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WO2021089680A1 - Solution-based synthesis of lithium transition metal halides - Google Patents

Solution-based synthesis of lithium transition metal halides Download PDF

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Publication number
WO2021089680A1
WO2021089680A1 PCT/EP2020/081090 EP2020081090W WO2021089680A1 WO 2021089680 A1 WO2021089680 A1 WO 2021089680A1 EP 2020081090 W EP2020081090 W EP 2020081090W WO 2021089680 A1 WO2021089680 A1 WO 2021089680A1
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group
solid
coated particulate
general formula
lithium
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Application number
PCT/EP2020/081090
Other languages
French (fr)
Inventor
Park KEONHO
Linda Nazar
Xiaohan WU
Jörn Kulisch
Original Assignee
Basf Se
University Of Waterloo
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Publication of WO2021089680A1 publication Critical patent/WO2021089680A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/002—Compounds containing titanium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G27/00—Compounds of hafnium
    • C01G27/006—Compounds containing hafnium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C01G33/006—Compounds containing niobium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C01G35/006—Compounds containing tantalum, with or without oxygen or hydrogen, and containing two or more other elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • WO 2019/135343 A1 discloses a solid electrolyte material comprising: Li; Y; at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, La, Sm, Bi, Zr, Hf, Nb and Ta; and at least one element selected from the group consisting of Cl, Br, and I, wherein the X-ray diffraction pattern for the solid electrolyte material obtained using Cu-Ka radiation as the X-ray source includes a plurality of peaks in the diffraction angle (2Q) range of 25° to 35° and at least one peak in the diffraction angle (2Q) range of 43° to 51 °.
  • WO 2019/135345 A1 discloses a solid electrolyte material comprising: Li; Y; at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Zr, Nb and Ta; and at least one element selected from the group consisting of Cl, Br, and I.
  • An X-ray diffraction pattern for the solid electrolyte material obtained using Cu-Ka radiation as the X-ray source includes a peak in the diffraction angle (2Q) range of 30° to 33°, in the diffraction angle (2Q) range of 39° to 43°, and in the diffraction angle (2Q) range of 47° to 51 °.
  • Lithium transition metal halides as described in US 2019/0088995 A1 , WO 2019/135343 A1 and WO 2019/135345 A1 are obtained by means of mechano- chemical milling processes, e.g. ball milling, or by means of solid state thermochemical methods. Accordingly, there is a need for a more efficient, facile and scalable synthesis of lithium transition metal halides without compromising the ionic conductivity and other important properties like oxidative stability. It is an objective of the present invention to provide an efficient process for synthesizing solid materials from the group consisting of lithium transition metal halides and lithium transition metal pseudohalides having favorable ionic conductivity, as well as oxidative stability.
  • a coated particulate material for use in a cathode of a lithium- ion electrochemical cell and a process for preparing it a cathode for use in a lithium-ion electrochemical cell comprising said coated particulate material, an electrochemical cell comprising said coated particulate material and a use of said coated particulate material for preparing a cathode for use in a lithium-ion electrochemical cell
  • M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
  • M’ is one or more selected from the group consisting of Ti, Zr, Hf, Nb and Ta;
  • X is one or more selected from the group consisting of halides and pseudohalides
  • n is the difference between the valences of M’ and M;
  • Said process comprises the process steps of
  • M is three-valent
  • n is 1 if M’ is four-valent (as it is the case for Ti, Zr and Hf)
  • n is 2 if M’ is five-valent (as it is the case for Nb and
  • composition according to general formula (I) may be considered as a lithium transition metal halide resp. as a lithium transition metal pseudohalide.
  • pseudohalides denotes monovalent anions, which resemble halide anions with regard to their chemistry, and therefore can replace halide anions in a chemical compound without substantially changing the properties of such compound.
  • the term “pseudohalide ion” is known in the art, of. the lUPAC Goldbook. Examples of pseudohalide anions are N3 , SCN ⁇ , CN ⁇ , OCN-, BF4 and Bh .
  • the pseudohalide anion is preferably selected from the group consisting of BF 4 and BhU .
  • halide-containing solid materials having a composition according to general formula (I) the halide is preferably selected from the group consisting of Cl, Br and I.
  • a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein M is one or both of Y and Er, preferably Y (yttrium).
  • a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl.
  • a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein M is one or both of Y and Er, and X is one or more halides selected from the group consisting of Cl, Br and I.
  • a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein M is Y and X is Cl.
  • a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein 0.08 ⁇ x ⁇ 0.85, more preferably 0.18 ⁇ x ⁇ 0.8, most preferably 0.2 ⁇ x ⁇ 0.65.
  • a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein 5.85 ⁇ y ⁇ 6.15, more preferably 5.9 ⁇ y ⁇ 6.1 resp. 5.95 ⁇ y ⁇ 6.15, most preferably 5.95 ⁇ y ⁇ 6.1 .
  • a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) 0.08 ⁇ x ⁇ 0.85, more preferably 0.18 ⁇ x ⁇ 0.8, most preferably 0.2 ⁇ x ⁇ 0.65, and 5.85 ⁇ y ⁇ 6.15, more preferably 5.9 ⁇ y ⁇ 6.1 resp. 5.95 ⁇ y ⁇ 6.15, most preferably 5.95 ⁇ y ⁇ 6.1 .
  • a solid material having a composition according to general formula (I) obtained by the process described herein may contain a certain fraction of nitrogen resp. oxygen originating e.g. from the solvent in which the precursors are dissolved in step (a).
  • a solid material having a composition according to general formula (I) obtained by the process described herein may contain a certain fraction of oxygen as denoted by index “b” of formula (I).
  • a solvent containing nitrogen atoms e.g. H2O, alcohols CnH2n +i OH wherein 1 ⁇ n ⁇ 20, formic acid, acetic acid, tetrahydrofuran
  • a solid material having a composition according to general formula (I) obtained by the process described herein may contain a certain fraction of oxygen as denoted by index “b” of formula (I).
  • a solvent containing nitrogen atoms e.g.
  • a solid material having a composition according to general formula (I) obtained by the process described herein may contain a certain fraction of nitrogen as denoted by index “a” of formula (I).
  • formula (I) is an empirical formula (gross formula) determinable by means of elemental analysis. Accordingly, formula (I) defines a composition which is averaged over the solid material as a whole, and does not indicate a specific lattice structure or constitution of the solid material. The same applies to formulae (la) and (lb) (see below) which are derived from general formula (I).
  • step (a) of the process described herein a liquid reaction mixture comprising precursors for the reaction product to be formed in step (b) is provided. Said precursors are
  • X is one or more selected from the group consisting of Cl, Br and I.
  • X is the same, preferably Cl.
  • M is one or both of Y and Er, preferably Y.
  • X is one or more selected from the group consisting of Cl, Br and I, and in precursor (2) M is one or both of Y and Er. Further specifically, in each of precursors (1 ) to (3) X is Cl, and in precursor (2) M is Y.
  • a liquid reaction mixture is prepared by dissolving the above-mentioned precursors (1), (2) and (3) in a solvent selected from the group consisting of ethers, H2O, alcohols C n H2n+iOH (1 ⁇ n ⁇ 20), formic acid, acetic acid, tetrahydrofuran, dimethylformamide, N- methylformamide, pyridine, nitriles, dimethyl sulfoxide, acetone, ethyl acetate, dimethoxy- ethane, 1 ,3-dioxolane, N-methylpyrrolidinone, and alkylene carbonates.
  • Preferred solvents are ethers (especially tetrahydrofuran), alcohols with 1 ⁇ n ⁇ 6 and pyridine. Nitriles, especially acetonitrile, are less preferred in some cases.
  • the liquid reaction mixture prepared in step (a) is in the form of a solution of the above- defined precursors (1), (2) and (3) in a solvent selected from the group consisting of ethers, H2O, alcohols C n H2n+iOH (1 ⁇ n ⁇ 20), formic acid, acetic acid, tetrahydrofuran, dimethylformamide, N-methylformamide, pyridine, nitriles, dimethyl sulfoxide, acetone, ethyl acetate, dimethoxyethane, 1 ,3-dioxolane, N-methylpyrrolidinone, and alkylene carbonates.
  • Preferred solvents are ethers (especially tetrahydrofuran), alcohols with 1 ⁇ n ⁇ 6 and pyridine. Ni- triles, especially acetonitrile, are less preferred in some cases.
  • the total content of precursors (1), (2) and (3) in the liquid reaction mixture prepared in step (a) is in the range from 1 % to 80 %, and preferably in the range from 3 % to 30 %, based on the total weight ofthe liquid reaction mixture (sum of the weights of all precursors and solvents).
  • the process according to the first aspect of the present disclosure does not involve mechanochemical milling (i.e. reactive-milling) of the precursors (1), (2) and (3) resp. of a mixture thereof.
  • solution-based synthesis according to the process described herein provides an intimate mix of the precursors, potentially reducing the temperature and/or duration of the subsequent heat treatment in step (b), compared to the heat treatment to be applied in purely thermochemical synthesis of corresponding materials.
  • step (a) preferably any handling is performed under a protective gas atmosphere.
  • the precursors (1), (2) and (3) and their molar ratio are selected according to the target stoichiometry.
  • the precursor (3) is one or more from the group consisting of compounds MXt wherein M’ is one or more of Ti, Zr and Hf, and X is as defined above.
  • Such processes are suitable for preparing solid materials having a composition according to general formula (la) L -xMl-xM xXy-3a-2bNaOb (la) wherein
  • M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
  • M’ is one or more selected from the group consisting of Ti, Zr, and Hf;
  • X is one or more selected from the group consisting of halides and pseudohalides; 0.05 ⁇ x ⁇ 0.95, preferably 0.08 ⁇ x ⁇ 0.85, more preferably 0.18 ⁇ x ⁇ 0.8, most preferably
  • MX3 one or more compounds MX3, wherein M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
  • X is one or more selected from the group consisting of Cl, Br and I.
  • X is the same, preferably Cl.
  • M is one or both of Y and Er, preferably Y.
  • X is one or more selected from the group consisting of Cl, Br and I, and in precursor (2) M is one or both of Y and Er. Further specifically, in each of precursors (1 ) to (3) X is Cl, and in precursor (2) M is Y.
  • precursor (3) M’ is Zr.
  • X is one or more selected from the group consisting of Cl, Br and I
  • in precursor (2) M is one or both of Y and Er
  • in precursor (3) M’ is Zr.
  • X is Cl
  • in precursor (2) M is Y
  • in precursor (3) M’ is Zr.
  • the precursor (3) is one or more from the group consisting of compounds M’Xs wherein M’ is one or both of Nb and Ta, and X is as defined above.
  • Such processes are suitable for preparing solid materials having a composition according to general formula (lb)
  • M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
  • M’ is one or both selected from the group consisting of Nb and Ta;
  • X is one or more selected from the group consisting of halides and pseudohalides
  • MX3 one or more compounds MX3, wherein M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
  • X is one or more selected from the group consisting of Cl, Br and I.
  • X is the same, preferably Cl.
  • M is one or both of Y and Er, preferably Y.
  • X is one or more selected from the group consisting of Cl, Br and I
  • precursor (2) M is one or both of Y and Er.
  • X is Cl
  • precursor (2) M is Y.
  • step (b) removal of the solvents is preferably achieved by subjecting the solution to a reduced pressure (relative to standard pressure 101.325 kPa) at a temperature in the range from 0 °C to 100 °C, preferably from 20 °C to 40 °C under dynamic vacuum (continuous removal of the vapor of the solvent from the reaction vessel).
  • a reduced pressure relative to standard pressure 101.325 kPa
  • step (b) after removal of the solvents, heat treatment of the obtained residue is preferably performed in a closed vessel for a duration of 1 to 12 hours, preferably 4 to 12 hours, more preferably 4 to 8 hours, at a temperature in the range of from 100 °C up to 300 °C, preferably 105 °C to 300 °C, further preferably in the range of from 100 °C to 250 °C or 105 °C to 250 °C, most preferably in the range of from 100 °C to 200 °C or 105 °C to 200 °C.
  • step (b) The heat treatment in step (b) is carried out either under vacuum or under a protective gas atmosphere. If necessary, the solid material obtained by the process according to the invention as described above is ground into a powder.
  • M’ is one or more selected from the group consisting of Ti, Zr, Hf, Nb and Ta;
  • X is one or more selected from the group consisting of halides and pseudohalides; 0.05 ⁇ x ⁇ 0.95;
  • n is the difference between the valences of M’ and M;
  • formula (II) is an empirical formula (gross formula) determinable by means of elemental analysis. Accordingly, formula (II) defines a composition which is averaged over the solid material as a whole, and does not indicate a specific lattice structure or constitution ofthe solid material. The same applies to formulae (I I a) and (lib) (see below) which are derived from general formula (II).
  • a solid material having a composition according to general formula (II) as defined herein contains one or both of oxygen and nitrogen. Therefore, the solid electrolyte materials prepared according to table 1 of WO 2019/135343 A1 and table 1 of WO 2019/135345 A1 do not fall under formula (II) as defined herein.
  • a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein M is one or both of Y and Er, preferably Y.
  • a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl. More specifically, a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein M is one or both of Y and Er, and X is one or more halides selected from the group consisting of Cl, Br and I. Further specifically, a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein M is Y and X is Cl.
  • a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein 0.08 ⁇ x ⁇ 0.85, more preferably 0.18 ⁇ x ⁇ 0.8, most preferably 0.2 ⁇ x ⁇ 0.65.
  • a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein 5.85 ⁇ y ⁇ 6.15, more preferably 5.9 ⁇ y ⁇ 6.1 resp. 5.95 ⁇ y ⁇ 6.15, most preferably 5.95 ⁇ y ⁇ 6.1 . More specifically, a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein 0.08 ⁇ x ⁇ 0.85, more preferably 0.18 ⁇ x ⁇ 0.8, most preferably 0.2 ⁇ x ⁇ 0.65; and 5.85 ⁇ y ⁇ 6.15, more preferably 5.9 ⁇ y ⁇ 6.1 resp. 5.95 ⁇ y ⁇ 6.15, most preferably 5.95 ⁇ y ⁇ 6.1 .
  • a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein
  • M is one or both of Y and Er
  • X is one or more halides selected from the group consisting of Cl, Br and I;
  • a solid material according to the second aspect as defined herein may be crystalline as detectable by the X-ray diffraction technique.
  • a solid material is referred to as crystalline when it exhibits a long range order that is characteristic of a crystal, as indi- cated by the presence of clearly defined reflections in its X-ray diffraction pattern. In this context, a reflection is considered as clearly defined if its intensity is more than 10% above the background.
  • a crystalline solid material according to the second aspect as defined herein may be accompanied by secondary phases and/or impurity phases having a composition not according to general formula (II) as defined above.
  • the volume fraction of the phase formed of the crystalline solid material having a composition according to general formula (II) may be 60 % or more, sometimes 80 % or more, preferably 90 % or more, most preferably 95 % or more, based on the total volume of the solid material according to the second aspect as defined herein and all secondary phases and impurity phases.
  • the secondary phases and impurity phases mainly consist ofthe precursors used for preparing the solid material, e.g. LiX (wherein X is as defined above), and sometimes impurity phases which may originate from impurities of the precursors.
  • the precursors used for preparing the solid material e.g. LiX (wherein X is as defined above)
  • impurity phases which may originate from impurities of the precursors.
  • a solid material according to the second aspect as defined herein is in the form of a polycrystalline powder, or in the form of single crystals.
  • a solid material according to the second aspect as defined herein is glassy, i.e. amorphous.
  • a solid material is referred to as amorphous when it lacks the long range order that is characteristic of a crystal, as indicated by the absence of clearly defined reflections in its X-ray diffraction pattern. In this context, a reflection is considered as clearly defined if its intensity is more than 10% above the background.
  • a solid material according to the second aspect as described herein is glass-ceramics, i.e. a polycrystalline solid having at least 30 % by volume of a glassy phase.
  • a solid material according to the second aspect as described herein may have an ionic conductivity of 0.1 mS/cm or more, preferably 1 mS/cm or more, in each case at a temperature of 25 °C.
  • the ionic conductivity is determined in the usual manner known in the field of solid state battery materials development by means of electrochemical impedance spec- troscopy-
  • a solid material according to the second aspect as described herein may have an almost negligible electronic conductivity. More specifically, the electronic conductivity may be at least 3 orders of magnitude lower than the ionic conductivity, preferably at least 5 orders of magnitude lower than the ionic conductivity. In certain cases, a solid material according to the second aspect as described herein exhibits an electronic conductivity of 10 10 S/cm or less. The electronic conductivity is determined in the usual manner known in the field of battery materials development by means of direct-current (DC) polarization measurements at different voltages.
  • DC direct-current
  • a solid material according to the second aspect as described herein resp. obtained by the process according to the above-defined first aspect can be used as a solid electrolyte for an electrochemical cell.
  • the solid electrolyte may form a component of a solid structure for an electrochemical cell, wherein said solid structure is selected from the group consisting of cathode, anode and separator.
  • a solid material according to the second aspect as defined herein resp. obtained by the process according to the above- defined first aspect can be used alone or in combination with additional components for producing a solid structure for an electrochemical cell, such as a cathode, an anode or a separator.
  • the present disclosure further provides the use of a solid material according to the second aspect as defined herein resp.
  • the present disclosure further provides the use of a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect as a component of a solid structure for an electrochemical cell, wherein said solid structure is selected from the group consisting of cathode, anode and separator.
  • the electrode of an electrochemical cell where during discharging a net negative charge occurs is called the anode and the electrode of an electrochemical cell where during discharging a net positive charge occurs is called the cathode.
  • the separator electronically separates a cathode and an anode from each other in an electrochemical cell.
  • the cathode of an all-solid-state electrochemical cell usually comprises a solid electrolyte as a further component beside a cathode active material.
  • the anode of an all-solid-state electrochemical cell usually comprises a solid electrolyte as a further component beside an anode active material.
  • Said solid electrolyte may be a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect.
  • the form of the solid structure for an electrochemical cell, in particular for an all-solid-state lithium battery depends in particular on the form ofthe produced electrochemical cell itself.
  • the present disclosure further provides a solid structure for an electrochemical cell, wherein the solid structure is selected from the group consisting of cathode, anode and separator, wherein the solid structure comprises a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect.
  • the present disclosure further provides an electrochemical cell comprising a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect.
  • the solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect may form a component of one or more solid structures selected from the group consisting of cathode, anode and separator. More specifically, there is provided an electrochemical cell as described above wherein in certain preferred cases a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect may be in direct contact with a cathode active material having a redox potential of 4 V or more, preferably of 4.5 V or more vs. Li/Li + .
  • a first group of solid materials according to the second aspect as defined herein has a composition according to formula (II) wherein M and X are as defined above; and M’ is one or more of Ti, Zrand Hf. Since in a solid material of said first group M’ is a four- valent metal, n is 1 . Thus, a solid material of said first group has a composition according to formula (I la)
  • L -xMl-xM xXy-3a-2bNaOb (113) wherein M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
  • M’ is one or more selected from the group consisting of Ti, Zr, and Hf;
  • X is one or more selected from the group consisting of halides and pseudohalides
  • a solid material of the first group described herein may have a composition according to formula (I la) wherein M is one or both of Y and Er, preferably Y.
  • a solid material of the first group described herein may have a composition according to formula (I I a) wherein X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl.
  • a solid material of the first group described herein may have a composi- tion according to formula (I la) wherein M is one or both of Y and Er, and X is one or more halides selected from the group consisting of Cl, Br and I. Further specifically, a solid material of the first group described herein may have a composition according to formula (I la) wherein M is Y and X is Cl.
  • a solid material of the first group described herein may have a composition according to formula (I la) wherein M’ is Zr. More specifically, a solid material of the first group described herein may have a composition according to formula (I la) wherein M is one or both of Y and Er, M’ is Zr and X is one or more halides selected from the group consisting of Cl, Br and I.
  • a solid material of the first group described herein may have a composition according to formula (I la) wherein 0.08 ⁇ x ⁇ 0.85, more preferably 0.18 ⁇ x ⁇ 0.8, most preferably 0.2 ⁇ x ⁇ 0.65.
  • a solid material of the first group described herein may have a composition according to formula (I I a) wherein 5.85 ⁇ y ⁇ 6.15, more preferably 5.9 ⁇ y ⁇ 6.1 resp. 5.95 ⁇ y ⁇ 6.15, most preferably 5.95 ⁇ y ⁇ 6.1. More specifically, a solid material of the of the first group described herein may have a composition according to formula (I I a) wherein 0.08 ⁇ x ⁇ 0.85, more preferably 0.18 ⁇ x ⁇ 0.8, most preferably 0.2 ⁇ x ⁇ 0.65; and 5.85 ⁇ y ⁇ 6.15, more preferably 5.9 ⁇ y ⁇ 6.1 resp.
  • Specific solid materials of the first group described herein may have a composition according to formula (I I a) wherein M is one or both of Y and Er, and M’ is Zr, and X is Cl.
  • M is Y
  • M’ is Zr
  • X is Cl
  • a second group of solid materials according to the second aspect as defined herein has a composition according to formula (II) wherein M and X are as defined above; and M’ is one or both of Nb and Ta. Since in a solid material of said second group M’ is a five-valent metal, n is 2. Thus, a solid material of said second group has a composition according to formula (lib) Ll3-2xM 1 -xM ’xXy-3a-2bNaOb (lib) wherein
  • M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
  • M’ is one or both selected from the group consisting of Nb and Ta;
  • X is one or more selected from the group consisting of halides and pseudohalides; 0.05 ⁇ x ⁇ 0.95;
  • a solid material of the second group described herein may have a composition according to formula (lib) wherein M is one or both of Y and Er, preferably Y.
  • a solid material of the second group described herein may have a composition according to formula (lib) wherein X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl. More specifically, a solid material of the second group described herein may have a composition according to formula (lib) wherein M is one or both of Y and Er, X is one or more halides selected from the group consisting of Cl, Br and I. Further specifically, a solid material of the second group described herein may have a composition according to formula (lib) wherein M is Y and X is Cl.
  • a solid material of the second group described herein may have a composition according to formula (lib) wherein 0.08 ⁇ x ⁇ 0.85, more preferably 0.18 ⁇ x ⁇ 0.8, most preferably 0.2 ⁇ x ⁇ 0.65.
  • a solid material of the second group described herein may have a composition according to formula (lib) wherein 5.85 ⁇ y ⁇ 6.15, more preferably 5.9 ⁇ y ⁇ 6.1 resp. 5.95 ⁇ y ⁇ 6.15, most preferably 5.95 ⁇ y ⁇ 6.1. More specifically, a solid material of the second group described herein may have a composition according to formula (lib) wherein 0.08 ⁇ x ⁇ 0.85, more preferably 0.18 ⁇ x ⁇ 0.8, most preferably 0.2 ⁇ x ⁇ 0.65; and 5.85 ⁇ y ⁇ 6.15, more preferably 5.9 ⁇ y ⁇ 6.1 resp. 5.95 ⁇ y ⁇ 6.15, most preferably 5.95 ⁇ y ⁇ 6.1.
  • Specific solid materials of the second group described herein may have a composition ac- cording to formula (lib) wherein M is one or both of Y and Er, and M’ is one or both of Nb and Ta, and X is Cl.
  • M is Y
  • M’ is Nb orTa
  • X is Cl
  • M is Er
  • M’ is Nb or Ta
  • X is Cl
  • Preferred solid materials according to the second aspect as defined herein are those having one or more of the specific and preferred features disclosed herein.
  • a coated particulate material for use in a cathode of a lithium-ion electrochemical cell.
  • Said coated particulate material comprises
  • each core particle comprising at least one cathode active material
  • the electrode of an electrochemical cell where during discharging of the cell a net positive charge occurs is called the cathode, and the component of the cathode by reduction of which said net positive charge is generated is referred to as a “cathode active material”.
  • each core particle consists of at least one cathode active material.
  • Preferred cathode active materials are those having a redox potential of 4 V or more vs. Li/Li + (cathode active material ofthe “4 V class”), which enable obtaining a high cell voltage. Many such cathode active materials are known in the art.
  • Suitable cathode active materials are oxides comprising lithium, and one or more members ofthe group consisting of nickel, cobalt and manganese.
  • cathode active materials are oxides comprising - lithium, nickel and one or both members of the group consisting of cobalt and manganese.
  • Exemplary suitable cathode active materials have a composition according to general formula (III): Lii +t Ai-t02 (III), wherein
  • A comprises nickel and one or both members ofthe group consisting of cobalt and manganese, and optionally one or more further transition metals not selected from the group consisting of nickel, cobalt and manganese, wherein said further transition metals are preferably selected from the group consisting of molybdenum, titanium, tungsten, zirconium, - one or more elements selected from the group consisting of aluminum, barium, boron and magnesium, wherein at least 50 mole-% of the transition metal of A is nickel; and t is a number in the range of from -0.05 to 0.2.
  • Suitable cathode active materials having a composition according to formula (III) are de- scribed in a non-prepublished European patent application 19180075.4 - 1108.
  • the cathode active material having a composition according to general formula (III) may have a layered structure or a spinel structure.
  • Cathode active materials having a composition according to general formula (III) which have a layered structure as described in non- prepublished European patent application 19180075.4 - 1108 are preferred.
  • Preferred cathode active materials have a composition according to general formula (Ilia)
  • M is a member of the group consisting of aluminum, barium, boron, magnesium, molybdenum, titanium, tungsten, zirconium, and mixtures of at least two of the forego- ing elements, preferably is or comprises aluminum (preferably when v is 0), z is a number in the range of from -0.05 to 0.2, u is a number in the range of from 0.04 to 0.2, v is a number in the range of from 0 to 0.2, preferably of from 0.04 to 0.2, w is a number in the range of from 0 to 0.1 and (u + v + w) is ⁇ 0.4 and preferably is ⁇ 0.3.
  • the variable “M” can stand for any individual member of the group of elements as defined above (e.g. “M” can stand for tungsten, i.e. “W”) or it can stand for two or more members of the group of elements as defined above (e.g. the “M” can stand for a group consisting of tungsten, zirconium and titanium).
  • W tungsten
  • M can stand for two or more members of the group of elements as defined above
  • the index (number) “w” accompanying the variable “M” applies to the total of elements represented by “M”, as defined above.
  • Exemplary cathode active materials of formula (III) are Lii +t [Nio85Coo ioMnoo5]i-tC>2, Lii +t [Nio87Cooo5Mnoo8]i-t02, Lii +t [Nio83Cooi2Mnoo5]i -t02, Lii +t [NioeCoo2Mno2]i-t02, Lil +t [Nio88COo08Alo04]l-t02, Lil +t [Nio905COo0475Alo0475]l-t02, and Lil +t [Nio9lCOo045Alo045]l-t02, wherein in each case -0.05 ⁇ t ⁇ 0.2.
  • cathode active materials are UC0O2 and LiNio5Mn15O4.
  • the coating C2) is disposed on the surfaces of at least a part of the core particles C1), preferably it is disposed on the surfaces of > 50 % of the total number of core particles C1), more preferably on the surfaces of > 75 % ofthe total number of core particles C1), even more preferably on the surfaces of > 90 % of the total number of core particles C1) and yet even more preferably on the surfaces of > 95 % ofthe total number of core particles C1) present in the coated particulate material.
  • the part of the core particles C1) on whose surfaces the coating C2) is disposed can be determined by electron microscopy performed on a (representative) sample ofthe coated particulate material.
  • the coating C2) is disposed on at least a part ofthe surface of a (an individual) core particle 01), pref- erably it is disposed on > 50 % of the total surface of a core particle 01), more preferably on > 75 % of the total surface of a core particle 01) and even more preferably on > 90 % of the total surface of a core particle 01).
  • the part of the surface of a core particle 01) on which the coating 02) is disposed can be determined by electron microscopy performed on a (representative) sample of an (individ- ual) coated particle of the coated particulate material or a (representative) sample of the coated particulate material.
  • the lithium present in the coating 02) is preferably present as part of solid materials having a composition according to general formula (I) as described above and of lithium carbonate (L12CO3).
  • the total amount of lithium present in the coating 02) is present as part of solid materials having a composition according to general formula (I) as described above and of lithium carbonate (U2CO3).
  • the coating C2) may comprise carbonate anions in a total amount of > 0.12 %, or of > 0.15 %, in each case relative to the total mass of the plurality of (uncoated) core particles C1). More specifically, the coating C2) may comprise carbonate anions in a total amount in the range of from 0.12 % to 3.0 %, preferably of from 0.15 % to 2.5 %, more preferably of from 0.15 % to 2.0 %, even more preferably of from 0.15 % to 1 .0 %, relative to the total mass of the plurality of (uncoated) core particles C1). If the content of lithium carbonate in the coating C2) is too high, the lithium ion conductivity may be decreased.
  • the carbonate present on the surface of the core particles C1) originates from unavoidable impurities of the cathode active material which may be formed when the cathode active material is prepared or stored in the presence of traces of carbon dioxide and humidity, and/or in certain cases from using lithium carbonate as a precursor for the synthesis of the cathode active material, and/or from the decomposition ofthe organic solvent of the liquid reaction mixture used in preparing the coated particulate material (for details see below) in air resp. oxygen and reactivity with residual lithium on the particle surface of the cathode active material.
  • At least a part of the carbonate ions present in the coating C2) may be present as part of an ionic compound, e.g. as part of a salt.
  • at least a part of the carbonate ions present in the coating C2) preferably the total amount of carbonate ions present in the coating C2), is present as lithium carbonate.
  • the amount of carbonate ions present in the coating C2) may be determined by acid titration, coupled with mass spectroscopy, more preferably according to the method as defined in the examples section of non-prepublished European patent application 19180075.4 - 1108, performed on a (representative) sample of the coated particulate material.
  • the disclosure regarding solid materials having a composition according to general formula (I) resp. (II) provided above in the context ofthe first and the second aspect applies mutatis mutandis to the coated particulate material according to the third aspect.
  • preferred and specific solid materials having a composition according to general formula (I) resp. (II) reference is made to the disclosure provided above in the context of the first and second aspect.
  • the solid material having a composition according to general formula (I) is amorphous or is a glassy ceramics.
  • the thickness of the coating C2) may be in the range of from 1 nm to 1 pm, preferably of from 1 nm to 50 nm.
  • a coated particulate material according to the third aspect described herein comprises or consists of
  • each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition according to general formula (III) as defined above;
  • a coated particulate material according to the third aspect described herein comprises or consists of
  • each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition according to general formula (III) as defined above;
  • a coated particulate material according to the third aspect described herein comprises or consists of
  • each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition ac- cording to general formula (III) as defined above;
  • a coating comprising carbonate anions, preferably lithium carbonate; and at least one solid material having a composition according to general for- mula (II) as defined above.
  • a coated particulate material according to the third aspect described herein comprises or consists of
  • each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition according to general formula (III) as defined above;
  • a coated particulate material according to the third aspect described herein comprises or consist of
  • each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition ac- cording to general formula (III) as defined above;
  • Coated particles as defined herein may be used for preparing a cathode for a lithium-ion electrochemical cell.
  • said lithium-ion electrochemical cell is an all solid state cell.
  • Coated particles as defined herein may be used in a cathode for a lithium-ion electrochemical cell.
  • said lithium-ion electrochemical cell is an all solid state cell.
  • Preferred coated particulate materials according to the third aspect as defined herein are those having one or more of the specific and preferred features disclosed herein.
  • a process for preparing a coated particulate material according to the above-defined third aspect comprises the steps
  • step (iv) removing the solvents of the liquid reaction mixture, so that a solid residue is obtained, and heat-treating the solid residue in a temperature range of from 100 °C to 300 °C for a total duration of 1 to 12 hours, preferably 4 hours to 12 hours so that a coated particulate material according to the above-defined third aspect results.
  • Preparation of a liquid reaction mixture (step (i)) is disclosed above in the context of the first aspect.
  • preferred and specific precursors for the preparation of a liquid reaction mixture reference is made to the disclosure provided above in the context ofthe first aspect.
  • core particles C1) comprising at least one cathode active material (step (ii)), preferably consisting of at least one cathode active material, are known in the art.
  • Core particles C1) comprising or consisting of at least one cathode active material are commercially available.
  • preferred and specific cathode active materials reference is made to the disclosure provided above in the context of the coated particulate material according to the third aspect.
  • the core particles C1) and the liquid reaction mixture can be contacted with each other by means of any suitable technique, e.g. by mixing and/or spraying.
  • any suitable technique e.g. by mixing and/or spraying.
  • sonicating may be used, preferably at a temperature in the range of from 15 °C to 30 °C and for a time period in the range of from 15 min to 60 min.
  • step (iv) removal of the solvents of the liquid reaction mixture (as prepared in step (i)) is preferably achieved by subjecting the solution to a reduced pressure (relative to standard pressure 101 .325 kPa) at a temperature in the range of from 0°C to 100 °C, preferably of from 20 °C to 40 °C.
  • a reduced pressure relative to standard pressure 101 .325 kPa
  • heat treating the solid residue may comprise calcining the solid residue.
  • Heat treatment in step (iv) may be carried out in the presence of carbon dioxide, oxygen, air, nitrogen, N2O or argon.
  • step (iv) the solid residue may be ground prior to the heat treatment.
  • step (iv) after removal ofthe solvents, heat treatment is performed for a duration of 1 to 12 hours, preferably 4 to 12 hours, more preferably 4 to 8 hours, at a temperature in the range of from 100 °C up to 300 °C, preferably 105 °C to 300 °C, further preferably in the range of from 100 °C to 250 °C or 105 °C to 250 °C, most preferably in the range of from 100 °C to 200 °C or 105 °C to 200 °C.
  • the process according to the fourth aspect as described herein may be considered as a combination of solution-based synthesis (as described above in the context ofthe first aspect ofthe present disclosure) of a solid material having a composition according to general formula (I) and coating core particles C1) comprising a cathode active material with a coating C2) comprising said solid material having a composition according to general formula (I) obtained by solution-based synthesis.
  • the solution-based synthesis (as de- scribed above in the context ofthe first aspect ofthe present disclosure) of a solid material having a composition according to general formula (I) is carried out in the presence of core particles C1) comprising a cathode active material in the liquid reaction mixture.
  • solution-based synthesis (as described above in the context of the first aspect of the present disclosure) of a solid material having a composition according to general formula (I) enables direct formation of such solid material as part of a coating C2) on core particles C1) comprising a cathode active material.
  • a cathode for use in a lithium-ion electrochemical cell comprising a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above; a solid electrolyte material comprising lithium ions which is not part of the coated particulate material, wherein said solid electrolyte material may be a solid material having a composition according to general formula (I); optionally an electron conducting material comprising or consisting of elemental car- bon; optionally a binding agent.
  • a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above and a solid electrolyte material may be admixed with each other.
  • coated particulate materials provided above in the context of the third and fourth aspect applies mutatis mutandis to the cathode according to the fifth aspect.
  • preferred and specific coated particulate materials reference is made to the disclosure provided above in the context of the coated particulate material according to the third aspect.
  • the coating C2) serves the purpose of facilitating the transfer of lithium ions between the cathode active material (which is present in the cores C1) of the coated particulate material) and the solid electrolyte.
  • the cathode active material has a redox potential of 4 V or more vs. Li/Li + (cathode active material of the “4 V class”), while the solid electrolyte does not have electrochemical oxidation stability up to 4 V vs Li/Li +
  • the coating C2) serves as a protection layer protecting the solid electrolyte from being oxidized by the cathode material.
  • the solid electrolyte material admixed to the coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above may be a solid material having a composition according to general formula (I), preferably a solid material having a composition according to general formula (I) which is also present in the coating C2) of the coated particulate material of the cathode.
  • a solid material having a composition according to general formula (I) as the solid electrolyte in the cathode according to the fifth aspect described herein reduces the diversity of materials present in the cathode, resulting in reduced complexity of the cathode and omission of undesirable interactions between the different materials present in the cathode. Moreover, presence of the same solid material having a composition according to general formula (I) in the coating C2) of the coated particulate and in the solid electrolyte creates favorable conditions for the transfer of lithium ions between the cathode active material (which is present in the cores C1) of the coated particulate material) and the solid electrolyte.
  • a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above and a solid electrolyte material may be admixed with each other and with one or more binding agents and/or with one or more electron-conducting materials.
  • Typical electron-conducting materials are those comprising or consisting of elemental carbon, e.g. carbon black and graphite.
  • Typical binding agents are poly(vinylidenefluroride) (PVDF), styrene-butadiene rubber (SBR), polyisobutene, polyethylene vinyl acetate), polyacrylonitrile butadiene).
  • a cathode according to the fifth aspect as defined herein may comprise a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above preferably in a total amount of from 50 % to 99 %, more preferably of from 70 % to 97 %, relative to the total mass of the cathode.
  • a cathode according to the fifth aspect as defined herein may comprise a solid electrolyte in total amount of from 1 % to 50 %, more preferably of from 3 % to 30 %, relative to the total mass of the cathode.
  • a cathode according to the fifth aspect as defined herein may comprise electron conducting material comprising or consisting of elemental carbon in total amount from 1 % to 5%, more preferably from 1 % to 2 %, relative to the total mass of the cathode.
  • a cathode according to the fifth aspect as defined herein may comprise binding agents in a total amount of from 0.1 % to 3 %, relative to the total mass of the cathode.
  • Preferred cathodes according to the fifth aspect as defined herein are those having one or more of the specific and preferred features disclosed herein.
  • an electrochemical cell comprising a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above.
  • the coated particulate material is present in a cathode according to the fifth aspect as disclosed above.
  • the above-defined electrochemical cell may be a rechargeable electrochemical cell comprising the following constituents a) at least one anode, b) at least one cathode, y) at least one separator. Suitable separator materials, electrochemically active cathode materials (cathode active materials) and suitable electrochemically active anode materials (anode active materials) are known in the art.
  • the anode a) may comprise graphitic carbon, metallic lithium or a metal alloy comprising lithium as the anode active material.
  • Electrochemical cells as described herein may be alkali metal containing cells, especially lithium-ion containing cells. In lithium-ion containing cells, the charge transport is effected by Li + ions.
  • the electrochemical cell may be an all solid state electrochemical cell.
  • the electrochemical cell may have a disc-like or a prismatic shape.
  • the electrochemical cell can include a housing that can be made of steel or aluminum.
  • a plurality of electrochemical cells as described above may be combined to an all-solid- state battery, which has both solid electrodes and solid electrolytes.
  • a further aspect of the present disclosure refers to batteries, more specifically to an alkali metal ion battery, in particular to a lithium ion battery comprising at least one electrochemical cell as described above, for example two or more electrochemical cells as described above.
  • Electrochemical cells as described above can be combined with one another in alkali metal ion batteries, for example in series connection or in parallel connection. Series connection is preferred. The electrochemical cells resp.
  • batteries described herein can be used for making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and stationary applications such as energy storage devices for power plants.
  • a further aspect of the present invention is a method of making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment, remote car locks, and stationary applications such as energy storage devices for power plants by employing at least one inventive battery or at least one inventive electrochemical cell.
  • a further aspect ofthe present disclosure is the use ofthe electrochemical cell as described above in motor vehicles, bicycles operated by electric motor, robots, aircraft (for example unmanned aerial vehicles including drones), ships or stationary energy stores.
  • the present disclosure further provides a device comprising at least one inventive electrochemical cell as described above.
  • mobile devices such as are vehicles, for example automobiles, bicycles, aircraft, or water vehicles such as boats or ships.
  • Other examples of mobile devices are those which are portable, for example computers, especially laptops, telephones or electrical power tools, for example from the construction sector, especially drills, battery-driven screwdrivers or battery-driven tackers.

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Abstract

Described are a process for preparing solid materials which have ionic conductivity for lithium ions and materials obtainable by said process, a coated particulate material for use in a cathode of a lithium-ion electrochemical cell and a process for preparing it, a cathode for use in a lithium-ion electrochemical cell comprising said coated particulate material, an electrochemical cell comprising said coated particulate material, and a use of said coated particulate material for preparing a cathode for use in a lithium-ion electrochemical cell.

Description

Solution-based synthesis of lithium transition metal halides
Described are a process for preparing solid materials which have ionic conductivity for lithium ions and materials obtainable by said process, a coated particulate material for use in a cathode of a lithium-ion electrochemical cell and a process for preparing it, a cathode for use in a lithium-ion electrochemical cell comprising said coated particulate material, an electrochemical cell comprising said coated particulate material, and a use of said coated particulate material for preparing a cathode for use in a lithium-ion electrochemical cell.
Due to the wide-spread use of all-solid-state lithium batteries, there is an increasing demand for solid state electrolytes having a high conductivity for lithium ions. An important class of such solid electrolytes are lithium transition metal halides. US 2019/0088995 A1 discloses a solid electrolyte material represented by the compositional formula:
Lie-szYzXe where 0 < z < 2 is satisfied; and X represents Cl or Br. According to US 2019/0088995 A1 , these solid electrolyte materials exhibit ionic conductivity in the range of from 0.2*10-4 S/cm to 7.1*1 O 4 S/cm at around room temperature. WO 2019/135343 A1 discloses a solid electrolyte material comprising: Li; Y; at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, La, Sm, Bi, Zr, Hf, Nb and Ta; and at least one element selected from the group consisting of Cl, Br, and I, wherein the X-ray diffraction pattern for the solid electrolyte material obtained using Cu-Ka radiation as the X-ray source includes a plurality of peaks in the diffraction angle (2Q) range of 25° to 35° and at least one peak in the diffraction angle (2Q) range of 43° to 51 °.
WO 2019/135345 A1 discloses a solid electrolyte material comprising: Li; Y; at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Zr, Nb and Ta; and at least one element selected from the group consisting of Cl, Br, and I. An X-ray diffraction pattern for the solid electrolyte material obtained using Cu-Ka radiation as the X-ray source includes a peak in the diffraction angle (2Q) range of 30° to 33°, in the diffraction angle (2Q) range of 39° to 43°, and in the diffraction angle (2Q) range of 47° to 51 °.
There is an ongoing need for solid lithium ion conductors which exhibit suitable ionic conductivity for application as solid electrolytes in lithium batteries, especially in all-solid state lithium batteries, as well as electrochemical oxidative stability up to 4 V vs. Li/Li+ or more, preferably up to 4.5 V vs. Li/Li+, in order to enable application of cathode active materials having a redox potential of 4 V or more vs. Li/Li+ (cathode active material ofthe “4 V class”), so that a high cell voltage is obtainable.
Lithium transition metal halides as described in US 2019/0088995 A1 , WO 2019/135343 A1 and WO 2019/135345 A1 are obtained by means of mechano- chemical milling processes, e.g. ball milling, or by means of solid state thermochemical methods. Accordingly, there is a need for a more efficient, facile and scalable synthesis of lithium transition metal halides without compromising the ionic conductivity and other important properties like oxidative stability. It is an objective of the present invention to provide an efficient process for synthesizing solid materials from the group consisting of lithium transition metal halides and lithium transition metal pseudohalides having favorable ionic conductivity, as well as oxidative stability. Surprisingly it has been found that solid materials having the desired characteristics are obtainable by means of a solution-based synthesis followed by drying and heat treatment of the obtained product. In addition, it has been found that although the composition of the lithium transition metal halides obtainable by means of said solution-based synthesis may be slightly different from those obtainable by the conventional mechanochemical resp. thermochemical processes, they exhibit suitable lithium ion conductivity and electrochemical oxidative stability up to 4 V vs. Li/Li+.
It is an objective of the present disclosure to provide solid materials from the group consist- ing of lithium transition metal halides and lithium transition metal pseudohalides which are obtainable by a solution-based synthesis and may be used as a solid electrolyte for an electrochemical cell. More specifically, it is an object of the present disclosure to provide solid materials from the group consisting of lithium transition metal halides and lithium transition metal pseudohalides which may be used as solid electrolyte for an electrochemical cell, wherein the cathode of said electrochemical cell comprises a cathode active material having a redox potential of 4 V or more vs. Li/Li+.
In addition, there is provided a coated particulate material for use in a cathode of a lithium- ion electrochemical cell and a process for preparing it, a cathode for use in a lithium-ion electrochemical cell comprising said coated particulate material, an electrochemical cell comprising said coated particulate material and a use of said coated particulate material for preparing a cathode for use in a lithium-ion electrochemical cell
According to a first aspect, there is provided a process for preparing a solid material having a composition according to general formula (I)
Ll3-n*xMl-xM xXy-3a-2bNaOb (I) wherein
M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
M’ is one or more selected from the group consisting of Ti, Zr, Hf, Nb and Ta;
X is one or more selected from the group consisting of halides and pseudohalides;
0.05 < x < 0.95; 5.8 < y < 6.2; n is the difference between the valences of M’ and M;
0 < a < 0.8;
0 < b < 0.8. Said process comprises the process steps of
(a) preparing a liquid reaction mixture by dissolving the precursors
(1) one or more compounds selected from the group consisting of halides and pseudohalides of lithium;
(2) one or more compounds selected from the group consisting of halides and pseudohalides of elements M selected from the group consisting of Sc, In, Lu, Er, Y and Ho;
(3) one or more compounds selected from the group consisting of halides and pseudohalides of elements M’ selected from the group consisting of Ti, Zr, Hf, Nb and Ta; wherein the molar ratio of Li, M, M’, halides and pseudohalides matches general formula (I); in at least one solvent selected from the group consisting of ethers, H2O, alcohols CnH2n+iOH (1 < n < 20), formic acid, acetic acid, tetrahydrofuran, dimethylformamide, N-methylformamide, pyridine, nitriles, dimethyl sulfoxide, acetone, ethyl acetate, dimethoxyethane, 1 ,3-dioxolane, N-methylpyrrolidinone, and alkylene carbonates;
(b) removing the solvents from the liquid reaction mixture so that a solid residue is obtained, and heat-treating the solid residue in a temperature range of from 100 °C to 300 °C for a total duration of 1 to 12 hours, preferably 4 hours to 12 hours so that a solid material having a composition according to general formula (I) results.
Since in general formula (I) (as defined above) M is three-valent, n is 1 if M’ is four-valent (as it is the case for Ti, Zr and Hf), and n is 2 if M’ is five-valent (as it is the case for Nb and
V).
The composition according to general formula (I) may be considered as a lithium transition metal halide resp. as a lithium transition metal pseudohalide.
As used herein, the term “pseudohalides” (also referred to as “pseudohalogenides”) denotes monovalent anions, which resemble halide anions with regard to their chemistry, and therefore can replace halide anions in a chemical compound without substantially changing the properties of such compound. The term “pseudohalide ion” is known in the art, of. the lUPAC Goldbook. Examples of pseudohalide anions are N3 , SCN~, CN~, OCN-, BF4 and Bh . In pseudohalide-containing solid materials having a composition according to general formula (I) the pseudohalide anion is preferably selected from the group consisting of BF4 and BhU .
In halide-containing solid materials having a composition according to general formula (I) the halide is preferably selected from the group consisting of Cl, Br and I.
A solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein M is one or both of Y and Er, preferably Y (yttrium).
A solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl.
More specifically, a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein M is one or both of Y and Er, and X is one or more halides selected from the group consisting of Cl, Br and I. Further specifically, a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein M is Y and X is Cl.
A solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein 0.08 < x < 0.85, more preferably 0.18 < x < 0.8, most preferably 0.2 < x < 0.65.
A solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) wherein 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1 .
More specifically, a solid material obtainable by a process according to the first aspect as defined herein may have a composition according to formula (I) 0.08 < x < 0.85, more preferably 0.18 < x < 0.8, most preferably 0.2 < x < 0.65, and 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1 . It is noted that a solid material having a composition according to general formula (I) obtained by the process described herein may contain a certain fraction of nitrogen resp. oxygen originating e.g. from the solvent in which the precursors are dissolved in step (a). For instance, when a solvent containing oxygen atoms was used (e.g. H2O, alcohols CnH2n+iOH wherein 1 < n < 20, formic acid, acetic acid, tetrahydrofuran), a solid material having a composition according to general formula (I) obtained by the process described herein may contain a certain fraction of oxygen as denoted by index “b” of formula (I). For instance, when a solvent containing nitrogen atoms was used (e.g. dimethylformamide, N-methylformamide, pyridine, nitriles, N-methylpyrrolidinone), a solid material having a composition according to general formula (I) obtained by the process described herein may contain a certain fraction of nitrogen as denoted by index “a” of formula (I).
In some cases, a solid material having a composition according to general formula (I) contains neither oxygen nor nitrogen (a = b = 0). In other cases, a solid material having a composition according to general formula (I) contains oxygen and no nitrogen (a = 0, 0 < b < 0.8), in yet other cases nitrogen and no oxygen (b = 0, 0 < a < 0.8), and in still other cases both, oxygen and nitrogen (0 < b < 0.8 and 0 < a < 0.8, a + b > 0.01).
It is understood that formula (I) is an empirical formula (gross formula) determinable by means of elemental analysis. Accordingly, formula (I) defines a composition which is averaged over the solid material as a whole, and does not indicate a specific lattice structure or constitution of the solid material. The same applies to formulae (la) and (lb) (see below) which are derived from general formula (I).
In step (a) of the process described herein, a liquid reaction mixture comprising precursors for the reaction product to be formed in step (b) is provided. Said precursors are
(1) one or more compounds LiX; and (2) one or more compounds MX3, wherein M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho; and
(3) one or more from the group consisting of compounds MXt wherein M’ is one or more of Ti, Zr and Hf, and compounds M’Xs wherein M’ is one or both of Nb and Ta; wherein in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of halides and pseudohalides; wherein the molar ratio of Li, M, M’ and X matches general formula (I).
In certain cases, in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of Cl, Br and I. Preferably in each of precursors (1) to (3) X is the same, preferably Cl. In certain cases, in precursor (2) M is one or both of Y and Er, preferably Y.
In specific cases, in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of Cl, Br and I, and in precursor (2) M is one or both of Y and Er. Further specifically, in each of precursors (1 ) to (3) X is Cl, and in precursor (2) M is Y. In step (a) a liquid reaction mixture is prepared by dissolving the above-mentioned precursors (1), (2) and (3) in a solvent selected from the group consisting of ethers, H2O, alcohols CnH2n+iOH (1 < n < 20), formic acid, acetic acid, tetrahydrofuran, dimethylformamide, N- methylformamide, pyridine, nitriles, dimethyl sulfoxide, acetone, ethyl acetate, dimethoxy- ethane, 1 ,3-dioxolane, N-methylpyrrolidinone, and alkylene carbonates. Mixtures of two or more solvents selected from said group are also possible. Preferred solvents are ethers (especially tetrahydrofuran), alcohols with 1 < n < 6 and pyridine. Nitriles, especially acetonitrile, are less preferred in some cases.
The liquid reaction mixture prepared in step (a) is in the form of a solution of the above- defined precursors (1), (2) and (3) in a solvent selected from the group consisting of ethers, H2O, alcohols CnH2n+iOH (1 < n < 20), formic acid, acetic acid, tetrahydrofuran, dimethylformamide, N-methylformamide, pyridine, nitriles, dimethyl sulfoxide, acetone, ethyl acetate, dimethoxyethane, 1 ,3-dioxolane, N-methylpyrrolidinone, and alkylene carbonates. Mixtures of two or more solvents selected from said group are also possible. Preferred solvents are ethers (especially tetrahydrofuran), alcohols with 1 < n < 6 and pyridine. Ni- triles, especially acetonitrile, are less preferred in some cases.
The total content of precursors (1), (2) and (3) in the liquid reaction mixture prepared in step (a) is in the range from 1 % to 80 %, and preferably in the range from 3 % to 30 %, based on the total weight ofthe liquid reaction mixture (sum of the weights of all precursors and solvents). Different from the prior art, the process according to the first aspect of the present disclosure does not involve mechanochemical milling (i.e. reactive-milling) of the precursors (1), (2) and (3) resp. of a mixture thereof.
It is presently assumed that solution-based synthesis according to the process described herein provides an intimate mix of the precursors, potentially reducing the temperature and/or duration of the subsequent heat treatment in step (b), compared to the heat treatment to be applied in purely thermochemical synthesis of corresponding materials.
In step (a) preferably any handling is performed under a protective gas atmosphere.
The precursors (1), (2) and (3) and their molar ratio are selected according to the target stoichiometry.
In certain processes according to the first aspect described herein the precursor (3) is one or more from the group consisting of compounds MXt wherein M’ is one or more of Ti, Zr and Hf, and X is as defined above. Such processes are suitable for preparing solid materials having a composition according to general formula (la) L -xMl-xM xXy-3a-2bNaOb (la) wherein
M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
M’ is one or more selected from the group consisting of Ti, Zr, and Hf;
X is one or more selected from the group consisting of halides and pseudohalides; 0.05 < x< 0.95, preferably 0.08 < x < 0.85, more preferably 0.18 < x< 0.8, most preferably
0.2 < x< 0.65;
5.8 < y < 6.2; preferably 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1 ;
0 < a < 0.8; 0 < b < 0.8. Thus, suitable precursors for a solid material having a composition according to general formula (la) are
(1) one or more compounds LiX; and
(2) one or more compounds MX3, wherein M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho; and
(3) one or more compounds from the group consisting of compounds MXt wherein M’ is one or more of Ti, Zr and Hf, preferably Zr; wherein in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of halides and pseudohalides; wherein the molar ratio of Li, M, M’ and X matches general formula (la).
In certain cases, in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of Cl, Br and I. Preferably in each of precursors (1) to (3) X is the same, preferably Cl.
In certain cases, in precursor (2) M is one or both of Y and Er, preferably Y.
In specific cases, in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of Cl, Br and I, and in precursor (2) M is one or both of Y and Er. Further specifically, in each of precursors (1 ) to (3) X is Cl, and in precursor (2) M is Y.
In certain cases, in precursor (3) M’ is Zr.
In specific cases, in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of Cl, Br and I, in precursor (2) M is one or both of Y and Er, and in precursor (3) M’ is Zr. Further specifically, in each of precursors (1) to (3), X is Cl, in precursor (2) M is Y and in precursor (3) M’ is Zr.
In certain processes according to the first aspect described herein, the precursor (3) is one or more from the group consisting of compounds M’Xs wherein M’ is one or both of Nb and Ta, and X is as defined above. Such processes are suitable for preparing solid materials having a composition according to general formula (lb)
Ll3-2xMl-xM xXy-3a-2bNaOb (lb) wherein
M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
M’ is one or both selected from the group consisting of Nb and Ta;
X is one or more selected from the group consisting of halides and pseudohalides;
0.05 < x< 0.95, preferably 0.08 < x< 0.85, more preferably 0.18 < x < 0.8, most preferably 0.2 < x < 0.65;
5.8 < y < 6.2, preferably 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1 ;
0 < a < 0.8;
0 < b < 0.8.
Thus, suitable precursors for a solid material having a composition according to general formula (lb) are
(1) one or more compounds LiX; and
(2) one or more compounds MX3, wherein M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho; and
(3) one or more compounds from the group consisting of compounds M’Xs wherein M’ is one or both of Nb and Ta; wherein in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of halides and pseudohalides; wherein the molar ratio of Li, M, M’ and X matches general formula (lb).
In certain cases, in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of Cl, Br and I. Preferably in each of precursors (1) to (3) X is the same, preferably Cl.
In certain cases, in precursor (2) M is one or both of Y and Er, preferably Y.
In specific cases, in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of Cl, Br and I, and in precursor (2) M is one or both of Y and Er. Further specifically, in each of precursors (1 ) to (3) X is Cl, and in precursor (2) M is Y. In step (b), the liquid reaction mixture is transferred into a solid material according to general formula (I) by removing the solvents so that a solid residue is obtained, and subsequent heat treatment (sintering) of the solid residue.
In step (b) removal of the solvents is preferably achieved by subjecting the solution to a reduced pressure (relative to standard pressure 101.325 kPa) at a temperature in the range from 0 °C to 100 °C, preferably from 20 °C to 40 °C under dynamic vacuum (continuous removal of the vapor of the solvent from the reaction vessel).
In step (b), after removal of the solvents, heat treatment of the obtained residue is preferably performed in a closed vessel for a duration of 1 to 12 hours, preferably 4 to 12 hours, more preferably 4 to 8 hours, at a temperature in the range of from 100 °C up to 300 °C, preferably 105 °C to 300 °C, further preferably in the range of from 100 °C to 250 °C or 105 °C to 250 °C, most preferably in the range of from 100 °C to 200 °C or 105 °C to 200 °C.
The heat treatment in step (b) is carried out either under vacuum or under a protective gas atmosphere. If necessary, the solid material obtained by the process according to the invention as described above is ground into a powder.
Preferred processes according to the first aspect as defined herein are those having one or more of the specific and preferred features disclosed herein.
According to a further aspect of this disclosure, there is provided a solid material obtainable by the process according to the above-defined first aspect.
More specifically, according to a second aspect of this disclosure, there is provided a solid material having a composition according to general formula (II)
Ll3-n*xMl-xM xXy-3a-2bNaOb (I I) wherein M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
M’ is one or more selected from the group consisting of Ti, Zr, Hf, Nb and Ta;
X is one or more selected from the group consisting of halides and pseudohalides; 0.05 < x< 0.95;
5.8 < y < 6.2; n is the difference between the valences of M’ and M;
0 < a < 0.8; 0 < b < 0.8; a + b > 0.01.
It is understood that formula (II) is an empirical formula (gross formula) determinable by means of elemental analysis. Accordingly, formula (II) defines a composition which is averaged over the solid material as a whole, and does not indicate a specific lattice structure or constitution ofthe solid material. The same applies to formulae (I I a) and (lib) (see below) which are derived from general formula (II).
It is noted that a solid material having a composition according to general formula (II) as defined herein contains one or both of oxygen and nitrogen. Therefore, the solid electrolyte materials prepared according to table 1 of WO 2019/135343 A1 and table 1 of WO 2019/135345 A1 do not fall under formula (II) as defined herein.
In some cases, a solid material having a composition according to general formula (II) contains oxygen and no nitrogen (a = 0, 0.01 < b < 0.8), in other cases nitrogen and no oxygen (b = 0, 0.01 < a < 0.8), and in still other cases both, oxygen and nitrogen (0 < b < 0.8 and 0 < a < 0.8, a + b > 0.01). A solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein M is one or both of Y and Er, preferably Y.
A solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl. More specifically, a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein M is one or both of Y and Er, and X is one or more halides selected from the group consisting of Cl, Br and I. Further specifically, a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein M is Y and X is Cl.
A solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein 0.08 < x < 0.85, more preferably 0.18 < x < 0.8, most preferably 0.2 < x < 0.65.
A solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1 . More specifically, a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein 0.08 < x < 0.85, more preferably 0.18 < x < 0.8, most preferably 0.2 < x < 0.65; and 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1 .
Further specifically, a solid material according to the second aspect as defined herein may have a composition according to formula (II) wherein
M is one or both of Y and Er; and
X is one or more halides selected from the group consisting of Cl, Br and I; and
0.08 < x < 0.85, more preferably 0.18 < x< 0.8, most preferably 0.2 < x < 0.65; and
5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1 a and b are as defined above.
In certain cases, a solid material according to the second aspect as defined herein may be crystalline as detectable by the X-ray diffraction technique. A solid material is referred to as crystalline when it exhibits a long range order that is characteristic of a crystal, as indi- cated by the presence of clearly defined reflections in its X-ray diffraction pattern. In this context, a reflection is considered as clearly defined if its intensity is more than 10% above the background. A crystalline solid material according to the second aspect as defined herein may be accompanied by secondary phases and/or impurity phases having a composition not according to general formula (II) as defined above. In such case, the volume fraction of the phase formed of the crystalline solid material having a composition according to general formula (II) may be 60 % or more, sometimes 80 % or more, preferably 90 % or more, most preferably 95 % or more, based on the total volume of the solid material according to the second aspect as defined herein and all secondary phases and impurity phases.
If present, the secondary phases and impurity phases mainly consist ofthe precursors used for preparing the solid material, e.g. LiX (wherein X is as defined above), and sometimes impurity phases which may originate from impurities of the precursors. For details of preparing a solid material according to the second aspect of this disclosure, see the information provided in the context ofthe first aspect of this disclosure.
In certain cases, a solid material according to the second aspect as defined herein is in the form of a polycrystalline powder, or in the form of single crystals. In certain cases, a solid material according to the second aspect as defined herein is glassy, i.e. amorphous. A solid material is referred to as amorphous when it lacks the long range order that is characteristic of a crystal, as indicated by the absence of clearly defined reflections in its X-ray diffraction pattern. In this context, a reflection is considered as clearly defined if its intensity is more than 10% above the background. In certain cases, a solid material according to the second aspect as described herein is glass-ceramics, i.e. a polycrystalline solid having at least 30 % by volume of a glassy phase.
A solid material according to the second aspect as described herein may have an ionic conductivity of 0.1 mS/cm or more, preferably 1 mS/cm or more, in each case at a temperature of 25 °C. The ionic conductivity is determined in the usual manner known in the field of solid state battery materials development by means of electrochemical impedance spec- troscopy-
At the same time, a solid material according to the second aspect as described herein may have an almost negligible electronic conductivity. More specifically, the electronic conductivity may be at least 3 orders of magnitude lower than the ionic conductivity, preferably at least 5 orders of magnitude lower than the ionic conductivity. In certain cases, a solid material according to the second aspect as described herein exhibits an electronic conductivity of 1010 S/cm or less. The electronic conductivity is determined in the usual manner known in the field of battery materials development by means of direct-current (DC) polarization measurements at different voltages.
A solid material according to the second aspect as described herein resp. obtained by the process according to the above-defined first aspect can be used as a solid electrolyte for an electrochemical cell. Herein the solid electrolyte may form a component of a solid structure for an electrochemical cell, wherein said solid structure is selected from the group consisting of cathode, anode and separator. Accordingly, a solid material according to the second aspect as defined herein resp. obtained by the process according to the above- defined first aspect can be used alone or in combination with additional components for producing a solid structure for an electrochemical cell, such as a cathode, an anode or a separator. Thus, the present disclosure further provides the use of a solid material according to the second aspect as defined herein resp. obtained by the process according to the above- defined first aspect as a solid electrolyte for an electrochemical cell. More specifically, the present disclosure further provides the use of a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect as a component of a solid structure for an electrochemical cell, wherein said solid structure is selected from the group consisting of cathode, anode and separator.
In the context of the present disclosure, the electrode of an electrochemical cell where during discharging a net negative charge occurs is called the anode and the electrode of an electrochemical cell where during discharging a net positive charge occurs is called the cathode. The separator electronically separates a cathode and an anode from each other in an electrochemical cell. The cathode of an all-solid-state electrochemical cell usually comprises a solid electrolyte as a further component beside a cathode active material. Also the anode of an all-solid-state electrochemical cell usually comprises a solid electrolyte as a further component beside an anode active material. Said solid electrolyte may be a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect. The form of the solid structure for an electrochemical cell, in particular for an all-solid-state lithium battery, depends in particular on the form ofthe produced electrochemical cell itself.
The present disclosure further provides a solid structure for an electrochemical cell, wherein the solid structure is selected from the group consisting of cathode, anode and separator, wherein the solid structure comprises a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect.
The present disclosure further provides an electrochemical cell comprising a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect.
In said electrochemical cell, the solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect may form a component of one or more solid structures selected from the group consisting of cathode, anode and separator. More specifically, there is provided an electrochemical cell as described above wherein in certain preferred cases a solid material according to the second aspect as defined herein resp. obtained by the process according to the above-defined first aspect may be in direct contact with a cathode active material having a redox potential of 4 V or more, preferably of 4.5 V or more vs. Li/Li+.
A first group of solid materials according to the second aspect as defined herein has a composition according to formula (II) wherein M and X are as defined above; and M’ is one or more of Ti, Zrand Hf. Since in a solid material of said first group M’ is a four- valent metal, n is 1 . Thus, a solid material of said first group has a composition according to formula (I la)
L -xMl-xM xXy-3a-2bNaOb (113) wherein M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
M’ is one or more selected from the group consisting of Ti, Zr, and Hf;
X is one or more selected from the group consisting of halides and pseudohalides;
0.05 < x < 0.95;
5.8 < y < 6.2; 0 < a < 0.8;
0 < b < 0.8; a + b > 0.01.
A solid material of the first group described herein may have a composition according to formula (I la) wherein M is one or both of Y and Er, preferably Y.
A solid material of the first group described herein may have a composition according to formula (I I a) wherein X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl.
More specifically, a solid material of the first group described herein may have a composi- tion according to formula (I la) wherein M is one or both of Y and Er, and X is one or more halides selected from the group consisting of Cl, Br and I. Further specifically, a solid material of the first group described herein may have a composition according to formula (I la) wherein M is Y and X is Cl.
A solid material of the first group described herein may have a composition according to formula (I la) wherein M’ is Zr. More specifically, a solid material of the first group described herein may have a composition according to formula (I la) wherein M is one or both of Y and Er, M’ is Zr and X is one or more halides selected from the group consisting of Cl, Br and I.
A solid material of the first group described herein may have a composition according to formula (I la) wherein 0.08 < x < 0.85, more preferably 0.18 < x < 0.8, most preferably 0.2 < x< 0.65.
A solid material of the first group described herein may have a composition according to formula (I I a) wherein 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1. More specifically, a solid material of the of the first group described herein may have a composition according to formula (I I a) wherein 0.08 < x < 0.85, more preferably 0.18 < x< 0.8, most preferably 0.2 < x < 0.65; and 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1. Specific solid materials of the first group described herein may have a composition according to formula (I I a) wherein M is one or both of Y and Er, and M’ is Zr, and X is Cl.
In certain cases, M is Y, M’ is Zr, and X is Cl.
In certain other cases, M is Er, M’ is Zr, and X is Cl. A second group of solid materials according to the second aspect as defined herein has a composition according to formula (II) wherein M and X are as defined above; and M’ is one or both of Nb and Ta. Since in a solid material of said second group M’ is a five-valent metal, n is 2. Thus, a solid material of said second group has a composition according to formula (lib) Ll3-2xM 1 -xM ’xXy-3a-2bNaOb (lib) wherein
M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
M’ is one or both selected from the group consisting of Nb and Ta;
X is one or more selected from the group consisting of halides and pseudohalides; 0.05 < x< 0.95;
5.8 < y < 6.2;
0 < a < 0.8;
0 < b < 0.8; a + b > 0.01. A solid material of the second group described herein may have a composition according to formula (lib) wherein M is one or both of Y and Er, preferably Y.
A solid material of the second group described herein may have a composition according to formula (lib) wherein X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl. More specifically, a solid material of the second group described herein may have a composition according to formula (lib) wherein M is one or both of Y and Er, X is one or more halides selected from the group consisting of Cl, Br and I. Further specifically, a solid material of the second group described herein may have a composition according to formula (lib) wherein M is Y and X is Cl.
A solid material of the second group described herein may have a composition according to formula (lib) wherein 0.08 < x < 0.85, more preferably 0.18 < x < 0.8, most preferably 0.2 < x< 0.65.
A solid material of the second group described herein may have a composition according to formula (lib) wherein 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1. More specifically, a solid material of the second group described herein may have a composition according to formula (lib) wherein 0.08 < x < 0.85, more preferably 0.18 < x < 0.8, most preferably 0.2 < x< 0.65; and 5.85 < y < 6.15, more preferably 5.9 < y < 6.1 resp. 5.95 < y < 6.15, most preferably 5.95 < y < 6.1.
Specific solid materials of the second group described herein may have a composition ac- cording to formula (lib) wherein M is one or both of Y and Er, and M’ is one or both of Nb and Ta, and X is Cl.
In certain cases, M is Y, M’ is Nb orTa, and X is Cl.
In certain other cases, M is Er, M’ is Nb or Ta, and X is Cl.
Preferred solid materials according to the second aspect as defined herein are those having one or more of the specific and preferred features disclosed herein.
According to a third aspect of the present disclosure, there is provided a coated particulate material for use in a cathode of a lithium-ion electrochemical cell. Said coated particulate material comprises
C1) a plurality of core particles, each core particle comprising at least one cathode active material; and
C2) disposed on the surfaces of the core particles, a coating comprising carbonate anions, and at least one solid material having a composition according to general formula (I) as defined above.
In the context of the present disclosure, the electrode of an electrochemical cell where during discharging of the cell a net positive charge occurs is called the cathode, and the component of the cathode by reduction of which said net positive charge is generated is referred to as a “cathode active material”.
Preferably, each core particle consists of at least one cathode active material.
Preferred cathode active materials are those having a redox potential of 4 V or more vs. Li/Li+ (cathode active material ofthe “4 V class”), which enable obtaining a high cell voltage. Many such cathode active materials are known in the art.
Suitable cathode active materials are oxides comprising lithium, and one or more members ofthe group consisting of nickel, cobalt and manganese.
Certain suitable cathode active materials are oxides comprising - lithium, nickel and one or both members of the group consisting of cobalt and manganese.
Exemplary suitable cathode active materials have a composition according to general formula (III): Lii+tAi-t02 (III), wherein
A comprises nickel and one or both members ofthe group consisting of cobalt and manganese, and optionally one or more further transition metals not selected from the group consisting of nickel, cobalt and manganese, wherein said further transition metals are preferably selected from the group consisting of molybdenum, titanium, tungsten, zirconium, - one or more elements selected from the group consisting of aluminum, barium, boron and magnesium, wherein at least 50 mole-% of the transition metal of A is nickel; and t is a number in the range of from -0.05 to 0.2.
Suitable cathode active materials having a composition according to formula (III) are de- scribed in a non-prepublished European patent application 19180075.4 - 1108.
The cathode active material having a composition according to general formula (III) may have a layered structure or a spinel structure. Cathode active materials having a composition according to general formula (III) which have a layered structure as described in non- prepublished European patent application 19180075.4 - 1108 are preferred. Preferred cathode active materials have a composition according to general formula (Ilia)
Lii+z[Nii-u-v-wC0uMn Mw]i-zO2 (Ilia), wherein
M is a member of the group consisting of aluminum, barium, boron, magnesium, molybdenum, titanium, tungsten, zirconium, and mixtures of at least two of the forego- ing elements, preferably is or comprises aluminum (preferably when v is 0), z is a number in the range of from -0.05 to 0.2, u is a number in the range of from 0.04 to 0.2, v is a number in the range of from 0 to 0.2, preferably of from 0.04 to 0.2, w is a number in the range of from 0 to 0.1 and (u + v + w) is < 0.4 and preferably is < 0.3.
In formula (Ilia), the variable “M” can stand for any individual member of the group of elements as defined above (e.g. “M” can stand for tungsten, i.e. “W”) or it can stand for two or more members of the group of elements as defined above (e.g. the “M” can stand for a group consisting of tungsten, zirconium and titanium). Where “M” stands for two or more members ofthe group of elements as defined above, the index (number) “w” accompanying the variable “M” applies to the total of elements represented by “M”, as defined above.
Exemplary cathode active materials of formula (III) are Lii+t[Nio85Coo ioMnoo5]i-tC>2, Lii+t[Nio87Cooo5Mnoo8]i-t02, Lii+t[Nio83Cooi2Mnoo5]i -t02, Lii+t[NioeCoo2Mno2]i-t02, Lil+t[Nio88COo08Alo04]l-t02, Lil+t[Nio905COo0475Alo0475]l-t02, and Lil+t[Nio9lCOo045Alo045]l-t02, wherein in each case -0.05 < t < 0.2.
Other exemplary cathode active materials are UC0O2 and LiNio5Mn15O4.
In the coated particulate material according to the third aspect described herein, the coating C2) is disposed on the surfaces of at least a part of the core particles C1), preferably it is disposed on the surfaces of > 50 % of the total number of core particles C1), more preferably on the surfaces of > 75 % ofthe total number of core particles C1), even more preferably on the surfaces of > 90 % of the total number of core particles C1) and yet even more preferably on the surfaces of > 95 % ofthe total number of core particles C1) present in the coated particulate material. Forthe purposes of the present disclosure, the part of the core particles C1) on whose surfaces the coating C2) is disposed can be determined by electron microscopy performed on a (representative) sample ofthe coated particulate material.
In the coated particulate material according to the third aspect described herein, the coating C2) is disposed on at least a part ofthe surface of a (an individual) core particle 01), pref- erably it is disposed on > 50 % of the total surface of a core particle 01), more preferably on > 75 % of the total surface of a core particle 01) and even more preferably on > 90 % of the total surface of a core particle 01). For the purposes of the present disclosure, the part of the surface of a core particle 01) on which the coating 02) is disposed can be determined by electron microscopy performed on a (representative) sample of an (individ- ual) coated particle of the coated particulate material or a (representative) sample of the coated particulate material.
In the coated particulate material according to the third aspect described herein, the lithium present in the coating 02) is preferably present as part of solid materials having a composition according to general formula (I) as described above and of lithium carbonate (L12CO3). Preferably, the total amount of lithium present in the coating 02) is present as part of solid materials having a composition according to general formula (I) as described above and of lithium carbonate (U2CO3).
In the coated particulate material according to the third aspect described herein, the coating C2) may comprise carbonate anions in a total amount of > 0.12 %, or of > 0.15 %, in each case relative to the total mass of the plurality of (uncoated) core particles C1). More specifically, the coating C2) may comprise carbonate anions in a total amount in the range of from 0.12 % to 3.0 %, preferably of from 0.15 % to 2.5 %, more preferably of from 0.15 % to 2.0 %, even more preferably of from 0.15 % to 1 .0 %, relative to the total mass of the plurality of (uncoated) core particles C1). If the content of lithium carbonate in the coating C2) is too high, the lithium ion conductivity may be decreased.
Without wishing to be bound by any theory, it is presently assumed that the carbonate present on the surface of the core particles C1) originates from unavoidable impurities of the cathode active material which may be formed when the cathode active material is prepared or stored in the presence of traces of carbon dioxide and humidity, and/or in certain cases from using lithium carbonate as a precursor for the synthesis of the cathode active material, and/or from the decomposition ofthe organic solvent of the liquid reaction mixture used in preparing the coated particulate material (for details see below) in air resp. oxygen and reactivity with residual lithium on the particle surface of the cathode active material.
In the coated particulate material according to the third aspect described herein, at least a part of the carbonate ions present in the coating C2) may be present as part of an ionic compound, e.g. as part of a salt. Herein, at least a part of the carbonate ions present in the coating C2), preferably the total amount of carbonate ions present in the coating C2), is present as lithium carbonate.
For the purposes of the present disclosure, the amount of carbonate ions present in the coating C2) may be determined by acid titration, coupled with mass spectroscopy, more preferably according to the method as defined in the examples section of non-prepublished European patent application 19180075.4 - 1108, performed on a (representative) sample of the coated particulate material.
The disclosure regarding solid materials having a composition according to general formula (I) resp. (II) provided above in the context ofthe first and the second aspect applies mutatis mutandis to the coated particulate material according to the third aspect. Regarding preferred and specific solid materials having a composition according to general formula (I) resp. (II), reference is made to the disclosure provided above in the context of the first and second aspect. Preferably, in the coating C2) disposed on the surfaces of the core particles, the solid material having a composition according to general formula (I) is amorphous or is a glassy ceramics.
The thickness of the coating C2) may be in the range of from 1 nm to 1 pm, preferably of from 1 nm to 50 nm. In certain cases, a coated particulate material according to the third aspect described herein comprises or consists of
C1) a plurality of core particles, each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition according to general formula (III) as defined above; and
C2) disposed on the surfaces of the core particles, a coating comprising carbonate anions, preferably lithium carbonate; and at least one solid material having a composition according to general formula (la) as defined above. In certain cases, a coated particulate material according to the third aspect described herein comprises or consists of
C1) a plurality of core particles, each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition according to general formula (III) as defined above; and
C2) disposed on the surfaces of the core particles, a coating comprising carbonate anions, preferably lithium carbonate; and at least one solid material having a composition according to general formula (lb) as defined above. In certain cases, a coated particulate material according to the third aspect described herein comprises or consists of
C1) a plurality of core particles, each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition ac- cording to general formula (III) as defined above; and
C2) disposed on the surfaces of the core particles, a coating comprising carbonate anions, preferably lithium carbonate; and at least one solid material having a composition according to general for- mula (II) as defined above.
In certain cases, a coated particulate material according to the third aspect described herein comprises or consists of
C1) a plurality of core particles, each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition according to general formula (III) as defined above; and
C2) disposed on the surfaces of the core particles, a coating comprising carbonate anions preferably, lithium carbonate; and at least one solid material having a composition according to general formula (I I a) as defined above.
In certain cases, a coated particulate material according to the third aspect described herein comprises or consist of
C1) a plurality of core particles, each core particle comprising at least one cathode active material, preferably at least one cathode active material having a composition ac- cording to general formula (III) as defined above; and
C2) disposed on the surfaces of the core particles, a coating comprising carbonate anions, preferably lithium carbonate; and at least one solid material having a composition according to general formula (lib) as defined above.
Coated particles as defined herein may be used for preparing a cathode for a lithium-ion electrochemical cell. Preferably said lithium-ion electrochemical cell is an all solid state cell. Coated particles as defined herein may be used in a cathode for a lithium-ion electrochemical cell. Preferably said lithium-ion electrochemical cell is an all solid state cell.
Preferred coated particulate materials according to the third aspect as defined herein are those having one or more of the specific and preferred features disclosed herein.
According to a fourth aspect, there is provided a process for preparing a coated particulate material according to the above-defined third aspect. Said process comprises the steps
(i) preparing or providing a liquid reaction mixture as disclosed above in the context of the first aspect,
(ii) preparing or providing a plurality of core particles C1), each core particle comprising at least one cathode active material, (iii) contacting the core particles C1) and the liquid reaction mixture with each other,
(iv) removing the solvents of the liquid reaction mixture, so that a solid residue is obtained, and heat-treating the solid residue in a temperature range of from 100 °C to 300 °C for a total duration of 1 to 12 hours, preferably 4 hours to 12 hours so that a coated particulate material according to the above-defined third aspect results. Preparation of a liquid reaction mixture (step (i)) is disclosed above in the context of the first aspect. Regarding preferred and specific precursors for the preparation of a liquid reaction mixture, reference is made to the disclosure provided above in the context ofthe first aspect.
Methods for preparing core particles C1) comprising at least one cathode active material (step (ii)), preferably consisting of at least one cathode active material, are known in the art. Core particles C1) comprising or consisting of at least one cathode active material are commercially available. Regarding preferred and specific cathode active materials, reference is made to the disclosure provided above in the context of the coated particulate material according to the third aspect.
In step (iii) ofthe process according to the fourth aspect described herein, the core particles C1) and the liquid reaction mixture can be contacted with each other by means of any suitable technique, e.g. by mixing and/or spraying. For enhanced or completed contact, e.g. for finalizing the preparation of a mixture or a gel, sonicating may be used, preferably at a temperature in the range of from 15 °C to 30 °C and for a time period in the range of from 15 min to 60 min. In step (iv) removal of the solvents of the liquid reaction mixture (as prepared in step (i)) is preferably achieved by subjecting the solution to a reduced pressure (relative to standard pressure 101 .325 kPa) at a temperature in the range of from 0°C to 100 °C, preferably of from 20 °C to 40 °C.
In step (iv) heat treating the solid residue may comprise calcining the solid residue. Heat treatment in step (iv) may be carried out in the presence of carbon dioxide, oxygen, air, nitrogen, N2O or argon.
In step (iv), the solid residue may be ground prior to the heat treatment.
In step (iv), after removal ofthe solvents, heat treatment is performed for a duration of 1 to 12 hours, preferably 4 to 12 hours, more preferably 4 to 8 hours, at a temperature in the range of from 100 °C up to 300 °C, preferably 105 °C to 300 °C, further preferably in the range of from 100 °C to 250 °C or 105 °C to 250 °C, most preferably in the range of from 100 °C to 200 °C or 105 °C to 200 °C.
It is understood that the process according to the fourth aspect as described herein may be considered as a combination of solution-based synthesis (as described above in the context ofthe first aspect ofthe present disclosure) of a solid material having a composition according to general formula (I) and coating core particles C1) comprising a cathode active material with a coating C2) comprising said solid material having a composition according to general formula (I) obtained by solution-based synthesis. In other words, in the process according to the fourth aspect as described herein the solution-based synthesis (as de- scribed above in the context ofthe first aspect ofthe present disclosure) of a solid material having a composition according to general formula (I) is carried out in the presence of core particles C1) comprising a cathode active material in the liquid reaction mixture. Thus, solution-based synthesis (as described above in the context of the first aspect of the present disclosure) of a solid material having a composition according to general formula (I) enables direct formation of such solid material as part of a coating C2) on core particles C1) comprising a cathode active material.
According to a fifth aspect, there is provided a cathode for use in a lithium-ion electrochemical cell, comprising a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above; a solid electrolyte material comprising lithium ions which is not part of the coated particulate material, wherein said solid electrolyte material may be a solid material having a composition according to general formula (I); optionally an electron conducting material comprising or consisting of elemental car- bon; optionally a binding agent.
In the cathode according to the fifth aspect as defined herein, a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above and a solid electrolyte material may be admixed with each other.
The disclosure regarding coated particulate materials provided above in the context of the third and fourth aspect applies mutatis mutandis to the cathode according to the fifth aspect. Regarding preferred and specific coated particulate materials, reference is made to the disclosure provided above in the context of the coated particulate material according to the third aspect.
In the cathode according to the fifth aspect described herein, the coating C2) serves the purpose of facilitating the transfer of lithium ions between the cathode active material (which is present in the cores C1) of the coated particulate material) and the solid electrolyte. Moreover, in case that the cathode active material has a redox potential of 4 V or more vs. Li/Li+ (cathode active material of the “4 V class”), while the solid electrolyte does not have electrochemical oxidation stability up to 4 V vs Li/Li+, the coating C2) serves as a protection layer protecting the solid electrolyte from being oxidized by the cathode material.
Suitable solid electrolyte materials which are capable of conducting lithium ions are known in the art. In the cathode according to the fifth aspect described herein, the solid electrolyte material admixed to the coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above may be a solid material having a composition according to general formula (I), preferably a solid material having a composition according to general formula (I) which is also present in the coating C2) of the coated particulate material of the cathode. Applying a solid material having a composition according to general formula (I) as the solid electrolyte in the cathode according to the fifth aspect described herein reduces the diversity of materials present in the cathode, resulting in reduced complexity of the cathode and omission of undesirable interactions between the different materials present in the cathode. Moreover, presence of the same solid material having a composition according to general formula (I) in the coating C2) of the coated particulate and in the solid electrolyte creates favorable conditions for the transfer of lithium ions between the cathode active material (which is present in the cores C1) of the coated particulate material) and the solid electrolyte.
More specifically, in a cathode according to the fifth aspect as defined herein, a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above and a solid electrolyte material may be admixed with each other and with one or more binding agents and/or with one or more electron-conducting materials. Typical electron-conducting materials are those comprising or consisting of elemental carbon, e.g. carbon black and graphite. Typical binding agents are poly(vinylidenefluroride) (PVDF), styrene-butadiene rubber (SBR), polyisobutene, polyethylene vinyl acetate), polyacrylonitrile butadiene).
A cathode according to the fifth aspect as defined herein may comprise a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above preferably in a total amount of from 50 % to 99 %, more preferably of from 70 % to 97 %, relative to the total mass of the cathode. A cathode according to the fifth aspect as defined herein may comprise a solid electrolyte in total amount of from 1 % to 50 %, more preferably of from 3 % to 30 %, relative to the total mass of the cathode.
Optionally, a cathode according to the fifth aspect as defined herein may comprise electron conducting material comprising or consisting of elemental carbon in total amount from 1 % to 5%, more preferably from 1 % to 2 %, relative to the total mass of the cathode.
Optionally, a cathode according to the fifth aspect as defined herein may comprise binding agents in a total amount of from 0.1 % to 3 %, relative to the total mass of the cathode.
Preferred cathodes according to the fifth aspect as defined herein are those having one or more of the specific and preferred features disclosed herein.
According to a further aspect, there is provided an electrochemical cell comprising a coated particulate material according to the third aspect as disclosed above or provided by a process according to the fourth aspect as disclosed above. In said cell, preferably the coated particulate material is present in a cathode according to the fifth aspect as disclosed above. The above-defined electrochemical cell may be a rechargeable electrochemical cell comprising the following constituents a) at least one anode, b) at least one cathode, y) at least one separator. Suitable separator materials, electrochemically active cathode materials (cathode active materials) and suitable electrochemically active anode materials (anode active materials) are known in the art. Exemplary cathode active materials are disclosed above in the context of the third aspect. In an electrochemical cell as described herein the anode a) may comprise graphitic carbon, metallic lithium or a metal alloy comprising lithium as the anode active material. Electrochemical cells as described herein may be alkali metal containing cells, especially lithium-ion containing cells. In lithium-ion containing cells, the charge transport is effected by Li+ ions.
The electrochemical cell may be an all solid state electrochemical cell. The electrochemical cell may have a disc-like or a prismatic shape. The electrochemical cell can include a housing that can be made of steel or aluminum.
A plurality of electrochemical cells as described above may be combined to an all-solid- state battery, which has both solid electrodes and solid electrolytes. A further aspect of the present disclosure refers to batteries, more specifically to an alkali metal ion battery, in particular to a lithium ion battery comprising at least one electrochemical cell as described above, for example two or more electrochemical cells as described above. Electrochemical cells as described above can be combined with one another in alkali metal ion batteries, for example in series connection or in parallel connection. Series connection is preferred. The electrochemical cells resp. batteries described herein can be used for making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and stationary applications such as energy storage devices for power plants. A further aspect of the present invention is a method of making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment, remote car locks, and stationary applications such as energy storage devices for power plants by employing at least one inventive battery or at least one inventive electrochemical cell.
A further aspect ofthe present disclosure is the use ofthe electrochemical cell as described above in motor vehicles, bicycles operated by electric motor, robots, aircraft (for example unmanned aerial vehicles including drones), ships or stationary energy stores.
The present disclosure further provides a device comprising at least one inventive electrochemical cell as described above. Preferred are mobile devices such as are vehicles, for example automobiles, bicycles, aircraft, or water vehicles such as boats or ships. Other examples of mobile devices are those which are portable, for example computers, especially laptops, telephones or electrical power tools, for example from the construction sector, especially drills, battery-driven screwdrivers or battery-driven tackers.

Claims

Claims:
1. Process for preparing a solid material having a composition according to general formula (I)
Ll3-n*xMl-xM xXy-3a-2bNaOb (I) wherein
M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
M’ is one or more selected from the group consisting of Ti, Zr, Hf, Nb and Ta;
X is one or more selected from the group consisting of halides and pseudohalides;
0.05 < x< 0.95;
5.8 < y < 6.2; n is the difference between the valences of M’ and M;
0 < a < 0.8;
0 < b < 0.8; said process comprising the process steps of
(a) preparing a liquid reaction mixture by dissolving the precursors
(1) one or more solid materials selected from the group consisting of halides and pseudohalides of lithium;
(2) one or more solid materials selected from the group consisting of halides and pseudohalides of elements M selected from the group consisting of Sc, In, Lu, Er, Y and Ho;
(3) one or more solid materials selected from the group consisting of halides and pseudohalides of elements M’ selected from the group consisting of Ti, Zr, Hf, Nb and Ta; wherein the molar ratio of Li, M, M’, halides and pseudohalides matches general formula (I); in at least one solvent selected from the group consisting of ethers, H2O, alcohols CnH2n+iOH wherein 1 < n < 20, formic acid, acetic acid, dimethylformamide, N-methylformamide, pyridine, nitriles, N-methylpyrrolidinone, dimethyl sulfoxide, acetone, ethyl acetate, dimethoxyethane, 1 ,3-dioxolane, and alkylene carbonates;
(b) removing the solvents from the liquid reaction mixture, so that a solid residue is obtained, and heat-treating the solid residue in a temperature range of from 100 °C to 300 °C for a total duration of 4 hours to 12 hours; so that a solid material according to general formula (I) results.
2. Process according to claim 1 , wherein the precursors are
(1) one or more compounds LiX; and
(2) one or more compounds MX3 wherein M is one or more of La, Er and Y, preferably one or both of Er and Y; and
(3) one or more compounds from the group consisting of compounds MXt wherein M’ is one or more of Ti, Zr and Hf, and compounds M’Xs wherein M’ is one or both of Nb and Ta; wherein in each of precursors (1) to (3), independently from the other precursors, X is one or more selected from the group consisting of Cl, Br and I, preferably Cl; wherein the molar ratio of Li, M, M’ and X matches general formula (I).
3. A solid material having a composition according to general formula (II)
Ll3-n*xMl-xM xXy-3a-2bNaOb (I I) wherein M is one or more selected from the group consisting of Sc, In, Lu, La, Er, Y and Ho;
M’ is one or more selected from the group consisting of Ti, Zr, Hf, Nb and Ta;
X is one or more selected from the group consisting of halides and pseudohalides; 0.05 < x< 0.95;
5.8 < y < 6.2; n is the difference between the valences of M’ and M;
0 < a < 0.8;
0 < b < 0.8; a + b > 0.01.
4. Solid material according to claim 3, wherein M is one or more of La, Er and Y and/or M’ is one or more of Zr, Nb and Ta and/or
X is one or more selected from the group consisting of Cl, Br and I.
5. Solid material according to claim 3 or 4, wherein
M is one or both of Y and Er and M’ is Zr and X is Cl.
6. Solid material according to any of claims 3 to 5, wherein
0.08 < x< 0.85, preferably 0.18 < x< 0.8, more preferably 0.2 < x < 0.65; and 5.85 < y < 6.15, preferably 5.9 < y < 6.1.
7. Coated particulate material for use in a cathode of a lithium-ion electrochemical cell, said coated particulate material comprising
C1) a plurality of core particles, each core particle comprising at least one cathode active material; and
C2) disposed on the surfaces of the core particles, a coating comprising carbonate anions, and a solid material having a composition according to general formula (I).
8. Coated particulate material according to claim 7, wherein each core particle C1) comprises at least one cathode active material selected from the group consisting of complex layered oxides comprising lithium, - nickel and one or both members of the group consisting of cobalt and manganese.
9. Coated particulate material according to claim 7 or 8, wherein each core particle C1) comprises at least one cathode active material selected from the group consisting of compounds having a composition according to general formula (III):
Lii+tAi-t02 (III), wherein
A comprises nickel and one or both members of the group consisting of cobalt and manganese, and optionally one or more further transition metals not selected from the group consisting of nickel, cobalt and manganese, wherein said further transition metals are preferably selected from the group consisting of molybdenum, titanium, tungsten, zirconium, one or more elements selected from the group consisting of aluminum, barium, boron and magnesium, wherein at least 50 mole-% of the transition metal of A is nickel; t is a number in the range of from -0.05 to 0.2.
10. Coated particulate material according to any of claims 7 to 9, wherein at least a part of the carbonate ions, preferably the total amount of carbonate ions, present in the coating C2) are present as lithium carbonate.
11 . Coated particulate material according to any of claims 7 to 10, wherein in the coating C2) disposed on the surfaces of the core particles, the solid material having a composition according to general formula (I) is amorphous or is a glassy ceramics.
12. Process for preparing a coated particulate material according to any of claims 7 to 11 , said process comprising the steps:
(i) preparing or providing a liquid reaction mixture as defined in any of claims 1 and 2,
(ii) preparing or providing a plurality of core particles C1), each core particle comprising at least one cathode active material,
(iii) contacting the core particles C1) and the liquid reaction mixture with each other
(iv) removing the solvents of the liquid reaction mixture, so that a solid residue is obtained, and heat-treating the solid residue in a temperature range of from 100 °C to 300 °C for a total duration of 4 hours to 12 hours so that the coated particulate material results.
13. A cathode for use in a lithium-ion electrochemical cell, comprising a coated particulate material as defined in any of claims 7 to 11 ; a solid electrolyte material comprising lithium ions; optionally an electron conducting material comprising elemental carbon; optionally a binding agent.
14. An electrochemical cell comprising a coated particulate material as defined in any of claims 7 to 11 .
15. Use of a coated particulate material according to any of claims 7 to 11 for preparing a cathode for use in a lithium-ion electrochemical cell.
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XIAONA LI ET AL: "Water-Mediated Synthesis of a Superionic Halide Solid Electrolyte", ANGEWANDTE CHEMIE, vol. 131, no. 46, 30 September 2019 (2019-09-30), DE, pages 16579 - 16584, XP055768764, ISSN: 0044-8249, DOI: 10.1002/ange.201909805 *

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