CN115458810A - Electrolyte and lithium ion battery - Google Patents
Electrolyte and lithium ion battery Download PDFInfo
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- CN115458810A CN115458810A CN202211417646.0A CN202211417646A CN115458810A CN 115458810 A CN115458810 A CN 115458810A CN 202211417646 A CN202211417646 A CN 202211417646A CN 115458810 A CN115458810 A CN 115458810A
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- Prior art keywords
- electrolyte
- carbonate
- compound
- lithium ion
- ion battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 74
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- -1 p-toluenesulfonyl compounds Chemical class 0.000 claims abstract description 57
- 239000000654 additive Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910013870 LiPF 6 Inorganic materials 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims description 17
- 159000000002 lithium salts Chemical class 0.000 claims description 17
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 13
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 12
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 9
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical group [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 8
- 101150058243 Lipf gene Proteins 0.000 claims description 7
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- 150000005678 chain carbonates Chemical class 0.000 claims description 6
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- 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
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 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
- 125000004093 cyano group Chemical group *C#N 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
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 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
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 229910013872 LiPF Inorganic materials 0.000 claims description 2
- MYRUXGCOHIYOBX-UHFFFAOYSA-K [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O.FOC(=O)C(=O)OF Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O.FOC(=O)C(=O)OF MYRUXGCOHIYOBX-UHFFFAOYSA-K 0.000 claims 1
- 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 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 1
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910002804 graphite Inorganic materials 0.000 abstract description 7
- 239000010439 graphite Substances 0.000 abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- 229940037201 oris Drugs 0.000 description 6
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000009044 synergistic interaction Effects 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
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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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 invention provides an electrolyte and a lithium ion battery. The electrolyte comprises an organic solvent and LiPF 6 And additives, wherein the additives comprise trifluoromethanesulfonic acid compounds and p-toluenesulfonyl compounds. The trifluoromethane sulfonic acid compound and the toluene sulfonyl compound are used together, a stable interfacial film can be formed on the surfaces of an NCM ternary positive electrode and a graphite negative electrode, and through the full synergistic effect of the trifluoromethane sulfonic acid compound and the toluene sulfonyl compound, the interfacial film is thin and compact, and the benzene ring structure of the toluene sulfonyl compound has high rigidity, so that the interfacial film is more stable, the ionic conductivity of the interfacial film is improved, the generation of harmful products such as HF (hydrogen fluoride) in electrolyte and the dissolution of cathode transition metal in the circulation process are prevented, the impedance of a lithium ion battery is reduced to a certain extent, and the impedance of the lithium ion battery is improvedThe cycling performance of the cell.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an electrolyte and a lithium ion battery.
Background
In recent years, lithium ion batteries have become a new research focus and have received much attention. The electric vehicle field focuses on hybrid vehicles and mobile device power supplies, etc., due to their high energy density, environmental friendliness, and economic friendliness. It is well known that cycle performance is one of the important indicators of batteries. As the battery continues to charge, it results in a continuous increase in internal resistance and generates a large amount of heat, often worsening the cycle life over multiple cycle charging.
Disclosure of Invention
The invention mainly aims to provide an electrolyte and a lithium ion battery, and aims to solve the problem that the lithium ion battery in the prior art is high in impedance.
In order to achieve the above object, according to one aspect of the present invention, there is provided an electrolyte including an organic solvent, liPF 6 And additives, wherein the additives comprise trifluoromethanesulfonic acid compounds and p-toluenesulfonyl compounds.
Further, the trifluoromethanesulfonic acid compound is a compound represented by structural formula I:
structural formula I
Wherein R1 is selected from the group consisting of a silane group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C 1 ~C 4 Linear alkyl, substituted or unsubstituted C of 3 ~C 6 Preferably, the trifluoromethanesulfonic acid compound is selected from any of the branched alkyl groups of (1)、、、、Any one or more of。
Further, the trifluoromethanesulfonic acid compound is selected from the group consisting of、、Any one or more of them.
Further, the p-toluenesulfonyl compound is a compound represented by the formula II,
structural formula II
Wherein R2 is selected from any one of cyano, halogen and amino, preferably the p-toluenesulfonyl compound is selected from、、Any one or more of them.
Further, the mass of the additive is 0.1 to 5wt% of the total mass of the electrolyte, and the mass ratio of the trifluoromethanesulfonic acid compound to the p-toluenesulfonyl compound is preferably 1 to 5.
Further, the organic solvent includes one or more of cyclic carbonate, chain carbonate and carboxylic ester, preferably, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate and γ -butyrolactone, preferably, the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate and ethyl propyl carbonate, preferably, the carboxylic ester is selected from one or more of methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate and ethyl butyrate, preferably, the organic solvent is selected from a combination of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, preferably, the mass ratio of ethylene carbonate, diethyl carbonate and ethyl carbonate is 1~2:1~2:2~5.
The electrolyte further comprises a lithium salt additive, the concentration of the lithium salt additive is preferably 0.3 to 1mol/L, and the lithium salt additive is preferably selected from lithium bis (fluorosulfonyl) imide and LiBF 4 Lithium bis (oxalato) borate, lithium difluoro (oxalato) phosphate, lithium bis (trifluoromethylsulfonyl) imide, phenylsulfone, tris (trimethylsilane) phosphite, vinyl sulfate and methylene methyldi-sulfonate, and further, the lithium salt additive is preferably lithium bis (fluorosulfonyl) imide, vinyl sulfate and methylene methyldi-sulfonate, or the lithium salt additive is preferably phenylsulfone, tris (trimethylsilane) phosphite, vinyl sulfate and methylene methyldi-sulfonate.
Further, the above LiPF 6 The concentration of (3) is 0.5 to 1.5mol/L, and the electrolyte preferably comprises: ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, liPF 6 Vinyl sulfate, methylene methyldi-sulfonate, lithium bis-fluorosulfonylimide, andandwherein, in the step (A),is 2.5wt% of the electrolyte,0.5wt% of the electrolyte; orIs 0.5wt% of the electrolyte,2.5wt% of the electrolyte; orIs 0.8wt% of the electrolyte,2.2wt% of the electrolyte; orIs 1.2wt% of the electrolyte,is 1.8wt% of the electrolyte.
According to one aspect of the invention, a lithium ion battery is provided, which comprises a positive plate, a negative plate and an electrolyte, wherein the electrolyte is the electrolyte.
Further, the positive electrode sheet includes a positive electrode material, and preferably, the positive electrode material is LiNi (1-x-y) Co x Mn y Wherein x is more than or equal to 0 and less than or equal to 1,0 and less than or equal to 1.
By applying the technical scheme of the invention, the strong electron withdrawing property of trifluoromethyl in the trifluoromethanesulfonic acid compound enables methylsulfonyl directly connected with the trifluoromethanesulfonic acid compound to have stronger reaction activity, the trifluoromethanesulfonic acid compound can be used in combination with the tosyl compound to form a stable interface film on the surface of an NCM ternary positive electrode and a graphite negative electrode, and through the full synergistic action of the trifluoromethanesulfonic acid compound and the tosyl compound, the interface film is thin and compact, and the benzene ring structure of the tosyl compound has high rigidity, so that the interface film is more stable, the ionic conductivity of the interface film is improved, the generation of harmful products such as HF (hydrogen fluoride) in electrolyte and the dissolution of cathode transition metal in a circulating process are prevented, the impedance of a lithium ion battery is further reduced to a certain degree, and the comprehensive performances such as the circulating performance of the lithium ion battery are obviously improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art, the lithium ion battery in the prior art has a problem of high impedance, and in order to solve the problem, the invention provides an electrolyte and a lithium ion battery.
In an exemplary embodiment of the present application, there is provided an electrolyte including an organic solvent, liPF 6 And additives, wherein the additives comprise trifluoromethanesulfonic acid compounds and p-toluenesulfonyl compounds.
The strong electron withdrawing property of trifluoromethyl in the trifluoromethanesulfonic acid compound enables methylsulfonyl directly connected with the trifluoromethanesulfonic acid compound to have stronger reaction activity, and the trifluoromethanesulfonic acid compound and the toluenesulfonyl compound are used together to form a stable interfacial film on the surfaces of an NCM ternary positive electrode and a graphite negative electrode.
In order to improve the film forming property of the trifluoromethanesulfonic acid compound, the trifluoromethanesulfonic acid compound is preferably a compound represented by structural formula I:
structural formula I
Wherein R1 is selected from the group consisting of a silane group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C 1 ~C 4 Linear alkyl, substituted or unsubstituted C of 3 ~C 6 Any of the branched alkyl groups of (1), preferably a trifluoromethanesulfonic acid-based compound selected from、、、、Any one or more of them.
In order to further improve the synergistic interaction between the trifluoromethanesulfonic acid compound and the p-toluenesulfonyl compound, the trifluoromethanesulfonic acid compound is preferably selected from the group consisting of、、Any one or more of them.
In one embodiment of the present application, the above-mentioned p-toluenesulfonyl compound is a compound having a structural formula II,
structural formula II
Wherein R2 is selected from any one of cyano, halogen and amino, preferably the p-toluenesulfonyl compound is selected from、、Any one or more of them.
The p-toluenesulfonyl compound containing the substituent has higher oxidation-reduction property, and the p-toluenesulfonyl compound and the trifluoromethanesulfonic acid compound are coordinated to generate thinner and more compact CEI and SEI protective films on the surfaces of an NCM cathode and a graphite anode more easily under the synergistic action of the p-toluenesulfonyl compound and the trifluoromethanesulfonic acid compound, so that the cycling stability of the NCM cathode and the power of the graphite anode are greatly improved. On the other hand, the functional group of the p-toluenesulfonyl compound can inhibit LiPF 6 The hydrolysis reaction of the anode and the cathode can prevent harmful product HF from being generated and NCM cathode transition metal from being dissolved in the circulating process, and the circulating life of the NCM/graphite full cell is further obviously prolonged.
Preferably, the mass of the additive is 0.1 to 5wt% of the total mass of the electrolyte, and preferably, the mass ratio of the trifluoromethanesulfonic acid compound to the p-toluenesulfonyl compound is 1 to 5.
In one embodiment of the present application, preferably, the organic solvent includes any one or more of a cyclic carbonate, a chain carbonate and a carboxylic ester, preferably, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate and γ -butyrolactone, preferably, the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate and propyl ethyl carbonate, preferably, the carboxylic ester is selected from one or more of methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate and ethyl butyrate, preferably, the organic solvent is selected from a combination of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, and preferably, the volume ratio of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate is 1 to 2 to 5.
The organic solvent can better prevent the electrolyte from being damaged by water, and is beneficial to promoting the components in the electrolyte to be more fully dissolved, so that the cooperativity among the components is improved, and the electrolyte with excellent electrical property is obtained.
In order to enhance the coordination among the lithium salt additive, the lithium salt and the additive and further improve the comprehensive performance of the electrolyte, the electrolyte preferably further comprises the lithium salt additive, the concentration of the lithium salt additive is preferably 0.3 to 1mol/L, and the lithium salt additive is preferably selected from lithium bis (fluorosulfonyl) imide and LiBF 4 Lithium bis (oxalato) borate, lithium difluoro (oxalato) phosphate, lithium bis (trifluoromethylsulfonyl) imide, phenylsulfone, tris (trimethylsilane) phosphite, vinyl sulfate and methylene methyldi-sulfonate, and further, the lithium salt additive is preferably lithium bis (fluorosulfonyl) imide, vinyl sulfate and methylene methyldi-sulfonate, or the lithium salt additive is preferably phenylsulfone, tris (trimethylsilane) phosphite, vinyl sulfate and methylene methyldi-sulfonate.
LiPF 6 The electrolyte used as the electrolyte can enhance the conductivity, the energy storage property and the environmental protection property of the lithium ion battery, and further exert LiPF 6 The preferred LiPF is LiPF 6 The concentration of (b) is 0.5 to 1.5mol/L, and the electrolyte preferably comprises: ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, liPF 6 Vinyl sulfate, methylene methyldi-sulfonate, lithium bis-fluorosulfonylimide, andandwherein, in the step (A),is 2.5wt% of the electrolyte,is electricity0.5wt% of the hydrolysate; orIs 0.5wt% of the electrolyte,2.5wt% of the electrolyte; orIs 0.8wt% of the electrolyte,2.2wt% of the electrolyte; orIs 1.2wt% of the electrolyte,is 1.8wt% of the electrolyte. Further, the mass ratio of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate is preferably 1 6 Is 0.7mol/L, and the concentrations of the vinyl sulfate, the methylene methanedisulfonate and the lithium bis-fluorosulfonylimide are each independently 0.1mol/L.
In another exemplary embodiment of the present application, a lithium ion battery is provided, which includes a positive electrode sheet, a negative electrode sheet, and an electrolyte, where the electrolyte is the foregoing electrolyte.
The lithium ion battery adopting the electrolyte has lower impedance, and can obviously improve the comprehensive properties of the lithium ion battery, such as cycle performance and the like.
In order to improve the coordination of the electrolyte and the positive plate and further enable the lithium ion battery to have the performances of cycle stability, lower internal resistance and the like, the positive plate preferably comprises a positive electrode material, and the positive electrode material is preferably LiNi (1-x-y) Co x Mn y Wherein x is more than or equal to 0 and less than or equal to 1,0 and less than or equal to 1.
The advantageous technical effects of the present application will be described below with reference to specific examples and comparative examples.
The compounds of structural formula I and structural formula II were purchased from the alatin reagent in the trade-off.
Example 1
Preparation of electrolyte (in 1L of electrolyte): ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were mixed at a mass ratio of EC: DEC: EMC =1 6 ) 0.1mol of vinyl sulfate (DTD), 0.1mol of Methylene Methanedisulfonate (MMDS) and 0.1mol of lithium bis (fluorosulfonyl) imide (LiFSI) are added to the mixture until the lithium salt is completely dissolvedAnd 1 wt.%。
Preparing a positive plate: liNi prepared from nickel cobalt lithium manganate ternary material 0.7 Co 0.1 Mn 0.2 The conductive agent Super P, the adhesive PVDF and the Carbon Nano Tube (CNT) are uniformly mixed according to the mass ratio of 97.5 2 Drying at 85 ℃ and then carrying out cold pressing; then, the strips are divided, sliced and dried for 4 hours at the temperature of 85 ℃ in vacuum to prepare the lithium ion battery positive plate meeting the requirements.
Preparing a negative plate: preparing artificial graphite, a conductive agent Super P, a thickening agent CMC and a binding agent SBR (styrene butadiene rubber emulsion) into slurry according to the mass ratio of 95.5.
Preparing a lithium ion battery: and (3) preparing the positive plate, the negative plate and the diaphragm prepared by the process into the lithium ion battery with the thickness of 0.5mm, the width of 8mm and the length of 10 through a lamination process, wherein the capacity of the lithium ion battery is 3Ah, vacuum baking is carried out for 48 hours at the temperature of 85 ℃, and the electrolyte is injected to complete the battery preparation.
Examples 2 to 17 and comparative examples 1 to 4 were carried out while changing the ratio and kind of specific materials in the electrolyte, and a lithium ion battery was obtained by referring to the preparation method of example 1, and the electrolyte formulation was as shown in table 1 below.
TABLE 1
Example 10
Example 10 differs from example 4 in that,
Example 11
Example 11 differs from example 4 in that,
Example 12
Example 12 differs from example 4 in that,
the trifluoromethanesulfonic acid compound isAnd finally obtaining the lithium ion secondary battery.
Example 13
Example 13 differs from example 4 in that,
the trifluoromethanesulfonic acid compound isAnd finally obtaining the lithium ion secondary battery.
Example 14
Example 14 differs from example 4 in that,
Example 15
Example 15 differs from example 4 in that,
Example 16
Example 16 differs from example 4 in that the solvent was Ethyl Propionate (EP), and a lithium ion secondary battery was finally obtained.
Example 17
Example 17 differs from example 4 in that the lithium salt additive was 0.1mol/L LiFSI, 0.1mol Phenylsulfone (PS), and 0.1mol tris (trimethylsilane) phosphite (TMSP), and finally a lithium ion secondary battery was obtained.
(1) Initial direct current internal resistance (DCR) test
After capacity grading, the test cells of examples 1 to 17 and comparative example 1~4 were charged to a state of charge of 50% SOC, and after standing for 30min, the sample voltage V0 at the start of discharge was recorded, and after discharging at a current I of 2C for 10s, the sample voltage V1 at the end of discharge was recorded, and the initial DC discharge internal impedance DCR = (V1-V0)/I of the test cell was calculated.
(2) Cycle performance detection
The experimental batteries of examples 1 to 17 and comparative example 1~4 were subjected to a charge-discharge cycle performance test at a charge-discharge rate of 1C under a test condition of 25 ℃, the charge-discharge voltage interval was set to 2.8 to 4.25v, and the test results were shown in table 1 after 800 cycles at room temperature.
It can be seen from the comparison between the above examples and comparative examples that, compared with the conventional additives, the combination of the trifluoromethanesulfonic acid compound and the p-toluenesulfonyl compound of the present invention as the additive can greatly reduce the direct current internal resistance of the lithium ion battery, and at the same time, the cycle is significantly improved.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the strong electron withdrawing property of trifluoromethyl in the trifluoromethanesulfonic acid compound enables methylsulfonyl directly connected with the trifluoromethanesulfonic acid compound to have stronger reaction activity, and the trifluoromethanesulfonic acid compound and the toluenesulfonyl compound are used together to form a stable interfacial film on the surfaces of an NCM ternary positive electrode and a graphite negative electrode.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The electrolyte is characterized by comprising an organic solvent and LiPF 6 And an additive comprising a trifluoromethanesulfonic acid-based compound and a p-toluenesulfonyl-based compound.
2. The electrolyte of claim 1, wherein the trifluoromethanesulfonic acid-based compound is a compound having the formula I:
structural formula I
Wherein R1 is selected from the group consisting of silyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 1 ~C 4 Straight-chain alkyl, substituted or unsubstituted C 3 ~C 6 Any of the branched alkyl groups of (a).
7. The electrolyte according to claim 6, wherein the mass of the additive is 0.1 to 5wt% of the total mass of the electrolyte, and/or the mass ratio of the trifluoromethanesulfonic acid-based compound to the p-toluenesulfonyl-based compound is 1.
8. The electrolyte of claim 6, wherein the organic solvent comprises one or more of cyclic carbonate, chain carbonate and carboxylic ester, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolactone, the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate and propyl ethyl carbonate, and the carboxylic ester is selected from one or more of methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate and ethyl butyrate.
9. The electrolyte of claim 6, further comprising a lithium salt additive, wherein the concentration of the lithium salt additive is 0.3 to 1mol/L, and the lithium salt additive is selected from lithium bis (fluorosulfonyl) imide and LiBF 4 Any one or more of lithium bis (oxalate) borate, lithium difluoro (oxalate) phosphate, lithium bis (trifluoromethyl) sulfonyl imide, phenyl sulfone, tris (trimethylsilyl) phosphite, vinyl sulfate and methylene methyl disulfonate.
10. The electrolyte of claim 9, wherein the LiPF is 6 The concentration of (b) is 0.5 to 1.5mol/L, and the electrolyte preferably comprises: ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, liPF 6 Vinyl sulfate, methylene methyldi-sulfonate, lithium bis-fluorosulfonylimide, andandwherein, the2.5wt% of the electrolyte, the0.5wt% of the electrolyte;
11. A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, and an electrolyte, wherein the electrolyte is the electrolyte according to any one of claims 1 to 10.
12. The lithium ion battery of claim 11, wherein the positive plate comprises a positive electrode material, and the positive electrode material is LiNi (1-x-y) Co x Mn y Wherein x is more than or equal to 0 and less than or equal to 1,0 and less than or equal to 1.
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