CN107681198A - A kind of lithium-ion battery electrolytes and its lithium ion battery - Google Patents
A kind of lithium-ion battery electrolytes and its lithium ion battery Download PDFInfo
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- CN107681198A CN107681198A CN201710670590.2A CN201710670590A CN107681198A CN 107681198 A CN107681198 A CN 107681198A CN 201710670590 A CN201710670590 A CN 201710670590A CN 107681198 A CN107681198 A CN 107681198A
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- Prior art keywords
- lithium
- ion battery
- sulfuric acid
- acid vinyl
- ester
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 62
- 239000003792 electrolyte Substances 0.000 title claims abstract description 49
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 16
- -1 propane sultones Chemical class 0.000 claims abstract description 16
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims abstract description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 12
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000008053 sultones Chemical class 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001294 propane Substances 0.000 claims abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- GANXFQTZEVGPPI-UHFFFAOYSA-N fluorosulfonyloxyethene Chemical class FS(=O)(=O)OC=C GANXFQTZEVGPPI-UHFFFAOYSA-N 0.000 claims description 5
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 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
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- PNGAWASQASFPNE-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-dioxonin-2-one Chemical compound C1(OCCCCC=CO1)=O PNGAWASQASFPNE-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 229960002645 boric acid Drugs 0.000 claims description 2
- 235000010338 boric acid Nutrition 0.000 claims description 2
- DXYFOLDJYJXKAJ-UHFFFAOYSA-N bromosulfonyloxyethene Chemical class BrS(=O)(=O)OC=C DXYFOLDJYJXKAJ-UHFFFAOYSA-N 0.000 claims description 2
- OEJCMKJSESKDAK-UHFFFAOYSA-N chlorosulfonyloxyethene Chemical class ClS(=O)(=O)OC=C OEJCMKJSESKDAK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 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
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- GGCCAAZVCUPTEE-UHFFFAOYSA-N S=[I] Chemical compound S=[I] GGCCAAZVCUPTEE-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims 1
- 150000003459 sulfonic acid esters Chemical class 0.000 claims 1
- LKSCJMIATJONBS-UHFFFAOYSA-K trilithium oxalic acid phosphate Chemical compound P(=O)([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.[Li+].[Li+] LKSCJMIATJONBS-UHFFFAOYSA-K 0.000 claims 1
- 230000000996 additive effect Effects 0.000 abstract description 14
- 239000000654 additive Substances 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000006259 organic additive Substances 0.000 abstract description 2
- CVTFUPGFEADXOW-UHFFFAOYSA-N C(C)(=O)OC=C.COS(O)(=O)=O Chemical class C(C)(=O)OC=C.COS(O)(=O)=O CVTFUPGFEADXOW-UHFFFAOYSA-N 0.000 abstract 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 239000007767 bonding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- ZYMJSAWYDBRZIC-UHFFFAOYSA-N oxalic acid phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O.OC(=O)C(O)=O.OC(=O)C(O)=O ZYMJSAWYDBRZIC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/0042—Four or more solvents
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of lithium-ion battery electrolytes and its lithium ion battery.Described electrolyte includes electrolyte lithium salt, organic solvent and additive, using ring-type or the carbonic ester of chain in the organic solvent, and, the carboxylate of straight-chain or branched, the additive uses vinylene carbonate, sultones, fluorinated ethylene carbonate and sulfuric acid vinyl ester and its derivative;The sultones uses at least one of 1,3 propane sultones and 1,3 propene sultones;The sulfuric acid vinyl ester is using at least one of sulfuric acid vinyl ester, 4 methylsulfuric acid vinyl acetates, 4 fluorosulfuric acid vinyl acetates, 4 sulfuric chlorohydrin vinyl acetates, 4 bromine sulfuric acid vinyl esters, 4 iodine sulfuric acid vinyl esters and 4 cyano group sulfuric acid vinyl esters.The present invention form by optimizing solvent and selected plus Low ESR and high temperature additive reduce SEI low-temperature resistances, is reduced the pyroreaction between positive pole and electrolyte, is improved high-temperature behavior while raising battery low temperature properties so as to reach.
Description
Technical field
The invention belongs to field of lithium ion battery, and more particularly, the present invention relates to the electricity that a kind of high temperature performance is taken into account
Solve liquid and the lithium ion battery containing the electrolyte.
Background technology
Although lithium ion battery is more and more extensive in the application of the consumer electronics industry, the lithium ion battery of current commercialization
It is often difficult to meet the needs of key areas such as electric car, space technology and military project.For example, Vehicular dynamic battery requires that internal resistance is use up
Measure it is low to reach the purpose of high-output power, meanwhile, electrokinetic cell to high temperature circulation and electric discharge require it is also higher, to meet difference
Normal use under environment.The applicable temperature range of conventional lithium ion battery is narrow, otherwise low temperature discharge multiplying power is relatively low, otherwise it is high
Gentle storage is bad, thus research can improve the low temperature of lithium ion battery simultaneously and high-temperature behavior has important practical significance.By
The high temperature performance of battery is largely affected in the self character of electrolyte and its interface that is formed with both positive and negative polarity, because
This is proved to be feasible technical measures by electrolyte to improve low temperature and high-temperature behavior.
In order that lithium ion battery can under low temperature and hot environment normal discharge and recharge, it is necessary to use low viscosity and high temperature
Stable electrolyte.At present by electrolyte come to improve battery cryogenic property be mainly the dimethyl carbonate by adding low viscosity
(DMC), methyl ethyl carbonate (EMC) and carboxylate etc., and improve high-temperature behavior mainly by adding film for additive such as carbonic acid
Vinylene (VC), PS (PS) and 1,3- propene sultone (PST) etc..Therefore, in the carbonic acid of low viscosity
The additive such as vinylene carbonate and sultones is added on the basis of the organic solvents such as dimethyl ester, methyl ethyl carbonate and carboxylate
The high-temperature behavior of low temperature battery can be improved to a certain extent, but dramatically reduce the low temperature discharge property of battery
Energy.
The content of the invention
Therefore, the invention reside in provide a kind of electrolyte and propose a kind of lithium ion battery containing the electrolyte.
A kind of lithium-ion battery electrolytes, described electrolyte include electrolyte lithium salt, organic solvent and additive, wherein
The mass fraction that electrolyte lithium salt accounts for electrolyte gross weight is 5%-20%, and the mass fraction of organic solvent is 40%-94.6%,
The mass fraction of additive is 0.4%-40%.Using ring-type or the carbonic ester of chain in the organic solvent, and, straight-chain
Or the carboxylate of branched, the additive use vinylene carbonate, sultones, fluorinated ethylene carbonate and sulfuric acid ethene
Ester and its derivative;The sultones uses at least one of 1,3- propane sultones and 1,3- propene sultones;Institute
State sulfuric acid vinyl ester using sulfuric acid vinyl ester, 4- methyl-sulfuric acid vinyl ester, the fluoro- sulfuric acid vinyl esters of 4-, the chloro- sulfuric acid vinyl esters of 4-,
At least one of the bromo- sulfuric acid vinyl esters of 4-, the iodo- sulfuric acid vinyl esters of 4- and 4- cyano group-sulfuric acid vinyl ester.
Preferably, the electrolyte lithium salt is using lithium hexafluoro phosphate, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid phosphoric acid
One kind in lithium, double trifluoromethanesulfonimide lithiums, double (fluorine sulphonyl) imine lithiums, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium
It is or several;Lithium salt is 0.8-1.6mol/L.
Preferably, the cyclic carbonate is using ethylene carbonate, propene carbonate, butylene, vinylene carbonate
At least one of ester, ethylene sulfite, propylene sulfite, gamma-butyrolacton and tetrahydrofuran;The linear carbonate is adopted
With at least one of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate;The carboxylate of the straight-chain
Using methyl formate, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, propyl propionate, ethyl butyrate, ethyl propionate,
At least one of propyl butyrate is several;The carboxylate of the branched uses the methyl formate with halogenic substituent, first
In acetoacetic ester, methyl acetate, ethyl acetate, propyl acetate, propyl propionate, ethyl butyrate, ethyl propionate, propyl butyrate at least
It is one or more of.
Preferably, the mass percent of described carbonic ester in the electrolytic solution is 10%-90%;Carboxylate is in the electrolytic solution
Mass percent be 10%-70%;The mass percent of vinylene carbonate in the electrolytic solution is 0.01%-10%;Sulfonic acid
The mass percent of lactone in the electrolytic solution is 0.01%-10%;The mass percent of fluorinated ethylene carbonate in the electrolytic solution
It is 0.01%-10%;The mass percent of sulfuric acid vinyl ester and its derivative in the electrolytic solution is 0.01%-10%.
The present invention uses above technical scheme, the advantage is that, in the lithium ion battery electrolysis containing low viscosity carboxylate
Add vinylene carbonate in liquid, sultones, during fluorinated ethylene carbonate, its on both positive and negative polarity surface equal decomposable asymmetric choice net and formed
Stable performance and abundant film, and extend the existence time of the film at high temperature, because the film can reduce both positive and negative polarity and electrolyte
Contact, so as to avoid under high temperature electrolyte that continued oxidation and reduction reaction occurs on both positive and negative polarity surface, and then reduce electrolysis
The decomposition of liquid and the rising of lithium ion battery internal resistance, improve the high-temperature behavior of lithium ion battery.Simultaneously sulfuric acid vinyl ester or its
The introducing of derivative, lithium ion battery can form the stable SEI films containing lithium sulfite and sulfuric ester lithium in discharge and recharge, suppression
Carboxylate processed negative pole reaction, and this SEI film have it is good lead ion energy, further improve lithium ion interface and transmit,
Interface internal resistance is reduced, so as to maintain good cryogenic property.
Accordingly, the present invention also provides a kind of lithium ion battery, the lithium ion battery include housing, positive pole, negative pole, every
Film and electrolyte;The positive pole, negative pole, barrier film and electrolyte are contained in the housing;The electrolyte uses right such as will
Seek the lithium-ion battery electrolytes described in 6.
Preferably, the housing uses square aluminum hull, square Soft Roll, and at least one in cylindrical steel and cylindrical Soft Roll
Kind.
Present invention also provides a kind of lithium ion battery, the lithium ion battery include housing, positive pole, negative pole, barrier film and
Electrolyte;The positive pole, negative pole, barrier film and electrolyte are contained in the housing;The housing is square aluminum hull, square soft
Bag, cylindrical steel, cylindrical Soft Roll;The positive pole includes plus plate current-collecting body and the positive active material being arranged on collector
Layer, positive electrode active material layer include positive active material, conductive agent and bonding agent;The negative pole includes negative current collector and setting
In the negative electrode active material layer on collector, negative electrode active material layer includes negative electrode active material, conductive agent and bonding agent;It is described
Barrier film is between positive pole and negative pole and by the separated barrier film of the positive pole and the negative pole.
Present invention offers following beneficial effect:
The present invention form by optimizing solvent and selected plus Low ESR and high temperature additive reduce SEI low-temperature resistances, reduction
Pyroreaction between positive pole and electrolyte, improve high-temperature behavior while improving battery low temperature properties so as to reach.
Embodiment
The preferably embodiment of the present invention is described in further detail below:
In the following embodiments, used reality, material and instrument be not as having specified otherwise, commercially available, institute
The reagent used also can voluntarily synthesize acquisition by the synthetic method of routine, and used material is as follows:
Lithium salts:LiPF6
Cyclic carbonate:Ethylene carbonate (EC) and propene carbonate (PC)
Linear carbonate:Methyl ethyl carbonate (EMC)
Carboxylate:Ethyl acetate (EA)
Additive:Vinylene carbonate (VC), PS (PS), fluorinated ethylene carbonate (FEC) and 4- are fluoro-
Sulfuric acid vinyl ester (the fluoro- sulfuric acid vinyl esters of 4-)
Lithium ion battery preparation process corresponding to embodiment includes following steps:
1. the preparation of electrolyte
In water content<It is organic molten after dehydration and purification process by rectifying in 10ppm argon gas atmosphere glove box
Agent EC, PC, EMC and EA are well mixed to be used as solvent;By fully dry LiPF6It is dissolved in above-mentioned mixed organic solvents, so
The fluoro- sulfuric acid vinyl ester of additive VC, PS, FEC and 4- is added afterwards, is well mixed, and electrolyte is made.Wherein lithium salt is
0.95mol/L。
2. the preparation of positive plate
By LiCoO in nmp solvent2With conductive agent (carbon black), bonding agent (PVDF) by weight 98:1:1 weight ratio
Well mixed, anode sizing agent is made in vacuum stirring;By slurry even application on 15 μm of aluminium foil, pole piece is prepared;Pole piece is existed
Dried under 120 DEG C of environment, and positive plate is made through roll-in slitting.
3. the preparation of negative plate
In H2By graphite and conductive agent (carbon black), thickener (CMC), bonding agent (SBR) by weight 96 in O solvents:1:
1:2 ratio is well mixed, and cathode size is made in vacuum stirring;By slurry even application on 8 μm of copper foil, pole piece is prepared;
Pole piece is dried under 80 DEG C of environment, and negative plate is made through roll-in slitting.
4. the preparation of battery
Positive plate, negative plate and the thickness that the above method is prepared are that 16 μm of polyethylene diagrams stack gradually winding
The core square into one, and the core is loaded into square soft-package battery housing (material is aluminum plastic film), then vacuum bakeout is noted
Enter the electrolyte of above-mentioned preparation, through chemical conversion after sealing, be evacuated, square soft bag lithium ionic cell is obtained after integer and partial volume.
It is above-mentioned prepare battery during, solvent and additive in the electrolyte of each used in battery, each electrolyte
Species and content, as shown in table 1 below, content is the percetage by weight that the gross weight based on electrolyte is calculated.
The species and content of the electrolyte solvent of table 1. and additive
Battery performance test
1) low temperature discharge is tested
By the lithium ion battery obtained by above-mentioned preparation at 25 DEG C, with 0.5C electric currents constant-current constant-voltage charging to 4.2V, cut-off
Electric current 0.05C, stand lithium ion battery after 5min with 0.5C constant-current discharges to 3.0V, record the discharge capacity of lithium ion battery
C1.Then by lithium ion battery with 0.5C electric currents constant-current constant-voltage charging to 4.2V, cut-off current 0.05C, respectively -20 after completely filling
DEG C, after standing 4h under -10 DEG C and 0 DEG C of environment, with 0.5C constant-current discharges to 3.0V, record the discharge capacity C2 of lithium ion battery.
Electric discharge at C2/25 DEG C of discharge capacity under low temperature discharge capacity ratio (%)=different temperatures of lithium ion battery is held
Measure C1.
2) high temperature storage test in 60 DEG C/7 days
By the lithium ion battery obtained by above-mentioned preparation at 25 DEG C, with 0.5C electric currents constant-current constant-voltage charging to 4.2V, cut-off
Electric current 0.05C, stand lithium ion battery after 5min with 0.5C constant-current discharges to 3.0V, record the discharge capacity of lithium ion battery
C1.Then lithium ion battery cut-off current 0.05C, is recorded into lithium ion battery with 0.5C electric currents constant-current constant-voltage charging to 4.2V
Thickness T1.Battery is put into after completely filling after standing 7 days in 60 DEG C of baking ovens, records lithium ion battery thickness T2, and with 0.5C constant currents
3.0V is discharged to, records the discharge capacity C2 of lithium ion battery.The equality of temperature of the high temperature discharge Capacity Ratio (%) of lithium ion battery=not
The discharge capacity C1 at C2/25 DEG C of discharge capacity under degree, high temperature thickness swelling ratio (%)=(T2-T1) of lithium ion battery/
T1。
The low temperature performance of 2. different lithium ion batteries of table
60 DEG C/7 days high-temperature storage performances of 3. different lithium ion batteries of table
Table 1 is the electrolyte solvent of each used in battery and the species and content of additive.
Table 2 is the low temperature performance of different lithium ion batteries, and table 3 is the 60 DEG C/7 days high gentle of different lithium ion batteries
Store up performance.
It can be seen that from the performance difference of battery 1 and 2:After the carboxylic acid ester content increase added in the electrolytic solution, lithium ion
The low temperature discharge high rate performance of battery is obviously improved, but 60 DEG C of lithium ion battery/7 days high temperature storages deteriorate.
It can be seen that from the performance of battery 1- batteries 8:In lithium-ion battery electrolytes containing low viscosity carboxylate simultaneously
Sulfuric acid vinyl ester or derivatives thereof, vinylene carbonate are added, sultones, fluorinated ethylene carbonate, lithium ion battery is simultaneously
With good low temperature performance and high-temperature storage performance.Because one side sulfuric acid vinyl ester or derivatives thereof is in lithium
The stable SEI films containing lithium sulfite and sulfuric ester lithium can be formed during ion battery discharge and recharge, suppress carboxylate in negative pole
Reaction, and this SEI film leads ion energy with good, further improves lithium ion interface and transmits, reduction interface internal resistance;It is another
Aspect, vinylene carbonate, sultones, fluorinated ethylene carbonate can form stable interfacial film in positive pole, suppress carboxylic acid
Ester positive pole oxidation reaction, so as to effectively improve lithium ion battery low temperature performance and high-temperature storage performance.
From battery 1, the performance comparison of battery 4 and battery 8 can be seen that:With the increase of ethylene sulfite addition,
The low temperature performance of lithium ion battery is first improved and reduced afterwards, because when the mass fraction of ethylene sulfite is too high,
The increase of lithium ion battery SEI film thicknesses, it is led ion energy and can be affected, so as to have impact on low temperature performance.
In summary, sulfuric acid vinyl ester or derivatives thereof, carbonic acid are added simultaneously in the electrolyte containing carboxylate solvent
Vinylene, sultones, fluorinated ethylene carbonate, lithium ion battery can be made while there is excellent low temperature performance and height
Warm storage performance.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to is assert
The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (6)
1. a kind of lithium-ion battery electrolytes, it is characterised in that described electrolyte includes electrolyte lithium salt, organic solvent and added
Add agent, the carbonic ester of ring-type or chain is used in the organic solvent, and, the carboxylate of straight-chain or branched is described to add
Agent is added to use vinylene carbonate, sultones, fluorinated ethylene carbonate and sulfuric acid vinyl ester and its derivative;In the sulfonic acid
Ester uses at least one of 1,3- propane sultones and 1,3- propene sultones;The sulfuric acid vinyl ester uses sulfuric acid ethene
Ester, 4- methyl-sulfuric acid vinyl ester, the fluoro- sulfuric acid vinyl esters of 4-, the chloro- sulfuric acid vinyl esters of 4-, the bromo- sulfuric acid vinyl esters of 4-, the iodo- sulphur of 4-
At least one of vinyl acetate and 4- cyano group-sulfuric acid vinyl ester.
2. lithium-ion battery electrolytes as claimed in claim 1, it is characterised in that the electrolyte lithium salt uses hexafluorophosphoric acid
It is lithium, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate, double trifluoromethanesulfonimide lithiums, double(Fluorine sulphonyl)Imine lithium,
One or more in di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium;Lithium salt is 0.8-1.6mol/L.
3. lithium-ion battery electrolytes as claimed in claim 1, it is characterised in that the cyclic carbonate uses ethylene carbonate
Ester, propene carbonate, butylene, vinylene carbonate, ethylene sulfite, propylene sulfite, gamma-butyrolacton and four
At least one of hydrogen furans;The linear carbonate uses dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and carbonic acid first
At least one of propyl ester;The carboxylate of the straight-chain is using methyl formate, Ethyl formate, methyl acetate, ethyl acetate, second
At least one of propyl propionate, propyl propionate, ethyl butyrate, ethyl propionate, propyl butyrate are several;The carboxylic acid of the branched
Ester use with the methyl formate of halogenic substituent, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, propyl propionate,
At least one of ethyl butyrate, ethyl propionate, propyl butyrate are several.
4. lithium-ion battery electrolytes as claimed in claim 1, it is characterised in that the matter of described carbonic ester in the electrolytic solution
It is 10%-90% to measure percentage;The mass percent of carboxylate in the electrolytic solution is 10%-70%;Vinylene carbonate is in electrolyte
In mass percent be 0.01%-10%;The mass percent of sultones in the electrolytic solution is 0.01%-10%;Fluoro carbonic acid
The mass percent of vinyl acetate in the electrolytic solution is 0.01%-10%;The quality of sulfuric acid vinyl ester and its derivative in the electrolytic solution
Percentage is 0.01%-10%.
5. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes housing, positive pole, negative pole, barrier film and electrolysis
Liquid;The positive pole, negative pole, barrier film and electrolyte are contained in the housing;The electrolyte is using as claimed in claim 4
Lithium-ion battery electrolytes.
6. lithium ion battery as claimed in claim 5, it is characterised in that the housing uses square aluminum hull, square Soft Roll, circle
At least one of cylindricality box hat and cylindrical Soft Roll.
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