WO2022210674A1 - 部材の構成材料を分離する分離方法及び部材の処理方法 - Google Patents
部材の構成材料を分離する分離方法及び部材の処理方法 Download PDFInfo
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- WO2022210674A1 WO2022210674A1 PCT/JP2022/015345 JP2022015345W WO2022210674A1 WO 2022210674 A1 WO2022210674 A1 WO 2022210674A1 JP 2022015345 W JP2022015345 W JP 2022015345W WO 2022210674 A1 WO2022210674 A1 WO 2022210674A1
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- Prior art keywords
- solvent
- solid
- solid electrolyte
- lithium
- component
- Prior art date
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 50
- 239000000463 material Substances 0.000 title claims description 20
- 239000000470 constituent Substances 0.000 title claims description 13
- 239000002904 solvent Substances 0.000 claims abstract description 90
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 83
- 239000007787 solid Substances 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000011149 active material Substances 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- 238000004090 dissolution Methods 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- -1 lithium halide Chemical class 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 claims description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 description 29
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 230000007613 environmental effect Effects 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000013467 fragmentation Methods 0.000 description 7
- 238000006062 fragmentation reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002203 sulfidic glass Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 1
- 229910009142 Li2S—Li3PO4—P2S5 Inorganic materials 0.000 description 1
- 229910007860 Li3.25Ge0.25P0.75S4 Inorganic materials 0.000 description 1
- 229910013936 Li3.25P0.95S4 Inorganic materials 0.000 description 1
- 229910012007 Li4P2S6 Inorganic materials 0.000 description 1
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N tertiary amyl alcohol Natural products CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- the present invention relates to a separation method for separating constituent materials of a member having an active material and a solid electrolyte, and a processing method for the member.
- Lithium ion batteries have a metal can body or an aluminum foil laminate film as an exterior material, and inside it, a negative electrode material in which a negative electrode active material such as graphite is fixed to a current collector such as copper foil, nickel acid It has a structure in which a positive electrode material in which a positive electrode active material such as lithium or lithium cobaltate is fixed to a positive electrode current collector such as an aluminum foil is inserted and enclosed.
- a separator made of a polypropylene porous film or the like is placed between the positive electrode material and the negative electrode material, and an organic solvent containing a lithium salt electrolyte is enclosed as an electrolytic solution.
- the electrolyte is solid, powder of a material having lithium ion conductivity is filled between the cathode material and the anode material.
- Patent Literature 1 proposes a method for recovering lithium from waste of lithium ion batteries.
- Patent Document 2 leaching and neutralization separation are attempted as means for recovering lithium from burnt scrap of lithium ion batteries.
- an object of the present invention is to provide a method capable of satisfactorily separating and recovering predetermined constituent materials from members containing Li, S and P elements while reducing environmental impact.
- the present invention is a separation method for separating constituent materials of a member, a step of mixing the member having an active material and a solid electrolyte with a solvent to obtain a mixture; a step of solid-liquid separating the mixture to obtain a solid component and a separated liquid;
- the solid electrolyte contains a lithium (Li) element, a sulfur (S) element and a phosphorus (P) element,
- a separation method is provided in which the solid electrolyte is dissolved in the solvent by mixing the member and the solvent.
- the present invention provides a member having an active material and a solid electrolyte containing a lithium (Li) element, a sulfur (S) element and a phosphorus (P) element, and a solvent, and the solid electrolyte is dissolved in the solvent. obtaining a mixed mixture; a step of solid-liquid separating the mixture to obtain a solid component and a separated liquid; recovering from the separated liquid a compound containing at least one of lithium (Li) element, sulfur (S) element and phosphorus (P) element; A method for treating a member is provided, in which the solid electrolyte is dissolved in the solvent by mixing the member and the solvent.
- the present invention includes a step of mixing a member having an active material and a solid electrolyte with a solvent to obtain a mixture in which the solid electrolyte is dissolved in the solvent; a step of solid-liquid separating the mixture to obtain a solid component and a separated liquid; a step of dissolving the solid component with an acid to recover a carbon component that is a dissolution residue;
- the solid electrolyte contains a lithium (Li) element, a sulfur (S) element and a phosphorus (P) element,
- a method for treating a member is provided, in which the solid electrolyte is dissolved in the solvent by mixing the member and the solvent.
- the present invention uses M elements (M is lithium (Li), nickel (Ni), manganese (Mn), cobalt (Co), aluminum (Al), iron (Fe), titanium (Ti), tin (Sn), At least one of niobium (Nb), silicon (Si), carbon (C) and copper (Cu); is dissolved in said solvent, and a step of solid-liquid separating the mixture to obtain a solid component and a separated liquid; a step of dissolving the solid component in an acid to obtain a solution; recovering the M element from the solution,
- the solid electrolyte contains a lithium (Li) element, a sulfur (S) element and a phosphorus (P) element,
- a method for treating a member is provided, in which the solid electrolyte is dissolved in the solvent by mixing the member and the solvent.
- FIG. 1 is a schematic diagram of the steps in the present invention.
- both the separation method and treatment method of the present invention are intended for a member having an active material and a solid electrolyte. Unless otherwise specified, the following description appropriately applies to both the method for separating members and the method for treating members of the present invention (hereinafter collectively referred to as "this method").
- the active material and solid electrolyte are typically constituent members of a solid battery using a solid electrolyte.
- a solid battery has a positive electrode layer, a negative electrode layer, and a solid electrolyte layer positioned therebetween, which are integrally molded.
- the active material is included in at least one of the positive electrode layer and the negative electrode layer.
- a solid electrolyte is contained in at least the solid electrolyte layer.
- a solid battery includes a solid battery that does not contain any liquid or gel substance as an electrolyte, and also includes, for example, a mode that contains less than 50% by mass of a liquid substance or gel substance as an electrolyte.
- Specific examples of objects to be separated and treated in this method include a positive electrode layer, a negative electrode layer, a solid electrolyte layer, and a solid battery comprising these members.
- a member obtained by removing an electrode layer containing a solid electrolyte from a battery a member obtained by removing one electrode layer containing an active material and a solid electrolyte layer in an integrated state or in a separated state from a solid battery, or a solid battery
- Defective products, residual pieces and residual scraps generated in the manufacturing process are included.
- the solid electrolyte which is one of the objects of this method, contains lithium (Li) element, sulfur (S) element and phosphorus (P) element. That is, the solid electrolyte is preferably a mixture containing the above elements or a compound such as sulfide.
- Examples of solid electrolytes containing sulfides include Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -LiX (“X” represents one or more halogen elements), Li 2 SP2S5 - P2O5 , Li2S - Li3PO4 - P2S5 , Li3PS4 , Li4P2S6 , Li10GeP2S12 , Li3.25Ge _ 0.25P0.75S4 , Li7P3S11 , Li3.25P0.95S4 , LiaPSbXc ( X is at least one halogen element, a is 3.0 represents a number of not less than 6.0, b represents a number of not less than 3.5 and not more than 4.8, and c represents a number of not less than 0.1 and not more than 3.0.
- X represents one or more halogen elements
- Li 2 SP2S5 - P2O5 Li2S - Li3PO4 - P2S5 , Li3PS4
- these sulfide solid electrolytes have a crystal phase with an aldirodite type structure from the viewpoint of enhancing the efficiency of separation and recovery.
- materials to be separated and processed include raw compounds for solid electrolytes such as Li 2 S, P 2 S 5 and lithium halides.
- each of the active materials described above independently contain the M element.
- the M element in this specification means typical metal elements such as lithium (Li) and aluminum (Al), semimetal elements such as silicon (Si), nonmetal elements such as carbon (C), nickel (Ni), manganese (Mn), cobalt (Co), iron (Fe), titanium (Ti), tin (Sn), niobium (Nb), and at least one of transition metal elements such as copper (Cu).
- at least one element selected from the various metals and carbon described above is contained as a constituent element of the positive electrode active material and the conductive material contained in the positive electrode mixture that constitutes the positive electrode layer.
- At least one element selected from silicon and carbon is included as a constituent element of the negative electrode active material and the conductive material contained in the negative electrode mixture that constitutes the negative electrode layer.
- the M element in each active material may exist independently in each of the positive electrode active material and the negative electrode active material, and may exist as a compound such as an oxide, nitride, or halide, or as a mixture thereof. may be
- the M element described above is a valuable component, it can be reused by separating and recovering the M element from the member. Moreover, by adopting this method, an increase in environmental load can be suppressed.
- a step (mixing step) of obtaining a mixture by mixing a member having an active material and a solid electrolyte with a solvent is performed.
- the mixing step the solid electrolyte contained in the member is dissolved in the solvent by mixing the member and the solvent.
- the other constituent materials are preferably present in a dispersed state in the solvent.
- the mixing process can be performed under conditions in which the solid electrolyte can be dissolved in the solvent.
- Temperature conditions that can be employed in the mixing step include, for example, a non-heated state such as room temperature, and a heated state.
- the temperature condition for example, it is preferable that the temperature is below the boiling point of the solvent to be employed. Specifically, it is preferably 0° C. or higher, more preferably 50° C. or higher.
- the temperature conditions are, for example, preferably 300° C. or lower, more preferably 200° C. or lower, even more preferably 100° C. or lower, and even more preferably 80° C. or lower.
- the pressure conditions for the mixing process may be under atmospheric pressure or under pressure.
- the pressure in the mixing step may be, for example, 1 MPa or higher, 10 MPa or higher, or 15 MPa or higher.
- the pressure condition may be, for example, 50 MPa or less, 40 MPa or less, or 35 MPa or less.
- the mixing time in the mixing process can be changed as appropriate depending on the amount and form of the components, temperature conditions, and pressure conditions.
- the mixing time may be, for example, 0.5 hours or longer, 1 hour or longer, or 3 hours or longer.
- the mixing time may be, for example, 100 hours or less, 50 hours or less, or 20 hours or less.
- the mixing time is within the above range, the solid electrolyte can be sufficiently dissolved in the solvent.
- the solvent used in the mixing process dissolves the solid electrolyte.
- the solvent preferably has a degree of solubility capable of dissolving the solid electrolyte.
- a solvent having such physical properties only the solid electrolyte can be separated satisfactorily.
- the solvent does not dissolve the active material, the solid electrolyte and the active material can be separated satisfactorily, and each material can be recovered.
- the target object is a member in which the existence state and the existence ratio of the active material and the solid electrolyte are unknown, it becomes difficult for the separated and recovered material to mix with the other material, and the two materials are separated from each other. It becomes easier to separate and recover all the elements in the member.
- the solubility of the solvent in the solid electrolyte is, for example, preferably 1 mg/mL or more, more preferably 10 mg/mL or more, still more preferably 50 mg/mL or more, and 100 mg/mL at 1 atm and 20°C. mL or more is more preferable.
- the solubility of the solvent in at least one of the solid electrolytes satisfies the above range.
- the solubility of the solvent in all of the solid electrolytes contained in the member satisfies the above-described solubility. That is, in this step, one or more solid electrolytes may be partially dissolved, or one of the two or more solid electrolytes may be completely dissolved and the other solid electrolytes may be dissolved. Alternatively, a part of the solid electrolyte may be dissolved, but it is preferable to use a solvent in which the entire amount of the solid electrolyte is dissolved from the viewpoint of separation and recovery efficiency.
- the solvent used in the mixing step preferably has a solubility in the active material of, for example, less than 3 mg/mL at 1 atm and 20° C., more preferably less than 1 mg/mL, and the active material does not dissolve. is more preferred.
- the above solvent is preferably an organic solvent.
- the organic solvent may be, for example, a solvent having a hydroxyl group in its chemical structure or a solvent having no hydroxyl group.
- Solvents having a hydroxyl group include, for example, alcohol solvents and phenol solvents.
- Examples of solvents having no hydroxyl group include various solvents such as aliphatic or aromatic hydrocarbon solvents, ester solvents, aldehyde solvents, ketone solvents, ether solvents, and other solvents containing heteroatoms in their structures. . These can be used alone or in combination of two or more.
- hydrocarbon solvents examples include linear or branched aliphatic and saturated hydrocarbons having 5 to 12 carbon atoms such as pentane, hexane, heptane, octane and decane; Aliphatic and cyclic hydrocarbons having 5 or more and 12 or less carbon atoms such as octane can be mentioned.
- aromatic hydrocarbon solvent examples include substituted or unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms such as benzene, toluene, xylene, halogenated benzene and alkylated benzene.
- the alcohol solvent preferably has, for example, 1 or more carbon atoms, more preferably 2 or more carbon atoms, and even more preferably 4 or more carbon atoms.
- the upper limit of the number of carbon atoms is not particularly limited, but may be, for example, 12 or less, or 8 or less.
- Examples of alcohol solvents include alcohols having straight or branched chains having the number of carbon atoms described above. Specific examples include methanol, ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, and 2-methyl-2-propanol.
- Ester solvents include, for example, ethyl acetate and butyl acetate.
- aldehyde solvents include formaldehyde and acetaldehyde.
- Ketone solvents include, for example, acetone and methyl ethyl ketone.
- Ether solvents include, for example, diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane and the like.
- Other solvents containing heteroatoms in their structure include, for example, acetonitrile, dimethylsulfoxide, dimethylformamide, and the like.
- the component and the solvent may be mixed at the same time, or one of the component and the solvent may be added to the other and mixed.
- the members to be separated and processed may be mixed in a state in which they are not subjected to fragmentation treatment such as pulverization or crushing, and may be in the form of granules or powders that have undergone fragmentation treatment in advance. may be mixed, and after contacting the member with or without the fragmentation treatment to the solvent, the fragmentation treatment may be further performed in the solvent.
- the fragmentation treatment is a treatment for reducing the size of the member after treatment compared to the size of the member before treatment, and can be performed using, for example, a crusher or a crusher.
- the member that has not been subjected to the fragmentation treatment is brought into contact with the solvent, and then the fragmentation treatment is performed in the solvent.
- the fragmentation treatment is performed in the solvent.
- the concentration of the solid electrolyte in the separated liquid obtained by solid-liquid separation of the mixture of the member and the solvent is, for example, preferably 1% by mass or more, and preferably 5% by mass or more. More preferably, it is more preferably 10% by mass or more. Further, the concentration may be, for example, 50% by mass or less, or may be 30% by mass or less.
- the mixture obtained through the above mixing step is preferably a solution in which a solid electrolyte is dissolved in a solvent, and solid components such as active materials are dispersed or precipitated.
- the solution that constitutes the mixture contains Li element, S element, and P element that constitute the solid electrolyte, and other elements such as halogen elements that are contained as necessary, in the form of ions.
- a step (separation step) of obtaining a solid component and a separated liquid by solid-liquid separation of the mixture obtained through the mixing step is performed.
- the method of solid-liquid separation is not particularly limited as long as it is a method capable of separating solid and liquid, and examples thereof include filtration, centrifugation, sedimentation and the like. Thereby, a solid component and a separated liquid can be respectively obtained.
- the solid component and separated liquid may be stored as is or alternatively further subjected to subsequent recovery or processing steps herein.
- the solid component obtained by the separation step is a solid containing an active material, and preferably contains one or more of the M elements described above.
- the content of the M element contained in the solid component is, for example, preferably 20% by mass or more, more preferably 40% by mass or more. When the content ratio of the M element contained in the solid component is within the above range, the amount of acid used in the subsequent acid dissolution can be reduced.
- the separated liquid obtained by the separation step is derived from a solution in which a solid electrolyte is dissolved in a solvent, and preferably contains Li element, S element and P element.
- the solid component obtained through the separation step preferably contains the M element, and depending on the active material to be separated and treated, in addition to the metal element component in the M element, graphite, graphite, simple carbon such as hard carbon It may also contain a carbon element component such as In this case, from the viewpoint of efficiently separating the metal component and the carbon component and recovering the carbon component while facilitating the recovery of the metal component as a valuable component, the solid component obtained through the separation step is acidified. It is preferable to further perform a step of dissolving and recovering the carbon component (carbon recovery step). When multiple types of M elements such as metal components and carbon components are included in the solid component, the carbon recovery step separates and recovers the carbon element and the M elements other than the carbon element among the M elements. The carbon recovery step may be performed alone after performing the mixing step and the separation step, or may be performed by combining various suitable steps described later in any order.
- the metal component By bringing the solid component containing the metal component and the carbon component into contact with the acid, the metal component can be dissolved in the acid to obtain a solution in which the metal component is ionized.
- a carbon component that is insoluble in acid can be obtained in the form of a dispersion that exists as a solid dissolution residue in the solution.
- the carbon component which is the dissolution residue, can be recovered as a solid by performing the various solid-liquid separation methods described above. Since this carbon component can be obtained with little or almost no alteration, it should be recovered in consideration of the environmental burden by washing and drying it as necessary and reusing it for other products. It is also advantageous in that it can be performed.
- an acid capable of dissolving the metal component of the M element can be used, and examples thereof include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid.
- the amount of acid used for acid dissolution is preferably 1 mol or more, more preferably 2 mol or more, per 1 mol of the M element in the solid component.
- the amount of the acid used is preferably 5 mol or less, more preferably 3 mol or less.
- the temperature conditions, pressure conditions, etc. during acid dissolution can be the same as those for general acid dissolution.
- the solution obtained by dissolving the solid component with an acid is subjected to an electrolytic treatment to recover the M element, more specifically, the metal ions in the solution are reduced to recover the metal element. It is also preferable to further perform a step (M element recovery step).
- M element recovery step As a result, the M element can be precipitated from the solution, and a simple substance or compound of the M element with high purity can be easily recovered as a solid.
- the M element recovery step it is preferable to select an appropriate method according to the type of the M element, and more specifically, it is more preferable to use a method that can selectively recover the M element.
- a method for recovering the M element for example, (i) a method of subjecting the solution to electrolytic treatment to recover the M element as a solid, (ii) a compound containing other elements other than the M element by pH adjustment to a solid-liquid state After separating and removing by separation or the like, the pH is adjusted again to precipitate a compound containing the M element, and the compound is reduced to recover the M element as a solid.
- the extracting agent for example, materials similar to those described in JP-A-2013-139632 can be used, but as long as the effects of the present invention are exhibited, they are not limited to these.
- the M element recovery process may be performed independently after performing the mixing process and the separation process, or may be performed in combination with the carbon recovery process described above. In any case, it is more preferable to use a solution in which solids are not present in the solution to be subjected to the M element recovery step, from the viewpoint of efficiently recovering the M element with high purity. That is, from the acid solution obtained by dissolving the solid component in acid and then separating and removing the dissolution residue, at least one of the above methods (i) to (iv) is performed to selectively remove the M element. Collection is preferred.
- the separated liquid obtained through the separation step is a liquid in which solids are not present, and Li element, S element and P element derived from the solid electrolyte, and optionally contained halogen elements in the form of ions. contains. From the viewpoint of efficiently and simply recovering these elements that can be used as raw materials for solid electrolytes and further reducing the environmental load, at least one of Li element, S element and P element is removed from the above separated liquid. It is preferable to perform a step of recovering the contained compound (compound recovery step).
- the compound recovery step may be performed alone after the mixing step and the separation step, or the carbon recovery step and the M element recovery step described above may be combined in any order.
- a method for recovering the compound containing at least one of the Li element, S element and P element from the separated liquid includes, for example, a method of removing the liquid medium that constitutes the separated liquid.
- the above-mentioned compound can be obtained as a solid by removing the solvent in the separated liquid by a removal method such as drying by heating or drying under reduced pressure and drying the substances other than the solvent.
- the compound after drying and solidification obtained in the compound recovery step preferably contains one or more of phosphorus oxide, a compound containing two or more of Li element, S element and P element, and a compound containing a halogen element.
- the dry matter may also contain elements such as elemental sulfur and mixtures of the above compounds.
- the compound obtained in the compound recovery step preferably contains, for example, two or more of Li element, S element, P element and halogen element, and contains at least one of lithium sulfide, phosphorus sulfide and lithium halide. is more preferred.
- the temperature conditions, pressure conditions, etc. in the compound recovery process can be appropriately adjusted according to the type of separated liquid and the type of compound.
- the compound obtained through the compound recovery step has few impurities and contains the constituent elements of the solid electrolyte. It can also be reused as a raw material for manufacturing electrolytes. In particular, reuse as a raw material for producing a sulfide solid electrolyte is preferable in terms of convenience and production cost.
- the compound obtained through the compound recovery step is used as a raw material for producing a sulfide solid electrolyte, for example, the compound is mixed with other raw materials as necessary to prepare a mixed powder, and then the mixed A sulfide solid electrolyte can be obtained by heating the powder under flowing reducing gas such as hydrogen sulfide gas.
- the compound obtained through the compound recovery step preferably consists only of components derived from the solid electrolyte, but depending on the conditions adopted in each step, the compound may inevitably contain other components other than the constituent materials of the solid electrolyte. is not precluded from being included in In this case, the amount of other components contained in the compound is preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 5% by mass or less.
- the present invention has been described above based on its preferred embodiments, the present invention is not limited to the above-described embodiments.
- the method may perform only the mixing step and the separation step, or perform at least one of the carbon recovery step, the M element recovery step, and the compound recovery step in addition to the mixing step and the separation step. or all steps may be performed.
- the suitable steps to be performed after the mixing step and the separation step may be performed sequentially in any order, or may be performed simultaneously as necessary.
- the method of the present invention it is possible to satisfactorily separate the predetermined constituent material from the member containing the active material and the solid electrolyte while suppressing the environmental load.
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Abstract
Description
ところで、電解液を用いた液系電池から有価金属を回収する方法として、液系電池を燃焼して電解液を除去する技術がある。この技術のように燃焼工程を有すると、二酸化炭素が排出され環境負荷が増してしまう。そのため、固体電池への適用にも課題がある。また、硫化物固体電解質を用いた硫化物系の固体電池の場合には、燃焼工程により二酸化炭素に加えて硫黄酸化物が排出されてしまうという課題もある。更に、固体電池を燃焼することで、固体電池に含まれるP元素がリン酸塩等の化学安定性の高い物質を構成し、P元素の回収が困難になるといった課題がある。これらの課題を解決することについて、特許文献1及び2では何ら検討されていない。
活物質及び固体電解質を有する前記部材と溶媒とを混合して混合物を得る工程と、
前記混合物を固液分離して、固形成分及び分離液を得る工程と、を有し、
前記固体電解質が、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素を含有し、
前記部材と前記溶媒とを混合することで、前記固体電解質が前記溶媒に溶解する、分離方法を提供するものである。
前記混合物を固液分離して、固形成分及び分離液を得る工程と、
前記分離液から、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素の少なくとも1種を含有する化合物を回収する工程とを有し、
前記部材と前記溶媒とを混合することで、前記固体電解質が前記溶媒に溶解する、部材の処理方法を提供するものである。
前記混合物を固液分離して、固形成分及び分離液を得る工程と、
前記固形成分を酸溶解して、溶解残渣である炭素成分を回収する工程とを有し、
前記固体電解質が、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素を含有し、
前記部材と前記溶媒とを混合することで、前記固体電解質が前記溶媒に溶解する、部材の処理方法を提供するものである。
前記混合物を固液分離して、固形成分及び分離液を得る工程と、
前記固形成分を酸溶解して溶解液を得る工程と、
前記溶解液から前記M元素を回収する工程とを有し、
前記固体電解質が、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素を含有し、
前記部材と前記溶媒とを混合することで、前記固体電解質が前記溶媒に溶解する、部材の処理方法を提供するものである。
本方法では、まず、活物質及び固体電解質を有する部材と溶媒とを混合して混合物を得る工程(混合工程)を行う。混合工程では、部材と溶媒とを混合することで、部材に含まれる固体電解質を溶媒に溶解させる。このとき、他の構成材料は好ましくは溶媒中に分散状態で存在する。
アルコール溶媒としては、例えば、炭素数1以上であることが好ましく、2以上であることが更に好ましく、4以上であることが一層好ましい。一方、炭素数の上限は特に限定されないが、例えば、12以下であってもよく、8以下であってもよい。アルコール溶媒としては、例えば、上述した炭素数の直鎖又は分岐状鎖を有するアルコールが挙げられる。具体的には、メタノール、エタノール、1-プロパノール、1-ブタノール、2-メチル-1-プロパノール、2-ブタノール、及び2-メチル-2-プロパノール等が挙げられる。
エステル溶媒としては、例えば、酢酸エチルや酢酸ブチル等が挙げられる。
アルデヒド溶媒としては、例えば、ホルムアルデヒド、アセトアルデヒド等が挙げられる。
ケトン溶媒としては、例えば、アセトンやメチルエチルケトン等が挙げられる。
エーテル溶媒としては、例えば、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジメトキシエタン等が挙げられる。
構造中にヘテロ原子を含む他の溶媒としては、例えば、アセトニトリルやジメチルスルホキシド、ジメチルホルムアミド等が挙げられる。
小片化処理は、処理後の部材の寸法を処理前の部材の寸法よりも小さくする処理であり、例えば、粉砕装置や破砕装置を用いて行うことができる。
したがって、混合工程及び分離工程を行う本方法によれば、焼却処理などの環境負荷が比較的大きい処理を行わずに、M元素を含む有価成分を効率的に回収して再利用や売却を行える。また、従来技術では分離回収が困難であった硫黄やリンを効率的に回収することができる。その結果、資源の有効活用及び環境負荷の軽減を達成できる。
この場合、金属成分と炭素成分との分離を効率的に行って、炭素成分の回収を行いつつ、金属成分を有価成分として回収しやすくする観点から、分離工程を経て得られた固形成分を酸溶解して、炭素成分を回収する工程(炭素回収工程)を更に行うことが好ましい。金属成分及び炭素成分等のM元素を固形成分に複数種含む場合、炭素回収工程は、M元素のうち、炭素元素と、炭素元素以外のM元素とを分離回収するものである。炭素回収工程は、混合工程及び分離工程を行ったあと単独で行ってもよく、後述する各種の好適な工程を任意の順序で組み合わせて行ってもよい。
化合物回収工程を経て得られた化合物を硫化物固体電解質の製造原料とする場合には、例えば、当該化合物と、必要に応じて他の原料と混合して混合粉を調製し、その後、該混合粉を硫化水素ガス等の還元性ガス流通下で加熱することによって、硫化物固体電解質とすることができる。
Claims (17)
- 部材の構成材料を分離する分離方法であって、
活物質及び固体電解質を有する前記部材と溶媒とを混合して混合物を得る工程と、
前記混合物を固液分離して、固形成分及び分離液を得る工程と、を有し、
前記固体電解質が、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素を含有し、
前記部材と前記溶媒とを混合することで、前記固体電解質が前記溶媒に溶解する、分離方法。 - 前記溶媒は、前記固体電解質に対する溶解度が、20℃において1mg/mL以上である、請求項1に記載の分離方法。
- 前記溶媒は水酸基を有する、請求項1又は2に記載の分離方法。
- 前記活物質が、M元素(Mは、リチウム(Li)、ニッケル(Ni)、マンガン(Mn)、コバルト(Co)、アルミニウム(Al)、鉄(Fe)、チタン(Ti)、ニオブ(Nb)、ケイ素(Si)、炭素(C)及び銅(Cu)のうちの少なくとも一種である)を含有する、請求項1ないし3のいずれか一項に記載の分離方法。
- 前記固形成分が、M元素(Mは、リチウム(Li)、ニッケル(Ni)、マンガン(Mn)、コバルト(Co)、アルミニウム(Al)、鉄(Fe)、チタン(Ti)、スズ(Sn)、ニオブ(Nb)、ケイ素(Si)、炭素(C)及び銅(Cu)のうちの少なくとも一種である)を含有する、請求項1ないし4のいずれか一項に記載の分離方法。
- 前記分離液は、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素を含有する、請求項1ないし5のいずれか一項に記載の分離方法。
- 活物質と、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素を含有する固体電解質とを有する部材、並びに溶媒を混合して、前記固体電解質が前記溶媒に溶解した混合物を得る工程と、
前記混合物を固液分離して、固形成分及び分離液を得る工程と、
前記分離液から、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素の少なくとも1種を含有する化合物を回収する工程とを有し、
前記部材と前記溶媒とを混合することで、前記固体電解質が前記溶媒に溶解する、部材の処理方法。 - 前記溶媒は、前記固体電解質に対する溶解度が20℃において1mg/mL以上である、請求項7に記載の処理方法。
- 前記溶媒は水酸基を有する、請求項7又は請求項8に記載の処理方法。
- 前記化合物が、硫化リチウム、硫化リン及びハロゲン化リチウムのうちの少なくとも1種である、請求項7ないし9のいずれか一項に記載の処理方法。
- 活物質及び固体電解質を有する部材と溶媒とを混合して、前記固体電解質が前記溶媒に溶解した混合物を得る工程と、
前記混合物を固液分離して、固形成分及び分離液を得る工程と、
前記固形成分を酸溶解して、溶解残渣である炭素成分を回収する工程とを有し、
前記固体電解質が、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素を含有し、
前記部材と前記溶媒とを混合することで、前記固体電解質が前記溶媒に溶解する、部材の処理方法。 - 前記溶媒は、前記固体電解質に対する溶解度が20℃において1mg/mL以上である、請求項11に記載の処理方法。
- 前記溶媒は水酸基を有する、請求項11又は12に記載の処理方法。
- M元素(Mは、リチウム(Li)、ニッケル(Ni)、マンガン(Mn)、コバルト(Co)、アルミニウム(Al)、鉄(Fe)、チタン(Ti)、スズ(Sn)、ニオブ(Nb)、ケイ素(Si)、炭素(C)及び銅(Cu)のうちの少なくとも一種である)を含有する活物質と固体電解質とを有する部材、並びに溶媒を混合して、前記固体電解質が前記溶媒に溶解した混合物を得る工程と、
前記混合物を固液分離して、固形成分及び分離液を得る工程と、
前記固形成分を酸溶解して溶解液を得る工程と、
前記溶解液から前記M元素を回収する工程とを有し、
前記固体電解質が、リチウム(Li)元素、硫黄(S)元素及びリン(P)元素を含有し、
前記部材と前記溶媒とを混合することで、前記固体電解質が前記溶媒に溶解する、部材の処理方法。 - 前記固形成分を酸溶解して、溶解残渣である炭素成分を回収する工程を更に有する、請求項14に記載の処理方法。
- 前記溶媒は、前記固体電解質に対する溶解度が20℃において1mg/mL以上である、請求項14又は15に記載の処理方法。
- 前記溶媒は水酸基を有する、請求項14ないし16のいずれか一項に記載の処理方法。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006004884A (ja) * | 2004-06-21 | 2006-01-05 | Toyota Motor Corp | リチウム電池処理方法 |
JP2010040458A (ja) * | 2008-08-07 | 2010-02-18 | Idemitsu Kosan Co Ltd | リチウム回収方法及び金属回収方法 |
JP2013139632A (ja) | 2012-12-13 | 2013-07-18 | Jx Nippon Mining & Metals Corp | 金属混合溶液中の金属の分離方法 |
JP2016035809A (ja) * | 2014-08-01 | 2016-03-17 | トヨタ自動車株式会社 | 硫化物固体電池の正極活物質回収方法 |
JP2016058280A (ja) * | 2014-09-10 | 2016-04-21 | トヨタ自動車株式会社 | 正極活物質の回収方法 |
JP2019081953A (ja) * | 2017-10-31 | 2019-05-30 | 出光興産株式会社 | リチウム回収装置及びリチウム回収方法 |
JP2019099901A (ja) | 2017-12-05 | 2019-06-24 | ティーエムシー株式会社 | リチウム含有水溶液からリチウムを回収する方法 |
JP2019160429A (ja) | 2018-03-07 | 2019-09-19 | Jx金属株式会社 | リチウム回収方法 |
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006004884A (ja) * | 2004-06-21 | 2006-01-05 | Toyota Motor Corp | リチウム電池処理方法 |
JP2010040458A (ja) * | 2008-08-07 | 2010-02-18 | Idemitsu Kosan Co Ltd | リチウム回収方法及び金属回収方法 |
JP2013139632A (ja) | 2012-12-13 | 2013-07-18 | Jx Nippon Mining & Metals Corp | 金属混合溶液中の金属の分離方法 |
JP2016035809A (ja) * | 2014-08-01 | 2016-03-17 | トヨタ自動車株式会社 | 硫化物固体電池の正極活物質回収方法 |
JP2016058280A (ja) * | 2014-09-10 | 2016-04-21 | トヨタ自動車株式会社 | 正極活物質の回収方法 |
JP2019081953A (ja) * | 2017-10-31 | 2019-05-30 | 出光興産株式会社 | リチウム回収装置及びリチウム回収方法 |
JP2019099901A (ja) | 2017-12-05 | 2019-06-24 | ティーエムシー株式会社 | リチウム含有水溶液からリチウムを回収する方法 |
JP2019160429A (ja) | 2018-03-07 | 2019-09-19 | Jx金属株式会社 | リチウム回収方法 |
Non-Patent Citations (1)
Title |
---|
TERAGAWA, SHINGO; ASO, KEIGO; TADANAGA, KOYOHARU; HAYASHI, AKITOSHI; TATSUMISAGO, MASAHIRO: "3E17 Preparation of Li2S-P2S5 solid electrolyte via its solution and application for all-solid state batteries", 54TH BATTERY SYMPOSIUM IN JAPAN; OSAKA, JAPAN; OCTOBER 7 - 9, 2013, vol. 54, 6 October 2013 (2013-10-06) - 9 October 2013 (2013-10-09), pages 350, XP009540115 * |
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