CN107508000A - Lithium-ion battery electrolytes and lithium ion battery - Google Patents
Lithium-ion battery electrolytes and lithium ion battery Download PDFInfo
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- CN107508000A CN107508000A CN201710768382.6A CN201710768382A CN107508000A CN 107508000 A CN107508000 A CN 107508000A CN 201710768382 A CN201710768382 A CN 201710768382A CN 107508000 A CN107508000 A CN 107508000A
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- Prior art keywords
- lithium
- ion battery
- additive
- carbonate
- battery electrolytes
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 82
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- 239000000654 additive Substances 0.000 claims abstract description 42
- 230000000996 additive effect Effects 0.000 claims abstract description 42
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013538 functional additive Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 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 abstract description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 5
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 15
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical group OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 11
- 230000005611 electricity Effects 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 5
- -1 ethylene carbonate Ester Chemical class 0.000 claims description 5
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 claims description 4
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 229910007041 Li(CF3SO2)2 Inorganic materials 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- WKFDWSVVMAKCDI-UHFFFAOYSA-N C(C=1C(C(=O)OCC)=CC=CC1)(=O)OCC.[C] Chemical group C(C=1C(C(=O)OCC)=CC=CC1)(=O)OCC.[C] WKFDWSVVMAKCDI-UHFFFAOYSA-N 0.000 claims 1
- 229910001560 Li(CF3SO2)2N Inorganic materials 0.000 claims 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 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
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims 1
- 150000008053 sultones Chemical class 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000004087 circulation Effects 0.000 description 8
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 8
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 7
- 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 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 241001269238 Data Species 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 235000010338 boric acid Nutrition 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229960002645 boric acid Drugs 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- XCASEDBCMLBDON-UHFFFAOYSA-N C(C)(=O)OC=C.S(=O)(=O)(O)O Chemical compound C(C)(=O)OC=C.S(=O)(=O)(O)O XCASEDBCMLBDON-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- OUGOOSHGPCBMLD-UHFFFAOYSA-N [B].FOC(C(=O)OF)=O Chemical compound [B].FOC(C(=O)OF)=O OUGOOSHGPCBMLD-UHFFFAOYSA-N 0.000 description 1
- UPZVRQOMDANCRD-UHFFFAOYSA-N [S].C(C)(=O)OC=C Chemical compound [S].C(C)(=O)OC=C UPZVRQOMDANCRD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CJBYUPBUSUVUFH-UHFFFAOYSA-N buta-1,3-diene;carbonic acid Chemical group C=CC=C.OC(O)=O CJBYUPBUSUVUFH-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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 discloses a kind of lithium-ion battery electrolytes and lithium ion battery.The lithium-ion battery electrolytes include：11~17wt% of lithium salts；3~11wt% of functional additive, and the functional additive includes positive pole protection additive, film for additive and Low ESR additive；78~85wt% of organic solvent, and one or more of the organic solvent in ethylene carbonate, propene carbonate, ethyl propionate, propyl propionate, methyl ethyl carbonate, diethyl carbonate.The lithium-ion battery electrolytes of the present invention are a kind of high voltage and resistant to elevated temperatures rate lithium ion battery electrolyte, meet high-voltage lithium ion batteries heavy-current discharge cycle performance, while also meet the requirement of the storage performance under hot conditions.
Description
Technical field
The present invention relates to field of batteries, more particularly to a kind of lithium-ion battery electrolytes and lithium ion battery.
Background technology
With the expansion in lithium ion battery applications field, the requirement for battery performance also improves constantly.Lead in some markets
Domain such as unmanned plane market, its requirement on electric performance to battery core also more refine：High-energy-density, high current multiplying power discharging cyclicity
Energy and high-temperature storage performance.
It is to use high-voltage anode material to realize one of high-energy-density direction.And high-voltage anode material with charge into
OK, the abjection of lithium, the enhancing of its oxidisability, bad stability, one side oxidation electrolyte, the transition gold of another aspect positive electrode
Belong to dissolution, destroy positive electrode, cause its circulation and storage performance deterioration, such case shows brighter in high temperature environments
It is aobvious.Meet the one of importance of multiplying power discharging, it is desirable to which electrolyte has good electrical conductivity.
To improve drawbacks described above, there is an urgent need to a kind of electrolyte, had both taken into account high temperature storage and cycle performance requirement, while
Meet high current multiplying power discharging demand.
The content of the invention
In view of the above problems, the invention provides a kind of new lithium-ion battery electrolytes and lithium ion battery.The lithium from
Sub- battery electrolyte is a kind of high voltage and resistant to elevated temperatures rate lithium ion battery electrolyte, has both taken into account high temperature storage and circulation
Performance requirement, while meet high current multiplying power discharging demand again.
One aspect of the present invention is related to a kind of lithium-ion battery electrolytes, comprising：
Lithium salts 11~17%；
Functional additive 3~11%, and the functional additive include positive pole protection additive, film for additive and
Low ESR additive；
Organic solvent 78~85%, and the organic solvent be selected from ethylene carbonate, propene carbonate, ethyl propionate,
One or more in propyl propionate, methyl ethyl carbonate, diethyl carbonate.
In above-mentioned lithium-ion battery electrolytes, the organic solvent is by ethylene carbonate, propene carbonate, propionic acid second
Ester and propyl propionate composition, or be made up of ethylene carbonate, propene carbonate, ethyl propionate, diethyl carbonate.
In above-mentioned lithium-ion battery electrolytes, the lithium salts is LiPF6、LiClO4、LiBF4、LiAsF6、Li
(CF3SO2)2N、Li(CF3CO2)2N、LiCF3SO3、Li(CF3SO2)2One or more in N.
In above-mentioned lithium-ion battery electrolytes, the lithium salts is LiPF6, its molar concentration is 1.1~1.4mol/L.
In above-mentioned lithium-ion battery electrolytes, positive pole protection additive be succinonitrile, adiponitrile, malononitrile,
One or more in glutaronitrile, its addition account for the 1~3% of electrolyte gross mass.
In above-mentioned lithium-ion battery electrolytes, the positive pole protection additive is succinonitrile and/or adiponitrile.
In above-mentioned lithium-ion battery electrolytes, the film for additive is PS, fluoro ethylene
One or more in alkene ester, vinylene carbonate, vinylethylene carbonate, its addition account for electrolyte gross mass 1~
9.5%.
In above-mentioned lithium-ion battery electrolytes, the Low ESR additive is selected from sulfuric acid vinyl ester, difluoro oxalate boron
One or more in sour lithium and difluorophosphate, its addition accounts for the 0.5~2% of electrolyte gross mass.
In above-mentioned lithium-ion battery electrolytes, the Low ESR additive is sulfuric acid vinyl ester.
Another aspect of the present invention is related to a kind of lithium ion battery, comprising above-mentioned lithium-ion battery electrolytes, and
Charge cutoff voltage is more than 4.2V and is less than or equal to 4.4V.
The lithium-ion battery electrolytes of the present invention are a kind of high voltage and resistant to elevated temperatures rate lithium ion battery electrolyte,
Meet high-voltage lithium ion batteries heavy-current discharge cycle performance, while also meet the requirement of the storage performance under hot conditions.
Brief description of the drawings
In order to illustrate more clearly of technical scheme, letter will be made to the required accompanying drawing used in embodiment below
Singly introduce, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as to the present invention
The restriction of protection domain.
Fig. 1 shows the circulation test result of the normal temperature 1C charging 5C electric discharges of the embodiment of the present invention and comparative example
Figure.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, rather than whole embodiments.Embodiments of the invention it is detailed
Description is not intended to limit the scope of claimed invention, but is merely representative of the selected embodiment of the present invention.Based on this
The embodiment of invention, the every other implementation that those skilled in the art are obtained on the premise of creative work is not made
Example, belongs to the scope of protection of the invention.It should be noted that the percentage referred in the application is mass percent.
The present invention provides a kind of lithium-ion battery electrolytes, is calculated in mass percent, comprising：
11~17% lithium salts, for example, 12%, 13%, 14%, 15% or 16% etc.；
3~11% functional additive, and the functional additive include positive pole protection additive, film for additive with
And Low ESR additive, the content of functional additive can be such as 4%, 5%, 6%, 7%, 8%, 9% or 10%；
78~85% organic solvent, and the organic solvent can be ethylene carbonate (EC), propene carbonate
(PC), the one or more in ethyl propionate (EP), propyl propionate (PP), methyl ethyl carbonate (EMC), diethyl carbonate (DEC),
The content of organic solvent can be such as 79%, 80%, 81%, 82%, 83% and 84%.
In above-mentioned lithium-ion battery electrolytes, the organic solvent is preferably by ethylene carbonate, propene carbonate, third
Acetoacetic ester and propyl propionate composition, for example, the mass ratio between them is preferably 30:(10~15):20:(35~40), or
It is made up of ethylene carbonate, propene carbonate, ethyl propionate, diethyl carbonate, for example, the mass ratio between them is preferably
30:(10~15):20:(35~40).
In above-mentioned lithium-ion battery electrolytes, the lithium salts is preferably LiPF6、LiClO4、LiBF4、LiAsF6、Li
(CF3SO2)2N、Li(CF3CO2)2N、LiCF3SO3、Li(CF3SO2)2One or more in N.
In above-mentioned lithium-ion battery electrolytes, the lithium salts is more preferably LiPF6, its molar concentration be 1.1~
1.4mol/L。
In above-mentioned lithium-ion battery electrolytes, positive pole protection additive is preferably succinonitrile, adiponitrile, the third two
One or more in nitrile, glutaronitrile, its addition account for the 1~3% of electrolyte gross mass.
In above-mentioned lithium-ion battery electrolytes, the positive pole protection additive is preferably succinonitrile and/or adiponitrile.
In above-mentioned lithium-ion battery electrolytes, the film for additive is preferably PS, fluoro carbon
One or more in vinyl acetate, vinylene carbonate, vinylethylene carbonate, its addition account for the 1 of electrolyte gross mass
~9.5%.
In above-mentioned lithium-ion battery electrolytes, the Low ESR additive is preferably sulfuric acid vinyl ester, difluoro oxalate
Lithium borate, difluorophosphate, its addition account for the 0.5~2% of electrolyte gross mass.
In above-mentioned lithium-ion battery electrolytes, the Low ESR additive more preferably sulfuric acid vinyl ester.
Another aspect of the present invention is related to a kind of lithium ion battery, comprising above-mentioned lithium-ion battery electrolytes, and
Charge cutoff voltage is more than 4.2V and is less than or equal to 4.4V.
With reference to specific embodiment, the present invention and its advantage are described in detail, but the protection model of the present invention
Enclose and be not limited to this.
Embodiment 1
1. prepared by electrolyte：
In moisture ＜ 5ppm inert gas environment, by ethylene carbonate, propene carbonate, ethyl propionate, propionic acid third
Ester by weight percentage 30:15:20:35 is well mixed.Then, lithium hexafluoro phosphate is added, lithium hexafluoro phosphate is in the electrolytic solution
Mass concentration is 14%.Then functional additive is added：As the adiponitrile (ADN) of positive pole protection additive, add as film forming
Add the 1,3- propane sultones (PS) and fluorinated ethylene carbonate (FEC) of agent.Wherein adiponitrile addition is to account for the total matter of electrolyte
The 1% of amount, PS addition are account for electrolyte gross mass 3%, and fluorinated ethylene carbonate addition is to account for electricity
Solve the 5% of liquid gross mass.The sulfuric acid vinyl ester (DTD) as Low ESR additive is eventually adding, addition is total to account for electrolyte
The 0.5% of quality.Electrolyte sample is obtained after stirring.
2. prepared by positive pole：
By cobalt acid lithium, CNT, carbon black, poly- two vinylidene (PVDF) in proportion 96:1:1.5:1.5 dissolve in N- methyl
In pyrrolidones (NMP), vacuum stirring is well mixed to be made slurry, and is evenly applied in 15 μm of aluminium foils, is toasted through 120 DEG C,
Positive plate is made after roll-in slitting.
3. prepared by negative pole：
By graphite, carbon black, carboxymethyl cellulose (CMC), butadiene-styrene rubber (SBR) in proportion 95:1.5:1.5:2 dissolve in distillation
In water, it is uniformly mixed and slurry is made, and be evenly applied in 8 μm of copper foils, through 100 DEG C of bakings, is made after roll-in slitting negative
Pole piece.
4. prepared by battery：
Above-mentioned positive plate, negative plate and 20 microns of thick polypropylene diaphragms are wound into rectangular lithium ion battery battery core, filled
Enter in cell aluminum-plastic membrane shell, after 85 DEG C of vacuum bakeout 8h, injected in glove box it is above-mentioned electro-hydraulic, after sealing through shaping, change
Into, pumping, partial volume process Soft Roll rectangular lithium ion battery is made.
Battery is tested：
(1) normal temperature multiplying power discharging is tested
By battery obtained above at 25 DEG C, with 1C constant-current constant-voltage chargings to 4.35V, cut-off current 0.05C, 10 are shelved
With 1C electric currents constant-current discharge to 3.0V after minute, discharge capacity C1 is recorded, this is 1C discharge datas.
Then again with 1C constant-current constant-voltage chargings to 4.35V, cut-off current 0.05C, with 5C electric current constant currents after shelving 10 minutes
3.0V is discharged to, records discharge capacity C2, this is 5C discharge datas.
Then again with 1C constant-current constant-voltage chargings to 4.35V, cut-off current 0.05C, with 10C electric current constant currents after shelving 10 minutes
3.0V is discharged to, records discharge capacity C3, this is 10C discharge datas.
5C multiplying powers percentage (%)=C2/C1,10C multiplying powers percentage (%)=C3/C1.Mean voltage holds for electric discharge 50%
Corresponding magnitude of voltage during amount.
(2) the lower 85 DEG C of 4 hours high temperature storage test of full electricity
By battery obtained above at 25 DEG C, with 1C constant-current constant-voltage chargings to 4.35V, cut-off current 0.05C, 10 are shelved
With 3.3C electric currents constant-current discharge to 3.0V, recording capacity C1 after minute.
Normal temperature shelf records internal resistance R1, thickness data T1 after 1 hour, battery is placed under 85 DEG C of environment and deposited 4 hours.So
Take out afterwards in normal temperature environment and stands test internal resistance R2, thickness T2 after cooling in 2 hours, and with 3.3C electric currents constant-current discharge to 3.0V,
Recording capacity C is charged.
After shelving 10 minutes, with 1C constant-current constant-voltage chargings to 4.35V, cut-off current 0.05C, with 3.3C after shelving 10 minutes
Electric current constant-current discharge is to 3.0V, recording capacity C3.
Again with 1C constant-current constant-voltage chargings to 4.35V, cut-off current 0.05C, put after shelving 10 minutes with 3.3C electric current constant currents
Electricity is to 3.0V, recording capacity C4.
Again with 1C constant-current constant-voltage chargings to 4.35V, cut-off current 0.05C, put after shelving 10 minutes with 3.3C electric current constant currents
Electricity is to 3.0V, recording capacity C5.
Maximum is recorded as C recoveries as capacity is recovered in the amount of trying to please C3, C4, C5.High temperature storing capacity conservation rate (%)
=C is charged/C1.High temperature storing capacity recovery rate (%)=C recoveries/C1.High temperature thickness swelling ratio (%)=(T2-T1)/T1.It is high
Warm internal resistance increase is than (%)=(R2-R1)/R1.
(3) normal temperature circulation is tested
By battery obtained above at 25 DEG C, with 1C constant-current constant-voltage chargings to 4.35V, cut-off current 0.05C, 10 are shelved
With 5C electric currents constant-current discharge to 3.0V after minute, shelve 10 minutes, then repeat 300 circulations of test work step above.
Embodiment 2
It is substantially same as Example 1, unlike ethylene carbonate in the solvent, propene carbonate, ethyl propionate,
Weight ratio between propyl propionate is 30:10:20:40, the dosage of organic solvent changes and phase according to the dosage of functional additive
It should increase and decrease, the additive and dosage are that adiponitrile addition is account for electrolyte gross mass 2%, and PS adds
Measure to account for the 2% of electrolyte gross mass, vinylene carbonate addition is account for electrolyte gross mass 2.5%, sulfuric acid vinyl ester
Addition is account for electrolyte gross mass 1%.
Embodiment 3
It is substantially same as Example 1, unlike ethylene carbonate in the solvent, propene carbonate, ethyl propionate,
Weight ratio between diethyl carbonate is 30:15:20:35, the dosage of organic solvent changed according to the dosage of functional additive and
Corresponding increase and decrease, the adiponitrile addition are account for electrolyte gross mass 2%, and PS addition is to account for electrolyte
The 2.5% of gross mass, fluorinated ethylene carbonate addition are account for electrolyte gross mass 4%, and sulfuric acid vinyl ester addition is to account for
The 1% of electrolyte gross mass.
Embodiment 4
It is substantially same as Example 1, unlike the lithium hexafluoro phosphate account for the 12.3% of electrolyte gross mass, it is organic
The dosage of solvent changes according to the dosage of functional additive and lithium salts and accordingly increased and decreased, and the additive and dosage add for adiponitrile
Dosage is account for electrolyte gross mass 2%, and PS addition is account for electrolyte gross mass 2%, carbonic acid Asia second
Alkene ester addition is account for electrolyte gross mass 2.5%, and difluorine oxalic acid boracic acid lithium addition is to account for electrolyte gross mass
1.7%.
Embodiment 5
It is substantially same as Example 1, unlike the lithium hexafluoro phosphate account for the 15.2% of electrolyte gross mass, it is organic
The dosage of solvent changes according to the dosage of functional additive and lithium salts and accordingly increased and decreased, and the additive and dosage add for succinonitrile
Dosage is account for electrolyte gross mass 2.0%, and PS addition is account for electrolyte gross mass 2.0%, carbonic acid
Vinylethylene addition is account for electrolyte gross mass 1.5%, and sulfuric acid vinyl ester addition is to account for electrolyte gross mass
1.5%.
Comparative example 1
It is substantially same as Example 1, unlike ethylene carbonate in the solvent, propene carbonate, ethyl propionate,
Weight ratio between propyl propionate is 30:10:20:40, the dosage of organic solvent changes and phase according to the dosage of functional additive
It should increase and decrease, the film for additive and dosage are that PS addition is account for electrolyte gross mass 2%, and carbonic acid is sub-
Vinyl acetate addition is account for electrolyte gross mass 1.3%.It is not added with Low ESR additive.
Comparative example 2
It is substantially same as Example 1, unlike the solvent ethylene carbonate, propene carbonate, methyl ethyl carbonate,
Dimethyl carbonate percentage by weight is 20:10:30:40, the dosage of organic solvent changes and phase according to the dosage of functional additive
It should increase and decrease, the additive and dosage are that adiponitrile addition is account for electrolyte gross mass 1.0%, and PS adds
Dosage is account for electrolyte gross mass 3%, and fluorinated ethylene carbonate addition is account for electrolyte gross mass 2%.
The normal temperature multiplying power discharging test data of table 1
The lower 85 DEG C of 4 hours high temperature storage test data of the full electricity of table 2
Table 1 is each embodiment normal temperature multiplying power discharging test data, and table 2 is the lower 85 DEG C of 4 hours high temperature storage test number of full electricity
According to Fig. 1 fills 5C for normal temperature 1C puts circulation test result figure.
In terms of the data of table 1, the discharge-rate of embodiment 1~5 and electric discharge mean voltage have very big lifting compared with contrast groups, wherein
10C mean voltages lift 50~60mV, 10C discharge-rates lifting 2.5%~3%, illustrate to the addition of Low ESR additive sulfuric acid
Vinyl acetate, difluorine oxalic acid boracic acid lithium etc. are advantageous to lift battery discharge multiplying power and discharge platform.
In terms of table 2, Fig. 1 data, two nitrile positive poles protection additive, PS, fluoro ethylene with the addition of
Alkene ester, vinylene carbonate, vinylethylene carbonate film for additive and dicyandiamide solution are advantageous to high-temperature storage performance and again
The lifting of rate cycle performance.Solvent, which introduces dimethyl carbonate low boiling point solvent, in comparative example 2 causes battery high-temperature inflatable occur,
Electrical properties in high temperatures is deteriorated.
The present invention meets high-voltage battery high temperature storage by selecting suitable dicyandiamide solution, and matching function additive
And multiplying power discharging circulation requires.
CN bases in positive pole protection additive succinonitrile, adiponitrile, malononitrile, especially glutaronitrile, succinonitrile and adiponitrile
Group and the cobalt ions of high oxidation state are complexed, and are balanced the electric charge of positive electrode surface, can effectively be suppressed the dissolution and electrolysis of cobalt
Oxidation Decomposition of the liquid under high potential, improves high temperature storage under the high voltage of battery.
Film for additive 1,3- propane sultones, fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate energy
It is enough that well stable SEI films are formed in electrode surface, further reaction of the electrolyte in electrode surface is avoided, lifts the height of battery
Gentle storage and cycle performance.
Low ESR additive sulfur vinyl acetate can generate the good organic sulfonate of ionic conductivity in negative terminal surface, reduce
The interface impedance of pole piece.Difluorine oxalic acid boracic acid lithium, difluorophosphate have larger anionic group, easily dissociation and solvent
Change, and become electrical conductivity and be beneficial to battery high current multiplying power discharging greatly.
To sum up, high pressure-temperature rate electrolyte of the present invention had both met high temperature under charging voltage 4.35V high voltages and deposited
It is required that meeting heavy-current discharge and multiplying power discharging circulation demand again, good balance has been obtained between three.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements done etc., should be included within the scope of protection of the invention with principle.
Claims (10)
- A kind of 1. lithium-ion battery electrolytes, it is characterised in that it is calculated in mass percent, comprising：Lithium salts 11~17%；Functional additive 3~11%, and the functional additive includes positive pole protection additive, film for additive and low-resistance Anti- additive；Organic solvent 78~85%, and the organic solvent is selected from ethylene carbonate, propene carbonate, ethyl propionate, propionic acid One or more in propyl ester, methyl ethyl carbonate, diethyl carbonate.
- 2. lithium-ion battery electrolytes according to claim 1, it is characterised in that the organic solvent is by ethylene carbonate Ester, propene carbonate, ethyl propionate and propyl propionate composition, or by ethylene carbonate, propene carbonate, ethyl propionate, carbon Diethyl phthalate forms.
- 3. lithium-ion battery electrolytes according to claim 1, it is characterised in that the lithium salts is LiPF6、LiClO4、 LiBF4、LiAsF6、Li(CF3SO2)2N、Li(CF3CO2)2N、LiCF3SO3、Li(CF3SO2)2One or more in N.
- 4. lithium-ion battery electrolytes according to claim 3, it is characterised in that the lithium salts is LiPF6, its mole dense Spend for 1.1~1.4mol/L.
- 5. lithium-ion battery electrolytes according to claim 1, it is characterised in that the positive pole protection additive is fourth two One or more in nitrile, adiponitrile, malononitrile, glutaronitrile, its addition account for the 1~3% of electrolyte gross mass.
- 6. lithium-ion battery electrolytes according to claim 5, it is characterised in that the positive pole protection additive is fourth two Nitrile and/or adiponitrile.
- 7. lithium-ion battery electrolytes according to claim 1, it is characterised in that the film for additive is 1,3- propane One or more in sultone, fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, its addition account for electricity Solve the 1~9.5% of liquid gross mass.
- 8. lithium-ion battery electrolytes according to claim 1, the Low ESR additive is selected from sulfuric acid vinyl ester, difluoro One or more in Lithium bis (oxalate) borate and difluorophosphate, its addition accounts for the 0.5~2% of electrolyte gross mass.
- 9. lithium-ion battery electrolytes according to claim 8, the Low ESR additive is sulfuric acid vinyl ester.
- 10. a kind of lithium ion battery, it is characterised in that include the lithium ion battery electrolysis any one of claim 1-9 Liquid, and charge cutoff voltage is more than 4.2V and is less than or equal to 4.4V.
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Application publication date: 20171222 |