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WO2024227729A1 - Électrolyte solide conducteur d'halogénure mixte lithium-ion à base de sulfure et ses procédés de production - Google Patents

Électrolyte solide conducteur d'halogénure mixte lithium-ion à base de sulfure et ses procédés de production Download PDF

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Publication number
WO2024227729A1
WO2024227729A1 PCT/EP2024/061743 EP2024061743W WO2024227729A1 WO 2024227729 A1 WO2024227729 A1 WO 2024227729A1 EP 2024061743 W EP2024061743 W EP 2024061743W WO 2024227729 A1 WO2024227729 A1 WO 2024227729A1
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range
solid material
solid
mixture
melt
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Inventor
Antoine BREHAULT
Pol BRIANTAIS
Yann Guimond
Stef KERKHOFS
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Umicore NV SA
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Umicore NV SA
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Priority to CN202480029192.0A priority Critical patent/CN121079268A/zh
Publication of WO2024227729A1 publication Critical patent/WO2024227729A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/18—Compositions for glass with special properties for ion-sensitive glass
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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

  • the present invention relates to solid materials which are obtainable by meltquenching mixtures of lithium sulphide, boron sulphide and boron oxide, thereby forming a glassy solid which is suitable for use as a lithium-ion conducting electrolyte.
  • the present invention further relates to methods to prepare said solid materials, to electrochemical cells such as solid-state batteries comprising said solid materials and to uses of the solid material in electrochemical cells such as solid-state batteries, in particular as an electrolyte.
  • the three primary functional components of a lithium-ion battery are the anode, the cathode, and the electrolyte. While many variations exist, the anode of a conventional lithium-ion cell is typically made from carbon, the cathode is typically made from transition metal oxides (in particular oxides of cobalt, nickel and/or manganese), and the electrolyte is typically a non-aqueous solvent containing a lithium salt. For example, mixtures of organic carbonates with lithium hexafluorophosphate are well known liquid electrolytes for lithium-ion batteries.
  • a significant disadvantage of liquid electrolytes is that the compositions, in particular the solvents are inflammable, which poses a large safety risk during normal operation and in particular in case of an incident.
  • Another disadvantage is inherent to the liquid nature of the electrolyte, associated with risks of leakage and with increased risk of environmental pollution in case of a spill or leakage.
  • solid electrolytes which allow the provision of a solid-state lithium-ion battery.
  • solid-state batteries have significantly reduced EHS (environmental, health and safety) hazards.
  • An emerging class of lithium-ion conducting solid electrolytes are sulphide based amorphous solids (interchangeably referred to as glassy solids) such as LizS-SiSz, U2S-P2S5 or U2S-B2S3.
  • glassy solid electrolyte materials the absence of crystalline pathways leads to isotropic conduction substantially without any grain boundary resistance.
  • the absence of grain boundaries in glassy electrolyte materials may also prevent dendrite formation because glassy amorphous electrolyte materials may be obtained as dense, defect free films by a melt-quench approach.
  • US5500291 contemplates sulphide based lithium-ion conducting solid electrolytes of the type Li2S-SiS2-Li4SiO4.
  • WO2020/254314 Al contemplates sulphide based lithium-ion conducting solid electrolytes of the type U2S-B2S3 obtained from mixtures further comprising P, Si, Ge, As or Sb oxides in combination with lithium halides.
  • the resulting glassy solids are said to have favourable lithium-ion conductivity as well as electrochemical stability in direct contact with lithium metal and chemical stability against air and moisture.
  • WO2016/089899 Al contemplates a plethora of glass systems (many of which are speculative or unsupported). Paragraphs 188 and 189 of WO2016/089899 Al describes several Li2O-B2S3-SiS2 based systems.
  • a drawback related to most sulphide based lithium-ion conducting solid electrolytes known in the art is that they have a low ionic conductivity. Presently, there is therefore a significant need to provide sulphide based lithium-ion conducting solid electrolytes combining both properties.
  • the present inventors have found that one or more objects of the invention can be achieved by providing sulphide based lithium-ion conducting solid electrolytes obtainable by melt-quenching a combination of U2S; B2S3; B2O3; Lil and LiX in well- defined ratios, wherein X represents Cl, Br or combinations thereof.
  • sulphide based lithium-ion conducting solid electrolytes obtainable by melt-quenching a combination of U2S; B2S3; B2O3; Lil and LiX in well- defined ratios, wherein X represents Cl, Br or combinations thereof.
  • X represents Cl, Br or combinations thereof.
  • X represents Br or Cl, or combinations thereof; a is within the range of 0.015 to 0.15; b is within the range of 0 to 0.04; c is within the range of 0.07 to 0.25; d is within the range of 0.001 to 0.24; and e is within the range of 0.001 to 0.24.
  • a solid material which is obtainable by melt-quenching a mixture of A, B and C, wherein the molar ratio of A, B and C in the mixture before quenching is within the range of 40:30:30 to 98: 1 : 1.
  • step (ii) preparing a mixture comprising the precursors provided in step (i) wherein
  • step (iii) heat-treating the mixture prepared in step (ii) to obtain a melt
  • step (iv) quenching the melt obtained in step (iii) to obtain the solid material.
  • a solid composition comprising a first solid material which is the solid material as described herein, and further comprising at least a second solid material having a different composition than the first solid material.
  • an electrochemical cell comprising the solid material as described herein.
  • the use of the solid material as described herein, or of the solid composition as described herein, as a solid electrolyte for an electrochemical cell in another aspect of the invention, concerns batteries, more specifically a lithium ion battery or a lithium metal battery comprising at least one electrochemical cell comprising the solid material as described herein, for example two or more electrochemical cells as described herein.
  • 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 battery or at least one electrochemical cell comprising the solid material as described herein (i.e. the electrochemical cell as described herein).
  • a further aspect of the present disclosure is the use of the electrochemical cell comprising the solid material of the invention (i.e. the electrochemical cell as described herein) in motor vehicles, bicycles operated by electric motor, robots, aircraft (for example unmanned aerial vehicles including drones), ships or stationary energy stores.
  • the electrochemical cell comprising the solid material of the invention (i.e. the electrochemical cell as described herein) in motor vehicles, bicycles operated by electric motor, robots, aircraft (for example unmanned aerial vehicles including drones), ships or stationary energy stores.
  • the ionic conductivity as referred to herein refers to the ionic conductivity determined by electrochemical impedance spectroscopy (EIS) at 25 °C. It is preferably determined with ion-blocking electrodes on hot pressed samples which were densified at 350 MPa at 125 °C for 5 min after which the ionic conductivity was measured at 25 °C under an operational pressure of 125 MPa. Preferably an excitation voltage of 10 mV was applied in the frequency range of 7 MHz - 1 Hz and the data was interpreted by means of an equivalent circuit analysis.
  • a suitable conductivity analyzer is a potentiostat with frequency analyzer such as is available from Biologic.
  • the electronic conductivity as referred to herein refers to the electronic conductivity determined at 25 °C. It is preferably determined with ion-blocking electrodes on hot pressed samples which were densified at 350 MPa at 125 °C for 5 min after which the electronic conductivity was measured at 25 °C under an operational pressure of 125 MPa. Preferably the electronic conductivity was measured via stepwise potentiostatic polarization at 0.2, 0.4 and 0.6 V for 20 min.
  • a suitable conductivity analyzer is a potentiostat with frequency analyzer such as is available from Biologic.
  • molar ratios as referred to herein for example the molar ratios of components A, B and C mean that the ratio of A, B and C is defined in the following unit mol/mol/mol.
  • X represents Br or Cl, or combinations thereof; a is within the range of 0.015 to 0.15; b is within the range of 0 to 0.04; c is within the range of 0.07 to 0.25; d is within the range of 0.001 to 0.24; and e is within the range of 0.001 to 0.24.
  • the present inventors believe that the solid materials according to formula (I) are the result obtained when melt quenching a mixture LizS; B2S3; B2O3; Lil and LiX in well-defined ratios, wherein X represents Cl, Br or combinations thereof as is explained herein in the context of other aspects of the invention, and in the examples.
  • the solid material having a composition according to general formula (I) is preferably provided wherein a is within the range of 0.02 to 0.09; b is within the range of 0 to 0.03; c is within the range of 0.09 to 0.20; d is within the range of 0.001 to 0.21; and e is within the range of 0.001 to 0.21; more preferably wherein a is within the range of 0.03 to 0.085; b is within the range of 0.007 to 0.02; c is within the range of 0.10 to 0.20; d is within the range of 0.001 to 0.15; and e is within the range of 0.001 to 0.15;
  • d and e are within the range 0.005 to 0.15, preferably within the range of 0.009 to 0.10, more preferably within the range 0.01 to 0.07. In some embodiments, d and e are within the range of 0.001 to 0.15, preferably within the range of 0.005 to 0.15, more preferably within the range of 0.01 to 0.15. In some embodiments, d and e are within the range of 0.005 to 0.10, preferably within the range of 0.009 to 0.08, more preferably within the range of 0.01 to 0.07.
  • the solid material having a composition according to general formula (I) wherein a is within the range of 0.03 to 0.085; b is within the range of 0 to 0.03; c is within the range of 0.10 to 0.20; d is within the range of 0.001 to 0.15, preferably within the range of 0.005 to 0.10, more preferably within the range of 0.01 to 0.07; and e is within the range of 0.001 to 0.15, preferably within the range of 0.005 to 0.10, more preferably within the range of 0.01 to 0.07; more preferably wherein a is within the range of 0.04 to 0.085; b is within the range of 0.007 to 0.025; c is within the range of 0.10 to 0.18; d is within the range of 0.001 to 0.15, preferably within the range of 0.005 to 0.10, more preferably within the range of 0.01 to 0.07; and e is within the range of 0.001 to 0.15, preferably within the
  • the solid material having a composition according to general formula (I) is provided wherein a is within the range of 0.050 to 0.080; b is within the range of 0.009 to 0.020; c is within the range of 0.11 to 0.18; d is within the range of 0.005 to 0.15; and e is within the range of 0.005 to 0.15.
  • the solid material having a composition according to general formula (I) is provided wherein a is within the range of 0.053 to 0.066, preferably within the range of 0.056 to 0.063, more preferably within the range of 0.058 to 0.061, most preferably a is about 0.060; b is within the range of 0.009 to 0.011 preferably within the range of 0.0095 to 0.010, more preferably b is about 0.010; c is within the range of 0.11 to 0.14 preferably within the range of 0.0125 to 0.135, more preferably c is about 0.0130; d is within the range of 0.045 to 0.09, preferably within the range of 0.055 to 0.075, more preferably within the range of 0.060 to 0.070, most preferably d is about 0.066; and e is within the range of 0.045 to 0.09, preferably within the range of 0.055 to 0.075, more preferably within the range of 0.060 to 0.070; and e is within the range
  • the solid material having a composition according to general formula (I) is provided wherein a is within the range of 0.055 to 0.075, preferably within the range of 0.06 to 0.07, more preferably a is about 0.066; b is within the range of 0.0085 to 0.015 preferably within the range of 0.009 to 0.01, more preferably b is about 0.011; c is within the range of 0.0135 to 0.0155 preferably within the range of 0.014 to 0.015, more preferably c is about 0.0143; d is within the range of 0.035 to 0.055, preferably within the range of 0.04 to 0.05, more preferably d is about 0.047; and e is within the range of 0.035 to 0.055, preferably within the range of 0.04 to 0.05, more preferably e is about 0.047.
  • the solid material having a composition according to general formula (I) is provided wherein a is within the range of 0.065 to 0.080, preferably within the range of 0.069 to 0.075, more preferably within the range of 0.070 to 0.072, most preferably a is about 0.071; b is within the range of 0.010 to 0.015 preferably within the range of 0.011 to 0.013, more preferably b is about 0.012; c is within the range of 0.13 to 0.17 preferably within the range of 0.15 to 0.16, more preferably c is 0.155; d is within the range of 0.025 to 0.045, preferably within the range of 0.027 to 0.040, more preferably within the range of 0.029 to 0.035, most preferably d is about 0.030; and e is within the range of 0.025 to 0.045, preferably within the range of 0.027 to 0.040, more preferably within the range of 0.029 to 0.035, most preferably d is about 0.0
  • the solid material having a composition according to general formula (I) is provided wherein a is within the range of 0.070 to 0.080, preferably within the range of 0.072 to 0.079, more preferably within the range of 0.074 to 0.077, most preferably a is about 0.076; b is within the range of 0.010 to 0.015 preferably within the range of 0.012 to 0.014, more preferably b is about 0.013; c is within the range of 0.15 to 0.18 preferably within the range of 0.16 to 0.17, more preferably c is about 0.166; d is within the range of 0.005 to 0.025, preferably within the range of 0.008 to 0.020, more preferably within the range of 0.010 to 0.017, most preferably d is about 0.014; and e is within the range of 0.005 to 0.025, preferably within the range of 0.008 to 0.020, more preferably within the range of 0.010 to 0.020, more preferably within the range of
  • the molar ratios have been calculated such that the total of 5a+5b+3c+2d+2e is within the range of 0.9-1.1, preferably within the range of 0.99- 1.01, most preferably about 1.
  • the solid material having a composition according to general formula (I), if prepared by e.g. melt-quenching, may be accompanied by minor amounts of impurity phases which typically mainly consist of the precursors used for preparing the solid material, or intermediates formed from said precursors.
  • the solid material which is obtainable by melt-quenching a mixture of A, B and C is provided wherein x is about 65; y is about 30; and z is about 5.
  • the molar ratio of A, B and C in the mixture before quenching is within the range of 50:25:25 to 98: 1 : 1, preferably 56:22:22 to 90:5:5, more preferably 64: 18: 18 to 80: 10: 10.
  • the molar ratio of A, B and C in the mixture before quenching is within the range of 60:20:20 to 95:3:2, preferably within the range of 76: 12: 12 to 90:5:5, more preferably within the range of 70: 15: 15 to 82:9:9.
  • the molar ratio of A, B and C in the mixture before quenching is within the range of 50:25:25 to 96:2:2, preferably within the range of 60:20:20 to 90:5:5, more preferably within the range of 70: 15: 15 to 80: 10: 10.
  • the molar ratio of A, B and C in the mixture before quenching is within the range of 50:25:25 to 70: 15: 15, preferably 56:22:22 to 64: 18: 18, more preferably 58:21 :21 to 62: 19: 19 to, most preferably about 60:20:20.
  • the molar ratio of A, B and C in the mixture before quenching is within the range of 64: 18: 18 to 76: 12: 12 preferably 66: 17: 17 to 74: 13: 13, more preferably 68: 16: 16 to 72: 14: 14, most preferably about 70: 15: 15.
  • the molar ratio of A, B and C in the mixture before quenching is within the range of 75: 15: 15 to 88:6:6, preferably 76: 12: 12 to 84:8:8, more preferably 78: 11 : 11 to 82:9:9, most preferably about 80: 10: 10. In some embodiments.
  • the molar ratio of A, B and C in the mixture before quenching is within the range of 84:8:8 to 98: 1 : 1, preferably 86:7:7 to 94:3:3, more preferably 88:6:6 to 92:4:4, most preferably about 90:5:5.
  • the solid material which is obtainable by melt-quenching a mixture of A, B and C as described herein is the solid material having a composition according to general formula (I) as described herein (i.e. the solid material of the first aspect of the invention).
  • the solid material according to the different aspects of the invention described herein namely the solid material having a composition according to general formula (I) as described herein (i.e. the solid material of the first aspect of the invention) and the solid material which is obtainable by melt-quenching a mixture of A, B and C as described herein (i.e. the solid material of the second aspect of the invention), are collectively referred to as "the solid material” (i.e. the solid material of the first or second aspect of the invention).
  • the solid material is provided wherein X represents Br, Cl or a combination thereof.
  • the solid materials of the present invention are typically glassy solids, obtainable by melt-quenching a mixture of precursors as explained herein elsewhere.
  • the solid material is in the form of a monolithic glass, such as a meltcase monolithic glass. It is preferred that the glassy solid is essentially free of crystalline phases. This may mean that in some embodiments the amount of crystalline phases as determined by X-ray diffraction is less than 5 vol% of the solid material, preferably less than 2 vol%, more preferably less than 1 vol%. A phase is considered crystalline if the intensity of its reflection if more than 10% above the background.
  • the solid material is provided wherein X represents Br, Cl or a combination thereof and wherein at least 50 mol% of X represents Br, preferably at least 80 mol% of X represents Br.
  • the solid materials of the present invention have a surprisingly high ionic conductivity.
  • the solid material is provided wherein the material has an ionic conductivity at 25 °C of at least 0.1 mS/cm, preferably at least 0.2 mS/cm.
  • the present inventors have surprisingly found that in case at least 50 mol% of X represents Br, preferably at least 80 mol% of X represents Br, most preferably X represents Br, the ionic conductivity at 25 °C can be as high as 0.93 mS/cm.
  • the solid material is provided wherein the material has an ionic conductivity at 25 °C of at least 0.3 mS/cm, preferably at least 0.40 mS/cm, more preferably at least 0.54 mS/cm.
  • the solid materials of the present invention have:
  • At least 80 mol% of X represents Br and the ionic conductivity at 25 °C of the solid material is at least 0.3 mS/cm, or X represents Br and the ionic conductivity at 25 °C of the solid material is at least 0.54 mS/cm, such as at least 0.60 mS/cm or at least 0.75 mS/cm.
  • the solid material is provided wherein X represents Br, Cl or a combination thereof and wherein at least 50 mol% of X represents Cl, preferably at least 80 mol% of X represents Cl.
  • the present inventors have surprisingly found that in case at least 50 mol% of X represents Cl, preferably at least 80 mol% of X represents Cl, most preferably X represents Cl, the ionic conductivity at 25 °C can be as high as 0.71 mS/cm.
  • the solid material is provided wherein the material has an ionic conductivity at 25 °C of at least 0.40 mS/cm, preferably at least 0.50 mS/cm, more preferably at least 0.62 mS/cm
  • the solid materials of the present invention have:
  • the solid material of the invention at least 80 mol% of X represents Cl and the ionic conductivity at 25 °C of the solid material is at least 0.3 mS/cm, or X represents Cl and the ionic conductivity at 25 °C of the solid material is at least 0.62 mS/cm, such as at least 0.65 mS/cm or at least 0.70 mS/cm. It was found that the solid materials of the present invention combine said high ionic conductivity with surprisingly low electronic conductivity, which makes them extremely attractive solid state battery electrolyte materials.
  • the solid material is provided wherein the material has an electronic conductivity at 25 °C of less than lxlO' 4 mS/cm, preferably less than lxlO' 5 mS/cm.
  • the present inventors have surprisingly found that in case X represents Br, Cl or a combination thereof, the electronic conductivity at 25 °C can be very low, such as less than lxlO' 5 mS/cm or less than 8xl0' 6 mS/cm.
  • the solid material has an electronic conductivity at 25 °C of less than l.OxlO' 6 mS/cm or less than l.OxlO' 5 mS/cm.
  • materials are provided combining a high ionic conductivity with a low electronic conductivity. As is shown in the appended examples, this is possible when X represents Br.
  • X represents Br.
  • solid material of the invention in some embodiments of the solid material of the invention:
  • X represents Br, preferably at least 80 mol% of X represents Br, most preferably X represents Br;
  • the solid material has an ionic conductivity at 25 °C of at least 0.30 mS/cm, preferably at least 0.40 mS/cm, more preferably at least 0.54 mS/cm;
  • the solid material has an electronic conductivity at 25 °C of less than 5.0xl0' 4 mS/cm or less than lxlO' 5 mS/cm.
  • At least 50 mol% of X represents Br, preferably at least 80 mol% of X represents Br, most preferably X represents Br;
  • the solid material has an ionic conductivity at 25 °C of at least 0.54 mS/cm and the solid material has an electronic conductivity at 25 °C of less than 5xl0' 4 mS/cm.
  • materials are provided combining a high ionic conductivity with a low electronic conductivity. As is shown in the appended examples, this is possible when X represents Cl.
  • X represents Cl.
  • solid material of the invention in some embodiments of the solid material of the invention:
  • - at least 50 mol% of X represents Cl, preferably at least 80 mol% of X represents Cl, most preferably X represents Cl;
  • -the solid material has an ionic conductivity at 25 °C of at least 0.40 mS/cm, preferably at least 0.50 mS/cm, more preferably at least 0.62 mS/cm;
  • the solid material has an electronic conductivity at 25 °C of less than 5xl0' 5 mS/cm or less than lxlO' 5 mS/cm.
  • At least 50 mol% of X represents Cl, preferably at least 80 mol% of X represents Cl, most preferably X represents Cl;
  • the solid material has an ionic conductivity at 25 °C of at least 0.62 mS/cm and the solid material has an electronic conductivity at 25 °C of less than lxlO' 5 mS/cm.
  • the solid materials of the invention are obtainable by melt-quenching a mixture of precursors to obtain a glassy solid.
  • the material is provided in the form of a particulate solid, such as a powder. This may facilitate blending with e.g. cathode material.
  • the solid may be obtained directly in the form of a particulate solid (such as a powder) or may be comminuted (such as by milling, grinding, etc.) to a particulate solid (such as a powder).
  • the solid material is provided in the form of a thin sheet or film, preferably a sheet or film having a thickness of less than 500 micron, preferably less than 100 micron.
  • the present inventors contemplate that the addition of small amounts of other materials during synthesis in such a way that the general formula (I) of the resulting solid material is no longer respected or in such a way that the general formula (II) is no longer respected; but wherein the changes do not materially affect the basic and novel characteristic(s) of the solid materials of the invention is possible. Such modifications are considered within the scope of the general formula (I) or (II) for the purposes of the present invention.
  • a method for preparing a solid material comprising the steps of:
  • X represents Br or Cl, or combinations thereof; a is within the range of 0.015 to 0.15; b is within the range of 0 to 0.04; c is within the range of 0.07 to 0.25; d is within the range of 0.001 to 0.24; and e is within the range of 0.001 to 0.24; or
  • the preferred embodiments of the solid materials of the invention i.e. according to the first or second aspect of the invention
  • in general e.g. regarding the identity of X, the conductivities, etc.
  • melt-quench method of the third aspect of the invention are equally applicable to the melt-quench method of the third aspect of the invention.
  • step (i) should be interpreted to mean the provision of elemental boron and elemental sulfur.
  • the elemental boron and elemental sulfur may be provided in in amorphous or crystalline form, wherein the specific allotrope used is not particularly limiting for the invention.
  • Preparing the mixture of step (ii) may be performed by any suitable means, preferably by mechanical milling (e.g. ball milling).
  • Step (iii) involves heating the mixture prepared in step (ii) to obtain a melt, i.e. heat- treating at a temperature above the melting temperature of the mixture prepared in step (ii).
  • Step (iii) preferably comprises heat-treating the mixture prepared in step (ii) at a temperature of at least 400 °C, preferably at least 600 °C, more preferably at least 800 °C.
  • the mixture is preferably kept at this temperature for at least 1 hour, preferably at least 2 hours, more preferably at least 4 hours.
  • Heat-treating may be performed in a closed vessel.
  • the closed vessel may be a sealed quartz tube or any other type of container which his capable of withstanding the temperature of the thermal treatment and is not subject to reaction with the constituents of the glass, such a closed vessel made from a material selected from magnesium oxide, boron nitride, copper, tungsten, silicon nitride, aluminum nitride, carbon and combinations thereof.
  • the heat-treatment of step (iii) may be a single stage or a multiple stage heat-treatment.
  • step (iii) is performed under an inert gas atmosphere, preferably an inert atmosphere comprising one or more noble gases (such as argon) and/or at a pressure of less than 1 atm, preferably of less than 0.1 atm, more preferably of less than 0.01 atm.
  • step (iii) is performed at a pressure of less than 10' 4 atm, preferably less than 10' 5 atm and preferably under an inert gas atmosphere, preferably an inert atmosphere comprising one or more noble gases (such as argon).
  • the use of nitrogen as inert atmosphere is generally to be avoided in view of potential reaction with the glass precursors.
  • melt-quench method of the invention is for the preparation of the solid material according to the first or second aspect of the invention.
  • step (iv) further comprises the steps of:
  • step (iv)b comminuting the solid material of step (iv)a to obtain a particulate solid, such as a powder
  • (iv)c optionally forming a thin film or sheet, preferably a film or sheet having a thickness of less than 500 micron, preferably less than 100 micron by:
  • step (iv)b dissolving or suspending the particulate solid of step (iv)b in a liquid phase to obtain a solution or suspension, followed by deposition from the solution or suspension to obtain the thin film or sheet;
  • step (iv)b reheating the particulate solid of step (iv)b to a temperature sufficient to allow drawing a film or sheet, and drawing said film or sheet.
  • step (iv) comprises quenching the melt of step (iii) while maintaining the temperature sufficiently high to allow drawing a thin film or sheet, and drawing said film or sheet, preferably drawing a film or sheet having a thickness of less than 500 micron, preferably less than 100 micron.
  • the method is operated in the form of a continuous process to produce a continuous glass film or sheet which is cut to a desired size.
  • step (iv) is preferably performed by contacting the melt obtained in step (iii) directly, or by contacting the vessel while closed or opened (preferably while closed), with water, ice, an optionally cooled gas (such as air), an optionally cooled metal plate (such as via roller quenching), and/or a chemically inert mold.
  • an optionally cooled gas such as air
  • an optionally cooled metal plate such as via roller quenching
  • a chemically inert mold is preferably performed by contacting the melt obtained in step (iii) directly, or by contacting the vessel while closed or opened (preferably while closed), with water, ice, an optionally cooled gas (such as air), an optionally cooled metal plate (such as via roller quenching), and/or a chemically inert mold.
  • a solid composition comprising a first solid material which is the solid material as described herein (i.e. the solid material according to the first or second aspect of the invention), and further comprising at least a second solid material having a different composition than the first solid material.
  • the first solid material may be present in the form of discrete particles embedded in a matrix of the second solid material.
  • the first solid material and the second solid material may be present in the form of discrete particles which have been blended, optionally in combination with a binder material and one or more further materials, and wherein the blend is preferably compacted.
  • first solid material and the second solid material may be present in the form of different layers of a multilayer thin sheet or film, preferably a multilayer thin sheet or film having a total thickness of less than 500 micron, preferably less than 200 micron.
  • Such solid compositions comprising a first solid material which is the solid material as described herein, and further comprising at least a second solid material having a different composition than the first solid material are particularly useful as cathodes, anodes or separators for an electrochemical cell, in particular as separator or cathode.
  • the second solid material is a cathode material, such as a Nickel-Cobalt or a Nickel-Manganese-Cobalt cathode material.
  • an electrochemical cell comprising the solid material as described herein (i.e. the solid material of the first and second aspect of the invention).
  • the cathode, anode and/or separator comprises the solid material as defined herein.
  • the cathode, anode and/or separator comprises the solid material as defined herein in the form of a solid composition comprising a first solid material which is the solid material as described herein, and further comprising at least a second solid material having a different composition than the first solid material.
  • the separator comprises, the solid material as defined herein, optionally in the form of the solid composition as described herein.
  • the separator consists of the solid material as described herein.
  • a solid material as described herein i.e. the solid material according to the first or second aspect of the invention
  • the solid composition as described herein i.e. the solid composition of the fourth aspect of the invention
  • the use of the solid material as described herein as a solid electrolyte for an electrochemical cell Preferably, there is provided the use of the solid material as described herein as a solid electrolyte for an electrochemical cell.
  • suitable electrochemically active cathode materials and suitable electrochemically active anode materials are those known in the art.
  • the anode may comprises graphitic carbon, metallic lithium or a metal alloy comprising lithium as the anode active material.
  • the cathode may comprise a Nickel-Cobalt or a Nickel- Manganese-Cobalt cathode material.
  • Electrochemical cells as described herein are preferably lithium-ion containing cells wherein the charge transport is effected by Li + ions.
  • the electrochemical cell may have a disc-like or a prismatic shape.
  • the electrochemical cells can include a housing that can be from steel or aluminum. A plurality of electrochemical cells may be combined to an all solid- state battery, which has both solid electrodes and solid electrolytes.
  • a seventh aspect of the present invention concerns batteries, more specifically a lithium ion battery or a lithium metal battery comprising at least one electrochemical cell comprising the solid material as described herein (i.e. the solid material according to the first or second aspect of the invention), for example two or more electrochemical cells as described in the fifth aspect of the invention.
  • Certain embodiments relate to a solid state battery, preferably a lithium solid state battery comprising at least one electrochemical cell comprising the solid material as described herein (i.e. the solid material of the first or second aspect of the invention), for example two or more electrochemical cells as described in the fifth aspect of the invention.
  • Electrochemical cells as described in the fifth aspect of the invention can be combined with one another, for example in series connection or in parallel connection. Series connection is preferred.
  • the electrochemical cells respectively 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 battery or at least one electrochemical cell comprising the solid material as described herein (i.e. the electrochemical cell as described in the fifth aspect of the invention).
  • a eighth aspect of the present disclosure is the use of the electrochemical cell comprising the solid material of the invention (i.e. the electrochemical cell as described in the fifth aspect of the invention) in motor vehicles, bicycles operated by electric motor, robots, aircraft (for example unmanned aerial vehicles including drones), ships or stationary energy stores.
  • the present invention further provides a device comprising at least one electrochemical cell as described in the fifth aspect of the invention.
  • 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.
  • 15g of final material has been produced using the following starting products: amorphous B2S3 (99 wt.%), U2S (99.9 wt.%), B2O3 (99.95 wt.%), Lil (99.95 wt.%) and LiBr (99.9 wt.%) or LiCI (99.9 wt.%).
  • amorphous B2S3 99 wt.%), U2S (99.9 wt.%), B2O3 (99.95 wt.%), Lil (99.95 wt.%) and LiBr (99.9 wt.%) or LiCI (99.9 wt.%).
  • argon filled glovebox appropriate amounts of starting materials were weighed, mixed and introduced in a boron nitride crucible placed in a silica ampoule. The tube was sealed and introduced in a vertical rocking furnace. The melt was homogenized for 5 hours at an internal temperature of 850 °C and then quenched in water at room
  • an alternative synthesis was performed and successful wherein the amount of Boron and Sulfur brought by B2S3 was provided in the form of amorphous elemental B (99 wt.%) and elemental S (99.999 wt.%).
  • 15g of final material has been produced using the following starting products: amorphous B 2 S 3 (99 wt.%), l_i 2 S (99.9 wt.%) and B 2 O 3 (99.95 wt.%) and X (detailed in the below table).
  • amorphous B 2 S 3 99 wt.%), l_i 2 S (99.9 wt.%) and B 2 O 3 (99.95 wt.%) and X (detailed in the below table).
  • argon filled glovebox appropriate amounts of starting materials were weighed, mixed and introduced in a carbon coated silica ampoule. The tube was sealed and introduced in a vertical rocking furnace. The melt was homogenized for 30 minutes at an internal temperature of 950 °C and then quenched in water at room temperature. The ampoule was then opened in the argon filled glovebox. Glassy material was obtained having yellow, orange or brown color with good transparency.
  • Ionic conductivity was measured by electrochemical impedance spectroscopy (EIS) at room temperature (25 °C) on hot pressed samples in a pellet cell with ion blocking electrodes. The samples were densified at 350 MPa at 125 °C for 5 min. The ionic conductivity was measured under an operational pressure of 125 MPa. For the EIS an excitation voltage of 10 mV was applied in the frequency range of 7 MHz - 1 Hz. The data was interpreted by means of an equivalent circuit analysis.
  • EIS electrochemical impedance spectroscopy
  • Electronic conductivity was measured at room temperature (25 °C) on hot pressed samples in a pellet cell with ion blocking electrodes. The samples were densified at 350 MPa at 125 °C for 5 min. The electronic conductivity was measured under an operational pressure of 125 MPa. The electronic conductivity was measured via stepwise potentiostatic polarization at 0.2, 0.4 and 0.6 V for 20 min. Both measurements were conducted with a potentiostat with frequency analyzer (Biologic).
  • ICP-OES Inductively Coupled Plasma Optical Emission Spectroscopy
  • a sample of the glassy material is weighed in a glovebox under Ar atmosphere to avoid reaction with water or O2 and added to a microwave vessel. A combination of acids is added, the vessels are closed and digested in a microwave until clear.
  • the matrix elements (Li & B) are analyzed using a high-precision ICP-OES method.
  • S is determined via elemental analysis after sample preparation in an Ar-filled glovebox.
  • Sample preparation consists of inserting about 100 mg sample in a sealable capsule, followed by adding the sealed capsule and additives to the ceramic crucible.
  • the filled crucible is subsequently heated in induction furnace under a O2 atmosphere.
  • the S present is released from the sample, converted into SO2 gas and detected by a SO2-specific IR detector.
  • the detected SO2 signal is finally converted into a S concentration by using a calibration line and taking the exact sample mass into consideration.
  • composition of the glasses was found to correspond within the expected margin of experimental error and variation to the overall formula expected based on the molar ratios of the precursors which were submitted to melt-quenching.
  • Table 1 overall formulas of the synthesized compositions.

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Abstract

La présente invention concerne des matériaux solides qui peuvent être obtenus par extinction à l'état fondu de mélanges de sulfure de lithium, de sulfure de bore, d'oxyde de bore et d'halogénures de lithium, formant ainsi un solide vitreux qui est approprié pour une utilisation en tant qu'électrolyte conducteur d'ions lithium. Ces électrolytes solides conducteurs d'ions lithium à base de sulfure présentent une conductivité ionique élevée.
PCT/EP2024/061743 2023-05-03 2024-04-29 Électrolyte solide conducteur d'halogénure mixte lithium-ion à base de sulfure et ses procédés de production Pending WO2024227729A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
US5500291A (en) 1993-03-22 1996-03-19 Matsushita Electric Industrial Co., Ltd. Lithium ion conductive solid electrolyte and process for synthesizing the same
WO2016089899A1 (fr) 2014-12-02 2016-06-09 Polyplus Battery Company Feuilles vitreuses d'électrolyte solide d'un verre à base de soufre conducteur d'ions lithium (li) ainsi que structures, cellules et procédés associés
WO2020254314A1 (fr) 2019-06-17 2020-12-24 Basf Se Haloboro-oxysulfures conducteurs d'ions lithium
US20210320328A1 (en) * 2014-12-02 2021-10-14 Polyplus Battery Company Lithium ion conducting sulfide glass fabrication

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US5500291A (en) 1993-03-22 1996-03-19 Matsushita Electric Industrial Co., Ltd. Lithium ion conductive solid electrolyte and process for synthesizing the same
WO2016089899A1 (fr) 2014-12-02 2016-06-09 Polyplus Battery Company Feuilles vitreuses d'électrolyte solide d'un verre à base de soufre conducteur d'ions lithium (li) ainsi que structures, cellules et procédés associés
US20210320328A1 (en) * 2014-12-02 2021-10-14 Polyplus Battery Company Lithium ion conducting sulfide glass fabrication
WO2020254314A1 (fr) 2019-06-17 2020-12-24 Basf Se Haloboro-oxysulfures conducteurs d'ions lithium

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