Battery with novel components

Abstract

Battery cells having an anode or cathode comprising an acidified metal oxide ("AMO") material in monodisperse nanoparticle form, preferably of a size of 20 nm or less, said acidified metal oxide ("AMO") material having a pH < 7 when suspended at 5 wt% in an aqueous solution and having a Hammett function H0 > -12 at least on its surface.

Description

[0001] Citation of relevant applications

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 62 / 483,789, filed April 10, 2017, entitled "Blended Acidified Metal Oxide Additive for Use in a Battery Electrode"; U.S. Provisional Patent Application No. 62 / 507,655, filed May 17, 2017, entitled "Battery with Acidified Electrode"; and U.S. Provisional Patent Application No. 62 / 507,660, filed May 17, 2017, entitled "Battery with Novel Cathode," and these provisional applications are incorporated herein by reference as if fully set forth herein. Technical Field

[0003] This disclosure pertains to the field of materials that can be used in chemical energy storage and power devices (e.g., but not limited to batteries). More specifically, this disclosure relates to battery cells having cathodes and / or anodes comprising acidified metal oxide (“AMO”) nanomaterials. Background Technology

[0004] Metal oxides are compounds formed by the combination of oxygen and metal, and have the general formula M. m O x These substances exist in nature but can also be synthesized artificially. In synthesized metal oxides, the synthetic method can have a wide range of effects on surface properties, including their acidity / basicity. Changes in surface properties can alter the properties of the oxide, affecting things like its catalytic activity and electron mobility. However, the mechanisms of surface-controlled reactions are not always well characterized or understood. For example, in photocatalysis, surface hydroxyl groups are thought to promote electron transfer from conduction to chemisorbed oxygen molecules.

[0005] Despite the importance of surface properties, the literature on metal oxides (scientific papers and patents) has primarily focused on generating novel nanoscale crystalline forms of metal oxides to improve energy storage and power applications. Surface properties of metal oxides have been neglected, and outside of the chemistry catalysis literature, few innovations have addressed controlling or altering the surface of known metal oxides to achieve performance targets.

[0006] Chemical catalysis literature primarily focuses on producing “superacids”—acids stronger than pure sulfuric acid (18.4 M H₂SO₄)—typically used in large-scale reactions such as hydrocarbon cracking. Superacidity cannot be measured on the traditional pH scale but is quantified using the Hammett number. The Hammett number (H₀) can be considered as an extension of the pH scale to negative numbers less than zero. Pure sulfuric acid has an H₀ of -12.

[0007] However, there are many reaction systems and applications where superacidity is too strong. For example, superacidity can degrade system components or catalyze unwanted side reactions. However, acidity can still be used in these same applications to provide enhanced reactivity and rate properties or improved electron mobility.

[0008] Battery literature teaches that acidic groups are harmful in batteries, as they corrode metal current collectors and the casing, and cause degradation of other electrode components. Furthermore, existing technology teaches that active catalytic electrode surfaces lead to electrolyte decomposition, which can cause gas generation within the battery cell and ultimately result in cell failure.

[0009] There is a need to realize batteries with synthetic metal oxides, wherein the synthetic metal oxides are at least acidic but not superacidic on their surface and are configured in the anode and / or cathode. Summary of the Invention

[0010] This application describes materials corresponding to acidified metal oxides (“AMOs”) and applications using AMOs, including in batteries, such as as catalysts in battery electrode materials, as photovoltaic or photosensitive components, and as sensors. Techniques for preparing AMOs and apparatus including AMOs are further disclosed. Optionally, the disclosed AMOs are used in combination with acidic substances to enhance their practicality.

[0011] The described AMOs include those in nanomaterial form, such as nanoparticle form, which may be monodisperse or substantially monodisperse and have a particle size, for example, less than 100 nm. For example, when suspended in water at a specific concentration (e.g., 5 wt%) or dried and then resuspended in water, the disclosed AMOs exhibit a low pH, for example, less than 7 (e.g., between 0 and 7), and further exhibit a Hammett function H0 greater than -12 (i.e., non-superacidity), at least on the surface of the AMO.

[0012] Optionally, the surface of AMO can be functionalized, for example, by acidic substances or other electron-withdrawing substances. Synthesis and surface functionalization can be performed in a "single-reactor" hydrothermal process, wherein the surface of the metal oxide is functionalized as the metal oxide is synthesized from a suitable precursor. In some embodiments, this single-reactor process does not require any additional one or more acidification steps beyond the steps necessary for synthesizing the metal oxide itself, and imparts the desired surface acidity (but not hyperacidity) to the AMO material.

[0013] Alternatively, strong electron-withdrawing groups (“EWG”) – such as SO4, PO4, or halogens (Br, Cl, etc.) – can be used for surface functionalization, either alone or in combination with each other. Weaker EWGs than SO4, PO4, or halogens can also be used for surface functionalization. For example, synthesized metal oxides can be surface functionalized with acetate (CH3COO), oxalate (C2O4), and citrate (C6H5O7) groups.

[0014] Although acidic substances are generally considered undesirable in batteries because they corrode metal current collectors and casings and cause deterioration of other electrode components, and because active catalytic electrode surfaces can lead to electrolyte decomposition, gas generation within the battery cell, and ultimately battery cell failure, the inventors have discovered that acidic substances and components are advantageous in batteries using AMO materials in the battery electrodes.

[0015] For example, the combination or use of AMO with acidic substances can enhance the performance of the resulting materials, systems, or devices, resulting in improved capacity, cycle life, and lifespan. For instance, batteries employing AMO materials combined with acidic electrolytes or electrolytes containing the acidic substances described herein exhibit considerable capacity gains, such as up to 100 mAh / g or more compared to similar batteries using non-acidified electrolytes or electrolytes lacking acidic substances. In some embodiments, capacity improvements of 50 mAh / g to 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 greater. Moreover, the use of acidic electrolytes or electrolytes containing acidic substances can improve battery cycle life, for example, extending the battery cycle life by up to 100 or more charge-discharge cycles.

[0016] Additionally or alternatively, batteries that include electrodes that are inherently acidic or that incorporate acidic substances (e.g., organic acids) are also beneficial, again contrary to conventional teachings in battery technology. For example, batteries incorporating acidic electrodes or incorporating acidic substances within the electrodes can enhance performance and produce improved capacity, cycle life, and lifespan, particularly when used in electrodes incorporating AMO materials. 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 cycle life of the battery 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 superacidic), for example, when the components of the electrode are suspended in water at 5 wt% (or dried and then resuspended in water).

[0017] As another example, it would be beneficial to use a slurry to form the electrode, contrary to conventional teachings in battery technology. As described herein, alternatively, an AMO material can be formed into a battery electrode by first forming a slurry of the AMO material together with one or more binder compounds, solvents, additives (e.g., conductive or acidic additives), and / or other wet-processing materials. The slurry can be deposited onto a conductive material or current collector to form the electrode. Optionally, such a slurry and / or solvent can be acidic or include acidic substances, again allowing for improved capacity, cycle life, and lifespan of the resulting battery. Optionally, all or part of the solvent can be evaporated, leaving the AMO material, binder, additives, etc. Optionally, for example, when suspended in water at 5 wt% (or dried and then resuspended in water), the resulting material can exhibit its own acidity, such as having a pH less than 7 (but not hyperacidity).

[0018] As described above, optionally, acidic substances may be included as additives in any component of the battery, such as electrodes or electrolytes. Optionally, batteries including AMO may include an electrolyte located between the electrodes, wherein the acidic substance is dissolved in a solvent. Such an electrolyte may also be referred to herein as an acidified electrolyte. Optionally, 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 located 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., a separator) optionally located between the electrodes.

[0019] Exemplary acidic substances that can be used in the AMO electrodes and electrolytes described herein include, but are not limited to, organic acids, such as carboxylic acids. Exemplary acidic substances include those that exhibit a pKa of -10 to 7, -5 to 6, 1 to 6, 1.2 to 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. Exemplary organic acids include dicarboxylic acids, such as those having the general formula... Those dicarboxylic acids, wherein R is a substituted or unsubstituted C1-C20 hydrocarbon, such as a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic or heteroaromatic group, a substituted or unsubstituted amine, etc. Exemplary organic acids also include those having the general formula Those organic acids, where L is a substituted or unsubstituted C1-C20 divalent hydrocarbon, such as substituted or unsubstituted alkylene, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted amine, etc. Organic acids may include organic acid anhydrides, such as those having the general formula The organic acid anhydride, wherein R1 and R2 are substituted or unsubstituted C1-C20 hydrocarbons, such as substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aryl or heteroaryl groups, substituted or unsubstituted amines, etc. Optionally, R1 and R2 may form a ring. Exemplary organic acid anhydrides include any anhydride of the aforementioned organic acids. Specific organic acid anhydrides include, but are not limited to, glutaric anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, and itaconic anhydride.

[0020] The effective concentration of acidic substances in one or both of the electrolyte and AMO electrode includes 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%.

[0021] Effective solvents include those used in lithium-ion battery systems, such as ethylene carbonate, butyl carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, vinyl fluorocarbonate, and mixtures thereof. Other effective solvents will be understood by those skilled in the art. Optionally, when acidic substances and metal salts are dissolved in the solvent to form an electrolyte, the electrolyte itself exhibits acidic conditions (i.e., pH less than 7).

[0022] Exemplary adhesives that can be used in the batteries and electrodes described herein include styrene-butadiene copolymer (SBR), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), acrylonitrile, polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyamide-imide (PAI), and any combination thereof. Optionally, conductive polymers may be used as adhesives.

[0023] Other exemplary additives that can be used in the AMO and electrodes described herein include, but are not limited to, conductive additives. Exemplary conductive additives include graphite, conductive carbon, carbon black, Ketjen black, and conductive polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS complexes, polyaniline (PANI), and polypyrrole (PPY). For example, conductive additives may be present in the electrode at any suitable concentration, such as at a weight percentage greater than 0 and up to 35 wt%, 40 wt%, or even higher. Optionally, conductive additives may be present at 1 wt% to 95 wt%, 1 wt% to 35 wt%, 1 wt% to 25 wt%, 5 wt% to 40 wt%, ...1 wt% to 25 wt%, 1 wt% The following ranges exist in the electrode: 0wt% to 40wt%, 15wt% to 40wt%, 20wt% to 40wt%, 25wt% to 40wt%, 30wt% to 40wt%, 35wt% to 40wt%, 40wt% to 45wt%, 40wt% to 50wt%, 40wt% to 55wt%, 40wt% to 60wt%, 40wt% to 65wt%, 40wt% to 70wt%, 40wt% to 75wt%, 40wt% to 80wt%, 40wt% to 85wt%, 40wt% to 90wt%, or 40wt% to 95wt%.

[0024] This document also describes methods for manufacturing batteries. Exemplary methods for manufacturing batteries include manufacturing AMO nanomaterials; forming a first electrode comprising the AMO nanomaterials or a first electrode including the AMO nanomaterials; 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 manufacturing batteries includes manufacturing AMO nanomaterials; forming a first electrode comprising the AMO nanomaterials and one or more metal salts or a first electrode including the AMO nanomaterials and one or more metal salts; and positioning the electrolyte between the first electrode and a second electrode.

[0025] This document also discloses electrolytes for use in batteries. For example, the disclosed electrolytes can be used in batteries comprising a first electrode (e.g., a first electrode comprising an acidified metal oxide (AMO) nanomaterial) and a second electrode. Exemplary electrolytes comprise a solvent and one or more metal salts dissolved in the solvent. Optionally, an acidic substance, such as an acidic substance different from the one or more metal salts, is dissolved in the solvent.

[0026] As described above, a variety of acidic substances, including organic acids and / or organic anhydrides, can be used in the disclosed electrolytes. Exemplary 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, citracic acid, or any combination thereof. Exemplary organic anhydrides include, but are not limited to, glutaric anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, itaconic anhydride, or any combination thereof. Examples of other acidic substances have been described above. Effective acidic substances include, but are not limited to, those with a pKa of -10 to 7, -5 to 6, 1 to 6, 1.2 to 5.6, or about 4. Optionally, the acidic substance 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%.

[0027] It should be understood that lithium metal salts, such as LiPF6, LiAsF6, LiClO4, LiBF4, and LiCF3SO3, can be effective components of the disclosed acidified electrolyte. Exemplary solvents include, but are not limited to, ethylene carbonate, butyl carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, vinyl fluorocarbonate, and mixtures thereof. Exemplary solvents can be used in metal-ion batteries, such as lithium-ion batteries. Attached Figure Description

[0028] Figure 1 This is a simplified cross-sectional view of an exemplary lithium-ion battery cell.

[0029] Figure 2 This is another simplified cross-sectional view of a lithium-ion battery cell, where the electrolyte is essentially enclosed by a separator.

[0030] Figure 3 This is a schematic diagram of a lithium-ion battery that includes multiple battery cells.

[0031] Figure 4 The cyclic voltammetry of AMO tin prepared by the method disclosed herein is shown to differ from that of commercially available non-AMO tin when compared with Li cycling.

[0032] Figure 5The results show that the total reflectance of AMO tin oxide differs from that of commercially available non-AMO tin oxide.

[0033] Figure 6 This displays X-ray photoelectron spectroscopy (XPS) data for the surface functionalizations intrinsically generated by the synthesis method disclosed herein. The figures shown are atomic concentrations in percent (%). The rightmost column lists the corresponding pH values ​​of the synthesized nanoparticles when dispersed at 5 wt% in an aqueous solution.

[0034] Figure 7 Electron micrographs are provided, showing the morphological differences between AMO nanoparticles synthesized under the same conditions, except for the use of different functionalization groups.

[0035] Figure 8 The differences in morphology and properties of AMO nanoparticles synthesized under the same conditions, except for having two different total reaction times, are shown.

[0036] Figure 9 Representative half-cell data are provided, showing the performance differences between spherical and elongated (needle-shaped or rod-shaped) AMOs relative to lithium cycling.

[0037] Figure 10 X-ray photoelectron spectroscopy analysis of the surface of AMO nanoparticles synthesized using both strong (phosphorus-containing) and weak (acetic acid) electron-withdrawing groups is provided, showing that the atomic concentration of phosphorus is greater than the atomic concentration of bonds associated with the acetic acid groups.

[0038] Figure 11A Provides data showing the visible light-sensitive degradation activity of different AMOs.

[0039] Figure 11B Provides data showing the UV-active degradation of different AMOs.

[0040] Figure 12 The graphs compare two AMOs: one with higher capacity for primary (single-use) battery applications, and the other with higher cycle life for secondary (rechargeable) battery applications.

[0041] Figure 13 The data provided includes charge and discharge capacity data as well as coulombic efficiency data, demonstrating that AMO can lead to enhanced battery performance without degrading battery components or generating gas.

[0042] Figure 14 The capacity and cycling data of AMO in standard, acidified, and alkaline electrolyte systems are displayed.

[0043] Figure 15The capacity and cycling data for AMO, as well as the same AMO after acidification was removed by solvent washing, are shown.

[0044] Figure 16 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0045] Figure 17 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0046] Figure 18 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0047] Figure 19 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0048] Figure 20 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0049] Figure 21 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0050] Figure 22 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0051] Figure 23 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0052] Figure 24Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0053] Figure 25 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0054] Figure 26 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0055] Figure 27 Electron micrographs and data of the synthesized material are provided, including graphs of capacity versus cycle number measured during cycling for a battery cell including electrodes containing the synthesized material, and graphs of voltage versus time.

[0056] Figure 28 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0057] Figure 29 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0058] Figure 30 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0059] Figure 31 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0060] Figure 32 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0061] Figure 33 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0062] Figure 34 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0063] Figure 35 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0064] Figure 36 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0065] Figure 37 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0066] Figure 38 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0067] Figure 39 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0068] Figure 40 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0069] Figure 41 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0070] Figure 42 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0071] Figure 43 The data provided includes graphs of capacity versus cycle number measured during cycling for battery cells including electrodes containing AMO material, and graphs of voltage versus time.

[0072] Figure 44 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0073] Figure 45 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0074] Figure 46 Electron micrographs and data of AMO material are provided, including graphs of capacity versus cycle number and voltage versus time for a battery cell including electrodes containing AMO material, measured during cycling.

[0075] definition

[0076] For the purposes of this disclosure, the following terms shall have the following meanings:

[0077] Acidic oxides—a term commonly used in scientific literature—refer to binary compounds of oxygen and nonmetallic elements. An example is carbon dioxide (CO2). Some oxides of half-metals (such as Si, Te, and Po) also exhibit weak acidity in their pure molecular state.

[0078] Acidified metal oxides (“AMOs”) – used herein to denote binary compounds of oxygen and a metal element that have been synthesized or modified to have a higher acidity than their natural mineral form and also possess a Hammett function, H0 > -12 (not superacidic). The average particle size is also smaller than that of the natural mineral form. Naturally occurring mineral 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 naturally occurring mineral forms (equivalent stoichiometry) but not superacidic fall within the scope of this disclosure and can be considered AMO materials provided they meet certain other conditions discussed herein.

[0079] Acidity—a term commonly used in scientific literature—refers to compounds with a pH less than 7 in aqueous solution.

[0080] Electron-withdrawing groups (“EWGs”) are atomic or molecular groups that attract electrons to themselves. The strength of an EWG is based on its known properties in chemical reactions. For example, halogens are known to be strong EWGs. Organic acid groups such as acetate are known to be weakly electron-withdrawing.

[0081] The Hammett function—another method for quantifying acidity in highly concentrated acid solutions and superacids, where acidity is defined by the equation: H0 = pK BH+ +log([B] / [BH + On this scale, 18.4 moles of pure H₂SO₄ has an H₀ value of -12. The H₀ value of pure sulfuric acid = -12 cannot be interpreted as pH = -12; rather, it implies that the acid present has an equivalent hypothetical (ideal) concentration of 10⁻⁶. 12 mol / L H3O + The protonation ability of a material is measured by its ability to protonate weak bases. The Hammett acidity function avoids water in its equation. This paper uses it to provide a quantitative means of distinguishing AMO materials from superacids. The Hammett function can be correlated with colorimetric indication tests and temperature-programmed desorption results.

[0082] Metal oxides—a term commonly used in scientific literature—refer to binary compounds of oxygen and metallic elements. 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 are oxides of lithium, sodium, magnesium, potassium, calcium, rubidium, strontium, indium, cesium, barium, and tellurium. Amphoteric oxides are oxides of beryllium, aluminum, gallium, germanium, astatine, tin, antimony, lead, and bismuth.

[0083] Monodisperse – Characterized by particles of uniform size that are largely separated from each other and do not aggregate into larger particles.

[0084] pH—a numerical scale commonly used in scientific literature to specify the acidity or alkalinity of aqueous solutions. It is the concentration of hydrated hydrogen ions [H3O]. + The negative of the logarithm of . As used in this paper, it describes the relative acidity of nanoparticles suspended in aqueous solution.

[0085] Surface functionalization—the connection of small atoms or molecular groups to the surface of a material.

[0086] Superacids are substances with an acidity higher than 100% H2SO4, possessing a Hammett function, where H0 < -12. Detailed Implementation

[0087] Now for reference Figure 1 A simplified cross-sectional view shows a lithium-ion battery cell 100. The battery cell 100 may include a housing or container 102. In some embodiments, the housing 102 is a polymer or alloy. The housing 102 chemically and electrically isolates the contents of the battery cell 100 from adjacent battery cells, preventing contamination of the contents and protecting it from damage to other components of the device on which the battery cell 100 is mounted. The entire battery may contain multiple battery cells arranged in a series and / or parallel configuration. As is known in the art, the battery may have another housing or mounting mechanism that combines multiple battery cells together.

[0088] Battery cell 100 provides a cathode 104 and an anode 106. When a conductive path is provided between the cathode 104 and the anode 106 outside the battery cell 100, the contents of the battery cell 100 undergo a chemical reaction. As a result of the chemical reaction, electrons are provided at the anode 106, which flow to the cathode 104 via a circuit (sometimes called a load) disposed outside the battery. During discharge of battery cell 100, the material including the anode 106 is alkaline-oxidized to provide electrons flowing through the circuit. The material including the cathode 104 (as a receiver of electrons released by the anode 106) is reduced.

[0089] During discharge, metal cations move from the anode 106 to the cathode 104 within the battery cell 100 via the electrolyte 108. In the case of a lithium-based battery, the metal cation may be a lithium cation (Li+). The electrolyte 108 may be a liquid electrolyte, such as a lithium salt in an organic solvent, for example, LiClO4 in ethylene carbonate. Other lithium-based electrolyte / solvent combinations known in the art may be used. In some cases, the electrolyte 108 may be a solid electrolyte, such as a lithium salt in polyethylene oxide. Optionally, the electrolyte may include a polymeric electrolyte. Exemplary electrolytes include those described in U.S. Patent Application Publication No. US2017 / 0069931, which is incorporated herein by reference.

[0090] A separator 110 can be used to prevent contact between electrodes 104 and 106. The separator 110 can be a porous material layer that is permeable to lithium ions and electrolyte 108 but non-conductive, thereby preventing internal short circuits in the battery cell 100. As known in the art, the separator 110 may comprise glass fiber or may comprise a polymer that may have a semi-crystalline structure. Other components, such as current collectors, may also be included in the battery cell 100, but... Figure 1 Not shown in the image.

[0091] The anode 104, cathode 106, electrolyte 108, and separator 110 together form a complete battery cell 100. Because the separator 110 is porous, the electrolyte 108 can flow into or be contained within the separator 110. Under normal operating conditions, the porosity of the separator 110 allows for the accumulation of ions (Li... + The electrolyte 108 flows between electrodes 104 and 106. As is known in the art, the separator can be configured to melt and close the internal pore structure to shut down the battery cell in the event of exposure to excessive heat or runaway exothermic reactions.

[0092] Most lithium-based battery cells are so-called secondary batteries. They can be discharged and recharged many times before the battery's chemical or structural integrity falls below acceptable limits. The battery cells and batteries according to this disclosure are considered as primary batteries (e.g., single-use) and secondary batteries.

[0093] In the case where battery cell 100 is a secondary battery cell (or part of a secondary battery), it should be understood that battery cell 100 can be recharged individually or as part of an entire system in which multiple battery cells are recharged simultaneously (and may be in the same parallel or series circuit).

[0094] A reverse voltage is applied to the battery cell 100 to achieve charging. It should be understood that various methods can be employed for the efficient recharging of lithium batteries. Constant current, variable current, constant voltage, variable voltage, partial duty cycle, etc., can be used. Unless stated in the claims, this disclosure is not intended to limit it to any particular charging method. During charging of the battery cell 100, element 115 represents a voltage source applied between the cathode 104 and the anode 106 to provide electrons from the cathode 105 to the anode 106 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.

[0095] As an example, cathode 104 or anode 106 may independently comprise the AMO material disclosed herein. For the use of AMO material as the cathode, the anode may correspond to lithium metal or a lithium-intercalated material, such as graphite. Optionally, electrolyte 108 may comprise, for example, an acidic substance dissolved in an organic solvent containing a lithium salt. As a complement or alternative to the use of an acidic substance in electrolyte 108, the electrode (i.e., cathode 104 or anode 106) may optionally comprise AMO and an acidic substance. Oxalic acid is an exemplary acidic substance.

[0096] Without wishing to be bound by any 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, resulting in improved lithium ion absorption capacity during discharge and improved overall capacity compared to similar battery cells lacking acidic substances or having alkaline electrodes or electrolytes (i.e., including alkaline substances). Alternatively or additionally, the presence of acidic substances may allow for additional active sites in the cathode 104 for lithium absorption.

[0097] It should be understood that Figure 1 It is not drawn to scale. For example... Figure 2 As shown, in most applications, the diaphragm 110 occupies most or all of the space between the electrodes 104 and 106 and is in contact with the electrodes 104 and 106. In this case, the electrolyte 108 is contained within the diaphragm 110 (but may also penetrate into the pores or surfaces of the anode or cathode). Figure 2 It's not necessarily drawn to scale. The actual geometry of a battery cell can range from a relatively thin and flat pouch to a cylindrical construction to a button cell. Battery cell construction techniques such as windings, spools, or pin-shaped assemblies can be used.

[0098] The battery cell 100 can also be formed into a commercially viable package using current collectors and other components (not shown) known in the art. While the overall shape or geometry may vary, the battery cell or battery will typically contain separate, non-contact electrodes 104, 106 at some locations or cross-sections, with an electrolyte 108 and possibly a separator 110 between them. The battery cell can also be configured to have multiple layers of anodes and cathodes. The battery cell can be configured such that two cathodes are located on opposite sides of a single anode, or vice versa.

[0099] Functional or working batteries for a specific purpose may include multiple battery cells arranged according to the needs of a particular application. Figure 3 An example of such a battery is schematically shown. Here, battery 300 includes four lithium battery cells 100 arranged in series to increase voltage. Capacity can be increased by providing an additional battery stack of four battery cells 100 connected in parallel with the illustrated battery stack. Different voltages can be achieved by changing the number of battery cells 100 arranged in series.

[0100] The positive electrode 306 is visible on the outside of the casing 302 of the battery 300. A negative electrode 304 is also provided. The physical shape factors of electrodes 304 and 306 can vary depending on the application. Various adhesives, glues, tapes, and / or other fixing mechanisms (not shown) can be used within the battery casing 302 to secure other components. Lithium-based batteries are generally functional, rechargeable, and can be stored in any orientation (if they are secondary batteries). As described above, the battery cell 100 can have various different geometries. Therefore, Figure 3 This does not imply any particular physical shape factor of battery 300.

[0101] The battery 300 may also include various auxiliary circuits 308 that insert the positive electrode 306 and the lithium battery cell 100 within the housing 302 of the battery 300. In other embodiments, as an alternative or supplement to inserting the positive electrode 306 and the lithium battery cell 100, the regulating circuit inserts the negative electrode 304 and the lithium battery cell 100. The auxiliary circuits 308 may include short-circuit protection, overcharge protection, overheat shutdown, and other circuits known in the art to protect the battery 300, the battery cell 100, and / or any load connected to the battery 300.

[0102] The selection of the composition of materials used for the cathode 104, anode 106, and electrolyte can be crucial to the performance of the battery cell 100 and any battery in which the battery cell 100 forms a part. Various examples of AMOs and their manufacturing methods are provided in the context of this disclosure. These AMOs are suitable for forming anodes or cathodes in half-cell cells, battery cells, and batteries. Furthermore, the AMOs of this disclosure are compatible with known lithium-ion battery technologies, including existing anode and cathode compositions, electrolyte formulations, and separator compositions.

[0103] Within the context of this disclosure, various examples of AMOs and methods of their production and use are provided. These AMOs are suitable for forming cathodes or anodes in half-cell cells, cell units, and batteries. Furthermore, the disclosed AMOs are compatible with conventional lithium-ion battery technologies, including existing anode components, cathode components, electrolyte formulations, and separator components. It should be understood that the material of the anode 106 selected for a cell or battery according to this disclosure may have a lower electronegativity than the cathode material to appropriately complement the cathode material. In one specific embodiment, the disclosed AMO can be used as the cathode of a battery having a lithium metal anode.

[0104] In several embodiments of the invention, the cathode 104 comprises an AMO material having an acidic but not superacidic surface. This contrasts with previously known materials used as cathodes (e.g., lithium cobalt or lithium manganese materials). The AMO material of this disclosure and its preparation method are described below. In other embodiments, the anode 106 comprises the AMO material of this disclosure having an acidic but not superacidic surface.

[0105] 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, the array is imperfect and susceptible to the effects of vacancies, deformation, and surface adhesion. Regardless, any exposed metal center is a cation (positively charged) and can accept electrons, thus acting as a Lewis acid site by definition. Oxygen centers are anions (negatively charged) and act as Lewis base sites, donating electrons. This results in the well-known acidity and basicity of metal oxide surfaces.

[0106] Under normal atmospheric conditions, the presence of water vapor causes molecular (hydration) or dissociative (hydroxylation) adsorption onto the surface of metal oxides. OH - and H + All substances can be adsorbed onto the surface of oxides. Negatively charged hydroxyl groups will attach to the center of the metal cation (Lewis acid, accepting electrons), H... + It will attach to the oxygen anion (Lewis base, electron-donating) center. Both adsorptions result in the presence of the same functional group—hydroxyl group—on the surface of the metal oxide.

[0107] These surface hydroxyl groups can function as proton acids or proton bases because these groups can release or accept protons. The tendency of a single hydroxyl group to become a proton donor or acceptor is influenced by the coordination of the metal cation or oxygen anion it is attached to. Defects on the metal oxide surface, such as oxygen vacancies, or the coordination of surface groups with other chemicals, mean that not all cations and anions are equally coordinated. The number and strength of acid-base sites will vary. When generally "totaled" on an oxide surface, this can impart an overall acidic or basic nature to the surface.

[0108] The number and strength of Lewis acid and Lewis base sites (derived from exposed metal cations and oxygen anions, respectively), as well as protonic acid and protonic base sites (derived from surface hydroxyl groups), add extensive practicality and functionality to metal oxides and their applications in chemical reactions and equipment. These sites strongly contribute to the chemical reactivity of metal oxides. They can serve as anchoring sites, to which other chemical groups or even other metal oxides can attach. Furthermore, they can influence surface charge, hydrophilicity, and biocompatibility.

[0109] 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 result in a more polarized bond and thus a more acidic proton. The acidity of the Lewis site can be increased by inducing polarization, which promotes the contribution of electrons to that site. When a compound prepared in this way is placed in water, the acidic protons will dissociate and thus lower the pH measurement of the aqueous solution.

[0110] While working with solid acid / base systems instead of liquid ones may be somewhat less precise, the acidity of metal oxides dispersed in aqueous solutions can be evaluated using conventional pH measurement methods employing titration, pH test strips, and pH probes. These measurements can be supplemented with techniques including, but not limited to, colorimetric indicators, infrared spectroscopy, and temperature-programmed desorption data to establish the acidity properties of metal oxide surfaces. Surface functional groups can be examined using standard analytical techniques, including but not limited to X-ray photoelectron spectroscopy.

[0111] 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 groups. It can also be achieved via a solid-state method, where the metal oxide is mixed and / or ground with a solid containing the desired functional groups. However, all these methods require additional surface functionalization steps beyond those necessary for synthesizing the metal oxide itself.

[0112] The synthesis and surface functionalization of AMO materials can be carried out in a single-pot hydrothermal synthesis method or its equivalent, wherein the surface of the metal oxide is functionalized when the metal oxide is synthesized from a suitable precursor. A precursor salt containing EWG is dissolved, and the resulting solution is acidified with an acid containing a second EWG. The acidified solution is then alkalized, heated, and washed. A drying step yields solid AMO material.

[0113] As an example, the preferred embodiment of AMO in the form of tin oxide was synthesized using the following single-reactor method, while simultaneously performing surface functionalization:

[0114] 1. First, dissolve 7 g (7 g) of tin(II) chloride dihydrate (SnCl2 2H2O) in a solution of 35 mL anhydrous ethanol and 77 mL distilled water.

[0115] 2. Stir the resulting solution for 30 minutes.

[0116] 3. Acidify the solution by adding 7 mL of 1.2 M HCl dropwise, and stir the resulting solution for 15 minutes.

[0117] 4. Alkalinize the solution by adding 1M alkaline aqueous solution dropwise until the pH of the solution is approximately 8.5.

[0118] 5. Then place the resulting opaque white suspension in a hot water bath (~60°C to 90°C) and stir for at least 2 hours.

[0119] 6. Then wash the suspension with distilled water and anhydrous ethanol.

[0120] 7. The washed suspension was dried in air at 100°C for 1 hour, and then annealed in air at 200°C for 4 hours.

[0121] This method yields tin AMO surface-functionalized with chlorine, which, when resuspended and measured at 5 wt% in aqueous solution at room temperature, has a pH of approximately 2. By definition, its Hammett function H0 > -12. Although an open system such as a flask is described herein, a closed system such as an autoclave can also be used.

[0122] Using the single-reactor method disclosed above, many AMOs have been synthesized. Table 1 below describes the precursors and acids used. In some cases, dopants were also used:

[0123]

[0124]

[0125] Ac is an acetic acid group with the chemical formula C2H3O2.

[0126] In some embodiments, the electron-withdrawing group has a carbon chain length of 5 or less, or 6 or less, and / or an organic mass of 200 or less (AMU). In some embodiments, the electron-withdrawing group has a carbon chain length of 8 or less, or 10 or less, and / or an organic mass of 500 or less.

[0127] 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 can be varied individually or in any combination of possible experimental design methods. Furthermore, other methods for synthesizing metal oxides—such as spray pyrolysis, vapor-phase growth, electrodeposition, solid-phase methods, and hydrothermal or solvothermal treatments—can be used to achieve the same or similar results as the method disclosed herein.

[0128] Various annealing conditions can be used to prepare AMO nanomaterials. Exemplary annealing temperatures can be below 300°C, for example, from 100°C to 300°C. Exemplary annealing times can range from about 1 hour to about 8 hours or longer. Annealing can be performed under various atmospheric conditions. For example, annealing can occur in air at atmospheric pressure. Annealing can occur at elevated pressure (greater than atmospheric pressure) or depreciated pressure (less than atmospheric pressure or in a vacuum). Alternatively, annealing can 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).

[0129] Various drying conditions can be used to prepare AMO nanomaterials. Exemplary drying temperatures can range from 50°C to 150°C. Exemplary drying times can range from about 0.5 hours to about 8 hours or longer. Drying can be carried out under various atmospheric conditions. For example, drying can occur in air at atmospheric pressure. Drying can be carried out at elevated pressure (greater than atmospheric pressure) or degraded pressure (less than atmospheric pressure or in a vacuum). Alternatively, drying can 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).

[0130] The performance characteristics of the AMO nanomaterials disclosed herein differ from those of non-acidified metal oxide nanoparticles. As an example, Figure 4 The cyclic voltammetry (CV) of AMO tin prepared by a single-reactor method is shown to differ from that of commercially available non-AMO tin when cycled relative to lithium. For example, surface-functionalized AMO materials exhibit better reversibility than non-AMO materials. The presence of different peaks in the CV of AMO materials may indicate multiple electron transfer steps occurring during charge / discharge. For instance, peaks at higher voltages may indicate direct oxidation / reduction of the AMO material, while peaks at lower voltages may be due to structural changes (i.e., alloying) in the AMO material.

[0131] As another example, Figure 5 This indicates that the total reflectivity of AMO tin oxide differs from that of commercially available non-AMO tin oxide. The data also show that AMO, in addition to being used as the anode according to this disclosure, has a lower band gap, thus possessing more desirable properties as a component of a photovoltaic system.

[0132] AMO materials can be considered to have a general formula.

[0133] M m O x / G

[0134] in

[0135] M m Ox For metal oxides, m is at least 1 and no greater than 5, and x is at least 1 and no greater than 21;

[0136] Is G at least one of the hydroxyl radicals in the form of EWG, and

[0137] Simply distinguishing between metal oxides and EWG indicates that there is no fixed mathematical relationship or ratio between the two.

[0138] G can represent a single type of EWG or more than one type of EWG.

[0139] An example AMO is oxidized tin oxide (Sn). x O y ), acidified titanium dioxide (Ti a O b ), acidified iron oxide (Fe) c O d ) and acidified zirconium oxide (Zr e O f Exemplary electron-withdrawing groups (“EWG”) are Cl, Br, BO3, SO4, PO4, and CH3COO. Regardless of the specific metal or EWG, according to this disclosure, the AMO material is acidic but not hyperacidic, producing a pH < 7 when suspended in an aqueous solution at 5 wt%, and exhibiting a Hammett function H0 > -12 at least on its surface.

[0140] The AMO material structure can be crystalline or amorphous (or a combination thereof) and can be used alone or as a mixture with non-acidified metal oxides, other additives, binders, or conductive aids known in the art. In other words, the anode prepared using the AMO of this disclosure may or may not include other materials. In one embodiment, AMO can be laminated on a conductive material to form a cathode 104. In some embodiments, the AMO material is added to a conductive aid material, such as graphite or conductive carbon (or equivalents), in the range of 10 wt% to 80 wt% and up to 90 wt% to 95 wt%. In preferred embodiments, AMO is added at 10 wt%, 33 wt%, 50 wt%, and 80 wt%.

[0141] To maximize the amount of total available surface area, AMO should be in nanoparticle form (i.e., with a size less than 1 micrometer) and substantially monodisperse. More preferably, the nanoparticle size is less than 100 nm, and even more preferably, less than 20 nm or 10 nm.

[0142] Mixed metal AMOs (in which another metal or metal oxide is present in addition to a pure oxide or binary oxide) have been reduced for use as anodes in half-cell cells, battery cells, and batteries. These mixed metal AMOs can be considered to have a general formula.

[0143] M m N n O x / G and M m N n R r O x / G

[0144] in:

[0145] M is a metal and m is at least 1 and no greater than 5;

[0146] N is a metal and n is greater than 0 and not greater than 5;

[0147] R is a metal and r is greater than 0 and not greater than 5;

[0148] O is the total oxygen associated with all metals, and x is at least 1 and no greater than 21;

[0149] Simply distinguishing between metal oxides and electron-withdrawing surface groups indicates that there is no fixed mathematical relationship or ratio between the two; and

[0150] G is at least one EWG containing hydroxide ions.

[0151] G can represent a single type of EWG or more than one type of EWG.

[0152] Some prior art mixed metal oxide systems (of which zeolites are the most prominent example) exhibit strong acidity, even if each pure oxide does not exhibit strong acidity. The preferred embodiments of the mixed metal AMO disclosed herein differ from those systems in that any embodiment must include at least one acidic (but not hyperacidic) pure M m O x AMO in the form of / G. A preferred mixed metal and metal oxide system is Sn. x Fe c O y+d and Sn x Ti a O y+b , where y+d and y+b can be integer or non-integer values.

[0153] In another embodiment, the mixed metal AMO material is produced via a single-reactor method with a modification: synthesis is initiated with two metal precursor salts in any proportion instead of one. For example, step 1 of the single-reactor method can be modified as follows: First, 3.8 g of tin(II) chloride dihydrate (SnCl2 2H2O) and 0.2 g of lithium chloride (LiCl) are dissolved in a solution of 20 mL anhydrous ethanol and 44 mL distilled water.

[0154] Metal precursor salts as shown in Table 1 can also be used in any proportion. Depending on the desired product, the metal precursor salts may have the same or different anionic groups; the metal precursor salts may be introduced at different time points during synthesis; or the metal precursor salts may be introduced as solids or introduced into a solvent. In some embodiments, a first metal precursor salt may be used as the main structure (i.e., in a larger proportion) of the resulting AMO, and a second (and optionally a third) metal precursor salt may be added as a dopant or as a minor component of the resulting AMO.

[0155] The single-reactor experiments led to seven significant findings. First, in all cases, surface functionalization and acidity were generated endogenously (see [link to study]). Figure 6 Instead of being generated after synthesis, the single-reactor method utilizes hydroxyl-containing organic compounds or hydrogen peroxide, rather than the surface functionalization methods of existing technologies.

[0156] Second, this method can be widely extended to a wide 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, with simultaneous surface functionalization using chlorides, sulfuric acid, acetic acid, nitric acid, phosphoric acid, citric acid, oxalic acid, boric acid, 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 achieved using EWGs that are weaker than halogens and SO4 but still produce acidic but not hyperacidic surfaces. For example, this method has also been used to synthesize AMOs surface functionalized with acetate (CH3COO), oxalate (C2O4), and citrate (C6H5O7). Various examples are described below.

[0157] Third, there is a synergistic relationship between EWG and other properties of nanoparticles such as size, morphology (e.g., plate-like, spherical, needle-like, or rod-like), oxidation state, and crystallinity (amorphous, crystalline, or a mixture thereof). For example, morphological differences can occur between AMO nanoparticles synthesized under the same conditions, except that different EWGs are used for surface functionalization (see [link to article]). Figure 7Surface functionalization can act as a "pin" for the size of nanoparticles, halting their growth. Depending on the precise synthesis conditions, this pinning can occur in only one dimension of the nanoparticle, or it can occur in more than one dimension.

[0158] Fourth, the properties of AMO are highly sensitive to synthesis conditions and processes. For example, when synthesized under identical conditions except for two different total reaction times, differences in the morphology and properties of AMO nanoparticles can occur (see [link to article]). Figure 8 and Figure 9 Experimental design methods can be used to determine the optimal or best synthesis conditions and processes for producing desired properties or sets of properties.

[0159] Fifth, both the anions present in the precursor salt and the anions present in the acid contribute to the surface functionalization of AMO. In a preferred embodiment, tin chloride precursor and hydrochloric acid are used for the synthesis of tin-based AMO. The properties of these particles differ from those in embodiments using tin chloride precursor and sulfuric acid, or from embodiments using tin sulfate precursor and hydrochloric acid. Therefore, in some embodiments, matching the precursor anions and acid radicals is preferred.

[0160] Sixth, when using a precursor with a weak EWG and an acid with a strong EWG, or vice versa, strong anion adsorption will dominate surface functionalization. This opens up a wider range of synthetic possibilities, allowing for ion functionalization that is not readily available in both the precursor salt and the acid. It can also allow for mixed functionalization with strong and weak EWG. In one example, tin acetate precursor and phosphoric acid were used to synthesize tin AMO. X-ray photoelectron spectroscopy analysis of the surface showed that the atomic concentration of phosphorus was greater than the atomic concentration of the bonds associated with the acetate groups (see [link to article]). Figure 10 ).

[0161] Seventh, and finally, while the disclosed method is a general process for synthesizing AMOs, the synthesis process and conditions can be tuned to produce sizes, morphologies, oxidation states, and crystalline states desired for different applications. As an example, catalytic applications may require AMO materials that are more active in visible light (see [link to documentation]). Figure 11A Or AMO materials that are more active in ultraviolet light (see Figure 11B ).

[0162] In another example, AMO materials can be used as battery electrodes. Primary (single-use) battery applications may require AMOs with properties that result in the highest capacity, while secondary (rechargeable) battery applications may require the same AMOs but with properties that result in the highest cycle life. Figure 12The cycle life of two different batteries constructed from AMO materials, including chlorinated AMO and sulfur-containing AMO, was compared. The AMO materials improved battery performance without degrading battery components or generating gases. This is the exact opposite of what the prior art teaches.

[0163] exist Figure 13 The image shows the charge-discharge cycle capability of a half-cell cell constructed with AMO nanomaterial electrodes relative to lithium metal, demonstrating a cycle capability of up to 900 charge-discharge cycles while still maintaining effective capacity and excellent coulombic efficiency. Such a long cycle capability is excellent, especially relative to a lithium metal reference electrode, as lithium metal is known to grow dendrites even at low cycle numbers, which can expand and lead to dangerous and fatal failure of the cell.

[0164] According to this disclosure, in a complete battery cell, the anode 106, comprising the disclosed AMO, can be used with a known electrolyte 108 and a cathode 104 comprising a known material such as lithium cobalt oxide (LiCoO2). Similarly, the material comprising the separator 110 can be derived from materials currently known in the art.

[0165] In a complete battery, the cathode 104, including the disclosed AMO, can be used with a known electrolyte 108 and an anode 106 comprising a known material such as carbon on copper foil, which exhibits lower electronegativity than the AMO of this disclosure. The materials comprising the separator 110 and the electrolyte 108 can also be obtained from those currently known in the art as discussed above.

[0166] Various layering and other enhancement techniques can be employed to maximize the capacity used to retain lithium ions for powering battery cell 100. It should also be understood that the battery based on the AMO cathode 104 according to this disclosure can be used 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 battery cell or cell constructed as described herein can be satisfactorily used as a primary battery cell or cell. In some embodiments, the battery cell and cell constructed according to this disclosure do not require initialization and are therefore prepared for use as primary battery cells and cells. In other cases, limited or rapid formation may be employed. Furthermore, by using the battery cell and cell of this disclosure as a primary battery not intended for recharging, some safety issues that may be inherent in lithium battery chemistry are mitigated, as it is known in the art that safety issues occur more frequently during battery cycling.

[0167] In other embodiments according to this disclosure, the cathode 104 comprises tin oxide (SnO2), but it is not acidified according to the AMO described above. Known electrolytes 108, anodes 106, and diaphragms 110, or those otherwise described in this disclosure, may be used in these embodiments.

[0168] It should be understood that other battery structures using AMO materials are also possible. For example, a battery may include a first electrode comprising AMO nanomaterials, a second electrode, and an electrolyte located between the first and second electrodes. As an example in a lithium-ion battery, the first electrode may serve 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. Effective materials 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.

[0169] Optionally, the AMO material of this disclosure may be used in conjunction with acidic components such as binders, acidic electrolytes, or acidic electrolyte additives. This can be in the case of anodes, cathodes, half-cell cells, complete cell cells, integrated cells, or other components. The inventors have surprisingly discovered that including acidic components and / or acidic substances, such as organic acids or organic anhydrides, in batteries containing AMO materials results in an increase in capacity compared to batteries that do not contain acidic substances. Again, the prior art teaches that acidic substances should not be used because these substances may degrade the metal current collector and casing and cause degradation of other electrode components.

[0170] like Figure 14 As shown, this paper provides comparative cycle capability data for multiple 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 acidic electrolyte. The 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 dimethyl carbonate, diethylene carbonate, and ethylene carbonate, plus 1M LiPF6; the acidic electrolyte is a 3wt% succinic anhydride standard electrolyte; and the alkaline electrolyte is a 3wt% dimethylacetamide standard electrolyte. All batteries are cycled at the same discharge rate. As shown, the battery with the acidic electrolyte system exhibits the best cycle capability, maintaining the highest capacity at the maximum number of cycles.

[0171] Figure 15Comparative cycle capacity data are provided for two additional batteries with the same battery construction (including an acidified electrolyte), the difference being that the AMO material in one battery was deacidified by solvent washing. The batteries comprised a cathode containing AMO material; an electrolyte consisting of a 1:1:1 mixture of dimethyl carbonate, diethylene carbonate, and ethylene carbonate, along with 1 M LiPF6 and 3 wt% succinic anhydride; and a lithium metal anode. 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, suggesting that the acidified surface of the AMO interacts with the acidified electrolyte, providing enhanced performance.

[0172] Several acidic electrolytes have been developed and / or tested and found to work favorably with the battery chemistry described herein.

[0173] Example 1: Acetate / chloride functionalized tin oxide (AMO)

[0174] Tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, gray material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 16 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0175] Example 2: Acetate / sulfate functionalized tin oxide (AMO)

[0176] Tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a gray, sheet-like material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 17 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0177] Example 3: Acetate / nitrate functionalized tin oxide (AMO)

[0178] Tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by the addition of nitric acid (HNO3). The resulting AMO nanomaterial was a gray, sheet-like material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 18 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0179] Example 4: Acetate / phosphate functionalized tin oxide AMO

[0180] Tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by the addition of phosphoric acid (H3PO4). The resulting AMO nanomaterials were brown, soft, sheet-like materials that formed electrodes. These electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 19 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0181] Example 5: Acetate / citric acid functionalized tin oxide (AMO)

[0182] Tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by the addition of citric acid (C6H8O7). The resulting AMO nanomaterials were brown, sheet-like materials that formed electrodes. These electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 20 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0183] Example 6: Acetate / citric acid functionalized tin oxide (AMO)

[0184] Tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified by the addition of oxalic acid (C2H2O4). The resulting AMO nanomaterials were brown, sheet-like materials that formed electrodes. These electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 21 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0185] Example 7: Tin oxide AMO doped with iron oxide and functionalized with acetate / chloride

[0186] Doped tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution containing a small amount of ferric acetate. The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, sheet-like, milky-gray material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 22 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0187] Example 8: Tin oxide AMO doped with iron oxide and functionalized with acetate / sulfuric acid

[0188] Doped tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution containing a small amount of ferric acetate. The solution was acidified by adding sulfuric acid (H2SO4). The resulting AMO nanomaterials were light brown, soft, and sheet-like, forming electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 23 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0189] Example 9: Tin oxide AMO doped with iron oxide and functionalized with acetate / nitrate

[0190] Two types of doped tin oxide (AMO) samples were synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution containing a small amount of ferric acetate (Fe(CH3COO)3). The solution was acidified by adding nitric acid (HNO3). The resulting AMO nanomaterials were soft, white materials that formed electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 24 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0191] Example 10: Tin oxide AMO doped with iron oxide and functionalized with acetate / oxalate

[0192] Doped tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution containing a small amount of ferric acetate (Fe(CH3COO)3). The solution was acidified by adding oxalic acid (C2H2O4). The resulting AMO nanomaterial was a soft, white material and formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 25 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0193] Example 11: Tin oxide AMO doped with iron oxide and functionalized with acetate / phosphate

[0194] Doped tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution containing a small amount of ferric acetate (Fe(CH3COO)3). The solution was acidified by adding phosphoric acid (H3SO4). The resulting AMO nanomaterial was a white, sheet-like material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 26 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0195] Example 12: Tin oxide doped with iron oxide and functionalized with acetate / citric acid

[0196] Doped tin oxide was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution containing a small amount of ferric acetate (Fe(CH3COO)3). The solution was acidified by adding citric acid (C6H8O7). The resulting material did not form particles but 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 zero volts and then charging to 1.5 volts. Figure 27 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0197] Example 13: Acetate / bromine functionalized tin oxide (AMO)

[0198] Tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified with hydrobromic acid (HBr). The resulting AMO nanomaterial was a gray, soft powder that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 28 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0199] Example 14: Acetate / boric acid functionalized tin oxide (AMO)

[0200] Tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / water solution and acidified with boric acid (H3BO3). The resulting AMO nanomaterials were gray, sheet-like materials that formed electrodes. These electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 29 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0201] Example 15: Tin oxide AMO doped with manganese oxide and functionalized with sulfuric acid / chloride

[0202] Doped tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin sulfate (SnSO4) was dissolved in an ethanol / water solution containing a small amount of manganese chloride (MnCl2). The solution was acidified by adding sulfuric acid (H2SO4). The resulting AMO nanomaterials were very soft, brownish-red materials that formed electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 30 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0203] Example 16: Tin oxide (AMO) doped with manganese oxide and functionalized with chloride

[0204] Doped tin oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, tin chloride (SnCl2) was dissolved in an ethanol / water solution containing a small amount of manganese chloride (MnCl2). The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, grayish-brown material and formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 31 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0205] Example 17: Tin oxide (AMO) doped with iron oxide and aluminum oxide and functionalized with chloride

[0206] Two types of doped tin oxide (AMO) samples were synthesized using a single-reactor hydrothermal synthesis method. In short, tin chloride (SnCl2) was dissolved in an ethanol / water solution containing small amounts of ferric chloride (FeCl3) and aluminum chloride (AlCl3). The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial for the first sample was a light brown, sheet-like material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 32 The measured capacity was plotted as a function of the number of cycles, and the voltage as a function of time during the cycling period was also plotted. The resulting AMO nanomaterial for the second sample was a light gray, sheet-like material.

[0207] Example 18: Iron oxide AMO doped with tin oxide and functionalized with chloride

[0208] Doped iron oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, ferric chloride (FeCl3) was dissolved in an ethanol / water solution containing a small amount of tin chloride (SnCl2). The iron to tin ratio was 95:5. The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, reddish material and formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 33 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0209] Example 19: Iron oxide AMO doped with tin oxide and functionalized with chloride

[0210] Doped iron oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, ferric chloride (FeCl3) was dissolved in an ethanol / water solution containing a small amount of tin chloride (SnCl2). 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 an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 34 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0211] Example 20: Iron oxide AMO functionalized with nitric acid

[0212] Iron oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, ferric nitrate (Fe(NO3)3)3 was dissolved in an ethanol / water solution and acidified by the addition of nitric acid (HNO3). The resulting AMO nanomaterial was a black, glassy material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 35 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0213] Example 21: Bismuth oxide AMO with chloride functionalization

[0214] Bismuth oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, bismuth chloride (BiCl3) was dissolved in an ethanol / water solution and acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, white material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 36 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0215] Example 22: Zirconia AMO functionalized with sulfuric acid

[0216] Zirconia AMO was synthesized using a single-reactor hydrothermal synthesis method. In short, zirconium sulfate (Zr(SO4)2) was dissolved in an ethanol / water solution and acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a sheet-like white material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 37 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0217] Example 23: Titanium oxide AMO functionalized with sulfuric acid

[0218] Titanium oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, titanium oxysulfate (TiOSO4) was dissolved in an ethanol / water solution and acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a white, sheet-like material that formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 38 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0219] Example 24: Antimony oxide AMO functionalized with sulfuric acid

[0220] Antimony oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, antimony sulfate (Sb₂(SO₄)₃) was dissolved in an ethanol / water solution and acidified by the addition of sulfuric acid (H₂SO₄). The resulting AMO nanomaterials were very soft, white materials that formed electrodes. These electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 39 The graphs depict the measured capacity relative to the number of cycles, as well as the voltage change over time during the cycle.

[0221] Example 25: Indium AMO with chloride functionalization

[0222] Indium oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, indium chloride (InCl3) was dissolved in an ethanol / water solution and acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was white and formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 40 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0223] Example 26: Indium oxide (AMO) functionalized with sulfuric acid

[0224] Indium oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, indium sulfate (In₂(SO₄)₃) was dissolved in an ethanol / water solution and acidified by the addition of sulfuric acid (H₂SO₄). The resulting AMO nanomaterial was a white material and formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 41 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0225] Example 27: Indium AMO functionalized with bromide

[0226] Indium oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, indium bromide (InBr3) was dissolved in an ethanol / water solution and acidified with hydrobromic acid (HBr). The resulting AMO nanomaterial was a bluish-white material and formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 42Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0227] Example 28: Indium AMO with chloride functionalization

[0228] Indium oxide (AMO) was synthesized using a single-reactor hydrothermal synthesis method. In short, indium chloride (InCl3) was dissolved in an ethanol / water solution and acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterials were gray with yellow rings and formed electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 43 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0229] Example 29: A mixture of lithium oxide and iron oxide AMO doped with tin oxide and functionalized with chloride / acetate

[0230] Doped mixed lithium oxide and iron oxide AMOs were synthesized using a single-reactor hydrothermal synthesis method. In short, lithium acetate (Li(CH3COO)) and ferric chloride (FeCl3) were dissolved in an ethanol / water solution containing a small amount of tin chloride (SnCl2). The solution was acidified by adding hydrochloric acid (HCl). During the synthesis, brownish-pink nanoparticles with green rings formed on the flask. However, the final AMO nanomaterials were gray and formed electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 44 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0231] Example 30: A mixture of lithium oxide and iron oxide AMO doped with tin oxide and functionalized with chloride / acetate

[0232] Doped mixed lithium oxide and iron oxide AMOs were synthesized using a single-reactor hydrothermal synthesis method. In short, lithium acetate (Li(CH3COO)) and ferric chloride (FeCl3) were dissolved in an ethanol / water solution containing a small amount of tin chloride (SnCl2). The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterials were gold-white and formed electrodes. The electrodes were assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 45 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0233] Example 31: A mixture of lithium oxide and iron oxide AMO doped with tin oxide and functionalized with chloride / acetate

[0234] Doped mixed lithium oxide and iron oxide AMO was synthesized using a single-reactor hydrothermal synthesis method. In short, lithium acetate (Li(CH3COO)) and ferric chloride (FeCl3) were dissolved in an ethanol / water solution containing a small amount of tin chloride (SnCl2). The solution was acidified by adding hydrochloric acid (HCl). The resulting AMO nanomaterial was a pale milky white material and formed an electrode. The electrode was assembled relative to lithium metal in a battery cell and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 46 Electron micrographs of the AMO nanomaterials, a graph of the measured capacity versus the number of cycles, and a graph of voltage versus time during cycling were depicted.

[0235] In several embodiments, this disclosure provides materials comprising solid metal oxides in the form of monodisperse nanoparticles. AMO nanomaterials may include tin oxide, titanium dioxide, iron oxide, zirconium oxide, or any combination thereof. AMO nanomaterials may be surface-functionalized by one or more electron-withdrawing groups selected from the group consisting of Cl, Br, BO3, SO4, PO4, NO3, CH3COO, C2O4, and C6H5O7. The first battery electrode may further include a second acidic material. The second electrode may include 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. The acidic material may include one or more organic acids selected from the group consisting of oxalic acid, acetic acid, citric acid, maleic acid, methylmalonic acid, glutaric acid, succinic acid, methylsuccinic acid, methylene succinic acid, and citralic acid. The acidic substance may include one or more organic acid anhydrides selected from the group consisting of glutaric anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, and itaconic anhydride. The concentration of the acidic substance in the solvent may be selected from 0.01 wt% to 10 wt%. The acidic substance may exhibit a pKa of 1 to 6 in water. The electrolyte may further include a lithium salt dissolved in the solvent.

[0236] This disclosure includes a method for preparing a battery, comprising preparing an acidified metal oxide (AMO) nanomaterial, forming a first electrode of the AMO nanomaterial, forming an electrolyte by dissolving one or more salts and an acidic substance in a solvent, and positioning the electrolyte between the first and second electrodes. Preparing the AMO nanomaterial may include forming a solution comprising 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. The method may also include forming the first electrode by mixing the precipitate with a second acidic substance. The AMO nanomaterial includes tin oxide, titanium dioxide, iron oxide, zirconium oxide, or any combination thereof. The AMO nanomaterial may be surface functionalized by one or more electron-withdrawing groups selected from the group consisting of Cl, Br, BO3, SO4, PO4, NO3, CH3COO, C2O4, and C6H5O7. The second electrode 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), or any combination thereof. The acidic substance may comprise one or more organic acids selected from the group consisting of oxalic acid, acetic acid, citric acid, maleic acid, methylmalonic acid, glutaric acid, succinic acid, methylsuccinic acid, methylenesuccinic acid, and citraconic acid, or wherein the acidic substance comprises one or more organic acid anhydrides selected from the group consisting of glutaric anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, and itaconic anhydride. The concentration of the acidic substance in the solvent may be selected from 0.01 wt% to 10 wt%. The acidic substance may exhibit a pKa of 1 to 6 in water.

[0237] This disclosure provides an acidified electrolyte for use in a battery including a first electrode and a second electrode, wherein the first electrode comprises an acidified metal oxide (AMO) nanomaterial, and the electrolyte comprises a solvent, one or more metal salts dissolved in the solvent, and an acidic substance dissolved in the solvent, wherein the acidic substance is different from the one or more metal salts. The acidic substance may include one or more organic acids selected from the group consisting of oxalic acid, acetic acid, citric acid, maleic acid, methylmalonic acid, glutaric acid, succinic acid, methylsuccinic acid, methylenesuccinic acid, and citraconic acid, or wherein the acidic substance includes one or more organic acid anhydrides selected from the group consisting of glutaric anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, and itaconic anhydride. The acidic substance may exhibit a pKa of 1 to 6 in water.

[0238] All references throughout this application, including patent documents, patent application publications, non-patent documents, or other sources, including published or granted patents or equivalents, are incorporated herein by reference in their entirety as if they were incorporated separately by reference.

[0239] All patents and publications mentioned in this specification demonstrate the skill of a person skilled in the art to which this invention pertains. References cited herein are incorporated in their entirety to indicate, in some cases, the state of the prior art up to the date of their application, and, if necessary, are intended to be used herein to exclude (e.g., not protect) specific embodiments in the prior art. For example, when a compound is claimed, it should be understood that compounds known in the prior art, including certain compounds disclosed in the references disclosed herein (particularly the cited patent documents), are not intended to be included in the claims.

[0240] When a set of substituents is disclosed herein, it should be understood that all individual members of those groups, as well as all subgroups and classes that can be formed using the substituents, are disclosed separately. When Markush groups or other groups are used herein, all individual members of the group, as well as all possible combinations and subcombinations of the group, are included separately 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".

[0241] Unless otherwise stated, every formulation or combination of components described or illustrated is applicable to the practice of this invention. Specific names of materials are intended to be exemplary, as it is known that those skilled in the art may name the same materials differently. Those skilled in the art will recognize that methods, apparatus elements, raw materials, and synthesis methods other than those specifically illustrated can be employed in the practice of this invention without requiring excessive experimentation. Functional equivalents of all such methods, apparatus elements, raw materials, and synthesis methods known in the art are included in this invention. Whenever ranges (e.g., temperature ranges, time ranges, or composition ranges) are given in the specification, all intermediate ranges and sub-ranges, as well as all individual values ​​included within the given ranges, are intended to be included in this disclosure.

[0242] As used herein, "comprising" is synonymous with "including" or "characterized in" and is inclusive or unrestrictive, and does not exclude additional, 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 substantially affect the elements and novel features of the claims. Any use of the term "comprising" herein, particularly in the description of the components of a composition or the elements of a device, should be understood to include compositions and methods that are substantially composed of and constituted by the stated components or elements. The invention exemplarily described herein may be suitably practiced without any elements or limitations not specifically disclosed herein.

[0243] The terms and expressions used are descriptive and not limiting, and their use is not intended to exclude any equivalents of the features shown and described or any part thereof. However, it should be recognized that various modifications are possible within the scope of the claimed invention. Therefore, it should be understood that while the invention has been specifically disclosed through preferred embodiments and optional features, modifications and variations can be made to the concepts disclosed herein by those skilled in the art, and such modifications and variations are considered to be within the scope of the invention as defined in the claims.

Claims

1. A battery cell comprising two electrodes, The first electrode of the two electrodes is a cathode and contains solid metal oxide nanomaterials with a particle size of less than 1 μm. The solid metal oxide nanomaterials have a pH < 5 and a Hammett function H0 > -12. The pH is measured when the solid metal oxide nanomaterials are suspended in water at 5 wt% at room temperature. The solid metal oxide nanomaterials are selected from the group consisting of tin oxide, iron oxide, manganese oxide, titanium oxide and indium oxide. The second electrode of the two electrodes is an anode and includes an anode material.

2. The battery cell according to claim 1, wherein: The electrolyte is an acidic electrolyte containing lithium salts or an electrolyte containing acidic substances.

3. The battery cell according to claim 2, wherein: wherein The lithium salt is at least one lithium salt selected from the group consisting of LiPF6, LiAsF6, LiClO4, LiBF4 and LiCF3SO3.

4. The battery cell according to claim 2, wherein: The acidic substance includes one or more organic acids, one or more organic acid anhydrides, or a combination thereof; Wherein, the one or more organic acids are selected from the group consisting of oxalic acid, acetic acid, citric acid, maleic acid, methylmalonic acid, glutaric acid, succinic acid, methylsuccinic acid, methylenesuccinic acid, and citralic acid; and The one or more organic acid anhydrides are selected from the group consisting of glutaric anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride and itaconic anhydride.

5. The battery cell of claim 1, wherein under the same charge-discharge cycles as the reference battery cell: The battery cell has a larger initial capacity and a greater cycle life than the reference battery cell; and The battery cell has a larger capacity per cycle than the reference battery cell; wherein The reference battery cell has the same dimensions as the battery cell, and the reference battery cell includes: The cathode, corresponding to the cathode of the first electrode, comprises a solid metal oxide nanomaterial, wherein the particle size of the solid metal oxide nanomaterial is less than 100 nm, and it is both acid- and base-tolerant, and is selected from the group consisting of tin oxide, iron oxide, manganese oxide and titanium oxide. The anode corresponds to the second electrode and includes the anode material.

6. The battery cell of claim 5, wherein the greater cycle capability is in the range of 15% to 45% increase in charge-discharge cycles.

7. The battery cell according to claim 1, wherein the content of the solid metal oxide nanomaterial is in the range of 10 wt% to 33 wt% of the first electrode.

8. The battery cell according to claim 1, wherein the content of the solid metal oxide nanomaterial is in the range of 33 wt% to 50 wt% of the first electrode.

9. The battery cell according to claim 1, wherein the content of the solid metal oxide nanomaterial is in the range of 50 wt% to 80 wt% of the first electrode.

10. The battery cell according to claim 1, wherein the solid metal oxide nanomaterial is substantially monodisperse.

11. The battery cell according to claim 1, wherein the solid metal oxide nanomaterial is surface functionalized with electron-withdrawing groups with a molecular weight of less than 200.

12. The battery cell according to claim 11, wherein the electron-withdrawing group is a chloride.

13. The battery cell according to claim 11, wherein the electron-withdrawing group is a sulfate.

14. The battery cell of claim 1, wherein the cathode comprises a second solid metal oxide nanomaterial different from the solid metal oxide nanomaterial, and the second solid metal oxide nanomaterial is selected from the group consisting of tin oxide, iron oxide, manganese oxide and titanium oxide.

15. The battery cell of claim 14, wherein the second solid metal oxide nanomaterial has a pH ≤ 5, wherein the pH is measured when the second solid metal oxide nanomaterial is suspended in water at 5 wt% at room temperature.

16. The battery cell of claim 14, wherein the cathode comprises a third solid metal oxide nanomaterial, different from the solid metal oxide nanomaterial and the second solid metal oxide nanomaterial, the third solid metal oxide nanomaterial being selected from the group consisting of tin oxide, iron oxide, manganese oxide and titanium oxide.

17. The battery cell of claim 16, wherein the third solid metal oxide nanomaterial has a pH ≤ 5, wherein the pH is measured when the third solid metal oxide nanomaterial is suspended in water at 5 wt% at room temperature.

18. The battery cell of claim 1, wherein the anode material comprises lithium.

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