CN116895836A - 电解液及锂离子电池 - Google Patents
电解液及锂离子电池 Download PDFInfo
- Publication number
- CN116895836A CN116895836A CN202310856291.3A CN202310856291A CN116895836A CN 116895836 A CN116895836 A CN 116895836A CN 202310856291 A CN202310856291 A CN 202310856291A CN 116895836 A CN116895836 A CN 116895836A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- lithium
- dimercaptopyrimidine
- alkali metal
- additive
- 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
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- -1 2, 4-dimercaptopyrimidine alkali metal salt Chemical class 0.000 claims abstract description 60
- 239000000654 additive Substances 0.000 claims abstract description 36
- 230000000996 additive effect Effects 0.000 claims abstract description 36
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- ZEQIWKHCJWRNTH-UHFFFAOYSA-N 1h-pyrimidine-2,4-dithione Chemical compound S=C1C=CNC(=S)N1 ZEQIWKHCJWRNTH-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 15
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- 238000003860 storage Methods 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 125000004434 sulfur atom Chemical group 0.000 abstract description 5
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000012065 filter cake Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229910013870 LiPF 6 Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 229910001429 cobalt ion Inorganic materials 0.000 description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- ABSOMGPQFXJESQ-UHFFFAOYSA-M cesium;hydroxide;hydrate Chemical compound O.[OH-].[Cs+] ABSOMGPQFXJESQ-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003298 rubidium compounds Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种电解液及锂离子电池,其中电解液包括锂盐、非水有机溶剂,还包括2,4‑二巯基嘧啶碱金属盐添加剂,2,4‑二巯基嘧啶碱金属盐添加剂包括结构式I和结构式II中的至少一种:其中M⊕为碱金属阳离子。本发明的2,4‑二巯基嘧啶碱金属盐添加剂中含有结构稳定的2,4‑二巯基嘧啶阴离子,使得该添加剂在500℃以下具有优异的热稳定性;同时含有裸露的两个氮、硫原子,与金属离子有较强的键合能力,因此该添加剂还能够使正极材料的结构在高温高电压下不被破坏;另外,该添加剂在电池的化成阶段参与SEI膜的形成,使SEI膜更加稳固。因此本发明的电解液可提升锂离子电池的高温存储和高温快充循环性能。
Description
技术领域
本发明属于锂离子电池技术领域,尤其涉及一种电解液及锂离子电池。
背景技术
锂电池因为其能量密度高、使用寿命长和对环境友好等优点,目前已经被人们广泛应用到消费电子、航天航空、军事、电动工具及电动汽车等领域。但随着市场对更高能量密度的储能设备的需求的增长,人们对锂离子电池的能量密度要求越来越高。
钴酸锂电池最早是由1990年索尼公司进行开发的,钴酸锂作为锂离子电池的正极具有高的克容量、高的质量和体积能量密度等优点,特别是充电截止电压从4.2V提高到4.5V时,钴酸锂的克容量能提高25%以上,因此发展高电压钴酸锂成为提高能量密度的重要路径之一。然而,人们在研发高电压钴酸锂的过程中遇到了一系列问题,传统的电解液在高电压下极易在正极发生氧化分解反应,尤其是电池经过高温多次循环后,电解液中的碳酸酯溶剂会被氧化分解产生气体二氧化碳、一氧化碳等,造成电池体积膨胀和容量的衰减。
因此,亟需一种电解液及锂离子电池,以解决现有技术问题的不足。
发明内容
本发明的目的是提供一种电解液,该电解液能提高锂离子电池在高电压(4.53V)下的高温存储和高温快充循环性能。
本发明的另一目的是提供一种锂离子电池,该锂离子电池在高电压(4.53V)下具有较好的高温存储性能和高温快充循环性能。
为实现以上目的,本发明提供了一种电解液,包括锂盐、非水有机溶剂,还包括2,4-二巯基嘧啶碱金属盐添加剂,2,4-二巯基嘧啶碱金属盐添加剂包括结构式I和结构式II中的至少一种:
其中M⊕为碱金属阳离子。
与现有技术相比,本发明的电解液中含有2,4-二巯基嘧啶碱金属盐添加剂,该添加剂的结构中含有结构稳定的2,4-二巯基嘧啶阴离子,这使得该添加剂在500℃以下具有优异的热稳定性,故本发明的电解液能够提高锂离子电池在高电压(4.53V)下的高温存储和高温快充循环性能;同时该添加剂结构中含有裸露的两个氮、硫原子,与金属离子(如Li、Na、K、Cs、Co、Cu、Mn)有较强的键合能力,因此该添加剂还能够稳定正极材料,使正极材料的结构在高温、高电压下不被破坏,从而提高锂电池于高电压(4.53V)下的高温存储和高温快充循环性能;另外本发明的添加剂在电池的化成阶段参与SEI膜的形成,使SEI膜更加稳固,从而提升锂离子电池的高温存储和高温快充循环性能。
较佳地,本发明的结构式I选自化合物1~化合物5中的至少一种:
较佳地,本发明的结构式II选自化合物6~化合物10中的至少一种:
较佳地,本发明的2,4-二巯基嘧啶碱金属盐添加剂的质量占电解液总质量的0.01~2%;具体地可为但不限于0.01%、0.05%、0.08%、0.1%、0.14%、0.18%、1%、1.3%、1.5%、1.7%、1.8%、1.9%、2.0%。
较佳地,本发明的锂盐选自六氟磷酸锂(LiFP6)、四氟硼酸锂(LiBF4)、高氯酸锂(LiClO4)、双氟磺酰亚胺锂(LiFSI)、双三氟甲烷磺酰亚胺锂(LiTFSI)、二氟草酸硼酸锂(LiDFOB)、双草酸硼酸锂(LiBOB)、二氟磷酸锂(LiPO2F2)和二氟双草酸磷酸锂(LiDFOP)中的至少一种。具体地,锂盐的质量占电解液总质量的5~25%,具体的可为但不限于5%、6%、7%、8%、9%、10%、11%、12%、13%、14%、15%、16%、17%、18%、19%、20%、21%、22%、23%、24%、25%。
较佳地,本发明的非水有机溶剂选自碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、乙酸丁酯(EB)、γ-丁内酯(GBL)、丙酸丙酯(PP)、丙酸丁酯(EP)和丁酸乙酯(EB)中的至少一种。具体地,本发明的非水有机溶剂的质量占电解液总质量的70~90%,具体可为但不限于70%、72%、74%、75%、77%、78%、80%、82%、83%、84%、86%、88%、90%。
较佳地,本发明的2,4-二巯基嘧啶碱金属盐添加剂的制备方法包括:
(1)将2,4-二巯基嘧啶和溶剂混合,于一定温度下搅拌得到悬浊液;
(2)将碱金属化合物分批次加入到悬浊液中进行反应得到混合液;
(3)调节混合液的pH值,继续反应一定时间;
(4)将步骤(3)反应结束后的产物降温结晶、过滤、干燥得到2,4-二巯基嘧啶碱金属盐添加剂。
较佳地,本发明的溶剂为极性质子类、卤代烃类、脂肪烃类、醚类、酮类、酯类和腈类溶剂中的至少一种。具体地,极性质子类溶剂可为水、甲醇、乙醇、异丙醇、正丙醇或正丁醇,卤代烃类溶剂可为二氯甲烷、三氯甲烷、1,2-二氯乙烷或四氯乙烷,脂肪烃类溶剂可为正己烷或者环己烷,醚类溶剂可为乙醚、甲基叔丁基醚、乙二醇二甲醚、四氢呋喃或二氧六环,酮类溶剂可为丙酮、环己酮或4-甲基-2-戊酮,酯类溶剂为碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、乙酸甲酯、乙酸乙酯或乙酸丙酯,腈类溶剂可为乙腈。优选地,本发明的溶剂为甲醇或水。
较佳地,本发明的步骤(1)包括于0~90℃下搅拌得到悬浊液。优选地,本发明的步骤(1)包括于35~60℃下搅拌得到悬浊液。
较佳地,本发明的2,4-二巯基嘧啶和碱金属化合物的摩尔比为1:1~1.1。优选地,本发明的2,4-二巯基嘧啶和碱金属化合物的摩尔比为1:1~1.05。
较佳地,本发明的碱金属化合物为锂化合物、钠化合物、钾化合物、铷化合物或铯化合物。具体地,锂化合物为氢氧化锂、一水合氢氧化锂、碳酸锂、甲醇锂、乙醇锂或者叔丁醇锂,钠化合物为氢氧化钠、碳酸钠、碳酸氢钠、甲醇钠、乙醇钠或者叔丁醇钠,钾化合物为氢氧化钾、碳酸钾、碳酸氢钾、甲醇钾或者叔丁醇钾,铷化合物为氢氧化铷或碳酸铷,铯化合物为氢氧化铯、一水合氢氧化铯、碳酸铯或者碳酸氢铯。优选地,碱金属化合物为氢氧化锂、一水合氢氧化锂、氢氧化钠、氢氧化钾、氢氧化铷、氢氧化铯或一水合氢氧化铯。
较佳地,本发明的步骤(3)包括调节混合液的pH值为7~8。优选地,调节混合液的pH值为7~7.5。
较佳地,本发明的步骤(4)中降温结晶的温度为-20~25℃,时间为2~4h,干燥的温度为60~200℃。优选地,本发明的步骤(4)中降温结晶的温度为0~5℃,时间为2h,干燥的温度为120~150℃。
为实现以上目的,本发明还提供了一种锂离子电池,包括正极和负极,还包括上述的电解液,正极由钴酸锂材料制成。
与现有技术相比,本发明的锂离子电池的电解液中含有2,4-二巯基嘧啶碱金属盐添加剂,该添加剂的结构中含有2,4-二巯基嘧啶阴离子,这使得该添加剂在500℃以下具有优异的热稳定性,故本发明的电解液能够提高锂离子电池在高电压(4.53V)下的高温存储和高温快充循环性能;同时该添加剂结构中含有裸露的两个氮、硫原子,对钴离子有较好的络合作用,减缓了钴离子的溶出,稳定了钴酸锂正极材料的结构,从而保护了溶出的钴离子对电解液的催化分解,提高了锂电池于高电压体系下的高温快充循环和高温存储性能;另外本发明的添加剂在电池的化成阶段参与SEI膜的形成,使SEI膜更加稳固,从而提升锂离子电池的高温存储和高温快充循环性能。
较佳地,本发明的负极选自人造石墨、天然石墨、硅碳复合材料和钛酸锂中的任意一种。
附图说明
图1为本发明的实施例1中的2,4-二巯基嘧啶二锂盐的H1NMR谱图。
具体实施方式
为了进一步说明本发明的目的、技术方案及有益效果,下面将结合具体实施例对本发明作进一步说明。需要说明的是,实施例和对比例中未注明具体条件者,可按照常规条件或制造商建议的条件进行,所用试剂或仪器未注明生产厂商者,均为可通过市售而获得的常规产品。
下面将阐明本发明的2,4-二巯基嘧啶碱金属盐添加剂的制备方法的反应路线,具体如下所示:
其中M⊕表示碱金属阳离子,具体可为锂、钠、钾、铷、铯的一价阳离子;L-表示与碱金属离子相抗衡的阴离子,具体可为氢氧根离子、碳酸根离子、碳酸氢根离子、甲氧基、乙氧基和叔丁氧基。结构式Ⅰ和结构式Ⅱ表示同一种物质的互变异构体,即2,4-二巯基嘧啶二锂盐包括化合物1和化合物6两种互变异构体;2,4-二巯基嘧啶二钠盐包括化合物2和化合物7两种互变异构体;2,4-二巯基嘧啶二钾盐包括化合物3和化合物8两种互变异构体;2,4-二巯基嘧啶二铷盐包括化合物4和化合物9两种互变异构体;2,4-二巯基嘧啶二铯盐包括化合物5和化合物10两种互变异构体。更具体地,在弱极性或非极性溶液中,因为氮原子的电负性比硫原子的电负性更大,因此N-更容易与碱金属阳离子进行配位,故2,4-二巯基嘧啶碱金属盐添加剂在常规电解液中主要以结构式Ⅱ的形式存在,少部分以结构式I的形式存在;而在强极性质子溶剂中或有与氮离子结合能力更强的阳离子存在情况下,2,4-二巯基嘧啶碱金属盐添加剂中主要以结构式I的形式存在,少部分以结构式II的形式存在;更具体地可通过控制电解液极性强弱来调整2,4-二巯基嘧啶碱金属盐添加剂中结构式I和结构式II的比例。
实施例1
本发明提供了一种2,4-二巯基嘧啶二锂盐,其制备方法包括:
(1)将28g(0.194mol)2,4-二巯基嘧啶和120ml甲醇装入500ml三口烧瓶中,于50℃下搅拌10min得到微黄色的悬浊液;
(2)将8.23g(0.196mol)一水合氢氧化锂分批次加入到悬浊液中进行反应得到混合液;
(3)调节混合液的pH为7.0,继续反应3h;
(4)将步骤(3)反应结束后的产物自然冷却至室温后得到带沉淀悬浊液,将带沉淀悬浊液进行过滤得到滤饼,滤饼用新鲜的甲醇进行洗涤1~2次,滤饼在真空120℃下干燥12h,得到26g 2,4-二巯基嘧啶二锂盐,收率为85.8%,所得的2,4-二巯基嘧啶二锂盐的H1NMR谱图如图1所示。
实施例2
本发明提供了一种2,4-二巯基嘧啶二锂盐,其制备方法包括:
(1)将28g(0.194mol)2,4-二巯基嘧啶和120ml去离子水装入500ml三口烧瓶中,于60℃下搅拌10min得到微黄色的悬浊液;
(2)将8.23g(0.196mol)一水合氢氧化锂分批次加入到悬浊液中进行反应得到混合液;
(3)调节混合液的pH为7.0,继续反应2h;
(4)将步骤(3)反应结束后的产物自然冷却至室温后得到澄清透明的溶液,然后对溶液浓缩,降温至5℃进行结晶2h,然后过滤得到滤饼,滤饼用冷水进行洗涤1~2次,滤饼在真空150℃下干燥24h,得到27.1g 2,4-二巯基嘧啶二锂盐,收率为89.4%。
实施例3
本发明提供了一种2,4-二巯基嘧啶二钠盐,其制备方法包括:
(1)将28g(0.194mol)2,4-二巯基嘧啶和120ml甲醇装入500ml三口烧瓶中,于50℃下搅拌10min得到微黄色的悬浊液;
(2)将7.84g(0.196mol)氢氧化钠分批次加入到悬浊液中进行反应得到混合液;
(3)调节混合液的pH为7.3,继续反应3h;
(4)将步骤(3)反应结束后的产物自然冷却至室温后得到带沉淀悬浊液,将带沉淀悬浊液进行过滤得到滤饼,滤饼用新鲜的甲醇进行洗涤1~2次,滤饼在真空120℃下干燥12h,得到32.9g 2,4-二巯基嘧啶二钠盐,收率为90%。
实施例4
本发明提供了一种2,4-二巯基嘧啶二钾盐,其制备方法包括:
(1)将28g(0.194mol)2,4-二巯基嘧啶和120ml甲醇装入500ml三口烧瓶中,于50℃下搅拌10min得到微黄色的悬浊液;
(2)将10.89g(0.195mol)氢氧化钾分批次加入到悬浊液中进行反应得到混合液;
(3)调节混合液的pH为7.4,继续反应3h;
(4)将步骤(3)反应结束后的产物自然冷却至室温后得到带沉淀悬浊液,将带沉淀悬浊液进行过滤得到滤饼,滤饼用新鲜的甲醇进行洗涤1~2次,滤饼在真空120℃下干燥12h,得到39.3g 2,4-二巯基嘧啶二钾盐,收率为92%。
实施例5
本发明提供了一种2,4-二巯基嘧啶二铯盐,其制备方法包括:
(1)将28g(0.194mol)2,4-二巯基嘧啶和120ml甲醇装入500ml三口烧瓶中,于50℃下搅拌10min得到微黄色的悬浊液;
(2)将29.08g(0.194mol)氢氧化铯分批次加入到悬浊液中进行反应得到混合液;
(3)调节混合液的pH为7.5,继续反应3h;
(4)将步骤(3)反应结束后的产物自然冷却至室温后得到带沉淀悬浊液,将带沉淀悬浊液进行过滤得到滤饼,滤饼用新鲜的甲醇进行洗涤1~2次,滤饼在真空150℃下干燥24h,得到75.2g 2,4-二巯基嘧啶二铯盐,收率为95%。
进一步地,以下为采用2,4-二巯基嘧啶碱金属盐应用于锂离子电池的具体实施方式:
实施例6
电解液的制备:
在充满氮气的手套箱内(水含量≤1ppm,氧含量≤1ppm)将原料碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)进行脱水处理使溶液的水分≤1ppm(加入5%溶液质量活化后的4A分子筛),再按EC:EMC:DEC=1:1:1的质量比例配置87g混合溶液A,然后往溶液A中缓慢的加入六氟磷酸锂12.9g,搅拌均匀使其完全溶解,然后再加入0.1g实施例1制得的2,4-二巯基嘧啶二锂盐,搅拌均匀使其溶解完全,形成电解液。
正极材料的制备:
将钴酸锂材料、粘接剂PVDF和导电剂Super P按质量比95:1.5:3.5混合均匀,配制成浆料,然后把浆料涂布在铝箔的两面,然后进行烘干、辊压后得到正极片。
负极材料的制备:
将人造石墨、导电剂SuperP、增稠剂CMC、粘接剂SBR(丁苯橡胶乳液)按质量比95:2:1:2混合均匀,配制成浆料,然后把浆料涂布在铜箔的两面后,然后进行烘干、辊压后得到负极片。
锂离子电池的制备:
将正极、隔膜、负极叠片制成方形电芯,采用聚合物包装,然后在60℃下真空烘干12h,然后在手套箱内往电芯中注入电解液,后经化成、分容等工序制成容量为1000mAh的锂离子电池。
实施例6~12和对比例1的锂离子电池电解液的组成成分如表1所示,实施例7~12和对比例1的锂离子电池电解液、正极片、负极片、锂离子电池的制备工艺均与实施例6相同,其中2,4-二巯基嘧啶二锂盐通过实施例1制得,2,4-二巯基嘧啶二铯盐通过实施例5制得。
表1实施例和对比例的电解液的组成成分
组别 | 非水有机溶剂/g | 锂盐/g | 添加剂/g |
实施例6 | EC:EMC:DEC=1:1:1/87g | LiPF6/12.9g | 2,4-二巯基嘧啶二锂盐/0.1g |
实施例7 | EC:EMC:DEC=1:1:1/87g | LiPF6/12.7g | 2,4-二巯基嘧啶二锂盐/0.3g |
实施例8 | EC:EMC:DEC=1:1:1/87g | LiPF6/12.5g | 2,4-二巯基嘧啶二锂盐/0.5g |
实施例9 | EC:EMC:DEC=1:1:1/87g | LiPF6/11.2g | 2,4-二巯基嘧啶二锂盐/1.8g |
实施例10 | EC:EMC:DEC=1:1:1/87g | LiPF6/12.9g | 2,4-二巯基嘧啶二铯盐0.1g |
实施例11 | EC:EMC:DEC=1:1:1/87g | LiPF6/12.7g | 2,4-二巯基嘧啶二铯盐/0.3g |
实施例12 | PC:EMC:DEC=1:2:1/87g | LiPF6/12.5g | 2,4-二巯基嘧啶二铯盐/0.5g |
对比例1 | EC:EMC:DEC=1:1:1 87g | LiPF6 13.0g | / |
将实施例6~实施例12和对比例1的电解液配制成的锂离子电池进行高温存储性能测试和高温快充循环性能测试,其测试条件如下,测试结果如表2所示。高温存储性能测试:
在常温(25℃)且上限电压为4.53V下,对锂离子电池进行一次0.3C/0.3C充电和放电,放电容量记录为C0,然后再将电池放置于60℃的烘箱中静置7d,取出待电池温度降至25℃,再进行0.3C放电,放电容量记录为C1;然后对锂离子电池进行一次0.3C/0.3C充电和放电,放电容量记录为C2,容量保持率=C1/C0*100%,容量恢复率=C2/C0*100%。
高温快充循环性能测试:
将锂离子电池置于45℃恒温箱中,静置30分钟,使锂离子电池达到恒温。以2C恒流充电至电压为4.53V,然后以4.53V恒压充电至电流为0.05C,接着以1C恒流放电至电压为3.0V,记录电池的首圈放电容量为C0。此为一个充放电循环。然后在45℃条件下进行2C/1C充电和放电300周,放电容量记为C1。容量保持率=C1/C0*100%。
表2锂离子电池性能测试结果
由表2可知,相较于对比例1,实施例6~12的锂离子电池的高温存储和高温快充循环性能具有较大明显的提升,这是因为本发明的锂离子电池的电解液中含有2,4-二巯基嘧啶碱金属盐添加剂,该添加剂的结构中含有结构稳定的2,4-二巯基嘧啶阴离子,这使得该添加剂在500℃以下具有优异的热稳定性,故本发明的电解液能够提高锂离子电池在高电压(4.53V)下的高温存储和高温快充循环性能;同时该添加剂结构中含有裸露的两个氮、硫原子,对钴离子有较好的络合作用,减缓了钴离子的溶出,稳定了钴酸锂正极材料的结构,从而保护了溶出的钴离子对电解液的催化分解,提高了锂电池于高电压体系下的高温快充循环和高温存储性能;另外本发明的添加剂在电池的化成阶段参与SEI膜的形成,使SEI膜更加稳固,从而提升锂离子电池的高温存储和高温快充循环性能。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,但是也并不仅限于上文中所列的实施例,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种电解液,包括锂盐、非水有机溶剂,其特征在于,还包括2,4-二巯基嘧啶碱金属盐添加剂,所述2,4-二巯基嘧啶碱金属盐添加剂包括结构式I和结构式II中的至少一种:
其中M⊕为碱金属阳离子。
2.如权利要求1所述的电解液,其特征在于,所述结构式I选自化合物1~化合物5中的至少一种:
3.如权利要求1所述的电解液,其特征在于,所述结构式II选自化合物6~化合物10中的至少一种:
4.如权利要求1所述的电解液,其特征在于,所述2,4-二巯基嘧啶碱金属盐添加剂的质量占所述电解液总质量的0.01~2%。
5.如权利要求1所述的电解液,其特征在于,所述锂盐选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、双氟磺酰亚胺锂、双三氟甲烷磺酰亚胺锂、二氟草酸硼酸锂、双草酸硼酸锂、二氟磷酸锂和二氟双草酸磷酸锂中的至少一种。
6.如权利要求1所述的电解液,其特征在于,所述非水有机溶剂选自碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、碳酸丙烯酯、乙酸丁酯、γ-丁内酯、丙酸丙酯、丙酸丁酯和丁酸乙酯中的至少一种。
7.如权利要求1所述的电解液,其特征在于,所述2,4-二巯基嘧啶碱金属盐添加剂的制备方法包括:
(1)将2,4-二巯基嘧啶和溶剂混合,于一定温度下搅拌得到悬浊液;
(2)将碱金属化合物分批次加入到所述悬浊液中进行反应得到混合液;
(3)调节所述混合液的pH值,继续反应一定时间;
(4)将步骤(3)反应结束后的产物降温结晶、过滤、干燥得到2,4-二巯基嘧啶碱金属盐添加剂。
8.如权利要求7所述的电解液,其特征在于,所述2,4-二巯基嘧啶和所述碱金属化合物的摩尔比为1:1~1.1。
9.如权利要求7所述的电解液,其特征在于,步骤(1)包括于0~90℃下搅拌得到悬浊液。
10.一种锂离子电池,包括正极和负极,其特征在于,还包括如权利要求1~9任一项所述的电解液,所述正极由钴酸锂材料制成。
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