EP4677663A1 - Method for manufacturing a lgps-type solid sulfide electrolyte - Google Patents

Method for manufacturing a lgps-type solid sulfide electrolyte

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Publication number
EP4677663A1
EP4677663A1 EP24709070.7A EP24709070A EP4677663A1 EP 4677663 A1 EP4677663 A1 EP 4677663A1 EP 24709070 A EP24709070 A EP 24709070A EP 4677663 A1 EP4677663 A1 EP 4677663A1
Authority
EP
European Patent Office
Prior art keywords
solid
temperature
electrolyte
manufacturing
sulfide electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24709070.7A
Other languages
German (de)
French (fr)
Inventor
Enora LAVANANT
Vasily TARNOPOLSKIY
Dan BABINDAMANA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore NV SA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Umicore NV SA
Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Umicore NV SA, Commissariat a lEnergie Atomique CEA, Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Umicore NV SA
Publication of EP4677663A1 publication Critical patent/EP4677663A1/en
Pending legal-status Critical Current

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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
    • H01M10/056—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/188—Processes of manufacture
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • C01P2006/80—Compositional purity
    • 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

  • This invention relates to a method for manufacturing a solid sulfide electrolyte and the solid sulfide electrolyte obtainable from said method.
  • electrolytes conventionally used in lithium secondary batteries are liquid electrolytes such as organic solvents. Accordingly, safety problems such as leakage of electrolytes and risk of fire may continuously occur.
  • solid state batteries including solid electrolytes, rather than liquid electrolytes, are being developed to improve the safety feature of the lithium secondary battery and have attracted much attention.
  • solid electrolytes are typically safer than liquid electrolytes due to non-combustible or flame retardant properties.
  • Solid electrolytes may include oxide-based solid electrolytes, polymer-based electrolytes and sulfide-based electrolytes.
  • Sulfide-based electrolytes have been generally used due to their higher lithium ionic conductivity range compared to oxidebased and polymer-based solid electrolytes, such as sulfide-based solid electrolytes having an argyrodite-type crystal structure or an LGPS-type crystal structure.
  • an object of the present invention is achieved by providing a method for manufacturing a solid sulfide electrolyte represented by formula (I)
  • the present inventors have surprisingly found that by heat-treating of the mixed set of precursors at this high temperature and high pressure the solid sulfide electrolyte is obtained in high purity and in a short reaction time, as demonstrated in the appended examples.
  • a classical calcination step without applying the high pressure does not result in the formation of the solid sulfide electrolyte represented by formula (I).
  • the invention provides the solid sulfide electrolyte obtainable by the method according to the invention.
  • the invention provides the battery comprising the solid sulfide electrolyte obtainable by the method according to the invention. In a further aspect the invention provides an use of the solid electrolyte according to the invention in a battery.
  • Figure 1 X-ray diffraction pattern of the conventional heat-treated ball-milled powder in a Beryllium-capped tightcell.
  • Figure 2 X-ray diffraction pattern of the conventional heat-treated and quenched ball-milled powder in a Beryllium-capped tightcell.
  • Figure 3 X-ray diffraction pattern of the hot-pressed ball-milled powder in a Beryllium-capped tightcell.
  • compositions comprising components A and B
  • the scope of the expression "a composition comprising components A and B” should not be limited to compositions consisting only of components A and B. It means that with respect to the present invention, the only relevant components of the composition are A and B. Accordingly, the terms “comprising” and “including” encompass the more restrictive terms “consisting essentially of” and “consisting of”.
  • solid-state battery refers to a cell or battery that includes only solid or substantially solid-state components such as solid electrodes (e.g. anode and cathode) and solid electrolyte.
  • X-ray diffraction refers to XRD experiments performed using Bruker D8 diffractometers equipped with either Cu (Kai-Kaz) or Mo (Kai-Kaz) radiation in a 0-0 configuration.
  • XRD X-ray diffraction
  • an air-tight sample holder with a Be window was used for the measurements.
  • the invention provides a method for manufacturing a solid sulfide electrolyte comprising the following steps: i) providing a set of precursors comprising Li, X, P and S; and ii) mixing of the set of precursors to obtain a solid electrolyte mixture; and iii) heat-treating of the solid electrolyte mixture at temperature of at least 100 °C and a pressure of at least 1 MPa, preferably between 1 and 1000 MPa, to obtain a solid sulfide electrolyte; wherein the solid sulfide electrolyte is represented by formula (I)
  • the set of precursors may comprise a liquid or is essentially free of any liquid, preferably the set of precursors is essentially free of any liquid.
  • the term "essentially free of liquid” means that the set of precursors comprises less than 10 wt.% of a liquid by total weight of the set of precursors, preferably less than 7.5 wt.%, more preferably less than 5 wt.%, even more preferably less than 2.5 wt.%, most preferably less than 1 wt.% by total weight of the set of precursors.
  • the set of precursors comprises less than 1000 ppm of a liquid by total weight of the set of precursors, preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm, most preferably less than 10 ppm by total weight of the set of precursors.
  • a liquid shall be considered to be an organic or aqueous compound which is liquid in standard conditions for temperature and pressure as defined by the IUPAC.
  • the boiling point and the melting point shall be considered to be the boiling point and the melting point at standard atmospheric pressure, i.e. at 101325 Pa.
  • the presence of the organic liquid can be determined via thermogravimetric analysis (TGA) or nuclear magnetic resonance (NMR.) spectroscopy and the presence of the aqueous liquid can be determined via Karl Fisher titration.
  • solid electrolyte mixture refers to an electrolyte mixture being essentially free of any liquid.
  • essentially free of liquid means that the solid electrolyte mixture comprises less than 10 wt.% of a liquid by total weight of the solid electrolyte mixture, preferably less than 7.5 wt.%, more preferably less than 5 wt.%, even more preferably less than 2.5 wt.%, most preferably less than 1 wt.% by total weight of solid electrolyte mixture.
  • the solid electrolyte mixture comprises less than 1000 ppm of a liquid by total weight of the solid electrolyte mixture, preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm, most preferably less than 10 ppm by total weight of the solid electrolyte mixture.
  • solid electrolyte refers to an electrolyte being essentially free of any liquid.
  • essentially free of liquid means that the solid electrolyte comprises less than 10 wt.% of a liquid by total weight of the solid electrolyte, preferably less than 7.5 wt.%, more preferably less than 5 wt.%, even more preferably less than 2.5 wt.%, most preferably less than 1 wt.% by total weight of the solid electrolyte.
  • the solid electrolyte comprises less than 1000 ppm of a liquid by total weight of the solid electrolyte, preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm, most preferably less than 10 ppm by total weight of the solid electrolyte.
  • a more preferred embodiment is the method according to the invention, wherein the X-containing compound is elemental X or XS2, preferably XS2.
  • a highly preferred embodiment is the method according the invention, wherein the set of precursors comprises lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and XS2, preferably lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and SiS2.
  • the set of precursors comprises lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and XS2, preferably lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and SiS2.
  • a highly preferred embodiments is the method according the invention, wherein the set of precursors consists of lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and a X-containing compound, preferably the set of precursors consists of lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and XS2, more preferably the set of precursors consists of lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and SiS2 .
  • the set of precursors consists of lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and a X-containing compound
  • the set of precursors consists of lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and XS2 .
  • the solid sulfide electrolyte is provided, wherein at least 50 mol% of X represents Si, preferably at least 80 mol% of X represents Si, most preferably X represents Si.
  • the solid sulfide electrolyte is provided, wherein X represents Si, Ge, Sn or a combination thereof and wherein at least 50 mol% of X represents Si, preferably at least 80 mol% of X represents Si.
  • the solid sulfide electrolyte is provided, wherein at least 50 mol% of X represents Ge, preferably at least 80 mol% of X represents Ge, most preferably X represents Ge.
  • the solid sulfide electrolyte is provided, wherein X represents Si, Ge, Sn or a combination thereof and wherein at least 50 mol% of X represents Ge, preferably at least 80 mol% of X represents Ge.
  • the solid sulfide electrolyte is provided, wherein at least 50 mol% of X represents Sn, preferably at least 80 mol% of X represents Sn, most preferably X represents Sn.
  • the solid sulfide electrolyte is provided, wherein X represents Si, Ge, Sn or a combination thereof and wherein at least 50 mol% of X represents Sn, preferably at least 80 mol% of X represents Sn.
  • a preferred embodiment is the method according to the invention, wherein 0 ⁇ y ⁇ 1, preferably 0.05 ⁇ y ⁇ 0.95, more preferably 0.1 ⁇ y ⁇ 0.9, even more preferably 0.2 ⁇ y ⁇ 0.85, even more preferably 0.25 ⁇ y ⁇ 0.8, even more preferably 0.3 ⁇ y ⁇ 0.75, most preferably 0.6 ⁇ y ⁇ 0.7.
  • y is about 0.65.
  • a preferred embodiment is the method according to the invention, wherein the solid sulfide electrolyte is represented by formula (II)
  • a preferred embodiment is the method according to the invention, wherein the solid sulfide electrolyte is represented by formula (III)
  • a preferred embodiment is the method according to the invention, wherein the molar ratios of of Li:X:P:S are between (10-ll):(l-2):(l-2):(ll-13), preferably between (10.2-10.7):(l.l-1.9):(l.l-1.9):(11.5-12.5), more preferably between (10.3-10.4):(1.3-1.4):(1.6-1.7):(11.9-12.1), most preferably about
  • a preferred embodiment is the method according to the invention by mixing the set of precursors with a mixing speed between 1 and 1500 rpm, more preferably between 100 and 1000 rpm, most preferably between 300 and 750 rpm.
  • a preferred embodiment is the method according to the invention, wherein the mixing occurs at a mixing time of at least 1 min, preferably at least 30 minutes, more preferably at least 1 hour, even more preferably at least 2 hours, even more preferably at least 5 hours, most preferably at least 10 hours.
  • a preferred embodiment is the method according to the invention, wherein the mixing occurs at a mixing time of less than 72 hours, preferably less than 60 hours, more preferably less than 50 hours, even more preferably less than 36 hours, even more preferably less than 30 hours, most preferably less than 20 hours.
  • a preferred embodiment is the method according to the invention by mixing of the solid electrolyte precursor wherein the mixing of the set of precursors occurs at a mixing time between 1 hour and 72 hours, preferably between 2 hours and 50 hours, more preferably between 5 hours and 20 hours.
  • a mixing speed between 1 and 1500 rpm, preferably between 100 and 1000 rpm, more preferably between 300 and 750 rpm;
  • - a mixing time between 1 hour and 72 hours, preferably between 2 hours and 50 hours, more preferably between 5 hours and 20 hours.
  • a preferred embodiment is the method according the invention, wherein the mixing of the set of precursors occurs a temperature of at least 5 °C, preferably at least 10 °C, more preferably at least 15 °C.
  • a preferred embodiment is the method according to the invention, wherein the mixing occurs at a temperature of less than 50 °C, preferably less than 40 °C, more preferably less than 30 °C.
  • a preferred embodiment is the method according to the invention, wherein the mixing occurs at a temperature between 5 and 50 °C, preferably a temperature between 10 and 40 °C, more preferably a temperature between 15 and 30 °C.
  • the mixing of the set of precursors is the same as milling, mechanical milling, ball-milling, pulverization, grinding or dry-grinding of the set of precursors.
  • a preferred embodiment is the method according to the invention, wherein the mixing of the set of precursors is carried out by using a mixing means, wherein mechanical stress is applied to the set of precursors to form the solid electrolyte mixture.
  • applying mechanical stress refers to mechanically apply shear stress, impact force or the like.
  • the mixing means include a pulverizer such as a planetary ball mill, a vibration mill and a rolling mill; and a kneader; or the like.
  • An example of a suitable mixing means, but not limiting to the invention, is a planetary ball mill Retsch PM 100.
  • the mixing of the set of precursors is carried out by adding one or more ceramic or zirconia balls, preferably zirconia balls, to the set of precursors to obtain the solid electrolyte mixture.
  • the amount and size of the ceramic or zircona balls is changed in view of the total solid amount of the solid electrolyte precursor mixture.
  • 16 zirconia balls of 20 mm diameter can be used with a balkpowder ratio of 30: 1 (g/g).
  • these ceramic or zirconia balls are removed from the solid electrolyte mixture before heat-treating the solid electrolyte mixture.
  • the mixing of the set of precursors is carried out by dry-mixing of the set of precursors, i.e. dry-mixing means that no additional liquid is added to the set of precursors to obtain the solid electrolyte mixture.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a temperature of at least 100 °C, preferably at least 200 °C, more preferably at least 300 °C, more preferably at least 400 °C, even more preferably at least 450 °C, most preferably at least 500 °C.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a temperature of less than 1000 °C, preferably less than 900 °C, more preferably less than 800 °C, even more preferably less than 700 °C, even more preferably less than 650 °C, most preferably less than 600 °C.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a temperature between 100 and 1000 °C, preferably between 300 and 700 °C, more preferably between 450 and 650 °C. In highly preferred embodiments the heat-treating occurs at a temperature between 500 and 600 °C, preferably at a temperature between 525 and 575 °C, most preferably about 550 °C.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating occurs under an inert atmosphere, preferably an argon atmosphere, or under an atmosphere comprising a hydrogen sulfide gas, preferably an atmosphere consisting of a hydrogen sulfide gas.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a pressure of at least 1 MPa, preferably at least 50 MPa, more preferably at least 100 MPa, even more preferably at least 175 MPa, most preferably at least 250 MPa.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a pressure of less than 1000 MPa, preferably less than 850 MPa, more preferably less than 700 MPa, even more preferably less than 600 MPa, most preferably less than 500 MPa.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
  • the heat- treating occurs at a pressure between 325 and 390 MPa, preferably at a pressure between 350 and 380 MPa, most preferably about 375 MPa.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating is at least 1 min, preferably at least 30 minutes, more preferably at least 1 hour, even more preferably at least 1.5 hours, most preferably at least 2 hours.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture is less than 48 hours, preferably less than 24 hours, more preferably less than 18 hours, even more preferably less than 10 hours, most preferably less than 5 hours.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating is between 0.5 hour and 24 hours, preferably between 1 hours and 12 hours, more preferably between 1.5 hours and 5 hours.
  • a preferred embodiment is the method according to the invention, wherein
  • the heat-treating occurs at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C;
  • the heat-treating occurs at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
  • a highly preferred embodiment is the method according to the invention, wherein
  • the heat-treating occurs at a temperature between 500 and 600 °C, preferably at a temperature between 525 and 575 °C, most preferably about 550 °C;
  • the heat-treating occurs at a pressure between 300 and 400 MPa, preferably at a pressure between 350 and 390 MPa, most preferably about 375 MPa.
  • the heat-treating of the solid electrolyte mixture at the defined temperature and at the defined pressure is called hot-pressing of the solid electrolyte mixture thereby affording the solid sulfide electrolyte represented by formula (I), preferably the solid sulfide electrolyte represented by formula (II), most preferably the solid sulfide electrolyte represented by formula (III).
  • the heat-treating of the solid electrolyte mixture at the defined temperature and at the defined pressure occurs through simultaneous application of the defined heat and defined pressure.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture is carried by a means for applying heat and pressure, for example by hot pressing and/or spark plasma sintering, preferably hot pressing.
  • a means for applying heat and pressure for example by hot pressing and/or spark plasma sintering, preferably hot pressing.
  • a suitable example of a means for applying heat and pressure is a hot press, for example a Fontijne hot pressing equipment.
  • the solid electrolyte mixture obtained in step ii) is placed in mold, preferably a tungsten carbide mold, which is placed in the means for applying heat and pressure, preferably the hot press.
  • the means for applying heat and pressure is then placed under vacuum, preferably below 1 bar, more preferably below 0.5 bar, most preferably below 0.2 bar, such as about 0.1 bar.
  • the heat-treating step as defined in the present invention is then applied to the mold comprising the solid electrolyte mixture obtained in step ii).
  • a preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture of step iii) comprises two steps: iii-a) raising the temperature of the solid electrolyte mixture to a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C at a heating rate of at least 10 °C / minute, preferably at least 15 °C / minute, more preferably at least 18 °C / minute; and iii-b) heat-treating the solid electrolyte mixture at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture of step iii) comprises two steps: iii-a) raising the temperature of the solid electrolyte mixture to a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C at a heating rate of at most 50 °C / minute, preferably at most 30 °C / minute, more preferably at most 25 °C / minute; and iii-b) heat-treating the solid electrolyte mixture at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
  • a preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture of step iii) comprises two steps: iii-a) raising the temperature of the solid electrolyte mixture to a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C at a heating rate between 10 and 50 °C I minute, preferably between 15 and 30 °C / minute, more preferably between 18 and 25 °C / minute; and iii-b) heat-treating the solid electrolyte mixture at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
  • a highly preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture of step iii) comprises two steps: iii-a) raising the temperature of the solid electrolyte mixture to a temperature between 500 and 600 °C, preferably a temperature between 525 and 575 °C, more preferably about 550 °C at a heating rate of 10-50 °C / minute, preferably of 15-30 °C / minute, more preferably about 18 - 25 °C / minute; iii-b) the heat-treating occurs at a temperature between 500 and 600 °C, preferably at a temperature between 525 and 575 °C, most preferably about 550 °C; and a pressure between 300 and 400 MPa, preferably at a pressure between 350 and 390 MPa, most preferably about 375 MPa.
  • the present inventors believe that by applying the heating rate as defined above the solid sulfide electrolyte is obtained in high purity.
  • a preferred embodiment is the method according to the invention, wherein - the heat-treating occurs at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and
  • the heat-treating is between 0.5 hour and 24 hours, preferably between 1 hour and 12 hours, more preferably between 1.5 hour and 5 hours.
  • a preferred embodiment is the method according to the invention, wherein
  • the heat-treating occurs at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa;
  • the heat-treating is between 0.5 hour and 24 hours, preferably between 1 hour and 12 hours, more preferably between 1.5 hour and 5 hours.
  • a preferred embodiment is the method according to the invention, wherein
  • the heat-treating occurs at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C;
  • the heat-treating occurs at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa;
  • the heat-treating is between 0.5 hour and 24 hours, preferably between 1 hour and 12 hours, more preferably between 1.5 hour and 5 hours.
  • the method of the invention comprises a further step iv), wherein the sulfide solid electrolyte is cooled to a temperature between 10 and 40 °C, preferably a temperature between 10 and 30 °C, more preferably a temperature between 15 and 25 °C, by applying a cooling rate of at least 10 °C / minute, preferably at least 15 °C / minute, more preferably at least 18 °C/ minute.
  • the sulfide solid electrolyte is cooled to a temperature between 10 and 40 °C, preferably a temperature between 10 and 30 °C, more preferably a temperature between 15 and 25 °C, by applying a cooling rate of at most 50 °C / minute, preferably at most 40 °C / minute, more preferably at most 30 °C / minute.
  • the sulfide solid electrolyte is cooled to a temperature between 10 and 40 °C, preferably a temperature between 10 and 30 °C, more preferably a temperature between 15 and 25 °C, preferably by applying a cooling rate between 10 and 50 °C / minute, preferably between 15 and 30 °C / minute, more preferably between 18 and 25 °C / minute, most preferably about 20 °C / minute.
  • the sulfide solid electrolyte is cooled to room temperature as defined in above-mentioned ranges.
  • the method of the invention comprises the following steps: i) providing a set of precursors as defined above, ii) mixing of the set of precursors as defined above, iii) heat-treating of the solid electrolyte mixture as defined above, and iv) cooling the solid sulfide electrolyte obtained in step iii) to a temperature between 10 and 40 °C, preferably a temperature between 10 and 30 °C, more preferably a temperature between 15 and 25 °C, preferably by applying a cooling rate between 10 and 50 °C / minute, preferably between 15 and 30 °C / minute, more preferably between 18 and 25 °C / minute, most preferably about 20 °C / minute.
  • the present inventors believe that by applying the cooling rate as defined above the solid sulfide electrolyte is obtained in high purity.
  • the method of the invention comprises the following steps: i) providing a set of precursors as defined above, ii) mixing of the set of precursors as defined above, iii) heat-treating of the solid electrolyte mixture as defined above, preferably raising the temperate as defined in step iii-a) above followed by heat treating as defined in step iii-b) above; and iv) cooling the solid sulfide electrolyte and defined above
  • formula (I) the peak intensities of U2S, P2S5, XS2, and/or U3PS4 are less than 30% of the peak intensities of the solid sulfide electrolyte represented by formula (I), preferably the solid sul
  • the solid sulfide electrolyte has a purity of at least 70% as determined by XRD, preferably a purity of at least 75%, more preferably a purity of at least 80%, even more preferably a purity of at least 90%, most preferably a purity of at least 95%, as determined by XRD.
  • a second aspect of the invention provides a solid sulfide electrolyte obtainable by the method according to the invention.
  • a more preferred embodiment is the solid sulfide electrolyte obtainable by the method according to the invention, wherein the solid sulfide electrolyte is represented by formula (I)
  • y is about 0.65; and wherein X is Si, Ge, Sn or a combination thereof, preferably X is Si.
  • a highly preferred embodiment is the solid sulfide electrolyte obtainable by the method according to the invention, wherein the solid sulfide electrolyte obtainable by the method according to the invention is represented by formula (II)
  • a highly preferred embodiment is solid sulfide electrolyte obtainable by the method according to the invention, wherein the solid sulfide electrolyte obtainable by the method according to the invention is represented by formula (III)
  • the solid sulfide electrolyte according to the invention has a purity of at least 70% as determined by XRD, preferably a purity of at least 75%, more preferably a purity of at least 80%, even more preferably a purity of at least 90%, most preferably a purity of at least 95%, as determined by XRD.
  • a third aspect of the invention is providing a solid sulfide electrolyte represented by formula (I)
  • y is about 0.65; and wherein X is Si, Ge, Sn or a combination thereof, preferably X is Si.
  • a highly preferred embodiment is the solid sulfide electrolyte according to the third aspect of the invention, wherein the solid sulfide electrolyte is represented by formula (II) Li 10.35X1.35P1.65S12 (II).
  • a highly preferred embodiment is the solid sulfide electrolyte according to the third aspect of the invention, wherein the solid sulfide electrolyte is represented by formula (III)
  • the solid sulfide electrolyte according to the invention has a purity of at least 70% as determined by XRD, preferably a purity of at least 75%, more preferably a purity of at least 80%, even more preferably a purity of at least 90%, most preferably a purity of at least 95%, as determined by XRD.
  • a fourth aspect of the invention concerns a battery comprising a negative electrode, a positive electrode and a solid electrolyte layer, wherein at least one of the negative electrode, the positive electrode and the solid electrolyte layer comprises the solid sulfide electrolyte according to the invention, such as the solid sulfide electrolyte according to the second aspect of the invention and/or the solid sulfide electrolyte according to the third aspect of the invention.
  • the present solid sulfide electrolyte of the invention can be used as a solid electrolyte layer of a solid lithium ion battery or a solid lithium primary cell, or as a solid electrolyte that is mixed with an electrode mixture for a positive electrode or a negative electrode.
  • the battery is a solid-state battery, preferably a lithium solid-state battery.
  • a fifth aspect of the invention concerns a use of the solid sulfide electrolyte according to the invention, such as the solid sulfide electrolyte such as the solid sulfide electrolyte according to the second aspect of the invention and/or the solid sulfide electrolyte according to the third aspect of the invention, in a battery, preferably a solid-state-battery, more preferably a lithium solid-state-battery.
  • a sixth aspect of the present invention concerns a use of the battery according to invention in either one of a portable computer, a tablet, a mobile phone, an energy storage system, an electric vehicle or in a hybrid electric vehicle, preferably in an electric vehicle or in a hybrid electric vehicle.
  • the precursors were initially milled at 100 rpm for 60 minutes to homogenize the mixture followed by ball milling at 550 rpm for a total duration of 12 hours. Each cycle constituted in 5-minute milling and 5-minute rest. The ball-milled powder was then submitted to the three different heat treatments.
  • the ball-milled powder was uniaxially pressed into a 13 mm pellet and placed in dried quartz tubes which were then closed under Ar and placed in a furnace (Nabertherm) for annealing.
  • the temperature of the furnace was slowly increased to 550-600 °C at a ramp rate of 5 °C/min, held for 6 to 72 hours, and naturally cooled to room temperature.
  • the reacted pellets were then pulverized using a pestle and mortar and subjected to XR.D analysis (see Figure 1).
  • the ball-milled powder was uniaxially pressed into a 13 mm pellet and placed in dried quartz tubes which were then closed under Ar and placed in a furnace (Nabertherm) for annealing.
  • the temperature of the furnace was slowly increased to 575 °C at a ramp rate of 5 °C/min, held for 6 hours, and quenched to room temperature (25 °C) by removing the quartz tube from the oven.
  • the ball-milled powder was uniaxially pressed into a 26 mm pellet in WC (tungsten carbide) mold and the mold was placed in a hot pressing equipment (Fontijne), which was placed under vacuum (0.1 bar).
  • the temperature was increased to 550 °C at a ramp rate of 20 °C/min with a pressure of 375 MPa, held for 3 hours, and cooled to room temperature at a ramp rate of 20°C/min.
  • the reacted pellets were then pulverized using a pestle and mortar and subjected to XR.D analysis (see Figure 3) : a pure Liio.ssSii.ssPi.esSiz phase is obtained without any side products such as U3PS4.

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Abstract

The present invention relates to a method for manufacturing a LGPS-type solid sulfide electrolyte. The present inventors have surprisingly found that by heat-treating of the mixed set of precursors at this high temperature and high pressure the solid sulfide electrolyte is obtained in high purity and in a short reaction time.

Description

Method for manufacturing a LGPS-type solid sulfide electrolyte
TECHNICAL FIELD AND BACKGROUND
This invention relates to a method for manufacturing a solid sulfide electrolyte and the solid sulfide electrolyte obtainable from said method.
As the development of small and lightweight electronic products, electronic devices, communication devices and the like has advanced rapidly and a need for electric vehicles has widely emerged with respect to environmental issues, there is a demand for improvement of performance of secondary batteries used as power sources for these products. Among these, a lithium secondary battery has come into the spotlight as a high-performance battery due to a high energy density and a high reference electrode potential.
However, electrolytes conventionally used in lithium secondary batteries are liquid electrolytes such as organic solvents. Accordingly, safety problems such as leakage of electrolytes and risk of fire may continuously occur.
Recently, solid state batteries including solid electrolytes, rather than liquid electrolytes, are being developed to improve the safety feature of the lithium secondary battery and have attracted much attention. For example, solid electrolytes are typically safer than liquid electrolytes due to non-combustible or flame retardant properties.
Solid electrolytes may include oxide-based solid electrolytes, polymer-based electrolytes and sulfide-based electrolytes. Sulfide-based electrolytes have been generally used due to their higher lithium ionic conductivity range compared to oxidebased and polymer-based solid electrolytes, such as sulfide-based solid electrolytes having an argyrodite-type crystal structure or an LGPS-type crystal structure.
Efforts have been made to manufacture solid sulfur electrolyte having a LGPS- type crystal structure. Whiteley et al (Journal of The Electrochemical Society 2014, 161, A1812-A1817) reports the synthesis of LiioSiPzSiz by ball milling a precursor mixture of U2S, P2S5 and SiS2 followed by pressing the ball-milled powder at 375 MPa and heat-treating this pressed powder at 550 °C for 8 hours. However, this synthesis protocol only affords a composition having a purity of 85% with 15% of Li3.2Sio.2Po.8S4 as side product. Hori et al (Acta Cryst. 2015, B71, 727-736) discloses the synthesis of Liio.35Sii.35Pi.65Si2 by ball milling U2S, P2S5 and SiS2, followed by pelletizing the samples and heating at 550 °C and 10 Pa for 72 h. However, obtaining these LGPS- type electrolytes in high purity and short reaction time remains an issue. Hence, there is therefore a need to provide a method for manufacturing a solid sulfur electrolyte having a LGPS-type crystal structure.
It is an object of the present invention to provide a method for manufacturing a LGPS-type solid sulfide electrolyte.
It is a further object of the present invention to provide the solid sulfide electrolyte obtainable from said method.
It is a further object of the present invention to provide a battery comprising said solid sulfide electrolyte.
SUMMARY OF THE INVENTION
In a first aspect an object of the present invention is achieved by providing a method for manufacturing a solid sulfide electrolyte represented by formula (I)
Li H-yX2-yPl+yS12 (I) wherein 0 < y < 2, preferably 0 < y < 1, and wherein X is Si, Ge, Sn or a combination thereof; by mixing and heat-treating a set of precursors at a temperature of at least 100 °C and a pressure of at least 1 MPa, preferably a pressure between 1 and 1000 Mpa.
The present inventors have surprisingly found that by heat-treating of the mixed set of precursors at this high temperature and high pressure the solid sulfide electrolyte is obtained in high purity and in a short reaction time, as demonstrated in the appended examples. In contrast, a classical calcination step without applying the high pressure does not result in the formation of the solid sulfide electrolyte represented by formula (I).
Without wishing to be bound by any theory, the present inventors believe that this method allows to obtain samples with a higher purity due to the fact that the combination of the high temperature and high pressure results in complete interdiffusion of atoms of precursors and less sulfur loss due to evaporation during the heat-treatment step.
In a further aspect the invention provides the solid sulfide electrolyte obtainable by the method according to the invention.
In a further aspect the invention provides the battery comprising the solid sulfide electrolyte obtainable by the method according to the invention. In a further aspect the invention provides an use of the solid electrolyte according to the invention in a battery.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 : X-ray diffraction pattern of the conventional heat-treated ball-milled powder in a Beryllium-capped tightcell.
Figure 2: X-ray diffraction pattern of the conventional heat-treated and quenched ball-milled powder in a Beryllium-capped tightcell.
Figure 3: X-ray diffraction pattern of the hot-pressed ball-milled powder in a Beryllium-capped tightcell.
DETAILED DESCRIPTION
In the drawings and the following detailed description, preferred embodiments are described in detail to enable practice of the invention. Although the invention is described with reference to these specific preferred embodiments, it will be understood that the invention is not limited to these preferred embodiments. In contrast, the invention includes numerous alternatives, modifications and equivalents as will become apparent from consideration of the following detailed description and accompanying drawings.
The term "comprising", as used herein and in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It needs to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression "a composition comprising components A and B" should not be limited to compositions consisting only of components A and B. It means that with respect to the present invention, the only relevant components of the composition are A and B. Accordingly, the terms "comprising" and "including" encompass the more restrictive terms "consisting essentially of" and "consisting of".
The term "solid-state battery" as used herein refers to a cell or battery that includes only solid or substantially solid-state components such as solid electrodes (e.g. anode and cathode) and solid electrolyte.
The term "LGPS-type crystal structure" as used herein refers to a tetragonal crystal structure comprising of negatively charged PS43- and XS44- tetrahedra, wherein X is Si, Ge or Sn, preferably Si. In some embodiments, preferably when X = Si, the LGPS-crystal structure has lattice parameters about a = 8.70 A and c = 12.60 A. In some embodiments the LGPS-type crystal structure may also be empirically determined, for example by X-ray diffraction by observing peaks around at 20 = 20.18±0.50 °, 20.44±0.50 °, 26.96±0.50 ° and 29.58±0.50 ° using CuKa-ray.
X-ray diffraction (XRD) as referred to herein, refers to XRD experiments performed using Bruker D8 diffractometers equipped with either Cu (Kai-Kaz) or Mo (Kai-Kaz) radiation in a 0-0 configuration. Preferably, an air-tight sample holder with a Be window was used for the measurements. Preferably, the patterns were collected between 20 = 10 ° - 50 ° with a step size of 0.02° at 25 °C.
Method for manufacturing
As discussed above in a first aspect the invention provides a method for manufacturing a solid sulfide electrolyte comprising the following steps: i) providing a set of precursors comprising Li, X, P and S; and ii) mixing of the set of precursors to obtain a solid electrolyte mixture; and iii) heat-treating of the solid electrolyte mixture at temperature of at least 100 °C and a pressure of at least 1 MPa, preferably between 1 and 1000 MPa, to obtain a solid sulfide electrolyte; wherein the solid sulfide electrolyte is represented by formula (I)
Li H-yX2-yPl+yS12 (I) wherein 0 < y < 2, preferably 0 < y < 1, and wherein X is Si, Ge, Sn or a combination thereof, preferably X is Si, Ge or Sn, preferably X is Si.
As appreciated by the skilled person the set of precursors may comprise a liquid or is essentially free of any liquid, preferably the set of precursors is essentially free of any liquid. The term "essentially free of liquid" means that the set of precursors comprises less than 10 wt.% of a liquid by total weight of the set of precursors, preferably less than 7.5 wt.%, more preferably less than 5 wt.%, even more preferably less than 2.5 wt.%, most preferably less than 1 wt.% by total weight of the set of precursors. In a more preferred embodiment the set of precursors comprises less than 1000 ppm of a liquid by total weight of the set of precursors, preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm, most preferably less than 10 ppm by total weight of the set of precursors.
In the context of the present invention a liquid shall be considered to be an organic or aqueous compound which is liquid in standard conditions for temperature and pressure as defined by the IUPAC. Hereby the boiling point and the melting point shall be considered to be the boiling point and the melting point at standard atmospheric pressure, i.e. at 101325 Pa. As appreciated by the skilled person the presence of the organic liquid can be determined via thermogravimetric analysis (TGA) or nuclear magnetic resonance (NMR.) spectroscopy and the presence of the aqueous liquid can be determined via Karl Fisher titration.
The term "solid electrolyte mixture" as used herein refers to an electrolyte mixture being essentially free of any liquid. The term "essentially free of liquid" means that the solid electrolyte mixture comprises less than 10 wt.% of a liquid by total weight of the solid electrolyte mixture, preferably less than 7.5 wt.%, more preferably less than 5 wt.%, even more preferably less than 2.5 wt.%, most preferably less than 1 wt.% by total weight of solid electrolyte mixture. In a more preferred embodiment the solid electrolyte mixture comprises less than 1000 ppm of a liquid by total weight of the solid electrolyte mixture, preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm, most preferably less than 10 ppm by total weight of the solid electrolyte mixture.
The term "solid electrolyte" as used herein refers to an electrolyte being essentially free of any liquid. The term "essentially free of liquid" means that the solid electrolyte comprises less than 10 wt.% of a liquid by total weight of the solid electrolyte, preferably less than 7.5 wt.%, more preferably less than 5 wt.%, even more preferably less than 2.5 wt.%, most preferably less than 1 wt.% by total weight of the solid electrolyte. In a more preferred embodiment the solid electrolyte comprises less than 1000 ppm of a liquid by total weight of the solid electrolyte, preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm, most preferably less than 10 ppm by total weight of the solid electrolyte.
A preferred embodiment is the method according the invention, wherein the set of precursors comprises one or more selected from the group consisting of metallic or elemental lithium, lithium sulfide (LizS), lithium oxide (U2O), lithium carbonate (U2CO3), lithium hydrosulfide (LiHS), lithium trithiocarbonate (U2CS3), lithium polysulfide (Li2Sx with x=2 to 100), phosphorus sulfide such as diphosphorus trisulfide (P2S3) and diphosphorus pentasultide (P2S5), sodium phosphate (NasPC ), PSZ3 with Z is an element selected from F, Cl, Br and I, a phosphorus elementary substance such as P4, lithium phosphorus sulfide (U3PS4), and a X-containing compound; preferably the set of precursors comprises one or more selected from the group consisting of lithium sulfide, phosphorus sulfide and a X-containing compound; more preferably the set of precursors comprises lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and a X-containing compound.
A more preferred embodiment is the method according to the invention, wherein the X-containing compound is elemental X or XS2, preferably XS2.
A highly preferred embodiment is the method according the invention, wherein the set of precursors comprises lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and XS2, preferably lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and SiS2.
A highly preferred embodiments is the method according the invention, wherein the set of precursors consists of lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and a X-containing compound, preferably the set of precursors consists of lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and XS2, more preferably the set of precursors consists of lithium sulfide (U2S), diphosphorus pentasultide (P2S5) and SiS2 .
In accordance with highly preferred embodiments of the invention, the solid sulfide electrolyte is provided, wherein at least 50 mol% of X represents Si, preferably at least 80 mol% of X represents Si, most preferably X represents Si.
In accordance with highly preferred embodiments of the invention, the solid sulfide electrolyte is provided, wherein X represents Si, Ge, Sn or a combination thereof and wherein at least 50 mol% of X represents Si, preferably at least 80 mol% of X represents Si.
In accordance with preferred embodiments of the invention, the solid sulfide electrolyte is provided, wherein at least 50 mol% of X represents Ge, preferably at least 80 mol% of X represents Ge, most preferably X represents Ge.
In accordance with preferred embodiments of the invention, the solid sulfide electrolyte is provided, wherein X represents Si, Ge, Sn or a combination thereof and wherein at least 50 mol% of X represents Ge, preferably at least 80 mol% of X represents Ge.
In accordance with preferred embodiments of the invention, the solid sulfide electrolyte is provided, wherein at least 50 mol% of X represents Sn, preferably at least 80 mol% of X represents Sn, most preferably X represents Sn. In accordance with preferred embodiments of the invention, the solid sulfide electrolyte is provided, wherein X represents Si, Ge, Sn or a combination thereof and wherein at least 50 mol% of X represents Sn, preferably at least 80 mol% of X represents Sn.
A highly preferred embodiment is the method according to the invention, wherein X = Si.
A preferred embodiment is the method according to the invention, wherein 0 < y < 1, preferably 0.05 < y < 0.95, more preferably 0.1 < y < 0.9, even more preferably 0.2 < y < 0.85, even more preferably 0.25 < y < 0.8, even more preferably 0.3 < y < 0.75, most preferably 0.6 < y < 0.7. In highly preferred embodiments y is about 0.65.
A preferred embodiment is the method according to the invention, wherein the solid sulfide electrolyte is represented by formula (II)
Li 10.35X1.35P1.65S12 (II).
A preferred embodiment is the method according to the invention, wherein the solid sulfide electrolyte is represented by formula (III)
Li io.3sSi 1.35P1.65S 12 (III) .
A preferred embodiment is the method according to the invention, wherein the molar ratios of of Li:X:P:S are between (10-ll):(l-2):(l-2):(ll-13), preferably between (10.2-10.7):(l.l-1.9):(l.l-1.9):(11.5-12.5), more preferably between (10.3-10.4):(1.3-1.4):(1.6-1.7):(11.9-12.1), most preferably about
10.35: 1.35: 1.65: 12.
A preferred embodiment is the method according to the invention by mixing the set of precursors with a mixing speed between 1 and 1500 rpm, more preferably between 100 and 1000 rpm, most preferably between 300 and 750 rpm. In accordance with highly preferred embodiment mixing of the solid electrolyte precursor mixture with a mixing speed between 300 and 700 rpm, preferably between 350 and 650 rpm, more preferably between 400 and 600 rpm.
A preferred embodiment is the method according to the invention, wherein the mixing occurs at a mixing time of at least 1 min, preferably at least 30 minutes, more preferably at least 1 hour, even more preferably at least 2 hours, even more preferably at least 5 hours, most preferably at least 10 hours. A preferred embodiment is the method according to the invention, wherein the mixing occurs at a mixing time of less than 72 hours, preferably less than 60 hours, more preferably less than 50 hours, even more preferably less than 36 hours, even more preferably less than 30 hours, most preferably less than 20 hours. A preferred embodiment is the method according to the invention by mixing of the solid electrolyte precursor wherein the mixing of the set of precursors occurs at a mixing time between 1 hour and 72 hours, preferably between 2 hours and 50 hours, more preferably between 5 hours and 20 hours.
In accordance with highly preferred embodiments of the invention the mixing of the set of precursors with:
- a mixing speed between 1 and 1500 rpm, preferably between 100 and 1000 rpm, more preferably between 300 and 750 rpm; and
- a mixing time between 1 hour and 72 hours, preferably between 2 hours and 50 hours, more preferably between 5 hours and 20 hours.
A preferred embodiment is the method according the invention, wherein the mixing of the set of precursors occurs a temperature of at least 5 °C, preferably at least 10 °C, more preferably at least 15 °C. A preferred embodiment is the method according to the invention, wherein the mixing occurs at a temperature of less than 50 °C, preferably less than 40 °C, more preferably less than 30 °C. A preferred embodiment is the method according to the invention, wherein the mixing occurs at a temperature between 5 and 50 °C, preferably a temperature between 10 and 40 °C, more preferably a temperature between 15 and 30 °C.
As appreciated by the skilled person in certain embodiments the mixing of the set of precursors is the same as milling, mechanical milling, ball-milling, pulverization, grinding or dry-grinding of the set of precursors.
A preferred embodiment is the method according to the invention, wherein the mixing of the set of precursors is carried out by using a mixing means, wherein mechanical stress is applied to the set of precursors to form the solid electrolyte mixture. The term "applying mechanical stress" as used herein refers to mechanically apply shear stress, impact force or the like. Examples of the mixing means include a pulverizer such as a planetary ball mill, a vibration mill and a rolling mill; and a kneader; or the like. An example of a suitable mixing means, but not limiting to the invention, is a planetary ball mill Retsch PM 100. In a more preferred embodiment the mixing of the set of precursors is carried out by adding one or more ceramic or zirconia balls, preferably zirconia balls, to the set of precursors to obtain the solid electrolyte mixture. As appreciated by the skilled person the amount and size of the ceramic or zircona balls is changed in view of the total solid amount of the solid electrolyte precursor mixture. For example, but not limiting to the invention, in a 250 mL zirconia ball-milling jar 16 zirconia balls of 20 mm diameter can be used with a balkpowder ratio of 30: 1 (g/g). As appreciated by the skilled person these ceramic or zirconia balls are removed from the solid electrolyte mixture before heat-treating the solid electrolyte mixture.
In a highly preferred embodiment, and as appreciated by the skilled person, the mixing of the set of precursors is carried out by dry-mixing of the set of precursors, i.e. dry-mixing means that no additional liquid is added to the set of precursors to obtain the solid electrolyte mixture.
A preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a temperature of at least 100 °C, preferably at least 200 °C, more preferably at least 300 °C, more preferably at least 400 °C, even more preferably at least 450 °C, most preferably at least 500 °C. A preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a temperature of less than 1000 °C, preferably less than 900 °C, more preferably less than 800 °C, even more preferably less than 700 °C, even more preferably less than 650 °C, most preferably less than 600 °C. A preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a temperature between 100 and 1000 °C, preferably between 300 and 700 °C, more preferably between 450 and 650 °C. In highly preferred embodiments the heat-treating occurs at a temperature between 500 and 600 °C, preferably at a temperature between 525 and 575 °C, most preferably about 550 °C.
A preferred embodiment is the method according to the invention, wherein the heat-treating occurs under an inert atmosphere, preferably an argon atmosphere, or under an atmosphere comprising a hydrogen sulfide gas, preferably an atmosphere consisting of a hydrogen sulfide gas.
A preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a pressure of at least 1 MPa, preferably at least 50 MPa, more preferably at least 100 MPa, even more preferably at least 175 MPa, most preferably at least 250 MPa. A preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a pressure of less than 1000 MPa, preferably less than 850 MPa, more preferably less than 700 MPa, even more preferably less than 600 MPa, most preferably less than 500 MPa. A preferred embodiment is the method according to the invention, wherein the heat-treating occurs at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa. In highly preferred embodiments the heat- treating occurs at a pressure between 325 and 390 MPa, preferably at a pressure between 350 and 380 MPa, most preferably about 375 MPa.
A preferred embodiment is the method according to the invention, wherein the heat-treating is at least 1 min, preferably at least 30 minutes, more preferably at least 1 hour, even more preferably at least 1.5 hours, most preferably at least 2 hours. A preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture is less than 48 hours, preferably less than 24 hours, more preferably less than 18 hours, even more preferably less than 10 hours, most preferably less than 5 hours. A preferred embodiment is the method according to the invention, wherein the heat-treating is between 0.5 hour and 24 hours, preferably between 1 hours and 12 hours, more preferably between 1.5 hours and 5 hours.
A preferred embodiment is the method according to the invention, wherein
- the heat-treating occurs at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and
- the heat-treating occurs at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
A highly preferred embodiment is the method according to the invention, wherein
- the heat-treating occurs at a temperature between 500 and 600 °C, preferably at a temperature between 525 and 575 °C, most preferably about 550 °C; and
- the heat-treating occurs at a pressure between 300 and 400 MPa, preferably at a pressure between 350 and 390 MPa, most preferably about 375 MPa.
As appreciated by the skilled person the heat-treating of the solid electrolyte mixture at the defined temperature and at the defined pressure is called hot-pressing of the solid electrolyte mixture thereby affording the solid sulfide electrolyte represented by formula (I), preferably the solid sulfide electrolyte represented by formula (II), most preferably the solid sulfide electrolyte represented by formula (III). Moreover, the heat-treating of the solid electrolyte mixture at the defined temperature and at the defined pressure occurs through simultaneous application of the defined heat and defined pressure.
A preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture is carried by a means for applying heat and pressure, for example by hot pressing and/or spark plasma sintering, preferably hot pressing. A suitable example of a means for applying heat and pressure, but not limiting to the invention, is a hot press, for example a Fontijne hot pressing equipment.
As appreciated by the skilled person the solid electrolyte mixture obtained in step ii) is placed in mold, preferably a tungsten carbide mold, which is placed in the means for applying heat and pressure, preferably the hot press. The means for applying heat and pressure is then placed under vacuum, preferably below 1 bar, more preferably below 0.5 bar, most preferably below 0.2 bar, such as about 0.1 bar. The heat-treating step as defined in the present invention is then applied to the mold comprising the solid electrolyte mixture obtained in step ii).
A preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture of step iii) comprises two steps: iii-a) raising the temperature of the solid electrolyte mixture to a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C at a heating rate of at least 10 °C / minute, preferably at least 15 °C / minute, more preferably at least 18 °C / minute; and iii-b) heat-treating the solid electrolyte mixture at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
A preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture of step iii) comprises two steps: iii-a) raising the temperature of the solid electrolyte mixture to a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C at a heating rate of at most 50 °C / minute, preferably at most 30 °C / minute, more preferably at most 25 °C / minute; and iii-b) heat-treating the solid electrolyte mixture at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
A preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture of step iii) comprises two steps: iii-a) raising the temperature of the solid electrolyte mixture to a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C at a heating rate between 10 and 50 °C I minute, preferably between 15 and 30 °C / minute, more preferably between 18 and 25 °C / minute; and iii-b) heat-treating the solid electrolyte mixture at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
A highly preferred embodiment is the method according to the invention, wherein the heat-treating of the solid electrolyte mixture of step iii) comprises two steps: iii-a) raising the temperature of the solid electrolyte mixture to a temperature between 500 and 600 °C, preferably a temperature between 525 and 575 °C, more preferably about 550 °C at a heating rate of 10-50 °C / minute, preferably of 15-30 °C / minute, more preferably about 18 - 25 °C / minute; iii-b) the heat-treating occurs at a temperature between 500 and 600 °C, preferably at a temperature between 525 and 575 °C, most preferably about 550 °C; and a pressure between 300 and 400 MPa, preferably at a pressure between 350 and 390 MPa, most preferably about 375 MPa.
The present inventors believe that by applying the heating rate as defined above the solid sulfide electrolyte is obtained in high purity.
A preferred embodiment is the method according to the invention, wherein - the heat-treating occurs at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and
- the heat-treating is between 0.5 hour and 24 hours, preferably between 1 hour and 12 hours, more preferably between 1.5 hour and 5 hours.
A preferred embodiment is the method according to the invention, wherein
- the heat-treating occurs at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa; and
- the heat-treating is between 0.5 hour and 24 hours, preferably between 1 hour and 12 hours, more preferably between 1.5 hour and 5 hours.
A preferred embodiment is the method according to the invention, wherein
- the heat-treating occurs at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C;
- the heat-treating occurs at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa; and
- the heat-treating is between 0.5 hour and 24 hours, preferably between 1 hour and 12 hours, more preferably between 1.5 hour and 5 hours.
In certain preferred embodiments the method of the invention comprises a further step iv), wherein the sulfide solid electrolyte is cooled to a temperature between 10 and 40 °C, preferably a temperature between 10 and 30 °C, more preferably a temperature between 15 and 25 °C, by applying a cooling rate of at least 10 °C / minute, preferably at least 15 °C / minute, more preferably at least 18 °C/ minute. In certain preferred embodiment of the method of the invention the sulfide solid electrolyte is cooled to a temperature between 10 and 40 °C, preferably a temperature between 10 and 30 °C, more preferably a temperature between 15 and 25 °C, by applying a cooling rate of at most 50 °C / minute, preferably at most 40 °C / minute, more preferably at most 30 °C / minute. In certain preferred embodiment of the method of the invention the sulfide solid electrolyte is cooled to a temperature between 10 and 40 °C, preferably a temperature between 10 and 30 °C, more preferably a temperature between 15 and 25 °C, preferably by applying a cooling rate between 10 and 50 °C / minute, preferably between 15 and 30 °C / minute, more preferably between 18 and 25 °C / minute, most preferably about 20 °C / minute. As appreciated by the skilled person the sulfide solid electrolyte is cooled to room temperature as defined in above-mentioned ranges. Worded differently, in certain preferred embodiments the method of the invention comprises the following steps: i) providing a set of precursors as defined above, ii) mixing of the set of precursors as defined above, iii) heat-treating of the solid electrolyte mixture as defined above, and iv) cooling the solid sulfide electrolyte obtained in step iii) to a temperature between 10 and 40 °C, preferably a temperature between 10 and 30 °C, more preferably a temperature between 15 and 25 °C, preferably by applying a cooling rate between 10 and 50 °C / minute, preferably between 15 and 30 °C / minute, more preferably between 18 and 25 °C / minute, most preferably about 20 °C / minute.
The present inventors believe that by applying the cooling rate as defined above the solid sulfide electrolyte is obtained in high purity.
In certain highly preferred embodiments the method of the invention comprises the following steps: i) providing a set of precursors as defined above, ii) mixing of the set of precursors as defined above, iii) heat-treating of the solid electrolyte mixture as defined above, preferably raising the temperate as defined in step iii-a) above followed by heat treating as defined in step iii-b) above; and iv) cooling the solid sulfide electrolyte and defined above
In a preferred embodiment of the method of the invention, the method affords the solid sulfide electrolyte, which does not substantially contain a phase formed of U2S, P2S5, XS2 with X = Si, Ge, Sn or a combination thereof, and/or U3PS4 as determined by XRD, wherein the peak intensities of U2S, P2S5, XS2, and/or U3PS4 are less than 30% of the peak intensities of the solid sulfide electrolyte represented by formula (I), preferably the solid sulfide electrolyte represented by formula (II), more preferably the solid sulfide electrolyte represented by formula (III); preferably less than 25%; more preferably less than 20%; even more preferably less than 10%; most preferably less than 5%. In accordance with preferred embodiment the solid sulfide electrolyte has a purity of at least 70% as determined by XRD, preferably a purity of at least 75%, more preferably a purity of at least 80%, even more preferably a purity of at least 90%, most preferably a purity of at least 95%, as determined by XRD.
In a preferred embodiment of the method of the invention, the solid sulfide electrolyte has XRD patterns at around 20 = 20.18±0.50 °, 20.44±0.50 °, 26.96±0.50 0 and 29.58±0.50 0 using CuKa-ray.
The solid sulfide electrolyte
A second aspect of the invention provides a solid sulfide electrolyte obtainable by the method according to the invention.
As appreciated by the skilled person all embodiments related to the method for manufacturing the solid sulfide electrolyte according to the invention equally apply to the solid sulfide electrolyte obtainable by the method according to the invention.
In particular, a more preferred embodiment is the solid sulfide electrolyte obtainable by the method according to the invention, wherein the solid sulfide electrolyte is represented by formula (I)
Li H-yX2-yPl+yS12 (I) wherein 0 < y < 2, preferably 0 < y < 1, more preferably 0.05 < y < 0.95, even more preferably 0.1 < y < 0.9, even more preferably 0.2 < y < 0.85, even more preferably 0.25 < y < 0.8, even more preferably 0.3 < y < 0.75, most preferably 0.6 < y < 0.7. In highly preferred embodiments y is about 0.65; and wherein X is Si, Ge, Sn or a combination thereof, preferably X is Si.
A highly preferred embodiment is the solid sulfide electrolyte obtainable by the method according to the invention, wherein the solid sulfide electrolyte obtainable by the method according to the invention is represented by formula (II)
Li 10.35X1.35P1.65S12 (II).
A highly preferred embodiment is solid sulfide electrolyte obtainable by the method according to the invention, wherein the solid sulfide electrolyte obtainable by the method according to the invention is represented by formula (III)
Li io.3sSi 1.35P1.65S 12 (HI) . A preferred embodiment is the solid sulfide electrolyte obtainable by the method according to the invention, which does not substantially contain a phase formed of U2S, P2S5, XS2 with X = Si, Ge, Sn or a combination thereof, and/or U3PS4 as determined by XRD, wherein the peak intensities of U2S, P2S5, XS2, and/or U3PS4 are less than 30% of the peak intensities of the solid sulfide electrolyte represented by formula (I), preferably the solid sulfide electrolyte represented by formula (II), more preferably the solid sulfide electrolyte represented by formula (III); preferably less than 25%; more preferably less than 20%; even more preferably less than 10%; most preferably less than 5%. In accordance with preferred embodiment the solid sulfide electrolyte according to the invention has a purity of at least 70% as determined by XRD, preferably a purity of at least 75%, more preferably a purity of at least 80%, even more preferably a purity of at least 90%, most preferably a purity of at least 95%, as determined by XRD.
A preferred embodiment is the solid sulfide electrolyte obtainable by the method according to the invention having XRD patterns at around 20=20.18±0.50°, 20.44±0.50°, 26.96±0.50° and 29.58±0.50° using CuKa-ray.
A third aspect of the invention is providing a solid sulfide electrolyte represented by formula (I)
Li H-yX2-yPl+yS12 (I) wherein 0 < y < 2, preferably 0 < y < 1, more preferably 0.05 < y < 0.95, even more preferably 0.1 < y < 0.9, even more preferably 0.2 < y < 0.85, even more preferably 0.25 < y < 0.8, even more preferably 0.3 < y < 0.75, most preferably 0.6 < y < 0.7. In highly preferred embodiments y is about 0.65; and wherein X is Si, Ge, Sn or a combination thereof, preferably X is Si.
As appreciated by the skilled person all embodiments related to the method for manufacturing the solid sulfide electrolyte according to the invention and all embodiments related to the solid sulfide electrolyte obtainable by the method for manufacturing the solid sulfide electrolyte equally apply to the solid sulfide electrolyte according to the third aspect of the invention.
A highly preferred embodiment is the solid sulfide electrolyte according to the third aspect of the invention, wherein the solid sulfide electrolyte is represented by formula (II) Li 10.35X1.35P1.65S12 (II).
A highly preferred embodiment is the solid sulfide electrolyte according to the third aspect of the invention, wherein the solid sulfide electrolyte is represented by formula (III)
Li io.3sSi 1.35P1.65S 12 (III) .
A preferred embodiment is the solid sulfide electrolyte according to the third aspect of the invention, which does not substantially contain a phase formed of U2S, P2S5, XS2 with X = Si, Ge, Sn or a combination thereof, and/or U3PS4 as determined by XRD, wherein the peak intensities of U2S, P2S5, XS2, and/or U3PS4 are less than 30% of the peak intensities of the solid sulfide electrolyte represented by formula (I), preferably the solid sulfide electrolyte represented by formula (II), more preferably the solid sulfide electrolyte represented by formula (III), preferably less than 25%, more preferably less than 20%, even more preferably less than 10%, most preferably less than 5%. In accordance with preferred embodiment the solid sulfide electrolyte according to the invention has a purity of at least 70% as determined by XRD, preferably a purity of at least 75%, more preferably a purity of at least 80%, even more preferably a purity of at least 90%, most preferably a purity of at least 95%, as determined by XRD.
A preferred embodiment is the solid sulfide electrolyte solid sulfide electrolyte obtainable by the method according to the invention having XRD patterns at around 20 = 20.18±0.50°, 20.44±0.50°, 26.96±0.50° and 29.58±0.50° using CuKa-ray.
Batery
A fourth aspect of the invention concerns a battery comprising a negative electrode, a positive electrode and a solid electrolyte layer, wherein at least one of the negative electrode, the positive electrode and the solid electrolyte layer comprises the solid sulfide electrolyte according to the invention, such as the solid sulfide electrolyte according to the second aspect of the invention and/or the solid sulfide electrolyte according to the third aspect of the invention. The present solid sulfide electrolyte of the invention can be used as a solid electrolyte layer of a solid lithium ion battery or a solid lithium primary cell, or as a solid electrolyte that is mixed with an electrode mixture for a positive electrode or a negative electrode.
In a preferred embodiment the battery is a solid-state battery, preferably a lithium solid-state battery.
Use
A fifth aspect of the invention concerns a use of the solid sulfide electrolyte according to the invention, such as the solid sulfide electrolyte such as the solid sulfide electrolyte according to the second aspect of the invention and/or the solid sulfide electrolyte according to the third aspect of the invention, in a battery, preferably a solid-state-battery, more preferably a lithium solid-state-battery.
A sixth aspect of the present invention concerns a use of the battery according to invention in either one of a portable computer, a tablet, a mobile phone, an energy storage system, an electric vehicle or in a hybrid electric vehicle, preferably in an electric vehicle or in a hybrid electric vehicle.
The invention is further illustrated in the following examples.
EXAMPLES
Description of testing method
XRD analysis
The powder X-ray diffraction patterns were collected using Bruker D8 diffractometers equipped with either Cu (Kai-Kaz) or Mo (Kai-Kaz) radiation in a 0-0 configuration. An air-tight sample holder with a Be window was used for the measurements. The patterns were collected between 20 = 10 ° - 50 ° with a step size of 0.02 0 at 25 °C.
Examples
Ball milling synthesis
All the synthesis work and sample treatment were carried out in Ar filled glovebox with O2 and H2O levels <0.1 ppm. Stoichiometric ratios of reagents, U2S (Albemarle, 99.9%), P2S5 (Sigma Aldrich, 99%), SiS2 (LTS US, 99%) were weighed to obtain a 15 g batch of precursor. The precursors were transferred into a Restch PM 100 using 250 mL zirconia ball-milling jar along with 16 zirconia balls of 20 mm diameter (Ball: powder ratio was 30: 1 (g/g)). The precursors were initially milled at 100 rpm for 60 minutes to homogenize the mixture followed by ball milling at 550 rpm for a total duration of 12 hours. Each cycle constituted in 5-minute milling and 5-minute rest. The ball-milled powder was then submitted to the three different heat treatments.
Heat treatment synthesis i) Conventional heat treatment(comparative example)
The ball-milled powder was uniaxially pressed into a 13 mm pellet and placed in dried quartz tubes which were then closed under Ar and placed in a furnace (Nabertherm) for annealing. The temperature of the furnace was slowly increased to 550-600 °C at a ramp rate of 5 °C/min, held for 6 to 72 hours, and naturally cooled to room temperature. The reacted pellets were then pulverized using a pestle and mortar and subjected to XR.D analysis (see Figure 1). Clearly, only U3PS4 was observed as main phase in all calcination routes (600 °C for 48 h, 550 °C for 72 h, 575 °C for 6 h or 575 °C for 18 h) and no Liio.ssSii.ssPi.esSiz phase was observed. ii) Conventional heat treatment followed by quenching (comparative example)
The ball-milled powder was uniaxially pressed into a 13 mm pellet and placed in dried quartz tubes which were then closed under Ar and placed in a furnace (Nabertherm) for annealing. The temperature of the furnace was slowly increased to 575 °C at a ramp rate of 5 °C/min, held for 6 hours, and quenched to room temperature (25 °C) by removing the quartz tube from the oven. The reacted pellets were then pulverized using a pestle and mortar and subjected to XR.D analysis (see Figure 2) : quenching of the calcined mixture promotes formation of the Liio.ssSii.ssPi.esSiz phase, but still a mixture of U3PS4 phase as main phase and Liio.ssSii.ssPi.esSiz phase is obtained. iii) Heat treatment performed with hot pressing
The ball-milled powder was uniaxially pressed into a 26 mm pellet in WC (tungsten carbide) mold and the mold was placed in a hot pressing equipment (Fontijne), which was placed under vacuum (0.1 bar). The temperature was increased to 550 °C at a ramp rate of 20 °C/min with a pressure of 375 MPa, held for 3 hours, and cooled to room temperature at a ramp rate of 20°C/min. The reacted pellets were then pulverized using a pestle and mortar and subjected to XR.D analysis (see Figure 3) : a pure Liio.ssSii.ssPi.esSiz phase is obtained without any side products such as U3PS4.

Claims

1. A method for manufacturing a solid sulfide electrolyte comprising the following steps: i) providing a set of precursors comprising Li, X, P and S; ii) mixing of the set of precursors to obtain a solid electrolyte mixture; and iii) heat-treating of the solid electrolyte mixture at temperature of at least 100 °C and a pressure between 1 and 1000 MPa by hot-pressing to obtain a solid sulfide electrolyte; wherein the solid sulfide electrolyte is represented by formula (I)
Li H-yX2-yPl+yS12 (I) wherein 0 < y < 1, and wherein X is Si, Ge, Sn or a combination thereof.
2. Method for manufacturing the solid sulfide electrolyte according to claim 1, wherein the set of precursors comprises one or more selected from the group consisting of metallic or elemental lithium, lithium sulfide (U2S), lithium oxide (U2O), lithium carbonate (U2CO3), lithium hydrosulfide (LiHS), lithium trithiocarbonate (U2CS3), lithium polysulfide (Li2Sx with x=2 to 100), phosphorus sulfide such as diphosphorus trisulfide (P2S3) and diphosphorus pentasultide (P2S5), sodium phosphate (NasPC ), PSZ3 with Z is an element selected from F, Cl, Br and I, a phosphorus elementary substance such as P4, lithium phosphorus sulfide (U3PS4), and a X-containing compound; preferably the set of precursors comprises one or more selected from the group consisting of lithium sulfide, phosphorus sulfide and a X-containing compound.
3. Method for manufacturing the solid sulfide electrolyte according to claim 1 or 2, wherein the X-containing compound is elemental X or XS2, preferably XS2.
4. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-3, wherein X = Si.
5. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-4, wherein 0.1 < y < 0.90, preferably 0.3 < y < 0.8, more preferably 0.6 < y < 0.7.
6. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-5, wherein the solid sulfide electrolyte is represented by formula (II)
Li 10.35X1.35P1.65S12 (II).
7. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-6, wherein the solid sulfide electrolyte is represented by formula (III)
Li io.3sSi 1.35P1.65S 12 (III) .
8. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-7, wherein the mixing of the set of precursors with:
- a mixing speed between 1 and 1500 rpm, preferably between 100 and 1000 rpm, more preferably between 300 and 750 rpm; and
- a mixing time between 1 hour and 72 hours, preferably between 2 hours and 50 hours, more preferably between 5 hours and 20 hours.
9. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-8, wherein the heat-treating occurs at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C.
10. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-9, wherein the heat-treating occurs at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
11. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-10, wherein the heat-treating is between 30 minutes and 24 hours, preferably between 1 hour and 12 hours, more preferably between 1.5 hour and 5 hours.
12. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-11, wherein the heat-treating of the solid electrolyte mixture of step iii) comprises two steps: iii-a) raising the temperature of the solid electrolyte mixture to a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C at a heating rate between 10 and 50 °C I minute, preferably between 15 and 30 °C / minute, more preferably between 18 and 25 °C / minute; and iii-b) heat-treating the solid electrolyte mixture at a temperature between 100 and 1000 °C, preferably a temperature between 300 and 700 °C, more preferably a temperature between 450 and 650 °C; and at a pressure between 100 and 700 MPa, preferably a pressure between 250 and 500 MPa, more preferably a pressure between 300 and 400 MPa.
13. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-12 further comprising a step iv), wherein the sulfide solid electrolyte is cooled to a temperature between 10 and 40 °C, preferably a temperature between 10 and 30 °C, more preferably a temperature between 15 and 25 °C, preferably by applying a cooling rate between 10 and 50 °C / minute, preferably between 15 and 30 °C / minute, more preferably between 18 and 25 °C / minute, most preferably about 20 °C / minute.
14. Method for manufacturing the solid sulfide electrolyte according to any one of claims 1-13, wherein the solid sulfide electrolyte has a purity of at least 95% as determined via XR.D.
15 The solid sulfide electrolyte obtainable by the method according to any one of claims 1-14.
EP24709070.7A 2023-03-08 2024-03-07 Method for manufacturing a lgps-type solid sulfide electrolyte Pending EP4677663A1 (en)

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