CN106848381A - A kind of electrolyte and the lithium secondary battery containing the electrolyte - Google Patents
A kind of electrolyte and the lithium secondary battery containing the electrolyte Download PDFInfo
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- CN106848381A CN106848381A CN201710029575.XA CN201710029575A CN106848381A CN 106848381 A CN106848381 A CN 106848381A CN 201710029575 A CN201710029575 A CN 201710029575A CN 106848381 A CN106848381 A CN 106848381A
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- Prior art keywords
- electrolyte
- tricyano
- functional compounds
- secondary battery
- lithium secondary
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- 239000003792 electrolyte Substances 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- -1 phosphate compound Chemical class 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000006259 organic additive Substances 0.000 claims abstract description 3
- 239000006258 conductive agent Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 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 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical class CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 2
- 229910010941 LiFSI Inorganic materials 0.000 claims 1
- DWJFPXCDDHKKKI-UHFFFAOYSA-N S1(=O)OCC(C)CCO1.S(O)(O)(=O)=O Chemical compound S1(=O)OCC(C)CCO1.S(O)(O)(=O)=O DWJFPXCDDHKKKI-UHFFFAOYSA-N 0.000 claims 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 238000004458 analytical method Methods 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 229940017219 methyl propionate Drugs 0.000 description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229940090181 propyl acetate Drugs 0.000 description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- BKIWAQYWKUFSRE-UHFFFAOYSA-N prop-1-ene;sulfuric acid Chemical group CC=C.OS(O)(=O)=O BKIWAQYWKUFSRE-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-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
- H01M10/052—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
-
- 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
- H01M10/056—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
-
- 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)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to lithium secondary battery field, a kind of electrolyte and the lithium secondary battery containing the electrolyte are disclosed.The electrolyte includes electrolyte, organic solvent, additive and functional compounds, and the functional compounds are at least one in tricyano bi-ester of phosphite and tricyano phosphate compound.The tricyano bi-ester of phosphite or tricyano phosphate compound contained in electrolyte of the invention, can be in both positive and negative polarity surface filming, and energy and complexing of metal ion, prevent the abjection of cathode metal ion molten in electrolyte and prevent it to be deposited on negative pole, so as to reach stabilization anode structure and improve the effect of negative pole SEI films, lithium secondary battery cycle performance and high-temperature behavior are improved.Functional compounds of the invention can reduce the analysis lithium problem charged into membrane impedance, improvement low temperature under low temperature environment simultaneously.
Description
Technical field
The invention belongs to lithium secondary battery field, and in particular to a kind of electrolyte and the secondary electricity of the lithium containing the electrolyte
Pond.
Background technology
Lithium secondary battery has that operating voltage is high, specific energy density big, have extended cycle life, self-discharge rate is low, memoryless effect
, the advantages of environmental pollution is small, consumer electronics, energy storage and power product should be had been widely used for.In recent years, with portable
Formula electronic product develops to lighting, high-performance, and this energy density to lithium secondary battery proposes requirements at the higher level.Reply battery is more
The continuous pursuit of high-energy-density, the strategy for generally using at present in the industry is the compacting for improving both positive and negative polarity and the cut-off for improving battery
Voltage.The thing followed is the deterioration of battery performance, and particularly under high pressure-temperature, the SEI films that battery pole piece surface is formed hold
It is easily destroyed；When low temperature charges, because the dynamic performance of battery is not good enough, easily lithium, cell safety are analysed during low temperature discharge and recharge
Performance is affected.
Patent CN201510564696 discloses a kind of dicyanogen methyl isophorone compound N C-R-CN that contains and is electrolysed as lithium ion battery
Solution additive, can improve the high-temperature storage performance and cycle performance of battery.Similar, patent CN201510964662 is disclosed
A kind of compound simultaneously containing unsaturated carbon-carbon bond and cyano group, can in electrode used as lithium-ion battery electrolytes additive
There is polymerisation and form the compound containing multiple cyano group in surface, the compound can be with the metal ion on positive electrode surface
Complexing, so as to suppress electrolyte be decomposed in electrode surface, improves the high-temperature storage and cycle performance of battery.But this area
Scientific research personnel has found that the compound of the double or triple bonds of carbon containing unsaturated carbon can increase into membrane impedance, and low temperature is more easy to analyse lithium when charging,
Reduce battery safety.
Therefore, exploitation one kind can improve high temperature storage and cycle performance, while can improve the lithium of low temperature charging performance again
Secondary cell electrolyte is significant.
The content of the invention
It is an object of the invention to solve above-mentioned technical problem, there is provided one kind can improve high temperature storage and cycle performance,
The electrolyte and the lithium secondary battery containing the electrolyte of low temperature charging performance can be improved again simultaneously.
The object of the invention is achieved through the following technical solutions：
A kind of electrolyte, including electrolyte, organic solvent, additive and functional compounds, the functional compounds are three
At least one in cyano group bi-ester of phosphite and tricyano phosphate compound, the tricyano bi-ester of phosphite and
Tricyano phosphate compound has the structural formula as shown in following formula (I) and formula (II) respectively：
R in formula11、R12、R13、R21、R22、R23It is each independently selected from the alkylidene or fluorianted alkylene of C1~C5.
Functional compounds weight/mass percentage composition in the electrolytic solution is preferably 0.05%~10%, when less than 0.05%
When, it is impossible to both positive and negative polarity is protected well, so as to be difficult to fully improve the high-temperature storage performance and cycle performance of battery, and is exceeded
When 10%, the viscosity of electrolyte is increased due to it, cause battery performance to deteriorate.It is highly preferred that its quality hundred in the electrolytic solution
Content is divided to be 0.2%~5%.
The electrolyte is preferably lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), trifluoromethyl sulfonic acid lithium
(LiSO3CF3), biethyl diacid lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), double trifluoromethanesulfonimide lithiums
(LiTFSI), double fluorine sulfimide lithiums (LiFSI), difluorophosphate
(LiPO2F2) at least one.
The organic solvent includes ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), carbonic acid two
Ethyl ester (DEC), methyl ethyl carbonate (EMC), gamma-butyrolacton (GBL), methyl acetate (MA), ethyl acetate (EA), propyl acetate
(PA), butyl acetate (BA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), butyl propionate (BP), butyric acid first
In ester (MB), ethyl butyrate (EB), propyl butyrate (PB) at least two.
Preferably, the organic solvent is at least two in EC, PC, EMC, DEC, PA, MP, EP, PP, EB.
The additive is additive commonly used in the art, and as an example, the additive is fluorinated ethylene carbonate
(FEC), vinylene carbonate (VC), vinylethylene carbonate (VEC), 1,3- propane sultones (PS), 1,4- butyl sultones
(BS), sulfuric acid vinyl ester (DTD), methane-disulfonic acid methylene ester (MMDS), propene sultone (PES), sulfuric acid propylene, sulfurous
Vinyl acetate, succinonitrile (SN), adiponitrile (ADN), pimelic dinitrile (PN), the nitrile of 1,3,6- hexanes three (HTCN), ethylene glycol double (third
Nitrile) ether (DENE), succinic anhydride, maleic anhydride, 2- methyl maleic anhydrides, 2,3- dimethyl maleic anhydrides, in itaconic anhydride
It is at least one.
The invention further relates to a kind of lithium secondary battery containing above-mentioned electrolyte, including the positive pole containing positive electrode active materials
Piece, the negative plate containing negative active core-shell material, barrier film and above-mentioned electrolyte；Positive plate includes embedded or deintercalate lithium ions
Positive electrode active materials, conductive agent, collector and the binding agent for combining the positive electrode active materials, conductive agent, collector；Negative pole
Piece includes being embedded in or the negative active core-shell material of deintercalate lithium ions, conductive agent, collector and by the negative active core-shell material, lead
The binding agent that electric agent, collector are combined.
Electrolyte of the invention has the following advantages that and beneficial effect：
The tricyano bi-ester of phosphite or tricyano phosphate compound contained in electrolyte of the invention, Ke Yi
Both positive and negative polarity surface filming, and energy and complexing of metal ion, prevent the abjection of cathode metal ion molten in electrolyte and prevent it from sinking
Product, so as to reach stabilization anode structure and improve the effect of negative pole SEI films, improves lithium secondary battery cycle performance and height in negative pole
Warm nature energy.Simultaneously functional compounds of the invention can reduce under low temperature environment into membrane impedance, improve the analysis lithium that low temperature charges and ask
Topic, so as to significantly improve the security performance of battery.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
The structure of tricyano bi-ester of phosphite and tricyano phosphate compound used in the embodiment of the present invention point
Not as shown in Table 1 and Table 2.
The tricyano bi-ester of phosphite of table 1
The tricyano phosphate compound of table 2
The preparation of lithium secondary battery and performance test step are as follows in the embodiment of the present invention：
(1) preparation of electrolyte：In the glove box of argon atmosphere, organic solvent is pressed into certain mass than mixing, then add
Enter additive, tricyano bi-ester of phosphite or tricyano phosphate compound, electrolyte to stir, that is, obtain this
The described electrolyte of invention.
(2) preparation of anode pole piece：By certain mass than Kynoar (PVDF) be dissolved in 1- methyl -2- pyrrolidines
In ketone (NMP) solution, then by certain mass than positive electrode active materials and conductive agent add above-mentioned solution and be well mixed, will be mixed
After the slurry of system is coated on the two sides of aluminium foil, anode pole piece is obtained after drying, roll-in.
(3) preparation of cathode pole piece：The SBR binding agents and CMC thickeners of mass ratio are dissolved in the aqueous solution, then will be certain
The negative material and conductive agent of mass ratio add above-mentioned solution and are well mixed, and the slurry that will be blended is coated on the two sides of Copper Foil
Afterwards, cathode pole piece is obtained after drying, roll-in.
(4) preparation of lithium secondary battery：The anode pole piece of above-mentioned preparation, cathode pole piece and barrier film are made battery core, are noted
Enter step (1) gained electrolyte, lithium secondary battery is made after the techniques such as chemical conversion.
(5) battery performance test
High temperature circulation is tested：Charge and discharge cycles test is carried out to battery with the multiplying power of 0.5/0.5C in 45 DEG C of insulating boxs.
High-temperature storage performance is tested：Battery is first carried out into discharge and recharge once with the multiplying power of 0.5/0.5C under normal temperature state to battery, then
With 0.5C by battery it is fully charged after carry out high temperature storage, the thickness of hot test battery, treats that battery is complete after storage certain hour
Charge-discharge test is carried out with 0.5C after cooling and calculates capability retention and capacity restoration rate.Low temperature charging measurement：First battery is existed
Discharged with 0.5C under normal temperature state, then 0 DEG C of low temperature is fully charged by battery with 0.3C after shelving 4 hours in the high-low temperature chamber, then
Disassemble whether battery observation negative terminal surface analyses lithium in the glove box of argon atmosphere.
The electrolyte composition of the embodiment of the present invention 1~25 and comparative example 1~6 is as shown in table 3.
The electrolyte component of the embodiment of table 3 and comparative example
Percentage composition refers to the weight/mass percentage composition accounted in final electrolyte in table, and concentration refers in final electrolyte
Concentration.
The performance test results of the lithium secondary battery that the electrolyte of embodiment 1~25 and comparative example 1~6 the is obtained such as institute of table 4
Show.
The test result of the embodiment of table 4 and comparative example
Contrasted with comparative example 1~6 by embodiment 1~25, find to add tricyano bi-ester of phosphite or three
Cyano group phosphate compound can be effectively improved the cycle performance of battery, can significantly improve the capacity after battery high-temperature storage and keep
Rate, suppresses thickness swelling, and the analysis lithium problem that charged to low temperature also has improvement.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. a kind of electrolyte, it is characterised in that：The electrolyte includes electrolyte, organic solvent, additive and functional compounds,
The functional compounds are at least one in tricyano bi-ester of phosphite and tricyano phosphate compound, three cyanogen
Base bi-ester of phosphite and tricyano phosphate compound have the structural formula as shown in following formula (I) and formula (II) respectively：
R in formula11、R12、R13、R21、R22、R23It is each independently selected from the alkylidene or fluorianted alkylene of C1~C5.
2. a kind of electrolyte according to claim 1, it is characterised in that：Functional compounds quality in the electrolytic solution
Percentage composition is 0.05%~10%.
3. a kind of electrolyte according to claim 2, it is characterised in that：Functional compounds quality in the electrolytic solution
Percentage composition is 0.2%~5%.
4. a kind of electrolyte according to claim 1, it is characterised in that：The electrolyte is LiPF6、LiBF4、
LiSO3CF3、LiBOB、LiDFOB、LiTFSI、LiFSI、LiPO2F2In at least one.
5. a kind of electrolyte according to claim 1, it is characterised in that：The organic solvent include EC, PC, DMC, DEC,
In EMC, GBL, MA, EA, PA, BA, MP, EP, PP, BP, MB, EB, PB at least two.
6. a kind of electrolyte according to claim 5, it is characterised in that：The organic solvent be EC, PC, EMC, DEC,
In PA, MP, EP, PP, EB at least two.
7. a kind of electrolyte according to claim 1, it is characterised in that：The additive be FEC, VC, VEC, PS, BS,
DTD, MMDS, PES, sulfuric acid propylene, ethylene sulfite, SN, ADN, PN, HTCN, DENE, succinic anhydride, maleic anhydride, 2-
At least one in methyl maleic anhydride, 2,3- dimethyl maleic anhydrides, itaconic anhydride.
8. a kind of lithium secondary battery, including the positive plate containing positive electrode active materials, the negative plate containing negative active core-shell material, every
From film and electrolyte；Positive plate includes the positive electrode active materials of embedded or deintercalate lithium ions, conductive agent, collector and will be described
The binding agent that positive electrode active materials, conductive agent, collector are combined；Negative plate includes being embedded in or the negative pole of deintercalate lithium ions is lived
Property material, conductive agent, collector and the binding agent that combines the negative active core-shell material, conductive agent, collector, its feature exists
In：The electrolyte is the electrolyte described in any one of claim 1~7.
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Application publication date: 20170613 |