CN110661051B - Solid-state battery material recovery processing method - Google Patents
Solid-state battery material recovery processing method Download PDFInfo
- Publication number
- CN110661051B CN110661051B CN201810687285.9A CN201810687285A CN110661051B CN 110661051 B CN110661051 B CN 110661051B CN 201810687285 A CN201810687285 A CN 201810687285A CN 110661051 B CN110661051 B CN 110661051B
- Authority
- CN
- China
- Prior art keywords
- solid
- less
- battery material
- solvent
- sulfide electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 78
- 238000003672 processing method Methods 0.000 title claims abstract description 17
- 238000011084 recovery Methods 0.000 title claims description 19
- 238000000034 method Methods 0.000 claims abstract description 68
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 58
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003792 electrolyte Substances 0.000 claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003960 organic solvent Substances 0.000 claims abstract description 44
- 239000007772 electrode material Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 229920001021 polysulfide Polymers 0.000 claims abstract description 23
- 239000005077 polysulfide Substances 0.000 claims abstract description 23
- 150000008117 polysulfides Polymers 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000007790 solid phase Substances 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 239000007774 positive electrode material Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 239000007773 negative electrode material Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000002001 electrolyte material Substances 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 8
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- -1 lithium halide Chemical class 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002203 sulfidic glass Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910005842 GeS2 Inorganic materials 0.000 description 1
- 229910008706 Li2NiMn3O8 Inorganic materials 0.000 description 1
- 229910009099 Li2S-Al2S3 Inorganic materials 0.000 description 1
- 229910009292 Li2S-GeS2 Inorganic materials 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910009329 Li2S—Al2S3 Inorganic materials 0.000 description 1
- 229910009351 Li2S—GeS2 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- 229910012808 LiCoMnO4 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910011638 LiCrO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 1
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013084 LiNiPO4 Inorganic materials 0.000 description 1
- 229910012981 LiVO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910003884 O2-bNb Inorganic materials 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910020343 SiS2 Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Secondary Cells (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
The invention relates to the field of battery materials, in particular to a treatment method for recovering a solid battery material. The invention provides a processing method for recovering a solid-state battery material, wherein the battery material comprises a sulfide electrolyte and an electrode material, and the processing method comprises the following steps: contacting the cell material with elemental sulfur in the presence of a solvent to produce a solution of at least a portion of a lithium polysulfide compound in the solvent; obtaining sulfur-containing compounds from the obtained liquid phase matter, and/or obtaining electrode materials from the obtained solid phase matter. According to the treatment method for recovering the solid-state battery material, provided by the invention, the sulfide electrolyte is dissolved in the organic solvent through the reaction of the low-cost sulfur powder and the sulfide electrolyte, and the electrode material is insoluble in the organic solvent, so that the sulfide electrolyte and the electrode material are effectively separated.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a treatment method for recovering a solid battery material.
Background
The lithium secondary battery has the advantages of large output power, high energy density, long service life, high average output voltage, small self-discharge, no memory effect, rapid charge and discharge, excellent cycle performance, no environmental pollution and the like, is a preferred object of rechargeable power supplies for digital electronic products at present, and is considered to be the most competitive power battery for vehicles. At present, liquid electrolyte materials are mainly adopted by the lithium secondary battery, and a large amount of organic solvents are contained in the liquid electrolyte materials, so that potential safety hazards of the liquid lithium secondary battery are raised. The all-solid-state lithium secondary battery has incomparable safety with the liquid-state lithium secondary battery, is expected to thoroughly eliminate potential safety hazards in the use process, and more meets the future development requirements of electric vehicles and the field of large-scale energy storage. Therefore, researchers in various countries are actively developing all solid-state lithium secondary batteries. Solid electrolytes are widely varied and classified into organic polymers, inorganic oxides, inorganic sulfides, and the like according to types. Wherein the sulfide electrolyte material can exhibit a conductivity of 10 at room temperature-2Has S/cm level, wide electrochemical window and excellent performanceAnd the application prospect is good.
Currently, all reported sulfide solid-state batteries adopt a sandwich type structure of a positive electrode layer, an electrolyte layer and a negative electrode layer. The three layers of the structure all contain sulfide electrolyte, and the mass ratio reaches more than 30%. Therefore, it is necessary to separate and recover the sulfide electrolyte. Since sulfide electrolyte has a special odor and is sensitive to moisture and the like, highly toxic H is easily generated2S gas, and therefore, the limit on the treating ability and condition of the sulfide electrolyte is high.
Disclosure of Invention
In view of the problems in the background art, it is an object of the present invention to provide a method for recycling a solid-state battery material, which solves the problems in the prior art.
To achieve the above and other related objects, the present invention provides a processing method for solid-state battery material recovery, the battery material including a sulfide electrolyte and an electrode material, the processing method including: contacting the cell material with elemental sulfur in the presence of a solvent to produce a solution of at least a portion of a lithium polysulfide compound in the solvent;
obtaining sulfur-containing compounds from the obtained liquid phase matter, and/or obtaining electrode materials from the obtained solid phase matter.
In some embodiments of the invention, the lithium polysulfide compound has the chemical formula M-Sx-Li, wherein 1<x.ltoreq.8, preferably, 3. ltoreq. x.ltoreq.8.
In some embodiments of the invention, the molar ratio of the-S-Li structure in the sulfide electrolyte to the added elemental sulfur is 1: 0.1 to 7, preferably 1: 2 to 7.
In some embodiments of the invention, the battery material is in the form of pieces and/or powder, preferably obtained by crushing a solid-state battery, and the particle size of the battery material is less than or equal to 10 mm.
In some embodiments of the present invention, the processing method specifically includes: the battery material is mixed with a solvent to form a first slurry, and elemental sulfur is introduced into the first slurry to form a second slurry.
In some embodiments of the present invention, the reaction product is subjected to solid-liquid separation to obtain a liquid phase and/or a solid phase.
In some embodiments of the invention, the resulting liquid phase is desolventized to obtain sulfide.
In some embodiments of the invention, the resulting solid phase is washed and dried to obtain a regenerated electrode material.
In some embodiments of the invention, the viscosity of the second slurry is 1000 to 500000cP, preferably 5000 to 100000 cP.
In some embodiments of the invention, the elemental sulfur is sulfur powder.
In some embodiments of the invention, the reaction is carried out under anhydrous conditions, preferably, the reaction is also carried out in a dry environment with a relative humidity below 1% and/or a dew point below-30 ℃.
In some embodiments of the present invention, the reaction is carried out under a gas blanket, preferably, the gas is selected from inert gases, the gas has a moisture content of less than 1000ppm and an oxygen content of less than or equal to 500 ppm.
In some embodiments of the present invention, the solvent is selected from one or more of an ether organic solvent, a hydrocarbon organic solvent, an ester organic solvent, a nitrile organic solvent, an amide organic solvent, an alcohol organic solvent, a halogenated organic solvent, and a heterocyclic organic solvent.
In some embodiments of the invention, the recovery of the electrode material is greater than or equal to 90%.
In some embodiments of the invention, the recovery of sulfide electrolyte is greater than or equal to 90%.
Drawings
FIG. 1 is a schematic process flow diagram of example 1 of the present invention.
Detailed Description
The present inventors have made intensive studies to produce a lithium polysulfide compound by treating a solid-state battery material with elemental sulfur, and further have conducted separation of materials by utilizing a difference in solubility between the lithium polysulfide compound and other materials (for example, an electrode material, etc.) in a solvent, and have completed the present invention.
The solid-state battery material recycling treatment method comprises the following steps:
in one aspect, the present invention provides a processing method for solid-state battery material recycling, the battery material may include a sulfide electrolyte and an electrode material, the processing method may include: contacting the battery material with elemental sulfur in the presence of a solvent, and dissolving at least a portion of the resulting lithium polysulfide compound in the solvent.
In the processing method for recovering the solid-state battery material, which is provided by the invention, the solid-state battery generally refers to an energy storage device which is basically composed of a solid material and basically contains no liquid, elemental sulfur can react with the sulfide electrolyte material in the battery material, more specifically, elemental sulfur can react with a compound with a-S-Li structure (group) in the sulfide electrolyte material, so that a lithium polysulfide compound (M-S) can be generatedx-Li), the reaction principle of which is shown by the following formula:
where x > 1, M may include, but is not limited to, P, Si, Ge, Sn, Al, and the like. The obtained lithium polysulfide compound can be usually at least partially dissolved in the solvent, and can further utilize the difference or advantage of the solubility of the lithium polysulfide compound in a solvent (e.g., a suitable organic solvent) relative to other materials (e.g., an electrode material), for example, the lithium polysulfide compound can have good solubility in a suitable solvent, while the electrode material can be substantially insoluble in the corresponding solvent, so that separation of the sulfide electrolyte and the electrode material can be achieved.
In the treatment method for recovering the solid-state battery material, the sulfide electrolyte is usually solid and has the lithium ion conductivity, and at least part of sulfide components in the sulfide electrolyte can react with elemental sulfur, so that a lithium polysulfide compound can be generated.A suitable kind of sulfide electrolyte may be selected by those skilled in the art to be suitable for the treatment method provided by the present invention, and specifically, the sulfide electrolyte may generally include lithium and sulfur, and may further include other elements, for example, a combination including but not limited to one or more of P, Si, Ge, Sn, Al, and the like. For another example, the general structural formula of the sulfide electrolyte may be yLi2S- (100-y) MS, wherein, 0<y<100, the MS may be, but is not limited to, P2S5、SiS2、GeS2、SnS2、Al2S3And the like. As another example, the solid electrolyte system can be one including, but not limited to, Li2S-P2S5System, Li2S-SiS2System, Li2S-GeS2System, Li2S-SnS2System, Li2S-Al2S3Systems, and the like. For another example, the sulfide electrolyte state may be a crystalline state, an amorphous state, or a composite state of a crystalline-amorphous state, or the like.
In the processing method for recovering the solid-state battery material, the sulfide electrolyte can further comprise a doping material, and the doping material is preferably a compound LiQ containing lithium elements. For example, the general structure of the sulfide electrolyte containing the dopant material may be z [ yLi ]2S-(100-y)MS]- (100-z) LiQ, wherein 0<y<Z is more than or equal to 100 and more than or equal to 90 and less than 100. One skilled in the art can select a suitable kind of lithium element-containing compound LiQ as the doping material, for example, the doping material LiQ may be a combination including, but not limited to, one or more of lithium halide, lithium oxide, lithium nitride, lithium oxysalt, and the like. More specifically, the LiQ may be a compound including, but not limited to LiF, LiCl, LiBr, LiI, Li2O、Li3N、LiAlO2、Li3PO4、Li2SO4、Li3BO3、Li4SiO4、LiN(SO2F)2、LiN(SO2RF)2、LiN(SO2F)(SO2RF) (wherein, the substituent RF＝CnF2n+1Is a saturated perfluoroalkyl group, preferably, n is 1 or 2), and the like.
In the treatment method for recovering the solid-state battery material provided by the present invention, the electrode material may generally include a cathode material which is generally not chemically reactive with elemental sulfur and has a solubility in a solvent used in the treatment method that is significantly lower than that of the lithium polysulfide compound, for example, the cathode material is substantially insoluble in the solvent used in the treatment method, and a person skilled in the art can select a suitable cathode material to be applied to the treatment method provided by the present invention. Further, the positive electrode material may generally include a positive electrode current collector and/or a positive electrode active material, which are suitable for a solid-state battery and should be known to those skilled in the art, for example, the positive electrode current collector may be a metal foil or the like, and further, for example, the positive electrode active material may include a combination of one or more of a layered positive electrode active material, a spinel-type positive electrode active material, an olivine-type positive electrode active material, a metal sulfide or the like, and more particularly, the positive electrode active material may include, but is not limited to, a chemical formula such as Li, for exampleaNixCoyMzO2-bNb(wherein 0.95. ltoreq. a.ltoreq.1.2, x > 0, y. gtoreq.0, z. gtoreq.0, and x + y + z. ltoreq.1, 0. ltoreq. b.ltoreq.1, M is selected from one or more combinations of Mn and Al, and N is selected from one or more combinations of F, P, S), and the positive electrode active material may be selected from one or more of compounds including but not limited to LiCoO2、LiNiO2、LiVO2、LiCrO2、LiMn2O4、LiCoMnO4、Li2NiMn3O8、LiNi0.5Mn1.5O4、LiCoPO4、LiMnPO4、LiFePO4、LiNiPO4、LiCoFSO4、CuS2、FeS2、MoS2、NiS、TiS2And the like. The positive electrode material can also be subjected to modification treatment to form a positive electrodeThe method of modifying the material is known to those skilled in the art, for example, the positive electrode material may be modified by cladding, doping, etc., and the material used in the modification may be one or more of Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W, etc., but is not limited thereto.
In the treatment method for recovering the solid-state battery material provided by the present invention, the electrode material may generally include a negative electrode material which is generally not chemically reacted with elemental sulfur and has a solubility in a solvent used in the treatment method which is significantly lower than that of the lithium polysulfide compound, for example, the negative electrode material is substantially insoluble in the solvent used in the treatment method, and a person skilled in the art may select a suitable negative electrode material to be applied to the treatment method provided by the present invention. Further, the negative electrode material may generally include a negative electrode current collector and/or a negative electrode active material, which may be known to those skilled in the art as suitable for solid state batteries, for example, the negative electrode current collector may be a metal foil or the like, and further for example, the negative electrode active material may generally be a metal negative electrode active material and/or a non-metal negative electrode active material, which may be a combination including, but not limited to, one or more of metallic lithium, metallic indium, metallic aluminum, metallic tin, or alloys thereof or the like, and the non-metal negative electrode active material may be a combination including, but not limited to, one or more of a carbon-containing active material, a silicon-based active material, a tin-based active material, a sulfur-containing active material, lithium titanate or the like, and more specifically, the carbon-containing active material may include, but not limited to, soft carbon, The silicon-based active substance can be one or more of elemental silicon, silicon-oxygen compound, silicon-carbon compound, silicon alloy and the like, the tin-based material can be one or more of elemental tin, tin-oxygen compound, tin alloy and the like, and the sulfur-containing active substance can be sulfur and the like.
In the processing method for recycling the solid-state battery material, the electrode material can also comprise a conductive agent, and the conductive agent generally refers to a compound which plays a role in transporting ions and electrons in the electrode. Those skilled in the art can select a suitable type and amount of conductive agent, for example, the conductive agent can be a combination including, but not limited to, one or more of a carbon black conductive agent, a graphite conductive agent, and the like, and more specifically, the conductive agent can be a combination including, but not limited to, one or more of conductive carbon black (e.g., super-P), acetylene black, carbon fiber (e.g., VGCF), carbon nanotubes, graphite, and the like, and for example, the conductive agent can be present in the electrode material in a mass ratio of 5% or less, 0.5% to 1% or less, 1% to 2% or less, 2% to 3% or less, 3% to 4% or 4% to 5% or less.
In the treatment method for recovering a solid-state battery material provided by the present invention, the battery material may be generally in the form of pieces and/or powder, for example, the battery material may generally have a particle size of 10mm or less, 8mm or less, 6mm or less, 5mm or less, 4mm or less, 3mm or less, 2mm or less, or 1mm or less, the elemental sulfur may generally be a sulfur powder, for example, the sulfur powder may generally have a particle size of 10mm or less, 8mm or less, 6mm or less, 5mm or less, 4mm or less, 3mm or less, 2mm or less, or 1mm or less. The reduction of the particle size of the reaction raw materials can ensure sufficient contact between the reaction raw materials, thereby ensuring the reaction efficiency. The fragments and/or powders of the battery material can be obtained by crushing the solid-state battery, and the method for crushing the battery material is known to those skilled in the art, and for example, manual crushing and/or mechanical crushing can be adopted.
In the processing method for recovering the solid-state battery material provided by the invention, the battery material can be contacted with the elemental sulfur in the presence of the solvent, specifically, the battery material, the elemental sulfur and the solvent can be mixed to form slurry, more specifically, the battery material and the solvent can be mixed to form first slurry, and the elemental sulfur is introduced into the first slurry to form second slurry. The viscosity of a slurry (for example, a second slurry) formed by mixing a battery material, elemental sulfur, and a solvent may be 1000 to 500000cP, 5000 to 100000cP, 1000 to 3000cP, 3000 to 5000cP, 5000 to 10000cP, 10000 to 20000cP, 20000 to 30000cP, 30000 to 50000cP, 100000 to 200000cP, 200000 to 300000cP, or 300000 to 500000 cP.
In the method for recycling solid-state battery materials provided by the invention, the reaction is usually carried out under anhydrous conditions, so that the side reaction of water and sulfur-containing substances, such as the generation of toxic and highly corrosive H by the reaction, can be avoided2And S. The anhydrous conditions generally refer to a moisture content in the reaction system of less than or equal to 5000ppm, less than or equal to 4000ppm, less than or equal to 3000ppm, less than or equal to 2000ppm, less than or equal to 1000ppm, less than or equal to 500ppm, less than or equal to 300ppm, or less than or equal to 100 ppm. Methods for achieving anhydrous reaction conditions will be known to those skilled in the art, for example, the reaction can be carried out in a dry environment (e.g., in a dry house) which can be an environment having a relative humidity of 2% or less, 1.5% or less, 1% or less, 0.8% or less, or 0.5% or less, or a dew point of 20 ℃ or less, 25 ℃ or less, 30 ℃ or less, 35 ℃ or less, or 40 ℃ or less, and for example, the reaction can be carried out under gas shielding conditions, the moisture content in the shielding gas providing the gas shielding typically being 5000ppm or less, 4000ppm or less, 3000ppm or less, 2000ppm or less, 1000ppm or less, 500ppm or less, 300ppm or less, or 100ppm or less. The reaction is carried out under a gas blanket, and it is also possible to avoid introducing other substances which may introduce side reactions, for example, oxygen, etc., into the reaction system, and for example, the oxygen content in the reaction system may be 500ppm or less, 300ppm or less, 100ppm or less, 50ppm or less, 30ppm or less, 10ppm or less, 5ppm or less, or 1ppm or less. Methods of achieving gas-blanketing reaction conditions will be known to those skilled in the art, for example, inert gases and the like may be employed, which may specifically be combinations including, but not limited to, one or more of nitrogen, helium, neon, argon, krypton, and the like.
In the processing method for recovering the solid-state battery material provided by the invention, the lithium polysulfide compound generally has certain advantages relative to the solubility of other materials (such as the electrode material) in a solvent, for example, the lithium polysulfide compound can have good solubility in a suitable solvent, and the electrode material can be basically insoluble in the corresponding solvent. Those skilled in the art can select a suitable kind and amount of solvent to be suitable for the processing method provided by the present invention, for example, the solvent may be an organic solvent, and for example, the solvent may be a combination including but not limited to one or more of an ether organic solvent, a hydrocarbon organic solvent, an ester organic solvent, a nitrile organic solvent, an amide organic solvent, an alcohol organic solvent, a halogenated organic solvent, a heterocyclic organic solvent, and the like, and the ether organic solvent may be a combination including but not limited to one or more of diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, and the like; the hydrocarbon organic solvent may be a combination including, but not limited to, one or more of n-pentane, n-hexane, cyclohexane, toluene, xylene, trimethylbenzene, and the like; the ester organic solvent may be a combination including, but not limited to, one or more of ethyl acetate, methyl formate, dimethyl phthalate, and the like; the nitrile organic solvent may be a combination including, but not limited to, one or more of acetonitrile, succinonitrile, and the like; the amide-based organic solvent may be a combination including, but not limited to, one or more of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), and the like; the alcoholic organic solvent may be, but is not limited to, ethanol, etc.; the halogenated organic solvent may be a combination including, but not limited to, one or more of dichloromethane, 1, 2-dichloroethane, and the like; the heterocyclic organic solvent may be a combination including, but not limited to, one or more of pyridine, pyrrole, piperidine, and the like. In a particular embodiment of the invention, the solvent is selected from pyridine and/or tetrahydrofuran. For another example, the increase of the solvent dosage may cause the cost to increase, while too small dosage may cause the viscosity of the reaction system to be too high, which is not favorable for stirring and dispersing, specifically, the viscosity of the reaction system may be 1000 to 500000cP, 5000 to 100000cP, 1000 to 3000cP, 3000 to 5000cP, 5000 to 10000cP, 10000 to 20000cP, 20000 to 30000cP, 30000 to 50000cP, 100000 to 100000cP, 100000 to 200000cP, 200000 to 300000cP, or 300000 to 500000 cP.
In the treatment method for recovering the solid-state battery material, the chemical structural formula of the lithium polysulfide compound is M-Sx-Li, wherein 1<x≤8、1<x is not less than 2, x is not less than 2 and not more than 3, x is not less than 3 and not more than 4, x is not less than 4 and not more than 5, x is not less than 5 and not more than 6, x is not less than 6 and not more than 7, or x is not less than 7 and not more than 8, and in a specific embodiment of the invention, x is not less than 3 and not more than 8. As a result of the studies of the inventors, the amount of elemental sulfur used may be related to the-S-Li structure in the sulfide solid electrolyte, and for example, the molar ratio of the-S-Li structure to the amount of elemental sulfur used may be in the range of 1: 0.1-7, 1: 0.1-0.5, 1: 0.5-1, 1: 1-2 and 1: 2-3, 1: 3-4, 1: 4-5, 1: 5-6, or 1: 6-7, the usage amount of the elemental sulfur can be used together with Li used for synthesizing sulfide solid electrolyte2The quantity of S being dependent, e.g. Li used for synthesis of sulfide solid electrolytes2The molar ratio of S to elemental sulfur may range from 1: 0.1-14, 1: 0.1-0.5, 1: 0.5-1, 1: 1-2 and 1: 2-4, 1: 4-6, 1: 6-8, 1: 8-10, 1: 10-12, or 1: 12 to 14. When elemental sulfur is used in a relatively low amount, the resulting lithium polysulfide compound will generally have a relatively low value for x, which may be, for example<3, the solubility is usually low, a large amount of organic solvent is required to be added for dissolution, which is not beneficial to subsequent separation, and if the addition amount of the elemental sulfur is too high, a solid material recovery procedure is required to be additionally added for treating the elemental sulfur which does not participate in the reaction.
In the treatment method for recovering the solid-state battery material provided by the invention, the reaction can be generally carried out under the temperature condition from room temperature to solvent reflux, for example, the temperature of the reaction system can be 0-200 ℃, 0-10 ℃, 10-20 ℃, 20-30 ℃, 30-40 ℃, 40-50 ℃, 50-60 ℃, 60-80 ℃, 80-100 ℃, 100-120 ℃, 120-140 ℃, 140-160 ℃, 160-180 ℃ or 180-200 ℃. The reaction time can be adjusted by those skilled in the art according to the reaction progress and the like, and the method for monitoring the reaction progress is known to those skilled in the art, and for example, the reaction progress can be monitored by monitoring the dissolution of the added elemental sulfur, and for example, the reaction time can be 1h or less, 1 to 6h or 6 to 12h or 12 to 24h or 24 to 48h or more.
In the treatment method for recovering the solid-state battery material provided by the present invention, the method for obtaining the liquid phase and/or the solid phase from the product obtained by the reaction of the battery material and the elemental sulfur should be known to those skilled in the art, and for example, a suitable solid-liquid separation method may be adopted, and specifically, the method may include, but is not limited to, filtration, centrifugation and the like.
The treatment method for recovering the solid-state battery material provided by the invention can also comprise the following steps: and obtaining sulfur-containing compounds from the obtained liquid phase, wherein the obtained sulfur-containing compounds can be regenerated sulfide electrolyte and/or be used for preparing regenerated sulfide electrolyte. The liquid phase obtained from the reaction is usually enriched with lithium polysulfide compound, and those skilled in the art can select a suitable method to obtain the sulfur-containing compound in the liquid phase, for example, the solvent can be removed from the obtained liquid phase to obtain the sulfur-containing compound, which usually includes the lithium polysulfide compound as described above, so as to achieve the recovery of sulfide electrolyte, and the recovery rate of sulfide electrolyte usually refers to the ratio of the mass of the recovered polysulfide electrolyte to the total mass of sulfide electrolyte and added sulfur powder contained in the initial battery system, specifically, the recovery rate of sulfide electrolyte can be 80% or more, 85% or more, 90% or more, 91% or more, or 92% or more.
The treatment method for recovering the solid-state battery material provided by the invention can also comprise the following steps: obtaining electrode material from the obtained solid phase, wherein the obtained electrode material can be regenerated electrode material. The solid phase obtained by the reaction is usually mainly an electrode material which does not react with elemental sulfur and is substantially insoluble in a solvent, and a person skilled in the art can select a suitable method to obtain the electrode material in the solid phase, for example, the obtained solid phase can be washed and dried, and further, for example, a classification treatment can be further performed to obtain the electrode material, wherein the recovery rate of the obtained electrode material refers to the ratio of the mass of the recovered electrode material to the mass of the electrode contained in the initial battery system, wherein the recovery rate of the positive electrode material can be more than or equal to 75%, more than or equal to 80%, more than or equal to 85%, more than or equal to 90%, or more than or equal to 95%, the recovery rate of the negative electrode material can be more than or equal to 75%, more than or equal to 80%, more than or equal to 85%, more than or equal to 90%, or more than or equal to 95%, the specific capacity loss of the positive electrode can be less than or equal to 20%, more than or equal to 15%, more than or equal to 10%, more than, Less than or equal to 15 percent, less than or equal to 10 percent, less than or equal to 8 percent, less than or equal to 6 percent or less than or equal to 5 percent. The resulting solid phase may be washed with a suitable detergent selected by one skilled in the art, for example, the selected detergent may be any one of, but not limited to, pyridine, carbon disulfide, diethyl ether, and the like, in one embodiment of the invention, the detergent is a combination of pyridine and carbon disulfide, the pyridine solution remaining from filtration may be washed out by fresh pyridine, elemental sulfur in the solids may be dissolved by carbon disulfide washing, and the sulfur content of the resulting electrode material recovered is typically 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.5% by mass.
According to the treatment method for recovering the solid-state battery material, provided by the invention, the sulfide electrolyte is dissolved in the organic solvent through the reaction of the low-cost sulfur powder and the sulfide electrolyte, and the electrode material is insoluble in the organic solvent, so that the sulfide electrolyte and the electrode material are effectively separated. The method provided by the invention has simple separation steps and mild reaction conditions, can efficiently separate sulfide electrolyte and electrode materials, and does not generate highly toxic and highly corrosive H2S gas, the separated sulfide material can be continuously used as an electrolyte material, and also can be used as a precursor material of the electrolyte material for preparing regenerated sulfide electrolyte, and the recovered electrode material can still be continuously used as a battery electrode material without structural damage.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1
The process of separating electrode material from electrolyte of sulfide solid battery is shown in flow chart 1.
Solid-state battery: the laminated sulfide solid state cell of the "sandwich" structure was prepared by dry pressing according to the reference reported method (j.power Sources,2014,248,943): the positive electrode layer is made of lithium cobaltate and sulfide electrolyte Li3PS4The sulfide electrolyte layer is composed of Li at a mass ratio of 80:20 (total weight is 10g)3PS4The negative electrode layer is composed of natural graphite and sulfide electrolyte Li (5 g in weight)3PS4According to the mass ratio of 50:50 (the total weight is 10 g).
Material recovery: in a drying room, the sulfide solid-state battery is crushed by a 10T hydraulic press and then is further ball-milled and ground until the particle size of solid fragments is about 3 mm. 25g of the crumb was mixed with 100mL of pyridine solvent and stirred to form a homogeneous slurry. 4.8g of sulfur powder is slowly and continuously added into the slurry, and the mixture is continuously stirred until the sulfur powder is completely dissolved, so that the electrolyte material Li3PS4Conversion to Li3PS7. Standing for 2h to allow the system to stratify, wherein the upper layer is light yellow clear liquid, and the lower layer is black insoluble solid, and filtering under reduced pressure to separate the solution and the solid. Performing rotary evaporation on the solution to obtain a concentrated solution, and performing vacuum reduced pressure drying at 100 ℃ to obtain Li3PS7Solid powder 12.8 g. To pairThe black insoluble matter obtained by filtration was washed with fresh pyridine 3 times, and then dried under vacuum at 100 ℃ to obtain solid powder, which was then subjected to classification treatment to obtain 7.9g of lithium cobaltate as a positive electrode material and 4.8g of graphite as a negative electrode material. The test results are shown in Table 1.
And (3) material testing: and carrying out electrochemical test on the recovered material, wherein the electrolyte is subjected to room temperature conductivity test, and the anode material and the cathode material are subjected to specific capacity test. The test results are shown in Table 2.
The specific test method is as follows:
(1) electrolyte room temperature conductivity test
Pressing 100mg of recovered sulfide electrolyte into a sheet material with the diameter of 10mm under the pressure of 20MPa, forming a symmetrical battery by using stainless steel as a blocking electrode, testing the impedance of the sulfide electrolyte at 25 ℃, and calculating the conductivity of the sulfide electrolyte by a formula of sigma l/(RS), wherein sigma is the conductivity, l is the thickness of the sheet material, R is the impedance value of the solid electrolyte, and S is the frontal area of the sheet material.
(2) Testing specific capacity of positive and negative electrode materials
Testing the specific capacity of the anode material: 7mg of the recovered positive electrode material was mixed with 3mg of sulfide electrolyte Li3PS4(non-recovery), pressing into layers after mixing uniformly to obtain the anode active material layer. 100mg of sulfide electrolyte Li3PS4(non-recycled) was pressed into a sheet having a diameter of 10mm at a pressure of 20MPa as an electrolyte layer. And a metal lithium sheet is adopted as the counter electrode. And sequentially superposing the positive active material layer, the solid electrolyte and the electrode lithium sheet, and then assembling the positive active material layer, the solid electrolyte and the electrode lithium sheet into the all-solid-state lithium secondary battery in a 20MPa pressure forming mode. Setting the working voltage range of the all-solid-state lithium secondary battery to be 2.8V-4.2V, and performing cycle test in a constant-current charging and discharging mode, wherein the test current is 0.1C (the current density is 0.13 mA/cm)2) The test temperature was 25 ℃. The first cycle discharge specific capacity of the all-solid-state lithium secondary battery was tested.
Testing the specific capacity of the negative electrode material: 7mg of the recovered anode material was mixed with 3mg of sulfide electrolyte Li3PS4(non-recycled) is uniformly mixed and then pressed into a layer to obtain a negative active material layer. 100mg of sulfide electrolyte Li3PS4(non-recycled) was pressed into a sheet having a diameter of 10mm at a pressure of 20MPa as an electrolyte layer. And a metal lithium sheet is adopted as the counter electrode. And sequentially superposing the negative electrode active material layer, the solid electrolyte and the counter electrode lithium sheet, and then assembling the positive electrode active material layer, the solid electrolyte and the counter electrode lithium sheet into the all-solid-state lithium secondary battery in a 20MPa pressure forming mode. Setting the working voltage range of the all-solid-state lithium secondary battery to be 2.8V-0.05V, and performing cycle test in a constant-current charging and discharging mode, wherein the test current is 0.1C (the current density is 0.31 mA/cm)2) The test temperature was 25 ℃. The first cycle discharge specific capacity of the all-solid-state lithium secondary battery was tested.
Example 2
Solid-state battery: the procedure was the same as described in example 1.
Material recovery: the same procedure as described in example 1, except that 20g of sulfur powder was added; after filtration, the solid component was washed with fresh pyridine 3 times and then with carbon disulfide three times. The test results are shown in Table 1.
And (3) material testing: the procedure was the same as that described in example 1, and the test results are shown in Table 2.
TABLE 1
| Positive electrode | Electrolyte | Negative electrode | |
| Example 1 | Lithium cobaltate | Li3PS4 | Graphite (II) |
| Example 2 | Lithium cobaltate | Li3PS4 | Graphite (II) |
TABLE 2
As can be seen from tables 1 and 2, the method provided by the present invention can efficiently separate the sulfide electrolyte and the electrode material, and not only has a high recovery rate, but also the separated sulfide material can be continuously used as an electrolyte material, and can also be used as a precursor material of the electrolyte material for preparing a regenerated sulfide electrolyte, and the recovered electrode material can still be continuously used as a battery electrode material without structural damage.
In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (20)
1. A process for solid state battery material recovery, the battery material comprising a sulfide electrolyte and an electrode material, the process comprising: contacting the battery material with elemental sulfur in the presence of an organic solvent, the resulting lithium polysulfide compound being at least partially dissolved in the organic solvent;
obtaining sulfur-containing compounds from the obtained liquid phase matter, and/or obtaining electrode materials from the obtained solid phase matter.
2. The process of claim 1, wherein the lithium polysulfide compound has a chemical formula of M-Sx-Li, wherein 1<x≤8。
3. The process of claim 2, wherein the lithium polysulfide compound has a chemical formula of M-Sx-Li, where 3. ltoreq. x.ltoreq.8.
4. The treatment method according to claim 1, wherein the molar ratio of the-S-Li structure in the sulfide electrolyte to the added elemental sulfur is 1: 0.1 to 7.
5. The treatment method according to claim 4, wherein the molar ratio of the-S-Li structure in the sulfide electrolyte to the added elemental sulfur is 1: 2 to 7.
6. The process according to claim 1, wherein the battery material is in the form of pieces and/or powder, and the particle size of the battery material is 10mm or less.
7. The process of claim 6, wherein the battery material is obtained by crushing a solid-state battery.
8. The processing method according to claim 1, wherein the processing method specifically comprises: the battery material is mixed with an organic solvent to form a first slurry, and elemental sulfur is introduced into the first slurry to form a second slurry.
9. The process of claim 8, wherein the viscosity of the second slurry is from 1000 to 500000 cP.
10. The process of claim 9, wherein the viscosity of the second slurry is from 5000 to 100000 cP.
11. The process according to claim 1, wherein the reaction product is subjected to solid-liquid separation to obtain a liquid phase and/or a solid phase.
12. The process according to claim 1, wherein the resulting liquid phase is freed from the solvent to obtain sulfide compounds.
13. The process according to claim 1, wherein the resulting solid phase is washed and dried to obtain a regenerated electrode material.
14. The process of claim 1, wherein the elemental sulfur is sulfur powder.
15. The process of claim 1 wherein the reaction is carried out under anhydrous conditions.
16. The process of claim 1, wherein the reaction is further carried out in a dry environment having a relative humidity of less than 1% and/or a dew point of less than-30 ℃.
17. The process of claim 1 wherein the reaction is carried out under a gas blanket.
18. The process of claim 17 wherein the gas is selected from inert gases having a moisture content of less than 1000ppm and an oxygen content of less than or equal to 500 ppm.
19. The method according to claim 1, wherein the organic solvent is selected from the group consisting of ether organic solvents, hydrocarbon organic solvents, ester organic solvents, nitrile organic solvents, amide organic solvents, alcohol organic solvents, halogenated organic solvents, and heterocyclic organic solvents.
20. The process of any one of claims 1 to 19, wherein the recovery of electrode material is 90% or more; and/or the recovery rate of the sulfide electrolyte is more than or equal to 90 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810687285.9A CN110661051B (en) | 2018-06-28 | 2018-06-28 | Solid-state battery material recovery processing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810687285.9A CN110661051B (en) | 2018-06-28 | 2018-06-28 | Solid-state battery material recovery processing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110661051A CN110661051A (en) | 2020-01-07 |
| CN110661051B true CN110661051B (en) | 2021-01-22 |
Family
ID=69026298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810687285.9A Active CN110661051B (en) | 2018-06-28 | 2018-06-28 | Solid-state battery material recovery processing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110661051B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620336B (en) * | 2021-07-27 | 2022-10-25 | 西安交通大学 | Method for recovering germanium, aluminum and lithium in LAGP solid electrolyte |
| CN117977044B (en) * | 2024-04-01 | 2024-07-16 | 四川新能源汽车创新中心有限公司 | Method for recycling sulfide-based all-solid-state battery material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101919107A (en) * | 2009-03-16 | 2010-12-15 | 丰田自动车株式会社 | Method for treating battery member |
| JP2011175914A (en) * | 2010-02-25 | 2011-09-08 | Mitsubishi Materials Corp | METHOD OF TREATING NaS BATTERY |
| JP2016058280A (en) * | 2014-09-10 | 2016-04-21 | トヨタ自動車株式会社 | Method for recovering positive electrode active material |
| CN107221724A (en) * | 2017-06-27 | 2017-09-29 | 湖南邦普循环科技有限公司 | A kind of method that lithium is reclaimed from waste lithium cell |
-
2018
- 2018-06-28 CN CN201810687285.9A patent/CN110661051B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101919107A (en) * | 2009-03-16 | 2010-12-15 | 丰田自动车株式会社 | Method for treating battery member |
| JP2011175914A (en) * | 2010-02-25 | 2011-09-08 | Mitsubishi Materials Corp | METHOD OF TREATING NaS BATTERY |
| JP2016058280A (en) * | 2014-09-10 | 2016-04-21 | トヨタ自動車株式会社 | Method for recovering positive electrode active material |
| CN107221724A (en) * | 2017-06-27 | 2017-09-29 | 湖南邦普循环科技有限公司 | A kind of method that lithium is reclaimed from waste lithium cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110661051A (en) | 2020-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111244458B (en) | Pre-lithiation electrode | |
| CN108155383B (en) | Binder for lithium-sulfur battery, preparation method of binder and lithium-sulfur battery anode | |
| CN103700820B (en) | A kind of lithium ion selenium battery with long service life | |
| CN111270072B (en) | Recycling method of waste lithium iron phosphate battery positive electrode material | |
| US11011321B2 (en) | Electrochemical energy storage device | |
| EP3675248B1 (en) | Sulfur-carbon composite and lithium-sulfur battery including same | |
| CN111304679B (en) | Device and method for preparing high-purity lithium hexafluorophosphate through electrolysis by electrochemical ion extraction method | |
| CN110838575A (en) | Cathode for improving rate capability of lithium ion energy storage device and application thereof | |
| CN110661051B (en) | Solid-state battery material recovery processing method | |
| KR20240089773A (en) | Method for manufacturing sodium or potassium ion battery cells | |
| CN111204822A (en) | Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure | |
| CN112542612B (en) | Solid electrolyte with self-bonding effect and preparation method thereof | |
| US20160126540A1 (en) | Lithium ionic energy storage element and method for making the same | |
| KR101959195B1 (en) | Lithium sulfur cell and preparation method | |
| US20240250262A1 (en) | Cobalt-free positive electrode material slurry, preparation method therefor and application technical field thereof | |
| CN110048060B (en) | Graphene oxide loaded column pentaarene lithium-sulfur battery diaphragm, preparation method and application thereof | |
| CN110416605B (en) | Unsaturated sulfur-containing composite electrolyte, and preparation method and application thereof | |
| CN103247776B (en) | The preparation method of electrode composite material | |
| JP2009043535A (en) | Manufacturing method of nonaqueous electrolyte battery | |
| KR20170006693A (en) | Negative electrode for secondary battery and secondary battery comprising the same | |
| JP2016012406A (en) | Method for manufacturing nonaqueous secondary battery electrode | |
| CN114613996B (en) | High-capacity molybdenum polysulfide composite positive electrode material for all-solid-state battery, and preparation method and application thereof | |
| CN111902975A (en) | Anode active material for lithium-sulfur secondary battery and method for preparing same | |
| JP6315267B2 (en) | Method for producing electrode for non-aqueous secondary battery | |
| CN115275525B (en) | Diaphragm for inhibiting polysulfide shuttle effect, preparation process thereof and lithium sulfur battery using diaphragm |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |