CN117410558A - Electrolyte and battery - Google Patents
Electrolyte and battery Download PDFInfo
- Publication number
- CN117410558A CN117410558A CN202311312697.1A CN202311312697A CN117410558A CN 117410558 A CN117410558 A CN 117410558A CN 202311312697 A CN202311312697 A CN 202311312697A CN 117410558 A CN117410558 A CN 117410558A
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- Prior art keywords
- electrolyte
- lithium
- battery
- additive
- organic solvent
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 109
- 239000000654 additive Substances 0.000 claims abstract description 43
- 230000000996 additive effect Effects 0.000 claims abstract description 42
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 21
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 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 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229940093499 ethyl acetate Drugs 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-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
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-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
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 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
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims 1
- 238000002347 injection Methods 0.000 abstract description 24
- 239000007924 injection Substances 0.000 abstract description 24
- 239000007788 liquid Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008595 infiltration Effects 0.000 abstract description 6
- 238000001764 infiltration Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 3
- 101150065749 Churc1 gene Proteins 0.000 description 3
- 102100038239 Protein Churchill Human genes 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 description 1
- UCCWJJZPOSPPIC-UHFFFAOYSA-N COOCF Chemical compound COOCF UCCWJJZPOSPPIC-UHFFFAOYSA-N 0.000 description 1
- RFGOKUXULFJHDS-UHFFFAOYSA-N FN=S(F)F.FN=S(F)F.[Li] Chemical compound FN=S(F)F.FN=S(F)F.[Li] RFGOKUXULFJHDS-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
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011570 LiFe 1-x Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- IYDWBHJEYMDOBU-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].OC(=O)C(O)=O.OC(=O)C(O)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].OC(=O)C(O)=O.OC(=O)C(O)=O IYDWBHJEYMDOBU-UHFFFAOYSA-N 0.000 description 1
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
-
- 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
- H01M10/0567—Liquid materials characterised by the additives
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 invention provides an electrolyte and a battery, wherein the electrolyte comprises lithium salt, an organic solvent and an additive; the additive comprises a compound having a structure represented by formula 1, wherein R 1 、R 2 、R 3 At least one of which is selected from the group consisting of C1-C10 fluorocarbon radicals. The electrolyte provided by the invention can improve the infiltration effect of the battery cell, shorten the liquid injection time of the battery, and simultaneously maintain the cycle performance of the battery.
Description
Technical Field
The invention relates to an electrolyte, in particular to an electrolyte and a battery, and belongs to the technical field of lithium ion batteries.
Background
In recent years, various portable electronic devices, new energy electric vehicles and energy storage systems have been rapidly developed and widely applied, and the demand for lithium ion batteries with high energy density, long cycle life and safe use has been increasing.
At present, a high-energy density battery generally uses positive and negative electrode plates with high compaction density, but the high compaction density electrode plates can cause slow absorption of electrolyte by a battery core during liquid injection, particularly the electrolyte in the battery core is easy to cause uneven distribution, so that a series of problems of low capacity, large resistance, short service life and the like occur after the preparation of the battery core is completed, the wettability of an electrode is poor, the liquid injection time of the battery is long, and the production efficiency is low.
So far, there have been researches on improving wettability of battery cells, however, degradation of electrochemical performance of a battery is serious while improving wettability of an electrode.
Based on the above-mentioned shortcomings, there is an unprecedented need to develop an electrolyte solution that can achieve both wettability of an electrode and cycle performance of a battery.
Disclosure of Invention
The invention provides an electrolyte which can improve the infiltration effect of a battery cell, shorten the liquid injection time of the battery and simultaneously maintain the cycle performance of the battery.
The invention provides a battery which has the advantages of short liquid injection time, low production cost, good cycle performance and the like.
The invention provides an electrolyte, which comprises lithium salt, an organic solvent and an additive; the additive includes a compound having a structure represented by formula 1:
wherein R is 1 、R 2 、R 3 At least one of which is selected from the group consisting of C1-C10 fluorocarbon radicals.
The electrolyte as described above, wherein the additive includes a compound having one of structures represented by formulas 2 to 20:
the electrolyte comprises the additive, wherein the mass percentage of the additive in the electrolyte is 0.2-8%.
The electrolyte comprises the additive, wherein the mass percentage of the additive in the electrolyte is 1-8%.
The electrolyte as described above, wherein the lithium salt comprises at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonimide, lithium bistrifluorosulfimide, and lithium bisoxalato borate.
The electrolyte as described above, wherein the molar concentration of the lithium salt is 0.8mol/L to 1.2mol/L.
The electrolyte as described above, wherein the organic solvent comprises at least one of a carbonate-based organic solvent and a carboxylate-based organic solvent.
The electrolyte as described above, wherein the organic solvent comprises at least one of ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate.
The electrolyte comprises the organic solvent, wherein the mass percentage of the organic solvent in the electrolyte is 75-90%.
The invention also provides a battery comprising an electrolyte as described above.
The electrolyte provided by the invention comprises the additive with the special structure shown in the formula 1, the contact angle between the electrolyte and the battery pole piece can be reduced by the additive, the wetting effect of the battery cell is improved, the liquid injection time of the battery is shortened, and meanwhile, the additive has good compatibility effect with the negative electrode in the electrolyte, so that the cycle performance of the battery is maintained.
The battery is prepared based on the electrolyte, and has the advantages of short liquid injection time, good cycle performance and the like.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an electrolyte, which comprises lithium salt, an organic solvent and an additive; the additive includes a compound having a structure represented by formula 1:
wherein R is 1 、R 2 、R 3 At least one of which is selected from the group consisting of C1-C10 fluorocarbon radicals.
The electrolyte comprises lithium salt and an organic solvent, wherein the lithium salt can be common lithium salt in the field, such as lithium hexafluorophosphate, lithium difluorosulfimide, lithium tetrafluoroborate, lithium difluorooxalato borate and the like, and the invention does not make excessive selection; the organic solvent used for dissolving the lithium salt to prepare the electrolyte with good lithium conducting performance can be common organic solvents in the field, such as carbonic ester, carboxylic ester, ether and the like, and the invention does not make excessive selection.
The electrolyte also comprises an additive which is an organic fluoro phosphate compound, wherein R in the structural formula 1 of the additive 1 、R 2 、R 3 At least one of which is selected from the group consisting of C1-C10 fluorocarbon radicals. The C1-C10 fluorocarbon group of the present invention means a fluorocarbon group having 1 to up to carbon atoms10, a saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 6 to 10 carbon atoms. When specified as an alkyl or aromatic hydrocarbon group having a specific carbon number, all geometric isomers having that carbon number are included. Meanwhile, any hydrogen atom in the hydrocarbon group may be substituted with a fluorine atom, and the number of substitution with fluorine atoms is not limited, for example, difluoromethyl, trifluoromethyl, 1-difluoroethyl, 1, 2-difluoroethyl 2, 2-difluoroethyl, 2-trifluoroethyl, pentafluoroethyl, 2, 3-tetrafluoropropyl 2, 2-difluoroethyl group, 2-trifluoroethyl group pentafluoroethyl, 2, 3-tetrafluoropropyl.
The present invention is not limited to the presence or absence of a non-fluorine substituent in the fluorinated hydrocarbon group, and the type of the non-fluorine substituent is not limited, and may be selected according to actual needs, and for example, the non-fluorine substituent may be one selected from a halogen atom other than fluorine, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, and a phosphate group. The present invention is also not limited to the substitution position of the substituent in the fluorohydrocarbon group, for example, the fluorohydrocarbon group may be selected from-CF 2 OH、-CF 2 CF 2 COOH、-CF 2 CH 2 COOH、-CF 2 CF 2 COOCH 3 、-CF 2 CCl 3 、-CF 2 CN、-CH(CF 3 )CH 2 OH、-CH(CF 3 )CH 2 COOH、-CH(CF 3 )CH(COOH)CH 3 、-CH(CF 3 )COOCH 3 、-CH 3 COOCF 3 、-CH(CF 3 )COOCH 2 CH 3 、-CH(NO 2 )CH 2 COOCH(CH 3 ) 2 、-NHCH 2 COOCH(CF 3 )、-C 6 F 4 OH (p-hydroxytetrafluorophenyl), -Ch=c (CF) 3 )CH 2 OH、-C≡CCH(CF 3 )COOCH 3 Etc.
In addition, R 1 、R 2 、R 3 At least one of the fluorinated hydrocarbon groups selected from C1-C10, is R 1 、R 2 、R 3 Wherein there is one fluoroalkyl group, or two fluoroalkyl groups, or three fluoroalkyl groups, if there is only one fluoroalkyl group or two fluoroalkyl groups in the formulaIn the case of the substituted hydrocarbon group, the other substituent is not limited to a specific substituent type and may be selected according to practical needs, and for example, a hydrocarbon group having a non-fluorine substituent or unsubstituted, a halogen atom other than fluorine, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group or a phosphate group, etc., may be selected specifically from-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 2 CH 3 、-CH＝CHCH 3 、-CH＝CHCH 2 CH 3 、-CH＝CHCH(CH 3 ) 2 、-C≡CCH 2 CH 3 、-C 6 H 5 、-CCl 3 、-CH 2 OH、-CH 2 COOH、-CH 2 COOCH 3 、-CH 2 COOCH 2 CH 3 、-CH 2 COOCH(CH 3 ) 2 、-NHCH 3 、-NHCH 2 COOCH(CH 3 ) 2 、-NHCH(CH 3 )COOCH(CH 3 ) 2 、-CH 2 C 6 H 5 . The invention is not limited to R 1 、R 2 、R 3 Whether the functional groups are the same or not can be selected according to actual requirements.
According to the scheme provided by the invention, after the electrolyte is applied to the lithium ion battery, the lithium ion battery has short liquid injection time and excellent cycle performance. The inventor analyzes the principle, and considers that the reason may be that on one hand, an organic fluorinated phosphate compound with the structural formula is added into electrolyte, the structural formula comprises a phosphate bond, meanwhile, a fluorine atom group containing an electron withdrawing group is introduced, the compound has lower surface energy, the contact angle between the electrolyte and a pole piece can be reduced, the electrolyte spreads on the surface of the pole piece material rapidly, the wettability of the pole piece is obviously improved, the wettability and the permeability of the electrolyte to the pole piece are improved, the infiltration effect of a battery cell is improved, the liquid injection time is shortened, and the production cost is saved; on the other hand, the organic fluoro phosphate compound with the structural formula can exert good compatible effect with the negative electrode of the battery, and can not influence the formation of the SEI film on the surface of the negative electrode and the performance of the SEI film, thereby maintaining the cycle performance of the battery.
In one embodiment, the additive comprises a compound having one of the structures shown in formulas 2-20:
the additive of the formulas 2-20 can enable the contact angle between the electrolyte and the pole piece to be smaller, the infiltration degree of the battery core to be better, the liquid injection time of the battery to be further shortened, and therefore production cost is saved more, meanwhile, the additive has excellent compatibility with the negative electrode in the electrolyte, so that the circulating operation of the battery is more stable, and the circulating performance of the battery is not affected. And the additives having the structures of formulas 2 to 20 are more easily obtained, enabling further reduction in the production cost of the battery.
In a specific embodiment, the mass percentage of the additive in the electrolyte is 0.2% -8%, that is, each hundred grams of electrolyte comprises 0.2-8 g of the additive, and specifically, the additive can be selected from any value between 0.2%, 1%, 4%, 8% or 0.2% -8%. In the above range, the addition of the additive enables the contact angle between the electrolyte and the pole piece to be smaller, the infiltration effect of the battery core to be better, the liquid injection time of the battery to be shortened greatly, the preparation cost of the battery to be saved, and meanwhile, the compatibility of the additive in the electrolyte and the negative pole to be better, and the cycle performance of the battery to be maintained to a greater extent.
In a specific embodiment, the mass percentage of the additive in the electrolyte is 1% -8%, that is, each hundred grams of electrolyte comprises 1-8 g of the additive, and the additive can be specifically selected from 1%, 5%, 8% or any value between 1% -8%. In the above range, the contact angle between the electrolyte and the pole piece can be further reduced, so that the infiltration effect of the battery core is better, the liquid injection time of the battery can be shortened to a greater extent, the preparation cost of the battery is further saved, the compatibility of the additive and the negative electrode is better, and the cycle performance of the battery is further maintained. If the additive amount exceeds 8%, the additive can still continuously reduce the contact angle between the electrolyte and the pole piece, and shorten the liquid injection time of the battery, but the electrolyte can have problems of reduced conductivity, increased impedance and the like, and the cycle performance of the battery is deteriorated.
The lithium salt in the electrolyte comprises at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethane sulfonate, lithium bis (trifluoromethane sulfonyl imide), lithium bis (fluorine sulfonyl imide) and lithium bis (oxalic acid) borate. The lithium salt is applied to electrolyte, and can form electrolyte with high conductivity and high stability, so that a lithium ion battery with excellent electrochemical performance can be prepared.
In a specific embodiment, the molar concentration of the lithium salt is 0.8mol/L to 1.2mol/L, i.e. 0.8mol to 1.2mol of lithium salt is included in each liter of electrolyte, and specifically may be selected from 0.8mol/L, 1.0mol/L, 1.2mol/L or any value between 0.8mol/L and 1.2mol/L. When the molar concentration of the lithium salt is within the above range, the lithium salt can be thoroughly dissolved, thereby preparing an electrolyte with high stability, and at the same time, the viscosity of the electrolyte is made suitable, so that the lithium ion mobility of the electrolyte is excellent, thereby better maintaining the cycle performance of the battery.
The organic solvent of the present invention includes at least one of a carbonate-based organic solvent and a carboxylate-based organic solvent. The organic solvents can dissolve lithium salt, realize electrolyte with high conductivity and strong stability, and ensure that the electrochemical performance of the battery is stable.
In one embodiment, the organic solvent comprises at least one of ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate. According to the invention, the organic solvent is selected, so that the electrolyte with higher conductivity and better stability can be prepared, the electrochemical performance of the battery is more stable, and the cycle performance of the battery is further maintained.
In a specific embodiment, the mass percentage of the organic solvent in the electrolyte is 75% -90%, namely, each hundred grams of electrolyte comprises 75-90 g of the organic solvent, and the organic solvent can be specifically selected from 75%, 80%, 85%, 90% or any value between 75% -90% of the organic solvent. When the organic solvent is in the above range, the viscosity of the electrolyte is more suitable, so that the lithium ion mobility of the electrolyte is more excellent, thereby maintaining the cycle performance of the battery to a greater extent.
The present invention is not limited to the method for preparing the electrolyte, and in one embodiment, the lithium salt, the organic solvent, and the additive may be mixed in a predetermined ratio.
The invention also provides a battery, which comprises the electrolyte. The battery has the advantages of short liquid injection time, low production cost, good cycle performance and the like.
In a specific embodiment, besides the electrolyte provided by the invention, the electrolyte further comprises a positive electrode plate, a negative electrode plate and a diaphragm, and specifically:
the positive electrode sheet comprises a positive electrode current collector and a positive electrode active material layer arranged on the surface of the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material, a conductive agent and a binder, the positive electrode current collector is generally aluminum foil, and the positive electrode active material is selected from transition metal oxides of lithium, such as LiCoO 2 、LiMn 2 O 4 、LiMnO 2 、Li 2 MnO 4 、LiFePO 4 、Li 1+a Mn 1-x M x O 2 、LiCo 1-x M x O 2 、LiFe 1-x M x PO 4 、Li 2 Mn 1-x O 4 M is selected from one or more of Ni, co, mn, al, cr, mg, zr, mo, V, ti, B, F, a is more than or equal to 0 and less than or equal to 0.2, and x is more than or equal to 0<1。
The negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer arranged on the surface of the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material, a conductive agent and a binder, the negative electrode current collector is generally copper foil, and the negative electrode active material is one or more selected from carbonaceous materials, silicon-carbon materials, alloy materials and lithium-containing metal composite oxides.
The choice of the conductive agent and binder in the positive electrode active material layer and the negative electrode active material layer may be conventional materials in the art.
The separator is a separator which is well known in the art, can be used in a battery and is stable to the electrolyte used, and may include one or more of polyolefin, aromatic polyamide, polytetrafluoroethylene, polyether sulfone, and may be specifically set as needed.
Hereinafter, the present invention will be described in further detail with reference to specific examples.
Example 1
The electrolyte provided by the implementation comprises: the molar concentration of lithium hexafluorophosphate is 1mol/L, the organic solvent comprises 25% of ethylene carbonate, 59.8% of methyl ethyl carbonate, 2% of vinylene carbonate and 0.2% of additive, wherein the structure of the additive is shown in formula 2 (CAS: 66489-68-7).
The preparation method of the electrolyte of the embodiment comprises the following steps: preparing electrolyte in a BRADN glove box, filling nitrogen with the purity of 99.999%, controlling the water content in the glove box to be less than or equal to 0.1ppm, controlling the temperature to be in a room temperature state, fully mixing ethylene carbonate, methyl ethyl carbonate and ethylene carbonate, adding an additive for fully mixing, and finally mixing lithium hexafluorophosphate in a mixed solvent, and uniformly mixing to obtain the electrolyte.
The electrolyte formulations provided in examples 2-68 and comparative examples 1-2 were substantially the same as in example 1, and the specific parameters are shown in Table 1.
TABLE 1 compositions of electrolytes provided in examples 1 to 68 and comparative examples 1 to 2
The electrolytes provided in examples 1 to 68 and comparative examples 1 to 2 were prepared with positive electrode sheets, negative electrode sheets and separators to obtain lithium ion batteries, specifically: dispersing a positive electrode active material lithium iron phosphate, conductive carbon black super-p of a conductive agent and PVDF (polyvinylidene fluoride) of a binder in NMP (N-methyl pyrrolidone) according to a mass ratio of 96:2:2 to obtain a positive electrode active material layer slurry; uniformly coating the slurry of the positive electrode active material layer on the surface of an aluminum foil of a positive electrode current collector, and obtaining a positive electrode plate after drying, rolling, baking, slitting and spot welding the electrode lug, wherein the compacted density of the positive electrode plate is 2.6g/m 3 。
Dispersing negative electrode active material graphite, conductive carbon black super-p of a conductive agent, a binder SBR and a dispersant sodium hydroxymethyl cellulose (CMC) in deionized water according to a mass ratio of 95:1.5:2:1.5, and uniformly stirring to obtain negative electrode active material layer slurry; uniformly coating the slurry of the anode active material layer on the surface of a copper foil of an anode current collector, and obtaining an anode pole piece after drying, rolling, baking, slitting and spot welding the pole lug, wherein the compaction density of the anode pole piece is 1.6g/m 3 。
And sequentially stacking the prepared positive electrode plate, negative electrode plate and diaphragm, placing the diaphragm between the positive electrode plate and the negative electrode plate, winding to obtain a battery cell, placing the battery cell in an outer package, injecting the electrolyte into the battery cell in a glove box, standing for 24 hours, pre-charging for primary formation, sealing, and secondarily forming to prepare the lithium ion battery.
The electrolyte solutions prepared in examples 1 to 68 and comparative examples 1 to 2 were subjected to a wet performance test and a liquid injection rate test, and lithium batteries prepared therefrom were subjected to a battery performance test in the following manner:
contact angle test: and 3 mug of electrolyte is dripped on the surface of the positive pole piece, and a special system for testing the chemical properties of an interface based on an optical imaging method is adopted for testing by adopting a German Defei OCA15EC contact angle tester. Principle of action of impregnating compound: the wetting process between the electrolyte and the positive electrode plate is a wetting process, and the action between the adhesion work and the contact angle of the electrolyte is shown as a Young equation (formula 3):
wa=γsg+γlg- γsl=γlg (1+cos θ) 3
Wherein, gamma SG is air/positive pole piece surface free energy, gamma LG is electrolyte surface free energy, gamma SL is positive pole piece/electrolyte surface free energy, wa is adhesion work, θ is contact angle between positive pole piece and electrolyte. From formula 3, the wettability of the electrolyte to the positive electrode sheet can be measured by the contact angle, and the smaller the contact angle is, the larger the adhesion work is, so that the wettability of the electrolyte to the positive electrode sheet is better.
And (3) liquid injection rate test: 5-6 g electrolyte is injected into a 18650 cell with the capacity of 2600mAh, timing is carried out from the beginning of the electrolyte injection until the electrolyte is completely injected, the time required by the electrolyte injection is recorded, and the influence of the electrolyte on the electrolyte injection rate is detected.
And (3) testing the cycle performance: charging the battery to 3.65V at constant current of 1.0C at 25 ℃, charging to cut-off current of 0.05C at constant voltage, standing for five minutes, discharging the battery to 2.0V at constant current of 1.0C, and recording the discharge capacity as C 0 After standing for five minutes, repeating the charge and discharge process step 500 times, and recording the 500 th discharge capacity C 500 500-week cycle capacity retention η 1 ＝C 500 /C 0 *100％。
The test results are shown in Table 2.
Table 2 results of performance tests of examples 1 to 68 and comparative examples 1 to 2
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As can be seen from table 2, comparing examples 1 to 68 with comparative examples 1 to 2, it was found that the use of the organic fluorophosphate compound having the structure of formula 1 as the additive is conducive to reducing the contact angle between the electrolyte and the electrode sheet, shortening the liquid injection time, and maintaining the cycle performance of the battery; according to the comparison of the examples 1-25 and the examples 30-64, when the mass percentage of the additive in the electrolyte is 0.2% -8%, the contact angle between the electrolyte and the pole piece is reduced, the liquid injection time is shortened, and the cycle performance of the battery is maintained; according to comparison of examples 1 to 25 and examples 30 to 64, when the mass percentage of the additive in the electrolyte is preferably 1 to 8%, the reduction of the contact angle between the electrolyte and the pole piece, the shortening of the liquid injection time and the maintenance of the battery cycle performance are facilitated; as is clear from the comparison of examples 25, 65 to 68, when the molar concentration of the lithium salt in the electrolyte is 0.8mol/L to 1.2mol/L, the contact angle between the electrolyte and the electrode sheet is smaller, the liquid injection time is shorter, and the maintenance of the battery cycle performance is better. In conclusion, the electrolyte provided by the invention can obviously reduce the contact angle between the electrolyte and the battery pole piece in the lithium ion battery, shorten the liquid injection time and maintain the cycle performance of the battery.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. An electrolyte is characterized by comprising lithium salt, an organic solvent and an additive; the additive includes a compound having a structure represented by formula 1:
wherein R is 1 、R 2 、R 3 At least one of which is selected from C1-C10 hydrocarbon groups.
2. The electrolyte of claim 1, wherein the additive comprises a compound having one of structures represented by formulas 2 to 20:
3. electrolyte according to claim 1 or 2, characterized in that the additive is present in the electrolyte in an amount of 0.2-8% by mass.
4. The electrolyte according to claim 3, wherein the additive is 1-8% by mass of the electrolyte.
5. The electrolyte of any one of claims 1-4 wherein the lithium salt comprises at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethane sulfonate, lithium bistrifluoromethane sulfonimide, lithium bisfluoro sulfonimide, lithium bisoxalato borate.
6. The electrolyte according to claim 5, wherein the molar concentration of the lithium salt is 0.8mol/L to 1.2mol/L.
7. The electrolyte according to any one of claims 1 to 6, wherein the organic solvent comprises at least one of a carbonate-based organic solvent and a carboxylate-based organic solvent.
8. The electrolyte of any one of claims 1-7 wherein the organic solvent comprises at least one of ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate.
9. The electrolyte according to claim 7 or 8, wherein the mass percentage of the organic solvent in the electrolyte is 75-90%.
10. A battery, characterized in that it comprises the electrolyte according to any one of claims 1-9.
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