CN103887557B - A kind of nonaqueous electrolytic solution and lithium ion battery - Google Patents
A kind of nonaqueous electrolytic solution and lithium ion battery Download PDFInfo
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- CN103887557B CN103887557B CN201210559348.5A CN201210559348A CN103887557B CN 103887557 B CN103887557 B CN 103887557B CN 201210559348 A CN201210559348 A CN 201210559348A CN 103887557 B CN103887557 B CN 103887557B
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- electrolytic solution
- nonaqueous electrolytic
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 39
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical group O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 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 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- HJTVQHVGMGKONQ-LUZURFALSA-N Curcumin II Natural products C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=CC(O)=CC=2)=C1 HJTVQHVGMGKONQ-LUZURFALSA-N 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002530 phenolic antioxidant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 206010016766 flatulence Diseases 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 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 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 hexafluoroarsenate lithium Chemical compound 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 101000608720 Helianthus annuus 10 kDa late embryogenesis abundant protein Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000007774 positive electrode material 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
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- 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 a kind of nonaqueous electrolytic solution, comprise lithium salts, nonaqueous solvents and antioxidant, described antioxidant has structure shown in formula 1 or formula 2, wherein, and R1、R2Be the alkyl that H or carbon number are 1-5 independently of one another, R3 is that carbon number is the alkyl of 1-5. The present invention also provides a kind of lithium ion battery that adopts this nonaqueous electrolytic solution. Adopt the lithium ion battery of this nonaqueous electrolytic solution to there is good high-temperature storage performance and cycle performance simultaneously.
Description
Technical field
The invention belongs to lithium ion battery field, the lithium that relates in particular to a kind of nonaqueous electrolytic solution and contain this nonaqueous electrolytic solutionIon battery.
Background technology
Lithium ion battery is with the advantage such as its high voltage, high power capacity, low consumption, memory-less effect, nuisanceless and volume be littleFrom numerous battery varieties, show one's talent, be widely used in mobile phone, listen at any time, numerous electronic products such as PDA, NotebookIn.
In prior art, disclose a kind of electrolyte containing antioxidant, this antioxidant has structure shown in formula 3, in this antioxidantContaining a phenyl ring, be connected with a hydroxyl on phenyl ring, is single phenolic antioxidant. This antioxidant can reduce battery in hot environmentThe too large problem of lower expansion, but its addition is too much unsuitable, otherwise can make other performances of battery as bad in the generation such as capacity, circulationChange, its addition is generally 0.01-5000ppm at present.
Prior art also discloses a kind of electrolyte containing antioxidant, and this antioxidant has structure shown in formula 4 or formula 5, and this is anti-Oxygen agent contains a phenyl ring, is connected with two hydroxyls on phenyl ring, is diphenols antioxidant. The addition of this antioxidant generally exists0.01-2%, this can cause other performance degradation of battery while being more because of its addition, so also need to add other to add simultaneouslyAdding agent improves.
Formula 3
Formula 4
Formula 5.
But the addition of antioxidant is very few in electrolyte, its to battery high-temperature expand improvement again too a little less than. Therefore seek onePlant suitable antioxidant high-temperature expansion is played to larger improvement simultaneously under the prerequisite that ensures other performance that does not reduce battery,Become the task of top priority.
Summary of the invention
The invention solves the expansion to battery high-temperature of antioxidant in the nonaqueous electrolytic solution existing in prior art improvesWeak, technical problem that simultaneously also can deteriorated other performance of battery.
The invention provides a kind of nonaqueous electrolytic solution, comprise lithium salts, nonaqueous solvents and antioxidant, described antioxidant has formula1 or formula 2 shown in structure:
Formula 1
Formula 2
Wherein, R1、R2Be the alkyl that H or carbon number are 1-5 independently of one another, R3 is that carbon number is the alkyl of 1-5.
The present invention also provides a kind of lithium ion battery, and comprise housing and be contained in battery core, the nonaqueous electrolytic solution in housing,Battery core comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, described nonaqueous electrolytic solution is provided by the inventionNonaqueous electrolytic solution.
In nonaqueous electrolytic solution of the present invention, described antioxidant is structure shown in formula 1 or formula 2, and it contains two electron-withdrawing groupsGroup's (being phenyl ring), entirety is symmetrical structure, therefore can be influenced each other, attract each other or be supported by two phenyl ring that are symmetrical structureDisappear, form more orderly electron cloud. Nonaqueous electrolytic solution provided by the invention not only has and can form tunicle and have at electrode surfaceBe beneficial to the advantage that suppresses high-temperature storage flatulence, and very little on cycle performance of battery impact; Addition can be many, and needn'tAdd other auxiliary additive. Adopt the lithium ion battery of this nonaqueous electrolytic solution, there is good high-temperature storage performance and followRing performance.
Detailed description of the invention
The invention provides a kind of nonaqueous electrolytic solution, comprise lithium salts, nonaqueous solvents and antioxidant, described antioxidant has formula1 or formula 2 shown in structure:
Formula 1
Formula 2
Wherein, R1、R2Be the alkyl that H or carbon number are 1-5 independently of one another, R3 is that carbon number is the alkyl of 1-5.
In prior art, adopt single phenolic antioxidant, it adds membership makes the cycle performance of battery understand variation, has a strong impact on electricityThe service life in pond. The present inventor finds in the structure due to single phenolic antioxidant, to only have a phenyl ring by analysisAs electron withdraw group, polarity is very strong; Although this antioxidant can form tunicle and be conducive to suppress high temperature storage at electrode surfaceDeposit flatulence, but increased to a great extent the internal resistance of cell, sacrificial electrode activity, has sacrificed battery life simultaneously; Cause this list phenolThe addition of kind antioxidant in electrolyte is considerably less, and it is not correspondingly obvious especially to high-temperature storage improvement effect;Or other auxiliary additive that adds again some can effectively suppress single phenolic antioxidant inferior position, but can increase so again electricitySeparate liquid cost, and preparation complexity increases.
Therefore, in the present invention, make a concrete analysis of by the mechanism of action to antioxidant, thereby the molecule of antioxidant is enteredRow improves, and finds: adopt the antioxidant with structure shown in formula 1 or formula 2 provided by the invention, contain two and inhale electricity in its structureSubbase group's (being phenyl ring), and entirety is symmetrical structure, influenced each other, attracts each other or supported by two phenyl ring that are symmetrical structureDisappear, form more orderly electron cloud, thereby can not increase the internal resistance of cell. Therefore, nonaqueous electrolytic solution provided by the invention not only hasCan form tunicle and be conducive to suppress the advantage of high-temperature storage flatulence at electrode surface, and cycle performance of battery is affected veryLittle. Meanwhile, the antioxidant adopting due to the present invention can not produce considerable influence to the internal resistance of cell, can not reduce circulating batteryCan, therefore its addition can be many, thereby further improve the high-temperature storage security of battery, and unnecessary interpolation otherAuxiliary additive. Adopt the lithium ion battery of this nonaqueous electrolytic solution, there is good high-temperature storage performance and cycle performance.
Under preferable case, R1For the tert-butyl group-C (CH3)3，R2For methyl-CH3, R3 is methylene-CH2-. Accordingly, described inAntioxidant can be the compound shown in formula 6 or formula 7, but is not limited to this.
Formula 6
Formula 7.
More preferably in situation, described antioxidant is selected the compound shown in formula 6, and 2,2 '-di-2-ethylhexylphosphine oxide-(4-methyl-6Tert-butyl phenol), be called for short antioxidant 2246.
In nonaqueous electrolytic solution of the present invention, the consumption of the antioxidant of employing can be in the usual range of this area antioxidant;Meanwhile, because antioxidant of the present invention can not reduce the cycle performance of battery, therefore its content can be higher, but can notToo high, otherwise can reduce lithium salt content in electrolyte, cause battery capacity to reduce. Under preferable case, with the non-water of 100 weight portionsElectrolyte is benchmark, and the content of antioxidant is 0.1-5 weight portion. More preferably in situation, taking the nonaqueous electrolytic solution of 100 weight portions asBenchmark, the content of antioxidant is 2-3 weight portion. More preferably in scope, can ensure to adopt the lithium ion of this nonaqueous electrolytic solution at thisBattery has good high-temperature storage performance and cycle performance, ensures battery capacity simultaneously.
Under preferable case, in nonaqueous electrolytic solution of the present invention, the concentration of lithium salts is 0.5-1.5mol/L. Described lithium salts is thisThe various lithium salts that those skilled in the art commonly use, for example, can be selected from lithium perchlorate (LiClO4), lithium hexafluoro phosphate (LiPF6), tetrafluoroLithium borate (LiBF4), hexafluoroarsenate lithium (LiAsF6), in biethyl diacid lithium borate (LiBOB) any one or multiple. PreferablyIn situation, the present invention adopts LiPF6As main lithium salts, its concentration is 0.5-1.5mol/L, more preferably 0.8-1.3mol/L。
In the present invention, the various nonaqueous solvents that described nonaqueous solvents adopts those skilled in the art to commonly use, for example canBe selected from least one in carboxylic acid esters solvent, carbonates solvent, sulfuric acid ester solvent, nitrile solvents, ketones solvent. PreferablyIn situation, described nonaqueous solvents is selected from vinyl carbonate (EC), propylene carbonate (PC), ethyl-methyl carbonic ester (EMC), carbonDiethyl phthalate (DEC), dimethyl carbonate, ethyl acetate, ethyl butyrate, acetonitrile, valeronitrile, succinonitrile, glutaronitrile a kind of orMultiple, but be not limited to this.
As a kind of preferred embodiment of the present invention, in nonaqueous electrolytic solution provided by the invention, also can add other interpolationAgent, to give other performance of battery. Its for example, described additive can be selected from vinylene carbonate (VC), fluorinated ethylene carbonic acidOne or more in ester (FEC), propane sultone (PS), vinyl acetate (VA), glutaronitrile (GLN).
The preparation method of nonaqueous electrolytic solution provided by the invention is those skilled in the art's common method, by each groupDivide (comprising lithium salts, nonaqueous solvents and antioxidant, contain or do not contain other additive) to mix, the present invention does not have special limitFixed.
The present invention also provides a kind of lithium ion battery, and comprise housing and be contained in battery core, the nonaqueous electrolytic solution in housing,Battery core comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, described nonaqueous electrolytic solution is provided by the inventionNonaqueous electrolytic solution.
Because the preparation technology of negative plate, positive plate, barrier film is technology known in the field, and the assembling of battery is alsoTechnology known in the field, just repeats no more at this.
Below in conjunction with embodiment to nonaqueous electrolytic solution of the present invention and the lithium ion battery that contains this nonaqueous electrolytic solution do intoOne step explanation. In embodiment and comparative example, adopt all and be commercially available.
Embodiment 1
(1) preparation of nonaqueous electrolytic solution:
Using EC, DEC, EMC in mass ratio the ratio of 40:50:10 mix as nonaqueous solvents, add 0.9mol/L hexafluoro phosphorusAcid lithium, as lithium salts, adds and accounts for the antioxidant 2246 (compound shown in formula 6) of electrolyte gross mass 1%, then adds that to account for electrolyte totalThe additive VC of quality 1.5%, obtains the nonaqueous electrolytic solution S1 of the present embodiment.
(2) preparation of lithium ion battery:
Using lithium nickel cobalt alumina and cobalt acid lithium in mass ratio the ratio of 40:60 mix as positive electrode active materials, with natural stoneChina ink and Delanium in mass ratio the ratio of 85:15 as negative active core-shell material, taking tri-layers of barrier film of PP/PE/PP as ion-exchangeFilm, adopts the nonaqueous electrolytic solution S1 of the present embodiment, and makes by passing method in the industry the flexible-packed battery that model is SL454261,Be designated as S10.
Embodiment 2
Adopt the step identical with embodiment 1 to prepare nonaqueous electrolytic solution S2 and battery S20, difference is:
In step (1), the consumption of antioxidant 2246 accounts for 2.5% of electrolyte gross mass.
Embodiment 3
Adopt the step identical with embodiment 1 to prepare nonaqueous electrolytic solution S3 and battery S30, difference is:
In step (1), the consumption of antioxidant 2246 accounts for 5% of electrolyte gross mass.
Embodiment 4
Adopt the step identical with embodiment 1 to prepare nonaqueous electrolytic solution S4 and battery S40, difference is:
In step (1), the compound shown in employing formula 7 is as the antioxidant of the present embodiment, the antioxygen in alternate embodiment 1Agent 2246.
Embodiment 5
Adopt the step identical with embodiment 1 to prepare nonaqueous electrolytic solution S5 and battery S50, difference is:
In step (1), in electrolyte, do not add additive VC.
Comparative example 1
Adopt the step identical with embodiment 1 to prepare nonaqueous electrolytic solution DS1 and battery DS10, difference is:
In step (1), adopt antioxidant BHT (being BHT) as the antioxidant of this comparative example, to replaceFor the antioxidant 2246 in embodiment 1.
Comparative example 2
Adopt the step identical with comparative example 1 to prepare nonaqueous electrolytic solution DS2 and battery DS20, difference is:
In step (1), the consumption of antioxidant BHT accounts for 2% of electrolyte gross mass.
Comparative example 3
Adopt the step identical with embodiment 1 to prepare nonaqueous electrolytic solution DS3 and battery DS30, difference is:
In step (1), adopt antioxidant TBHQ(TBHQ) as the antioxidant of this comparative example, substitute and implementAntioxidant 2246 in example 1.
Performance test:
(1) battery high-temperature stores test
Each battery sample S10-S50 and DS10-DS30 are charged to 4.2V in the mode of constant current constant voltage, electric current at normal temperaturesBe set to 1C, charging cut-off current 0.05C; Test battery thickness, then puts into after the high temperature roaster of 85 DEG C stores 5 hours and getsGo out, under normal temperature, shelve after 2 hours test battery thickness again, record the varied in thickness of battery before and after high-temperature storage, test resultAverage, single result computational methods are that after storing, thickness deducts the difference that stores front thickness, divided by thickness before storing, then take advantage ofWith 100%.
(2) circulating battery test
By each battery sample S10-S50 and DS10-DS30 at normal temperatures with 0.2C constant-current constant-voltage charging to 4.2V, cut-off electricityStream 0.05C; Discharge into 3.0V with 0.2C again, be designated as 1 circulation. Taking the capacity of emitting in circulating for the first time as 100%, followEncircle 300-400 time, record the variation of each cyclic discharge capacity.
Test result is as shown in table 1.
Table 1
。
Test result by table 1 can find out, battery sample prepared by embodiment of the present invention 1-5 has good high temperature storageSustainability energy and cycle performance, before and after high-temperature storage, thickness change is lower than 6%, and it is surplus that cycle-index still has higher capacity for 400 timesRemaining rate (capacity surplus ratio is more than 80%).
Claims (8)
1. a nonaqueous electrolytic solution, comprises lithium salts, nonaqueous solvents and antioxidant, it is characterized in that, with the non-water power of 100 weight portionsSolution liquid is benchmark, and the content of described antioxidant is 1-3 weight portion, and described antioxidant has structure shown in formula 1 or formula 2:
Formula 1
Formula 2
Wherein, R1、R2Be the alkyl that H or carbon number are 1-5 independently of one another, R3For the carbon number alkyl that is 1-5.
2. nonaqueous electrolytic solution according to claim 1, is characterized in that, R1For the tert-butyl group-C (CH3)3，R2For methyl-CH3，R3For methylene-CH2-。
3. nonaqueous electrolytic solution according to claim 1, is characterized in that, in described nonaqueous electrolytic solution, the concentration of lithium salts is0.5-1.5mol/L。
4. according to the nonaqueous electrolytic solution described in claim 1 or 3, it is characterized in that, lithium salts is selected from LiClO4、LiPF6、LiBF4、LiAsF6, any one or a few in LiBOB.
5. nonaqueous electrolytic solution according to claim 1, is characterized in that, described nonaqueous solvents be selected from carboxylic acid esters solvent,At least one in carbonates solvent, sulfuric acid ester solvent, nitrile solvents, ketones solvent.
6. nonaqueous electrolytic solution according to claim 5, is characterized in that, described nonaqueous solvents be selected from EC, PC, EMC,One or more of DEC, DMC, ethyl acetate, ethyl butyrate, acetonitrile, valeronitrile, succinonitrile, glutaronitrile.
7. nonaqueous electrolytic solution according to claim 1, is characterized in that, also contains additive in described nonaqueous electrolytic solution,Described additive is selected from vinylene carbonate, fluorinated ethylene carbonic ester, propane sultone, vinyl acetate, glutaronitrileOne or more.
8. a lithium ion battery, comprises housing and is contained in battery core, the nonaqueous electrolytic solution in housing, battery core comprises positive pole, negativeThe utmost point and the barrier film between positive pole and negative pole, is characterized in that, described nonaqueous electrolytic solution is described in claim 1-7 any oneNonaqueous electrolytic solution.
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| JP4374661B2 (en) * | 1999-06-30 | 2009-12-02 | パナソニック株式会社 | Non-aqueous electrolyte secondary battery |
| JP4407237B2 (en) * | 2002-12-24 | 2010-02-03 | 三菱化学株式会社 | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same |
| JP2005259592A (en) * | 2004-03-12 | 2005-09-22 | Sanyo Electric Co Ltd | Nonaqueous electrolytic solution for secondary battery, and nonaqueous electrolytic solution secondary battery |
| JP2011154987A (en) * | 2009-12-29 | 2011-08-11 | Sony Corp | Nonaqueous electrolyte and nonaqueous electrolyte battery |
| KR101565533B1 (en) * | 2011-03-15 | 2015-11-03 | 주식회사 엘지화학 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same |
| CN102263292B (en) * | 2011-06-24 | 2014-05-14 | 九江天赐高新材料有限公司 | Non-aqueous electrolytic solution used for lithium secondary batteries |
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