3PO4). The resulting AMO nanomaterial was a brown, soft, sheet-like material formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 25 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 5: Tin Oxide AMO Functionalized with Acetate / Citrate. Tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by adding citric acid (C6H8O7). The resulting AMO nanomaterial was a brown sheet-like material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 26 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 6: Tin oxide AMO functionalized with acetate / oxalate. Tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by adding oxalic acid (C2H2O4). The resulting AMO nanomaterial was a grayish-brown sheet material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 27 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 7: Tin oxide AMO doped with iron oxide and functionalized by acetate / chloride. The doped tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved with a small amount of iron acetate in an ethanol / water solution. The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, sheet-like, milky-gray material and was formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 28 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 8: Tin oxide AMO doped with iron oxide and functionalized by acetate / sulfate. The doped tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved with a small amount of iron acetate in an ethanol / water solution. The solution was acidified by adding sulfuric acid (H2SO4). The resulting AMO nanomaterial was a light grayish-brown, soft, sheet-like material and was formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 29 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 9: Tin Oxide AMO Doped with Iron Oxide and Functionalized by Acetate / Nitrate Two doped tin oxide AMO samples were synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) and a small amount of iron acetate (Fe(CH3COO)3) were dissolved together in an ethanol / water solution. The solution was acidified by adding nitric acid (HNO3). The resulting AMO nanomaterial was a soft, white material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 30 shows electron micrographs of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 10: Tin oxide AMO doped with iron oxide and functionalized by acetate / oxalate. The doped tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) and a small amount of iron acetate (Fe(CH3COO)3) were dissolved together in an ethanol / water solution. The solution was acidified by adding oxalic acid (C2H2O4). The resulting AMO nanomaterial was a soft, white material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 31 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 11: Tin oxide AMO doped with iron oxide and functionalized by acetate / phosphate. The doped tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) and a small amount of iron acetate (Fe(CH3COO)3) were dissolved together in an ethanol / water solution. The solution was acidified by adding phosphoric acid (H3SO4). The resulting AMO nanomaterial was a white sheet material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 32 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 12: Iron oxide-doped tin oxide functionalized with acetate / citrate was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) and a small amount of iron acetate (Fe(CH3COO)3) were dissolved together in an ethanol / water solution. The solution was acidified by adding citric acid (C6H8O7). The resulting material did not form particles and was a yellow, glassy, ​​hard material, which was used as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 33 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 13: Tin Oxide AMO Functionalized by Acetate / Bromide Tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by adding hydrobromic acid (HBr). The resulting AMO nanomaterial was a soft, gray powder and was formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 34 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 14: Tin Oxide AMO Functionalized with Acetate / Borate. Tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by adding boric acid (H3BO3). The resulting AMO nanomaterial was a gray sheet-like material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 35 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 15: Tin Oxide AMO Doped with Manganese Oxide and Functionalized by Sulfate / Chloride The doped tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin sulfate (SnSO₄) and a small amount of manganese chloride (MnCl₂) were dissolved together in an ethanol / water solution. The solution was acidified by adding sulfuric acid (H₂SO₄). The resulting AMO nanomaterial was an extremely soft, light brown material and was formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 36 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 16: Tin Oxide AMO Doped with Manganese Oxide and Functionalized by Chloride The doped tin oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, tin chloride (SnCl₂) and a small amount of manganese chloride (MnCl₂) were dissolved together in an ethanol / water solution. The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, grayish-brown material and formed into electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 37 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 17: Tin Oxide AMO Doped with Iron Oxide and Aluminum Oxide and Functionalized by Chloride Two doped tin oxide AMO samples were synthesized using a single-pot hydrothermal synthesis method. In short, tin chloride (SnCl₂) was dissolved together with small amounts of iron chloride (FeCl₃) and aluminum chloride (AlCl₃) in an ethanol / water solution. The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial used in the first sample was a light brown sheet-like material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 38 shows the measured capacity versus cycle number and the voltage versus time during cycling. The resulting AMO nanomaterial used in the second sample was a light gray sheet-like material. Example 18: Tin Oxide-Doped and Chloride-Functionalized Iron Oxide AMO. The doped iron oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, ferric chloride (FeCl₃) and a small amount of tin chloride (SnCl₂) were dissolved together in an ethanol / water solution. The iron to tin ratio was 95:5. The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, red material and formed into electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 39 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 19: Iron Oxide AMO Doped with Tin Oxide and Functionalized with Chloride The doped iron oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, ferric chloride (FeCl₃) and a small amount of tin chloride (SnCl₂) were dissolved together in an ethanol / water solution. The iron to tin ratio was 95:5. The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a black, glassy material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 40 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 20: Ferric Oxide AMO Functionalized with Nitrate. Ferric oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, ferric nitrate Fe(NO3)3 was dissolved in an ethanol / water solution and acidified by adding nitric acid (HNO3). The resulting AMO nanomaterial was a black, glassy material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 41 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 21: Bismuth oxide AMO functionalized by chloride. Bismuth oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, bismuth chloride (BiCl₃) was dissolved in an ethanol / water solution and acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, white material and formed into electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 42 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 22: Zirconia AMO Functionalized by Sulfate Zirconia AMO was synthesized using a single-pot hydrothermal synthesis method. In short, zirconium sulfate (Zr(SO₄)₂) was dissolved in an ethanol / water solution and acidified by adding sulfuric acid (H₂SO₄). The resulting AMO nanomaterial was a sheet-like white material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 43 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 23: Sulfate-functionalized Titanium Oxide AMO. Titanium oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, titanium oxysulfate (TiOSO4) was dissolved in an ethanol / water solution and acidified by adding sulfuric acid (H2SO4). The resulting AMO nanomaterial was a white, sheet-like material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 44 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 24: Antimony Oxide AMO Functionalized by Sulfate. Antimony oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, antimony sulfate (Sb₂(SO₄)₃) was dissolved in an ethanol / water solution and acidified by adding sulfuric acid (H₂SO₄). The resulting AMO nanomaterial was an extremely soft, white material and was formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 45 shows the measured capacity versus cycle number and the voltage versus time during cycling. Example 25: Indium Oxide (AMO) Functionalized by Chloride Indium oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. In short, indium chloride (InCl₃) was dissolved in an ethanol / water solution and acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was white and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 46 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 26: Indium Oxide (AMO) Functionalized by Sulfate Indium oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. In short, indium sulfate (In₂(SO₄)₃) was dissolved in an ethanol / water solution and acidified by adding sulfuric acid (H₂SO₄). The resulting AMO nanomaterial was white and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 47 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 27: Indium Oxide AMO Functionalized by Bromine Indium oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, indium bromide (InBr₃) was dissolved in an ethanol / water solution and acidified by adding hydrobromic acid (HBr). The resulting AMO nanomaterial was a blue-white material and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 48 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 28: Indium Oxide AMO Functionalized by Chloride Indium oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, indium chloride (InCl₃) was dissolved in an ethanol / water solution and acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was gray with yellow rings and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 49 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 29: Mixed AMO of Lithium Oxide and Iron Oxide Doped with Tin Oxide and Functionalized by Chloride / Acetate The mixed lithium oxide and iron oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, lithium acetate (Li(CH3COO)) and iron chloride (FeCl3) were dissolved together with a small amount of tin chloride (SnCl2) in an ethanol / water solution. The solution was acidified by adding hydrochloric acid (HCl). During synthesis, a light brownish-pink color with a green ring was produced on the flask. However, the final AMO nanomaterial was gray and formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 50 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 30: Mixed AMO of Lithium Oxide and Iron Oxide Doped with Tin Oxide and Functionalized by Chloride / Acetate The mixed lithium oxide and iron oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, lithium acetate (Li(CH3COO)) and iron chloride (FeCl3) were dissolved together with a small amount of tin chloride (SnCl2) in an ethanol / water solution. The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a light gold color and was formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 51 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Example 31: Mixed AMO of Lithium Oxide and Iron Oxide Doped with Tin Oxide and Functionalized by Chloride / Acetate The mixed lithium oxide and iron oxide AMO was synthesized using a single-pot hydrothermal synthesis method. In short, lithium acetate (Li(CH3COO)) and iron chloride (FeCl3) were dissolved together with a small amount of tin chloride (SnCl2) in an ethanol / water solution. The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a light milky white material and was formed as an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to 0 volts and then charging to 1.5 volts. Figure 52 shows an electron micrograph of the AMO nanomaterial, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling. Declaration Regarding the Inclusion and Variation of References: All references in this application (e.g., patent documents, including patents or equivalents granted or awarded; patent application publications and non-patent documents or other sources) are incorporated herein by reference in their entirety, as individually cited. All patents and publications mentioned in this specification indicate the skill of a person skilled in the art to which this invention pertains. References cited herein are incorporated in their entirety to indicate prior art, in some cases up to their application date, and where necessary, this information may be used to exclude (e.g., not claim) specific embodiments of the prior art. For example, when claiming a compound, it should be understood that compounds known in the prior art, including certain compounds disclosed in the references disclosed herein (especially in the cited patent documents), are not intended to be included within the scope of the claim. When a group of substitutes is disclosed herein, it should be understood that all individual members of such groups and all subgroups and categories formed using such substitutes are disclosed separately. When a Markush group or other grouping is used herein, all individual members of that group and all possible combinations and subcombinations of that group are individually included in this disclosure. As used herein, "and / or" means that one, all, or any combination of items separated by "and / or" in the list is included in the list; for example, "1, 2 and / or 3" is equivalent to "1 or "2 or "3" or "1 and 2" or "1 and 3" or "2 and 3" or "1, 2 and 3". Unless otherwise stated, every formulation or combination of the ingredients described or illustrated can be used to practice this invention. Specific names of materials are intended to be illustrative, as it is known that those skilled in the art may name the same materials in different ways. Those skilled in the art will understand that methods, apparatus elements, starting materials, and synthesis methods other than those specifically illustrated can be used in the practice of this invention without requiring extensive experimentation. This invention is intended to include all functionally equivalent forms known in the art of any such methods, apparatus elements, starting materials, and synthesis methods. Whenever a range (e.g., temperature range, time range, or composition range) is given in this specification, all intermediate ranges and sub-ranges, as well as all individual values ​​included within the given range, are intended to be included in this disclosure. As used herein, "comprising" is synonymous with "including," "containing," or "characterized in," and is inclusive or open-ended, and does not exclude other unlisted elements or method steps. As used herein, "consisting of" excludes any element, step, or component not specified in the elements of the claims. As used herein, "consisting substantially of" does not exclude materials or steps that do not materially affect the essential and novel characteristics of the claims. Any enumeration of the term "comprising" herein (particularly in the description of compositional components or device elements) should be understood to cover compositions and methods substantially composed of the enumerated components or elements and those compositions and methods composed of the enumerated components or elements. The invention illustrated herein by way of illustration may be suitably practiced in the absence of any elements or limitations not specifically disclosed herein. The terms and expressions used are descriptive and not restrictive, and are not intended to exclude any equivalent forms of the displayed and described features or portions thereof. It should be understood that various modifications are possible within the scope of the claimed invention. Therefore, it should be understood that although the invention has been specifically disclosed by preferred embodiments and optional features, modifications and variations of the concepts disclosed herein may be adopted by those skilled in the art, and such modifications and variations should be considered within the scope of the invention as defined by the claims.

[0006] 100: Lithium battery cell, cell, lithium unit 102: Shell or container, shell 104: Cathode, Electrode 106: Anode, Electrode 108: Electrolytes 110: partition 115: Components 300: Battery 302: Housing, battery housing 304: Negative electrode, electrode 306: Positive electrode, electrode 308: Additional Circuit 1800: Cathode 1802: Copper Foil 1804: Carbon layer 1806: Carbon / SnO2 electrode layer, layer containing SnO2AMO

Claims

1. A nanoparticle composition comprising: surface-functionalized solid metal oxide nanoparticles, wherein the diameter of the nanoparticles is less than one micrometer, wherein the nanoparticles contain oxygen and metal, wherein the nanoparticles are surface-functionalized with electron-withdrawing groups, and wherein the electron-withdrawing groups are one or more of the following: Cl, Br, SO4, PO4, NO3 or BO3.

2. The nanoparticle composition of claim 1, wherein the diameter is from 1 nm to 1000 nm.

3. The nanoparticle composition of claim 1, wherein the nanoparticles comprise monodisperse particles.

4. The nanoparticle composition of claim 1, wherein the nanoparticles are in the form of aggregates or individual particles.

5. The nanoparticle composition of claim 1, wherein the metal is selected from iron, tin, antimony, bismuth, titanium, zirconium, manganese, indium, or a combination thereof.

6. The nanoparticle composition of claim 1, wherein the metal is selected from tin, titanium, iron or zirconium, or a combination thereof.

7. The nanoparticle composition of claim 1, wherein the nanoparticles conform to mixed metal oxide nanoparticles comprising oxygen and a plurality of different metals.

8. The nanoparticle composition of claim 7, wherein the plurality of different metals include tin and iron, antimony and tin, aluminum and tin, lithium and iron, or lithium and tin.

9. The nanoparticle composition of claim 1, wherein the nanoparticles comprise acidified metal oxide nanoparticles that are not superacids.

10. The nanoparticle composition of claim 1, wherein the nanoparticles have a pH of less than 7 and a Hammett function (H0) of greater than -12, the pH being measured when the nanoparticles are suspended in water in a dry form at 5 wt%.

11. The nanoparticle composition of claim 1, wherein the electron-withdrawing group is one or more of the following: Cl, Br, BO3, NO3 or SO4.

12. The nanoparticle composition of claim 1, wherein the nanoparticles have amorphous properties, or a mixture of amorphous and crystalline properties.

13. The nanoparticle composition of claim 1, wherein the nanoparticles have crystalline properties, or a mixture of crystalline and amorphous properties.

14. The nanoparticle composition of claim 1, wherein the nanoparticles have a sheet-like, spherical, needle-like, or rod-like morphology.

15. A mixture or complex of nanoparticles comprising: the nanoparticle composition of claim 1; and one or more additives.

16. The nanoparticle mixture or complex of claim 15, wherein the one or more additives comprise an unacidified metal oxide, binder or conductive agent.

17. A battery electrode comprising: a mixture or complex of nanoparticles as claimed in claim 15, wherein the one or more additives comprise a binder or conductive carbon.

18. A battery comprising: a battery electrode as claimed in claim 17; a counter electrode; and an electrolyte disposed between the battery electrode and the counter electrode.

Images