JPWO2017203954A1 - 低対称ガーネット関連型構造固体電解質およびリチウムイオン二次電池 - Google Patents
低対称ガーネット関連型構造固体電解質およびリチウムイオン二次電池 Download PDFInfo
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- JPWO2017203954A1 JPWO2017203954A1 JP2018519168A JP2018519168A JPWO2017203954A1 JP WO2017203954 A1 JPWO2017203954 A1 JP WO2017203954A1 JP 2018519168 A JP2018519168 A JP 2018519168A JP 2018519168 A JP2018519168 A JP 2018519168A JP WO2017203954 A1 JPWO2017203954 A1 JP WO2017203954A1
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- Prior art keywords
- crystal
- garnet
- lithium
- solid electrolyte
- lithium ion
- Prior art date
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- Granted
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- 239000002223 garnet Substances 0.000 title claims abstract description 106
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 191
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims description 50
- 238000004519 manufacturing process Methods 0.000 claims description 21
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 239000010955 niobium Substances 0.000 description 62
- 238000000034 method Methods 0.000 description 38
- 229910052744 lithium Inorganic materials 0.000 description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 33
- 238000000634 powder X-ray diffraction Methods 0.000 description 21
- 239000000843 powder Substances 0.000 description 19
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 16
- 238000005259 measurement Methods 0.000 description 16
- 230000004913 activation Effects 0.000 description 14
- -1 nickel metal hydride Chemical class 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 10
- 150000001875 compounds Chemical group 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 9
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 229910052758 niobium Inorganic materials 0.000 description 7
- 238000012916 structural analysis Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 5
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 5
- 229910001936 tantalum oxide Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- SLODBEHWNYQCRC-UHFFFAOYSA-N [La+3].[O-2].[Zr+4] Chemical compound [La+3].[O-2].[Zr+4] SLODBEHWNYQCRC-UHFFFAOYSA-N 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910010629 Li6.75La3Zr1.75Nb0.25O12 Inorganic materials 0.000 description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229910000484 niobium oxide Inorganic materials 0.000 description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001460 tantalum ion Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002847 impedance measurement Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 150000002604 lanthanum compounds Chemical class 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002822 niobium compounds Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003482 tantalum compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- 241001580017 Jana Species 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- HRBKMZQLIFBQDK-UHFFFAOYSA-N lanthanum(3+) niobium(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Nb+5].[La+3] HRBKMZQLIFBQDK-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- JNQQEOHHHGGZCY-UHFFFAOYSA-N lithium;oxygen(2-);tantalum(5+) Chemical compound [Li+].[O-2].[O-2].[O-2].[Ta+5] JNQQEOHHHGGZCY-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
- C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
- C01G35/006—Compounds containing, besides tantalum, two or more other elements, with the exception of oxygen or hydrogen
-
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
- C04B35/6262—Milling of calcined, sintered clinker or ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
- C30B13/28—Controlling or regulating
-
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/30—Niobates; Vanadates; Tantalates
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H01M10/052—Li-accumulators
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- 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
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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
- H01M10/056—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
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- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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Abstract
Description
(原料の混合)
まず、炭酸リチウムLi2CO3(レアメタリック製、純度99.99%)7.972gと、酸化ランタンLa2O3(レアメタリック製、純度99.99%)12.620gと、酸化ジルコニウムZrO2(レアメタリック製、純度99.99%)6.22gと、酸化ニオブNb2O5(レアメタリック製、純度99.99%)0.172gをメノウ製乳鉢に入れて、エタノールを使用した湿式法によって均一に混合した。なお、酸化ランタンは、あらかじめ900℃で仮焼成したものを使用した。この混合物の金属のモル比Li:La:Zr:Nbは、目的物であるLi6.95La3Zr1.95Nb0.05O12の化学量論比よりもリチウムが20mol%過剰である。すなわち、化学組成がLi8.34La3Zr1.95Nb0.05O12に相当する分量である。
上記工程でふるいを通過した粉末を用いて、以下の手順で棒形状の原料を作製した。まず、ゴム製の型にこの粉末20.497gを充填して脱気した。つぎに、この型を密閉した状態で水中に入れて、40MPaで5分間維持した。そして、水の圧力を下げた後、成形体を型から取り出した。成形体は、直径1.0cm、高さ9.6cmの円柱形状をしていた。つぎに、箱型電気炉(デンケン製、型番KDF009)を用いて、この円柱状の成形体を1150℃で焼成した。取り出した成形体は、直径0.94cm、高さ9.2cmの円柱形状をしていた。
まず、1kWのハロゲンランプを装備した四楕円型赤外線集光加熱炉(FZ炉)(Crystal System社製、FZ−T−10000H型)に、上記工程で得られた棒形状の原料を設置して、乾燥空気雰囲気にした。つぎに、棒形状の原料を長手方向と垂直な面で40rpmで回転させながら、出力25.9%で加熱した。しばらくすると、原料の一部が溶融して溶融部を形成した。そして、棒形状の原料の設置台を10mm/hの移動速度で下降させて高密度のLi6.95La3Zr1.95Nb0.05O12結晶体(以下「試料1」ということがある)を育成した。なお、試料1の化学組成はX線結晶構造解析によって分析した。試料1の外観を図1に示す。図1に示すように、長さ5cmの高密度のLi6.95La3Zr1.95Nb0.05O12結晶体が作製できた。
二次元IP検出器および検出器にシンチレーションカウンターを有する単結晶X線回折装置(リガク社製、R−AXIS RAPID−II)を用いて、試料1の構造を調べた。試料1のX線回折パターンを図2に示す。図2に示すように、明瞭な回折点が測定できた。また、試料1の回折強度データを収集し、結晶構造解析プログラムJana2006によって結晶構造を調べたところ、試料1が斜方晶に属することがわかった。試料1をダイヤモンドカッターで切断して厚さ0.1mmの薄片を4枚作製し、上述の方法でこれらの相対密度を算出した。その結果、これらの相対密度はそれぞれ99.8%、99.2%、100%、99.5%であった。
金属のモル比Li:La:Ta:Zrが8.3:3.0:0.05:1.95となるように、すなわち原料のLi(7−x)zLa3Zr2−xTaxO12がx=0.05、z=1.2となるように、炭酸リチウムLi2CO3と、酸化ランタンLa2O3と、酸化ジルコニウムZrO2と、酸化タンタルTa2O5を混合した点を除いて、実施例1と同様にしてリチウム含有ガーネット結晶体を製造し、評価した。試料2の外観を図7に示す。また試料2のX線回折パターンを図8に示す。図8に示すように、明瞭な回折点が測定できた。得られた結晶体は、実施例1と同じ、新規斜方晶ガーネット関連型構造を有するリチウム複合酸化物であった。この結晶体の格子定数a=1.31073nm±0.0006nm、b=1.26803nm±0.0006nm、c=1.30982nm±0.0008nmであり、化学組成はLi6.92La3Zr1.952Ta0.048O12であった。図9は試料2の結晶構造を模式的に示している。この結晶構造解析の信頼度を示すR因子は4.09%であったため、結晶構造解析結果は妥当であると言える。
金属のモル比Li:La:Ta:Nb:Zrが8.3:3.0:0.025:0.025:1.95となるように、すなわち原料のLi(7−x+y)zLa3Zr2−x―yTaxNbyO12がx=0.025、y=0.025、z=1.2となるように、炭酸リチウムLi2CO3と、酸化ランタンLa2O3と、酸化ジルコニウムZrO2と、酸化タンタルTa2O5と、酸化ニオブNb2O5を混合した点を除いて、実施例1と同様にしてリチウム含有ガーネット結晶体を製造し、評価した。得られた結晶体は、斜方晶ガーネット関連型構造を有するリチウム複合酸化物であった。この結晶体の格子定数a=1.31091nm±0.0004nm、b=1.26763nm±0.0003nm、c=1.31082nm±0.0008nmであり、化学組成はLi6.91La3Zr1.953Ta0.022Nb0.025O12であった。この結晶構造解析の信頼度を示すR因子は2.11%であったため、結晶構造解析結果は妥当であると言える。
金属のモル比Li:La:Ta:Zrが10.2:3.0:0.20:1.8となるように、すなわち原料のLi(7−x)zLa3Zr2−xTaxO12がx=0.20、z=1.5となるように、炭酸リチウムLi2CO3と、酸化ランタンLa2O3と、酸化ジルコニウムZrO2と、酸化タンタルTa2O5を混合した点を除いて、実施例1の原料の混合と同様にして混合粉末を調製した。
金属のモル比Li:La:Zr:Taが9.9:3.0:1.60:0.40となるように、すなわち原料のLi(7−x)zLa3Zr2−xTaxO12がx=0.40、z=1.5となるように、炭酸リチウムLi2CO3と、酸化ランタンLa2O3と、酸化ジルコニウムZrO2と、酸化タンタルTa2O5を混合した点を除いて、実施例3と同様に焼結体(以下「試料4」ということがある)を作製し評価した。粉末X線回折パターンから、試料4は、斜方晶ガーネット関連型構造と立方晶ガーネット関連型構造の二相からなる焼結体であった。
金属のモル比Li:La:Zr:Taが9.6:3.0:1.40:0.60となるように、すなわち原料のLi(7−x)zLa3Zr2−xTaxO12がx=0.60、z=1.5となるように、炭酸リチウムLi2CO3と、酸化ランタンLa2O3と、酸化ジルコニウムZrO2と、酸化タンタルTa2O5を混合した点を除いて、実施例4と同様にして焼結体(以下「試料5」ということがある)を作製し評価した。粉末X線回折パターンから、試料5は、斜方晶ガーネット関連型構造と立方晶ガーネット関連型構造の二相からなる焼結体であった。
金属のモル比Li:La:Zr:Nbが10.125:3.0:1.75:0.25となるように、すなわち原料のLi(7−x)zLa3Zr2−xNbxO12がx=0.25、z=1.5となるように、炭酸リチウムLi2CO3と、酸化ランタンLa2O3と、酸化ジルコニウムZrO2と、酸化ニオブNb2O5を混合した点を除いて、実施例3と同様に焼結体(以下「試料6」ということがある)を作製し評価した。粉末X線回折パターンから、試料6は、斜方晶ガーネット関連型構造と立方晶ガーネット関連型構造の二相からなる焼結体であった。
酢酸リチウム2水和物(シグマアルドリッチ製)0.0105モルと、酢酸コバルト4水和物(和光純薬工業製)0.01モルを、エチレングリコール(和光純薬工業製)100gに溶解した。つぎに、ポリビニルピロリドン(和光純薬工業製、K−30)10gを加えて溶解させることで0.1モル/kgのコバルト酸リチウム前駆体溶液を調製した。酢酸リチウム量を酢酸コバルト量より5モル%多くしたのは、焼成時のリチウム蒸発分を加味したためである。
Claims (10)
- 化学組成がLi7―x―yLa3Zr2―x―yTaxNbyO12(0.05≦x+y≦0.2、x≧0、y≧0)で表され、結晶構造が斜方晶系であるガーネット関連型構造結晶体。
- 結晶構造の対称性を示す空間群がIbcaに属する請求項1に記載のガーネット関連型構造結晶体。
- 結晶構造の格子定数a、b、c、が、それぞれ1.29nm≦a≦1.32nm、1.26nm≦b≦1.29nm、1.29nm≦c≦1.32nmである請求項1または2に記載のガーネット関連型構造結晶体。
- 結晶構造中に4つ以上のリチウムイオンが占有する席が存在する請求項1から3のいずれかに記載のガーネット関連型構造結晶体。
- リチウムイオン伝導率が、25℃で1.0×10−4S/cm以上である請求項1から4のいずれかに記載のガーネット関連型構造結晶体。
- 相対密度が99%以上である請求項1から5のいずれかに記載のガーネット関連型構造結晶体。
- 前記相対密度が100%である請求項6に記載のガーネット関連型構造結晶体。
- 請求項1から7のいずれかに記載の結晶体と、化学組成がLi7―x―yLa3Zr2―x―yTaxNbyO12(0.2<x+y≦0.6、x≧0、y≧0)で表され、立方晶ガーネット関連型構造を有する結晶体とを含有するガーネット関連型構造焼結体。
- 正極と、負極と、請求項1から7のいずれかに記載の結晶体または請求項8に記載の焼結体を含有する固体電解質材料とを有する全固体リチウムイオン二次電池。
- 化学組成がLi(7―x―y)zLa3Zr2―x―yTaxNbyO12(0.05≦x+y≦0.2、x≧0、y≧0、1<z≦2)で表される原料の少なくとも一部を溶融して結晶成長させる溶融部を形成し、移動速度8mm/h以上で前記結晶成長させる溶融部を未結晶化原料へ移動して結晶成長させ、化学組成がLi7―x―yLa3Zr2―x―yTaxNbyO12(0.05≦x+y≦0.2、x≧0、y≧0)で表され、斜方晶系に属するガーネット関連型構造結晶体の製造方法。
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JP2016072210A (ja) * | 2014-09-30 | 2016-05-09 | セイコーエプソン株式会社 | 耐リチウム還元層形成用組成物、耐リチウム還元層の成膜方法およびリチウム二次電池 |
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EP3466888A4 (en) | 2020-01-29 |
CN109195918A (zh) | 2019-01-11 |
WO2017203954A1 (ja) | 2017-11-30 |
CN109195918B (zh) | 2020-12-08 |
US10763544B1 (en) | 2020-09-01 |
KR20190002660A (ko) | 2019-01-08 |
EP3466888B1 (en) | 2020-09-23 |
TW201741243A (zh) | 2017-12-01 |
US20200274193A1 (en) | 2020-08-27 |
EP3466888A1 (en) | 2019-04-10 |
JP6667182B2 (ja) | 2020-03-18 |
KR102137801B1 (ko) | 2020-07-24 |
TWI623496B (zh) | 2018-05-11 |
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