CN108615942A - Application containing (fluoro) methylene-disulfonic acid lithium salts and preparation method thereof and in nonaqueous electrolytic solution - Google Patents
Application containing (fluoro) methylene-disulfonic acid lithium salts and preparation method thereof and in nonaqueous electrolytic solution Download PDFInfo
- Publication number
- CN108615942A CN108615942A CN201810274949.9A CN201810274949A CN108615942A CN 108615942 A CN108615942 A CN 108615942A CN 201810274949 A CN201810274949 A CN 201810274949A CN 108615942 A CN108615942 A CN 108615942A
- Authority
- CN
- China
- Prior art keywords
- methylene
- disulfonic acid
- lithium
- fluoro
- lithium salts
- 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.)
- Pending
Links
- OHNXZTONCLMQAU-UHFFFAOYSA-L [Li+].[Li+].[O-]S(=O)(=O)C(F)S([O-])(=O)=O Chemical class [Li+].[Li+].[O-]S(=O)(=O)C(F)S([O-])(=O)=O OHNXZTONCLMQAU-UHFFFAOYSA-L 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000008151 electrolyte solution Substances 0.000 title claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- FISIIUFDCAMIGR-UHFFFAOYSA-N difluoromethanedisulfonic acid Chemical compound OS(=O)(=O)C(F)(F)S(O)(=O)=O FISIIUFDCAMIGR-UHFFFAOYSA-N 0.000 claims abstract description 13
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 claims abstract description 12
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims abstract description 10
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- -1 difluoro methylene disulfonic acid lithium Chemical compound 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ROFWWMIHWWLGDR-UHFFFAOYSA-N [Li].C(S(=O)(=O)O)S(=O)(=O)O Chemical compound [Li].C(S(=O)(=O)O)S(=O)(=O)O ROFWWMIHWWLGDR-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 5
- 229940090181 propyl acetate Drugs 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- 229910013098 LiBF2 Inorganic materials 0.000 claims description 2
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006259 organic additive Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 4
- RVBMCUUUPHHHAP-UHFFFAOYSA-N fluoromethanedisulfonic acid Chemical compound OS(=O)(=O)C(F)S(O)(=O)=O RVBMCUUUPHHHAP-UHFFFAOYSA-N 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
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- 239000007774 positive electrode material Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical group O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
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- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- ZQCQTPBVJCWETB-UHFFFAOYSA-N 4-fluoro-1,3-dioxol-2-one Chemical compound FC1=COC(=O)O1 ZQCQTPBVJCWETB-UHFFFAOYSA-N 0.000 description 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 description 1
- 229910012743 LiNi0.5Co0.3Mn0.2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 150000005686 dimethyl carbonates Chemical class 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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
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- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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Abstract
The invention discloses one kind containing (fluoro) methylene-disulfonic acid lithium salts, specifically, containing (fluoro) methylene-disulfonic acid lithium salts, general structure is that formula (I) is described：Wherein：X=CH2, Y=BF2When, formula (I) is methylene-disulfonic acid difluoro lithium borate；X=CF2, Y=BF2When, formula (I) is difluoro methylene disulfonic acid difluoro lithium borate；X=CH2, Y=PF4When, formula (I) is four lithium fluophosphate of methylene-disulfonic acid；X=CF2, Y=PF4When, formula (I) is four lithium fluophosphate of difluoro methylene disulfonic acid.The invention also discloses the above-mentioned preparation methods containing (fluoro) methylene-disulfonic acid lithium salts；In the case that the cycle performance and storge quality of the lithium salts battery Han (fluoro) methylene-disulfonic acid of the present invention will be got well, and additive is less in electrolyte prescription, the chemistry of lithium salts and influence of the electrochemical stability to battery performance are more obvious.
Description
Technical field
The present invention relates to electrochemical energy storage fields, more particularly it relates to which a kind of containing (fluoro) methylene-disulfonic acid
The preparation of lithium salts and its application in electrochemical energy storing device.
Background technology
Nonaqueous electrolytic solution is one of the critical material of high specific energy lithium ion battery, and lithium-ion battery electrolytes are mainly by organic
Solvent, electric conducting lithium salt and functional additive composition, it affects the transmission speed and efficiency of charge in battery charge and discharge process,
Determine the comprehensive performance (cycle, multiplying power, high/low temperature and security performance etc.) of lithium ion battery, therefore to the preparation of electrolyte lithium salt
And its research of the application in lithium ion battery is extremely important, it has also become domestic and international academia and world-famous electrolyte manufacturer
Research hotspot.
The lithium-ion battery electrolytes of Commercialization application generally use carbonic ester as solvent, LiPF at present6As support
Electrolyte.At a higher temperature (>55 DEG C), LiPF6Thermal decomposition generates phosphorus pentafluoride, in the electrolytic solution H2O or small molecule alcohol
In the presence of impurity, phosphorus pentafluoride is further converted into trifluoro oxygen phosphorus and hydrogen fluoride etc., and phosphorus pentafluoride and trifluoro oxygen phosphorus are made
For strong lewis acid, cause carbonate solvent that Autocatalytic decomposition reaction occurs.Therefore, LiPF6As electrolyte electric conducting lithium salt
High-temperature lithium ion battery performance is poor.Further, since LiPF6There are HF in/carbonic ester electrolyte system so that oxo transition metal
Positive electrode (such as the cobalt acid lithium and ternary of the LiFePO 4 of spinel lithium manganate, olivine structural, layer structure of compound
Material etc.) due to the dissolution of metallic atom, the structure of material is distorted or caves in, and becomes so as to cause the cyclicity of battery
Difference.With the growth requirement of power battery and large-scale energy storage device, LiPF6Defect be increasingly becoming the bottleneck of lithium power technology and asked
Topic, therefore develop chemistry and the superior novel conductive lithium salts of electrochemical stability and become academia and industrial circle is endeavoured jointly
Target.
Invention content
In view of the problems of background technology, the purpose of the present invention is to provide one kind containing (fluoro) methylene-disulfonic acid
Lithium salts and preparation method thereof.
It is a further object to provide the applications containing (fluoro) methylene-disulfonic acid lithium salts in nonaqueous electrolytic solution.
In order to solve the above technical problems, the general structure of the present invention containing (fluoro) methylene-disulfonic acid lithium salts is formula
(I) shown in：
Wherein：
X=CH2, Y=BF2When, formula (I) is methylene-disulfonic acid difluoro lithium borate；
X=CF2, Y=BF2When, formula (I) is difluoro methylene disulfonic acid difluoro lithium borate；
X=CH2, Y=PF4When, formula (I) is four lithium fluophosphate of methylene-disulfonic acid；
X=CF2, Y=PF4When, formula (I) is four lithium fluophosphate of difluoro methylene disulfonic acid；
The present invention provides above-mentioned formula (I) (difluoro) methylene-disulfonic acid difluoro lithium borate or (difluoro) methylene-disulfonic acid
The preparation method of four lithium fluophosphates, includes the following steps：
(1) methylene-disulfonic acid (or difluoro methylene disulfonic acid) is added in reaction bulb, suitable water is added, adds in batches
Enter lithium source, it is neutrality to adjust reaction solution.
(2) it is filtered to remove insoluble matter, is dried under reduced pressure to obtain methylene-disulfonic acid lithium (or difluoro methylene disulfonic acid lithium).
(3) methylene-disulfonic acid lithium (or difluoro methylene disulfonic acid lithium) and appropriate organic solvent are added in reaction bulb,
Controlling reaction temperature in the case of stirring is passed through boron trifluoride or phosphorus pentafluoride.
(4) after completion of the reaction, it is filtered to remove insoluble matter, organic solvent is removed under reduced pressure, selects intensive polar solvent/low pole molten
Agent mixed solvent is recrystallized, and product is obtained after being dried under reduced pressure.
Preferably, the lithium source described in step (1) includes lithium carbonate and lithium hydroxide.
Preferably, the organic solvent described in step (3) includes acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, carbonic acid
Methyl ethyl ester, ethyl acetate, propyl acetate, butyl acetate, ether, methyl tertiary butyl ether(MTBE), glycol dimethyl ether, dioxane, four
Hydrogen furans, dioxolane.The reaction temperature is 20~120 DEG C, preferably 50~100 DEG C.
Preferably, the intensive polar solvent described in step (4) includes acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, carbon
Sour methyl ethyl ester, ethyl acetate, propyl acetate, butyl acetate, ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, glycol dimethyl ether,
Dioxane.Weak polar solvent includes dichloromethane, chloroform, n-hexane, hexamethylene, toluene, dimethylbenzene, chlorobenzene, fluorobenzene.
The application in nonaqueous electrolytic solution provided by the invention containing (fluoro) methylene-disulfonic acid lithium salts, i.e., in lithium battery and
As the application of electrolyte in lithium ion battery.
In order to realize that above-mentioned technical proposal, the present invention provide a kind of electrolyte containing (fluoro) methylene-disulfonic acid lithium salts,
Including electric conducting lithium salt, non-aqueous organic solvent and additive, electric conducting lithium salt includes containing (fluoro) methylene-disulfonic acid lithium salts.
Preferably, the electric conducting lithium salt further includes LiBF4、LiPF6、LiAsF6、LiClO4、LiSO3CF3、LiB
(C2O4)2、LiBF2C2O4、LiN(SO2CF3)2、LiN(SO2F)2In it is one or more.
Preferably, the non-aqueous organic solvent be ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate,
Methyl ethyl carbonate, gamma-butyrolacton, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, third
One or more of acid butyl ester.
Preferably, the additive is vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate, two fluoro
Ethylene carbonate, 1,3- propane sultones, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethylene sulfite,
One or more of propylene sulfite, succinonitrile, adiponitrile, 1,2- cyanoethoxyl ethane.
The present invention also provides a kind of lithium secondary batteries：Including positive plate, negative plate, diaphragm and of the present invention contain
There is the electrolyte of fluorine phosphorimide lithium to constitute；Positive plate and negative plate include active material, conductive agent, collector, by the work
The bonding agent that property material and conductive agent are combined with the collector.
Preferably, the positive plate includes that can reversibly be embedded in the/positive electrode active materials of deintercalate lithium ions, positive-active
Material is preferably the metal composite oxide of lithium, and metal oxide includes nickel, cobalt, manganese element and its oxidation of any ratio combination
Object；Positive electrode active materials still further comprise the one or several kinds in chemical element, the chemical element include Mg,
Al, Ti, Sn, V, Ge, Ga, B, Zr, Cr, Fe, Sr and rare earth element；Positive electrode active materials still further comprise polyanion lithiumation
Close object LiMx(PO4)y(M Ni, Co, Mn, Fe, Ti, V, 0≤x≤5,0≤y≤5).
Preferably, the negative plate includes the negative electrode active material that can receive or discharge lithium ion, the negative electrode active
Material includes lithium metal, lithium alloy, crystalline carbon, agraphitic carbon, carbon fiber, hard carbon, soft carbon；Wherein crystalline carbon includes natural stone
Ink, graphitized coke, graphitization MCMB, graphitized intermediate-phase asphalt-based carbon fiber；The lithium alloy include lithium and aluminium, zinc, silicon,
The alloy of tin, gallium, antimony metal.
Specific implementation mode
Below in conjunction with specific embodiment, technical scheme in the embodiment of the invention is clearly and completely described.
The present invention is illustrated below by exemplary embodiment.It should be appreciated that the scope of the present invention should not be limited to
The range of embodiment.Any variation or change without departing from present subject matter can be understood by the person skilled in the art.This
The protection domain of invention is determined by scope of the appended claims.
Embodiment 1
88g (0.5mol) methylene-disulfonic acid is added in 1000mL reaction bulbs, 200mL deionized waters are added, are added portionwise
37g (0.5mol) lithium carbonate, it is neutrality to be stirred to react to system.It is dried under reduced pressure to obtain 92.1g white solid products, yield
98%.
94g (0.5mol) methylene-disulfonic acid lithium is added in the reaction bulb of 1000mL, and 200mL is added and dries acetonitrile, temperature control 60
DEG C, it is passed through 34g (0.5mol) boron trifluoride, 8 hours of insulated and stirred, cooled and filtered removes insoluble matter.Acetonitrile is removed under reduced pressure,
Methylene-disulfonic acid difluoro lithium borate crude product is obtained, acetonitrile/dichloromethane mixed solvent recrystallization is dried to obtain after filtering
97.8g white solid products, yield 85%.
Embodiment 2
94g (0.5mol) methylene-disulfonic acid lithium is added in the reaction bulb of 1000mL, and 200mL dimethyl carbonates, temperature control is added
80 DEG C, it is passed through 63g (0.5mol) phosphorus pentafluoride, 10 hours of insulated and stirred, cooled and filtered removes insoluble matter.Carbon is removed under reduced pressure
Dimethyl phthalate obtains four lithium fluophosphate crude product of methylene-disulfonic acid, dimethyl carbonate/toluene Mixed Solvent recrystallization, filtering
After be dried to obtain 119.5g white solid products, yield 83%.
Embodiment 3
106g (0.5mol) difluoro methylene disulfonic acid is added in 1000mL reaction bulbs, 300mL deionized waters are added, in batches
37g (0.5mol) lithium carbonate is added, it is neutrality to be stirred to react to system.It is dried under reduced pressure to obtain 108.6g white solid products, produce
Rate 97%.
112g (0.5mol) difluoro methylene disulfonic acid lithium is added in the reaction bulb of 1000mL, and 300mL is added and dries acetonitrile,
60 DEG C of temperature control, is passed through 34g (0.5mol) boron trifluoride, 8 hours of insulated and stirred, and cooled and filtered removes insoluble matter.Decompression removes
Acetonitrile is removed, difluoro methylene disulfonic acid difluoro lithium borate crude product, acetonitrile/dichloromethane mixed solvent recrystallization, filtering are obtained
After be dried to obtain 114.4g white solid products, yield 86%.
Embodiment 4
112g (0.5mol) difluoro methylene disulfonic acid lithium is added in the reaction bulb of 1000mL, and 300mL glycol dinitrates are added
Ether, 80 DEG C of temperature control are passed through 63g (0.5mol) phosphorus pentafluoride, 8 hours of insulated and stirred, and cooled and filtered removes insoluble matter.Decompression
Glycol dimethyl ether is removed, four lithium fluophosphate crude product of difluoro methylene disulfonic acid, glycol dimethyl ether/n-hexane mixing are obtained
Solvent recrystallization is dried to obtain 142.6g white solid products, yield 88% after filtering.
Embodiment 5
(1) preparation of electrolyte
(the H in the glove box of argon atmosphere2O<1ppm), it is EC (ethylene carbonate): DMC in mass ratio by organic solvent
(dimethyl carbonate)：EMC (methyl ethyl carbonate)=40: 40: 20 is mixed with methylene-disulfonic acid difluoro lithium borate (1.0M), is added
The VC (vinylene carbonate) of total weight 1%, 2% PS (propane sultone), 3% FEC (fluorinated ethylene carbonate), 3%
SN (succinonitrile).Above-mentioned each raw material is sequentially added, is stirred to get electric to lithium secondary battery of the present invention
Solve liquid (free acid<15ppm, moisture<10ppm).
(2) preparation of anode pole piece
The Kynoar (PVDF) that mass percent is 3% is dissolved in 1-Methyl-2-Pyrrolidone solution, by matter
Measure the LiCoO of percentage 94%2Above-mentioned solution is added with 3% conductive agent carbon black and is uniformly mixed, the slurry being blended is coated with
Behind the two sides of aluminium foil, anode pole piece is obtained after drying, rolling.Other positive electrode LiMn2O4、LiFePO4、
LiNi0.5Co0.3Mn0.2、LiNi0.3Co0.3Mn0.3It prepares in the same way.
(3) preparation of cathode pole piece
The SBR binders for being 4% by mass percent, the CMC thickeners that mass percent is 1% are dissolved in aqueous solution,
Above-mentioned solution is added in the graphite that mass percent is 95%, is uniformly mixed, after the slurry being blended is coated on the two sides of copper foil,
Cathode pole piece is obtained after drying, rolling.Other negative material Li4Ti5O12It prepares in a similar manner.
(4) making of lithium ion battery
Square electric cell is made with winding method in the anode pole piece, cathode pole piece and isolation film of above-mentioned preparation, using polymerization
Object is packed, and the electrolyte of above-mentioned preparation is perfused, and the lithium ion battery that capacity is 1600mAh is made after the techniques such as chemical conversion.
(5) battery performance test
Loop test condition：Charge and discharge cycles test is carried out to battery with the multiplying power of 1/1C charge and discharge；High-temperature storage is tested
Condition：It is first that the battery that finishes of chemical conversion is primary with 1C charge and discharge under normal temperature state, then with 1C by battery it is fully charged after carry out
The battery of taking-up is carried out discharge test by High temperature storage after battery is completely cooling with 1C.
Embodiment 6~16 is in addition to following table parameter, and other parameters and preparation method are the same as embodiment 5.
1 embodiment 5~16 of table and comparative example 1~9
It can be seen that the situation identical with additive component in solvent from the result of embodiment 6~17 and comparative example 1~9
Under, use LiPF using the battery ratio containing (fluoro) methylene-disulfonic acid lithium salts6Cycle performance of battery and storge quality to get well.
It can be seen that from the result of embodiment 13~16 and comparative example 1~5 and contain (fluoro) methylene-disulfonic acid lithium salts and LiPF6It is compound
It is used as electric conducting lithium salt, the cycle performance and storge quality of respective battery are also than being used alone LiPF6Battery it is more superior.
It can be seen that in the case that additive is less in electrolyte prescription from the result of comparative example 8,9 and comparative example 6,7, the change of lithium salts
It learns and influence of the electrochemical stability to battery performance is more obvious.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (10)
1. one kind containing (fluoro) methylene-disulfonic acid lithium salts, general structure is that formula (I) is described：
Wherein：
X=CH2, Y=BF2When, formula (I) is methylene-disulfonic acid difluoro lithium borate；
X=CF2, Y=BF2When, formula (I) is difluoro methylene disulfonic acid difluoro lithium borate；
X=CH2, Y=PF4When, formula (I) is four lithium fluophosphate of methylene-disulfonic acid；
X=CF2, Y=PF4When, formula (I) is four lithium fluophosphate of difluoro methylene disulfonic acid.
2. a kind of preparing the method as described in claim 1 for containing (fluoro) methylene-disulfonic acid lithium salts, which is characterized in that including
Following steps：
(1) methylene-disulfonic acid or difluoro methylene disulfonic acid are added in reaction bulb, suitable water is added, lithium is added portionwise
Source, it is neutrality to adjust reaction solution；
(2) it is filtered to remove insoluble matter, is dried under reduced pressure to obtain methylene-disulfonic acid lithium or difluoro methylene disulfonic acid lithium；
(3) methylene-disulfonic acid lithium or difluoro methylene disulfonic acid lithium and appropriate organic solvent are added in reaction bulb, stirring
In the case of controlling reaction temperature, be passed through boron trifluoride or phosphorus pentafluoride；
(4) after completion of the reaction, it is filtered to remove insoluble matter, organic solvent is removed under reduced pressure, selects intensive polar solvent/weak polar solvent mixed
Bonding solvent is recrystallized, and product is obtained after being dried under reduced pressure.
3. a kind of preparation method containing (fluoro) methylene-disulfonic acid lithium salts according to claim 2, it is characterised in that：Step
Suddenly the lithium source described in (1) includes lithium carbonate and lithium hydroxide.
4. a kind of preparation method containing (fluoro) methylene-disulfonic acid lithium salts according to claim 2, it is characterised in that：Step
Suddenly the organic solvent described in (3) includes acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, second
Propyl propionate, butyl acetate, ether, methyl tertiary butyl ether(MTBE), glycol dimethyl ether, dioxane, tetrahydrofuran, dioxolane；Institute
The reaction temperature stated is 20~120 DEG C.
5. a kind of preparation method containing (fluoro) methylene-disulfonic acid lithium salts according to claim 2, it is characterised in that：Step
Suddenly the intensive polar solvent described in (4) include acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate,
Propyl acetate, butyl acetate, ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, glycol dimethyl ether, dioxane.Weak polar solvent
Including dichloromethane, chloroform, n-hexane, hexamethylene, toluene, dimethylbenzene, chlorobenzene, fluorobenzene.
6. one kind containing the electrolyte of (fluoro) methylene-disulfonic acid lithium salts, including electric conducting lithium salt, non-aqueous organic solvent and additive,
It is characterized in that：The electric conducting lithium salt includes containing (fluoro) methylene-disulfonic acid lithium salts.
7. a kind of electrolyte containing (fluoro) methylene-disulfonic acid lithium salts according to claim 6, it is characterised in that：It is described
Electric conducting lithium salt further include LiBF4、LiPF6、LiAsF6、LiClO4、LiSO3CF3、LiB(C2O4)2、LiBF2C2O4、LiN
(SO2CF3)2、LiN(SO2F)2In it is one or more.
8. a kind of electrolyte containing (fluoro) methylene-disulfonic acid lithium salts according to claim 6, it is characterised in that：It is described
Non-aqueous organic solvent is ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-Ding Nei
One kind or several in ester, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate
Kind.
9. a kind of lithium secondary battery, including positive plate, negative plate, diaphragm, it is characterised in that：Further include that claim 6-8 such as appoints
The electrolyte containing (fluoro) methylene-disulfonic acid lithium salts described in one.
10. containing (fluoro) methylene-disulfonic acid lithium salts as electrolyte in the application in nonaqueous electrolytic solution.
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| US12100808B2 (en) | 2019-03-28 | 2024-09-24 | Dongwoo Fine-Chem Co., Ltd. | Compound, and lithium secondary battery electrolyte and lithium secondary battery which comprise same |
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| CN113135947B (en) * | 2021-03-11 | 2022-08-16 | 常德市大度新材料有限公司 | Lithium acetylsulfanilate complex, preparation method thereof and application thereof in non-aqueous electrolyte |
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