WO2023239215A1 - 황화물계 고체 전해질, 황화물계 고체 전해질의 제조 방법, 및 황화물계 고체 전해질을 포함하는 전고체 전지 - Google Patents
황화물계 고체 전해질, 황화물계 고체 전해질의 제조 방법, 및 황화물계 고체 전해질을 포함하는 전고체 전지 Download PDFInfo
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- WO2023239215A1 WO2023239215A1 PCT/KR2023/007979 KR2023007979W WO2023239215A1 WO 2023239215 A1 WO2023239215 A1 WO 2023239215A1 KR 2023007979 W KR2023007979 W KR 2023007979W WO 2023239215 A1 WO2023239215 A1 WO 2023239215A1
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- WIPO (PCT)
- Prior art keywords
- solid electrolyte
- sulfide
- based solid
- group
- lithium
- Prior art date
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 145
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 5
- 239000007787 solid Substances 0.000 title abstract 2
- 229910001849 group 12 element Inorganic materials 0.000 claims abstract description 64
- 239000013078 crystal Substances 0.000 claims abstract description 39
- 150000002367 halogens Chemical class 0.000 claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 25
- 229910001416 lithium ion Inorganic materials 0.000 description 25
- 150000002500 ions Chemical class 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 239000012535 impurity Substances 0.000 description 16
- 239000011701 zinc Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- -1 sulfide Chemical class 0.000 description 7
- 239000004020 conductor Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 229910018091 Li 2 S Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 229910052984 zinc sulfide Inorganic materials 0.000 description 5
- 241000567769 Isurus oxyrinchus Species 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000000101 thioether group Chemical group 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 239000006091 Macor Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- 238000000465 moulding Methods 0.000 description 2
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- 230000001737 promoting effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052950 sphalerite Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910018127 Li 2 S-GeS 2 Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910007969 Li-Co-Ni Inorganic materials 0.000 description 1
- 229910008163 Li1+x Mn2-x O4 Inorganic materials 0.000 description 1
- 229910009130 Li2S—GeS2—ZnS Inorganic materials 0.000 description 1
- 229910009142 Li2S—Li3PO4—P2S5 Inorganic materials 0.000 description 1
- 229910009181 Li2S—LiI—P2S5 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910006555 Li—Co—Ni Inorganic materials 0.000 description 1
- 229910018584 Mn 2-x O 4 Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 229910020346 SiS 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QDDVNKWVBSLTMB-UHFFFAOYSA-N [Cu]=O.[Li] Chemical compound [Cu]=O.[Li] QDDVNKWVBSLTMB-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 239000006233 lamp black Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910021445 lithium manganese complex oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical group [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical group [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
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- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- sulfide-based solid electrolytes such as Li 10 GeP 2 S 12 have the advantage of having a high ionic conductivity close to that of the electrolyte and being soft, making it easy to obtain adhesion to the active material, making them suitable for all-solid-state batteries using sulfide-based solid electrolytes. Practical implementation is expected.
- Lithium metal is attracting attention as a negative electrode material for all-solid-state batteries because it can increase mass energy density (Wh/kg) due to low weight per unit volume and large theoretical capacity.
- mass energy density Wh/kg
- sulfide-based solid electrolytes such as Li 10 GeP 2 S 12 have low stability to lithium metal, making it difficult to use them with lithium metal anodes.
- Patent Documents 1 to 3 are sulfide-based materials having an argylodite-type crystal structure represented by Li 7-x-2y PS 6-xy Cl x which is stable to lithium metal.
- a solid electrolyte is disclosed.
- Patent Document 4 discloses a sulfide-based solid electrolyte with improved stability to lithium metal by precisely controlling the composition of the sulfide-based solid electrolyte having a Li 10 GeP 2 S 12 crystal structure.
- Patent Document 1 Japanese Patent No. 5873533
- Patent Document 2 Japanese Patent Publication No. 2018-45997
- Patent Document 3 Japanese Patent Publication No. 2018-203569
- Patent Document 4 Japanese Patent Publication No. 2016-27545
- the purpose of the present invention is to provide a sulfide-based solid electrolyte with improved ionic conductivity, a method for producing the sulfide-based solid electrolyte, and an all-solid-state battery including the sulfide-based solid electrolyte.
- the sulfide-based solid electrolyte is represented by the chemical formula Li 7-x-2y M y PS 6-x Ha x ,
- M is one or more elements selected from Group 12 elements
- Ha is one or more elements selected from halogen elements
- x may satisfy 1.3 ⁇ x ⁇ 2.0.
- x may satisfy 1.3 ⁇ x ⁇ 1.8.
- M may be Zn.
- Ha may include Br.
- the present invention provides a method for producing a sulfide-based solid electrolyte according to any one of the above embodiments,
- a method comprising the step of calcining the mixture at a temperature of 250°C to 600°C is provided.
- the present invention is an all-solid-state battery comprising an anode, a cathode, and a solid electrolyte layer,
- An all-solid-state battery is provided wherein the solid electrolyte layer includes the sulfide-based solid electrolyte according to any one of the above embodiments.
- the present invention can provide a sulfide-based solid electrolyte with improved ionic conductivity, a method for manufacturing the sulfide-based solid electrolyte, and an all-solid-state battery including the sulfide-based solid electrolyte.
- Figure 1 shows X-ray diffraction (XRD) patterns of Examples 1 to 4.
- Figure 2 shows the XRD patterns of Examples 5 and 6 and Comparative Examples 1 and 2.
- Figure 3 is a graph showing lithium ion conductivity for the composition of the sulfide-based solid electrolyte.
- the sulfide-based solid electrolyte may have a crystal structure of ajirodite type, NASICON type, perovskite type, garnet type, or LGePS type.
- the sulfide-based solid electrolyte has an azyrodite-type crystal structure. Since the sulfide-based solid electrolyte with an ajirodite-type crystal structure has high stability to lithium metal, it allows lithium metal with a high mass energy density to be used as a negative electrode material.
- the sulfide-based solid electrolyte may include a crystalline phase and an amorphous phase.
- the sulfide-based solid electrolyte may include a crystal phase containing an ajirodite-type crystal structure (herein referred to as an ajirodite phase) and other phases (herein referred to as an impurity phase or an unknown phase).
- the azyrodite-type crystal structure is preferably cubic.
- the other phases may be crystalline or amorphous.
- Other phases regardless of whether they are crystalline or amorphous, include Li 2 S phase, P 2 S 5 phase, LiCl phase, LiBr phase, Li 3 PS 4 phase, MgS phase, CaS phase, SrS phase, BaS phase, and ZnS phase.
- the sulfide-based solid electrolyte contains no or substantially no impurity phases other than the azirodite phase. That is, preferably, the sulfide-based solid electrolyte may consist of only the ajirodite phase.
- the sulfide-based solid electrolyte does not contain or substantially does not contain an impurity phase, lithium ion conduction is difficult to be inhibited, so the sulfide-based solid electrolyte can have a high lithium ion conductivity.
- the proportion of the crystalline phase contained in the sulfide-based solid electrolyte can be evaluated quantitatively or semi-quantitatively from an XRD pattern.
- One way is to evaluate the proportion of crystalline phases by comparing the peak intensities (height or area) of the XRD patterns.
- the sulfide-based solid electrolyte according to an embodiment of the present invention is represented by the chemical formula Li 7-x-2y M y PS 6-x Ha x .
- M is one or more elements selected from Group 12 elements
- Ha is one or more elements selected from halogen elements, and satisfies 1.0 ⁇ x ⁇ 2.5 and 0 ⁇ y ⁇ 0.45.
- Such a sulfide-based solid electrolyte can have high lithium ion conductivity.
- the azirodite-type crystal structure of the sulfide-based solid electrolyte cannot be maintained, and the impurity phase that inhibits lithium ion conduction in the sulfide-based solid electrolyte increases, which may lower the ion conductivity.
- the positive electrode and the negative electrode include a current collector and an electrode active material layer formed on at least one surface of the current collector, and the electrode active material layer includes a plurality of electrode active material particles and a solid electrolyte.
- the electrode may further include one or more of a conductive material and a binder resin, if necessary. Additionally, the electrode may further include various additives for the purpose of supplementing or improving the physicochemical properties of the electrode.
- Example 1 As shown in Table 1, a solid electrolyte was obtained in the same manner as in Example 1, except that the Group 12 element (M) was changed and the addition amount y of the Group 12 element (M) was changed to 0.025.
- This sealed port was installed in a planetary ball mill device, and ball milling was performed at 380 rpm for 20 hours, and then the port was opened in the glove box to recover the powder.
- This powder was placed in a carbon crucible, sealed, and fired at 460°C for 8 hours while flowing Ar gas. The fired powder was ground in a mortar for 10 minutes to obtain a solid electrolyte.
- the solid electrolyte Li 6.95 P 0.05 Sn 0.95 S 5 I obtained in Comparative Example 3 is a sulfide-based solid electrolyte containing Sn as an element other than a Group 12 element, and the ionic conductivity of the sulfide-based solid electrolyte of Comparative Example 3 is The result was 0.81mS/cm.
- a predetermined amount of solid electrolyte was placed in a sealed holder within an Ar gas flow glove box and XRD measurement was performed.
- the lattice constant, lattice volume, and half width were calculated from the obtained XRD (X-ray diffraction) pattern.
- a predetermined amount of solid electrolyte was placed in a MACOR ® pipe, and the MACOR pipe and pellet forming jig (upper press pin and lower press pin) were combined and press formed at 5 MPa using a single axis press. After that, a predetermined amount of gold powder was placed on both sides of the pellet, and then press molded at 7.5 MPa using a single-axis press to obtain a Mako pipe cell.
- the obtained Mako pipe cell was installed in a jig cell for electrochemical measurement and pressurized to 5.0 N ⁇ m using a torque wrench to obtain an ion conductivity measurement cell.
- Table 1 shows the evaluation results of the crystal phase (crystal structure) identified from the XRD pattern by XRD measurement. Additionally, the measured XRD patterns are shown in Figures 1 and 2.
- Example 2 and Comparative Example 2 As shown in Table 1, in Example 2 and Comparative Example 2, almost no impurity phase (also called unknown phase) was observed, and most of the peaks were azyrodite phase. Additionally, in Examples 1 and 3 to 6, peaks of the azyrodite phase and trace amounts of impurity phases other than the ajirodite phase were present. On the other hand, in Comparative Example 1, the peak of the azyrodite phase was hardly observed, and a large amount of impurity phases other than the ajirodite phase existed.
- the impurity phase was, for example, a phase derived from raw materials such as Li 2 S and ZnS.
- Figures 1 and 2 show the XRD patterns of Examples 1 to 6 and Comparative Examples 1 and 2.
- the lattice volume of the crystal was reduced by about 2.1 to 3.3%.
- the crystal volume of the sulfide-based solid electrolyte could be changed by replacing one of the two lithium sites with a Group 12 element (M) and the other becoming a lithium vacancy. It is thought that lithium pores serve as a path for hopping conduction of lithium ions, contributing to an increase in ion conductivity.
- the Group 12 element (M) substituted at the lithium site may have a divalent value, so the power to attract anions around the Group 12 element (M) site may change compared to the monovalent lithium ion. As a result, it is believed that the crystal volume of the sulfide-based solid electrolyte changed, resulting in a structure suitable for hopping conduction of lithium ions.
- Comparative Example 1 it is believed that because the addition amount y of Zn, a Group 12 element (M), was too large, the crystallinity of the azyrodite-type crystal structure decreased and the ionic conductivity decreased. In Comparative Example 2 in which the Group 12 element (M) was not added, the ionic conductivity was 10.70 mS/cm. Additionally, in the case of Comparative Example 3 in which the Group 12 element (M) was not added but the Sn element was added, the ionic conductivity was 0.81 mS/cm.
- M Group 12 element
- the sulfide-based solid electrolyte of Example 2 When the sulfide-based solid electrolyte of Example 2 was used in an all-solid-state battery, the sulfide-based solid electrolyte had high stability to lithium metal as a negative electrode material, and the all-solid-state battery showed excellent charge/discharge characteristics and capacity characteristics.
- the initial discharge capacity relative ratio of capacity was 106%. That is, by using the solid electrolyte of Example 2, which has high ionic conductivity, in the all-solid-state battery, the initial discharge capacity of the all-solid-state battery could be improved.
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Abstract
Description
Claims (8)
- 제12족 원소를 포함하고 아지로다이트형 결정 구조를 갖는 황화물계 고체 전해질로서,상기 황화물계 고체 전해질이 화학식 Li7-x-2yMyPS6-xHax로 표시되고,상기 화학식에서, 상기 M이 제12족 원소로부터 선택되는 1종 이상의 원소이고, 상기 Ha가 할로겐 원소로부터 선택되는 1종 이상의 원소이고, 1.0<x<2.5, 0<y<0.45를 만족하는 황화물계 고체 전해질.
- 제1항에 있어서,상기 y가 0<y<0.25를 만족하는 황화물계 고체 전해질.
- 제1항에 있어서,상기 x가 1.3≤x≤2.0을 만족하는 황화물계 고체 전해질.
- 제1항에 있어서,상기 x가 1.3≤x≤1.8을 만족하는 황화물계 고체 전해질.
- 제1항 내지 제4항 중 어느 한 항에 있어서,상기 M이 Zn인 황화물계 고체 전해질.
- 제5항에 있어서,상기 Ha가 Br을 포함하는 황화물계 고체 전해질.
- 제1항에 기재된 황화물계 고체 전해질의 제조 방법으로서,리튬원, 제12족 원소원, 인원, 황원 및 할로겐원을 혼합해 혼합물을 얻는 단계와,상기 혼합물을 250℃∼600℃의 온도에서 소성하는 단계를 포함하는 방법.
- 양극, 음극, 및 고체 전해질층을 포함하는 전고체 전지로서,상기 고체 전해질층이 제1항에 기재된 황화물계 고체 전해질을 포함하는 전고체 전지.
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EP23820150.3A EP4376149A1 (en) | 2022-06-10 | 2023-06-09 | Sulfide-based solid electrolyte, method for preparing sulfide-based solid electrolyte, and all-solid battery comprising sulfide-based solid electrolyte |
CN202380013260.XA CN117836992A (zh) | 2022-06-10 | 2023-06-09 | 硫化物类固体电解质、其制备方法以及包含其的固态电池 |
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- 2023-06-09 EP EP23820150.3A patent/EP4376149A1/en active Pending
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JP2016027545A (ja) | 2014-06-25 | 2016-02-18 | 国立大学法人東京工業大学 | 硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法 |
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KR20240049582A (ko) | 2024-04-16 |
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