Electrode materials comprising layered potassium metal oxides, electrodes comprising the electrode materials, and uses of the electrode materials in electrochemistry

Abstract

1. An electrode material comprising an electrochemically active material, wherein the electrochemically active material comprises a layered potassium metal oxide, the layered potassium metal oxide having the formula K x The present invention also relates to an electrode, an electrochemical cell, and a battery comprising the electrode material. For example, the battery may be a lithium battery or a lithium ion battery, a sodium battery or a sodium ion battery, or a potassium battery or a potassium ion battery. According to one embodiment, the present technology provides an electrode material comprising an electrochemically active material, wherein the electrochemically active material has the formula K x MO2 layered potassium metal oxide, where x is 0

Description

[Technical Field]

[0001] Related Applications This application claims priority under applicable law to U.S. Provisional Patent Application No. 62 / 855,537, filed May 31, 2019, the entire contents of which are incorporated herein by reference for all purposes.

[0002] Technical Field This application relates to the field of electrochemically active materials and their use in electrochemical applications. More specifically, this disclosure generally relates to electrode materials comprising layered potassium metal oxides as electrochemically active materials, electrodes comprising such electrode materials, processes for manufacturing such electrode materials, and the use of such electrode materials in electrochemical cells. [Background technology]

[0003] background All-solid-state batteries are a new solution for electric vehicle batteries or main batteries for next-generation electric vehicles. Compared to conventional lithium-ion batteries using liquid electrolytes, all-solid-state batteries can generally be manufactured at lower cost and can achieve improved lifespan, short charging times, high performance, and high safety.

[0004] Due to their higher theoretical capacity, solid-state batteries have been recognized as being able to solve certain energy density problems associated with conventional lithium-ion batteries (batteries containing lithium metal or sodium metal anodes) and have been adapted to replace graphite anodes in high-density energy storage systems.

[0005] However, conventional commercially available cathode materials for lithium-ion batteries (e.g., lithium cobalt oxide (LiCoO) and lithium nickel manganese cobalt oxide (NMC) (LiNi 0.33 Mn 0.33 Co 0.33 O2(NMC111), LiNi 0.6 Mn 0.2 Co 0.2O2 (NMC622), and LiNi 0.8 Mn 0.1 Co 0.1 O2 (NMC 811), etc.) are costly, and the process of synthesizing or producing lithium-free electrode materials is complex. Therefore, the adoption of all-solid-state batteries, especially in large-scale energy storage systems, is limited.

[0006] Therefore, it is necessary to develop new electrode materials that do not have one or more drawbacks of conventional commercially available cathode materials. For example, materials for all-solid-state batteries with low cost, high capacity, and high voltage are required. Summary of the Invention Means for Solving the Problems

[0007] Abstract According to one aspect, the present technology is an electrode material containing an electrochemically active substance, wherein the aforementioned electrochemically active substance contains a layered potassium metal oxide of the formula K x MO2, where x is a numerical value such that 0 < x ≤ 0.7, and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these, and relates to an electrode material.

[0008] In one embodiment, the electrochemically active substance contains a layered potassium metal oxide of the formula K x M y Mn 1-y O2, where x is as defined herein, y is a numerical value such that 0 ≤ y ≤ 1.0, and M is selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these. For example, the layered potassium metal oxide is of the formula K x Fe y Mn 1-y O2, where x and y are as defined herein.

[0009] In another embodiment, the layered potassium metal oxide is K x Ni 0.5x Mn1-0.5x O2, where x is as defined herein.

[0010] In another embodiment, the layered potassium metal oxide is K x Ni 0.5x Mn 1-0.5x-y M y O2, where x is as defined herein, y is a number such that 0≦y≦(1.0−0.5x), and M is selected from Co, Fe, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two thereof. For example, layered potassium metal oxide is K x Ni 0.5x Mn 1-0.5x Ti y O2, where x and y are as defined herein.

[0011] In another embodiment, the layered potassium metal oxide is K 0.67 Ni 0.33 Mn 0.67 O2, K 0.6 Ni 0.3 Mn 0.7 O2, K 0.5 Ni 0.25 Mn 0.75 O2, K 0.4 Ni 0.2 Mn 0.8 O2, K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O2, K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O2, K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O2, K 0.4 Fe 0.4 Mn 0.6 O2, K 0.4 Ni 0.1 Mn 0.9 O2, K 0.4 MnO2, K 0.3 Ni 0.15 Mn 0.85 O2, K 0.3 Ni0.2 Mn 0.8 O2, K 0.3 MnO2, K 0.2 Ni 0.1 Mn 0.9 O2, K 0.2 Ni 0.2 Mn 0.8 O2, K 0.2 MnO2, K 0.1 Ni 0.05 Mn 0.95 O2, K 0.1 Ni 0.1 Mn 0.9 It is selected from the group consisting of O2 and combinations of at least two of these.

[0012] According to another aspect, the present technology is an electrode material containing an electrochemically active material, wherein the aforementioned electrochemically active material has the formula Na z K x It relates to an electrode material containing a layered potassium metal oxide of MO2, where x is a numerical value such that 0 < x ≦ 0.7, z is a numerical value such that 0 < x ≦ 0.8, and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these.

[0013] In one embodiment, the electrochemically active material has the formula Na z K x M y Mn 1-y It contains a layered potassium metal oxide of O2, where x and z are as defined herein, y is a numerical value such that 0 ≦ y ≦ 1.0, and M is selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these.

[0014] In another embodiment, the layered potassium metal oxide is of the formula Na z K x Ni y Mn 1-y Of the formula O2, where x and z are as defined herein, and y is a numerical value such that 0 ≦ y ≦ 1.0.

[0015] In another embodiment, the layered potassium metal oxide is Na 0.74 K 0.08 Ni 0.41 Mn 0.59 O2, Na 0.6 K 0.08 Ni 0.34 Mn 0.66 O2, Na 0.74 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.6 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.32 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.2 K 0.2 Ni 0.2 Mn 0.8 O2, and a combination of at least two thereof.

[0016] In another embodiment, the electrode material further comprises an electron-conducting material selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fiber, carbon nanofiber, carbon nanotube, and a combination of at least two thereof.

[0017] In another embodiment, the electrode material further comprises a binder. According to one example, the binder is selected from the group consisting of polyether-type polymer binders, fluoropolymers, and water-soluble binders.

[0018] According to another aspect, the present technology relates to an electrode comprising an electrode material, as defined herein, on a current collector.

[0019] In one embodiment, the electrode is a positive electrode.

[0020] According to another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein said positive electrode is as defined herein.

[0021] In one embodiment, the negative electrode comprises lithium metal, sodium metal, potassium metal, or an alloy comprising at least one of these.

[0022] In another embodiment, the negative electrode comprises at least one of a lithium pre-doped alloy, a lithium pre-doped graphite, a lithium pre-doped silicon, a lithium pre-doped oxide, or a combination of at least two of these.

[0023] In another embodiment, the negative electrode includes at least one of a sodium pre-doped alloy, a sodium pre-doped hard carbon, and a sodium pre-doped oxide.

[0024] In another embodiment, the negative electrode comprises at least one of a potassium pre-doped alloy, a potassium pre-doped graphite, a potassium pre-doped hard carbon, and a potassium pre-doped oxide.

[0025] In another embodiment, the electrolyte is a liquid electrolyte comprising a salt in a solvent.

[0026] In another embodiment, the electrolyte is a gel electrolyte comprising a solvent and optionally a salt in a solvating polymer.

[0027] In another embodiment, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.

[0028] According to one example, the salt is selected from lithium salts, sodium salts, potassium salts, and combinations of at least two of these.

[0029] In another embodiment, the electrolyte is a glass electrolyte or a ceramic electrolyte. For example, the electrolyte may be a site-deficient perovskite-type electrolyte, a garnet-type electrolyte, a NASICON-type glass-ceramic electrolyte, a LISICON-type electrolyte, a lithium-stabilized sodium ion (Na +) conductive aluminum oxide (Al2O3), and other similar glass or ceramic electrolytes.

[0030] According to another aspect, the present technology relates to a battery comprising at least one electrochemical cell as defined herein.

[0031] In one embodiment, the battery is selected from the group consisting of a lithium battery, a lithium ion battery, a sodium battery, a sodium ion battery, a potassium battery, and a potassium ion battery. [Brief explanation of the drawings]

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[0073] Detailed Description The following detailed description and examples are offered for purposes of illustration only and are not to be construed as further limiting the scope of the present invention.

[0074] All technical and scientific terms and expressions used herein have definitions that are commonly understood by those skilled in the art. However, definitions of some of the terms and expressions used are provided below.

[0075] When the term "approximately" or its equivalent term "about" is used herein, it means within or around the range.For example, when "approximately" or "about" is used in relation to a numerical value, these terms modify the numerical value up or down by 10% of the apparent value.This term can also take into account, for example, experimental error or rounding of measuring device.

[0076] Whenever a range of numerical values ​​is referred to in this application, the upper and lower limits of the range are always included in the definition, unless otherwise specified.

[0077] The present technology relates to an electrode material comprising layered potassium oxide and at least one metallic element as electrochemically active materials, a method for producing the same, and its use in electrochemical cells (e.g., lithium-ion batteries, sodium-ion batteries, or potassium-ion batteries).

[0078] According to one example, the present technology provides an electrode material comprising an electrochemically active material, wherein the electrochemically active material has the formula K xIt relates to an electrode material containing a layered potassium metal oxide of MO₂, where x is a numerical value such that 0 < x ≤ 0.7, and M is selected from Na, Li, Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and combinations of at least two of these.

[0079] According to another example, the electrochemically active material is of the formula K x It contains a layered potassium metal oxide of MO₂, where x is a numerical value such that 0 < x ≤ 0.7, and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these.

[0080] According to another example, the electrochemically active material is of the formula K x M y Mn 1-y It may contain a layered potassium metal oxide of O₂, where x is as defined herein, y is a numerical value such that 0 ≤ y ≤ 1.0, and M is selected from Na, Li, Co, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and combinations of at least two of these. According to one example, M may be selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these. For example, the electrochemically active material is of the formula K x Fe y Mn <s 1-y It may contain a layered potassium metal oxide of O₂, where y is as defined herein.

[0081] According to another example, the electrochemically active material is of the formula K x Ni 0.5x Mn 1-0.5x It may contain a layered potassium metal oxide of O₂, where x is as defined herein.

[0082] According to another example, the electrochemically active material is of the formula K x Ni 0.5x Mn 1-0.5x-y M ymay contain a layered potassium metal oxide of O2, where x is as defined herein, y is a numerical value such that 0 ≦ y ≦ (1.0 - 0.5x), and M is selected from Na, Li, Co, Fe, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and combinations of at least two of these. According to one example, M is selected from Co, Fe, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these. For example, the electrochemically active material has the formula K x Ni 0.5x Mn 1-0.5x Ti y may contain a layered potassium metal oxide of O2, where x and y are as defined herein. For example, the electrochemically active material has the formula K 0.4 Ni 0.2 Mn 0.8-y Ti y may contain a layered potassium metal oxide of O2, where y is a numerical value such that 0 ≦ y ≦ 0.8.

[0083] According to another example, the electrochemically active material contains a layered potassium metal oxide of the formula Na z K x MO2, where x is as defined herein, z is a numerical value such that 0 < x ≦ 0.8, and M is selected from Li, Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and combinations of at least two of these.

[0084] According to another example, the electrochemically active material contains a layered potassium metal oxide of the formula Na z K x MO2, where x and z are as defined herein, and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these.

[0085] According to another example, the electrochemically active material has the formula Na z K x M y Mn 1-yThe electrochemically active material may comprise a layered potassium metal oxide of formula NaO, where x and z are as defined herein, y is a number such that 0≦y≦1.0, and M is selected from Li, Co, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and combinations of at least two thereof. According to one example, M may be selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two thereof. For example, the electrochemically active material may comprise a layered potassium metal oxide of formula Na z K x Ni y Mn 1-y O2, where x, y, and z are as defined herein.

[0086] According to another example, the electrochemically active material may be of the formula K x MnO2, K x NiMnO2, K x NiMnTiO2, or K x Layered potassium metal oxides may include FeMnO2, where x is as defined herein. Non-limiting examples of layered potassium metal oxides include K 0.67 Ni 0.33 Mn 0.67 O2, K 0.6 Ni 0.3 Mn 0.7 O2, K 0.5 Ni 0.25 Mn 0.75 O2, K 0.4 Ni 0.2 Mn 0.8 O2, K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O2, K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O2, K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O2, K 0.4 Fe 0.4 Mn 0.6 O2, K 0.4 Ni 0.1 Mn 0.9O2, K 0.4 MnO2, K 0.3 Ni 0.15 Mn 0.85 O2, K 0.3 Ni 0.2 Mn 0.8 O2, K 0.3 MnO2, K 0.2 Ni 0.1 Mn 0.9 O2, K 0.2 Ni 0.2 Mn 0.8 O2, K 0.2 MnO2, K 0.1 Ni 0.05 Mn 0.95 O2, K 0.1 Ni 0.1 Mn 0.9 O2, Na 0.74 K 0.08 Ni 0.41 Mn 0.59 O2, Na 0.6 K 0.08 Ni 0.34 Mn 0.66 O2, Na 0.74 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.6 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.32 K 0.08 Ni 0.2 Mn 0.8 O2, and Na 0.2 K 0.2 Ni 0.2 Mn 0.8 Contains O2.

[0087] The electrochemically active material may be doped, for example, by including smaller amounts of other elements or impurities as needed to modify or optimize its electrochemical properties. In some cases, the electrochemically active material may be doped by partially substituting other ions for the metal. For example, the electrochemically active material may be doped with transition metals (e.g., Fe, Co, Ni, Mn, Ti, Cr, Cu, V, Zn, and / or Y) and / or metals other than transition metals (e.g., Mg, Al, and / or Sb).

[0088] The electrode material may be substantially free of lithium and / or sodium. For example, the electrochemically active material may contain less than 2 wt. %, less than 1 wt. %, less than 0.5 wt. %, less than 0.1 wt. %, less than 0.05 wt. %, or less than 0.01 wt. % lithium and / or sodium. For example, the electrochemically active material may be delithiated and / or desodium.

[0089] According to another example, the electrochemically active material may be in the form of particles (e.g., microparticles or nanoparticles), which may be newly formed and further include a coating material, which may be an electronically conductive material (e.g., a carbon coating).

[0090] According to another example, the electrode materials described herein may further comprise an electronically conductive material. Non-limiting examples of electronically conductive materials include carbon sources such as carbon black (e.g., Ketjen™ carbon or Super P™ carbon), acetylene black (e.g., Shawinigan carbon or Denka™ carbon black), graphite, graphene, carbon fibers (e.g., vapor-grown carbon fibers (VGCF)), carbon nanofibers, carbon nanotubes (CNTs), or combinations of at least two of these. According to one embodiment of the invention, the electronically conductive material is selected from Ketjen™ carbon, Super P™ carbon, VGCF, and combinations thereof.

[0091] According to another example, the electrode materials described herein may also include a binder. For example, the binder may be selected to be compatible with the various elements of the electrochemical cell. Any known compatible binder is contemplated. For example, the binder may be a fluorinated polymer binder, a water-soluble (water-soluble) binder, or an ion-conducting polymer binder (such as a copolymer composed of at least one lithium ion solvating segment (such as a polyether) and, optionally, at least one crosslinkable segment (e.g., a poly(ethylene oxide) (PEO)-based polymer containing methyl methacrylate units)). According to one example, the binder is a fluorinated polymer (such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE)). According to another example, the binder is a water-soluble binder (such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), epichlorohydrin rubber (CHR), or acrylate rubber (ACM)), optionally containing a thickener (such as carboxymethyl cellulose (CMC)), or a polymer (such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMMA)), or a combination thereof. According to another example, the binder is a polyether-type polymer binder. For example, polyether-type polymer binders are linear, branched, and / or crosslinked and are based on PEO, poly(propylene oxide) (PPO), or a combination thereof (such as an EO / PO copolymer), and optionally contain crosslinkable units. According to one embodiment of the invention, the binder is PVDF or a polyether-type polymer as defined herein.

[0092] The electrode materials described herein may further include additional components or additives, such as inorganic particles, glass or ceramic particles, ionic conductors, salts, and other similar additives.

[0093] The present technology also relates to an electrode comprising the electrode material defined herein on a current collector (e.g., aluminum foil or copper foil). Alternatively, the electrode may be self-supporting. According to one embodiment of the present invention, the electrode is a positive electrode.

[0094] The present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the positive electrode is as defined herein.

[0095] According to one example, the negative electrode (counter electrode) comprises an electrochemically active material selected from any known compatible electrochemically active material, for example, the electrochemically active material of the negative electrode may be selected to be electrochemically compatible with the various elements of the electrochemical cell defined herein.

[0096] Non-limiting examples of the negative electrode electrochemically active material include alkali metals, alkali metal alloys, lithium-doped electrochemically active materials, sodium-doped electrochemically active materials, and potassium-doped electrochemically active materials. According to one example, the negative electrode electrochemically active material may be lithium metal, sodium metal, potassium metal, or an alloy containing at least one of these. According to another example, the negative electrode electrochemically active material may be a lithium-doped alloy, lithium-doped graphite, lithium-doped silicon, lithium-doped oxide, or a suitable combination thereof. According to another example, the negative electrode electrochemically active material may be a sodium-doped alloy, sodium-doped hard carbon, or sodium-doped oxide. According to another example, the negative electrode electrochemically active material may be a potassium-doped alloy, potassium-doped graphite, potassium-doped hard carbon, or potassium-doped oxide.

[0097] According to another example, the electrolyte may also be selected to be compatible with the various elements of the electrochemical cell. Any type of compatible electrolyte is contemplated. According to one example, the electrolyte may be a liquid electrolyte comprising a salt in a solvent. According to one alternative, the electrolyte may be a gel electrolyte comprising a salt in a solvent and, optionally, a solvating polymer. According to another alternative, the electrolyte may be a solid polymer electrolyte comprising a salt in a solvating polymer. According to another alternative, the electrolyte may be a glass electrolyte or a ceramic electrolyte. According to one embodiment of the invention, the electrolyte is a solvent-free solid polymer electrolyte, a glass electrolyte, or a ceramic electrolyte.

[0098] The salt, when present in the electrolyte, may be a metal salt (such as a lithium, sodium, or potassium salt). Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPF), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO), lithium hexafluoroarsenate (LiAsF), lithium trifluoromethanesulfonate (LiSOCF) (LiTf), lithium fluoroalkyl phosphates Lithium salts include Li[PF(CFCF)] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF)] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate [B(CO)] (LiBBB), and combinations thereof. According to one embodiment of the invention, the lithium salt is LiPF, LiFSI, LiTFSI, or LiTDI. Non-limiting examples of sodium salts include sodium hexafluorophosphate (NaPF), sodium perchlorate (NaClO), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium bis(fluorosulfonyl)imide (NaFSI), sodium 2-trifluoromethyl-4,5-dicyanoimidazolate (NaTDI), sodium bis(pentafluoroethylsulfonyl)imide (NaBETI), sodium trifluoromethanesulfonate (NaTF), sodium fluoride (NaF), sodium nitrate (NaNO), and combinations thereof. According to one embodiment of the invention, the sodium salt is NaPF, NaFSI, NaTFSI, or NaClO.Non-limiting examples of potassium salts include potassium hexafluorophosphate (KPF6), potassium bis(trifluoromethanesulfonyl)imide (KTFSI), potassium bis(fluorosulfonyl)imide (KFSI), potassium trifluoromethanesulfonate (KSO3CF3) (KTf), and combinations thereof. According to one embodiment of interest, the potassium salt is KPF6.

[0099] The solvent, when present in the electrolyte, may be a non-aqueous solvent. Non-limiting examples of non-aqueous solvents include cyclic carbonates (such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC)); acyclic carbonates (such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC)); lactones (such as γ-butyrolactone (γ-BL) and γ-valerolactone (γ-VL)); linear ethers (such as 1,2-dimethoxyethylene carbonate (DMF)); ethane (DME), 1,2-diethoxyethane (DEE), and ethoxymethoxyethane (EME); cyclic ethers (such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, and dioxolane derivatives); and other solvents (such as dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, phosphoric acid triesters, sulfolane, methyl sulfolane, propylene carbonate derivatives, and its derivatives).

[0100] According to one example, the electrolyte comprises a salt selected from lithium hexafluorophosphate (LiPF), sodium hexafluorophosphate (NaPF), sodium perchlorate (NaClO), or potassium hexafluorophosphate (KPF), dissolved in a non-aqueous solvent mixture (such as a mixture of ethylene carbonate and diethyl carbonate (EC / DEC) in a volume ratio of 3:7, a mixture of ethylene carbonate and dimethyl carbonate (EC / DMC) in a volume ratio of 4:6), or dissolved in dimethyl carbonate (DMC) or propylene carbonate.

[0101] According to one example, the electrolyte is a liquid electrolyte, and the electrode material comprises an electrochemically active material, an electronically conductive material, and a binder in a composition ratio of about 80:10:10. For example, the electrode material comprises about 80% by weight of the electrochemically active material, about 10% by weight of the electronically conductive material, and about 10% by weight of the binder.

[0102] When the electrolyte is a gel electrolyte or a gel polymer electrolyte, the gel polymer electrolyte may contain, for example, a polymer precursor and a salt (e.g., a salt as defined above), a solvent (e.g., a solvent as defined above), and a polymerization initiator and / or a cross-linking initiator, if necessary. Non-limiting examples of gel electrolytes include, but are not limited to, the gel electrolytes described in PCT Patent Application Publication Nos. WO2009 / 111860 (Zaghib et al.) and WO2004 / 068610 (Zaghib et al.).

[0103] The electrolyte may also be a solid polymer electrolyte. For example, the solid polymer electrolyte may be selected from any known solid polymer electrolyte and may be selected to be compatible with various elements of the electrochemical cell. For example, the solid polymer electrolyte may be selected to be compatible with lithium, sodium, and / or potassium. The solid polymer electrolyte generally includes a salt and one or more solid polar polymer(s), optionally crosslinked. Polyether-type polymers (such as PEO-based) may be used, although several other compatible polymers are also known for preparing solid polymer electrolytes and are contemplated. The polymer may be crosslinked. Examples of such polymers include branched polymers, such as star polymers or comb polymers (such as those described in PCT patent application published as WO 2003 / 063287 (Zaghib et al.)).

[0104] According to one example, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer. According to an embodiment of the present invention, the polymer of the solid polymer electrolyte is PEO and the salt is LiTFSI, LiFSI, LiTDI, NaTFSI, or NaFSI.

[0105] According to another example, the electrolyte is a solid polymer electrolyte, and the electrode material comprises about 50% to about 75% by weight of an electrochemically active material, about 1% to about 5% by weight of an electronically conductive material, and about 20% to about 49% by weight of a binder.

[0106] According to another example, the electrolyte is a ceramic electrolyte. For example, the ceramic electrolyte may include a crystalline ion-conducting ceramic or an amorphous ion-conducting ceramic (e.g., an amorphous ion-conducting glass) or an ion-conducting glass-ceramic. Non-limiting examples of glass or ceramic electrolytes include site-deficient perovskite-type electrolytes, garnet-type electrolytes, NASICON-type glass-ceramic electrolytes, LISICON-type electrolytes, lithium-stabilized sodium ion (Na +) conductive aluminum oxide (Al2O3), and other similar glass or ceramic electrolytes.

[0107] The gel electrolyte or liquid electrolyte defined above may also be impregnated into a separator, such as a polymer separator. Non-limiting examples of separators include polyethylene (PE), polypropylene (PP), cellulose, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and polypropylene-polyethylene-polypropylene (PP / PE / PP). For example, the separator may be a commercially available polymer separator of the Celgard™ type.

[0108] The electrolyte may also optionally contain further components or additives, such as ionic conductors, inorganic particles, glass or ceramic particles (e.g., nanoceramics such as Al2O3, TiO2, SiO2, and other similar compounds) and other such additives.

[0109] The present technology also relates to a battery comprising at least one electrochemical cell as defined herein. For example, the battery may be a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery, or a potassium-ion battery.

[0110] According to at least one example, the battery is a lithium battery or a lithium-ion battery. According to one example, the electrolyte is a liquid electrolyte as defined herein, and the electrochemically active material of the negative electrode comprises lithium metal, a lithium-based alloy, a lithium-pre-doped alloy, lithium-pre-doped graphite, lithium-pre-doped silicon, or lithium-pre-doped oxide. According to another example, the electrolyte is a gel electrolyte as defined herein, and the electrochemically active material of the negative electrode comprises lithium metal, a lithium-based alloy, a lithium-pre-doped alloy, lithium-pre-doped graphite, or lithium-pre-doped silicon. According to another example, the electrolyte is a solid polymer electrolyte, and the electrochemically active material of the negative electrode comprises lithium metal, a lithium-based alloy, lithium-pre-doped graphite, or lithium-pre-doped silicon. According to another example, the electrolyte is a ceramic electrolyte, and the electrochemically active material of the negative electrode comprises lithium metal, a lithium-based alloy, or lithium-pre-doped graphite, and / or lithium-pre-doped silicon.

[0111] According to at least one example, the battery is a sodium battery or a sodium-ion battery. According to one example, the electrolyte is a liquid electrolyte as defined herein, and the electrochemically active material of the negative electrode includes sodium metal, a sodium-based alloy, a sodium-pre-doped alloy, a sodium-pre-doped hard carbon, or a sodium-pre-doped oxide. According to another example, the electrolyte is a gel electrolyte as defined herein, and the electrochemically active material of the negative electrode includes sodium metal, a sodium-based alloy, a sodium-pre-doped alloy, or a sodium-pre-doped hard carbon. According to another example, the electrolyte is a solid polymer electrolyte, and the electrochemically active material of the negative electrode includes sodium metal, a sodium-based alloy, or a sodium-pre-doped hard carbon. According to another example, the electrolyte is a ceramic electrolyte, and the electrochemically active material of the negative electrode includes sodium metal, a sodium-based alloy, or a sodium-pre-doped hard carbon.

[0112] According to at least one example, the battery is a potassium battery or a potassium ion battery. According to one example, the electrolyte is a liquid electrolyte as defined herein, and the electrochemically active material of the negative electrode includes potassium metal, a potassium-based alloy, a potassium pre-doped alloy, potassium pre-doped graphite, potassium pre-doped hard carbon, or a potassium pre-doped oxide. According to another example, the electrolyte is a gel electrolyte as defined herein, and the electrochemically active material of the negative electrode includes potassium metal, a potassium-based alloy, a potassium pre-doped alloy, potassium pre-doped graphite, or potassium pre-doped hard carbon. According to another example, the electrolyte is a solid polymer electrolyte, and the electrochemically active material of the negative electrode includes potassium metal, a potassium-based alloy, potassium pre-doped graphite, or potassium pre-doped hard carbon. According to another example, the electrolyte is a ceramic electrolyte, and the electrochemically active material of the negative electrode includes potassium metal, a potassium-based alloy, potassium pre-doped graphite, or potassium pre-doped hard carbon.

[0113] Also, the present technology is in a crystalline form and is a layered potassium metal oxide of the formula K x MO2, where x is a numerical value such that 0 < x ≦ 0.7, and M is selected from Li, Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and combinations thereof, and relates to a layered potassium metal oxide.

[0114] Also, the present technology is in a crystalline form and is a layered potassium metal oxide of the formula K x MO2, where x is a numerical value such that​​​​​​​​​​​

[0116] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.6 Ni 0.3 Mn 0.7 O2 and has an XRD pattern substantially as shown in FIG.

[0117] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.5 Ni 0.25 Mn 0.75 O2 and has an XRD pattern substantially as shown in FIG.

[0118] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.4 Ni 0.2 Mn 0.8 O2 and has an XRD pattern substantially as shown in FIG.

[0119] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O2 and has an XRD pattern substantially as shown in FIG.

[0120] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O2 and has an XRD pattern substantially as shown in FIG.

[0121] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O2 and has an XRD pattern substantially as shown in FIG.

[0122] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.4 Fe 0.4 Mn 0.6O2 and has an XRD pattern substantially as shown in FIG.

[0123] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.4 Ni 0.1 Mn 0.9 O2 and has an XRD pattern substantially as shown in FIG.

[0124] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.4 MnO2 and has an XRD pattern substantially as shown in FIG.

[0125] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.3 Ni 0.15 Mn 0.85 O2 and has an XRD pattern substantially as shown in FIG.

[0126] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.3 Ni 0.2 Mn 0.8 O2 and has an XRD pattern substantially as shown in FIG.

[0127] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.3 MnO2 and has an XRD pattern substantially as shown in FIG.

[0128] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.2 Ni 0.1 Mn 0.9 O2 and has an XRD pattern substantially as shown in FIG.

[0129] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.2 Ni 0.2 Mn 0.8 O2 and has an XRD pattern substantially as shown in FIG.

[0130] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.2 MnO2 and has an XRD pattern substantially as shown in FIG.

[0131] According to another alternative, the layered potassium metal oxide in crystalline form is of the formula K 0.1 Ni 0.05 Mn 0.95 O2 and has an XRD pattern substantially as shown in FIG.

[0132] According to another alternative, the layered potassium metal oxide in crystalline form has the formula Na 0.74 K 0.08 Ni 0.41 Mn 0.59 O2, Na 0.6 K 0.08 Ni 0.34 Mn 0.66 O2, Na 0.74 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.6 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.32 K 0.08 Ni 0.2 Mn 0.8 O2, or Na 0.2 K 0.2 Ni 0.2 Mn 0.8 O2 and has an XRD pattern substantially as shown in FIG.

[0133] According to at least one example, formula K x Layered potassium metal oxides in the crystalline form of MO2 have XRD 2θ (°) reflections substantially as shown in Figure 39. According to one alternative, x Layered potassium metal oxide in the crystalline form of MO2 has XRD 2θ (°) reflections substantially as shown in FIG. 40. According to another alternative, the layered potassium metal oxide of formula K x Layered potassium metal oxide in the crystalline form of MO2 has XRD 2θ (°) reflections substantially as shown in FIG.

[0134] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.4 Ni 0.2 Mn 0.8 O2 and has an XRD pattern substantially as shown in FIG. 4 or XRD 2θ reflections (°) substantially as shown in FIG.

[0135] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O2 and has an XRD pattern substantially as shown in FIG.

[0136] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O2 and having an XRD pattern substantially as shown in FIG. 6 or XRD 2θ reflections (°) substantially as shown in FIG.

[0137] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O2 and having an XRD pattern substantially as shown in FIG. 7 or XRD 2θ reflections (°) substantially as shown in FIG.

[0138] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.4 Fe 0.4 Mn 0.6 O2 and having an XRD pattern substantially as shown in FIG. 8 or XRD 2θ reflections (°) substantially as shown in FIG.

[0139] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.4 Ni 0.1 Mn 0.9O2 and having an XRD pattern substantially as shown in FIG. 9 or having XRD 2θ reflections (°) substantially as shown in FIG. 39 and / or FIG.

[0140] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.3 Ni 0.15 Mn 0.85 O2 and having an XRD pattern substantially as shown in FIG. 11 or XRD 2θ reflections (°) substantially as shown in FIG.

[0141] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.3 Ni 0.2 Mn 0.8 O2 and having an XRD pattern substantially as shown in FIG. 12 or XRD 2θ reflections (°) substantially as shown in FIG.

[0142] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.2 Ni 0.1 Mn 0.9 O2 and having an XRD pattern substantially as shown in FIG. 14 or having XRD 2θ reflections (°) substantially as shown in FIG. 40 and / or FIG.

[0143] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.2 Ni 0.2 Mn 0.8 O2 and having an XRD pattern substantially as shown in FIG. 15 or XRD 2θ reflections (°) substantially as shown in FIG.

[0144] According to another embodiment of the object, the layered potassium metal oxide in crystalline form has the formula K 0.1 Ni 0.05 Mn 0.95 O2 and having an XRD pattern substantially as shown in FIG. 17 or XRD 2θ reflections (°) substantially as shown in FIG. [Example]

[0145] The following examples are for illustrative purposes and should not be construed to further limit the scope of the invention as contemplated. These examples will be better understood by reference to the accompanying drawings. Example 1: Synthesis of electrochemically active materials a) Solid phase synthesis

[0146] formula K 0.67 Ni 0.33 Mn 0.67 O2, K 0.6 Ni 0.3 Mn 0.7 O2, K 0.5 Ni 0.25 Mn 0.75 O2, K 0.4 Ni 0.2 Mn 0.8 O2, K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O2, K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O2, K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O2, K 0.4 Fe 0.4 Mn 0.6 O2, K 0.4 Ni 0.1 Mn 0.9 O2, K 0.4 MnO2, K 0.3 Ni 0.15 Mn 0.85 O2, K 0.3 Ni 0.2 Mn 0.8 O2, K 0.3 MnO2, K 0.2 Ni 0.1 Mn 0.9 O2, K 0.2 Ni 0.2 Mn 0.8 O2, K 0.2 MnO2, K 0.1 Ni 0.05 Mn 0.95 O2, K 0.1 Ni 0.1 Mn 0.9O2, Na 0.74 K 0.08 Ni 0.41 Mn 0.59 O2, Na 0.6 K 0.08 Ni 0.34 Mn 0.66 O2, Na 0.74 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.6 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.32 K 0.08 Ni 0.2 Mn 0.8 O2, and Na 0.2 K 0.2 Ni 0.2 Mn 0.8 Layered potassium metal oxides of O2 were prepared using a solid-state reaction technique. The respective precursors (K2CO3 / KOH and metal oxides such as Na2CO3, Mn2O3, Co2O3, CuO, ZrO2, NiO, Fe2O3, and TiO2) were weighed to obtain the desired stoichiometry. Samples were prepared by grinding and mixing the precursor powders. The ground and mixed precursor powders were then placed in a furnace and heated to temperatures between 600 and 1000°C in an air or oxygen atmosphere for 5 to 24 hours. For example, samples were heated to temperatures between 800 and 1000°C for 6 to 8 hours. b) Wet chemical synthesis

[0147] Alternatively, the layered potassium metal oxides defined herein may be prepared using wet chemical synthesis techniques. For example, the layered potassium metal oxides defined herein may be prepared by a sol-gel method, such as the sol-gel (333SG) method similar to that described by Hashem et al. (Hashem, Ahmed M., et al. Research on Engineering Structures and Materials 1.2 (2015): 81-97). For example, using this sol-gel method, sol-gel powder (333SG) is synthesized using citric acid as a chelating agent. Each precursor (metal acetate salt, where the metal is Na, Mn, Ti, K, Fe, or Ni) is weighed to obtain the desired stoichiometry and dissolved in distilled water. The solution is added dropwise to a continuously stirred solution of approximately 1 mol / L citric acid in water. The pH is adjusted to between approximately pH 7.0 and approximately pH 8.0 using ammonium hydroxide. The solution was then heated to between approximately 70 and 80 °C while stirring to evaporate the solvent until a transparent sol-gel precursor was obtained. The resulting sol-gel precursor was then calcined in an oven at approximately 450 °C in an air or oxygen atmosphere for approximately 8 hours to remove organic content. Finally, the resulting powder was crushed in a mortar and calcined at approximately 900 °C for approximately 12 hours. Example 2: Characterization of electrochemically active materials a) Powder X-ray diffraction (XRD)

[0148] The atomic and molecular structure of the electrochemically active material was studied by X-ray diffraction performed on the layered potassium metal oxide powder prepared in Example 1(a). 0.67 Ni 0.33 Mn 0.67 O2, K 0.6 Ni 0.3 Mn 0.7 O2, K 0.5 Ni 0.25 Mn 0.75 O2, K 0.4 Ni 0.2 Mn 0.8 O2, K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O2, K0.4 Ni 0.2 Mn 0.7 Ti 0.1 O2, K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O2, K 0.4 Fe 0.4 Mn 0.6 O2, K 0.4 Ni 0.1 Mn 0.9 O2, K 0.4 MnO2, K 0.3 Ni 0.15 Mn 0.85 O2, K 0.3 Ni 0.2 Mn 0.8 O2, K 0.3 MnO2, K 0.2 Ni 0.1 Mn 0.9 O2, K 0.2 Ni 0.2 Mn 0.8 O2, K 0.2 MnO2, and K 0.1 Ni 0.05 Mn 0.95 The X-ray diffraction pattern of the layered potassium metal oxide powder of O2 is shown in (A). 0.74 K 0.08 Ni 0.41 Mn 0.59 O2, Na 0.6 K 0.08 Ni 0.34 Mn 0.66 O2, Na 0.74 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.6 K 0.08 Ni 0.2 Mn 0.8 O2, Na 0.32 K 0.08 Ni 0.2 Mn 0.8 O2, and Na 0.2 K 0.2 Ni 0.2 Mn 0.8 1 shows the X-ray diffraction pattern of layered potassium metal oxide powder of O2.

[0149] X-ray spectra were obtained using a Rigaku Smartlab™ X-ray diffractometer equipped with a cobalt X-ray source emitting X-rays at a wavelength λ=1.78901 Å. b) Crystal structure characteristics

[0150] Data processing and crystal structure characterization were performed by indexing and comparison of XRD spectra with database patterns to confirm the crystal structure of layered potassium metal oxides.

[0151] 1 to 3(B) and FIG. 9(C) respectively show the crystal structure of formula K 0.67 Ni 0.33 Mn 0.67 O2, K 0.6 Ni 0.3 Mn 0.7 O2, K 0.5 Ni 0.25 Mn 0.75 O2, and K 0.4 Ni 0.1 Mn 0.9 A diagram of the crystal structure of layered potassium metal oxide of O2 is shown. [Table 1]

[0152] The reflectance parameters of layered potassium metal oxides having the crystal structure characteristics shown in Table 1 are shown in FIG.

[0153] 4, 6, 7, 9, 11, 12, and 14(B) show the crystal structure of formula K, which has the characteristics of the crystal structure shown in Table 2. 0.4 Ni 0.2 Mn 0.8 O2, K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O2, K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O2, K 0.4 Ni 0.1 Mn 0.9 O2, K 0.3 Ni 0.15 Mn 0.85O2, K 0.3 Ni 0.2 Mn 0.8 O2, and K 0.2 Ni 0.1 Mn 0.9 A diagram of the crystal structure of layered potassium metal oxide of O2 is shown. [Table 2]

[0154] The reflectance parameters of layered potassium metal oxides having the crystal structure characteristics shown in Table 2 are shown in FIG.

[0155] 8(B), 14(C), 15(B), and 17(B) show the crystal structure of formula K, respectively, which has the crystal structure characteristics shown in Table 3. 0.4 Fe 0.4 Mn 0.6 O2, K 0.2 Ni 0.1 Mn 0.9 O2, K 0.2 Ni 0.2 Mn 0.8 O2, and K 0.1 Ni 0.05 Mn 0.95 A diagram of the crystal structure of layered potassium metal oxide of O2 is shown. [Table 3]

[0156] The reflectance parameters of layered potassium metal oxides having the crystal structure characteristics shown in Table 3 are shown in FIG.

[0157] 10 and 13 respectively show the crystal structure of formula K 0.4 MnO2 and K 0.3 A diagram of the crystal structure of the layered potassium metal oxide MnO2 is shown in (B). [Table 4]

[0158] Figure 16 shows the formula K 0.2The crystal structure of the layered potassium metal oxide MnO2 is shown in (B). The main phase consists of tetragonal manganese oxide Mn3O4.

[0159] As mentioned above, the formula K 0.4 Ni 0.1 Mn 0.9 O2 (Fig. 9, Tables 1 and 2) and K 0.2 Ni 0.1 Mn 0.9 Two structures of the layered potassium metal oxide of O2 (Figure 14, Tables 2 and 3) are proposed. Indeed, according to the X-ray diffraction patterns, these two structures may be possible. Example 3: Electrochemical properties

[0160] The electrochemical properties of the electrochemically active material prepared in Example 1(a) were investigated. An electrochemical cell was assembled according to the electrochemical cell configuration shown in Table 5. a) Electrochemical cell configuration

[0161] [Table 5]

[0162] All electrochemical cells were assembled in 2032-type coin cell casings using the components listed above on an aluminum current collector and a negative electrode comprising a thin metallic film of lithium or sodium. The electrochemical cells contained electrode materials including approximately 80% by weight of electrochemically active material, approximately 10% by weight of binder (PVDF), and approximately 10% by weight of electronically conductive material (Ketjen™ black, Super P™, or VGCF). All electrochemical cells containing liquid electrolytes were assembled using Celgard™ separators.

[0163] The separator of an electrochemical cell containing a negative electrode containing a lithium metal thin film was impregnated with a 1 M LiPF6 solution of an EC / DMC mixture (volume ratio [4:6]) and approximately 2 vol% VC as the liquid electrolyte.

[0164] The separator of an electrochemical cell containing a negative electrode containing a sodium metal thin film was impregnated with a 1 M NaPF6 solution of EC / DEC (volume ratio [3:7]) or EC / DMC (volume ratio [4:6]) as a liquid electrolyte. b) Electrochemical behavior of layered potassium metal oxides

[0165] This example describes the electrochemical behavior of the electrochemical cell described in Example 3(a).

[0166] FIG. 19 shows the formula K recorded for x between 0.1 and 0.7. x Ni 0.5x Mn 1-0.5x Capacity (mAh.g) of layered potassium metal oxides of O -1 19 shows a graph of x vs. the results for a lithium-ion battery (red line) and a sodium-ion battery (black line). As shown in FIG. 19, x may preferably be about 0.4.

[0167] Figures 20-37 show the charge-discharge profiles of cells 1-28 and 33-35. Between 1.5 V and 4.5 V vs. Li for all electrochemical cells containing lithium metal thin film as the negative electrode. + / Li at 0.1 C, and between 1.5 V and 4.2 V vs. Na for all electrochemical cells containing sodium metal thin film as the negative electrode. + The cells were charged and discharged at 0.1 C with 0.1% Na / Na. Starting from the discharge, the cells were charged and discharged at a temperature of 25°C. Results are shown for the first (black line, 1), second (red line, 2), and finally third (blue line, 3) charge-discharge cycles. The capacity delivered by each electrochemical cell is shown in Table 6. [Table 6]

[0168] Figure 38 shows the capacity (mAh g) as a function of cycle number for cells 1, 3, 5, 17, 19, 25, and 31 in (A); and cells 2, 4, 6, 18, 26, and 32 in (B). -1Graphs showing the efficiency (%) and charge / discharge current (C / 10) were used for long-term cycling experiments at a temperature of about 25°C. The results shown in Figure 38(A) show the charge / discharge current vs. Li for about 45 cycles. + (B) shows the results of the 35 cycles recorded at 1000kJ / Li vs. Na + Recorded in / Na.

[0169] Many modifications can be made to any of the above embodiments without departing from the contemplated scope of the invention. All references, patents, or scientific papers mentioned in this application are incorporated herein by reference in their entirety for all purposes. The present invention provides, for example, the following items. (Item 1) An electrode material containing an electrochemically active material, wherein the electrochemically active material contains a layered potassium metal oxide of the formula K x MO 2 where x is a numerical value such that 0 < x ≦ 0.7, and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these, an electrode material. (Item 2) The electrode material according to Item 1, wherein the electrochemically active material contains a layered potassium metal oxide of the formula K x M y Mn 1-y O 2 where x is as defined in Item 1, y is a numerical value such that 0 ≦ y ≦ 1.0, and M is selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these. (Item 3) ​ x ​ y ​ 1-y O 2 ​ ​ ​ x ​ 2 ​ ​ ​ x ​ 2 ​ ​ ​ x ​ 2 ​ ​ ​ x ​ 2 ​ ​ ​ x ​ 0.5x ​ 1-0.5x O 2 ​ ​ ​ x ​ 0.5x ​ 1-0.5x-y M y O 2 It is as defined in item 1, where x is as defined in item 1, y is a numerical value such that 0 ≦ y ≦ (1.0 - 0.5x), and M is an electrode material described in item 1 or 2 selected from Co, Fe, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these. (Item 10) The layered potassium metal oxide has the formula K x Ni 0.5x Mn 1-0.5x Ti y O 2 It is as defined in item 1, where x is as defined in item 1 and y is as defined in item 9, and is the electrode material described in item 9. (Item 11) The layered potassium metal oxide has the formula K 0.4 Ni 0.2 Mn 0.8-y Ti y O 2 It is as defined in item 9 or 10, where y is a numerical value such that 0 ≦ y ≦ 0.8, and is the electrode material described in item 9 or 10. (Item 12) The layered potassium metal oxide is K 0.67 Ni 0.33 Mn 0.67 O 2 、K 0.6 Ni 0.3 Mn 0.7 O 2 、K 0.5 Ni 0.25Mn 0.75 O 2 、K 0.4 Ni 0.2 Mn 0.8 O 2 、K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O 2 、K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O 2 、K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O 2 、K 0.4 Fe 0.4 Mn 0.6 O 2 、K 0.4 Ni 0.1 Mn 0.9 O 2 、K 0.4 MnO 2 、K 0.3 Ni 0.15 Mn 0.85 O 2 、K 0.3 Ni 0.2 Mn 0.8 O 2 、K 0.3 MnO 2 、K 0.2 Ni 0.1 Mn 0.9 O 2 、K 0.2 Ni 0.2 Mn 0.8 O 2 、K 0.2 MnO 2 、K 0.1 Ni 0.05 Mn 0.95 O 2 、K 0.1 Ni 0.1 Mn 0.9 O 2 and is the electrode material described in any one of items 1 to 11 selected from the group consisting of these and combinations of at least two of these. (Item 13) The layered potassium metal oxide is K 0.4 Ni 0.2 Mn 0.8 O 2 and is the electrode material described in item 12. (Item 14) The layered potassium metal oxide is K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O 2 and is the electrode material described in item 12. (Item 15) The layered potassium metal oxide is K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O 2 and is the electrode material described in item 12. (Item 16) The layered potassium metal oxide is K 0.4 Fe 0.4 Mn 0.6 O 2 and is the electrode material described in item 12. (Item 17) An electrode material containing an electrochemically active substance, wherein the electrochemically active substance contains a layered potassium metal oxide of the formula Na z K x MO 2 where x is a numerical value such that 0 < x ≦ 0.7, z is a numerical value such that 0 < x ≦ 0.8, and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these. (Item 18) The electrochemically active substance contains a layered potassium metal oxide of the formula Na z K x M y Mn 1-y O 2 where x and z are as defined in item 17, y is a numerical value such that 0 ≦ y ≦ 1.0, and M is selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, Sb, and combinations of at least two of these, and is the electrode material described in item 17. (Item 19) The layered potassium metal oxide has the formula Na z K x Ni y Mn 1-y O 2 19. The electrode material according to item 17 or 18, wherein x and z are as defined in item 17, and y is a number such that 0≦y≦1.0. (Item 20) The layered potassium metal oxide is Na 0.74 K 0.08 Ni 0.41 Mn 0.59 O 2 , Na 0.6 K 0.08 Ni 0.34 Mn 0.66 O 2 , Na 0.74 K 0.08 Ni 0.2 Mn 0.8 O 2 , Na 0.6 K 0.08 Ni 0.2 Mn 0.8 O 2 , Na 0.32 K0.08 Ni 0.2 Mn 0.8 O 2 , Na 0.2 K 0.2 Ni 0.2 Mn 0.8 O 2 20. The electrode material according to any one of items 17 to 19, selected from the group consisting of: and a combination of at least two of them. (Item 21) The layered potassium metal oxide is Na 0.74 K 0.08 Ni 0.41 Mn 0.59 O 2 21. The electrode material according to item 20, (Item 22) The layered potassium metal oxide is Na 0.6 K 0.08 Ni 0.34 Mn 0.66 O 2 21. The electrode material according to item 20, (Item 23) The layered potassium metal oxide is Na 0.74 K 0.08 Ni 0.2 Mn 0.8 O 2 21. The electrode material according to item 20, (Item 24) The layered potassium metal oxide is Na 0.6 K 0.08 Ni 0.2 Mn 0.8 O 2 21. The electrode material according to item 20, (Item 25) The layered potassium metal oxide is Na 0.32 K 0.08 Ni0.2 Mn 0.8 O 2 21. The electrode material according to item 20, (Item 26) The layered potassium metal oxide is Na 0.2 K 0.2 Ni 0.2 Mn 0.8 O 2 21. The electrode material according to item 20, (Item 27) 27. The electrode material according to any one of items 1 to 26, further comprising an electron-conducting material. (Item 28) Item 28. The electrode material according to item 27, wherein the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fiber, carbon nanofiber, carbon nanotube, and a combination of at least two thereof. (Item 29) Item 29. The electrode material according to item 28, wherein the electronically conductive material comprises carbon fiber. (Item 30) 30. The electrode material according to item 29, wherein the carbon fiber is vapor grown carbon fiber (VGCF). (Item 31) Item 29. The electrode material according to item 28, wherein the electronically conductive material comprises carbon black. (Item 32) 32. The electrode material according to item 31, wherein the carbon black is Super P™ carbon. (Item 33) 32. The electrode material according to item 31, wherein the carbon black is Ketjen™ carbon. (Item 34) 34. The electrode material according to any one of items 1 to 33, further comprising a binder. (Item 35) Item 35. The electrode material according to item 34, wherein the binder is selected from the group consisting of polyether-type polymer binders, fluorinated polymers, and water-soluble binders. (Item 36) 36. The electrode material according to item 35, wherein the binder is a fluorinated polymer selected from polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE). (Item 37) 37. The electrode material according to item 36, wherein the binder is polyvinylidene fluoride (PVDF). (Item 38) 36. The electrode material according to item 35, wherein the binder is a polyether type polymer binder. (Item 39) 39. The electrode material according to item 38, wherein the polyether type polymer binder is branched and / or crosslinked. (Item 40) 40. The electrode material according to item 38 or 39, wherein the polyether type polymer binder is a polyethylene oxide (PEO) based polymer. (Item 41) 41. An electrode comprising an electrode material as defined in any one of items 1 to 40 on a current collector. (Item 42) 42. The electrode according to item 41, wherein the electrode is a positive electrode. (Item 43) 43. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the positive electrode is as defined in item 41 or 42. (Item 44) Item 44. The electrochemical cell of item 43, wherein the negative electrode comprises lithium metal, sodium metal, potassium metal, or an alloy containing at least one of these. (Item 45) Item 44. The electrochemical cell of item 43, wherein the negative electrode comprises at least one of a lithium pre-doped alloy, a lithium pre-doped graphite, a lithium pre-doped silicon, a lithium pre-doped oxide, or a combination of at least two thereof. (Item 46) Item 44. The electrochemical cell of item 43, wherein the negative electrode comprises at least one of a sodium pre-doped alloy, a sodium pre-doped hard carbon, and a sodium pre-doped oxide. (Item 47) Item 44. The electrochemical cell of item 43, wherein the negative electrode comprises at least one of a potassium pre-doped alloy, a potassium pre-doped graphite, a potassium pre-doped hard carbon, and a potassium pre-doped oxide. (Item 48) 48. The electrochemical cell according to any one of items 43 to 47, wherein the electrolyte is a liquid electrolyte comprising a salt in a solvent. (Item 49) 48. The electrochemical cell according to any one of items 43 to 47, wherein the electrolyte is a gel electrolyte comprising a solvent and optionally a salt in a solvating polymer. (Item 50) 48. The electrochemical cell of any one of items 43 to 47, wherein the electrolyte is a solid polymer electrolyte comprising a salt in a solvated polymer. (Item 51) 51. The electrochemical cell of any one of items 48 to 50, wherein the salt is selected from a lithium salt, a sodium salt, a potassium salt, and a combination of at least two thereof. (Item 52) 52. The electrochemical cell according to any one of items 48 to 51, wherein the salt is a lithium salt. (Item 53) The lithium salt is lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF 4 ), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO 3 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiSO 3 CF 3 )(LiTf), lithium fluoroalkylphosphate Li[PF 3 (CF 2 CF 3 ) 3 ](LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF 3 ) 4 ](LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate [B(C 6 O 2 ) 2 53. The electrochemical cell of item 52, wherein the lithium ion battery is selected from the group consisting of: 1) LiBBB; 2) LiBBB; and combinations of at least two thereof. (Item 54) The lithium salt is LiPF 6 54. The electrochemical cell according to item 52 or 53, wherein the lithium ion source is selected from LiFSI, LiTFSI, LiTDI, and a combination of at least two thereof. (Item 55) 52. The electrochemical cell according to any one of items 48 to 51, wherein the salt is a sodium salt. (Item 56) The sodium salt is sodium hexafluorophosphate (NaPF 6 ), sodium perchlorate (NaClO 4 ), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium bis(fluorosulfonyl)imide (NaFSI), sodium 2-trifluoromethyl-4,5-dicyanoimidazolate (NaTDI), sodium bis(pentafluoroethylsulfonyl)imide (NaBETI), sodium trifluoromethanesulfonate (NaTF), sodium fluoride (NaF), sodium nitrate (NaNO 3 56. The electrochemical cell of claim 55, wherein the compound is selected from the group consisting of: (Item 57) The sodium salt is NaPF 6 57. The electrochemical cell of item 55 or 56, wherein the cation exchange material is selected from NaFSI, NaTFSI, NaClO4, and a combination of at least two thereof. (Item 58) 52. The electrochemical cell according to any one of items 48 to 51, wherein the salt is a potassium salt. (Item 59) The potassium salt is potassium hexafluorophosphate (KPF 6 ), potassium bis(trifluoromethanesulfonyl)imide (KTFSI), potassium bis(fluorosulfonyl)imide (KFSI), potassium trifluoromethanesulfonate (KSO 3 CF 3 )(KTf), and a combination of at least two thereof. (Item 60) The potassium salt is KPF 6 60. The electrochemical cell according to item 58 or 59, wherein (Item 61) 48. The electrochemical cell according to any one of items 43 to 47, wherein the electrolyte is a glass electrolyte or a ceramic electrolyte. (Item 62) The electrolyte may be a site-deficient perovskite-type electrolyte, a garnet-type electrolyte, a NASICON-type glass ceramic electrolyte, a LISICON-type electrolyte, a lithium-stabilized sodium ion (Na + ) Conductive Aluminum Oxide (Al 2 O 3 62. The electrochemical cell of claim 61, wherein the electrolyte is a glass or ceramic electrolyte selected from the group consisting of: (Item 63) A battery comprising at least one electrochemical cell as defined in any one of paragraphs 43 to 62. (Item 64) Item 64. The battery of item 63, wherein the battery is selected from the group consisting of a lithium battery, a lithium ion battery, a sodium battery, a sodium ion battery, a potassium battery, and a potassium ion battery. (Item 65) 65. The battery of item 63 or 64, wherein the battery is a lithium ion battery. (Item 66) 65. The battery of item 63 or 64, wherein the battery is a sodium ion battery. (Item 67) 65. The battery of item 63 or 64, wherein the battery is a potassium ion battery.

Claims

1. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, The positive electrode comprises an electrode material including an electrochemically active material, the electrochemically active material having the formula K ｘ MO ２ wherein x is a number such that 0<x≦0.7 and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, and combinations of at least two thereof; The negative electrode contains metallic lithium or metallic sodium. Electrochemical cell.

2. The anhydrous layered potassium metal oxide is represented by the formula K ｘ M ｙ Mn １－ｙ O ２ 10. The electrochemical cell of claim 1, wherein x is a number such that 0<x≦0.7, y is a number such that 0≦y≦1.0, and M is selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, and combinations of at least two thereof.

3. The anhydrous layered potassium metal oxide has the formula K ｘ Fe ｙ Mn １－ｙ O ２ 3. The electrochemical cell of claim 1, wherein x is a number such that 0<x≦0.7 and y is a number such that 0≦y≦1.

0.

4. The anhydrous layered potassium metal oxide has the formula K ｘ MnO ２ , K. ｘ Ni y Mn 1-y O ２ , K. ｘ Ni y M n 1-y-w Ti w O ２ , K. ｘ Fe y Mn 1-y O ２ or K ｘ Ni ０．５ｘ Mn １－０．５ｘ O ２ 3. The electrochemical cell of claim 1 or 2, wherein x is a number such that 0<x≦0.7, y is a number such that 0≦y≦1.0, and w is a number such that 0≦w≦1.0, so that y+w+(1−y−w)=1.

5. The anhydrous layered potassium metal oxide has the formula K ｘ Ni ０．５ｘ Mn １－０．５ｘ－ｙ M ｙ O ２ wherein x is a number such that 0<x≦0.7, y is a number such that 0≦y≦(1.0−0.5x), and M is selected from Co, Fe, Ti, Cr, V, Cu, Zr, and a combination of at least two thereof, or the anhydrous layered potassium metal oxide has the formula K ｘ Ni ０．５ｘ Mn １－０．５ｘ Ti ｙ O ２ wherein x is a number such that 0<x≦0.7 and y is a number such that 0≦y≦(1.0−0.5x), or the anhydrous layered potassium metal oxide has the formula K ０．４ Ni ０．２ Mn ０．８－ｙ Ti ｙ O ２ 3. The electrochemical cell of claim 1, wherein y is a number such that 0≦y≦0.

8.

6. The anhydrous layered potassium metal oxide is ０．６７ Ni ０．３３ Mn ０．６７ O ２ , K. ０．６ Ni ０．３ Mn ０．７ O ２ , K. ０．５ Ni ０．２５ Mn ０．７５ O ２ , K. ０．４ Ni ０．２ Mn ０．８ O ２ , K. ０．４ Ni ０．２ Mn ０．６ Ti ０．２ O ２ , K. ０．４ Ni ０．２ Mn ０．７ Ti ０．１ O ２ , K. ０．４ Ni ０．２ Mn ０．７５ Ti ０．０５ O ２ , K. ０．４ Fe ０．４ Mn ０．６ O ２ , K. ０．４ Ni ０．１ Mn ０．９ O ２ , K. ０．４ MnO ２ , K. ０．３ Ni ０．１５ Mn ０．８５ O ２ , K. ０．３ Ni ０．２ Mn ０．８ O ２ , K. ０．３ MnO ２ , K. ０．２ Ni ０．１ Mn ０．９ O ２ , K. ０．２ Ni ０．２ Mn ０．８ O ２ , K. ０．２ MnO ２ , K. ０．１ Ni ０．０５ Mn ０．９５ O ２ , K. ０．１ Ni ０．１ Mn ０．９ O ２ 6. The electrochemical cell of claim 1, wherein the compound is selected from the group consisting of:

7. The anhydrous layered potassium metal oxide is ０．４ Ni ０．２ Mn ０．８ O ２ 7. The electrochemical cell of claim 6, wherein:

8. The anhydrous layered potassium metal oxide is ０．４ Ni ０．２ Mn ０．６ Ti ０．２ O ２ 7. The electrochemical cell of claim 6, wherein:

9. The anhydrous layered potassium metal oxide is ０．４ Ni ０．２ Mn ０．７５ Ti ０．０５ O ２ 7. The electrochemical cell of claim 6, wherein:

10. The anhydrous layered potassium metal oxide is ０．４ Fe ０．４ Mn ０．６ O ２ 7. The electrochemical cell of claim 6, wherein:

11. The electrode material of the positive electrode is an electronically conductive material selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and combinations of at least two thereof; and / or a binder selected from the group consisting of polyether-type polymer binders, fluorinated polymers, and water-soluble binders; 11. The electrochemical cell of claim 1, further comprising:

12. The electrolyte a liquid electrolyte containing a salt in a solvent, or a gel electrolyte comprising a salt in a solvent and a solvating polymer; or a solid polymer electrolyte comprising a salt in a solvated polymer, or 12. The electrochemical cell according to any one of claims 1 to 11, wherein the electrolyte is a glass or ceramic electrolyte.

13. When the salt is present, Lithium salts include lithium hexafluorophosphate (LiPF ６ ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF ４ ), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO ３ ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO ４ ), lithium hexafluoroarsenate (LiAsF ６ ), lithium trifluoromethanesulfonate (LiSO ３ CF ３ ) (LiTf), lithium fluoroalkyl phosphate Li[PF ３ (CF ２ CF ３ ) ３ ] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF ３ ) ４ ] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate [B(C ６ O ２ ) ２ ] (LiBBB), and combinations of at least two thereof; Sodium salts include sodium hexafluorophosphate (NaPF ６ ), sodium perchlorate (NaClO ４ ), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium bis(fluorosulfonyl)imide (NaFSI), sodium 2-trifluoromethyl-4,5-dicyanoimidazol- ate (NaTDI), sodium bis(pentafluoroethylsulfonyl)imide (NaBETI), sodium trifluoromethanesulfonate (NaTF), sodium fluoride (NaF), sodium nitrate (NaNO ３ ), and combinations of at least two thereof; or Potassium salts include potassium hexafluorophosphate (KPF ６ ), potassium bis(trifluoromethanesulfonyl)imide (KTFSI), potassium bis(fluorosulfonyl)imide (KFSI), potassium trifluoromethanesulfonate (KSO ３ CF ３ ) (KTf), and combinations of at least two thereof; 13. The electrochemical cell of claim 12, wherein:

14. A battery comprising at least one electrochemical cell as defined in any one of claims 1 to 13.

15. 15. The battery of claim 14, wherein the battery is a lithium-ion battery or a sodium-ion battery.

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