Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
• • 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
  • H01M10/056—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
• • 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
  • H01M10/058—Construction or manufacture
  • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/431—Inorganic material
• • 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
• • 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

• TITLE Process for preparing a solid electrolyte
• the present invention relates to the field of all-solid batteries. More particularly, the present invention relates to a particular process for the preparation of a solid electrolyte.
• the present invention also relates to a method for preparing an all-solid-state battery cell.
• all-solid batteries comprise one or more positive electrodes, one or more negative electrodes, a solid electrolyte forming a separator, an anode current collector and a cathode current collector.
• the performance of a battery depends on the properties of ionic and electronic transport.
• ion transport at the electrode scale takes place through the network formed by the solid electrolyte.
• this network is percolated, forming ionic conduction paths through the entire volume of the electrode, to ensure the transport of ions to or from all the particles of active material. .
• All-solid batteries use different types of materials as solid electrolytes, for example polymers, such as poly(ethylene oxide) (PEO), ..., Oxides such as Garnets, perovskites, Nasicon, , .. or even sulphides (LGPS, LPS, LPSCL, etc.).
• polymers such as poly(ethylene oxide) (PEO), ..., Oxides such as Garnets, perovskites, Nasicon, , .. or even sulphides (LGPS, LPS, LPSCL, etc.).
• the synthesis of solid electrolyte materials from the oxide family is to be carried out at high temperature.
• the shaping of solid electrolytes of the family of oxides and sulphides is difficult.
• the ionic conductivities of solid electrolyte materials are also generally low.
• a subject of the invention is therefore a method for preparing a solid electrolyte comprising the following steps: a) mixing a solid electrolyte chosen from sulphides with an agent comprising at least sulphur; b) adding the mixture obtained at the end of step a) in an organic solvent; c) recovering the solid electrolyte obtained.
• Another object of the invention is a process for preparing a battery cell comprising the preparation of a solid electrolyte according to the process according to the invention.
• FIG. 1 represents diffractograms of argyrodite involving the implementation of a comparative process
• FIG 2 represents diffractograms of a solid electrolyte involving the implementation of a method according to the invention
• FIG 3 represents diffractograms of a solid electrolyte involving the implementation of a method according to the invention
• FIG 4 is a graph indicating the ionic conductivity of solid electrolytes obtained from various processes.
• a solid electrolyte chosen from sulphides is mixed with an agent comprising at least sulphur.
• the solid electrolyte chosen from sulphides is chosen from materials of formula:
• A denotes Cu, Ag or Li
• B denotes Ge, Si, Al or P
• Ch denotes O, S, Se or Te, preferably Ch denotes S
• X denotes Cl, Br or I;
• - n is equal to 3, 4 or 5;
• Liii-zM 2 -zPi +z Si2 in which M denotes Ge, Sn or Si and z varies from 0 to 1.75, preferably LF- t PS ô-t X, in which X denotes Cl, Br or I and t varies from 0 to 2, more preferentially LhPS X, in which X denotes Cl, Br or I, even more preferentially LhPS Cl.
• the agent comprising at least sulfur is chosen from P2S5, L14P2S6, Ss, L13PS4, L14P2S7 and their mixtures, preferably from P2S5, L14P2S7 and their mixture.
• the content of agent comprising at least sulfur ranges from 1 to 30% by weight, preferably from 5 to 15% by weight, more preferably from 8 to 12% by weight relative to the total weight of the mixture comprising the electrolyte solid chosen from sulphides and the agent comprising at least sulphur.
• step b) of the process according to the invention the mixture obtained at the end of step a) is added to an organic solvent.
• the organic solvent is chosen from alcoholic solvents, ethers such as tetrahydrofuran (THF), aromatic solvents such as toluene, and nitriles such as acetonitrile.
• the organic solvent is chosen from alcoholic solvents, more preferably ethanol.
• the method according to the invention may also comprise a step d) drying the solid electrolyte obtained at the end of step c) at a temperature ranging from 40 to 550° C., preferably from 40 to 150 °C.
• the invention also relates to a process for preparing a battery cell comprising a negative electrode, a positive electrode and a separator comprising the following steps:
• the coatings are dried at a temperature ranging from 40 to
• a diffractogram of the material in the initial state is produced, as shown in Figure 1 (material la).
• the characteristic peaks of argyrodite can be identified on this diffractogram.
• the argyrodite is added in ethanol, then dried at 40°C, to obtain the material lb.
• a diffractogram of material lb is then produced, as shown in Figure 1.
• the argyrodite is added in ethanol, then dried at 100°C, to obtain the material le.
• a diffractogram of the material is then produced, as shown in Figure 1. It clearly appears again that the structure of argyrodite was destroyed after dissolution in ethanol.
• Example 1 shows that such a material is not stable in an organic solvent. It cannot therefore be used in electrode coating processes when preparing a battery cell, in particular an all-solid-state battery cell. Indeed, a process for coating an electrode necessarily involves a step of dissolving it in an organic solvent.
• a diffractogram of the mixture of materials is produced, as shown in Figure 2 (material 2a).
• the mixture is added in ethanol, then dried at 40°C, to obtain material 2b.
• a diffractogram of material 2b is then produced, as shown in Figure 2.
• the mixture is added in ethanol, then dried at 100°C, to obtain material 2c.
• a diffractogram of material 2c is then produced, as shown in Figure 2.
• Example 2 clearly shows a beneficial effect of the presence of the material of formula P2S5 on the chemical stability of argyrodite.
• Argyrodite thanks to the presence of the material of formula P2S5, is chemically stable in an organic solvent. It can therefore be used in processes for coating electrodes during the preparation of a battery cell, in particular an all-solid battery cell.
• the mixture is added in ethanol, then dried at 40°C, to obtain material 3b.
• a diffractogram of material 3b is then produced, as shown in Figure 3.
• the mixture is added in ethanol, then dried at 100°C, to obtain material 3c.
• a diffratogram of material 3c is then produced, as shown in Figure 3.
• Example 3 clearly shows a beneficial effect of the presence of the material of formula L1 4 P 2 S 7 on the chemical stability of argyrodite.
• Argyrodite thanks to the presence of the material of formula L1 4 P 2 S 7, is chemically stable in an organic solvent. It can therefore be used in processes for coating electrodes during the preparation of a battery cell, in particular an all-solid battery cell. Ionic conductivity
• the ionic conductivity at 25°C was measured for each of the materials 1a to 3c.
• the set of measurements of the ionic conductivities can be found in figure 4.
• the ionic conductivity of material 3b is much higher than that of material 1b.
• the ionic conductivity of material 3c is much higher than that of material 1e.

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• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Inorganic Chemistry (AREA)
• Organic Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Physics & Mathematics (AREA)
• Secondary Cells (AREA)
• Conductive Materials (AREA)
• Battery Electrode And Active Subsutance (AREA)
• Primary Cells (AREA)

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• 2021
  • 2021-06-15 FR FR2106345A patent/FR3124027B1/fr active Active
• 2022
  • 2022-06-13 KR KR1020247001599A patent/KR20240024184A/ko unknown
  • 2022-06-13 US US18/570,396 patent/US20240234943A1/en active Pending
  • 2022-06-13 JP JP2023577666A patent/JP2024523365A/ja active Pending
  • 2022-06-13 EP EP22732269.0A patent/EP4356452A1/de active Pending
  • 2022-06-13 WO PCT/EP2022/065955 patent/WO2022263344A1/fr active Application Filing
  • 2022-06-13 CN CN202280042553.6A patent/CN118077065A/zh active Pending

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