Electrode materials comprising layered potassium metal oxide, electrodes comprising electrode materials, and use of electrode materials in electrochemistry

Abstract

To provide electrode materials comprising a layered potassium metal oxide, electrodes comprising the electrode materials, and use of the electrode materials in electrochemistry.SOLUTION: The electrode materials comprise an electrochemically active material, where the electrochemically active material comprises a layered potassium metal oxide. The layered potassium metal oxide may be of formula KxMO2. The invention also relates to electrodes, electrochemical cells and batteries comprising the electrode material. For example, the battery may be a lithium or lithium-ion battery, a sodium or sodium-ion battery, or a potassium or potassium-ion battery.SELECTED DRAWING: None

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 content of which is incorporated herein by reference for all purposes.

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

Background Art

[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 low cost and can achieve improved lifespan, rapid charging, high performance, and high safety.

[0004] Since all-solid-state batteries have a higher theoretical capacity, it has been recognized again that all-solid-state batteries can solve certain energy density problems associated with conventional lithium-ion batteries (batteries containing lithium metal or sodium metal anodes), and have been improved 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 (LiCoO2) 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 The cost of materials such as O2 (NMC 811), etc.) is high, and the process of synthesizing or producing lithium-free electrode materials is complex. Therefore, the adoption of all-solid-state batteries in large-scale energy storage systems is particularly limited.

[0006] Therefore, it is necessary to develop a new electrode material without 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 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 x M y Mn 1-y metal oxide of the formula 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 Fe x Mn y O2, where x and y are as defined herein. 1-y In another embodiment, the layered potassium metal oxide is K

[0009] In another embodiment, the layered potassium metal oxide is K x Ni0.5x Mn 1-0.5x of the formula MnO₂, 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 of the formula KNiMnO₂, where x is as defined herein, y is a numerical value 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 of these. For example, the layered potassium metal oxide is K x Ni 0.5x Mn 1-0.5x Ti y of the formula KNiMnO₂, 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, K0.3 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 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 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 is selected from the group consisting of at least two combinations thereof.

[0016] In another embodiment, the electrode material further includes an electronically conductive material. According to one example, the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fiber, carbon nanofiber, carbon nanotube, and at least two combinations thereof.

[0017] In another embodiment, the electrode material further includes 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 including the electrode material 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 the aforementioned 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, lithium pre-doped graphite, lithium pre-doped silicon, lithium pre-doped oxide, or at least one combination of at least two of these.

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

[0024] In another embodiment, the negative electrode comprises at least one of a potassium pre-doped alloy, potassium pre-doped graphite, potassium pre-doped hard carbon, and 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 salt in a solvent and, optionally, a solvated polymer.

[0027] In another embodiment, the electrolyte is a solid polymer electrolyte comprising a salt in a solvated 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 is a site-defect 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 a glass electrolyte or a ceramic electrolyte selected from other similar glass electrolytes or ceramic electrolytes.

[0030] According to another aspect, the present technology relates to a battery including at least one electrochemical cell 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 Description of the Drawings

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DETAILED DESCRIPTION OF THE INVENTION

[0073] DETAILED DESCRIPTION The following detailed description and examples are provided for illustrative purposes only and are not to be construed as further limiting the scope of the invention.

[0074] All technical and chemical terms and expressions used herein have definitions commonly understood by those skilled in the art to which this technology belongs. However, definitions of some of the terms and expressions used are provided below.

[0075] When the term "about" or its equivalent term "approximately" is used in this specification, it means within or around that range. For example, when "about" or "approximately" is used with respect to a numerical value, these terms modify that numerical value to be plus or minus 10% of the apparent value. This term can also take into account experimental errors or rounding of measurement devices, for example.

[0076] When referring to a numerical range in this application, unless otherwise specified, the upper and lower limits of the range are always included in the definition.

[0077] The present technology relates to an electrode material containing layered potassium oxide and at least one metal element as an electrochemically active material, a method for producing the same, and its use in an electrochemical cell (for example, a lithium-ion battery, a sodium-ion battery, or a potassium-ion battery).

[0078] According to one example, the present technology is an electrode material containing an electrochemically active material, wherein the aforementioned electrochemically active material has the formula K x MO2 layered potassium metal oxide, 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, relates to an electrode material.

[0079] According to another example, the electrochemically active material 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.

[0080] According to another example, the electrochemically active material has the formula K x M y Mn 1-yIt 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 has the formula K x Fe y Mn 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 has 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 has the formula K x Ni 0.5x Mn 1-0.5x-y M 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 - 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 may be 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 It 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 yIt 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 has the formula Na z K x and contains a layered potassium metal oxide of 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 has the formula Na z K x and contains a layered potassium metal oxide of 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-y and may contain 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 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 has the formula Na z K x Ni y Mn 1-y and may contain a layered potassium metal oxide of O2, where x, y, and z are as defined herein.

[0086] According to another example, the electrochemically active material has the formula K x MnO2, Kx NiMnO2, K x NiMnTiO2, or K x It may contain a layered potassium metal oxide of FeMnO2, where x is as defined herein. Non-limiting examples of the layered potassium metal oxide 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 0.9 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 0.9 O2, Na 0.74 K 0.08 Ni 0.41 Mn 0.59 O2, Na0.6 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 O2 is included.

[0087] The electrochemically active material may be doped, for example, by including, if necessary, smaller amounts of other elements or impurities in order to modify or optimize its electrochemical properties. In some cases, the electrochemically active material may be doped by partially substituting a metal with other ions. 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 not substantially contain 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% of lithium and / or sodium. For example, the electrochemically active material may be delithiated and / or desodiated.

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

[0090] According to another example, the electrode material described herein may further include an electron conductive material. Non-limiting examples of the electron conductive material include carbon black (e.g., Ketjen™ carbon or Super P™ carbon), acetylene black (e.g., Shawinigan carbon or Denka™ carbon black), graphite, graphene, carbon fiber (e.g., vapor grown carbon fiber (VGCF)), carbon nanofiber, carbon nanotube (CNT), or a combination of at least two of these and the like carbon sources are included. According to one embodiment of the object, the electron conductive material is selected from Ketjen™ carbon, Super P™ carbon, VGCF, and combinations thereof.

[0091] According to another example, the electrode material 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 binder, or an ion-conductive polymer binder (such as a copolymer composed of at least one lithium-ion solvated segment (such as polyether) and, optionally, at least one crosslinkable segment (such as 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)), and optionally includes a thickening agent (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, the polyether-type polymer binder may be linear, branched, and / or crosslinked, and is based on PEO, poly(propylene oxide) (PPO), or a combination thereof (such as an EO / PO copolymer), and optionally includes crosslinkable units. According to one embodiment of interest, the binder is PVDF or a polyether-type polymer as defined herein.

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

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

[0094] Further, the present technology 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 all known compatible electrochemically active materials. 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 as defined herein.

[0096] Non-limiting examples of the electrochemically active material of the negative electrode 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 electrochemically active material of the negative electrode may be lithium metal, sodium metal, potassium metal, or an alloy containing at least one of these. According to another example, the electrochemically active material of the negative electrode may be a lithium-doped alloy, lithium-doped graphite, lithium-doped silicon, lithium-doped oxide, or a combination thereof if compatible. According to another example, the electrochemically active material of the negative electrode may be a sodium-doped alloy, sodium-doped hard carbon, or sodium-doped oxide. According to another example, the electrochemically active material of the negative electrode may be a potassium-doped alloy, potassium-doped graphite, pot assium-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 example, the electrolyte may be a gel electrolyte comprising a salt in a solvent and optionally a solvated polymer. According to another alternative example, the electrolyte may be a solid polymer electrolyte comprising a salt in a solvated polymer. According to another alternative example, the electrolyte may be a glass electrolyte or a ceramic electrolyte. According to one embodiment of the purpose, the electrolyte is a solid polymer electrolyte, a glass electrolyte, or a ceramic electrolyte that does not contain a solvent.

[0098] When present in the electrolyte, the salt may be a metal salt (such as a lithium salt, a sodium salt, or a potassium salt). Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPF6), 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 (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO3), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiSO3CF3) (LiTf), lithium fluoroalkyl phosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O’)borate [B(C6O2)2] (LiBBB), and combinations thereof. According to one embodiment of the object, the lithium salt is LiPF6, LiFSI, LiTFSI, or LiTDI. Non-limiting examples of sodium salts include sodium hexafluorophosphate (NaPF6), sodium perchlorate (NaClO4), 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 (NaNO3), and combinations thereof. According to one embodiment of the object, the sodium salt is NaPF6, NaFSI, NaTFSI, or NaClO4.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 the object, 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-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), and ethoxymethoxyethane (EME)); cyclic ethers (tet rahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, and dioxolane derivatives); and other solvents (such as dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, phosphate triesters, sulfolane, methylsulfolane, propylene carbonate derivatives, and derivatives thereof).

[0100] According to one example, the electrolyte comprises a salt selected from lithium hexafluorophosphate (LiPF6), sodium hexafluorophosphate (NaPF6), sodium perchlorate (NaClO4), or potassium hexafluorophosphate (KPF6), dissolved in a non-aqueous solvent mixture (such as a mixture of ethylene carbonate and diethyl carbonate (EC / DEC) (volume ratio [3:7]), a mixture of ethylene carbonate and dimethyl carbonate (EC / DMC) (volume ratio [4:6]), etc.), 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 electrochemical active material, an electronic conductive material, and a binder in a composition ratio of about 80:10:10. For example, the electrode material comprises about 80 wt% of the electrochemical active material, about 10 wt% of the electronic conductive material, and about 10 wt% of the binder.

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

[0103] Alternatively, the electrolyte may 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 the various elements of the electrochemical cell. For example, the solid polymer electrolyte may be selected to be compatible with lithium, sodium, and / or potassium. Solid polymer electrolytes generally include salts and, optionally, one or more cross-linked solid polar polymer(s). Polyether-type polymers (such as PEO-based) may be used, but several other compatible polymers are also known in the preparation of solid polymer electrolytes and these are also contemplated. The polymer may be cross-linked. Examples of such polymers include branched polymers such as star polymers or comb polymers (such as those described in the PCT patent application published as WO2003 / 063287 (Zaghib et al.)).

[0104] According to one example, the electrolyte is a solid polymer electrolyte comprising a salt in a solvated polymer. According to the desired embodiment, 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 from about 50 wt% to about 75 wt% of an electrochemically active material, from about 1 wt% to about 5 wt% of an electronically conductive material, and from about 20 wt% to about 49 wt% of a binder.

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

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

[0108] Also, the electrolyte may optionally contain further components or additives (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] Also, the present technology relates to a battery including at least one electrochemical cell 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 includes lithium metal, a lithium-based alloy, a lithium pre-doped alloy, a lithium pre-doped graphite, a lithium pre-doped silicon, or a 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 includes lithium metal, a lithium-based alloy, a lithium pre-doped alloy, a lithium pre-doped graphite, or a lithium pre-doped silicon. According to another example, the electrolyte is a solid polymer electrolyte, and the electrochemically active material of the negative electrode includes lithium metal, a lithium-based alloy, a lithium pre-doped graphite, or a lithium pre-doped silicon. According to another example, the electrolyte is a ceramic electrolyte, and the electrochemically active material of the negative electrode includes lithium metal, a lithium-based alloy, or a lithium pre-doped graphite, and / or a 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 comprises 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 comprises potassium metal, a potassium-based alloy, a potassium pre-doped alloy, potassium pre-doped graphite, or potassium pre-doped hard carbon. According to another exam ple, the electrolyte is a solid polymer electrolyte, and the electrochemically active material of the negative electrode comprises 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 comprises potassium metal, a potassium-based alloy, potassium pre-doped graphite, or potassium pre-doped hard carbon.

[0113] Also, the present technology relates to a layered potassium metal oxide in crystalline form and 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.

[0114] Also, the present technology relates to a layered potassium metal oxide in crystalline form and 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 thereof.

[0115] According to at least one example, the crystalline layered potassium metal oxide is of the formula K 0.67 Ni 0.33 Mn 0.67 O2 and has an XRD pattern substantially shown in FIG. 1.

[0116] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.6 Ni 0.3 Mn 0.7 O2 and has an XRD pattern substantially shown in Figure 2.

[0117] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.5 Ni 0.25 Mn 0.75 O2 and has an XRD pattern substantially shown in Figure 3.

[0118] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.4 Ni 0.2 Mn 0.8 O2 and has an XRD pattern substantially shown in Figure 4.

[0119] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O2 and has an XRD pattern substantially shown in Figure 5.

[0120] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O2 and has an XRD pattern substantially shown in Figure 6.

[0121] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O2 and has an XRD pattern substantially shown in Figure 7.

[0122] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.4 Fe 0.4 Mn0.6 It is of O2 and has an XRD pattern substantially shown in FIG. 8.

[0123] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.4 Ni 0.1 Mn 0.9 O2 and has an XRD pattern substantially shown in FIG. 9.

[0124] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.4 MnO2 and has an XRD pattern substantially shown in FIG. 10.

[0125] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.3 Ni 0.15 Mn 0.85 O2 and has an XRD pattern substantially shown in FIG. 11.

[0126] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.3 Ni 0.2 Mn 0.8 O2 and has an XRD pattern substantially shown in FIG. 12.

[0127] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.3 MnO2 and has an XRD pattern substantially shown in FIG. 13.

[0128] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.2 Ni 0.1 Mn 0.9 O2 and has an XRD pattern substantially shown in FIG. 14.

[0129] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.2 Ni 0.2 Mn 0.8 O2 and has an XRD pattern substantially shown in FIG. 15.

[0130] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.2 MnO2 and has an XRD pattern substantially shown in FIG. 16.

[0131] According to another alternative example, the crystalline form of the layered potassium metal oxide has the formula K 0.1 Ni 0.05 Mn 0.95 O2 and has an XRD pattern substantially shown in FIG. 17.

[0132] According to another alternative example, the crystalline form of the layered potassium metal oxide 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 shown in FIG. 18.

[0133] According to at least one example, the crystalline form of the layered potassium metal oxide of the formula K x MO2 has XRD 2θ(°) reflections substantially shown in FIG. 39. According to one alternative example, the crystalline form of the layered potassium metal oxide of the formula K x MO2 has XRD 2θ(°) reflections substantially shown in FIG. 40. According to another alternative example, the crystalline form of the layered potassium metal oxide of the formula K x MO2 has XRD 2θ(°) reflections substantially shown in FIG. 41.

[0134] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.4 Ni 0.2 Mn 0.8 O2 and has an XRD pattern substantially shown in FIG. 4 or an XRD 2θ reflection (°) substantially shown in FIG. 40.

[0135] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 O2 and has an XRD pattern substantially shown in FIG. 5.

[0136] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.4 Ni 0.2 Mn 0.7 Ti 0.1 O2 and has an XRD pattern substantially shown in FIG. 6 or an XRD 2θ reflection (°) substantially shown in FIG. 40.

[0137] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.4 Ni 0.2 Mn 0.75 Ti 0.05 O2 and has an XRD pattern substantially shown in FIG. 7 or an XRD 2θ reflection (°) substantially shown in FIG. 40.

[0138] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.4 Fe 0.4 Mn 0.6 O2 and has an XRD pattern substantially shown in FIG. 8 or an XRD 2θ reflection (°) substantially shown in FIG. 41.

[0139] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.4 Ni 0.1 Mn 0.9It is of O2, having an XRD pattern substantially shown in FIG. 9, or having an XRD 2θ reflection (°) substantially shown in FIGS. 39 and / or 40.

[0140] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.3 Ni 0.15 Mn 0.85 O2, having an XRD pattern substantially shown in FIG. 11, or having an XRD 2θ reflection (°) substantially shown in FIG. 40.

[0141] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.3 Ni 0.2 Mn 0.8 O2, having an XRD pattern substantially shown in FIG. 12, or having an XRD 2θ reflection (°) substantially shown in FIG. 40.

[0142] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.2 Ni 0.1 Mn 0.9 O2, having an XRD pattern substantially shown in FIG. 14, or having an XRD 2θ reflection (°) substantially shown in FIGS. 40 and / or 41.

[0143] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.2 Ni 0.2 Mn 0.8 O2, having an XRD pattern substantially shown in FIG. 15, or having an XRD 2θ reflection (°) substantially shown in FIG. 41.

[0144] According to another embodiment of the object, the crystalline layered potassium metal oxide has the formula K 0.1 Ni 0.05 Mn 0.95 O2, having an XRD pattern substantially shown in FIG. 17, or having an XRD 2θ reflection (°) substantially shown in FIG. 41.

Examples

[0145] The following examples are for illustrative purposes and should not be construed as further limiting the scope of the present invention to be considered. These examples will be better understood by referring to the accompanying drawings. Example 1: Synthesis of Electrochemical Active Material 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 The layered potassium metal oxide of O2 was prepared using a solid-state reaction technique. Each precursor (such as K2CO3 / KOH and metal oxides like Na2CO3, Mn2O3, Co2O3, CuO, ZrO2, NiO, Fe2O3, and TiO2) was weighed to obtain the desired stoichiometric amount. The sample was prepared by pulverizing and mixing the precursor powders. Subsequently, the pulverized and mixed precursor powders were placed in a furnace and heated at a temperature between 600 °C and 1000 °C for 5 - 24 hours in an air atmosphere or an oxygen atmosphere. For example, it was heated at a temperature between 800 °C and 1000 °C for 6 - 8 hours. b) Wet chemical synthesis

[0147] Alternatively, the layered potassium metal oxide defined in this specification may be prepared using a wet chemical synthesis technique. For example, the layered potassium metal oxide defined in this specification may be prepared by a sol-gel method, such as the sol-gel (333SG) method similar to the method 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 where the metal is Na, Mn, Ti, K, Fe, or Ni) is weighed to obtain the desired stoichiometric amount and dissolved in distilled water. The solution is continuously stirred and dropped into an approximately 1 mol / L aqueous citric acid solution that is being continuously stirred. Ammonium hydroxide is used to adjust the pH to a value between approximately pH 7.0 and approximately pH 8.0. Then, the solution is heated between approximately 70°C and approximately 80°C while stirring to evaporate the solvent until a transparent sol-gel precursor is obtained. The obtained sol-gel precursor is calcined in an oven at a temperature of approximately 450°C for approximately 8 hours in an air atmosphere or an oxygen atmosphere to remove organic contents. Finally, the obtained powder is ground in a mortar and calcined at approximately 900°C for approximately 12 hours. Example 2: Characterization of the Electrochemical Active Material a) Powder X-ray Diffraction (XRD)

[0148] The atomic and molecular structures of the electrochemical active material were studied by X-ray diffraction performed on the layered potassium metal oxide powder prepared in Example 1(a). Figures 1 to 17 show the 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, 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). Figure 18 shows 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, and Na 0.2 K 0.2 Ni 0.2 Mn 0.8 shows the X-ray diffraction pattern of the layered potassium metal oxide powder of O2.

[0149] The X-ray spectrum was obtained using a Rigaku Smartlab (trademark) X-ray diffractometer equipped with a cobalt X-ray source that emits X-rays with a wavelength of λ = 1.78901 Å. b) Characteristics of the crystal structure

[0150] Data processing and characterization of the crystal structure were performed by indexing and comparing the XRD spectrum with the database pattern to confirm the crystal structure of the layered potassium metal oxide.

[0151] Figures 1 to 3(B) and Figure 9(C) respectively show the crystal structures of the layered potassium metal oxides of the 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 O2.

Table 1

[0152] The reflection parameters of the layered potassium metal oxide having the crystal structure characteristics shown in Table 1 are shown in Figure 39.

[0153] Figures 4, 6, 7, 9, 11, 12, and 14(B) respectively show the formula K having the crystal structure characteristics 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 Figure showing the crystal structure of the layered potassium metal oxide of O2.

Table 2

[0154] The reflection parameters of the layered potassium metal oxide having the crystal structure characteristics shown in Table 2 are shown in Figure 40.

[0155] Figures 8(B), 14(C), 15(B), and 17(B) each show the formula K having 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 Figure showing the crystal structure of the layered potassium metal oxide of O2.

Table 3

[0156] The reflection parameters of the layered potassium metal oxide having the crystal structure characteristics shown in Table 3 are shown in Figure 41.

[0157] Figures 10 and 13 each show the formula K having the crystal structure characteristics shown in Table 4 0.4 MnO2 and K 0.3 Figure (B) shows the crystal structure of the layered potassium metal oxide of MnO2.

Table 4

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

[0159] As described above, the formula K 0.4 Ni 0.1 Mn 0.9 O2 (Figure 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. In fact, according to the X-ray diffraction pattern, 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 studied. An electrochemical cell was assembled according to the configuration of the electrochemical cell shown in Table 5. a) Configuration of the electrochemical cell

[0161]

Table 5

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

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

[0164] The separator of an electrochemical cell including a negative electrode containing a sodium metal thin film was impregnated with a 1M 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] In this example, the electrochemical behavior of the electrochemical cell described in Example 3(a) is explained.

[0166] Figure 19 shows a graph of capacity (mAh g x Ni 0.5x Mn 1-0.5x ) versus x for the layered potassium metal oxide of K -1 Ni

[0167] Figures 20 to 37 show the charge-discharge profiles of Cells 1 to 28 and 33 to 35. For all electrochemical cells containing a lithium metal thin film as the negative electrode, charge-discharge was performed at 0.1C between 1.5V and 4.5V vs. Li + / Li, and for all electrochemical cells containing a sodium metal thin film as the negative electrode, charge-discharge was performed at 0.1C between 1.5V and 4.2V vs. Na + / Na. Charge-discharge was performed at a temperature of 25°C starting from discharge. The results of the first (black line, 1), second (red line, 2), and final third (blue line, 3) charge-discharge cycles are shown. The capacity supplied by each electrochemical cell is shown in Table 6.

Table 6

[0168] Figure 38 shows, for Cells 1, 3, 5, 17, 19, 25, and 31 in (A); and for Cells 2, 4, 6, 18, 26, and 32 in (B), capacity (mAh g -1)And a graph showing efficiency (%) is presented. A long-term cycle experiment was conducted at a temperature of about 25 °C with a constant charge-discharge current of C / 10. The results shown in Fig. 38(A) were recorded vs. Li + / Li for about 45 cycles, and those in (B) were recorded vs. Na + / Na for about 35 cycles.

[0169] Numerous modifications can be made to any of the above embodiments without departing from the scope of the invention contemplated herein. All references, patents, or scientific papers mentioned in this application are hereby incorporated by reference herein for all purposes.

Claims

1. An electrode material containing an electrochemically active material, wherein the electrochemically active material has the formula K ｘ MO ２ and contains a layered potassium metal oxide, 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, the electrode material.

2. 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 claim 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, the electrode material according to claim 1.

3. wherein the layered potassium metal oxide is of the formula K ｘ Fe ｙ Mn １－ｙ O ２ where x is as defined in claim 1, and y is a numerical value such that 0 ≦ y ≦ 1.0, the electrode material according to claim 1 or 2.

4. wherein the layered potassium metal oxide is of the formula K ｘ MnO ２ where x is as defined in claim 1, the electrode material according to claim 1 or 2.

5. wherein the layered potassium metal oxide is of the formula K ｘ NiMnO ２ where x is as defined in claim 1, the electrode material according to claim 1 or 2.

6. wherein the layered potassium metal oxide has the formula K ｘ NiMnO ２ where x is as defined in claim 1, the electrode material according to claim 1 or 2.

7. wherein the layered potassium metal oxide is of the formula K ｘ FeMnO ２ where x is as defined in claim 1, the electrode material according to claim 1 or 2.

8. wherein the layered potassium metal oxide has the formula K ｘ Ni ０．５ｘ Mn １－０．５ｘ O ２ where x is as defined in claim 1, the electrode material according to claim 1 or 2.

9. wherein the layered potassium metal oxide has the formula K ｘ Ni ０．５ｘ Mn １－０．５ｘ－ｙ M ｙ O ２ where x is as defined in claim 1, y is a numerical value 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 of these, the electrode material according to claim 1 or 2.

10. wherein the layered potassium metal oxide has the formula K ｘ Ni ０．５ｘ Mn １－０．５ｘ Ti ｙ O ２ where x is as defined in claim 1 and y is as defined in claim 9, the electrode material according to claim 9.

11. wherein the layered potassium metal oxide is of the formula K ０．４ Ni ０．２ Mn ０．８－ｙ Ti ｙ O ２ and wherein y is a numerical value such that 0 ≦ y ≦ 0.8, the electrode material according to claim 9 or 10.

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 ０．２５ 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 、 and selected from the group consisting of K, Ni, Mn, O, K, Ni, Mn, O, K, MnO, K, Ni, Mn, O, K, Ni, Mn, O, K, MnO, K, Ni, Mn, O, K, Ni, Mn, O, and combinations of at least two of these, the electrode material according to any one of claims 1 to 11.

13. wherein the layered potassium metal oxide is K ０．４ Ni ０．２ Mn ０．８ O ２ The electrode material according to claim 12, which is such.

14. wherein the layered potassium metal oxide is K ０．４ Ni ０．２ Mn ０．６ Ti ０．２ O ２ The electrode material according to claim 12, wherein the layered potassium metal oxide is as described above.

15. wherein the layered potassium metal oxide is K ０．４ Ni ０．２ Mn ０．７５ Ti ０．０５ O ２ The electrode material according to claim 12, wherein the layered potassium metal oxide is K

16. wherein the layered potassium metal oxide is K ０．４ Fe ０．４ Mn ０．６ O ２ The electrode material according to claim 12

17. An electrode material containing an electrochemically active material, wherein the electrochemically active material is of the formula Na ｚ K ｘ MO ２ and contains a layered potassium metal oxide, 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, an electrode material.

18. wherein the electrochemically active material 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 claim 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, the electrode material according to claim 17.

19. wherein the layered potassium metal oxide has the formula Na ｚ K ｘ Ni ｙ Mn １－ｙ O ２ where x and z are as defined in claim 17, and y is a numerical value such that 0 ≦ y ≦ 1.0, the electrode material according to claim 17 or 18.

20. wherein 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 K ０．０８ Ni ０．２ Mn ０．８ O ２ 、Na ０．２ K ０．２ Ni ０．２ Mn ０．８ O ２ ; and the electrode material according to any one of claims 17 to 19, selected from the group consisting of these and combinations of at least two of them.

21. wherein the layered potassium metal oxide is Na ０．７４ K ０．０８ Ni ０．４１ Mn ０．５９ O ２ The electrode material according to claim 20, which is as described above.

22. wherein the layered potassium metal oxide is Na ０．６ K ０．０８ Ni ０．３４ Mn ０．６６ O ２ The electrode material according to claim 20, which is such.

23. wherein the layered potassium metal oxide is Na ０．７４ K ０．０８ Ni ０．２ Mn ０．８ O ２ The electrode material according to claim 20, which is such.

24. wherein the layered potassium metal oxide is Na ０．６ K ０．０８ Ni ０．２ Mn ０．８ O ２ The electrode material according to claim 20, which is such.

25. wherein the layered potassium metal oxide is Na ０．３２ K ０．０８ Ni ０．２ Mn ０．８ O ２ The electrode material according to claim 20.

26. wherein the layered potassium metal oxide is Na ０．２ K ０．２ Ni ０．２ Mn ０．８ O ２ The electrode material according to claim 20, which is such.

27. The electrode material according to any one of claims 1 to 26, further comprising an electronically conductive material.

28. The electrode material according to claim 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 combinations of at least two of these.

29. The electrode material according to claim 28, wherein the electronically conductive material contains carbon fiber.

30. The electrode material according to claim 29, wherein the carbon fiber is vapor-grown carbon fiber (VGCF).

31. The electrode material according to claim 28, wherein the electronically conductive material contains carbon black.

32. The electrode material according to claim 31, wherein the carbon black is Super P (trademark) carbon.

33. The electrode material according to claim 31, wherein the carbon black is Ketjen (trademark) carbon.

34. The electrode material according to any one of claims 1 to 33, further comprising a binder.

35. The electrode material according to claim 34, wherein the binder is selected from the group consisting of polyether-type polymer binders, fluorinated polymers, and water-soluble binders.

36. The electrode material according to claim 35, wherein the binder is a fluorinated polymer selected from polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).

37. The electrode material according to claim 36, wherein the binder is polyvinylidene fluoride (PVDF).

38. The electrode material according to claim 35, wherein the binder is a polyether-type polymer binder.

39. The electrode material according to claim 38, wherein the polyether-type polymer binder is branched and / or crosslinked.

40. The electrode material according to claim 38 or 39, wherein the polyether-type polymer binder is a polyethylene oxide (PEO) - based polymer.

41. An electrode comprising the electrode material defined in any one of claims 1 to 40 on a current collector.

42. The electrode according to claim 41, wherein the electrode is a positive electrode.

43. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the positive electrode is as defined in claim 41 or 42.

44. The electrochemical cell according to claim 43, wherein the negative electrode comprises a lithium metal, a sodium metal, a potassium metal, or an alloy containing at least one of these.

45. The electrochemical cell according to claim 43, wherein the negative electrode comprises at least one of a lithium pre-doped alloy, lithium pre-doped graphite, lithium pre-doped silicon, lithium pre-doped oxide, or at least one combination of at least two of these.

46. The electrochemical cell according to claim 43, wherein the negative electrode comprises at least one of a sodium pre-doped alloy, sodium pre-doped hard carbon, and sodium pre-doped oxide.

47. The electrochemical cell according to claim 43, wherein the negative electrode comprises at least one of a potassium pre-doped alloy, potassium pre-doped graphite, potassium pre-doped hard carbon, and potassium pre-doped oxide.

48. The electrochemical cell according to any one of claims 43 to 47, wherein the electrolyte is a liquid electrolyte containing a salt in a solvent.

49. The electrochemical cell according to any one of claims 43 to 47, wherein the electrolyte is a gel electrolyte containing a salt in a solvent and, optionally, a solvated polymer.

50. The electrochemical cell according to any one of claims 43 to 47, wherein the electrolyte is a solid polymer electrolyte containing a salt in a solvated polymer.

51. The electrochemical cell according to any one of claims 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 of these.

52. The electrochemical cell according to any one of claims 48 to 51, wherein the salt is a lithium salt.

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 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 an electrochemical cell according to claim 52, selected from at least two combinations thereof.

54. wherein the lithium salt is selected from LiPF ６ , LiFSI, LiTFSI, LiTDI, and combinations of at least two of these, the electrochemical cell according to claim 52 or 53.

55. The electrochemical cell according to any one of claims 48 to 51, wherein the salt is a sodium salt.

56. wherein 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 ), and the electrochemical cell according to claim 55, selected from at least two combinations thereof.

57. wherein the sodium salt is NaPF ６ , NaFSI, NaTFSI, NaClO4, and a combination of at least two of these, the electrochemical cell according to claim 55 or 56.

58. The electrochemical cell according to any one of claims 48 to 51, wherein the salt is a potassium salt.

59. wherein the potassium salt is selected from potassium hexafluorophosphate (KPF ６ ), potassium bis(trifluoromethanesulfonyl)imide (KTFSI), potassium bis(fluorosulfonyl)imide (KFSl), potassium trifluoromethanesulfonate (KSO ３ CF ３ )(KTf), and combinations of at least two of these, the electrochemical cell according to claim 58.

60. wherein the potassium salt is KPF ６ The electrochemical cell according to claim 58 or 59.

61. The electrochemical cell according to any one of claims 43 to 47, wherein the electrolyte is a glass electrolyte or a ceramic electrolyte.

62. The electrolyte is a glass electrolyte or a ceramic electrolyte selected from a site-defect perovskite-type electrolyte, a garnet-type electrolyte, a NASICON-type glass-ceramic electrolyte, a LISICON-type electrolyte, a lithium-stabilized sodium ion (Na ＋ ), a conductive aluminum oxide (Al ２ O ３ ), and other similar glass electrolytes or ceramic electrolytes. The electrochemical cell according to claim 61.

63. A battery comprising at least one electrochemical cell as defined in any one of claims 43 to 62.

64. The battery according to claim 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.

65. The battery according to claim 63 or 64, wherein the battery is a lithium ion battery.

66. The battery according to claim 63 or 64, wherein the battery is a sodium ion battery.

67. The battery according to claim 63 or 64, wherein the battery is a potassium ion battery.

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