CN110718717A - 一种由溶剂和电解质组成的电解液 - Google Patents
一种由溶剂和电解质组成的电解液 Download PDFInfo
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- CN110718717A CN110718717A CN201910991522.5A CN201910991522A CN110718717A CN 110718717 A CN110718717 A CN 110718717A CN 201910991522 A CN201910991522 A CN 201910991522A CN 110718717 A CN110718717 A CN 110718717A
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- Prior art keywords
- electrolyte
- lithium
- methyl
- hexafluorophosphate
- tetrafluoroborate
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 73
- 239000002904 solvent Substances 0.000 title claims abstract description 30
- 150000002912 oxalic acid derivatives Chemical class 0.000 claims abstract description 18
- -1 cyclo-3-pentenyl Chemical group 0.000 claims description 62
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000003990 capacitor Substances 0.000 claims description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 125000006019 1-methyl-1-propenyl group Chemical group 0.000 claims description 2
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 claims description 2
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 claims description 2
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 claims description 2
- 125000006043 5-hexenyl group Chemical group 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims 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 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 150000003901 oxalic acid esters Chemical group 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
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- 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
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- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
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- 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
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Abstract
本发明涉及一种由溶剂和电解质组成的电解液,属于电解液领域。所述溶剂中含有草酸衍生物,所述草酸衍生物在所述溶剂中的质量百分含量范围为0.1%~95%。本申请所述电解液丰富了电解液溶剂种类,在调配电解液时,可选性更灵活,电化学性能优良,且能够在高温工作环境下使用的电解液中应用。
Description
技术领域:
本发明涉及一种由溶剂和电解质组成的电解液,属于电解液领域。
背景技术:
二次电池主要有锂电池和钠电池,两者的电解液溶剂都是以混合碳酸酯为主构成的体系。目前应用的碳酸酯溶剂主要有碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、碳酸丙烯酯五种。羧酸酯溶剂也偶尔用于二次电池电解液中的溶剂,但由于综合性能不如碳酸酯,所以用量不大,应用范围不广。
电容器、混合电容器等所用的非水电解液溶剂除了碳酸酯外,γ-丁内酯(属于羧酸酯类)、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺的用量也比较大。
由上述应用可以看出碳酸酯作为电解液溶剂成分的重要性及电解液溶剂的可选范围之窄。目前随着市场对二次电池及电容器的指标提出更高要求,例如寿命更长、能量密度更高、倍率性能更好等,对电解液的高低温性能、电化学窗口、特定离子电导率、安全性能等的要求也越来越高。但电解液溶剂的技术发展远落后于应用需求,主要应对策略是现有溶剂复配和添加剂的使用。所以电解液新溶剂的开发应用有着十分重要的意义,也是本领域的重要研究方向之一。
申请号为CN 109301327的中国发明专利公开了一种电解液与一种锂离子电池,其中电解液包含有含有草酸根基团的添加剂,并不涉及和本申请结构类似的化合物。
发明内容:
为了解决上述技术问题,本发明提供了一类包含有草酸衍生物溶剂的电解液,草酸衍生物在溶剂中的质量百分含量范围为0.1%~95%,与碳酸酯溶剂类似,合适的混合复配后能使电池得到更为优良的电化学性能;本专利所涉及到的电解液主要应用于二次电池和电容器(包括超级电容器、赝电容器和混合电容器)。
由溶剂和电解质组成的电解液,所述溶剂中含有草酸衍生物,所述草酸衍生物在所述溶剂中的质量百分含量范围为0.1%~95%。
从结构上看,草酸衍生物与碳酸酯类溶剂类似,而与羧酸酯类不同:草酸衍生物中的羰基和碳酸酯类中的羰基都不与烃基直接相连,羧酸中的羰基直接和烃基相连(甲酸酯类例外,羰基直接与氢原子相连,但甲酸酯类化学性质活泼,容易被氧化)。草酸酯类和碳酸酯类区别是草酸酯类比碳酸酯类多一个羰基,这导致草酸酯类的缺电子性更加突出,在本专利中,通过引入氮原子,以缓解草酸衍生物的缺电子性。作为上述技术方案的优选,所述草酸衍生物包含有分子结构为、或的物质中的至少一种。
作为上述技术方案的优选,所述R1、R2、R3、R4、R5、R6、R7、R8、R9为有机基团,这些有机基团结构可以相同,也可以不同。
作为上述技术方案的优选,所述R1、R2、R3、R4、R5、R6、R7、R8、R9为烃基或取代烃基,可以分别独立的选自戊基、异戊基、新戊基、环戊基、己基、环-3-戊烯基、环己基、环-3-己烯基、辛基、癸基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷基、甲基、乙基、丙基、异丙基、环丙基、丁基、异丁基、仲丁基、叔丁基、环丁基、乙烯基、丙烯基、烯丙基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-乙基乙烯基、1-甲基-2-丙烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、2-甲基-2-丙烯基、4-戊烯基、5-己烯基、2,2,2-三氟乙基、2,2,3,3,3-五氟丙基、1-三氟甲基-2,2,2-三氟乙基、2,2,3,3,4,4,4-七氟丁基。
作为上述技术方案的 一种特例,所述草酸衍生物中的任意两个有机基团可以成环。
作为上述技术方案的优选,所述溶剂中还含有下列溶剂中的至少一种: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,碳酸亚乙烯酯,乙酸乙酯、乙酸丙酯、乙酯丁酯、丙酸甲酯、丙酸乙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、γ-丁内酯、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮。
如上所述电解质中,至少含有下列化合物中的一种:六氟磷酸锂、双(三氟甲基磺酰)亚胺锂、双(氟磺酰)亚胺锂、三氟甲基磺酸锂、高氯酸锂、四氟硼酸锂、双草酸硼酸锂、二氟草酸硼酸锂、六氟磷酸钠、四氟硼酸钠、高氯酸钠、N,N,N,N-四甲基六氟磷酸铵、N,N,N,N-四乙基六氟磷酸铵、N,N,N,N-四丁基六氟磷酸铵、N,N,N -三甲基-N-乙基六氟磷酸铵、N-甲基-N,N,N -三乙基六氟磷酸铵、N,N,N,N-四甲基四氟硼酸铵、N,N,N,N-四乙基四氟硼酸铵、N,N,N,N-四丁基四氟硼酸铵、N,N,N -三甲基-N-乙基四氟硼酸铵、N-甲基-N,N,N -三乙基四氟硼酸铵。
作为上述技术方案的优选,所述电解质浓度范围在0.5mol/L~2mol/L之间。
作为上述技术方案的优选,所述电解液用于锂电池、钠电池、电容器、混合超级电容器、赝电容器中。
作为上述技术方案的优选,所述电解液的配方中,含有0%~5%的添加剂。
本申请实施例所述的电解液能够带来如下有益效果:
1.丰富了电解液溶剂种类,在调配电解液时,可选性更灵活;
2.电化学性能优良,特别在磷酸铁锂、钛酸锂材料制成的扣电中,一些电解液配方,如实施例3所示,能使材料的容量更易完全发挥且稳定性良好;
3.草酸衍生物类的沸点较碳酸酯类高,能够在高温工作环境下使用的电解液中应用。这里所说的高温工作环境,是指40-80℃的环境下。应用在乘用车、大巴车上的动力电池,储能上应用的蓄电池,在夏天高温天气时,都会有“过热”问题。
附图说明
图1为实施例1配制的电解液,用于镍钴锰三元富锂材料制成的扣电充放电曲线;
图2为实施例2配制的电解液,用于镍钴锰三元富锂材料制成的扣电充放电曲线;图3为实施例3配制的电解液,用于钛酸锂材料制成的扣电循环曲线;
图4为实施例4配制的电解液,用于钛酸锂材料制成的扣电充放电曲线;
图5为实施例5配制的电解液,用于钛酸锂材料制成的扣电充放电曲线;
图6为实施例6配制的电解液,用于磷酸铁锂材料制成的扣电充放电曲线;
图7为实施例7配制的电解液,用于磷酸铁锂材料制成的扣电充放电曲线;
图8为实施例8配制的电解液,用于磷酸铁锂材料制成的扣电充放电曲线。
具体实施方式:
以镍钴锰三元富锂材料为正极,金属锂片为负极,PP/PE复合膜为隔膜,配合上述电解液,做成纽扣电池(外形直径20mm,厚度3.2mm)。充放电曲线如图1所示。
以镍钴锰三元富锂材料为正极,金属锂片为负极,PP/PE复合膜为隔膜,配合上述电解液,做成纽扣电池(外形直径20mm,厚度3.2mm)。充放电曲线如图2所示。
以钛酸锂材料为正极,金属锂片为负极,PP/PE复合膜为隔膜, 配合上述电解液,做成纽扣电池(外形直径20mm,厚度3.2mm)。循环曲线如图3所示,钛酸锂材的理论克容量是175mAh,由图3可知,在实施例3中应用的电解液,使得钛酸锂的克容量基本完全发挥,接近175mAh;在20个循环过程中,无衰减迹象。
以钛酸锂材料为正极,金属锂片为负极,PP/PE复合膜为隔膜, 配合上述电解液,做成纽扣电池(外形直径20mm,厚度3.2mm)。充放电曲线如图4所示。
以钛酸锂材料为正极,金属锂片为负极,PP/PE复合膜为隔膜,配合上述电解液,做成纽扣电池(外形直径20mm,厚度3.2mm)。充放电曲线如图5所示。
以磷酸铁锂材料为正极,金属锂片为负极,PP/PE复合膜为隔膜, 配合上述电解液,做成纽扣电池(外形直径20mm,厚度3.2mm)。充放电曲线如图6所示。
以磷酸铁锂材料为正极,金属锂片为负极,PP/PE复合膜为隔膜, 配合上述电解液,做成纽扣电池(外形直径20mm,厚度3.2mm)。充放电曲线如图7所示。
实施例8:在无水惰性气氛下,将草酸二乙酯3g,碳酸二甲酯4g,碳酸丙烯酯3g混合,然后慢慢加入1.5g六氟磷酸锂。搅拌使六氟磷酸锂溶解,得到电解液。
以磷酸铁锂材料为正极,金属锂片为负极,PP/PE复合膜为隔膜, 配合上述电解液,做成纽扣电池(外形直径20mm,厚度3.2mm)。充放电曲线如图8所示。
表1实施例制得的电解液性能说明
Claims (10)
1.一种由溶剂和电解质组成的电解液,其特征在于:所述溶剂中含有草酸衍生物,所述草酸衍生物在所述溶剂中的质量百分含量范围为0.1%~95%。
3.如权利要求2所述的电解液,其特征在于:所述R1、R2、R3、R4、R5、R6、R7、R8、R9为有机基团。
4.如权利要求3所述的电解液,其特征在于:所述R1、R2、R3、R4、R5、R6、R7、R8、R9为烃基或取代烃基,可以分别独立的选自戊基、异戊基、新戊基、环戊基、己基、环-3-戊烯基、环己基、环-3-己烯基、辛基、癸基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷基、甲基、乙基、丙基、异丙基、环丙基、丁基、异丁基、仲丁基、叔丁基、环丁基、乙烯基、丙烯基、烯丙基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-乙基乙烯基、1-甲基-2-丙烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、2-甲基-2-丙烯基、4-戊烯基、5-己烯基、2,2,2-三氟乙基、2,2,3,3,3-五氟丙基、1-三氟甲基-2,2,2-三氟乙基、2,2,3,3,4,4,4-七氟丁基。
5.如权利要求3或权利要求4所述的电解液,其特征在于:所述草酸衍生物中的任意两个有机基团可以成环。
6.如权利要求1所述的电解液,其特征在于:所述溶剂中还含有下列溶剂中的至少一种: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,碳酸亚乙烯酯,乙酸乙酯、乙酸丙酯、乙酯丁酯、丙酸甲酯、丙酸乙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、γ-丁内酯、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮。
7.如权利要求1所述的电解液,其特征在于:所述电解质中,至少含有下列化合物中的一种:六氟磷酸锂、双(三氟甲基磺酰)亚胺锂、双(氟磺酰)亚胺锂、三氟甲基磺酸锂、高氯酸锂、四氟硼酸锂、双草酸硼酸锂、二氟草酸硼酸锂、六氟磷酸钠、四氟硼酸钠、高氯酸钠、N,N,N,N-四甲基六氟磷酸铵、N,N,N,N-四乙基六氟磷酸铵、N,N,N,N-四丁基六氟磷酸铵、N,N,N-三甲基-N-乙基六氟磷酸铵、N-甲基-N,N,N -三乙基六氟磷酸铵、N,N,N,N-四甲基四氟硼酸铵、N,N,N,N-四乙基四氟硼酸铵、N,N,N,N-四丁基四氟硼酸铵、N,N,N -三甲基-N-乙基四氟硼酸铵、N-甲基-N,N,N -三乙基四氟硼酸铵。
8.如权利要求1或权利要求7所述的电解液,其特征在于:所述电解质浓度范围在0.5mol/L~2mol/L之间。
9.如权利要求1所述的电解液,其特征在于:所述电解液用于锂电池、钠电池、电容器、混合超级电容器、赝电容器中。
10.如权利要求9所述的电解液,其特征在于:所述电解液的配方中,含有0%~5%的添加剂。
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