High-capacity battery and its components

Abstract

To provide improved batteries and related components. [Solution] A battery cell is provided comprising a cathode containing an active material, a binder, and an acidified metal oxide nanomaterial, an anode, and an electrolyte disposed between the cathode and the anode, wherein the acidified metal oxide nanomaterial constitutes 0.01 to 10 weight percent of the cathode.

Description

[Technical Field]

[0001] Cross-references to related applications

[0001] This application claims the benefit of and priority thereto of U.S. Provisional Applications No. 62 / 483,789 filed on April 10, 2017, No. 62 / 507,655 filed on May 17, 2017, No. 62 / 507,658 filed on May 17, 2017, No. 62 / 507,659 filed on May 17, 2017, No. 62 / 507,660 filed on May 17, 2017, No. 62 / 507,662 filed on May 17, 2017, and No. 62 / 651,002 filed on March 30, 2018, all of which are incorporated herein by reference for all purposes. Furthermore, this application incorporates by reference U.S. Provisional Applications No. 62 / 256,065 and No. 62 / 256,059, both filed on November 16, 2015; U.S. Provisional Application No. 62 / 422,483, filed on November 15, 2016; U.S. Non-Provisional Application No. 15 / 352,388, filed on November 15, 2016; current U.S. Patent No. 9,786,910; and U.S. Non-Provisional Application No. 15 / 814,094, filed on November 15, 2017.

[0002]

[0002] The present disclosure relates to the field of materials useful for chemical energy storage and power devices such as batteries, but is not limited thereto. More specifically, the present disclosure relates to battery cells having a cathode and / or anode comprising metal oxide, more specifically acidified metal oxide ("AMO") nanomaterials. [Background technology]

[0003]

[0003] Metal oxides are compounds in which oxygen is bonded to a metal, and their general formula is M m O xThese metal oxides are found in nature but can also be synthesized artificially. In synthetic metal oxides, the synthesis method can have a wide range of effects on surface properties, including their acid / base properties. Changes in surface properties can alter the properties of the oxide, affecting its catalytic activity and electron mobility. However, the mechanisms by which surfaces control reactivity are not always fully characterized or understood. For example, in photocatalytic reactions, surface hydroxyl groups are thought to promote electron transfer from the conduction band to chemiadsorbed oxygen molecules.

[0004]

[0004] Despite the importance of surface properties, the literature on metal oxides, both scientific papers and patents, is primarily focused on creating new nanoscale crystalline forms of metal oxides to improve energy storage and power applications. Surface properties of metal oxides are neglected, and, outside of the literature on chemical catalysts, there is little innovation toward controlling or modifying the surfaces of known metal oxides to achieve performance targets.

[0005]

[0005] The literature on chemical catalysts is mainly dedicated to the production of "superacids" (acidity higher than that of pure sulfuric acid (18.4 M H2SO4)) and is often used in large-scale reactions such as hydrocarbon decomposition. Superacids cannot be measured on the conventional pH scale and are instead quantified by the Hammett number. The Hammett number (H0) can be thought of as extending the pH scale to negative numbers less than zero. The H0 of pure sulfuric acid is -12.

[0006]

[0006] However, there are many reaction systems and many applications where superacidity is too strong. For example, superacidity can degrade the components of the system or catalyze undesirable side reactions. Nevertheless, acidity can still be useful in these same applications for improving reactivity and kinetic properties or electron mobility.

[0007]

[0007] Battery literature teaches that acidic groups are detrimental to batteries, attacking metal current collectors and housings and potentially causing degradation of other electrode components. Furthermore, prior art teaches that active catalytic electrode surfaces can cause electrolyte decomposition, resulting in gas generation within the cell and ultimately cell failure.

[0008]

[0008] There is a need for improved batteries and related components. [Overview of the project]

[0009]

[0009] This application describes a high-capacity electrochemical cell comprising electrodes containing metal oxides. Techniques for preparing metal oxides and electrochemical cells containing metal oxides are further disclosed. Optionally, the disclosed metal oxides are used in combination with conductive materials to form electrodes. The formed electrodes are useful as corresponding counter electrodes for lithium metal and conventional lithium-ion electrodes. The disclosed metal oxides are optionally used in combination with acidic species to enhance their usefulness.

[0010]

[0010] Electrochemical cells containing electrodes with metal oxides exhibit advantageously very high capacities, such as metal oxides with capacities of up to 15,000 mAh / g. Such capacities can be achieved by using layered electrode structures with low active material (i.e., metal oxide) loading, for example, less than 80% by weight of the active material in the electrodes. This is in contrast to conventional electrochemical cell techniques that seek to maximize the active material loading, which can be about 80% or more by weight, for example, 90%, 95%, or 99%. While high active material loading may be useful in increasing the capacity of conventional electrochemical cell techniques, the inventors of this application have found that high cell capacities can actually be achieved by reducing the active material loading. Such capacity increases can be achieved at least in part by enabling greater uptake of shuttle ions (i.e., lithium ions) because additional physical volume is available when the level of active material loading is low. Such capacity increases can be achieved at least in part by alternatively or additionally enabling more active sites for shuttle ion uptake and reducing the blockage of active sites by the additional mass of material.

[0011]

[0011] The disclosed electrochemical cell may optionally use metal oxides in the form of acidified metal oxide ("AMO") materials. Useful AMOs include, for example, those in the form of nanomaterials such as nanoparticles, which can be monodisperse or substantially monodisperse and may have particle sizes less than 100 nm, for example. The disclosed AMOs exhibit a low pH such as less than 7 (e.g., between 0 and 7) when suspended in water at a specific concentration (e.g., 5 wt%) or when resuspended in water after drying, and further exhibit a Hammett function H0 greater than -12 at least on the surface of the AMO (i.e., not superacidic).

[0012]

[0012] The surface of the metal oxide may optionally be functionalized by acidic species or other electron-withdrawing species, etc. Synthesis and surface functionalization can be achieved by a "single-pot" hydrothermal method in which the surface of the metal oxide is functionalized when the metal oxide is synthesized from a suitable precursor. In some embodiments, this single-pot method does not require an additional step for acidification beyond what is necessary to synthesize the metal oxide itself, resulting in a metal oxide having a desired surface acidity (but not super acidic).

[0013]

[0013] Optionally, strong electron-withdrawing groups ("EWGs") such as SO4, PO4, or halogens (Br, Cl, etc.) are used alone or in combination with each other for surface functionalization. Surface functionalization can also occur using EWGs weaker than SO4, PO4, or halogens. For example, the synthesized metal oxide can be surface-functionalized with acetate groups (CH3COO), oxalate groups (C2O4), and citrate groups (C6H5O7).

[0014]

[0014] Despite the conventional knowledge that acidic species can attack the metal current collector and the housing and cause degradation of other electrode components, and that an active catalytic electrode surface can lead to electrolyte decomposition, gas generation within the cell, and ultimately cell failure, the inventors have discovered that acidic species and components can be advantageous for batteries that use metal oxide materials such as AMO nanomaterials for the battery electrodes.

[0015]

[0015] For example, the combination or use of metal oxides with acidic species can improve the performance of the resulting material, system, or device, and improve the capacity, cycle life, and lifespan of the device. As an example, a battery using a metal oxide in combination with an acidic electrolyte or an electrolyte containing an acidic species as described herein shows a considerable capacity increase, such as up to 100 mAh / g or more, compared to a similar battery using a non-acidified electrolyte or an electrolyte lacking an acidic species. In some embodiments, a capacity improvement between 50 and 300 mAh / g can be achieved. Furthermore, an absolute capacity of up to 1000 mAh / g or more can be achieved using a battery having an acidified electrolyte or an electrolyte containing an acidic species. In addition, the cycle life of the battery can be improved by using an acidic electrolyte or an electrolyte containing an acidic species, such as when the cycle life of the battery is extended to up to 100 or more charge-discharge cycles.

[0016]

[0016] In one embodiment, high-capacity batteries and electrochemical cells are disclosed. Exemplary capacities of batteries and cells described herein include primary capacities between 2,000 mAh / g and 15,000 mAh / g of metal oxide, such as between 2,500 mAh / g and 15,000 mAh / g of metal oxide, and between 3,000 mAh / g and 15,000 mAh / g of metal oxide. For example, intermediate and specific values ​​of capacity are also achievable, including metal oxides or those with capacities ranging from approximately 3500, 4000, 4500, 5000, 5500, 6000, 6500, or 7000 mAh / g to approximately 10000, 10500, 11000, 11500, 12000, 12500, 13000, 13500, 14000, or 14500 mAh / g. When used as a rechargeable battery, examples of capacities include, for example, rechargeable capacities between metal oxides with 1000 mAh / g and 5000 mAh / g, or intermediate ranges or specific values ​​between these, such as metal oxides with 1500, 2000, or 2500 mAh / g or those, up to about 3000, 3500, 4000, or 4500 mAh / g or those.

[0017]

[0017] An exemplary high-capacity battery cell includes a first electrode, such as a first electrode comprising a metal oxide (optionally AMO nanomaterial), a conductive material, and a binder; a second electrode, such as a second electrode comprising metallic lithium; and an electrolyte placed between the first and second electrodes. Optionally, the metal oxide comprises less than 80 weight percent of the first electrode. Exemplary electrolytes include those comprising metal salts dissolved in a solvent, solid electrolytes, and gel electrolytes. Optionally, a separator is placed between the first and second electrodes.

[0018]

[0018] Optionally, the first electrode includes a layered structure comprising a first set of layers comprising a conductive material and a second set of layers comprising a metal oxide such as an acidified metal oxide (AMO) nanomaterial. However, the use of a layered structure for the electrode is optional. In some embodiments, the first electrode does not exhibit a layered structure. Optionally, the first set of layers and the second set of layers may be provided in an alternating configuration. Optionally, the first set of layers and the second set of layers independently comprise 1 to 20 layers. Optionally, the first set of layers and the second set of layers independently have thicknesses of 1 μm to 50 μm, 2 μm to 25 μm, 3 μm to 20 μm, 4 μm to 15 μm, or 5 μm to 10 μm. Optionally, the metal oxide includes a set of second layers ranging from 5 to 90 weight percent, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 weight percent. Optionally, the conductive material and binder each independently include a set of first layers ranging from 5 to 90 weight percent, such as 25, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 weight percent.

[0019]

[0019] The first electrode optionally contains a metal oxide in amounts up to 95% by weight of the first electrode, up to 80% by weight of the first electrode, up to 70% by weight of the first electrode, 1 to 50% by weight of the first electrode, 1 to 33% by weight of the first electrode, 15 to 25% by weight of the first electrode, 55 to 70% by weight of the first electrode, 20 to 35% by weight of the first electrode, and 5 to 15% by weight of the first electrode. Specific examples of the weight percentage of metal oxide in the first electrode include 1%, 5%, 11%, 12%, 13%, 14%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 60%, 61%, 62%, 63%, 64%, 65%, and so on. Optionally, the conductive material and binder each constitute the majority of the remaining portion of the first electrode independently. For example, the conductive material and binder each constitute 10–74 weight percent of the first electrode independently. Optionally, the conductive material and binder together constitute 20–90 weight percent of the first electrode. Optionally, the AMO nanomaterial is added as a 1–10 weight percent dopant to conventional lithium-ion electrodes such as graphite or lithium cobalt oxide.

[0020]

[0020] Various materials are useful for electrodes described herein. Examples of metal oxides include, but are not limited to, lithium-containing oxides, aluminum oxide, titanium oxide, manganese oxide, iron oxide, zirconium oxide, indium oxide, tin oxide, antimony oxide, bismuth oxide, or any combination thereof. Optionally, the oxide is in the form of AMO. As described herein, metal oxides optionally include and / or surface functionalize one or more electron-withdrawing groups selected from Cl, Br, BO3, SO4, PO4, NO3, CH3COO, C2O4, C2H2O4, C6H8O7, or C6H5O7. For example, conductive materials include graphite, conductive carbon, carbon black, Ketjenblack, or one or more conductive polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composite material, polyaniline (PANI), or polypyrrole (PPY).

[0021]

[0021] In some embodiments, electrodes containing AMO nanomaterials are used together with other electrodes to form a cell. For example, the second electrode of such a cell may include graphite, metallic lithium, sodium metal, lithium cobalt oxide, lithium titanate, lithium manganese oxide, lithium nickel manganese cobalt oxide (NMC), lithium iron phosphate, lithium nickel cobalt aluminum oxide (NCA), AMO nanomaterials, or any combination thereof. In one particular embodiment, the first electrode contains an AMO of SnO2 and the second electrode contains a lithium metal.

[0022]

[0022] The electrode and electrochemical cell structures described herein can achieve high capacities in both primary (assembled) and secondary batteries. Exemplary primary capacities include between 3000 mAh / g of AMO nanomaterials and 15000 mAh / g of metal oxides. Exemplary secondary capacities include between 1000 mAh / g of metal oxides and 5000 mAh / g of metal oxides. The cells disclosed herein optionally include a life cycle of 100 to 5000 charge-discharge cycles without failure, such as 100 to 1000 charge-discharge cycles. At assembly, the disclosed cells optionally exhibit an open-circuit voltage of 2V to 4V at the time of assembly. The disclosed cells are optionally recharged to a potential difference between the first and second electrodes of 1.0V to 3.2V. Such recharging may occur after the cell has been completely discharged (i.e., to 0V) or partially discharged (i.e., to a voltage above 0V).

[0023]

[0023] In one particular embodiment, the high-capacity battery cell comprises a first electrode comprising an acidified metal oxide (AMO) nanomaterial, a conductive material, and a binder, a second electrode, and an electrolyte disposed between the first electrode and the second electrode, wherein the AMO nanomaterial comprises 5-15, 20-35, or 55-70 weight percent of the first electrode, the AMO nanomaterial comprises 0-15 weight percent iron oxide and 85-100 weight percent tin oxide, and the AMO nanomaterial comprises one or more electron-withdrawing elements The conductive material comprises and / or is surface-functionalized with one or more electron-withdrawing groups, and includes one or more conductive polymers such as graphite, conductive carbon, carbon black, Ketjenblack, and poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonic acid (PSS), PEDOT:PSS composite material, polyaniline (PANI), and polypyrrole (PPY), and the second electrode comprises or contains metallic lithium. Such high-capacity battery cells may exhibit an assembled primary capacity between 3000 mAh / g and 15000 mAh / g of AMO nanomaterial, a secondary capacity of 1000 mAh / g to 5000 mAh / g of AMO nanomaterial, a life cycle of 100 to 1000 charge-discharge cycles without failure, and an assembled open-circuit voltage of 2V to 4V. Optionally, the first electrode comprises a layered structure comprising a first set of layers containing a conductive material and a second set of layers containing AMO nanomaterial, wherein the first set of layers and the second set of layers are provided in an alternating configuration, the first set of layers comprises 1 to 20 layers and the second set of layers comprises 1 to 20 layers, the first set of layers and the second set of layers independently have thicknesses between 1 μm and 50 μm, and the AMO nanomaterial comprises 5 to 70 weight percent of the second set of layers.

[0024]

[0024] In another embodiment, a method for manufacturing electrodes and high-capacity battery cells is disclosed. Optionally, the method for manufacturing electrodes or high-capacity battery cells includes: producing a metal oxide such as an acidified metal oxide (AMO) nanomaterial; forming a slurry using the metal oxide, a conductive material, a binder, and a solvent; depositing a layer of the slurry on a current collector; and evaporating at least a portion of the solvent to form an electrode containing the AMO nanomaterial. Optionally, an electrolyte is placed between the electrode and a second electrode. Optionally, the slurry containing the conductive material, a binder, and a solvent is first deposited on the current collector, and the solvent is evaporated to form a conductive coating on the current collector before the electrode layer is formed on the conductive coating.

[0025]

[0025] Various techniques may be used to produce metal oxides. Optionally, producing a metal oxide includes forming a solution containing a metal salt, ethanol, and water; acidifying the solution by adding an acid to the solution; basicizing the solution by adding a basic aqueous solution to the solution; collecting a precipitate from the solution; washing the precipitate; and drying the precipitate.

[0026]

[0026] Optionally, fabricating the electrode further includes depositing a further conductive layer on the electrode layer, such as a conductive layer containing a second conductive material. Optionally, depositing a conductive layer includes forming a conductive slurry using a second conductive material, a second binder, and a second solvent; depositing the conductive slurry layer on the electrode layer; and evaporating at least a portion of the second solvent to form a conductive layer. Optionally, fabricating the electrode includes forming 1 to 20 additional conductive layers containing a conductive material and 1 to 20 additional electrode layers containing a metal oxide. For example, the electrode may include a layered structure including a set of first layers containing a second conductive material and a set of second layers containing a metal oxide, such as when a set of first layers and a set of second layers are provided in an alternating configuration. Exemplary layers include those independently having a thickness between 1 μm and 50 μm. Exemplary layers include layers containing 10 to 90 weight percent of a metal oxide. An exemplary layer includes a layer independently containing 5 to 85 weight percent of a conductive material and / or binder.

[0027]

[0027] Electrodes formed using the method of this embodiment may have a metal oxide content of up to 80 weight percent. Electrodes formed using the method of this embodiment may have a conductive material and / or binder content of 10 to 70 weight percent of the electrode.

[0028]

[0028] Additionally or alternatively, batteries or electrochemical cells that include electrodes such as cathodes or anodes that are acidic themselves or contain acidic species such as organic acids may also be beneficial and may contradict conventional teachings of battery technology. For example, batteries incorporating acidic electrodes or acidic species into the electrodes can improve performance and increase capacity, cycle life and life, especially when used with electrodes containing metal oxides such as AMO nanomaterials. Capacity gains of up to 100 mAh / g or more can be achieved. Battery cycle life may also be improved by using electrodes containing acidic electrodes or acidic species, such as when the battery cycle life can be extended by up to 100 cycles or more. As an example, an acidic electrode or an electrode containing acidic species may have a pH of less than 7 (but not superacidic), such as when the electrode components are suspended in water at 5% by weight (or resuspended in water after drying).

[0029]

[0029] As a further example, batteries in which electrodes are formed using a slurry may also be beneficial and may contradict conventional teachings in battery technology. As described herein, AMO nanomaterials may be formed into battery electrodes by first forming a slurry of AMO nanomaterials together with one or more binder compounds, solvents, additives (e.g., conductive or acidic additives), and / or other wet processing materials. The slurry may be deposited on a conductive material or current collector to form electrodes. Such slurries and / or solvents may optionally be acidic or contain acidic species, and may also enable improvements in the capacity, cycleability, and lifespan of the resulting battery. Optionally, all or part of the solvent may be evaporated, leaving the AMO nanomaterials, binders, additives, etc. The resulting material may optionally exhibit its own acidity (but not superacidic), such as having a pH of less than 7 when suspended in 5% by weight water (or resuspended in water after drying).

[0030]

[0030] As described above, acidic species may optionally be included as additives to any of the battery components, such as electrodes or electrolytes. Optionally, batteries containing metal oxides may include an electrolyte placed between electrodes in which the acidic species is dissolved in a solvent. Such electrolytes may also be referred to herein as acidified electrolytes. The electrolyte may optionally include one or more lithium salts dissolved in a solvent, such as LiPF6, LiAsF6, LiClO4, LiBF4, LiCF3SO3, and combinations thereof. It will be understood that the electrolyte may not only be placed in the space separating the electrodes (i.e., between electrodes), but may also penetrate or permeate the pores of the electrodes and / or optionally penetrate or permeate the pores of any material or structure placed between the electrodes, such as a separator.

[0031]

[0031] The exemplary acidic species useful for metal oxides, electrodes, and electrolytes described herein include, but are not limited to, organic acids such as carboxylic acids. Exemplary acidic species have pK values ​​of -10 to 7, -5 to 6, 1 to 6, 1.2 to 5.6, or about 4 in water. a This includes those that exhibit the following characteristics. 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, citraconic acid, acetic acid, and benzoic acid. Exemplary organic acids include dicarboxylic acids, such as those having the following formula. JPEG2026097852000002.jpg1012 Here, 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, or a substituted or unsubstituted amine. Exemplary organic acids also include those having the following formula: JPEG2026097852000003.jpg1022 Here, L is a substituted or unsubstituted C1-C20 divalent hydrocarbon, such as a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, or a substituted or unsubstituted amine. Organic acids may include organic acid anhydrides such as those having the following formula. JPEG2026097852000004.jpg1021 Here, R 1 and R 2 R is independently 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, or a substituted or unsubstituted amine. Optionally, R 1 and R 2 These can form rings. Exemplary organic acid anhydrides include the anhydrides of the above-mentioned organic acids. Specific organic acid anhydrides include, but are not limited to, glutaric acid anhydride, succinic acid anhydride, methylsuccinic acid anhydride, maleic acid anhydride, and itaconic acid anhydride.

[0032]

[0032] Useful concentrations of acidic species of either or both the electrolyte and the AMO electrode include 0% to 10% by weight, 0.01% to 10% by weight, 0.1% to 10% by weight, 1% to 5% by weight, or 3% to 5% by weight.

[0033]

[0033] Useful solvents include, for example, those used in lithium-ion battery systems, such as ethylene carbonate, butylene carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, fluoroethylene carbonate, and mixtures thereof. Other useful solvents will be understood by those skilled in the art. Optionally, if acidic species and metal salts dissolve in the solvent to form an electrolyte, the electrolyte itself will exhibit an acidic state (i.e., pH less than 7).

[0034]

[0034] Exemplary binders useful for batteries, cells, and electrodes described herein include styrene-butadiene copolymer (SBR), polyvinylidene fluoride (PVDF), carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), acrylonitrile, polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyamide-imide (PAI), and any combination thereof. Optionally, conductive polymers may be useful as binders.

[0035]

[0035] Examples of other additives useful for metal oxides and electrodes described herein include, but are not limited to, conductive additives. Examples of exemplary conductive additives include graphite, conductive carbon, carbon black, Ketjenblack, and conductive polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composites, polyaniline (PANI), and polypyrrole (PPY). Conductive additives may be present in the electrode, for example, at any suitable concentration greater than 0 and up to 35% by weight, 40% by weight, or more. Optionally, conductive additives may be present in the electrodes in the following ranges: 1% to 95% by weight, 1% to 35% by weight, 1% to 25% by weight, 5% to 40% by weight, 10% to 40% by weight, 15% to 40% by weight, 20% to 40% by weight, 25% to 40% by weight, 30% to 40% by weight, 35% to 40% by weight, 40% to 45% by weight, 40% to 50% by weight, 40% to 55% by weight, 40% to 60% by weight, 40% to 65% by weight, 40% to 70% by weight, 40% to 75% by weight, 40% to 80% by weight, 40% to 85% by weight, 40% to 90% by weight, and 40% to 95% by weight.

[0036]

[0036] Methods for manufacturing batteries are also described herein. An exemplary method for manufacturing a battery includes: manufacturing a metal oxide such as an AMO nanomaterial; forming a first electrode of the metal oxide or a first electrode comprising a metal oxide; forming an electrolyte by dissolving one or more metal salts in a solvent; and arranging the electrolyte between the first electrode and the second electrode. Another exemplary method for manufacturing a battery includes: manufacturing a metal oxide such as an AMO nanomaterial; forming a first electrode of the metal oxide and one or more metal salts or a first electrode comprising a metal oxide and one or more metal salts; and arranging the electrolyte between the first electrode and the second electrode.

[0037]

[0037] Electrolytes for use in batteries are also disclosed herein. For example, the disclosed electrolytes are useful in batteries comprising a first electrode, such as a first electrode comprising an acidified metal oxide (AMO) nanomaterial, and a second electrode. An exemplary electrolyte comprises a solvent and one or more metal salts dissolved in the solvent. Optionally, an acidic species, such as an acidic species different from one or more metal salts, is dissolved in the solvent.

[0038]

[0038] As described above, various acidic species, including organic acids and / or organic acid anhydrides, are useful in the disclosed electrolytes. Examples of organic acids include, but are not limited to, oxalic acid, acetic acid, citric acid, maleic acid, methylmalonic acid, glutaric acid, succinic acid, methylsuccinic acid, methylenesuccinic acid, citraconic acid, or any combination thereof. Examples of organic acid 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 species are described above. Useful acidic species have pK values ​​in water of -10 to 7, -5 to 6, 1 to 6, 1.2 to 5.6, or about 4. a This includes, but is not limited to, those exhibiting the following characteristics. Acidic species may optionally be present in the electrolyte at any suitable concentration, such as 0.01% to 10% by weight, 0.1% to 10% by weight, 1% to 5% by weight, or 3% to 5% by weight.

[0039]

[0039] It will be understood that lithium metal salts such as LiPF6, LiAsF6, LiClO4, LiBF4, and LiCF3SO3 may be useful components of the disclosed acidified electrolyte. Exemplary solvents include, but are not limited to, ethylene carbonate, butylene carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, fluoroethylene carbonate, and mixtures thereof. Exemplary solvents may be useful in metal-ion batteries such as lithium-ion batteries.

[0040]

[0040] The above, along with other configurations and embodiments, will become more apparent with reference to the following description, claims, and accompanying drawings. For example, further details of the disclosed battery and method for manufacturing the battery are described in the following detailed description. [Brief explanation of the drawing]

[0041] [Figure 1] This is a simplified cross-sectional view of an exemplary lithium-ion battery cell. [Figure 2] This is another simplified cross-sectional view of a lithium-ion battery cell, where the electrolyte is substantially contained within the separator. [Figure 3] This is a schematic diagram of a lithium-ion battery containing multiple cells. [Figure 4] This document provides a plot showing the difference between a commercially available non-AMO tin cyclic voltammogram and a cyclic voltammogram of AMO tin prepared by the method disclosed herein, when cycled with Li. [Figure 5] This provides a plot showing that the total reflectance of AMO tin oxide differs from that of commercially available non-AMO tin oxide. [Figure 6]This specification provides X-ray photoelectron spectroscopy (XPS) data demonstrating intrinsically occurring surface functionalization from the synthesis methods disclosed herein. The numerical values ​​shown represent the percentage of atomic concentration. The rightmost column shows the corresponding pH of the synthesized nanoparticles when dispersed at 5% by weight in an aqueous solution. [Figure 7] This provides electron microscope images showing morphological differences between AMO nanoparticles synthesized under identical conditions, except for the use of different groups for functionalization. [Figure 8] This provides electron microscope images showing differences in the morphology of AMO nanoparticles synthesized under identical conditions except for having two different total reaction times. [Figure 9] This provides representative half-cell data illustrating the differences in behavior between spherical and elongated (needle-shaped or rod-shaped) AMOs during lithium cycling. [Figure 10] We provide X-ray photoelectron spectroscopy analysis of the surface of AMO nanoparticles synthesized using both strong (phosphorus-containing) and weak (acetic acid) electron-withdrawing groups, showing that the atomic concentration of phosphorus is higher than the atomic concentration of bonds associated with the acetate group. [Figure 11A] This provides data showing the visible light activity reduction data for different AMOs. [Figure 11B] This provides data showing UV light activity reduction data for different AMOs. [Figure 12] This provides data comparing two AMOs, one with a higher capacity for primary (single-use) battery applications and the other with a higher cycle capacity for secondary (rechargeable) battery applications. [Figure 13] We provide charge and discharge capacity data and Coulomb efficiency data, demonstrating that AMO can improve battery performance without degradation of battery components or gas generation. [Figure 14] This document presents volume and cycling data for AMO in standard, acidified, and basified electrolyte systems. [Figure 15] The volume and cycling data for AMO, and the volume and cycling data for the same AMO after acidification has been removed by solvent washing, are shown. [Figure 16] This provides data showing temperature and voltage as a function of time for battery cells subjected to a nail-piercing test. [Figure 17A] This provides data showing temperature and voltage as a function of time for battery cells subjected to overcharge testing. [Figure 17B] Figure 18A provides an enlarged view of the first approximately 1400 seconds of the data shown. [Figure 18] An illustrative schematic diagram of a battery cathode is provided. [Figure 19] This provides data showing battery capacity as a function of the number of charge-discharge cycles obtained during battery cycling. [Figure 20] This provides data showing the cell voltage as a function of time for numerous charge-discharge cycles obtained during cell cycling. [Figure 21] This provides photographs of the components of a pouch-type cell after it has been disassembled following 103 charge-discharge cycles. [Figure 22] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 23] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 24] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 25] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 26]For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 27] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 28] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 29] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 30] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 31] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 32] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 33] The data provided includes electron microscope images of the synthetic material, and for a battery cell containing electrodes made of the synthetic material, plots of measured capacity versus cycle count, and plots of voltage as a function of time during cycling. [Figure 34]The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 35] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 36] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 37] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 38] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 39] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 40] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 41] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 42]For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 43] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 44] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 45] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 46] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 47] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 48] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 49] For battery cells containing electrodes made of AMO material, the data includes plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling. [Figure 50]The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 51] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Figure 52] The report provides electron microscope images of AMO material, and data including plots of measured capacity versus cycle count, as well as plots of voltage as a function of time during cycling, for battery cells containing electrodes made of AMO material. [Modes for carrying out the invention]

[0042]

[0095] definition For the purposes of this disclosure, the following terms have the following meanings:

[0043]

[0096] Acidic oxides are a term commonly used in scientific literature to refer to two-component compounds of oxygen and nonmetallic elements. One example is carbon dioxide, CO2. Oxides of some metalloids (such as Si, Te, and Po) also possess weakly acidic properties in their pure molecular state.

[0044]

[0097] The term used herein to denote a binary compound of oxygen and a metal element synthesized or modified to have an acidity higher than that of the natural mineral state of the acidified metal oxide ("AMO"), AMO nanomaterial, or AMO material, and also to have a Hammett function H0 greater than -12 (i.e., not superacidic). It will be understood that AMO can have a surface pH of less than 7 when suspended in 5 wt% water (or when redispersed in water after drying). Optionally, AMO can exhibit a surface pH of less than 6, less than 5, less than 4, or less than 3. The average particle size of the AMO disclosed herein is also smaller than the average particle size of the natural mineral state. For example, AMO can include nanomaterials such as particles having at least one dimension less than 100 nm, less than 20 nm, less than 10 nm, or between 1 and 100 nm. Naturally occurring mineralogical forms are not included within the scope of the AMO materials of the present invention. However, synthetic metal oxides that are more acidic than their most abundant naturally occurring mineralogical form (of equivalent stoichiometry), but not superacidic, and that are within the scope of the present disclosure and meet certain other conditions discussed in the present disclosure can be said to be AMO materials.

[0045]

[0098] A term commonly used in the scientific literature to refer to a compound having a pH of less than 7 in an acidic aqueous solution.

[0046]

[0099] Electron-withdrawing group ("EWG") - An atom or molecular group that draws electron density towards itself. The strength of an EWG is based on its known behavior in chemical reactions. For example, halogens are known to be strong EWGs. Organic acid groups such as acetic acid are known to be weakly electron-withdrawing.

[0047]

[0100] Hammett function - An additional means of quantifying the acidity of highly concentrated acid solutions and superacids. Acidity is defined by the equation: H0 = p K BH+ +log([B] / [BH +]). On this scale, the H0 value of 18.4 moles of pure H2SO4 is -12. The value H0=-12 for pure sulfuric acid should not be interpreted as pH=-12, but rather as the ability of the acid species present to protonate a weak base, when measured by their ability to do so. 12 H3O at a hypothetical (ideal) concentration of mol / L + This means that it possesses a protonation capacity equivalent to [a certain value]. The Hammett acidity function avoids water in its equation. It is used herein to provide a quantitative means for distinguishing AMO materials from superacids. The Hammett function can be correlated with colorimetric indicator tests and temperature-programmed desorption results. The Hammett function is sometimes referred to herein as the Hammett number.

[0048]

[0101] Metal oxides are a term commonly used in scientific literature to refer to binary compounds of a metal element and oxygen. Depending on their position in the periodic table, metal oxides range from weakly basic to amphoteric (exhibiting both acidic and basic properties) in their pure molecular state. Weakly basic metal oxides include those of lithium, sodium, magnesium, potassium, calcium, rubidium, strontium, indium, cesium, barium, and tellurium. Amphoteric oxides include those of beryllium, aluminum, gallium, germanium, astatine, tin, antimony, lead, and bismuth. Optionally, these and other metal oxides may be useful as AMO materials.

[0049]

[0102] Metallic lithium is a term referring to lithium in a neutral atomic state (i.e., a non-ionic state). The term metallic lithium is intended to distinguish it from other forms of lithium, including lithium ions and lithium compounds. The term metallic lithium may also refer to neutral atomic lithium present in mixtures containing lithium atoms, such as mixtures of lithium with other elements, compounds, or substances. The term metallic lithium may also refer to neutral atomic lithium present in lithium alloys, such as metal mixtures containing lithium with one or more other metals. The term metallic lithium may also refer to neutral atomic lithium present in composite structures containing lithium with one or more other materials. Electrodes containing metallic lithium may also contain other materials in addition to lithium, but it will be understood that metallic lithium can correspond to the active material of such electrodes. In some cases, the anode of an electrochemical cell contains metallic lithium.

[0050]

[0103] Monodisperse particles are characterized by uniformly sized particles that are substantially separated from one another and do not aggregate as larger particles. Monodisperse particles can have a uniform size distribution, such as when at least 90% of the particle size distribution is within 5% of the median particle size.

[0051]

[0104] pH - A functional numerical scale commonly used in scientific literature to determine the acidity or alkalinity of an aqueous solution. This is the hydronium ion [H3O + It is the negative logarithm of the concentration of [the substance]. Where used herein, pH may be used to describe the relative acidity of nanoparticles suspended in an aqueous solution.

[0052]

[0105] Surface functionalization - the attachment of small atoms or molecular groups to the surface of a material. In embodiments, an AMO material can be surface functionalized by covalently bonding EWG to the surface of the AMO material.

[0053]

[0106] Superacids - Substances that are more acidic than 100% H2SO4 and have a Hammett function H0 less than -12.

[0054]

[0107] This specification describes high-capacity electrochemical cells and cell components (e.g., electrodes) for such cells. The disclosed electrochemical cells and electrodes contain acidified metal oxide ("AMO") nanomaterials and exhibit high capacity. In embodiments, the AMO nanomaterial is supplied in a relatively low loading (weight percentage) within the electrode, such as less than 30% by weight, with the majority of the remainder of the electrode consisting of conductive material and binder. Even with such low loading, capacities greater than 10,000 mAh / g of AMO nanomaterial have been observed. The electrodes may be supplied in a layered or non-layered configuration. Examples of layered configurations include separate layers containing the AMO nanomaterial and low-loaded or non-AMO-containing layers. However, layering of the electrodes is entirely optional, and high capacity is observed in both layered and non-layered electrodes.

[0055]

[0108] Referring here to Figure 1, a lithium battery cell 100 is shown in a simplified cross-sectional view. The cell 100 may include a casing or container 102. In some embodiments, the casing 102 is a polymer or alloy. The casing 102 chemically and electrically isolates the contents of the cell 100 from adjacent cells, from contamination, and from damaging or being damaged by other components of the device in which the cell 100 is installed. A complete battery may include multiple cells arranged in series and / or parallel configurations, but may optionally include only a single cell. The battery may have further casing or fixing mechanisms that bind multiple cells together, as is known in the art.

[0056]

[0109] Cell 100 provides a cathode 104 and an anode 106. The contents of cell 100 undergo a chemical reaction when a conduction path is provided between the cathode 104 and the anode 106, such as an element 115 located outside cell 100. As a result of the chemical reaction, electrons are supplied at the anode 106 and flow through the element 115 (sometimes called a load) to the cathode 104 via a circuit located outside the cell. At a basic level, during the discharge of cell 100, the material constituting the anode 106 is oxidized, supplying electrons to flow through the circuit. The material constituting the cathode 104 decreases, acting as an acceptor for the electrons emitted by the anode 106.

[0057]

[0110] Within cell 100, during discharge, metal cations move from anode 106 to cathode 104 through electrolyte 108. In the case of lithium-based batteries, the metal cations become lithium cations (Li + ) may be a liquid electrolyte. Electrolyte 108 may be a liquid electrolyte such as a lithium salt in an organic solvent (e.g., LiClO4 in ethylene carbonate). Other lithium-based electrolyte / solvent combinations may be used as are known in the art. In some cases, electrolyte 108 may be a solid electrolyte such as a lithium salt in polyethylene oxide. Optionally, the electrolyte may include a polymer electrolyte. Examples of electrolytes include those described in U.S. Patent Application Publication 2017 / 0069931, which are incorporated herein by reference.

[0058]

[0111] A separator 110 can be used to prevent contact between electrodes 104 and 106. The separator 110 may be a porous layer of a non-conductive material that allows lithium ions and electrolyte 108 to pass through, but prevents internal short circuits in the cell 100. As is known in the art, the separator 110 may include glass fibers or possibly a polymer having a semi-crystalline structure. Additional components such as current collectors may also be included in the cell 100, but are not shown in Figure 1.

[0059]

[0112] The anode 104, cathode 106, electrolyte 108, and separator 110 come together to form a completed 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 ions (Li) between electrodes 104 and 106 to pass through the electrolyte 108. + This allows for the flow of ) to occur. As is known in the art, separators can be constructed to melt and close their internal pore structure in order to shut down the cell when exposed to excessive heat or a runaway exothermic reaction.

[0060]

[0113] Most lithium-based cells are so-called rechargeable batteries. They can be discharged and recharged many times until the chemical or structural integrity of the cell falls below acceptable limits. The cells and batteries relating to this disclosure are considered to be both primary batteries (e.g., single-use) and rechargeable batteries.

[0061]

[0114] In the case of cell 100, which is a secondary battery (or part of a secondary battery), it should be understood that cell 100 can be recharged on its own or as a component of a complete system in which multiple cells are recharged simultaneously (possibly in the same parallel or series circuit).

[0062]

[0115] A reverse voltage is applied to cell 100 for charging. It should be understood that various schemes can be used to effectively recharge the lithium battery. Constant current, variable current, constant voltage, variable voltage, partial duty cycle, etc., can be used. This disclosure is not intended to be limited to any particular charging method unless otherwise stated in the claims. During charging of cell 100, element 115 represents a voltage source applied between cathode 104 and anode 106, supplying electrons from cathode 105 to anode 106 and enabling a chemical reaction to occur. Lithium ions are transferred from cathode 104 to anode 106 via electrolyte 108 and separator 110.

[0063]

[0116] For example, cathode 104 or anode 106 may independently include the AMO material disclosed herein. When the AMO material is used as the cathode, the anode may correspond to a lithium-inserted material such as lithium metal or graphite. Optionally, the electrolyte 108 may include an acidic species, such as a lithium salt dissolved in an organic solvent. In addition to, or instead of, the use of an acidic species in the electrolyte 108, the electrode (i.e., cathode 104 or anode 106) may optionally include the AMO and an acidic species. Oxalic acid is an example of an acidic species.

[0064]

[0117] While we do not wish to be bound by theory, the presence of acidic species in cathode 104 or anode 106 and / or electrolyte 108 is thought to improve the surface affinity of the AMO material to lithium ions, resulting in an improved ability to absorb lithium ions during discharge, and thus improving overall capacity compared to similar cells lacking acidic species or having basic electrodes or electrolytes (i.e., containing basic species). Alternatively or additionally, the presence of acidic species may enable an additional active site for lithium uptake at cathode 104.

[0065]

[0118] It should be understood that Figure 1 is not to scale. As shown in Figure 2, in most applications, the separator 110 occupies most or all of the space between electrodes 104 and 106 and is in contact with electrodes 104 and 106. In such cases, the electrolyte 108 is contained within the separator 110 (but also penetrates the pores or surface of the anode or cathode). Figure 2 is also not necessarily to scale. The actual shape of the cell can range from a relatively thin, flat pouch to a canister-type structure, a button cell, and others. Cell construction techniques such as winding or bobbin or pin-type assemblies can be used.

[0066]

[0119] Current collectors and other components (not shown) known in the art may also be relied upon to form the cell 100 into a commercially viable package. While the overall shape or geometric shape may vary, a cell or battery typically includes electrodes 104, 106 that are separated rather than in contact, in some place or cross-section, with an electrolyte 108 and possibly a separator 110 between them. A cell can also be constructed so that there are multiple layers of anodes and cathodes. A cell can be configured so that two cathodes are opposite a single anode, or vice versa.

[0067]

[0120] A functional or operable battery intended for a specific purpose may include multiple cells arranged according to the needs of a particular application. An example of such a battery is schematically shown in Figure 3. Here, battery 300 includes four lithium cells 100 arranged in series to increase the voltage. The capacity can be increased at this voltage by providing an additional stack of four cells 100 in parallel with the illustrated stack. Different voltages can be achieved by changing the number of cells 100 arranged in series.

[0068]

[0121] The positive electrode 306 may be accessible from 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 may vary depending on the application. Various binders, adhesives, tapes, and / or other fastening mechanisms (not shown) can be used within the battery casing 302 to stabilize the other components. Batteries based on lithium technology (in the case of secondary batteries) are typically operable, rechargeable, and storable in either direction. As described above, cell 100 can take on a variety of different geometric shapes. Therefore, Figure 3 is not intended to represent a specific physical shape factor of battery 300.

[0069]

[0122] The battery 300 may also include various auxiliary circuits 308 for inserting the positive electrode 306 and lithium cell 100 into the casing 302 of the battery 300. In other embodiments, the regulating circuit inserts a negative electrode 304 and lithium cell 100 instead of, or in addition to, inserting the positive electrode 306 and lithium cell 100. The auxiliary circuits 308 may include short-circuit protection, overcharge protection, overheating shutdown, and other circuits known in the art for protecting the battery 300, cell 100, and / or loads attached to the battery 300.

[0070]

[0123] The composition of the materials selected for cathode 104, anode 106, and electrolyte is critical to the performance of cell 100 and the battery in which it forms part. In the context of this disclosure, various examples of AMOs and methods for manufacturing them are provided in this regard. These AMOs are suitable for use in forming half-cells, cells, and anodes or cathodes of batteries. The AMOs of this disclosure are otherwise compatible with known lithium cell technologies, including existing anode and cathode compositions, electrolyte formulations, and separator compositions.

[0071]

[0124] In the context of this disclosure, various examples of AMOs, their manufacturing methods, and uses are provided. These AMOs are suitable for use in forming the cathodes or anodes of half-cells, cells, and batteries. The disclosed AMOs are otherwise compatible with conventional lithium battery technologies, including existing anode compositions, cathode compositions, electrolyte formulations, and separator compositions. It will be understood that the material of the anode 106 selected for the cell or battery according to this disclosure may have a lower electronegativity than the cathode material in order to adequately complement the cathode material. In a particular embodiment, the disclosed AMO is useful as the cathode of a cell having a lithium metal anode.

[0072]

[0125] In various embodiments of this disclosure, the cathode 104 includes an AMO material having an acidic but not superacidic surface. This is the opposite of previously known materials used as cathodes, such as lithium cobalt or lithium manganese materials. The AMO materials of this disclosure and methods for producing them are described below. In other embodiments, the anode 106 includes an AMO material of this disclosure having an acidic but not superacidic surface.

[0073]

[0126] Ideally, the surface of a metal oxide is an arrangement of metal and oxygen centers ordered according to the crystalline structure of the oxide. In reality, the array is imperfect and susceptible to vacancies, strain, and surface adhesion. Nevertheless, exposed metal centers are cationic (positively charged) and can accept electrons, thus functioning by definition as Lewis acid sites. Oxygen centers are anionic (negatively charged) and function as Lewis base sites that donate electrons. This allows metal oxide surfaces to behave amphoteric.

[0074]

[0127] Under normal atmospheric conditions, the presence of water vapor will result in molecular adsorption (hydration) or dissociative adsorption (hydroxylation) on the metal oxide surface. - and H + Both species can be adsorbed onto oxide surfaces. The negatively charged hydroxyl species binds to the metal, cation (Lewis acid, electron-accepting) center, and H + It will attack the oxygen and anion (Lewis base, electron-donating) centers. Due to the adsorption of both, the same functional group (hydroxyl) is present on the metal oxide surface.

[0075]

[0128] These surface hydroxyl groups can function as either a Brunstead acid or a Brunstead base, as the group can either donate or accept a proton. The tendency of individual hydroxyl groups to be proton donors or acceptors is influenced by the coordination of the metal cation or oxygen anion to which they are bound. Defects on the metal oxide surface, such as oxygen vacancies, or coordination between surface groups and other chemical species, mean that not all cations and anions are equally coordinated. The number and strength of acid-base sites vary. When widely "summed up" across the entire surface of the oxide, this can give the surface an overall acidic or basic character.

[0076]

[0129] The amount and intensity of Lewis acid and base sites (from exposed metal cations and oxygen anions, respectively) and Brønsted acid and base sites (from surface hydroxyl groups) add a wide range of utility and functionality to metal oxides and their uses in both chemical reactions and device applications. These sites significantly contribute to the chemical reactivity of metal oxides. They function as fixed sites to which other chemical groups, and even additional metal oxides, can adhere. They can also influence surface charge, hydrophilicity, and biocompatibility.

[0077]

[0130] One way to alter the surface of a metal oxide is by bonding small chemical groups or electron-withdrawing groups ("EWGs") in a process known as surface functionalization. EWGs induce polarization of hydroxide bonds, promoting the dissociation of hydrogen. For example, stronger EWGs should lead to more polarized bonds, and therefore more acidic protons. It will be understood that useful EWGs may include groups other than hydroxides. The acidity of a Lewis site can be increased by inducing polarization that promotes electron donation to the site. When compounds thus created are placed in water, the acidic protons dissociate, lowering the aqueous pH measurement.

[0078]

[0131] While somewhat less accurate when using solid acid / base systems instead of liquid systems, the acidity of metal oxides dispersed in aqueous solutions can be evaluated using conventional pH measurement methods, including titration, pH paper, and pH probes. These measurements can be complemented by techniques including, but not limited to, colorimetric indicators, infrared spectroscopy, and temperature-programmed desorption data to establish the acidified properties of the metal oxide surface. Surface groups can be examined by standard analytical techniques, including, but not limited to, X-ray photoelectron spectroscopy.

[0079]

[0132] Surface functionalization, including but not limited to exposing a metal oxide to an acidic solution or vapor containing the desired functional group, can be achieved after synthesis. It can also be achieved by a solid-state method, in which the metal oxide is mixed with and / or pulverized with a solid containing the desired functional group. However, all of these methods require one or more additional surface functionalization steps necessary for synthesizing the metal oxide itself.

[0080]

[0133] The synthesis and surface functionalization of AMO materials can be achieved by a "single-pot" hydrothermal synthesis method, or by its equivalent, where the surface of the metal oxide is functionalized when the metal oxide is synthesized from a suitable precursor. A precursor salt containing EWG is solubilized, and the resulting solution is acidified using an acid containing a second EWG. This acidified solution is then basicized, and the basicized solution is heated and washed. A drying step produces a solid AMO material.

[0081]

[0134] As an example, tin oxide in the exemplary AMO form was synthesized and simultaneously surface-functionalized using the following single-pot method: 1. First, dissolve 7 grams (7 g) of tin(II) chloride dihydrate (SnCl22H2O) in a solution of 35 mL of anhydrous ethanol and 77 mL of distilled water. 2. Stir the resulting solution for 30 minutes. Add 3.7 mL of 1.2 M HCl dropwise to acidify the solution, and stir the resulting solution for 15 minutes. The solution is made basic by adding a 4.1 M aqueous base, and the solution is added dropwise until its pH reaches approximately 8.5. 5. Then, place the resulting opaque white suspension in a warm water bath (approximately 60-90°C) for at least 2 hours while stirring. 6. Then, wash the suspension with distilled water and anhydrous ethanol. 7. The washed suspension is dried in air at 100°C for 1 hour, and then annealed in air at 200°C for 4 hours.

[0082]

[0135] This method yields an AMO of chlorine-functioned tin, whose pH is approximately 2 when resuspended in a 5% by weight aqueous solution at room temperature and measured. By definition, its Hammett function H0 is greater than -12. While open systems such as flasks are described here, closed systems such as autoclaves can also be used.

[0083]

[0136] Many AMOs have been synthesized using the single-pot method disclosed above. Table 1 below shows the precursors and acids used, where Ac represents the acetate group of the chemical formula C2H3O2 or CH3COO. In some cases, dopants are also used. [Table 1]

[0084]

[0137] In some embodiments, the electron-withdrawing group has a carbon chain length of 6 or less and / or an atomic mass of 200 AMU or less. In some embodiments, the electron-withdrawing group has a carbon chain length of 8 or less or 10 or less and / or an atomic mass of 500 AMU or less.

[0085]

[0138] It will be understood that the parameters of this method can be modified. 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 speed and time, number and type of washing steps, drying and calcination time and temperature, and gas exposure during drying and calcination. Modifications can be made individually or in combination, optionally using design of experiments. Furthermore, other metal oxide synthesis methods (e.g., spray pyrolysis, vapor deposition, electrodeposition, solid-state methods, and hydrothermal or sorbo-thermal treatments) may help achieve the same or similar results as the method disclosed herein.

[0086]

[0139] Various annealing conditions are useful for preparing AMO nanomaterials. Examples of annealing temperatures include those below 300°C, such as 100°C to 300°C. Examples of annealing times include those ranging from about 1 hour to about 8 hours or more. Annealing can be carried out under various atmospheric conditions. For example, annealing can be carried out in air at atmospheric pressure. Annealing can be carried out under high pressure (higher than atmospheric pressure) or low pressure (lower than atmospheric pressure or in a vacuum). Alternatively, annealing can be carried out in a controlled atmosphere, such as under an inert gas (e.g., nitrogen, helium, or argon) or in the presence of an oxidizing gas (e.g., oxygen or water).

[0087]

[0140] Various drying conditions are useful for preparing AMO nanomaterials. Examples of drying temperatures can range from 50°C to 150°C. Examples of drying times can range from approximately 0.5 hours to approximately 8 hours or more. Drying can be carried out under various atmospheric conditions. For example, drying can be carried out in air at atmospheric pressure. Drying can be carried out under high pressure (higher than atmospheric pressure) or reduced pressure (lower than atmospheric pressure or in a vacuum). Alternatively, drying can be carried out in a controlled atmosphere, such as under an inert gas (e.g., nitrogen, helium, or argon) or in the presence of an oxidizing gas (e.g., oxygen or water).

[0088]

[0141] The performance characteristics of AMO nanomaterials differ from those of unacidified metal oxide nanoparticles. For example, Figure 4 shows the difference in cyclic voltammograms (CVs) of AMO tin prepared by the single-pot method compared to commercially available non-AMO tin when cycled against lithium metal. For instance, surface-functionalized AMO materials exhibit superior reversibility compared to non-AMO materials. The presence of distinct peaks in the CV of AMO materials may indicate that multiple electron transfer steps occur during charging and discharging. For example, high-voltage peaks may indicate direct oxidation / reduction of the AMO material, while low-voltage peaks may be due to changes in the material structure of the AMO material (i.e., alloying).

[0089]

[0142] As another example, Figure 5 shows that the total reflectance of AMO tin oxide differs from that of commercially available non-AMO tin oxide. The data indicate that AMO has a lower band gap and therefore possesses more desirable properties as a component of a photovoltaic system, in addition to its use as an anode or cathode according to this disclosure.

[0090]

[0143] AMO material can optionally be expressed by the following formula: M m O x / G Here, M m O x is a metal oxide, m is between 1 and 5, x is between 1 and 21, G is at least one EWG that is not a hydroxide, and " / " distinguishes between metal oxides and EWGs, indicating that there is no fixed mathematical relationship or ratio between the two. G may represent a single type of EWG or multiple types of EWGs.

[0091]

[0144] An example of AMO is acidified 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 ) Preferred electron-withdrawing groups ("EWG") are Cl, Br, BO3, SO4, PO4, NO3, and CH3COO. Regardless of the specific metal or EWG, according to this disclosure, the AMO material is acidic but not superacidic, has a pH less than 7 when suspended in a 5 wt% aqueous solution, and has a Hammett function H0 greater than -12, at least on its surface.

[0092]

[0145] The AMO material structure can be crystalline or amorphous (or a combination thereof) and can be used alone or as a composite material in combination with non-acidified metal oxides, other additives, binders, or conductive additives known in the art. In other words, electrodes prepared to utilize the AMO of this disclosure may or may not contain other materials. In one embodiment, the AMO can be laminated on a conductive material to form a cathode 104. In some embodiments, the AMO material is added to a conductive auxiliary material such as graphite, carbon black, or conductive carbon (or equivalents thereof) in an amount ranging from 5% to 90% by weight, while the conductive auxiliary material and / or binder material may be present in an amount ranging from 10% to 95% by weight. Optionally, the AMO is added in amounts of 10%, 33%, 50%, or 80% by weight.

[0093]

[0146] To maximize the total surface area and amount of active sites for the reaction of the available active material, AMOs may exist in the form of nanoparticles (i.e., less than 1 micron in size) and be substantially monodisperse. Optionally, the nanoparticle size may be less than 100 nm, and even smaller, such as less than 20 nm or 10 nm. It will be understood that for a particular AMO, nanoparticle sizes in the range of 1 nm to 100 nm or 1000 nm may be useful.

[0094]

[0147] Mixed metal AMOs, which contain one or two oxides in addition to another metal or metal oxide, are useful for forming the anodes and cathodes of half-cells, electrochemical cells, and batteries. These mixed metal AMOs are represented by the following formula: M m N n O x / G and M m N n R r O x / G Here, M is a metal, m is between 1 and 5, N is a metal, n is greater than 0 and less than or equal to 5, R is a metal, r is greater than 0 and less than or equal to 5, O is total oxygen related to all metals, x is between 1 and 21, " / " distinguishes metal oxides from EWGs and does not indicate a fixed mathematical relationship or ratio between the two, and G is at least one EWG that is not a hydroxide. G may represent a single type of EWG or multiple types of EWGs.

[0095]

[0148] Several prior art mixed metal oxide systems, most notably zeolites, exhibit strong acidity, if not in each of the unified oxides. Preferred embodiments of the mixed metal AMOs of this disclosure differ from those systems in that any embodiment must include at least one AMO that is acidic (but not superacidic) in the form of simple MmOx / G. Examples of mixed metal and metal oxide systems include Sn x Fe c O y+d and Sn x Ti a O y+b This includes y+d and y+b, where y+d and y+b are integers or non-integer values.

[0096]

[0149] Optionally, mixed metal AMO materials can be produced by a single-pot method with one modification (the synthesis starts with two metal precursor salts instead of one, in any proportion). For example, step 1 of the single-pot method described above can be modified as follows: First, dissolve 3.8 g of tin(II) chloride dihydrate (SnCl22H2O) and 0.2 g of lithium chloride (LiCl) in a solution of 20 mL of anhydrous ethanol and 44 mL of distilled water.

[0097]

[0150] The three metal precursor salts shown in Table 1 can be optionally used in any proportion. The metal precursor salts may have the same or different anionic groups depending on the desired product. The metal precursor salts may be introduced at different points in the synthesis. The metal precursor salts may be introduced as solids or into a solvent. In some embodiments, the first metal precursor salt can be used for the primary structure (i.e., a larger proportion) of the resulting AMO, and the second (and optionally third) metal precursor salts can be added as dopants or trace components to the resulting AMO.

[0098]

[0151] Experiments using the single-pot method yielded seven useful results. Firstly, in all cases, both surface functionalization and acidity occur intrinsically, rather than being generated after synthesis (see Figure 6). Unlike prior art surface functionalization methods, the single-pot method does not require one or more additional steps for surface functionalization beyond what is necessary for the synthesis of the metal oxide itself, and does not utilize hydroxyl-containing organic compounds or hydrogen peroxide.

[0099]

[0152] Secondly, this method can be broadly generalized across a wide range of metal oxides and EWGs. Using the method of this disclosure, metal oxides of iron, tin, antimony, bismuth, titanium, zirconium, manganese, and indium have been synthesized and simultaneously surface-functionalized with chlorides, sulfates, acetates, nitrates, phosphates, citrates, oxalates, borates, and bromides. Mixed metal AMOs of tin and iron, tin and manganese, tin, 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 weaker EWGs than halogens or SO4, still producing acidic surfaces but not superacidic surfaces. For example, this method has also been used in the synthesis of AMOs surface-functionalized with acetic acid (CH3COO), oxalic acid (C2O4), and citric acid (C6H5O7). Various examples are described below.

[0100]

[0153] Thirdly, there is a synergistic relationship between the EWG and other properties of the nanoparticles (e.g., size, morphology (e.g., plate-like, spherical, needle-like, or rod-like), oxidation state, and crystallinity (amorphous, crystalline, or a mixture thereof)). For example, as shown in Figure 7, which provides electron micrograph images of two AMOs produced using different EWGs, morphological differences can occur between AMO nanoparticles synthesized under identical conditions, except for the use of different EWGs for surface functionalization. Surface functionalization can act to "fix" the dimensions of the nanoparticles, potentially halting their growth. This fixation may occur in only one dimension of the nanoparticle or in multiple dimensions, depending on the exact synthesis conditions.

[0101]

[0154] Fourth, the properties of AMOs are highly sensitive to synthesis conditions and procedures. For example, differences in the morphology and performance of AMO nanoparticles can occur when synthesized under identical conditions except for having two different total reaction times. For instance, Figure 8 provides electron microscope images of two AMOs reacted with different total reaction times, and Figure 9 provides a volume (mAh / g) versus cycle count plot showing a comparison of the cycleability of two AMOs reacted with different total reaction times, exhibiting different morphologies. Experimental design can be used to determine the best or optimal synthesis conditions and procedures to produce the desired properties or set of properties.

[0102]

[0155] Fifth, both the anions present in the precursor salt and the anions present in the acid contribute to the surface functionalization of the AMO. In one embodiment, a tin chloride precursor and hydrochloric acid are used to synthesize a tin AMO. The performance of these particles differs from embodiments in which a tin chloride precursor and sulfuric acid are used, or in embodiments in which a tin sulfate precursor and hydrochloric acid are used. In some embodiments, it may be advantageous to match the precursor anion with the acid anion.

[0103]

[0156] Sixth, when using a weak EWG precursor and a strong EWG acid, or vice versa, strongly abstracting anions will dominate surface functionalization. This opens up broader synthetic possibilities, allowing functionalization with ions not readily available in both the precursor salt and acid. It is also possible to mix functionalization with both strong and weak EWG. In one example, a tin acetate precursor and phosphoric acid are used to synthesize a tin AMO. Surface X-ray photoelectron spectroscopy shows a higher phosphorus atomic concentration than the bonds associated with the acetate group (see Figure 10).

[0104]

[0157] Seventh, while the disclosed method is a general procedure for the synthesis of AMOs, the synthesis procedure and conditions may be adjusted to yield sizes, morphologies, oxidation states, and crystalline states that may be desirable for different applications. For example, in catalytic applications, AMO materials that are more active in visible light or more active in ultraviolet light may be desired. Figure 11A shows the visible light exposure degradation times of methylene blue when exposed to two different AMO materials. Figure 11B shows the ultraviolet exposure degradation times of methylene blue when exposed to four different AMO materials.

[0105]

[0158] In another example, AMO materials can be used as battery electrodes. For primary (single-use) battery applications, an AMO with properties leading to maximum capacity may be desired, while for secondary (rechargeable) battery applications, the same AMO may be desired for properties that provide maximum cycle life. Figure 12 compares the cycle life of two different batteries composed of AMO materials, including chlorine-containing AMO and sulfur-containing AMO. AMO materials can improve battery performance without degradation of battery components or gas generation (see Figure 13). This is the opposite of what prior art teaches.

[0106]

[0159] Figure 13 shows the charge-discharge cycleability of a battery constructed with AMO nanomaterial electrodes versus lithium metal cells, demonstrating cycleability of up to 900 charge-discharge cycles while still maintaining effective capacity and exceptional Coulomb efficiency. Such long cycleability is exceptional, especially for lithium metal reference electrodes. Lithium metal is known to grow dendrites even at low cycle counts, which can lead to larger battery cells and potentially dangerous and catastrophic failures.

[0107]

[0160] According to this disclosure, in a complete cell, the anode 106 containing the disclosed AMO may be used together with a cathode 104 containing a known electrolyte 108 and a known material such as lithium cobalt oxide (LiCoO2). Similarly, the materials constituting the separator 110 can be derived from those currently known in the art.

[0108]

[0161] In a complete cell, the cathode 104 containing the disclosed AMO may be used with a known electrolyte 108 and anode 106, which may contain a known material such as carbon on copper foil that exhibits a lower electronegativity than the AMO of this disclosure. Other anode materials, such as lithium metal, sodium metal, magnesium metal, or other composite materials containing one or more of these metals, are also useful. In some embodiments, the anode 106 may consist of lithium or may consist of lithium in nature. Similarly, the materials comprising the separator 110 and electrolyte 108 may be derived from those currently known in the art as described above.

[0109]

[0162] To maximize the capacity to hold lithium ions for powering cell 100, various layering and other strengthening techniques known in the art can be employed. While a battery based on the AMO cathode 104 according to this disclosure can be developed as a secondary (e.g., rechargeable) battery, it should also be understood that it can function as a primary battery. While the AMO anode of this disclosure is useful in reversible battery chemistry, a cell or battery constructed as described herein can be fully developed as a primary cell or battery.

[0110]

[0163] In some contexts, the term "formation" is used to refer to the initial charging or discharging of a battery performed at a manufacturing facility before it becomes usable. The formation process can generally be very slow and may require multiple charge-discharge cycles aimed at converting the as-manufactured active material into a form more suitable for cell cycling. These conversions can incorporate changes in the structure, morphology, crystallinity, and / or stoichiometry of the active material.

[0111]

[0164] In contrast, cells and batteries constructed according to this disclosure do not require initial formation in some embodiments and are therefore ready for use as primary cells or batteries at the time of assembly. In other cases, limited or rapid formation may be employed. Furthermore, since safety issues frequently occur during battery cycling, some of the safety issues that may be inherent in the chemistry of lithium batteries are mitigated by deploying the cells and batteries of this disclosure as primary batteries not intended to be recharged. However, after the initial primary discharge, the cells and batteries disclosed herein are optionally suitable for use as secondary battery systems capable of undergoing many charge-discharge cycles, such as tens, hundreds, or even thousands of cycles.

[0112]

[0165] In some embodiments, cathode 104 comprises unacidified tin oxide (SnO2) nanoparticles according to the AMO described above. Known electrolytes 108, anode 106, and separator 110, or those otherwise described herein, may be used in conjunction with such embodiments.

[0113]

[0166] It will be understood that various battery configurations are possible using the AMO materials disclosed herein. For example, a battery may include a first electrode containing the AMO nanomaterial, a second electrode, and an electrolyte placed between the first and second electrodes. As an example of a lithium-ion battery, the first electrode may function as either a cathode or an anode. For example, in operation as a cathode, the second electrode may correspond to lithium metal, graphite, or another anode material. As another example, in operation as an anode, the second electrode may correspond to LiCoO2, LiMn2O4, LiNiO2, or another cathode material. Useful 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.

[0114]

[0167] It will be understood that the AMO materials disclosed herein may also be added to electrodes as dopants to the anode and / or cathode of conventional lithium-ion cells, for example, in amounts of 0.01% to 10% by weight, or for example, about 1% by weight, 5% by weight, or 10% by weight. The disclosed AMO materials provide remarkable capacity for storing lithium atoms, and by adding these materials to conventional lithium-ion cell electrodes, these composite materials provide the capabilities of those materials. In one particular example, the electrode comprises LiCoO2 and AMO. In another example, the electrode comprises a carbonaceous material such as graphite and AMO.

[0115]

[0168] Advantageously, AMO materials may optionally be used with acidic components such as binders, acidic electrolytes, or acidic electrolyte additives. This may be within the context of an anode, cathode, half-cell, complete cell, integrated battery, or other components. Surprisingly, the inventors have found that including acidic components and / or acidic species such as organic acids or organic acid anhydrides in batteries containing AMO materials increases capacity compared to batteries without acidic species. Again, prior art teaches against the use of acidic species, as these species can degrade metal current collectors and housings and cause degradation of other electrode components.

[0116]

[0169] As shown in Figure 14, cycle performance data for AMO-based batteries formed with the same materials and structure are compared, except for those with standard electrolytes, basic electrolytes, and acidic electrolytes. The batteries included the following structures: All cathodes contained the same AMO material. All anodes were lithium metal. The standard electrolyte was a 1:1:1 mixture of dimethylene carbonate, diethylene carbonate, and ethylene carbonate containing 1M LiPF6. The acidified electrolyte was the standard electrolyte containing 3 wt% succinic anhydride. The basic electrolyte was the standard electrolyte containing 3 wt% dimethylacetamide. All batteries were cycled at the same discharge rate. As illustrated, batteries with the acidified electrolyte system exhibited the best cycling capability and maintained the highest capacity over the maximum number of cycles.

[0117]

[0170] Figure 15 provides additional comparative cycling data for two different batteries having the same battery structure containing an acidified electrolyte, except that the AMO material in one battery was deoxidized by washing with a solvent. The batteries contained the following structures: The cathode contained AMO material. The electrolyte was a 1:1:1 mixture of dimethylene carbonate, diethylene carbonate, and ethylene carbonate, containing 1 M LiPF6 and 3 wt% succinic anhydride. The anode was lithium metal. The batteries were cycled at the same discharge rate. The battery with the acidified AMO material had a higher capacity retention rate relative to the number of cycles, indicating that the acidified surface of the AMO interacts with the acidified electrolyte, potentially improving performance. Several acidic electrolytes have been developed and / or tested and found to work favorably in the cell chemistry described herein.

[0118]

[0171] Currently, lithium batteries are recognized as posing safety risks in certain situations. For example, airline regulations now require lithium batteries to be partially discharged before being brought into the cargo hold. Fires have been reported in equipment using lithium batteries as a result of runaway exothermic reactions. Furthermore, conventional fire suppression systems and equipment may have difficulty extinguishing lithium fires. For these reasons, lithium-containing compounds, rather than metallic lithium, are used in many commercial battery cells.

[0119]

[0172] However, using lithium-containing compounds instead of lithium metal in the anode may limit the amount of lithium available for reaction and uptake into the cathode during discharge, and therefore may also limit the capacity of such cells. However, currently disclosed AMO materials have shown not only to be highly uptaken with lithium during discharge, but also to have improved safety properties. For example, when battery cells containing AMO materials in the cathode and lithium metal electrodes are subjected to safety tests such as nail penetration tests, short-circuit tests, and overvoltage tests, the cells function well and do not appear to pose an unacceptable risk of fire or explosion.

[0120]

[0173] Several cells were constructed using a cathode containing SnO2AMO and an anode containing conductive carbon black (Ketjenblack), polyvinylidene fluoride (PVDF), and polyarylamide (PAA) in a volume ratio of 63 / 10 / 26.1 / 0.9. The bifacial layers of this composition contained 4 mg / cm² per side. 2 The following materials were prepared. Six of these layers constituted the cathode. The size of the prepared cathode was 9 cm × 4 cm. A 25 μm thick polypropylene layer was obtained from Targray Technology International, Inc. and used as a separator. The size of the separator was 9.4 cm × 4.4 cm. The electrolyte was prepared from 1 M LiPF6 in a solvent of ethylene carbonate (EC), diethyl carbonate (DEC), and dimethyl carbonate (DMC) in a volume ratio of 1:1:1. The anode was a 50 μm thick layer of lithium metal with dimensions of 9.2 cm × 4.2 cm.

[0121]

[0174] Two of the constructed cells were discharged before safety testing, and their actual capacity was found to be 1.7 Ah, with a specific capacity of 1575 mAh / g SnO2.

[0122]

[0175] Figure 16 provides data showing the temperature and voltage of the cell constructed as described above and subjected to a nail-piercing test. The test was conducted at room temperature, and no events (such as fire) were observed. It can also be seen that the temperature and voltage remained stable.

[0123]

[0176] Figure 17A provides data showing the temperature and voltage of the cell configured as described above and subjected to the overcharge test. A current of 1A was applied. No adverse events were observed during the test period, except for gas release from the cell. Figure 17B provides a magnified view of the overcharge test results in Figure 17A, focusing on the start of the test.

[0124]

[0177] Embodiments of electrochemical cells constructed with AMO material as the cathode and lithium as the electrode were tested and successfully underwent more than 900 charge-discharge cycles without catastrophic or destructive failure. In other words, embodiments of electrochemical cells constructed with AMO material as the cathode and lithium as the electrode were tested and successfully underwent more than 900 charge-discharge cycles, still retaining charge and maintaining useful capacity.

[0125]

[0178] While we do not wish to be bound by theory, the improved safety provided by using AMO-based cathode materials in lithium cells may stem from the AMO material's ability to passivate lithium metal and prevent the formation of dendritic crystals. The inventors observed that, during cycling, the lithium metal anode did not appear to grow or otherwise form dendritic crystals, but rather exhibited a softer, less crystalline structure. In some embodiments, the lithium anode may be passedivated by cycling or the like as a component of the electrochemical cell described herein, subsequently removed from the electrochemical cell, and used as an electrode in a new electrochemical cell with a different cathode. Furthermore, cells constructed according to this disclosure utilize low operating voltages, such as 1–2 volts, in contrast to the typical voltages of lithium or lithium-ion battery cells, which usually operate at around 3–4.2 volts. Such a difference in operating voltage may explain the safety of the partially disclosed cells.

[0126]

[0179] Referring here to Figure 18, a schematic diagram of cathode 1800 according to an embodiment of this disclosure is provided. Figure 18 is not to scale. Cathode 1800 contains approximately 33.3% SnO2 in AMO form. AMO was prepared according to the method described herein. To form carbon layer 1804, Ketjenblack EC-300J (SA: ~800m 2A slurry of 10 μm thick copper foil 1802 was prepared using NMP solvent and coated onto it as a current collector. The slurry composition was 80 wt% Ketjenblack and 20 wt% PVDF. The coated tape was dried in a vacuum oven at 100°C.

[0127]

[0180] To form the carbon / SnO2 electrode layer 1806, a mixture of 33.3 wt% AMO SnO2, Ketjenblack, and PVDF was prepared, and a slurry was formed by adding NMP solvent. The slurry was coated onto portions of copper foil (1802, 1804) coated with Ketjenblack. The resulting tapes were dried in a vacuum oven at 100°C (overnight) and calendered at room temperature. The thickness of the tapes was measured using a micrometer in the SnO2 / Ketjenblack coated area and the Ketjenblack-only coated area. The thickness of the Ketjenblack layer 1704 was found to be approximately 8 μm. On the other hand, the thickness of the SnO2AMO-containing layer 1806 was found to be approximately 2 μm. The foil layer was approximately 10 μm thick, providing a total thickness of cathode 1800 of approximately 18–20 μm.

[0128]

[0181] Circular discs were punched out from calender tapes, separating the Ketjenblack-only coating area from the SnO2 / Ketjenblack coating area. To obtain the total mass of the electrode layer, the mass of the disc coated with Ketjenblack-only was subtracted from the mass of the disc coated with SnO2 / Ketjenblack. For one tested cell type, the total mass of the electrode material was 0.0005g (after subtracting the amount equivalent to the mass of the Ketjenblack-only coated disc), providing a total mass of approximately 0.000167g (33.3% mass) of active material (SnO2).

[0129]

[0182] Useful embodiments of the cathode 1800 include layering of a carbonaceous layer and an AMO-containing layer, use of Ketjenblack high-surface-area conductive carbon in both layers, a 33% active material content in the AMO-containing layer, thickness of the AMO-containing layer, use of PVDF as a binder, and use of copper foil as a current collector. Each of these embodiments may be optionally modified.

[0130]

[0183] For example, carbon other than Ketjenblack may be used. It will be understood that AMO materials used as active materials have very small particle sizes, such as 1–100 nm (e.g., 2–5 nm), with a narrow size distribution range. Graphite may be useful as the carbon for the cathode in this disclosure, but Ketjenblack has a particle size much closer to AMO particle size than commercially available graphite and several other conductive carbons. Ketjenblack particles, for example, have a size of about 30–300 nm and can have a broader distribution than AMO particles. In contrast, graphite particles tend to have a much larger size, such as about 100 μm. Such a close similarity in size may result in a mixture of Ketjenblack and AMO being more uniform on a local scale, allowing for more complete or better mixing and contact between the carbon particles and the AMO particles.

[0131]

[0184] As another example, the number of carbonaceous material layers and AMO-containing layers may be changed to form the electrode. In the example above, the electrode contains one carbonaceous material layer and one AMO-containing layer. Optionally, additional carbonaceous material layers may be included. Optionally, additional AMO-containing layers may be included. Advantageously, the carbonaceous material layers can be placed directly on the AMO-containing layer, followed by another carbonaceous material layer, followed by another AMO-containing layer, and so on. Examples are conceivable where any number of layer pairs, such as 1 to 20 layer pairs, can be included in the electrode. Also, acidic species can optionally be incorporated into the electrode and / or electrode layers as described above, and may be mixed together with the carbonaceous material, AMO, and / or binder.

[0132]

[0185] However, in some embodiments, no separate layers are used in the AMO-containing electrode, and the electrode may contain AMO, carbonaceous material, and one or more binders (e.g., PVDF, PAA, etc.) within a single mixed structure having a composition similar to the overall structure of the layered electrode described above. For example, the electrode may include a separate carbonaceous layer (0% AMO) and an AMO-containing layer (e.g., 33% AMO) to provide an overall composition having about 21% AMO. Alternatively, the electrode may include a single structure containing a 21% AMO mixture with carbonaceous material (and binder). Optionally, the single mixed electrode structure may be optionally assembled as multiple layers, each having a common composition of the mixed structure.

[0133]

[0186] As another example, the proportion of the active material can be varied. For instance, in the multilayer electrode described above, the carbonaceous layer did not contain AMO, while the AMO-containing layer contained approximately 33%. Overall, the composition of such layers could be approximately 21% by weight of the total AMO. However, the AMO-containing layer and / or the electrode as a whole may contain between 1% and 90% by weight of AMO, depending on the composition. In some embodiments, high AMO fractions, such as amounts of 50% or more AMO, may be useful.

[0134]

[0187] In other embodiments, low AMO fractions, such as amounts of 35% by weight or less of AMO, may be useful. In contrast to the conventional idea that the amount of active material in the electrode is usually kept high (e.g., 80% by weight or more) to enable the maximum capacity and specific capacity of the cell incorporating the electrode, we have found that loading lower active material (AMO) favorably enables the creation of batteries with higher overall capacity and specific capacity. While we do not wish to be bound by theory, the high capacity of the disclosed cell incorporating AMO material may be achieved by the specific affinity of the AMO material for lithium atoms. The incredible amount of lithium atoms that can be stored in an electrode incorporating AMO material may result in the need for extra space to accommodate the incorporated lithium. By including a smaller proportion of active material, additional space for lithium atoms can be achieved. In fact, the proportion of AMO active material in the entire electrode or in low electrode-containing layers of 15% or 20% may exhibit even higher capacity and specific capacity than electrodes with considerably higher AMO active material loading. Furthermore, conductive carbon may be activated by the presence of the AMO material, providing additional active sites for incorporating lithium during charging and / or discharging.

[0135]

[0188] Due to its incredible affinity for lithium atoms, in some embodiments AMO may be added to conventional lithium cell electrodes or lithium-ion electrodes. In this way, conventional electrodes can advantageously improve their lithiation ability with little or no alteration to the cell's electrochemistry. In some examples, AMO can be added to conventional lithium cell electrodes or lithium-ion electrodes in amounts of up to 5%.

[0136]

[0189] As another example, the thickness of the electrode layer containing AMO can be varied, for example, to improve performance or to modify other properties of the electrode, such as active material loading (i.e., weight percentage of AMO). For example, the thickness of the carbonaceous layer of the electrode can be 0.5 μm to 50 μm, 1.0 μm to 20 μm, or 1.5 μm to 10 μm. As yet another example, the thickness of the AMO-containing layer of the electrode can be 0.1 μm to 20 μm, 1 μm to 15 μm, or 5 μm to 10 μm. For example, electrodes with thicknesses of up to 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm may optionally be used for electrode thickness or values ​​outside these ranges for the electrode. However, the inventors have found that in some embodiments, it is not necessary to distinguish between the carbonaceous layer and the AMO-containing layer as described above, and the electrode can optionally include one or more AMO-containing layers or AMO-containing structures.

[0137]

[0190] As another example, the amount and type of binder included in the electrode may be varied to achieve specific results. In some embodiments, a large amount of binder may be included in the electrode or electrode layer. For example, the binder may be present in the electrode or electrode layer in an amount of 10% to 50% by weight, or in an amount similar to that of the carbonaceous material. The inventors have found that including a large or substantial amount of binder as conductive carbon may be advantageous in forming good quality electrodes with useful structural and capacitance properties. In some embodiments, conductive carbon is difficult to compress on its own, and including a substantial amount of binder may improve its ability to form useful carbonaceous and AMO-containing layers and / or electrodes.

[0138]

[0191] As another example, various current collector configurations can be used. As mentioned above, copper film current collectors may be used. Alternatively, other metals, including aluminum, stainless steel, brass, and titanium, may be used. Also, multiple current collectors may be used, such as in configurations where an AMO-containing layer and / or a carbonaceous layer may be placed between multiple current collectors. It will be understood that different current collectors may be used for the anode and cathode. Furthermore, the current collectors do not need to contain a film and may instead be constructed as a mesh, grid, pins, or other structure of any appropriate thickness or dimensions. In some embodiments, the current collectors may also be useful for temperature control and may function as a heat sink or heat carrier to remove excess thermal energy from the active material of the cell.

[0139]

[0192] Coin cell type battery cells were constructed and tested by repeated discharge-charge cycles. The cathode containing SnO2AMO was assembled as described above using a glass separator, a 1M LiPF6 electrolyte of DEC / EC / DMC in a 1:1:1 volume ratio, and a lithium metal anode. The cell was discharged from its as-assembled open-circuit voltage of 3.19V to 0.01V at a rate of C / 10. Next, the cell was charged from 0.01V to 1.5V at a rate of C / 10. After this, the cell was repeatedly cycled from 1.5V to 0.01V and from 0.01V to 1.5V at a rate of C / 5. The voltages and charge rates here are merely examples, and it will be understood that other charge and discharge rates and other charge and discharge voltages may be used. The cell was cycled for at least 111 charge-discharge cycles, and the discharge capacity (mAh / g SnO2AMO) was aggregated. Table 2 below shows the discharge and charge capacities for each cycle. [Table 2-1 (Continued)] [Table 2-2] Table 2 Discharge capacity and charge capacity

[0140]

[0194] Figure 19 provides data showing cell cycling as a function of observed charge capacity (CC) and discharge capacity (DC) in mAh / g SnO2AMO. As shown in Table 2 and Figure 19, a very high initial discharge capacity of 10,831 mAh / g is observed. This initial discharge capacity includes the irreversible lithiumization capacity within the cell. As shown in Table 2, the reversible delithiation capacity starts at 2,662 mAh / g. It should be understood that this very large initial lithiumization capacity is available in the system when deploying the cell from its assembled state for primary use. Figure 20 provides a plot of voltage over time during cycling of a cell constructed as described above.

[0141]

[0195] Initial discharge occurs from an open-circuit voltage of approximately 3.2 volts to 0.01 V, and it should also be understood that charge-discharge cycling occurs between 0.01 V and 1.5 V. Optionally, charge-discharge cycling may occur at higher upper limits, such as 2.0 V, 2.5 V, 3.0 V, 3.2 V, etc. By cycling at higher voltage upper limits, the amount of capacitance identified above as irreversible, although still below the open-circuit voltage at assembly, may be retained as reversible capacitance.

[0142]

[0196] Unusual capacities also presuppose a new “hybrid” battery system that features a very long initial discharge cycle utilizing a high initial lithium capacity, followed by shorter but reversible cycling at a lower delithiation capacity. Currently, no such system exists on the market.

[0143]

[0197] The capacity revealed by the tests roughly translates to an energy density of 12,584 Whr / kg SnO2, depending on the voltage range selected for cycling. This is comparable to the energy density of gasoline (12,889 Whr / kg) and, to the inventor's knowledge, the highest energy density achieved to date with any battery material.

[0144]

[0198] Figure 21 provides an image of a pouch-type cell constructed as described above, which was disassembled after 103 cycles. The clear and intact separator indicates that no lithium plating has occurred and cannot be the cause of the excess capacity exhibited by the cell. The cathode containing AMO SnO2 (appearing black on the copper current collector) is intact, firmly attached to the current collector, and shows no mechanical degradation. This exceptional capacity measurement is contrary to the teachings of the scientific literature, which claim that even a capacity of approximately 1000 mAh / g for oxide materials leads to inevitable volume changes and subsequent mechanical failure of the electrodes. In contrast, embodiments disclosed herein exhibit capacities up to 10 times this capacity without significant volume changes and associated mechanical structural changes.

[0145]

[0199] Furthermore, while the inventors do not wish to be bound by any theory, they believe that the structure of the disclosed cell having a lithium metal anode and a cathode containing an AMO material with incredible lithiation ability enables such high capacity, partly due to the low level of active material (AMO) in the cathode (e.g., 10% to 30% by weight). A low active material load may provide sufficient space for a large number of lithium atoms to be taken up and stored in the cathode during discharge. An optimal load of about 20-25% may represent a transition point where lower loads do not provide enough active material or active sites for the reaction and uptake of lithium atoms, and higher loads do not provide a sufficient volume for the uptake of lithium atoms.

[0146]

[0200] The specific energy densities of the AMO-based electrochemical cells disclosed herein are novel and taught to be impossible by the scientific literature. Such results may be possible here, as they would be driven by novel mechanisms other than those currently taught or understood by those skilled in the art, leading to the possibility of achieving even higher capacities than those disclosed herein. The novel availability of such energy densities would inevitably lead to other electrodes and batteries, which may embody unusual shapes and sizes, new electrolyte systems, separators, current collectors, etc. The disclosed and claimed electrodes, cells, and batteries should not be considered limited to auxiliary components currently available on the open market or disclosed herein or in the literature. Rather, it will be understood that the disclosed and claimed electrodes, cells, and batteries can take any suitable shape, size, or configuration, incorporate any suitable electrolyte, current collector, or separator, and use any suitable discharge and / or charge profile.

[0147]

[0201] The present invention may be further understood by referring to the following non-limiting embodiments illustrating the formation of electrodes for an electrochemical cell comprising a first electrode containing a metal oxide (i.e., AMO) and a second electrode containing metallic lithium. The first electrode was constructed to contain 80 weight percent of metal oxide, consistent with conventional practices for forming electrochemical cells in the battery industry. As described above, the capacity of such an electrochemical cell can be significantly improved by reducing the amount of metal oxide in the first electrode to less than 80 weight percent, for example, 5-15%, 20-35%, or 55-70%. The following embodiments illustrate examples of chemicals that can be optimized by constructing electrochemical cells with smaller weight percentages of metal oxide. Example 1: AMO of tin oxide functionalized with acetate / chloride

[0148]

[0202] Tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in ethanol / aqueous solution and acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft gray material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 22 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. Example 2: AMO of tin oxide functionalized with acetate / sulfate

[0149]

[0203] Tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in ethanol / aqueous solution and acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a gray, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 23 shows electron microscope images of the AMO nanomaterial, a plot of measured capacity versus number of cycles, and a plot of voltage as a function of time during cycling. Example 3: AMO of tin oxide functionalized with acetate / nitrate

[0150]

[0204] Tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in ethanol / aqueous solution and acidified by adding nitric acid (HNO3). The resulting AMO nanomaterial was a gray, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 24 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 4: AMO of tin oxide functionalized with acetate / phosphate

[0151]

[0205] Tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in ethanol / aqueous solution and acidified by the addition of phosphoric acid (H3PO4). The resulting AMO nanomaterial was a brown, soft, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 25 shows electron microscope images of the AMO nanomaterial, a plot of measured capacity versus number of cycles, and a plot of voltage as a function of time during cycling. Example 5: AMO of tin oxide functionalized with acetate / citrate

[0152]

[0206] Tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in ethanol / aqueous solution and acidified by the addition of citric acid (C6H8O7). The resulting AMO nanomaterial was a brown, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 26 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. Example 6: AMO of tin oxide functionalized with acetate / citrate

[0153]

[0207] Tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in ethanol / aqueous solution and acidified by the addition of oxalic acid (C2H2O4). The resulting AMO nanomaterial was a mole-colored, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 27 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. Example 7: Iron oxide-doped and tin oxide functionalized with acetate / chloride AMO

[0154]

[0208] Doped tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / aqueous solution containing a small amount of iron acetate. The solution was acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, flaky, creamy gray material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 28 shows electron microscope images of the AMO nanomaterial, a plot of measured capacity versus number of cycles, and a plot of voltage as a function of time during cycling. Example 8: Iron oxide-doped and tin acetate / sulfate-functionalized AMO

[0155]

[0209] Doped tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / aqueous solution containing a small amount of iron acetate. The solution was acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a pale mole-colored, soft, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 29 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. Example 9: Iron oxide-doped and tin acetate / nitrate-functionalized AMO

[0156]

[0210] Two doped tin oxide (AMO) samples were synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / aqueous solution containing a small amount of iron acetate (Fe(CH3COO)3). The solution was acidified by the addition of nitric acid (HNO3). The resulting AMO nanomaterial was a soft, white material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 30 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 10: Iron oxide-doped and functionalized tin oxide AMO

[0157]

[0211] Doped tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / aqueous solution containing a small amount of iron acetate (Fe(CH3COO)3). The solution was acidified by the addition of oxalic acid (C2H2O4). The resulting AMO nanomaterial was a soft, white material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 31 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 11: Iron oxide-doped and tin oxide functionalized with acetate / phosphate AMO

[0158]

[0212] Doped tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / aqueous solution containing a small amount of iron acetate (Fe(CH3COO)3). The solution was acidified by the addition of phosphoric acid (H3PO4). The resulting AMO nanomaterial was a white, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 32 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. Example 12: Iron oxide-doped and acetic acid / citrate-functionalized tin oxide

[0159]

[0213] Doped tin oxide was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in an ethanol / aqueous solution containing a small amount of iron acetate (Fe(CH3COO)3). The solution was acidified by the addition of citric acid (C6H8O7). The resulting material was a yellow, glassy, ​​hard material that did not form particles and was formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 33 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 13: AMO of tin oxide functionalized with acetate / bromide

[0160]

[0214] Tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in ethanol / aqueous solution and acidified by the addition of hydrobromic acid (HBr). The resulting AMO nanomaterial was a gray, soft powder material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 34 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 14: AMO of tin oxide functionalized with acetate / borate

[0161]

[0215] Tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin acetate (Sn(CH3COO)2) was dissolved in ethanol / aqueous solution and acidified by the addition of boric acid (H3BO3). The resulting AMO nanomaterial was a gray, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 35 shows electron microscope images of the AMO nanomaterial, a plot of measured capacity versus number of cycles, and a plot of voltage as a function of time during cycling. Example 15: AMO of tin oxide doped with manganese oxide and functionalized with sulfate / chloride

[0162]

[0216] Doped tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin sulfate (SnSO4) was dissolved in an ethanol / aqueous solution containing a small amount of manganese chloride (MnCl2). The solution was acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a very soft, yellowish-brown material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 36 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 16: AMO of tin oxide doped with manganese oxide and functionalized with chloride

[0163]

[0217] Doped tin oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, tin chloride (SnCl2) was dissolved in an ethanol / aqueous solution containing a small amount of manganese chloride (MnCl2). The solution was acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, grayish-brown material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 37 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 17: AMO of tin oxide doped with iron oxide and aluminum oxide and functionalized with chloride

[0164]

[0218] Two doped tin oxide (AMO) samples were synthesized using a single-pot hydrothermal synthesis method. Briefly, tin chloride (SnCl2) was dissolved in an ethanol / aqueous solution containing smaller amounts of both iron chloride (FeCl3) and aluminum chloride (AlCl3). The solution was acidified by the addition of hydrochloric acid (HCl). For the first sample, the resulting AMO nanomaterial was a light brown, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 38 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. For the second sample, the resulting AMO nanomaterial was a light gray, flaky material. Example 18: AMO of tin oxide-doped and chloride-functionalized iron oxide

[0165]

[0219] Doped iron oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, iron chloride (FeCl3) was dissolved in an ethanol / aqueous solution containing a small amount of tin chloride (SnCl2). The iron-to-tin ratio was 95:5. The solution was acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft red material and was formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 39 shows plots of measured capacity versus number of cycles, as well as plots of voltage as a function of time during cycling. Example 19: AMO of tin oxide-doped and chloride-functionalized iron oxide

[0166]

[0220] Doped iron oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, iron chloride (FeCl3) was dissolved in an ethanol / aqueous solution containing a small amount of tin chloride (SnCl2). The iron-to-tin ratio was 95:5. The solution was acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a black, glassy material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 40 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. Example 20: AMO of iron oxide functionalized with nitrate

[0167]

[0221] Iron oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, iron nitrate (Fe(NO3)3) was dissolved in ethanol / aqueous solution and acidified by the addition of nitric acid (HNO3). The resulting AMO nanomaterial was a black, glassy material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 41 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. Example 21: AMO of bismuth oxide functionalized with chloride

[0168]

[0222] Bismuth oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, bismuth chloride (BiCl3) was dissolved in ethanol / aqueous solution and acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a soft, white material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 42 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. Example 22: AMO of zirconium oxide functionalized with sulfate

[0169]

[0223] Zirconium oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, zirconium sulfate (Zr(SO4)2) was dissolved in ethanol / aqueous solution and acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a flaky white material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 43 shows plots of measured capacity versus number of cycles, as well as a plot of voltage as a function of time during cycling. Example 23: AMO of titanium dioxide functionalized with sulfate

[0170]

[0224] Titanium oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, titanium oxysulfate (TiOSO4) was dissolved in ethanol / aqueous solution and acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a white, flaky material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 44 shows electron microscope images of the AMO nanomaterial, a plot of measured capacity versus number of cycles, and a plot of voltage as a function of time during cycling. Example 24: AMO of antimony oxide functionalized with sulfate

[0171]

[0225] Antimony oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, antimony sulfate (Sb2(SO4)3) was dissolved in ethanol / aqueous solution and acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a very soft white material and was formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 45 shows plots of measured capacity versus number of cycles, as well as plots of voltage as a function of time during cycling. Example 25: AMO of indium oxide functionalized with chloride

[0172]

[0226] Indium oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, indium chloride (InCl3) was dissolved in ethanol / aqueous solution and acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a white material and was formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 46 shows electron microscope images of the AMO nanomaterial, a plot of measured capacity versus number of cycles, and a plot of voltage as a function of time during cycling. Example 26: AMO of indium oxide functionalized with sulfate

[0173]

[0227] Indium oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, indium sulfate (In2(SO4)3) was dissolved in ethanol / aqueous solution and acidified by the addition of sulfuric acid (H2SO4). The resulting AMO nanomaterial was a white material and was formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 47 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 27: AMO of indium oxide functionalized with bromide

[0174]

[0228] Indium oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, indium bromide (InBr3) was dissolved in ethanol / aqueous solution and acidified by the addition of hydrobromic acid (HBr). The resulting AMO nanomaterial was a bluish-white material and was formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 48 shows electron microscope images of the AMO nanomaterial, a plot of measured capacity versus number of cycles, and a plot of voltage as a function of time during cycling. Example 28: AMO of indium oxide functionalized with chloride

[0175]

[0229] Indium oxide (AMO) was synthesized using a single-pot hydrothermal synthesis method. Briefly, indium chloride (InCl3) was dissolved in ethanol / aqueous solution and acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was gray with a yellow ring and formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 49 shows electron microscope images of the AMO nanomaterial, a plot of measured capacity versus number of cycles, and a plot of voltage as a function of time during cycling. Example 29: Mixture of lithium oxide and iron oxide doped with tin oxide and functionalized with chloride / acetate AMO

[0176]

[0230] Doped and mixed lithium oxide and iron oxide AMO were synthesized using a single-pot hydrothermal synthesis method. Briefly, lithium acetate (Li(CH3COO)) and iron chloride (FeCl3) were dissolved in an ethanol / aqueous solution containing a small amount of tin chloride (SnCl2). The solution was acidified by the addition of hydrochloric acid (HCl). During synthesis, a yellowish-brownish-pink color with a green ring appeared in the flask. However, the final AMO nanomaterial was gray and formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 50 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 30: Mixture of lithium oxide and iron oxide doped with tin oxide and functionalized with chloride / acetate AMO

[0177]

[0231] Doped and mixed lithium oxide and iron oxide AMO were synthesized using a single-pot hydrothermal synthesis method. Briefly, lithium acetate (Li(CH3COO)) and iron chloride (FeCl3) were dissolved in an ethanol / aqueous solution containing a small amount of tin chloride (SnCl2). The solution was acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a pale, golden material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 51 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Example 31: Mixture of lithium oxide and iron oxide doped with tin oxide and functionalized with chloride / acetate AMO

[0178]

[0232] Doped and mixed lithium oxide and iron oxide AMO were synthesized using a single-pot hydrothermal synthesis method. Briefly, lithium acetate (Li(CH3COO)) and iron chloride (FeCl3) were dissolved in an ethanol / aqueous solution containing a small amount of tin chloride (SnCl2). The solution was acidified by the addition of hydrochloric acid (HCl). The resulting AMO nanomaterial was a pale, creamy white material formed into electrodes. The electrodes were assembled into a battery cell against lithium metal and cycled by discharging to zero volts and then charging to 1.5 volts. Figure 52 shows electron microscope images of the AMO nanomaterial, plots of measured capacity versus number of cycles, and plots of voltage as a function of time during cycling. Description of incorporation by reference and modification

[0179]

[0233] For example, all references to this application, including patent documents containing issued or granted patents or equivalents, patent application publications, and non-patent literature documents or other source materials, are incorporated herein by reference in their entirety, as if they were incorporated individually by reference.

[0180]

[0234] All patents and publications referenced herein represent the level of skill of those skilled in the art to which the present invention relates. References cited herein are incorporated herein by whole reference to represent the most current art in some cases at the time of filing, and it is intended that this information may be used herein to exclude (e.g., abandon) certain embodiments of the prior art as necessary. For example, if a compound is claimed, it should be understood that compounds known in the prior art, including certain compounds disclosed in the references disclosed herein (in particular the referenced patent documents), are not intended to be included in the claims.

[0181]

[0235] Where groups of substituents are disclosed herein, it is understood that all individual elements of those groups, as well as all subgroups and classes that may be formed using the substituents, are disclosed separately. Where Markush groups or other groupings are used herein, all individual elements of the groups, and all possible combinations and subcombinations of the groups, are included separately in this disclosure. Where used herein, "and / or" means that one, all, or any combination of items in the list separated by "and / or" 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"".

[0182]

[0236] Unless otherwise specified, the present invention can be carried out using all formulations or combinations of the components described or illustrated. Specific names of materials are intended to be illustrative, as it is known that the same material can be given different names. Those skilled in the art will understand that, without relying on excessive experimentation, methods, apparatus elements, starting materials, and synthesis methods other than those specifically illustrated can be used in carrying out the present invention. All technically known functional equivalents of such methods, apparatus elements, starting materials, and synthesis methods are intended to be included in the present invention. Where ranges, e.g., temperature ranges, time ranges, or composition ranges, are specified herein, all intermediate and partial ranges, as well as all individual values ​​within the specified ranges, are intended to be included in this disclosure.

[0183]

[0237] As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is comprehensive or unrestricted, without excluding additional, unmentioned elements or method steps. As used herein, “consisting of” excludes elements, steps, or components not specified in the claim elements. As used herein, “consisting essentially of” does not exclude materials or steps that do not substantially affect the basic and novel characteristics of the claim. In particular, the use herein of the term “comprising” in descriptions of the components of a composition or the elements of an apparatus is understood to encompass compositions and methods that consist essentially of the listed components or elements, and compositions and methods comprising them. The inventions described herein exemplary may be adequately implemented without any elements or limitations not specifically disclosed herein.

[0184]

[0238] The terms and expressions used herein are for illustrative purposes only and are not limiting. The use of such terms and expressions is not intended to exclude equivalents or parts thereof of the illustrated and described configurations, but it is acknowledged that various modifications are possible within the scope of the claimed invention. Therefore, while the invention is specifically disclosed by preferred embodiments and optional configurations, those skilled in the art should understand that modifications and variations of the concepts disclosed herein can be relied upon, and such modifications and variations are considered to fall within the scope of the invention as defined by the claims. The following is disclosed hereby: (Item 1) A first electrode comprising a metal oxide, a conductive material, and a binder, wherein the metal oxide comprises less than 80 weight percent of the first electrode, A second electrode containing metallic lithium, The electrode includes an electrolyte disposed between the first electrode and the second electrode, The first electrode and the second electrode provide a high-capacity battery cell that offers a primary capacity between 3000 mAh / g of the metal oxide and 15000 mAh / g of the metal oxide. (Item 2) The high-capacity battery cell according to item 1, wherein the first electrode comprises a layered structure including a set of first layers containing the conductive material and a set of second layers containing the metal oxide, and the set of first layers and the set of second layers are provided in an alternating configuration. (Item 3) The high-capacity battery cell described in item 2, wherein the first set of layers comprises 1 to 20 layers, and the second set of layers comprises 1 to 20 layers. (Item 4) The high-capacity battery cell according to item 2, wherein the set of the first layer and the set of the second layer independently have thicknesses between 1 μm and 50 μm. (Item 5) The high-capacity battery cell according to item 2, wherein the metal oxide comprises less than 90 weight percent of the set of the second layers. (Item 6) The high-capacity battery cell according to item 1, wherein the metal oxide comprises 5 to 15 weight percent of the first electrode, 20 to 35 weight percent of the first electrode, or 55 to 70 weight percent of the first electrode. (Item 7) The electrolyte is a high-capacity battery cell as described in item 1, comprising a solvent, a lithium salt, and an acidic species. (Item 8) The high-capacity battery cell described in item 7, wherein the acidic species is succinic anhydride or itaconic anhydride. (Item 9) The aforementioned metal oxide includes acidified metal oxide (AMO) nanomaterials, as described in item 1, for a high-capacity battery cell. (Item 10) The high-capacity battery cell described in Item 1, wherein the metal oxide includes lithium-containing oxide, aluminum oxide, titanium oxide, manganese oxide, iron oxide, zirconium oxide, indium oxide, tin oxide, antimony oxide, bismuth oxide, or any combination thereof. (Item 11) The large-capacity battery cell according to item 1, wherein the metal oxide contains one or more electron-withdrawing groups selected from Cl, Br, BO3, SO4, PO4, NO3, CH3COO, C2O4, C2H2O4, C6H8O7, or C6H5O7, and / or is surface-functionalized to those electron-withdrawing groups. (Item 12) The high-capacity battery cell described in item 1, wherein the conductive material comprises one or more of the following: graphite, conductive carbon, carbon black, Ketjenblack, conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composite material, polyaniline (PANI), or polypyrrole (PPY). (Item 13) A high-capacity battery cell as described in Item 1, showing the primary capacity at assembly between a metal oxide of 4000mAh / g and a metal oxide of 15000mAh / g. (Item 14) A high-capacity battery cell as described in item 1, exhibiting a secondary capacity between 1000mAh / g and 5000mAh / g of metal oxide. (Item 15) A high-capacity battery cell as described in item 1, exhibiting a life cycle of 100 to 1000 charge-discharge cycles without failure. (Item 16) A high-capacity battery cell as described in item 1, exhibiting an open-circuit voltage between 2V and 4V during assembly. (Item 17) A high-capacity battery cell as described in item 1, characterized by any combination of configurations from items 2 to 16. (Item 18) The metal oxide comprises an acidified metal oxide (AMO) nanomaterial, the AMO nanomaterial comprises 5 to 35 weight percent of the first electrode, the AMO nanomaterial comprises 85 to 100 weight percent tin oxide and 0 to 15 weight percent iron oxide, the AMO nanomaterial comprises one or more electron-withdrawing groups selected from Cl, Br, BO3, SO4, PO4, NO3, CH3COO, C2O4, C2H2O4, C6H8O7, or C6H5O7, and / or is surface-functionalized with those electron-withdrawing groups, the conductive material is graphite, conductive carbon, carbon black, Ketjen black, and The high-capacity battery cell described in item 1, comprising one or more conductive polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composite material, polyaniline (PANI), or polypyrrole (PPY), wherein the second electrode comprises metallic lithium, the high-capacity battery cell exhibits a secondary capacity of 1000 mAh / g to 5000 mAh / g of AMO nanomaterials, the high-capacity battery cell exhibits a life cycle of 100 to 1000 charge-discharge cycles without failure, and the high-capacity battery cell exhibits an open-circuit voltage of 2V to 4V at assembly. (Item 19) The high-capacity battery cell according to item 18, wherein the first electrode comprises a layered structure comprising a set of first layers comprising the conductive material and a set of second layers comprising the AMO, the set of first layers and the set of second layers being provided in an alternating configuration, the set of first layers comprising 1 to 20 layers and the set of second layers comprising 1 to 20 layers, the set of first layers and the set of second layers independently having a thickness between 1 μm and 50 μm, and the AMO comprising 25 to 35 weight percent of the set of second layers. (Item 20) The process of producing metal oxides, Forming a slurry using the aforementioned metal oxide, conductive material, binder, and solvent, Depositing a layer of the slurry on the current collector, A method for manufacturing an electrode, comprising evaporating at least a portion of the solvent to form an electrode layer containing the metal oxide. (Item 21) The process of producing the aforementioned metal oxide is to Forming a solution containing a metal salt, ethanol, and water, The solution is acidified by adding an acid to the solution, The solution is made basic by adding a basic aqueous solution to the aforementioned solution, Collecting the precipitate from the aforementioned solution, Washing the aforementioned precipitate, The method according to item 20, comprising drying the precipitate. (Item 22) The method according to item 20, further comprising depositing a conductive layer on a current collector, wherein the conductive layer comprises a second conductive material. (Item 23) Depositing the aforementioned conductive layer is Forming a conductive slurry using the second conductive material, the second binder, and the second solvent, Depositing a conductive slurry layer on the current collector, The method according to item 22, comprising evaporating at least a portion of the second solvent to form the conductive layer. (Item 24) The method according to item 23, wherein the conductive material and the second conductive material include one or more of graphite, conductive carbon, carbon black, ketjen black, conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composite material, polyaniline (PANI), or polypyrrole (PPY). (Item 25) The method according to item 22, further comprising forming 1 to 20 additional electrode layers containing the metal oxide and 1 to 20 additional conductive layers containing the conductive material. (Item 26) The method according to item 22, wherein the electrode includes a layered structure including a set of first layers containing the second conductive material and a set of second layers containing the metal oxide, and the set of first layers and the set of second layers are provided in an alternating configuration. (Item 27) The method according to item 22, wherein the electrode layer and the conductive layer independently have a thickness between 1 μm and 50 μm. (Item 28) The method according to item 22, wherein the metal oxide includes up to 90 weight percent of the electrode layer. (Item 29) The method according to item 22, wherein the conductive material and the binder independently include 5 to 90 weight percent of the electrode layer. (Item 30) The method according to item 20, wherein the metal oxide includes up to 80 weight percent of the electrode. (Item 31) The method according to item 20, wherein the conductive material and the binder independently include 10 to 70 weight percent of the electrode. (Item 32) The method according to item 20, wherein the metal oxide includes an acidified metal oxide (AMO) material. (Item 33) The method according to item 20, wherein the metal oxide includes lithium-containing oxide, aluminum oxide, titanium oxide, manganese oxide, iron oxide, zirconium oxide, indium oxide, tin oxide, antimony oxide, bismuth oxide, or any combination thereof. (Item 34) The method according to item 20, wherein the metal oxide contains one or more electron-withdrawing groups selected from Cl, Br, BO3, SO4, PO4, NO3, CH3COO, C2O4, C2H2O4, C6H8O7, or C6H5O7, and / or is surface-functionalized to those electron-withdrawing groups. (Item 35) The method described in item 20, characterized by a configuration of any combination of items 21 to 34. (Item 36) A method for manufacturing a large-capacity battery cell, The process of producing metal oxides, Forming the first electrode according to the method described in any one of items 20 to 34, A method comprising placing an electrolyte between the first electrode and a second electrode containing metallic lithium. (Item 37) The process of producing the aforementioned metal oxide is to Forming a solution containing a metal salt, ethanol, and water, The solution is acidified by adding an acid to the solution, The solution is made basic by adding a basic aqueous solution to the aforementioned solution, Collecting the precipitate from the aforementioned solution, Washing the aforementioned precipitate, The method according to item 36, comprising drying the precipitate. (Item 38) Forming the electrode described above is The method according to item 36, further comprising depositing a conductive layer on the current collector, wherein the conductive layer comprises a second conductive material. (Item 39) Depositing the aforementioned conductive layer is Forming a conductive slurry using the second conductive material, the second binder, and the second solvent, Depositing a conductive slurry layer on the current collector, The method according to item 38, comprising evaporating at least a portion of the second solvent to form the conductive layer. (Item 40) The method according to item 39, wherein the conductive material and the second conductive material include one or more of the following: graphite, conductive carbon, carbon black, Ketjenblack, conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composite material, polyaniline (PANI), or polypyrrole (PPY). (Item 41) Forming the electrode described above is The method according to item 38, further comprising forming 1 to 20 additional electrode layers containing the metal oxide and 1 to 20 additional conductive layers containing the conductive material. (Item 42) The method according to item 38, wherein the first electrode comprises a layered structure comprising a set of first layers comprising a second conductive material and a set of second layers comprising the metal oxide, and the set of first layers and the set of second layers are provided in an alternating configuration. (Item 43) The method according to item 38, wherein the electrode layer and the conductive layer independently have thicknesses between 1 μm and 50 μm. (Item 44) The method according to item 38, wherein the metal oxide comprises up to 90 weight percent of the electrode layer. (Item 45) The method according to item 36, wherein the metal oxide comprises up to 80 weight percent of the electrode. (Item 46) The method according to item 36, wherein the metal oxide includes acidified metal oxide (AMO) materials. (Item 47) The method according to item 36, wherein the metal oxide contains a lithium-containing oxide, aluminum oxide, titanium oxide, manganese oxide, iron oxide, zirconium oxide, indium oxide, tin oxide, antimony oxide, bismuth oxide, or any combination thereof. (Item 48) The method according to item 36, wherein the metal oxide contains one or more electron-withdrawing groups selected from Cl, Br, BO3, SO4, PO4, NO3, CH3COO, C2O4, C2H2O4, C6H8O7, or C6H5O7, and / or is surface-functionalized with these electron-withdrawing groups. (Item 49) The method according to item 36, wherein the second electrode contains 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), an acidified metal oxide (AMO) material, or any combination thereof. (Item 50) The method according to item 36, wherein the large-capacity battery cell exhibits a primary capacity during assembly between a metal oxide of 3000 mAh / g and a metal oxide of 15000 mAh / g. (Item 51) The method according to item 36, wherein the large-capacity battery cell exhibits a secondary capacity between a metal oxide of 1000 mAh / g and a metal oxide of 5000 mAh / g. (Item 52) The method according to item 36, wherein the large-capacity battery cell exhibits a life cycle of 100 to 1000 charge-discharge cycles without failure. (Item 53) The method according to item 36, wherein the large-capacity battery cell exhibits an open-circuit voltage between 2V and 4V during assembly. (Item 54) The method according to item 36, characterized by a configuration of any combination of items 37 to 53.

Claims

1. A cathode comprising an active material, a binder, and an acidified metal oxide nanomaterial, wherein the acidified metal oxide nanomaterial constitutes 0.01 to 10 weight percent of the cathode, A-scatter, The system comprises an electrolyte disposed between the cathode and the anode. Battery cell.

2. The battery cell according to claim 1, wherein the acidified metal oxide nanomaterial contains tin oxide.

3. The battery cell according to claim 1, wherein the acidified metal oxide nanomaterial is a dopant of the active material.

4. The battery cell according to claim 1, wherein the active material includes a lithium-ion cathode active material.

5. The battery cell according to claim 4, wherein the lithium ion cathode active material comprises lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, lithium nickel manganese cobalt oxide, lithium iron phosphate, lithium nickel cobalt aluminum oxide, or any combination thereof.

6. The battery cell according to claim 1, wherein the anode comprises lithium or a lithium-filled material.

7. The battery cell according to claim 6, wherein the lithium insertion material includes graphite.

8. The battery cell according to claim 1, wherein the acidified metal oxide nanomaterial includes aluminum oxide, titanium oxide, manganese oxide, iron oxide, zirconium oxide, indium oxide, tin oxide, antimony oxide, bismuth oxide, or any combination thereof.

9. The acidified metal oxide nanomaterial is Cl, Br, BO ３ , SO ４ , PO ４ , NO ３ , CH ３ COO, C ２ O ４ , C ２ H ２ O ４ , C ６ H ８ O ７ , or C ６ H ５ O ７ The battery cell according to claim 1, which is surface-functionalized by one or more electron-withdrawing groups selected from

10. The battery cell according to claim 1, wherein the cathode further comprises a conductive additive selected from one or more of the following: graphite, conductive carbon, carbon black, Ketjenblack, conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composite material, polyaniline, or polypyrrole.

11. The battery cell according to claim 1, wherein the binder comprises styrene-butadiene copolymer, polyvinylidene fluoride, carboxymethylcellulose, styrene-butadiene rubber, acrylonitrile, polyacrylic acid, polyvinyl alcohol, polyamide-imide, or any combination thereof.

12. An electrode for a lithium-ion battery, wherein the electrode is Lithium-ion cathode active material, Binder and, Equipped with acidified metal oxide nanomaterials, The acidified metal oxide nanomaterial constitutes 0.01 to 10 weight percent of the electrode. electrode.

13. The electrode according to claim 12, wherein the acidified metal oxide nanomaterial contains tin oxide.

14. The electrode according to claim 12, wherein the acidified metal oxide nanomaterial is a dopant of the lithium ion cathode active material.

15. The electrode according to claim 12, wherein the lithium ion cathode active material includes lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, lithium nickel manganese cobalt oxide, lithium iron phosphate, lithium nickel cobalt aluminum oxide, or any combination thereof.

16. The electrode according to claim 12, wherein the acidified metal oxide nanomaterial includes aluminum oxide, titanium oxide, manganese oxide, iron oxide, zirconium oxide, indium oxide, tin oxide, antimony oxide, bismuth oxide, or any combination thereof.

17. The acidified metal oxide nanomaterial contains Cl, Br, and BO. ３ SO ４ , PO ４ NO ３ ,CH ３ COO, C ２ O ４ , C ２ H ２ O ４ , C ６ H ８ O ７ , or C ６ H ５ O ７ The electrode according to claim 12, wherein the surface is functionalized with one or more electron-withdrawing groups selected from the above.

18. The electrode according to claim 12, further comprising a conductive additive selected from one or more of the following: graphite, conductive carbon, carbon black, Ketjenblack, conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate (PSS), PEDOT:PSS composite material, polyaniline, or polypyrrole.

19. The electrode according to claim 12, wherein the binder comprises styrene-butadiene copolymer, polyvinylidene fluoride, carboxymethylcellulose, styrene-butadiene rubber, acrylonitrile, polyacrylic acid, polyvinyl alcohol, polyamide-imide, or any combination thereof.

20. The electrode according to claim 12, further comprising a current collector.

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