Electrode materials containing layered potassium metal oxides, electrodes containing electrode materials, and the 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, in accordance with applicable law, to U.S. Provisional Patent Application No. 62 / 855,537, filed on 31 May 2019 (the entire contents of which are 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, this disclosure generally relates to electrode materials comprising layered potassium metal oxide as an electrochemical active material, electrodes comprising the said electrode material, processes for manufacturing the said electrode material, and the use of the said electrode material in an electrochemical cell. [Background technology]

[0003] background Solid-state batteries represent a novel solution for electric vehicle batteries or primary batteries for next-generation electric vehicles. Compared to conventional lithium-ion batteries that use liquid electrolytes, solid-state batteries can generally be manufactured at a lower cost and offer improved lifespan, faster charging times, high performance, and greater safety.

[0004] Because all-solid-state batteries have a higher theoretical capacity, it has been re-evaluated that they can solve certain energy density problems associated with conventional lithium-ion batteries (batteries containing lithium or sodium metal anodes), and they are being 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, especially in large-scale energy storage systems, is limited.

[0006] Therefore, it is necessary to develop a new electrode material that does 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 relates to 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.

[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 O2, where x and y are as defined herein.

[0009] In another embodiment, the layered potassium metal oxide is K x Ni0.5x Mn 1-0.5x This is the formula for O2, where x is as defined herein.

[0010] In another embodiment, layered potassium metal oxide is K x Ni 0.5x Mn 1-0.5x-y M y The formula for O2 is as defined herein, where x is a number such as 0 ≤ y ≤ (1.0 - 0.5x), and M is selected from Co, Fe, Ti, Cr, V, Cu, Zr, Sb, and at least two combinations thereof. For example, layered potassium metal oxide is K x Ni 0.5x Mn 1-0.5x Ti y This is the formula for 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, 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 contains a layered potassium metal oxide of the formula Na z K x M y Mn 1-y 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 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 comprises 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 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 the electrode material as defined herein on a current collector.

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

[0020] * In another embodiment, the present invention 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 a lithium metal, a sodium metal, a potassium metal, or an alloy containing at least one of these.

[0022] In another embodiment, the negative electrode includes 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, a sodium pre-doped hard carbon, and a sodium pre-doped oxide.

[0024] In another embodiment, the negative electrode comprises at least one of 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 containing 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 containing a salt in a solvated polymer.

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

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

[0030] In another embodiment, 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 lithium batteries, lithium-ion batteries, sodium batteries, sodium-ion batteries, potassium batteries, and potassium-ion batteries. [Brief explanation of the drawing]

[0032]

Figure 1

[0033]

Figure 2

[0034]

Figure 3

[0035]

Figure 4

[0036]

Figure 5

[0037]

Figure 6

[0038]

Figure 7

[0039]

Figure 8

[0040]

Figure 9

[0041]

Figure 10

[0042]

Figure 11

[0043]

Figure 12

[0044]

Figure 13

[0045]

Figure 14

[0046]

Figure 15

[0047]

Figure 16

[0048]

Figure 17

[0049]

Figure 18

[0050]

Figure 19

[0051]

Figure 20

[0052] Figure 21 shows two charge-discharge profiles for Cell 3 recorded at a cycling rate of 0.1C between 1.5V and 4.5V vs. Li+ / Li as described in Example 3(b) in (A); and two charge-discharge profiles for Cell 4 recorded at a cycling rate of 0.1C between 1.5V and 4.2V vs. Na+ / Na in (B). The results of the first (black line, 1) and second (red line, 2) charge-discharge cycles are shown.

[0053]

Figure 21

[0054]

Figure 22

[0055]

Figure 23

[0056]

Figure 24

[0057]

Figure 25

[0058]

Figure 26

[0059]

Figure 27

[0060]

Figure 28

[0061]

Figure 29

[0062]

Figure 30

[0063]

Figure 31

[0064]

Figure 32

[0065]

Figure 33

[0066]

Figure 34

[0067]

Figure 35

[0068]

Figure 36

[0069]

Figure 37

[0070]

Figure 38

[0071]

Figure 39

Figure 40-1

[0072]

Figure 40-2

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

[0074] All technical and chemical terms and expressions used herein have definitions that are generally understood by those skilled in the art. 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 vary up and down by 10% with respect to the apparent value. This term can also take into account, for example, experimental errors or rounding of measurement devices.

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

[0081] In another example, an electrochemical active material is given by formula K x Ni 0.5x Mn 1-0.5x It may contain layered potassium metal oxide of O2, where x is as defined herein.

[0082] In another example, an electrochemical active material is given by formula K x Ni 0.5x Mn 1-0.5x-y M y It may contain layered potassium metal oxides of O2, where x is as defined herein, y is a numerical value such as 0 ≤ y ≤ (1.0 - 0.5x), and M is selected from Na, Li, Co, Fe, Ti, Cr, V, Cu, Zn, Mg, Zr, Sb, and at least two combinations thereof. According to one example, M is selected from Co, Fe, Ti, Cr, V, Cu, Zr, Sb, and at least two combinations thereof. For example, the electrochemical active material is of formula K x Ni 0.5x Mn 1-0.5x Ti y The material may contain a layered potassium metal oxide of O2, where x and y are as defined herein. For example, the electrochemical active material may be of 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 at least two of these combinations.

[0085] According to another example, the electrochemically active material has the formula Na z K x M y Mn 1-y It 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 It 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 This may include layered potassium metal oxides of 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 0.9 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 It contains O2.

[0087] Electrochemical active materials may be doped, for example, by adding smaller amounts of other elements or impurities as needed to modify or optimize their electrochemical properties. In some cases, electrochemical active materials may be doped by partially substituting metals with other ions. For example, electrochemical active materials may be doped with transition metals (e.g., Fe, Co, Ni, Mn, Ti, Cr, Cu, V, Zn, and / or Y) and / or non-transition metals (e.g., Mg, Al, and / or Sb).

[0088] The electrode material does not need to contain substantially any lithium and / or sodium. For example, the electrochemical active material may contain less than 2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, less than 0.05% by weight, or less than 0.01% by weight of lithium and / or sodium. For example, the electrochemical active material may be delithiated and / or desodiumated.

[0089] In another example, the electrochemical active material may be in the form of particles (e.g., fine particles or nanoparticles), and the aforementioned particles may further contain newly formed coating material. The coating material may be an electronically conductive material (e.g., a carbon coating).

[0090] In another example, the electrode materials described herein may further include electronically conductive materials. Non-limiting examples of electronically conductive materials 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 at least two of these in combination. This includes carbon sources such as the following. According to one embodiment of the subject, the electronically conductive material is selected from Ketjen® carbon, Super P® carbon, VGCF, and combinations thereof.

[0091] In another example, the electrode materials described herein may also include a binder. For example, the binder may be selected to be compatible with various elements of the electrochemical cell. Any known compatible binder is intended. For example, the binder may be a fluorinated polymer binder, a water-soluble binder, or an ion-conducting polymer binder (such as a copolymer consisting of at least one lithium-ion solvable segment (such as a polyether) and optionally at least one crosslinkable segment (e.g., a poly(ethylene oxide) (PEO) polymer containing methyl methacrylate units)). In one example, the binder is a fluorinated polymer (such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE)). In 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 thickener (such as carboxymethylcellulose (CMC)), or a polymer (such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMMA)), or a combination thereof. In yet another example, the binder is a polyether-type polymer binder. For example, a polyether-type polymer binder is linear, branched, and / or crosslinked and is based on PEO, poly(propylene oxide) (PPO), or a combination thereof (such as EO / PO copolymer), and optionally includes crosslinkable units. In one embodiment of the subject, 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, ion conductors, salts, and other similar additives).

[0093] Furthermore, this 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 may be self-supporting. According to one embodiment of the object, the electrode is a positive electrode.

[0094] Furthermore, this 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] In one example, the negative electrode (counter electrode) comprises an electrochemical active material selected from all known and compatible electrochemical active materials. For example, the electrochemical active material of the negative electrode may be selected to be electrochemically compatible with various elements of the electrochemical cell as defined herein.

[0096] Non-limiting examples of electrochemical active materials for the negative electrode include alkali metals, alkali metal alloys, lithium pre-doped electrochemical active materials, sodium pre-doped electrochemical active materials, and potassium pre-doped electrochemical active materials. According to one example, the electrochemical active material for 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 electrochemical active material for the negative electrode may be lithium pre-doped alloy, lithium pre-doped graphite, lithium pre-doped silicon, lithium pre-doped oxide, or a combination thereof where applicable. According to yet another example, the electrochemical active material for the negative electrode may be sodium pre-doped alloy, sodium pre-doped hard carbon, or sodium pre-doped oxide. According to yet another example, the electrochemical active material for the negative electrode may be potassium pre-doped alloy, potassium pre-doped graphite, or potassium It may be umpredoped hard carbon or potassium predoped 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 intended. According to one example, the electrolyte may be a liquid electrolyte containing a salt in a solvent. According to one alternative example, the electrolyte may be a gel electrolyte containing a salt in a solvent and optionally in a solvating polymer. According to another alternative example, the electrolyte may be a solid polymer electrolyte containing a salt in a solvating polymer. According to yet another alternative example, the electrolyte may be a glass electrolyte or a ceramic electrolyte. According to one embodiment of the object, the electrolyte is a solvent-free solid polymer electrolyte, glass electrolyte, or ceramic electrolyte.

[0098] When present in an electrolyte, the salt may be a metal salt (such as a lithium salt, sodium salt, or 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 hexafluoroarcenate (LiAsF6), lithium trifluoromethanesulfonate (LiSO3CF3) (LiTf), and lithium fluoroalkyl phosphate. This includes 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 subject, 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 subject, the potassium salt is KPF6.

[0099] The solvent may be a non-aqueous solvent if it is present in the electrolyte. 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 (such as tetraphosphorus). This includes tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, and dioxolane derivatives; and other solvents (such as dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, triesters of phosphate, sulfolane, methylsulfolane, propylene carbonate derivatives, and their derivatives).

[0100] According to one example, the electrolyte includes salts selected from lithium hexafluorophosphate (LiPF6), sodium hexafluorophosphate (NaPF6), sodium perchlorate (NaClO4), or potassium hexafluorophosphate (KPF6), dissolved in a mixture of non-aqueous solvents (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])), 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 electronically conductive material, and a binder in a composition ratio of approximately 80:10:10. For example, the electrode material contains approximately 80% by weight of the electrochemical active material, approximately 10% by weight of the electronically conductive material, and approximately 10% by weight of the binder.

[0102] The electrolyte may be a gel electrolyte or a gel polymer electrolyte. A gel polymer electrolyte may, if necessary, include, for example, a polymer precursor and salt (e.g., a previously defined salt), a solvent (e.g., a previously defined solvent), and a polymerization initiator and / or a crosslinking initiator. Non-limiting examples of gel electrolytes include, but are not limited to, the gel electrolytes described in PCT patent applications published WO2009 / 111860 (Zaghib et al.) and WO2004 / 068610 (Zaghib et al.).

[0103] Furthermore, the electrolyte may be a solid polymer electrolyte. For example, the solid polymer electrolyte may be selected from any known solid polymer electrolytes 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 comprises one or more solid polar polymers (or more) that are crosslinked as needed, along with a salt. Polyether polymers (such as PEO-based polymers) may be used, but several other compatible polymers are also known and intended for the preparation of solid polymer electrolytes. The polymers may be crosslinked. Examples of such polymers include branched polymers, e.g., star-shaped polymers or comb-shaped polymers (such as those described in the PCT patent application published as WO2003 / 063287 (Zaghib et al.)).

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

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

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

[0107] Furthermore, the previously defined gel electrolyte or liquid electrolyte may 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 is a commercially available polymer separator of the Celgard® type.

[0108] Furthermore, the electrolyte may contain additional components or additives as needed (ion conductors, inorganic particles, glass or ceramic particles (e.g., nanoceramics (such as Al2O3, TiO2, SiO2, and other similar compounds) and other such additives)).

[0109] Furthermore, this technology 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 lithium-ion battery. According to one example, the electrolyte is a liquid electrolyte as defined herein, and the electrochemical active material of the negative electrode includes lithium metal, lithium-based alloy, 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 electrochemical active material of the negative electrode includes lithium metal, lithium-based alloy, lithium pre-doped alloy, lithium pre-doped graphite, or lithium pre-doped silicon. According to yet another example, the electrolyte is a solid polymer electrolyte, and the electrochemical active material of the negative electrode includes lithium metal, lithium-based alloy, lithium pre-doped graphite, or lithium pre-doped silicon. According to yet another example, the electrolyte is a ceramic electrolyte, and the electrochemical active material of the negative electrode includes lithium metal, 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 sodium-ion battery. According to one example, the electrolyte is a liquid electrolyte as defined herein, and the electrochemical active material of the negative electrode includes sodium metal, sodium-based alloy, sodium pre-doped alloy, sodium pre-doped hard carbon, or sodium pre-doped oxide. According to another example, the electrolyte is a gel electrolyte as defined herein, and the electrochemical active material of the negative electrode includes sodium metal, sodium-based alloy, sodium pre-doped alloy, or sodium pre-doped hard carbon. According to another example, the electrolyte is a solid polymer electrolyte, and the electrochemical active material of the negative electrode includes sodium metal, sodium-based alloy, or sodium pre-doped hard carbon. According to yet another example, the electrolyte is a ceramic electrolyte, and the electrochemical active material of the negative electrode includes sodium metal, sodium-based alloy, or 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 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 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 layered potassium metal oxide is given by formula K 0.6 Ni 0.3 Mn 0.7 It is of O2 and has the XRD pattern substantially shown in Figure 2.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0132] According to another alternative example, the crystalline form of layered potassium metal oxide is, 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 It is of O2 and has the XRD pattern substantially shown in Figure 18.

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

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

[0135] According to another embodiment of the objective, the layered potassium metal oxide in crystalline form is given by formula K 0.4 Ni 0.2 Mn 0.6 Ti 0.2 It is of O2 and has the XRD pattern substantially shown in Figure 5.

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

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

[0138] According to another embodiment of the objective, the layered potassium metal oxide in crystalline form is given by formula K 0.4 Fe 0.4 Mn 0.6 It is of O2 and has the XRD pattern substantially shown in Figure 8, or Figure It has the XRD 2θ reflection (°) substantially shown in 41.

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

[0140] According to another embodiment of the objective, the layered potassium metal oxide in crystalline form is given by formula K 0.3 Ni 0.15 Mn 0.85 It is of O2 and has an XRD pattern substantially shown in Figure 11 or an XRD 2θ reflection (°) substantially shown in Figure 40.

[0141] According to another embodiment of the objective, the layered potassium metal oxide in crystalline form is given by formula K 0.3 Ni 0.2 Mn 0.8 It is of O2 and has an XRD pattern substantially shown in Figure 12 or an XRD 2θ reflection (°) substantially shown in Figure 40.

[0142] According to another embodiment of the objective, the layered potassium metal oxide in crystalline form is given by formula K 0.2 Ni 0.1 Mn 0.9 It is of O2 and has an XRD pattern substantially shown in Figure 14, or an XRD 2θ reflection (°) substantially shown in Figure 40 and / or Figure 41.

[0143] According to another embodiment of the objective, the layered potassium metal oxide in crystalline form is given by formula K 0.2 Ni 0.2 Mn 0.8 It is of O2 and has an XRD pattern substantially shown in Figure 15, or an XRD 2θ reflection (°) substantially shown in Figure 41.

[0144] According to another embodiment of the objective, the layered potassium metal oxide in crystalline form is given by formula K 0.1 Ni 0.05 Mn 0.95 It is of O2 and has an XRD pattern substantially shown in Figure 17, or an XRD 2θ reflection (°) substantially shown in Figure 41. [Examples]

[0145] The following embodiments are for illustrative purposes only and should not be construed as further limiting the scope of the invention considered. These embodiments will be better understood by referring to the accompanying drawings. Example 1: Synthesis of electrochemically 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 Layered potassium metal oxides of O2 were prepared using solid-phase reaction techniques. Each precursor (K2CO3 / KOH, as well as metal oxides such as Na2CO3, Mn2O3, Co2O3, CuO, ZrO2, NiO, Fe2O3, and TiO2) was weighed to obtain the desired stoichiometric amount. The sample was prepared by grinding and mixing with the precursor powder. The ground and mixed precursor powder was then placed in a furnace and heated in an air or oxygen atmosphere for 5 to 24 hours at a temperature between 600°C and 1000°C. For example, it was heated at a temperature between 800°C and 1000°C for 6 to 8 hours. b) Wet chemical synthesis

[0147] Alternatively, the layered potassium metal oxides as defined herein may be prepared using wet chemical synthesis techniques. For example, the layered potassium metal oxides as defined herein may be prepared by a sol-gel method, e.g., a 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, a 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 added dropwise to an aqueous solution of approximately 1 mol / L of citric acid, which is continuously stirred. The pH is adjusted to a value between approximately pH 7.0 and approximately pH 8.0 using ammonium hydroxide. Next, the solution was heated between approximately 70°C and 80°C while stirring to evaporate the solvent until a clear sol-gel precursor was obtained. The resulting sol-gel precursor was baked in an oven at approximately 450°C for approximately 8 hours in an air or oxygen atmosphere to remove organic contaminants. Finally, the resulting powder was ground in a mortar and baked 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 structures of the electrochemically active material were studied by X-ray diffraction performed on the layered potassium metal oxide powder prepared in Example 1(a). Figures 1-17 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 Figure (A) shows the X-ray diffraction pattern of O2 layered potassium metal oxide powder. Figure 18 shows the 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 This shows the X-ray diffraction pattern of layered potassium metal oxide powder containing O2.

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

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

[0151] Figures 1-3(B) and 9(C) show the crystal structures of formula K, respectively, which have the characteristics shown in Table 1. 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 The crystal structure of O2 layered potassium metal oxide is shown in the diagram. [Table 1]

[0152] The reflection parameters of a 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) show the crystal structure characteristics of formula K, respectively, as 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 The crystal structure of O2 layered potassium metal oxide is shown in the diagram. [Table 2]

[0154] The reflection parameters of a 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) show the characteristics of the crystal structure of formula K, as 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 The crystal structure of O2 layered potassium metal oxide is shown in the diagram. [Table 3]

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

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

[0158] Figure 16 shows equation K 0.2The characteristic 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, 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 O2 (Figure 14, Tables 2 and 3) are proposed. In fact, these two structures are possible according to the X-ray diffraction patterns. Example 3: Electrochemical properties

[0160] The electrochemical properties of the electrochemical 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 an electrochemical cell

[0161] [Table 5]

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

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

[0164] The separator of an electrochemical cell containing a sodium metal thin film negative electrode was impregnated with a 1M NaPF6 solution of EC / DEC (volume ratio [3:7]) or EC / DMC (volume ratio [4:6]) as the 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] Figure 19 shows equation 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 oxide in O2 -1 The graph shows x versus x. The results for lithium-ion batteries (red line) and sodium-ion batteries (black line) are shown. As shown in Figure 19, x may preferably be about 0.4.

[0167] Figures 20–37 show the charge-discharge profiles of cells 1–28 and 33–35. The figures compare 1.5V and 4.5V for all electrochemical cells, including lithium metal thin film as the negative electrode, versus Li + / Li at 0.1C, and between 1.5V and 4.2V for all electrochemical cells including a sodium metal thin film as the negative electrode vs. Na + Charge and discharge cycles were performed at 0.1C with / Na. The cycles started with discharge and continued at a temperature of 25°C. 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 cells 1, 3, 5, 17, 19, 25, and 31 in (A); and Capacity (mAh g) as a function of the number of cycles for cells 2, 4, 6, 18, 26, and 32 in (B) -1The graphs show the performance and efficiency (%). Long-term cycle experiments were conducted at a constant charge / discharge current of C / 10 at a temperature of approximately 25°C. The results shown in Figure 38(A) are for approximately 45 cycles vs. Li + Recorded with / Li, and (B) vs. Na for approximately 35 cycles. + Recorded with / Na.

[0169] Many modifications can be made to any of the above embodiments without departing from the scope of the invention considered. All references, patents, or scientific papers referenced herein are incorporated herein by reference for all purposes.

Figure 41

Claims

1. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the positive electrode comprises an electrode material containing an electrochemical active material, and the electrochemical active material is of formula Na ｚ K ｘ MO ２ An electrochemical cell comprising an anhydrous layered potassium metal oxide, where z is a numerical value such as 0 < z ≤ 0.8, x is a numerical value such as 0 < x ≤ 0.7, and M is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Zr, and at least two combinations thereof, wherein the negative electrode comprises metallic lithium or metallic sodium.

2. The aforementioned anhydrous layered potassium metal oxide is, formula Na ｚ K ｘ M ｙ Mn １－ｙ O ２ The electrochemical cell according to claim 1, wherein z is a numerical value such as 0 < z ≤ 0.8, x is a numerical value such as 0 < x ≤ 0.7, y is a numerical value such as 0 ≤ y ≤ 1.0, and M is selected from Co, Fe, Ni, Ti, Cr, V, Cu, Zr, and at least two combinations thereof.

3. wherein the anhydrous layered potassium metal oxide has the formula Na ｚ K ｘ Ni ｙ Mn １－ｙ O ２ where z is a numerical value such that 0 < z ≦ 0.8, x is a numerical value such that 0 < x ≦ 0.7, and y is a numerical value such that 0 ≦ y ≦ 1.0, the electrochemical cell according to claim 1 or 2.

4. The aforementioned anhydrous 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 an electrochemical cell according to any one of claims 1 to 3, selected from the group consisting of, and at least two combinations thereof.

5. The anhydrous layered potassium metal oxide is Na ０．７４ K ０．０８ Ni ０．４１ Mn ０．５９ O ２ The electrochemical cell according to claim 4.

6. The anhydrous layered potassium metal oxide is Na ０．６ K ０．０８ Ni ０．３４ Mn ０．６６ O ２ The electrochemical cell according to claim 4.

7. The anhydrous layered potassium metal oxide is Na ０．７４ K ０．０８ Ni ０．２ Mn ０．８ O ２ The electrochemical cell according to claim 4.

8. The anhydrous layered potassium metal oxide is Na ０．６ K ０．０８ Ni ０．２ Mn ０．８ O ２ The electrochemical cell according to claim 4.

9. The anhydrous layered potassium metal oxide is Na ０．３２ K ０．０８ Ni ０．２ Mn ０．８ O ２ The electrochemical cell according to claim 4.

10. The anhydrous layered potassium metal oxide is Na ０．２ K ０．２ Ni ０．２ Mn ０．８ O ２ The electrochemical cell according to claim 4.

11. The electrode material of the positive electrode is - Electronically conductive materials; and / or - Binder An electrochemical cell according to any one of claims 1 to 10, further comprising:

12. The aforementioned electrolyte, - A liquid electrolyte containing a salt in the solvent; or - A gel electrolyte containing a solvent and, optionally, a salt in a solvating polymer; or - Solid polymer electrolytes containing salts in solvated polymers; or - Glass electrolyte or ceramic electrolyte The electrochemical cell according to any one of claims 1 to 11.

13. If the aforementioned salt is present, - Lithium salt; or - Sodium salt; or - Potassium salts The electrochemical cell according to claim 12.

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

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

Images