Classifications

• • 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
• • 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
  • 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
  • H01M10/056—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
  • 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 the field of batteries, and in particular solid electrolyte batteries, of the sulphide type.
• the solid sulphide electrolytes reach sufficient maturity to consider their industrial use. Their high values of ionic conductivity associated with their ductility and limited density make them serious candidates for the first generations of all-solid-state batteries that can compete with the energy densities of current Li-ion batteries with liquid electrolytes.
• the oxides for their part, are generally more stable (electrochemically and chemically) but have lower ionic conductivities and require heat treatments at high temperature (> 700 ° C) which are not suitable for industrial application.
• high temperature > 700 ° C
• their higher density and poor ductility limit the energy densities that can be achieved when in use.
• the present invention relates to a compound of formula
• the presence of oxide makes it possible to increase the stability of the sulphide electrolytes, to reduce the risks associated with their use while maintaining their electrochemical performance:
• the compounds of formula (I) allow the conduction of alkaline ions (especially lithium).
• the compounds of formula (I) thus make it possible to simplify the use of inorganic sulphide-based electrolytes and to accelerate the progress of all-solid technologies thanks to industrialization with limited risks in terms of safety.
• the compound of formula (I) is represented by formula (G):
• Li 3 (PS 4 ) i- x (OCI) x (I ') x being defined as above.
• x is preferably between 0.02 and 0.20.
• the inventors have demonstrated a synergistic effect for the mixed electrolytes according to the invention for values of x less than 0.2: for these values, the electrolyte causes a release of hhS lower than that of a mixed electrolyte with a higher amount of U 3 OCI (x greater than 0.2), whereas a lower release could be expected due to a lower amount of sulphide in the mixture.
• the present application also relates to the process for preparing the compounds of Formula (I) according to the invention, said process comprising the step of co-grinding the precursors of the compound of formula (I).
• said precursors can be chosen from the compounds of formula:
• A, B, Xi are defined as in formula (I).
• this co-grinding step is carried out by mixing said precursors in the desired proportions, typically, in the proportions respecting the molar ratios required by formula (I).
• the co-grinding can be carried out at room temperature.
• the co-grinding can be carried out by means of a ball mill (bail milling).
• the co-grinding can be carried out by a grinder marketed by Fritsch (Fritsch 7), with balls of diameter between 0.1 and 15 mm, in bowls of 10 to 50 ml, for cycles of a duration of between 1 min and 2 hours for a total duration of between 5 and 100 h, at a speed of between 100 and 1000 rpm.
• the particle size of the mixture after co-grinding is less than 10 ⁇ m, in particular less than 1 ⁇ m.
• the precursors A 2 0, BO, A 2 S, LiXi, LiX 2 , P 2 S 5 , AOFI are commercially available, for example, these materials are available from Aldrich or Alfa Aesar.
• the precursors are in crystalline form.
• the compounds of formula (I) obtained by the process according to the invention are of amorphous structure.
• the process for preparing compound (I') comprises the step of co-grinding the precursors Li 2 0, LiCl, Li 2 S and P 2 S 5 .
• some of these precursors can first be in the form of a mixture.
• compositions (II) and (III) are mixed for co-grinding in the proportions:
• the synthesis process according to the invention does not include high temperature annealing, unlike most oxides. It is therefore favorable to large-scale production of these materials.
• the present invention also relates to an electrolyte for a battery comprising a compound of formula (I) according to the invention.
• said electrolyte is of the solid type.
• said electrolyte is suitable for “all solid” type batteries.
• the present invention also relates to an electrochemical element comprising an electrolyte according to the invention.
• the electrochemical element according to the invention is particularly suitable for lithium accumulators, such as Li-ion, primary Li (non-rechargeable) and Li-S accumulators as well as their equivalents with other alkaline elements (Na-ion, K- ion, ...) for the corresponding formulations.
• lithium accumulators such as Li-ion, primary Li (non-rechargeable) and Li-S accumulators as well as their equivalents with other alkaline elements (Na-ion, K- ion, ...) for the corresponding formulations.
• the present invention also relates to an electrochemical module comprising the stack of at least two elements according to the invention, each element being electrically connected with one or more other element (s).
• module therefore refers here to the assembly of several electrochemical elements.
• the present invention also relates to a battery comprising one or more modules according to the invention.
• battery or "accumulator” is therefore understood here to mean the assembly of several modules, said assemblies may be in series and / or parallel.
• the invention preferably relates to accumulators whose capacity is greater than 100 mAh, typically 1 to 100Ah.
• FIG 1 shows the X-ray diffraction spectra of Li 3 (PS4) i- x (OCI) x compounds as a function of x during 29 hour ball mill grinding; the wavelength used is that of the Ka line of copper (1.5406 Angstrom).
• Figure 2 shows the X-ray diffraction spectrum of the compound Li 3 (PS4) o.884 (OCI) o.ii6 as a function of time for samples ground by a ball mill; the wavelength used is that of the Ka line of copper (1.5406 Angstrom).
• Figure 3 illustrates the comparison of the release of FI 2 S for a sample of sulfide electrolyte alone (amorphous LPS) and Li 3 (PS4) i- x (OCI) x compounds.
• Example 1 Preparation of a composite in the Li-PSO-CI system from Li2S-P2S5-Li 2 O-LiCI.
• the compounds Li 3 (PS4) i- x (OCI) x were prepared from the precursors Li 2 0, LiCl, Li 2 S and P 2 S 5 . The masses of precursors are calculated to obtain the desired stoichiometry.
• Table 1 indicates the masses of the various precursors for the production of the compounds Li 3 (PS4) i- x (OCI) x for the various values of x
• the mixtures are carried out by ball milling (bail milling, Fritsh 7) in 25 mL Zr0 2 bowls with 4 10 mm diameter balls. These bowls are rotated at 500 rpm for several cycles of 30 min. The powder inside the bowls is peeled from the walls every 5 hours in order to homogenize the sample.
• H 2 S To measure the release of H 2 S, 25 mg of powder are introduced at the initial time into a 2.5L container which can be hermetically closed and in which an H 2 S detector is placed (precision of 1 ppm ).
• the container contains ambient air at atmospheric pressure and ambient temperature in order to assess the risk associated with the release of H 2 S under conditions standard in which the materials could be found.
• the level of H 2 S in the chamber is recorded at regular time intervals as soon as the sample is introduced.
• Example 3 Measurement of conductivity
• the main function of the electrolyte being the conduction of ions, measurements of ionic conductivity were carried out to verify its evolution as a function of the compositions studied.
• the powder obtained from the synthesis is introduced into a cell similar to a pelletizing mold, the pistons of which are made of stainless steel and the body of an insulating material.
• a pressure of 2 t / cm 2 is maintained on the cell during the conductivity measurement.
• This measurement is made by impedance (1 MHz to 200 mHz), at several temperature values from 20 ° C to 60 ° C.
• the resistance value R resulting from this measurement allows us to calculate the value of the conductivity s via the relation [Math 1]
• the thickness e of the compressed pellet is measured with a micrometer (precision: 1 ⁇ m) and the area S is that of the cell used.

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

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• 2020
  • 2020-03-26 FR FR2002987A patent/FR3108790B1/fr active Active
• 2021
  • 2021-03-23 US US17/914,394 patent/US20230116369A1/en active Pending
  • 2021-03-23 EP EP21712877.6A patent/EP4128415A1/de active Pending
  • 2021-03-23 WO PCT/EP2021/057459 patent/WO2021191217A1/fr unknown
  • 2021-03-23 CN CN202180024712.5A patent/CN115699389A/zh active Pending

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