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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/582—Halogenides
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  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/16—Oxyacids of phosphorus; Salts thereof
  • C01B25/26—Phosphates
  • C01B25/30—Alkali metal phosphates
• • C—CHEMISTRY; METALLURGY
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  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/16—Oxyacids of phosphorus; Salts thereof
  • C01B25/26—Phosphates
  • C01B25/38—Condensed phosphates
  • C01B25/39—Condensed phosphates of alkali metals
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
  • C01D15/00—Lithium compounds
  • C01D15/04—Halides
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  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G30/00—Compounds of antimony
  • C01G30/002—Compounds containing antimony, with or without oxygen or hydrogen, and containing two or more other elements
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/581—Chalcogenides or intercalation compounds thereof
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  • C01P2002/00—Crystal-structural characteristics
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  • 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
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
• • 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

• a solid material which has ionic conductivity for lithium ions
• a process for preparing said solid material a use of said solid material as a solid electrolyte for an electrochemical cell, a solid structure selected from the group consisting of a cathode, an anode and a separator for an electrochemical cell comprising the solid material, and an electro- chemical cell comprising such solid structure.
• solid-state lithium batteries Due to the wide-spread use of solid-state lithium batteries, there is an increasing demand for solid-state electrolytes having a high conductivity for lithium ions.
• An important class of such solid electrolytes are lithium argyrodites.
• B is selected from the group P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, and Ta,
• X is selected from the group S, Se, and Te
• Y is selected from the group Cl, Br, I, F, CN, OCN, SCN, N3, and where 0 ⁇ x ⁇ 2.
• US 10,483,587 B2 discloses a sulfide solid electrolyte containing lithium, phosphorus, sulphur, and two or more of elements X selected from halogen elements, where the sulfide solid electrolyte has an argyrodite-type crystal structure and a molar ratio of sulphur to phosphorus “b(S/P)” and a molar ratio of the element X to phosphorus "c(X/P)" satisfying the formula 0.23 ⁇ c / b ⁇ 0.57.
• a process for preparing said solid material a use of said solid material as a solid electrolyte for an electrochemical cell, a solid structure selected from the group consisting of a cathode, an anode and a separator for an electrochemical cell comprising the solid material, and an electrochemical cell comprising such solid structure, wherein said solid structure comprises said solid material.
• a solid material having a composition derived from the parent composition
• Li6PY5X wherein X is one or more selected from F, Cl, Br and I, and Y is one or more selected from O, S, Se and Te wherein 10 to 90 atom% of P are substituted by cations selected from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W® + wherein at least three, and up to six different cations of said group are present.
• Solid materials of the parent composition Li6PY5X are known in the art, cf. e.g. the solid materials Li6PS5I, Li6PS5Cl and Li6PS5Br disclosed in US 2010/290969A1.
• solid materials of the parent composition Li6PY5X have an argyrodite structure. It is understood that solid materials having the above-defined parent composition Li6PY5X are not solid ma- terials according to the present invention.
• the solid materials according to the invention which have a composition derived from said parent composition, 10 to 90 atom% of the phosphorus are substituted by cations selected from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W 6+ .
• at least three, and up to six of said cations which sub- stitute phosphorus are present.
• substitution of phosphorus by the above- mentioned cations means that a fraction of the lattice sites, which in the parent material are occupied by phosphorus, in a material according to the invention is occupied by the above- mentioned cations. Accordingly, the phosphorus content of a solid material according to the invention is lower than in the parent composition, namely 10 to 90 atom% of the phos- phorus content of the parent composition.
• the cations substituting phosphorus may have a chemical valence (ionic charge) different from phosphorus.
• the lithium content may be lower or higher than in the parent composition.
• the configurational entropy and/or the vibrational entropy of the argyrodite ma- terial are assumed to be increased due to introduction of three to six different foreign cati- ons selected from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W 6+ which substitute 10 to 90 atom% of the phosphorus of the parent composition. It is assumed that this effects an increase of the lithium-ion migration, resulting in an increased ionic conduc- tivity.
• Preferred solid materials according to the first aspect of the invention have a composition according to general formula (I) Li6+mP1-xM1(z1)+(n1)M2(z2)+(n2)M3(z3)+(n3)M4(z4)+(n4)M5(z5)+(n5)M6(z6)+(n6)Y5X (I) wherein X is one or more selected from F, Cl, Br and I, preferably one of F, Cl, Br and I, Y is one or more selected from O, S, Se and Te, preferably one of O, S, Se and Te, M1 (z1)+ to M6 (z6)+ are selected from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W 6+ , each of (n1) to (n3) is a number in the range of from 0.05 to 0.3, (n4) is 0 or a number in the range of from 0.05 to 0.3, (n
• the three, four, five or six different cations are selected from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W 6+ .
• the variables (z1) to (z6) indicate the ionic charge (chemical valency) of the related cation M1 (z1)+ to M6 (z6)+ , i.e.
• (z1) is the ionic charge of cation M1 (z1)+
• (z2) is the ionic charge of M2 (z2)+
• (z3) is the ionic charge of M3 (z3)+
• (z4) is the ionic charge of M4 (z4)+
• (z5) is the ionic charge of M5 (z5)+
• (z6) is the ionic charge of M6 (z6)+ .
• the variables (n1) to (n6) indicate the fraction of the related cation M1 (z1)+ to M6 (z6)+ present in formula (I).
• Each of (n1) to (n3) is an independently selected number in the range of from 0.05 to 0.3.
• (n1) to (n6) are independently selected numbers in the range of from 0.05 to 0.3.
• (n1) to (n6) fulfill the following condition:
• the variable x which is the sum of (n1) to (n6) falls in the range of from 0.1 to 0.9, corresponding to a substitution of 10 to 90 atom% of phosphorus of the parent composition Li6PY5X by different cations M1 (z1)+ to M6 (z6)+ .
• the variable m indicates how the content of lithium ions changes compared to the parent composition Li6PY5X, in order to balance for any deviation of the ionic charges of cation M1 (z1)+ to M6 (z6)+ from the chemical valency of phosphorus (+5).
• the variable m is positive when the contribution of cations having an ionic charge smaller than 5+ is larger than the contribution of cations having an ionic charge equal to higher than 5+.
• the variable m is negative when the contribution of cations having an ionic charge above 5+ to m is larger than the contribution of cations having an ionic charge equal to or below 5+.
• the variable m is 0, when the contribution of cations having an ionic charge below 5+ to m is balanced by the contribution of cations having an ionic charge above 5+ to m.
• X is one or more selected from F, Cl, Br and I
• Y is one or more selected from O, S, Se and Te.
• X is one of F, Cl, Br and I
• Y is one of O, S, Se and Te. More preferably, X is one of F, Cl, Br and I, and Y is S. More preferred solid materials according to the first aspect of the invention have a compo- sition according to general formula (II) Li6+mP1-xM1(z1)+(n1)M2(z2)+(n2)M3(z3)+(n3)M4(z4)+(n4)Y5X (II) wherein X is one or more selected from F, Cl, Br and I, preferably one of F, Cl, Br and I, Y is one or more selected from O, S, Se and Te, preferably one of O, S, Se and Te, M1 (z1)+ to M4 (z4)+ are selected from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W 6+ , each of (n1)
• the three or four cations are se- lected from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W 6+ .
• the variables (z1) to (z4) indicate the ionic charge (chemical valency) of the related cation M1 (z1)+ to M4 (z4)+ , i.e. (z1) is the ionic charge of cation M1 (z1)+ , (z2) is the ionic charge of M2 (z2)+ , (z3) is the ionic charge of M3 (z3)+ , (z4) is the ionic charge of M4 (z4)+ .
• the variables (n1) to (n4) indicate the fraction of the related cation M1 (z1)+ to M4 (z4)+ present in formula (II).
• Each of (n1) to (n3) is an independently selected number in the range of from 0.05 to 0.3.
• (n4) is another independently selected number in the range of from 0.05 to 0.3.
• (n4) 0.
• (n1) to (n4) fulfill the following condition:
• the variable x which is the sum of (n1) to (n4) falls in the range of from 0.1 to 0.9, corresponding to a substitution of 10 to 90 atom% of phosphorus of the parent composition Li6PY5X by different cations M1 (z1)+ to M4 (z4)+ resp. M1 (z1)+ to M3 (z3)+ (if no fourth cation M4 (z4)+ is present).
• the variable m indicates how the content of lithium ions changes compared to the parent composition Li6PY5X, in order to balance for any deviation of the ionic charges of cation M1 (z1)+ to M4 (z4)+ resp.
• the variable m is positive when the contribution of cations having an ionic charge smaller than 5+ is larger than the contribution of cations having an ionic charge equal to higher than 5+.
• the variable m is negative when the contribution of cations having an ionic charge above 5+ to m is larger than the contribution of cations having an ionic charge equal to or below 5+.
• the variable m is 0, when the contribution of cations having an ionic charge below 5+ to m is balanced by the contribution of cations having an ionic charge above 5+ to m.
• X is one or more selected from F, Cl, Br and I
• Y is one or more selected from O, S, Se and Te.
• X is one of F, Cl, Br and I
• Y is one of O, S, Se and Te.
• X is one of F, Cl, Br and I
• Y is S.
• three differ- ent cations M1 (z1)+ , M2 (z2)+ , M3 (z3)+ are present which substitute a fraction of the phosphorus content of the parent composition Li6PY5X.
• three different cations M1 (z1)+ , M2 (z2)+ , M3 (z3)+ substitute a fraction of the phosphorus content of the parent composition Li6PY5X.
• the three different cations are selected from the group consisting of Si 4+ , Ge 4+ , Sn 4+ and Sb 5+ .
• the variables (z1) to (z3) indicate the ionic charge (chemical valency) of the related cation M1 (z1)+ to M3 (z3)+ , i.e.
• (z1) is the ionic charge of cation M1 (z1)+
• (z2) is the ionic charge of M2 (z2)+
• (z3) is the ionic charge of M3 (z3)+
• the variables (n1) to (n3) indicate the fraction of the related cation M1 (z1)+ to M3 (z3)+ present in formula (IIa).
• Each of (n1) to (n3) is an independently selected number in the range of from 0.05 to 0.3, fulfilling the following condition:
• the variable x which is the sum of (n1) to (n3) falls in the range of from 0.1 to 0.9, corresponding to a substitution of 10 to 90 atom% of phosphorus of the parent composition Li6PY5X by different cations M1 (z1)+ to M3 (z3)+ .
• the variable m indicates how the content of lithium ions changes compared to the parent composition Li6PY5X, in order to balance for any deviation of the ionic charges of cation M1 (z1)+ to M3 (z3)+ from the chemical valency of phosphorus (+5).
• variable m is positive since no cations having a charge above 5+ are present.
• X is one selected from F, Cl, Br and I
• Y is one selected from O, S, Se and Te.
• X is I (iodine).
• Y is S (sul- phur). More preferably, X is I (iodine) and Y is S (sulphur).
• the solid material has a composition according to formula (IIa’): Li6+mP1-xM1(z1)+(n1)M2(z2)+(n2)M3(z3)+(n3)S5I (IIa’) wherein x, n1, n2, n3, z1, z2, z3 and m are as defined above for formula (IIa).
• M1 (z1)+ is Si 4+
• M2 (z2)+ is Ge 4+
• M3 (z3)+ is Sb 5+
• X is I (iodine)
• Y is S (sulphur).
• the solid material has a composition according to for- mula (IIa’’): Li6+mP1-xSi(n1)Ge(n2)Sb(n3)S5I (IIa’’) wherein x, n1, n2, n3 and m are as defined above for formula (IIa).
• the three different cations M1 (z1)+ , M2 (z2)+ , M3 (z3)+ which substi- tute a fraction of the phosphorus content of the parent composition Li6PY5X are present in equal fractions n.
• three different cations M1 (z1)+ , M2 (z2)+ , M3 (z3)+ substitute a fraction of the phosphorus content of the parent composition Li6PY5X.
• the three cations are selected from the group consisting of Si 4+ , Ge 4+ , Sn 4+ and Sb 5+ .
• the var- iables (z1) to (z3) indicate the ionic charge (chemical valency) of the related cation M1 (z1)+ to M3 (z3)+ , i.e.
• (z1) is the ionic charge of cation M1 (z1)+
• (z2) is the ionic charge of M2 (z2)+
• (z3) is the ionic charge of M3 (z3)+
• n is a number in the range of from 0.05 to 0.3, preferably 0.2 to 0.28, fulfilling the following condition:
• the variable x which is the sum of the fractions of the three different cations M1 (z1)+ to M3 (z3)+ , i.e.
• x 3n, falls in the range of from 0.1 to 0.9, corresponding to a substitution of 10 to 90 atom% of phosphorus of the parent composition Li6PY5X by dif- ferent cations M1 (z1)+ to M3 (z3)+ .
• the variable m indicates how the content of lithium ions changes compared to the parent composition Li6PY5X, in order to balance for any deviation of the ionic charges of cation M1 (z1)+ to M3 (z3)+ from the chemical valency of phosphorus (+5).
• the variable m is positive since no cations having a charge above 5+ are present.
• X is one selected from F, Cl, Br and I
• Y is one selected from O, S, Se and Te.
• X is I (iodine).
• Y is S (sul- phur).
• X is I (iodine) and Y is S (sulphur).
• the solid material has a composition according to formula (IIc’): Li6+mP1-3nM1(z1)+nM2(z2)+nM3(z3)+nS5I (IIc’) wherein n, z1, z2, z3 and m are as defined above for formula (IIc).
• the solid material has a composition according to for- mula (IIc’’): Li6+mP1-3nSinGenSbnS5I (IIc’’) wherein n and m are as defined above for formula (IIc).
• Preferred solid materials of the above-defined first group are Li6.5P0.25Si0.25Ge0.25Sb0.25S5I, Li6.342P0.5Si0.166Ge0.166Sb0.166S5I and Li6.171P0.75Si0.083Ge0.083Sb0.083S5I.
• a second group of specially preferred solid materials according to the invention four dif- ferent cations M1 (z1)+ , M2 (z2)+ , M3 (z3)+ and M4 (z4)+ are present which substitute a fraction of the phosphorus content of the parent composition Li6PY5X.
• (z1) is the ionic charge of cation M1 (z1)+
• (z2) is the ionic charge of M2 (z2)+
• (z3) is the ionic charge of M3 (z3)+
• (z4) is the ionic charge of M4 (z4)+ .
• the variables (n1) to (n4) indicate the fraction of the related cation M1 (z1)+ to M4 (z4)+ present in formula (IIb).
• Each of (n1) to (n4) is an independently selected number in the range of from 0.05 to 0.3, fulfilling the following condition:
• the variable x which is the sum of (n1) to (n4) falls in the range of from 0.1 to 0.9, corresponding to a substitution of 10 to 90 atom% of phosphorus of the parent composition Li6PY5X by different cations M1 (z1)+ to M4 (z4)+ .
• the variable m indicates how the content of lithium ions changes compared to the parent composition Li6PY5X, in order to balance for any deviation of the ionic charges of cation M1 (z1)+ to M4 (z4)+ from the chemical valency of phosphorus (+5).
• variable m is positive since no cations having a charge above 5+ are present.
• X is one selected from F, Cl, Br and I
• Y is one selected from O, S, Se and Te.
• X is I (iodine).
• Y is S (sul- phur).
• X is I (iodine) and Y is S (sulphur).
• the solid material has a composition according to formula (IIb’): Li6+mP1-xSi(n1)Ge(n2)Sn(n3)Sb(n4)S5I (IIb’) wherein x, n1, n2, n3, n4 and m are as defined above for formula (IIb).
• the four different cations M1 (z1)+ , M2 (z2)+ , M3 (z3)+ , M4 (z4)+ which substitute a fraction of the phosphorus content of the parent composition Li6PY5X are pre- sent in equal fractions n.
• (z1) is the ionic charge of cation M1 (z1)+
• (z2) is the ionic charge of M2 (z2)+
• (z3) is the ionic charge of M3 (z3)+
• (z4) is the ionic charge of M4 (z4)+ .
• Each of cations M1 (z1)+ to M4 (z4)+ is present in the same fraction, represented by variable n, which is a number in the range of from 0.05 to 0.22, preferably 0.15 to 0.21, fulfilling the following condition:
• the variable x which is the sum of the fractions of the four different cations M1 (z1)+ to M4 (z4)+ , i.e.
• x 4n, falls in the range of from 0.1 to 0.9, corresponding to a substitution of 10 to 90 atom% of phosphorus of the parent composition Li6PY5X by dif- ferent cations M1 (z1)+ to M4 (z4)+ .
• the variable m indicates how the content of lithium ions changes compared to the parent composition Li6PY5X, in order to balance for any deviation of the ionic charges of cation M1 (z1)+ to M4 (z4)+ from the chemical valency of phosphorus (+5).
• the variable m is positive since no cations having a charge above 5+ are present.
• X is one selected from F, Cl, Br and I
• Y is one selected from O, S, Se and Te.
• X is I (iodine).
• Y is S (sul- phur).
• X is I (iodine) and Y is S (sulphur).
• the solid material has a composition according to formula (IId’): Li6+mP1-4nSinGenSnnSbnY5X (IId’) wherein n and m are as defined above for formula (IId).
• a solid material according to the above-defined first aspect may be crystalline as detectable by the X-ray diffraction (XRD) technique.
• a solid material is referred to as crystalline when it exhibits a long-range order that is characteristic of a crystal, as indicated by the presence of clearly defined reflections in its XRD pattern. In this context, a reflection is considered as clearly defined if its intensity is more than 10% above the background.
• a solid material according to the above-defined first aspect may consist of a single phase or of more than one phase, e.g. a main phase (primary phase) and minor amounts of im- purities and secondary phases. It is understood that formula (I) is an empirical formula (gross formula) as determinable by means of elemental analysis.
• formula (I) defines a composition which is averaged over all phases present in the solid material.
• a solid material according to the above-defined first aspect comprises at least one phase which as such has a composition according to formula (I).
• the weight fraction of phases which as such do not have a composition according to formula (I) e.g. impurity phases, secondary phases
• the total weight fraction of secondary phases and impurity phases may be 20 % or less, preferably 10 % or less, further preferably 5 % or less, most preferably 3 % or less, based on the total weight of the solid material.
• the secondary phases and impurity phases mainly consist of the precursors used for pre- paring the solid material, e.g. LiX (wherein X is as defined above) and Li2Y, (wherein Y is as defined above) and sometimes impurity phases which may originate from impurities of the precursors or from products formed by side reactions of the precursors (e.g. U3PS4).
• the precursors used for pre- paring the solid material e.g. LiX (wherein X is as defined above) and Li2Y, (wherein Y is as defined above) and sometimes impurity phases which may originate from impurities of the precursors or from products formed by side reactions of the precursors (e.g. U3PS4).
• a solid material according to the above-defined first aspect is in the form of a polycrystalline powder, or in the form of single crystals.
• a crystalline solid material according to the above-defined first aspect may have an argyrodite structure characterized by the cubic space group F-43m.
• the argyrodite structure is determined by powder XRD measurements as generally known in the art. Details are described in the examples section.
• a solid material according to the above-defined first aspect may have an ionic conductivity of 0.1 mS/cm or more, preferably 1 mS/cm or more, further preferably 10 mS/cm or more, in each case at a temperature of 25 °C.
• the ionic conductivity is determined in the usual manner known in the field of battery materials development by means of electrochemical impedance spectroscopy (for details see examples section below).
• Preferred solid materials according to the first aspect as defined above are those having one or more of the specific preferred features disclosed above.
• LiePYsX wherein X is one or more selected from Cl, Br and I, and Y is one or more selected from O, S, Se and Te, wherein 10 to 90 atom% of P are substituted by cations from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W® + ,
• LiePYsX wherein X is one or more selected from F, Cl, Br and I and Y is one or more selected from O, S, Se and Te, wherein 10 to 90 atom% of P are substituted by cations from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W® + , wherein at least three, and up to six different cations of said group are present.
• step a) of the process according to the above-defined second aspect a reaction mixture comprising precursors for the reaction product to be formed in step b) is provided.
• Said precursors are:
• reaction mixture provided in step (a) consists of precursors (1) to (4), or of precursors (1) to (5) a defined above.
• the molar ratio of the elements matches general formula (I) as defined above, preferably general formula (II) as defined above, most preferably one of general formulae (Ila), (Ila’), Ila”), (lib), (lib’), (lie), (He’), (lie”), (lid) and (lid’) as defined above.
• precursor (4) comprises or consists of compounds selected from the group consisting of metal oxides, sulfides, selenides or tellurides of at least three and up to six metal cations selected from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W e+ .
• precursor (4) comprises or consists of compounds selected from the group consisting of metal oxides, sulfides, selenides or tellurides of three or four metal cations selected from the group consisting of Zn 2+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , Sb 5+ and W 6+ .
• said precursor (1) is IJ2S, and/or said precursor (2) is P2S5, and/or said precursor (3) is Lil, and/or said precursor (4) is selected from the group consisting of SiS2, GeS2, SnS2 and Sb2S3, and/or said precursor (5) is elemental sulphur or is not present.
• precursor (4) comprises or consists of compounds selected from the group consisting of metal oxides, sulfides, selenides or tellurides of three cations selected from the group consisting of Si 4+ , Ge 4+ , Sn 4+ , and Sb 5+ .
• precursor (1) comprises or consists of Li2S
• precursor (2) comprises or consists of P2S5
• precursor (3) comprises or consists of Lil
• precursor (4) comprises or consists of three compounds selected from the group consisting of SiS2, GeS2, SnS2 and Sb2S3,
• precursor (5) comprises or consists of elemental sulphur or is not present.
• precursor (1) comprises or consists of Li2S
• precursor (2) comprises or consists of P2S5
• precursor (3) comprises or consists of Lil
• precursor (4) comprises or consists of SiS2, GeS2 and Sb2S3
• precursor (5) comprises or consists of elemental sulphur or is not present.
• pre- cursor (4) comprises or consists of compounds selected from the group consisting of oxides, sulfides, selenides or tellurides of all of Si 4+ , Ge 4+ , Sn 4+ , and Sb 5+ .
• precursor (1) comprises or consists of Li2S precursor (2) comprises or consists of P2S5 precursor (3) comprises or consists of Lil precursor (4) comprises or consists of SiS2, GeS2, SnS2 and Sb2S3, and precursor (5) comprises or consists of elemental sulphur or is not present.
• the reaction mixture may be obtained by mixing the precursors.
• Mixing the precursors may be performed by means of grinding the precursors together. Grinding can be done using any suitable means.
• step (a) any handling is performed under a protective gas atmosphere.
• step (b) of the above-defined process the precursors are reacted to obtain a solid material as defined above.
• the precursors in the reaction mixture react with each other to obtain a solid material having a composition according to general formula (I). Reacting of the precursors may be achieved e.g. by thermochemical processing or by mechanochemical processing.
• thermochemical processing comprises the following steps:
• the reaction mixture which is provided in step (a) may be formed into pellets, which are heat-treated in step (b1). Then, a solid material in the form of pellets or chunks is obtained, which may be ground into powder for further processing.
• reaction mixture prepared in process step (a) is heat-treated in step (b1) to enable the reaction of the precursors.
• Said reaction is considered to be substantially a solid-state reaction, i.e. it occurs with the reaction mixture being in the solid state.
• Heat-treating may be performed in a closed vessel.
• the closed vessel may be a sealed quartz tube or any other type of container which is capable of withstanding the temperature of the heat treatment and is not subject to reaction with any of the precursors, such as a glassy carbon crucible or a tantalum crucible.
• step (b1) the reaction mixture may be heat-treated in a temperature range of from 200 °C to 600 °C for a total duration of 1 hours to 48 hours so that a reaction product is formed. More specifically, in step (b1) the reaction mixture may be heat-treated in a temperature range of 350 °C to 550 °C for a total duration of 5 hours to 30 hours.
• the heat treatment in step (b1) may be carried out under vacuum or under a protective gas atmosphere.
• step (b1) When the duration of the heat treatment of step (b1) is completed, the formed reaction product is allowed to cool down. Thus, a solid material having a composition according to general formula (I) is obtained. Cooling of the reaction product may be performed using a cooling rate of 1 to 10 °C per minute. Alternatively, cooling is achieved by switching off the heating after the duration of heat treatment is completed (so-called natural cooling).
• step (b) reacting of the precursors in step (b) is achieved by mechanochemical treatment.
• mechanochemical treatment comprises the following steps:
• step (b2) mechanochemical treatment of the solid reaction mixture so that a solid material having a composition according to general formula (I) is obtained.
• mechanochemical treatment may be achieved by means of mechanochemical milling, e.g. ball-milling. Devices, e.g. ball mills, and their use for mechanochemical treatment are generally known in the art.
• Mechanochemical treatment is preferably performed at a rotation rate of from 100 rpm to 500 rpm over a duration of from 15 to 30 hours. In certain cases, mechanochemical treatment is performed for 0.5 to 3 hours at a rate in the range of from 100 rpm to 300 rpm, followed by further 12 to 29 hours at a rate of from 400 rpm to 500 rpm.
• the reaction product obtained by ball milling is typically in the form of a powder.
• the process according to the above-defined second preferred alternative may further comprise the following step:
• Annealing of the reaction product obtained by mechanochemical treatment in step (b1) results in an increased crystallinity which is indicated by the presence of more clearly defined reflections in the X-ray diffraction pattern, compared to a solid material having the same composition and prepared in the same manner (i.e. same steps (a) and (b2)) but without step (c).
• the powder obtained by step (b2) is pressed into pellets which are annealed in step (c2).
• Annealing may be performed in a closed vessel.
• the closed vessel may be a sealed quartz tube or any other type of container which is capable of withstanding the temperature of the annealing and is not subject to reaction with any of the precursors, such as a glassy carbon crucible or a tantalum crucible.
• step (c) the reaction mixture may be annealed in a temperature range of from 200 °C to 600 °C for a total duration of 1 hours to 48 hours. More specifically, in step (c) the reaction mixture may be annealed in a temperature range of 350 °C to 550 °C for a total duration of 5 hours to 30 hours.
• the heat treatment in step (c) may be carried out under vacuum or under a protective gas atmosphere. When the duration of the heat treatment of step (c) is completed, the formed reaction product is allowed to cool down. Thus, a solid material having a composition according to general formula (I) is obtained. Cooling of the reaction product may be performed using a cooling rate of 1 to 10 °C per minute, or by quenching, e.g. in liquid nitrogen. Alternatively, cooling is achieved by switching off the heating after the duration of heat treatment is completed (so-called natural cooling).
• a solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect can be used as a solid electrolyte for an electrochemical cell.
• the solid electrolyte may form a component of a solid structure for an electrochemical cell, wherein said solid structure is selected from the group consisting of cathode, anode and separator.
• a solid material according to the abovedefined first aspect resp. obtained by the process according to the above-defined second aspect can be used (if necessary in combination with additional components) for producing a solid structure for an electrochemical cell, such as a cathode, an anode or a separator.
• the present disclosure further provides the use of a solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect as a solid electrolyte for an electrochemical cell.
• the solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect may have a composition according to general formula (I) as defined above, preferably according to general formula (II) as defined above, most preferably according to one of general formulae (Ila), (Ila’), (Ila”), (lib), (lib’), (He), (He’), (He”), (lid) and (lid’) as defined above.
• the present disclosure further provides the use of a solid material according to the above-defined first aspect resp. obtained by the process according to the abovedefined second aspect as a component of a solid structure for an electrochemical cell, wherein said solid structure is selected from the group consisting of cathode, anode and separator.
• the electrode where during discharging a net negative charge occurs is called the anode and the electrode where during discharging a net positive charge occurs is called the cathode.
• Suitable electrochemically active cathode materials and suitable electrochemically active anode materials are known in the art.
• the cathode of a solid-state electrochemical cell usually comprises beside an active cathode material as a further component a solid electrolyte.
• anode of a solid-state electrochemical cell usually comprises a solid electrolyte as a further component beside an active anode material.
• Said solid electrolyte may be a solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect.
• a separator electronically separates a cathode and an anode from each other.
• the separator comprises a solid electrolyte.
• Said solid electrolyte may be a solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect.
• the present disclosure further provides a solid structure for an electrochemical cell, wherein the solid structure is selected from the group consisting of cathode, anode and separator, wherein the solid structure for an electrochemical cell comprises a solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect.
• the solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect may have a composition according to general formula (I) as defined above, preferably according to general formula (II) as defined above, most preferably according to one of general formulae (Ila), (Ila’), (Ila”), (lib), (lib’), (lie), (lie’), (He”), (lid) and (lid’) as defined above.
• the form of the solid structure for an electrochemical cell depends in particular on the form of the electrochemical cell itself.
• the present disclosure further provides a solid structure for an electrochemical cell, wherein the solid structure is selected from the group consisting of cathode, anode and separator, wherein the solid structure for an electrochemical cell comprises a solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect.
• the present disclosure further provides an electrochemical cell comprising a solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect.
• the solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect may form a component of one or more solid structures selected from the group consisting of cathode, anode and separator.
• the above-defined electrochemical cell may be a rechargeable electrochemical cell comprising the following constituents a) at least one anode, p) at least one cathode, y) at least one separator, wherein at least one of the three constituents is a solid structure selected from the group consisting of cathode, anode and separator comprises a solid material according to the above-defined first aspect resp. obtained by the process according to the above-defined second aspect.
• anode a may comprise graphitic carbon, metallic lithium or a metal alloy comprising lithium as the anode active material.
• Electrochemical cells as described above may be alkali metal containing cells, especially lithium-ion containing cells.
• the charge transport is effected by Li + ions.
• the electrochemical cell may have a disc-like or a prismatic shape.
• the electrochemical cells can include a housing that can be from steel or aluminum.
• a plurality of electrochemical cells as described above may be combined to a solid-state battery, which has both solid electrodes and solid electrolytes.
• a further aspect of the present disclosure refers to batteries, more specifically to an alkali metal ion battery, in particular to a lithium-ion battery comprising at least one electrochemical cell as described above, for example two or more electrochemical cells as described above.
• Electrochemical cells as described above can be combined with one another in alkali metal ion batteries, for example in series connection or in parallel connection. Series connection is preferred. The electrochemical cells resp.
• batteries described herein can be used for making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and stationary applications such as energy storage devices for power plants.
• a further aspect of this disclosure is a method of making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment, remote car locks, and stationary applications such as energy storage devices for power plants by employing at least one inventive battery or at least one inventive electrochemical cell.
• a further aspect of the present disclosure is the use of the electrochemical cell as described above in motor vehicles, bicycles operated by electric motor, robots, aircraft (for example unmanned aerial vehicles including drones), ships or stationary energy stores.
• the present disclosure further provides a device comprising at least one inventive electrochemical cell as described above.
• mobile devices such as are vehicles, for example automobiles, bicycles, aircraft, or water vehicles such as boats or ships.
• Other examples of mobile devices are those which are portable, for example computers, especially laptops, telephones or electrical power tools, for example from the construction sector, especially drills, battery-driven screwdrivers or battery-driven tackers.
• step (a) four different reaction mixtures (total amount around 1.5 g) consisting of the precursors IJ2S (99.99%, Sigma Aldrich), P2S5 (99%, Sigma Aldrich), GeS2 (99.9%, Good- Fellow), SiS2 (99.99%, GoodFellow), Sb2Ss (99.99%, Alfa Aesar), Ss (99.99%, Sigma Aldrich) and Lil (99.999%, Sigma Aldrich) was loaded into a 70 mL zirconia milling jar with 10 zirconia milling balls (10 mm diameter).
• the stoichiometric ratio of the precursors was selected so that it matches a composition selected from Li65Po 25Sio 25Geo 25Sbo 25S5l, Li6342Po 5Sio 166Geo 166Sbo 166S5l and Li617lPo75Sio O83GeoO83Sbo O83S5l.
• a reaction mixture consisting of the above-mentioned precursors except for P2S5 was provided.
• the stoichiometric ratio of the precursors was selected so that it matches a composition Lie ySio ssGeo ssSbo ssSsl.
• step (b) Reacting of the precursors was achieved by mechanochemical processing.
• step (b) the reaction mixture was milled for 1 h at 250 rpm, and then the speed was increased to 450 rpm and milling was continued for another 20 h.
• the recovered powder was pressed into the pellets ( ⁇ 300 mg, 10 mm diameter) at 3 1 and vacuum sealed (10 -3 bar) in quartz ampules.
• the ampules were pre-dried at 500 °C for 10 min using a heat gun under dynamic vacuum (10 -3 mbar) to avoid trace water.
• step (c) The samples were subsequent annealed at 400 °C for 24 h (step (c) with a heating and cooling rate of 5 °C/min.
• the cooling rate corresponds to natural cooling.
• the sample having the composition LieySio ssGeo ssSbossSsl (not according to the invention) and an additional sample of the composition Li65Po25Sio25Geo 25Sbo25S5l were annealed at 500 °C for 24 h (step (c) with a heating and cooling rate of 5 °C/min.
• step (c) For the composition Li65Po 25Sio25Geo 25Sbo25S5l, additional samples were prepared without annealing (step (c)).
• step (c) For the composition Li65Po 25Sio25Geo 25Sbo25S5l, additional samples were prepared to study the influence of the following alternative cooling conditions in step (c): either slow cooling over 48 hours, or quenching in liquid nitrogen.
• the three different materials having a composition according to general formula Li(6+m)P(i-3n)SinGe n Sb n S5l show typical single phase XRD pattern referring to the so called cubic argyrodite structure ( Figure 1 a). Moreover, a gradual shift of the reflections to lower 20 angles was observed with decreasing phosphorous content (fig. 1 b), indicating the presence of a solid solution between the different cationic substituents (P, Si, Ge and Sb).
• XRD patterns of a sample obtained without annealing (no step (c)) and another one obtained with annealing (step (c)) followed by natural cooling were compared. After annealing the reflections in the XRD pattern are more clearly defined, indicating an increased crystallinity than after ball milling without annealing (fig. 2).
• the cooling conditions did not show a significant influence on the XRD pattern of Li65P025Si025Ge025Sb025S5!.
• Fig. 3 shows XRD patterns (cf. fig. 3) of Li65Po 25Sio25Geo 25Sbo25S5l and Li67Sio 33Geo 33Sbo 33S5l (both annealed at 500 °C).
• the presence of four different elements (P, Si, Ge, Sb) at the lattice sites, which in the parent material LePSsl are occupied by phosphorus results in entropy stabilization so that a single phase is obtained.
• Electrochemical impedance spectroscopy was measured using a custom-made two- electrode cell, including two stainless steel plungers and a PEEK sleeve with an inner diameter of 10 mm. Around 150 mg powder was introduced into the cell and pressed at 3 t for 3 min (i.e. cold-pressed). EIS was measured from 0.1 Hz to 7 MHz with a 20 mV voltage amplitude using a SP-200 potentiostat (BioLogic) at room temperature. An external pressure of 2 t was applied during the measurement.
• EIS Electrochemical impedance spectroscopy
• the cooling conditions (natural cooling, or fast cooling by quenching, or slow cooling over 48 hours) appear to have a significant influence on the ionic conductivity of Li65P025Si025Ge025Sb025S5! . Accordingly, natural cooling (cooling rate approximately 5°C per minute) appears favorable, compared to both, quenching and slow cooling.

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