WO2018054709A1 - Électrolytes de lithium solides et procédé de production - Google Patents

Électrolytes de lithium solides et procédé de production Download PDF

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Publication number
WO2018054709A1
WO2018054709A1 PCT/EP2017/072758 EP2017072758W WO2018054709A1 WO 2018054709 A1 WO2018054709 A1 WO 2018054709A1 EP 2017072758 W EP2017072758 W EP 2017072758W WO 2018054709 A1 WO2018054709 A1 WO 2018054709A1
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range
general formula
mixture
compound
dme
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PCT/EP2017/072758
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Heino Sommer
Stefan Sedlmaier
Sylvio Indris
Juergen Janek
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Basf Se
Karlsruher Institut für Technologie
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Publication of WO2018054709A1 publication Critical patent/WO2018054709A1/fr

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    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a process for preparing solid electrolytes, to compounds, which can be used as precursors for the preparation of said solid electrolytes, to particular solid electrolytes, and to separators, electrochemical cells, batteries and devices all comprising said particular solid electrolytes.
  • Secondary batteries, accumulators or "rechargeable batteries” are just some embodiments by which electrical energy can be stored after generation and used when required. Owing to the significantly better power density, there has been in recent times a move away from the water- based secondary batteries toward development of those batteries in which the charge transport in the electrical cell is accomplished by lithium ions.
  • the solid electrolytes useful for all-solid-state lithium batteries have to fulfill many requirements such as high ionic conductivity, chemical compatibility with cathode and anode materials, electrochemical stability, mechanical stability and economic producibility.
  • J. Am. Chem. Soc. 2013, 135, 975-978 and US 2013/0295469 A1 both disclose a method for forming U3PS4 from L12S and P2S5 in a solvent such as THF.
  • a solvent such as THF.
  • 975-978 the formation of U3PS4 ⁇ 3THF and its conversion to U3PS4 is described.
  • US 2015/0318569 A1 discloses a method for manufacturing a sulfide solid electrolyte including loading a raw material for manufacturing a sulfide solid electrolyte which is mainly composed of a substance represented by the general formula of (100-x)(0.75Li2S.0.25P2Ss).xLil (here, 0 ⁇ x ⁇ 100), into a vessel; and amorphizing the raw material after said loading, wherein a reaction site temperature in the vessel is controlled so that x included in the general formula and the re- action site temperature y [degrees centigrade] in the vessel in said amorphizing satisfy y ⁇ -2.00x+1 .79x10 2 .
  • x is varied in the range from 15 to 30.
  • a first object of the invention was to provide an economic and reproducible process for the preparation of new or known solid electrolytes, which can be used as components of rechargeable electrochemical cells
  • a second object of the invention was to provide suitable new starting materials for the new process
  • a third object of the invention was to provide new solid electrolytes with improved properties, such as ionic conductivity, chemical compatibility with cathode and anode materials, electrochemical stability or mechanical stability.
  • the first object is achieved by a process for preparing a solid electrolyte of general formula (I) Li + 4-2a + c + 2d + e M 2+ a P 5+ 1-b-c-d As 5+ b D 4+ c E + d S 2 -4-e-f N " e T 2" f l " l-g X " g (I) in which the variables are each defined as follows:
  • M is Mg, Ca, Zn or a mixture thereof, preferably Mg or Zn, in particular Mg,
  • D is Si, Ti, Ge, Sn or a mixture thereof, preferably Ge,
  • E is B, Al, Ga, In or a mixture thereof, preferably Al,
  • T is O, Se, Te or a mixture thereof, preferably O or Se, in particular O,
  • X is F, CI, Br, CN, OCN, SCN, N 3 or a mixture thereof, preferably Br, a is in the range from 0 to 2, preferably from 0 to 1 , more preferably from 0 to 0.5, in particular from 0 to 0.25
  • b is in the range from 0 to 1 , preferably from 0 to 0.5,
  • c is in the range from 0 to 1 , preferably from 0 to 0.5,
  • d is in the range from 0 to 1 , preferably from 0 to 0.5,
  • e is in the range from 0 to 4, preferably from 0 to 2,
  • f is in the range from 0 to 4, preferably from 0 to 2,
  • g is in the range from 0 to 1 , preferably from 0 to 0.5, wherein the sum of b+c+d is in the range from 0 to 1 , preferably from 0 to 0.5, in particular from 0 to 0.25, and
  • Solv is a polar solvent molecule selected from the group consisting of ethers, acetals, amides, alcohols and mixtures thereof, preferably an ether selected from THF and DME, in particular DME, a' is in the range from 0 to 1 .5, preferably from 0 to 0.75,
  • a" is in the range from 0 to 0.5, preferably from 0 to 0.25,
  • h is in the range from 1 to 6, preferably from 1 to 4, and at least one organic solvent
  • the inventive process is characterized in that the solid electrolyte of general formula (I) is crystalline.
  • the inventive process is particularly useful for preparing new compounds of general formula (I), wherein the elements Li, P, S and I are at least partially substituted by other elements, without completely changing the original crystal structure type of U4PS4I.
  • the inventive process is characterized in that in above defined general formula (I) the sum of a+b+c+d+e is > 0, preferably in the range from 0.01 to 2, more preferably the range from 0.02 to 0.5.
  • the inventive process is characterized in that the variables are each defined as follows:
  • M is Mg
  • X is Br
  • a is in the range from 0 to 0.5, in particular from 0 to 0.25
  • b is in the range from 0 to 0.5, in particular from 0 to 0.25, is in the range from 0 to 0.5, in particular from 0 to 0.25,
  • Solv is an ether selected from THF and DME,
  • a' is in the range from 0 to 0.375
  • a" is in the range from 0 to 0.125
  • h is in the range from 1 to 6, preferably from 1 to 4, wherein the sum of b+c+d is in the range from 0 to 0.5, in particular from 0 to 0.25, and wherein the sum of e+f is in the range from 0 to 2, in particular from 0 to 1.
  • M is Mg
  • X is Br, is in the range from 0 to 0.5, in particular from 0 to 0.25,
  • Solv is an ether selected from THF and DME,
  • a' is in the range from 0 to 0.375
  • a" is in the range from 0 to 0.125
  • h is in the range from 1 to 6, preferably from 1 to 4, wherein the sum of b+c+d is in the range from 0 to 0.5, in particular from 0 to 0.25, the sum of e+f is in the range from 0 to 2, in particular from 0 to 1 , and the sum of a+b+c+d+e is > 0, preferably in the range from 0.01 to 2, more preferably the range from 0.02 to 0.5.
  • the first object is also achieved by a process for preparing a solid electrolyte of general formula (I)
  • M is Mg, Ca, Zn or a mixture thereof, preferably Mg or Ca, in particular Ca,
  • X is F, CI, Br, CN, OCN, SCN, N 3 or a mixture thereof, a is in the range from 0 to 2, preferably from 0 to 1 , more preferably from > 0 to 0.5, in particular from 0.01 to 0.5,
  • g is in the range from 0 to 1 , preferably from 0 to 0.5, comprising the process steps of a) preparing a mixture comprising a compound A) of general formula (II)
  • Solv is a polar solvent molecule selected from the group consisting of ethers, acetals, amides, alcohols and mixtures thereof
  • a' is in the range from 0 to 1 .5, preferably from 0 to 0.75, more preferably from 0 to 0.1
  • a" is in the range from 0 to 0.5, preferably from 0 to 0.25, more preferably from > 0 to 0.5, in particular from 0.01 to 0.5,
  • h is in the range from 1 to 6, preferably from 1 to 4, and at least one organic solvent
  • b) converting the mixture prepared in process step a) to the solid electrolyte of general formula (I) by removing the organic solvent and heating the formed solidified material at a temperature in the range from 50 °C up to 600 °C.
  • the above-mentioned inventive process characterized in that the variables are each defined as follows:
  • M is Mg
  • X is Br, is in the range from 0 to 0.5, in particular from 0 to 0.25,
  • Solv is an ether selected from THF and DME, in particular DME,
  • a' is in the range from 0 to 0.375
  • a" is in the range from 0 to 0.125
  • h is in the range from 1 to 6, preferably from 1 to 4.
  • M is Ca
  • X is Br
  • a is in the range from 0 to 0.5, preferably from 0 to 0.25, more preferably from > 0 to 0.25, in particular from 0.0.1 to 0.25,
  • g is in the range from 0 to 0.5, in particular from 0 to 0.25
  • Solv is an ether selected from THF and DME, in particular DME,
  • a' is in the range from 0 to 0.1.5, preferably from 0 to 0.5
  • a" is in the range from 0 to 0.5, preferably from > 0 to 0.5, more preferably from > 0.01 to 0.5, h is in the range from 1 to 6, preferably from 1 to 4.
  • Certain compounds A) of general formula (II) and compounds B) of general formula (III) are in principle known to the person skilled in the art.
  • Known examples of compound A) are for example U3PS4 ⁇ 3THF, U3PS4 ⁇ 2ACN or of Li 3 PS 4 ⁇ 2EtOAc.
  • Compounds B) are generally known, since all lithium halides and all halides of magnesium, calcium and zinc are commercially available.
  • Each component B) of general formula (III) is availa- ble by mixing the appropriate metal halides in the desired stoichiometry.
  • the inventive process is characterized in that in process step a) the compound A) of general formula (II) is crystalline U3PS4 ⁇ DME or U3PS4 ⁇ 2DME, in particular U3PS4 ⁇ DME, and compound B) of general formula (III) is Lil.
  • the inventive process is characterized in that in process step a) the compound A) of general formula (II) is crystalline L13 PS 4 ⁇ DME or L13 PS 4 ⁇ 2DME, in particular U3PS4 ⁇ DME, compound B) of general formula (III) is Lil and the organic solvent is DME.
  • the inventive process is characterized in that in process step a) the compound A) of general formula (II) is crystalline L13 PS 4 ⁇ DME, compound B) of general formula (III) is Li 2(0.25 - 0.3) Mg 2+ 0 .25 - o.3 1 " or L _ 2 (o.oi - 0.1) Ca 2+ o.oi - o.i I " and the organic solvent is DME.
  • the inventive process is characterized in that in process step a) the compound A) of general formula (II) is defined as compound A1 ) of general formula (11-1 ) as described below.
  • a mixture comprising as a first component a compound A) of general formula Li + 3-2a' + c + 2d+e M 2 V P 5+ i-b-c-d As 5+ b D 4+ c E 3+ d S 2" 4 -e-f N 3" e T 2" f * h Solv (II), as a second component a compound B) of general formula Li + i-2a- M 2 V - g X " g (III) and as a third component at least one organic solvent, wherein the variables are defined as described above.
  • the inventive process is characterized in that the variable Solv is a polar aprotic solvent molecule selected from the group consisting of ethers, acetals, amides and mixtures thereof.
  • Preferred polar aprotic solvent molecules are dimethoxy- ethane (DME), dichloromethane (DCM), tetrahydrofuran (THF), ethyl acetate (EtOAc), dimethyl- formamide (DMF), N-methylformamide (NMF), dimethylsulfoxide (DMSO), acetone, hexa- methylphosphoric triamide (HMPT), N-methylpyrrolidone (NMP) or 1 ,3-dioxolane, particularly preferred DME, DMF, NMF, DMSO, 1 ,3-Dioxolane, DCM, HMPT or NMP.
  • DME dimethoxy- ethane
  • DCM dichloromethane
  • THF tetrahydrofuran
  • the third component, the organic solvent can be varied in a wide range.
  • the organic solvent is a polar solvent, in particular an aprotic polar solvent.
  • a preferred aprotic polar solvent is dimethoxyethane (DME), dichloromethane (DCM), tetrahydrofuran (THF), ethyl acetate (EtOAc), acetonitrile (MeCN), dimethylformamide (DMF), N-methylformamide (NMF), dimethyl- sulfoxide (DMSO), acetone, hexamethylphosphoric triamide (HMPT), N-methylpyrrolidone (NMP) or 1 ,3-dioxolane.
  • DME dimethoxyethane
  • DCM dichloromethane
  • THF tetrahydrofuran
  • EtOAc ethyl acetate
  • MeCN dimethylformamide
  • NMF N-methylformamide
  • DMSO dimethyl- sulfoxide
  • the molar ratio of compound A) to compound B) in the mixture prepared in process step a) can be varied in a wide range.
  • the molar ratio of compound A) to compound B) in the mixture prepared in process step a) is in the range from 0.66 to 1 .5, more preferably from 0.75 to 1 .25, in particular from 0.9 to 1.1.
  • the inventive process is characterized in that in process step a) the molar ratio of compound A) to compound B) is in the range from 0.66 to 1 .5.
  • the sum of the mass fractions of components A), B) and the organic solvent, which are mixed together in process step a), can be varied in a broad range depending on the presence of further additional components in said mixture.
  • the sum of the mass fractions of components A), B) and the organic solvent in the mixture is in the range from 0.6 to 1 , more preferably in the range from 0.8 to 1 , in particular in the range from 0.9 to 1.
  • Components A) and B) are in most cases solid materials at room temperature (20 °C). Further compound A) and compound B) can be completely or partly soluble in the used organic solvent.
  • the order of mixing components A) and B) and the organic solvents can be varied. For exam- pie, a mixture of compound B) and the organic solvent is formed in form of a solution or a suspension followed by addition of compound A). Alternatively, a first mixture of compound A) and the organic solvent is combined with a second mixture of compound B) and the organic solvent. It is also possible to mix first compound A) with compound B), preferably both in powder form, and then combining said mixture with the organic solvent.
  • the inventive process is characterized in that in process step a) the compound A) and compound B) are both mixed in powder form, before the at least one organic solvent is added in order to form the mixture, preferably a liquid mixture, e.g. a solution or a suspension.
  • the mixture, which was prepared in process step a), is converted to the solid electrolyte of general formula (I) by removing the organic solvent or solvents and heating the formed solidified material at a temperature in the range from 50 °C up to 600 °C.
  • solidified material means that the material is structural rigid at room temperature (20 °C) and shows resistance to changes of shape or volume.
  • the solidified material usually still comprises certain amounts of organic solvents, in particular as long as the applied temperature is not higher than the boiling point of the respective solvent.
  • the organic solvent or solvents are usually removed from the mixture prepared in process step a) by evaporating the organic solvent molecules.
  • the conditions for evaporating one or more organic solvents from a solution and/or suspension are known to the person skilled in the art.
  • the decreasing content of organic solvent molecules in the mixture and in the formed solidified material can be easily monitored by FT-IR analysis.
  • process step b) can be performed under reduced pressure in order to accelerate the removal of organic solvent molecules.
  • the appropriate pressure in process step b) is preferably adjusted by considering the optimal temperature for the formation of the solid electrolyte of general formula (I) and the need for removal of organic solvent molecules.
  • the time needed for evaporating a solvent at a given temperature varies depending on the conditions applied. Dynamic conditions, e.g. atmosphere circulation or constant exchange of the atmosphere in order to remove solvent vapors continuously, decrease the time needed for evaporating a solvent when compared to static methods, wherein the atmosphere e.g. does not moved or is not exchanged (stagnant atmosphere).
  • process step b) the organic solvents molecules, which can be still present in the solidified material, are finally completely removed during the formation of the solid electrolyte of general formula (I), preferably at a temperature in the range from 50 °C up to 600 °C, preferably in the range from 90 °C up to 300 °C.
  • the time for converting the solidified material to the solid electrolyte of general formula (I) can be varied in a wide range depending on the final, usually highest temperature reached and on the heating rate used in order to reach the final temperature.
  • the heating rate itself, which is applied in process step b) in order to reach the final temperature can be varied in a wide range.
  • the final temperature of process step b) is reached by a heating rate in the range from 0.1 K/min to 200 K/min, more preferably in the range from 0.2 K/min to 50 K min, much more preferably in the range from 0.5 K/min to 20 K/min, in particular in the range from 0.5 K/min to 1 K/min.
  • the inventive process is characterized in that in process step b) the formed solidified material is heated for a period in the range from 0.003 h to 12 h, preferably in the range from 0.05 to 3 h.
  • the inventive process is characterized in that in process step b) the formed solidified material is heated at a temperature in the range from 50 °C up to 600 °C for a for a period in the range from 0.003 h to 12 h, preferably at a temperature in the range from 90 °C up to 300 °C for a for a period in the range from 0.04 h to 3 h.
  • a spray drying process can be used for process step a) via mixing the compound A) with compound B) in a twin nozzle, followed by process step b) in the drying chamber of the spray dryer and in a belt dryer or a rotary kiln, which are connected directly to the spray dryer.
  • the inventive process represents an economic and reproducible process, which gives access to the solid electrolytes of general formula (I).
  • the present invention further provides a compound A1 ) of general formula (11-1 )
  • M is Mg, Ca, Zn or a mixture thereof, preferably Mg or Zn, in particular Mg,
  • D is Si, Ti, Ge, Sn or a mixture thereof, preferably Ge,
  • E is B, Al, Ga, In or a mixture thereof, preferably Al,
  • T is O, Se, Te or a mixture thereof, preferably O or Se, in particular O,
  • Solv is DME, DMF, NMF, DMSO, 1 ,3-Dioxolane, DCM, HMPT or NMP, preferably DME a' is in the range from 0 to 1 .5, preferably from 0 to 0.75,
  • b is in the range from 0 to 1 , preferably from 0 to 0.5,
  • c is in the range from 0 to 1 , preferably from 0 to 0.5,
  • d is in the range from 0 to 1 , preferably from 0 to 0.5,
  • e is in the range from 0 to 4, preferably from 0 to 2,
  • f is in the range from 0 to 4, preferably from 0 to 2,
  • h is 1 , 2, 3 or 4, wherein the sum of b+c+d is in the range from 0 to 1 , preferably from 0 to 0.5, in particular from 0 to 0.25, and wherein the sum of e+f is in the range from 0 to 4, preferably from 0 to 2, in particular from 0 to 1 .
  • the inventive compound A1 is characterized the variables are each defined as follows:
  • M is Mg
  • Solv is DME, a' is in the range from 0 to 0.375,
  • b is in the range from 0 to 0.5, in particular from 0 to 0.25,
  • c is in the range from 0 to 0.5, in particular from 0 to 0.25,
  • d is in the range from 0 to 0.5, in particular from 0 to 0.25,
  • e is in the range from 0 to 2, in particular from 0 to 1 ,
  • f is in the range from 0 to 2, in particular from 0 to 1 ,
  • h is 1 , 2, 3 or 4, wherein the sum of b+c+d is in the range from 0 to 0.5, in particular from 0 to 0.25, and wherein the sum of e+f is in the range from 0 to 2, in particular from 0 to 1.
  • the present invention further provides a compound A1 ) of general formula (11-1 )
  • M is Mg, Ca, Zn or a mixture thereof, preferably Mg or Ca, in particular Ca,
  • Solv is DME, DMF, NMF, DMSO, 1 ,3-Dioxolane, DCM, HMPT or NMP, preferably DME a' is in the range from 0 to 1 .5, preferably from 0 to 0.75, more preferably from 0 to 0.1 , in particular 0,
  • h is 1 , 2, 3 or 4.
  • the inventive compound A1 ) is characterized in that Compounds A1 ) of general formula (11-1 )
  • Li Li, Li 2 S, Li 2 0, Li 2 Se or Li 3 PS 4 , n-BuLi, sec-BuLi, tert-BuLi
  • Mg Mgl 2 , MgBr 2 , MgCI 2 , MgS, Mg(Me) 2 ,
  • Ca CaCI 2 , CaBr 2 , Cab
  • Zn Znl 2 , ZnBr 2 , ZnCI 2
  • Si SiS 2 , Li 4 Si0 4
  • Ti TiS 2 , Li 4 Ti0 4
  • Ge GeS 2 , Li 4 GeS 4 ,
  • B B 2 S 3 , B(OH) 3 ,
  • N NH 3 , Li 7 PN 4 , OP(NH 2 ) 3 , SP(NH 2 ) 3
  • the present invention further provides a solid electrolyte of general formula (1-1 ) Li + 4-2a+ c +2 d + e M 2+ a P 5+ 1-b-c-d AS 5+ b D 4+ c E 3+ d S 2 - 4- e-f N 3" e T 2" f ⁇ -g X " g (1-1 ) in which the variables are each defined as follows:
  • M is Mg, Ca, Zn or a mixture thereof, preferably Mg or Zn, in particular Mg,
  • D is Si, Ti, Ge, Sn or a mixture thereof, preferably Ge,
  • E is B, Al, Ga, In or a mixture thereof, preferably Al,
  • T is O, Se, Te or a mixture thereof, preferably O or Se, in particular O,
  • X is F, CI, Br, CN, OCN, SCN, N 3 or a mixture thereof, preferably Br, a is in the range from 0 to 1 , preferably 0 to 0.5, more preferably 0 to 0.25,
  • b is in the range from 0 to 0.5, preferably 0 to 0.25,
  • c is in the range from 0 to 0.5, preferably 0 to 0.25
  • d is in the range from 0 to 0.5, preferably 0 to 0.25
  • e is in the range from 0 to 2, preferably 0 to 0.5,
  • f is in the range from 0 to 2, preferably 0 to 0.5
  • the present invention further provides a solid electrolyte of general formula
  • M is Mg, Ca, Zn or a mixture thereof, preferably Mg or Ca, in particular Ca,
  • X is F, CI, Br, CN, OCN, SCN, N 3 or a mixture thereof, preferably Br, a is in the range from > 0 to 0.5, preferably from 0.01 to 0.5, more preferably from 0.01 to 0.25,
  • g is in the range from 0 to 0.5, preferably 0 to 0.25, more preferably 0.
  • the inventive solid electrolyte of general formula (I- 1 ) is characterized in that it
  • M is Ca
  • X is F, CI, Br, CN, OCN, SCN, N 3 or a mixture thereof, preferably Br, a is in the range from 0.01 to 0.25, in particular 0.01 to 0.1
  • g is in the range from 0 to 0.25, preferably 0 to 0.1 , more preferably 0.
  • the inventive solid electrolyte of general formula (I- 1 ) is characterized in that it
  • M is Mg
  • X is F, CI, Br, CN, OCN, SCN, N 3 or a mixture thereof, preferably Br, a is in the range from 0.01 to 0.5, in particular 0.25 to 0.3
  • the inventive solid electrolyte is characterized in that it is Li 4 - 2(0.25 -o.3)Mgo.25-o.3PS4l or Li 4 - 2(o.oi - o.i)Cao.oi - o.i PS 4 l, preferably Li 3 .45Mgo.28PS 4 l or Li3.95Cao.o2PS 4 l, in particular Li 3 .95Cao.o2PS 4 l.
  • Solid electrolytes of general formula (1-1 ) show advantages compared to Li 4 PS 4 l with respect to at least one of the following properties: ionic conductivity, chemical compatibility with cathode and anode materials, electrochemical stability or mechanical stability.
  • the solid electrolytes of general formula (1-1 ) can be used alone or in combination with addi- tional components for producing a solid structure for an electrochemical cell, such as a cathode, an anode or a separator.
  • a separator separates a cathode and an anode from each other in an electrochemical cell, in particular in all-solid-state lithium batteries.
  • the cathode of an all-solid- state lithium battery usually comprises beside an active cathode material as a further component a solid electrolyte.
  • the anode of an all-solid-state lithium battery usually comprises be- side an active anode material as a further component a solid electrolyte.
  • the form of the solid structure for an electrochemical cell, in particular for an all-solid-state lithium battery depend in particular on the form of the produced electrochemical cell itself.
  • 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.
  • the present invention further provides the use of the solid electrolyte of general formula (1-1 ) as described above as component of a solid structure for an electrochemical cell selected from the group consisting of cathode, anode and separator.
  • the present invention further provides a solid structure for an electrochemical cell selected from the group consisting of cathode, anode and separator, wherein the solid structure for an electrochemical cell comprises the solid electrolyte of general formula (1-1 ) as described above.
  • the present invention further provides an electrochemical cell comprising at least one solid structure for an electrochemical cell as described above, which comprises at least the solid electrolyte of general formula (1-1 ).
  • the inventive electrochemical cell is preferably a rechargeable electrochemical cell comprising as components a) at least one anode a), ⁇ ) at least one cathode ⁇ ),
  • Y at least one separator, wherein at least one of the three components is a solid structure selected from the group consisting of cathode, anode and separator comprising the solid electrolyte of general formula (1-1 ) as described above.
  • suitable electrochemically active cathode materials and suitable electrochemically active anode materials reference is made to the relevant prior art, e.g. appropriate monographs and reference works: e.g. Wakihara et al. (editor): Lithium ion Batteries, 1 st edition, Wiley VCH, Weinheim, 1998; David Linden: Handbook of Batteries (McGraw-Hill Handbooks), 3 rd edition, Mcgraw-Hill Professional, New York 2008; J. O. Besenhard: Handbook of Battery Materials. Wiley-VCH, 1998.
  • inventive electrochemical cells are preferably selected from alkali metal containing cells. More preferably, inventive electrochemical cells are selected from lithium-ion containing cells. In lithium-ion containing cells, the charge transport is effected by Li + ions.
  • anode a) comprises metallic lithium
  • cathode ⁇ comprises an active material selected from the group consisting of:
  • lithium iron phosphates with olivine structure such as lithium iron phosphates (LiFeP0 4 ) and lithium manganese phosphate (LiMnP0 4 ) which can have a stoichiometric or non-stoichiometric composition and which can be doped or not doped, and
  • lithium containing transition metal spinels and lithium transition metal oxides with a layered crystal structure such as UC0O2, LiNio,5Mni, 5 0 4- d, LiMn20 4 or NCMs such as Lii + t(Nio,33Coo,33Mn 0 ,33)02, Lii + t(Nio,5Coo,2Mn 0 ,3)02, Lii +t (Nio, 4 Coo,3Mno, 4 )02,
  • inventive electrochemical cells can have a disc-like shape. In another embodiment, inventive electrochemical cells can have a prismatic shape.
  • inventive electrochemical cells can include a hous- ing that can be from steel or aluminium. In one embodiment of the present invention, inventive electrochemical cells are combined to all solid-state batteries, which have both solid electrodes and solid electrolytes.
  • Inventive electrochemical cells have overall advantageous properties. They have a long dura- tion with very low loss of capacity, good cycling stability, and a reduced tendency towards short circuits after longer operation and/or repeated cycling.
  • a further aspect of the present invention refers to batteries, more preferably to an alkali metal ion battery, in particular to a lithium ion battery comprising at least one inventive electrochemical cell, for example two or more.
  • inventive electrochemical cells can be combined with one another in inventive alkali metal ion batteries, for example in series connection or in parallel connection. Series connection is preferred.
  • Inventive batteries have advantageous properties. They have a long duration with very low loss of capacity, good cycling stability, and high temperature stability.
  • inventive electrochemical cells or inventive batteries can be used for making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and stationary applications such as energy storage devices for power plants.
  • a further aspect of the present invention is a method of making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment, remote car locks, and stationary applications such as energy storage devices for power plants by employing at least one inventive battery or at least one inventive electrochemical cell.
  • a further aspect of the present invention is the use of the electrochemical cell as described above in motor vehicles, bicycles operated by electric motor, aircraft, ships or stationary energy stores.
  • inventive electrochemical cells in devices gives the advantage of prolonged run time before recharging and a smaller loss of capacity in the course of prolonged run time. If the intention were to achieve an equal run time with electrochemical cells with lower energy density, a higher weight for electrochemical cells would have to be accepted.
  • the present invention 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.
  • the invention is illustrated by the examples which follow, but these do not restrict the invention.
  • Li3PS 4 ⁇ DME was synthesized by reacting L12S and P 4 Sio in DME. All manipulations were carried out in an argon-filled glovebox (MBraun) with an O2 and H2O content below 0.1 ppm or on a Schlenk line. In a typical approach Li 2 S (488.0 mg, 10.62 mmol; Alfa Aesar 99.9 %) and P2S5 (1 .012 g, 4.553 mmol; Sigma Aldrich 99 %) were mixed together and ground in an agate mortar and filled into a dried 100 ml Schlenk flask. After adding approx.
  • Table 1 Crystallographic data of U3PS4 ⁇ DME (PE1 ) and details of the data collection and relative structure solution and refinement (esd's in parentheses).
  • Table 3 Crystallographic data of Li 4 PS 4 l (E1 ) and details of the data collections and relative structure solution and refinement (esd's in parentheses).
  • the adducts of U3PS4 have been synthesized using the solvents DME, acetonitrile and THF.
  • the product from acetonitrile resulted in the ACN-adduct whose crystal structure appeared to be disordered (see both, sharp and broad reflections in XRD pattern in Figure 2b) and also con- sisting of additional L12S impurities (from incomplete reaction).
  • the structure of the THF-adduct could also not be solved due to a very low symmetry (see pattern with many overlapping reflections).

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Abstract

La présente invention concerne un procédé de préparation d'électrolytes solides, des composés, qui peuvent être utilisés en tant que précurseurs pour la préparation desdits électrolytes solides, en particulier des électrolytes solides, et des séparateurs, des cellules électrochimiques, des batteries et des dispositifs comprenant tous lesdits électrolytes solides particuliers.
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018174129A (ja) * 2017-03-31 2018-11-08 国立大学法人東京工業大学 固体電解質材料およびその製造方法
WO2020038960A1 (fr) 2018-08-23 2020-02-27 Basf Se Matériau solide conducteur d'ion lithium et son procédé de préparation
WO2020105737A1 (fr) 2018-11-22 2020-05-28 出光興産株式会社 Procédé de production d'électrolyte solide, et précurseur d'électrolyte
WO2020254314A1 (fr) 2019-06-17 2020-12-24 Basf Se Haloboro-oxysulfures conducteurs d'ions lithium
EP3798183A1 (fr) 2019-09-27 2021-03-31 AMG Lithium GmbH Électrolyte solide sulfurique et son précurseur
EP3798182A1 (fr) 2019-09-27 2021-03-31 AMG Lithium GmbH Électrolyte solide sulfidique et son précurseur
KR20220065755A (ko) 2019-09-17 2022-05-20 이데미쓰 고산 가부시키가이샤 고체 전해질의 제조 방법 및 전해질 전구체
DE112020005721T5 (de) 2019-11-21 2022-09-08 Idemitsu Kosan Co., Ltd. Verfahren zur herstellung eines sulfidfeststoff-elektrolyten
KR20230010639A (ko) 2020-05-13 2023-01-19 이데미쓰 고산 가부시키가이샤 고체 전해질의 제조 방법
CN115828685A (zh) * 2022-11-29 2023-03-21 上海玫克生储能科技有限公司 基于切比雪夫谱方法的锂电池温度仿真方法、装置及介质
EP4084019A4 (fr) * 2019-12-23 2024-03-06 Idemitsu Kosan Co., Ltd Procédé de production d'électrolyte solide
US11973185B2 (en) 2020-05-07 2024-04-30 Idemitsu Kosan Co., Ltd. Method for producing sulfide solid electrolyte
US11978848B2 (en) 2020-05-27 2024-05-07 Idemitsu Kosan Co., Ltd. Method for producing solid electrolyte
KR20240136977A (ko) 2022-01-18 2024-09-19 이데미쓰 고산 가부시키가이샤 황화물 고체 전해질의 제조 방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085953A (en) * 1990-09-18 1992-02-04 Eveready Battery Company, Inc. Vitreous compositions based on Li3 PO4 and LiPO3 as network formers and network modifiers
WO2012128374A1 (fr) * 2011-03-18 2012-09-27 Toyota Jidosha Kabushiki Kaisha Boue, procédé de production de couche d'électrolyte solide, procédé de production de couche de matériau actif d'électrode, et procédé de production de batterie entièrement solide
US20130295469A1 (en) 2012-05-03 2013-11-07 Ut-Battelle, Llc Lithium sulfide compositions for battery electrolyte and battery electrode coatings
WO2015086759A1 (fr) 2013-12-13 2015-06-18 Basf Se Membranes composites conductrices d'ions alcalins pour des applications électroniques
EP2940778A1 (fr) * 2012-12-27 2015-11-04 Toyota Jidosha Kabushiki Kaisha Procédé de fabrication d'un électrolyte solide de sulfure
WO2016014149A1 (fr) 2014-07-25 2016-01-28 Ut-Battelle, Llc Conducteur superionique li7p2s8i électrochimiquement stable

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085953A (en) * 1990-09-18 1992-02-04 Eveready Battery Company, Inc. Vitreous compositions based on Li3 PO4 and LiPO3 as network formers and network modifiers
WO2012128374A1 (fr) * 2011-03-18 2012-09-27 Toyota Jidosha Kabushiki Kaisha Boue, procédé de production de couche d'électrolyte solide, procédé de production de couche de matériau actif d'électrode, et procédé de production de batterie entièrement solide
US20140004257A1 (en) * 2011-03-18 2014-01-02 Toyota Jidosha Kabushiki Kaisha Slurry, production method for solid electrolyte layer, production method for electrode active material layer, and production method for all-solid-state battery
US20130295469A1 (en) 2012-05-03 2013-11-07 Ut-Battelle, Llc Lithium sulfide compositions for battery electrolyte and battery electrode coatings
EP2940778A1 (fr) * 2012-12-27 2015-11-04 Toyota Jidosha Kabushiki Kaisha Procédé de fabrication d'un électrolyte solide de sulfure
US20150318569A1 (en) 2012-12-27 2015-11-05 Toyota Jidosha Kabushiki Kaisha Method for manufacturing sulfide solid electrolyte
WO2015086759A1 (fr) 2013-12-13 2015-06-18 Basf Se Membranes composites conductrices d'ions alcalins pour des applications électroniques
WO2016014149A1 (fr) 2014-07-25 2016-01-28 Ut-Battelle, Llc Conducteur superionique li7p2s8i électrochimiquement stable

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
"Lithium ion Batteries", 1998, WILEY VCH
DAVID LINDEN: "Handbook of Batteries", 2008, MCGRAW-HILL HANDBOOKS
EZHIYLMURUGAN RANASAMY ET AL.: "AN IODIDE BASED Li7P2S8I SUPERIONIC CONDUCTOR", J.AM.CHEM.SOC, vol. 137, 20 January 2015 (2015-01-20), pages 1384 - 1387, XP002764658, DOI: 10.1021/ja508723m *
J. AM. CHEM. SOC., vol. 135, 2013, pages 975 - 978
J. AM. CHEM. SOC., vol. 137, 2015, pages 1384 - 1387
J. O. BESENHARD: "Handbook of Battery Materials", 1998, WILEY-VCH
YUICHI AIHARA ET AL: "The Electrochemical Characteristics and Applicability of an Amorphous Sulfide-Based Solid Ion Conductor for the Next-Generation Solid-State Lithium Secondary Batteries", FRONTIERS IN ENERGY RESEARCH, vol. 4, 13 May 2016 (2016-05-13), XP055430198, DOI: 10.3389/fenrg.2016.00018 *

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018174129A (ja) * 2017-03-31 2018-11-08 国立大学法人東京工業大学 固体電解質材料およびその製造方法
WO2020038960A1 (fr) 2018-08-23 2020-02-27 Basf Se Matériau solide conducteur d'ion lithium et son procédé de préparation
US20210391596A1 (en) * 2018-11-22 2021-12-16 Idemitsu Kosan Co.,Ltd. Method for producing solid electrolyte, and electrolyte precursor
WO2020105737A1 (fr) 2018-11-22 2020-05-28 出光興産株式会社 Procédé de production d'électrolyte solide, et précurseur d'électrolyte
KR20240142618A (ko) 2018-11-22 2024-09-30 이데미쓰 고산 가부시키가이샤 고체 전해질의 제조 방법 및 전해질 전구체
KR20210091047A (ko) 2018-11-22 2021-07-21 이데미쓰 고산 가부시키가이샤 고체 전해질의 제조 방법 및 전해질 전구체
US11139505B2 (en) 2018-11-22 2021-10-05 Idemitsu Kosan Co., Ltd. Method for producing solid electrolyte, and electrolyte precursor
WO2020254314A1 (fr) 2019-06-17 2020-12-24 Basf Se Haloboro-oxysulfures conducteurs d'ions lithium
DE112020004437T5 (de) 2019-09-17 2022-06-23 Idemitsu Kosan Co., Ltd. Verfahren zur herstellung für festelektrolyten und elektrolyt-vorläufer
KR20220065755A (ko) 2019-09-17 2022-05-20 이데미쓰 고산 가부시키가이샤 고체 전해질의 제조 방법 및 전해질 전구체
WO2021058620A1 (fr) 2019-09-27 2021-04-01 Amg Lithium Gmbh Électrolyte solide sulfuré et son précurseur
WO2021058621A1 (fr) 2019-09-27 2021-04-01 Amg Lithium Gmbh Électrolyte solide sulfuré et son précurseur ii
EP3798182A1 (fr) 2019-09-27 2021-03-31 AMG Lithium GmbH Électrolyte solide sulfidique et son précurseur
EP3798183A1 (fr) 2019-09-27 2021-03-31 AMG Lithium GmbH Électrolyte solide sulfurique et son précurseur
DE112020005721T5 (de) 2019-11-21 2022-09-08 Idemitsu Kosan Co., Ltd. Verfahren zur herstellung eines sulfidfeststoff-elektrolyten
US11746014B2 (en) 2019-11-21 2023-09-05 Idemitsu Kosan Co., Ltd. Method for producing sulfide solid electrolyte
EP4084019A4 (fr) * 2019-12-23 2024-03-06 Idemitsu Kosan Co., Ltd Procédé de production d'électrolyte solide
US11973185B2 (en) 2020-05-07 2024-04-30 Idemitsu Kosan Co., Ltd. Method for producing sulfide solid electrolyte
KR20230010639A (ko) 2020-05-13 2023-01-19 이데미쓰 고산 가부시키가이샤 고체 전해질의 제조 방법
US12119442B2 (en) 2020-05-13 2024-10-15 Idemitsu Kosan Co., Ltd. Method for producing sulfide solid electrolyte
US11978848B2 (en) 2020-05-27 2024-05-07 Idemitsu Kosan Co., Ltd. Method for producing solid electrolyte
KR20240136977A (ko) 2022-01-18 2024-09-19 이데미쓰 고산 가부시키가이샤 황화물 고체 전해질의 제조 방법
CN115828685B (zh) * 2022-11-29 2023-09-19 上海玫克生储能科技有限公司 基于切比雪夫谱方法的锂电池温度仿真方法、装置及介质
CN115828685A (zh) * 2022-11-29 2023-03-21 上海玫克生储能科技有限公司 基于切比雪夫谱方法的锂电池温度仿真方法、装置及介质

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