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CN102306833A - Flame retardant type non-aqueous electrolyte solution and battery thereof - Google Patents

Flame retardant type non-aqueous electrolyte solution and battery thereof Download PDF

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CN102306833A
CN102306833A CN201110235884A CN201110235884A CN102306833A CN 102306833 A CN102306833 A CN 102306833A CN 201110235884 A CN201110235884 A CN 201110235884A CN 201110235884 A CN201110235884 A CN 201110235884A CN 102306833 A CN102306833 A CN 102306833A
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electrolyte
carbonate
flame retardant
battery
flame
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占孝云
石桥
毛玉华
孙先保
王希敏
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Shenzhen Capchem Technology Co Ltd
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Shenzhen Capchem Technology Co Ltd
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Abstract

本发明涉及一种有机组合物，特别是一种阻燃型非水电解液及其制成的锂离子电池。这种阻燃型非水电解液，其包括电解质盐、非水溶剂、阻燃剂以及表面活性剂，所述非水溶剂包括环状碳酸酯和/或环状羧酸酯；所述阻燃剂包括氟醚类有机物；所述表面活性剂包括氟碳表面活性剂，所述阻燃剂的百分含量为10～50％，所述表面活性剂的百分含量为0.001％～2％。该电解液能大大提高锂离子电池的安全性能；同时对锂离子电池的电化学性能如循环性能，高温保存性能有明显改善。

Figure 201110235884

The invention relates to an organic composition, in particular to a flame-retardant non-aqueous electrolyte and a lithium ion battery made thereof. This flame retardant non-aqueous electrolytic solution includes electrolyte salt, non-aqueous solvent, flame retardant and surfactant, and the non-aqueous solvent includes cyclic carbonate and/or cyclic carboxylic acid ester; the flame retardant The agent includes fluoroether organic matter; the surfactant includes fluorocarbon surfactant, the percentage of the flame retardant is 10-50%, and the percentage of the surfactant is 0.001%-2%. The electrolyte can greatly improve the safety performance of the lithium-ion battery; meanwhile, the electrochemical performance of the lithium-ion battery, such as cycle performance and high-temperature storage performance, can be significantly improved.

Figure 201110235884

Description

A kind of flame retardant type nonaqueous electrolytic solution and battery thereof
Technical field
The present invention relates to a kind of organic composite, particularly a kind of flame retardant type nonaqueous electrolytic solution and the lithium ion battery of processing thereof.
Background technology
Lithium ion battery is the most competitive battery of a new generation, is called as " the environmental protection energy ", is the one preferred technique that solves contemporary problem of environmental pollution and energy problem.In recent years, lithium ion battery has been obtained immense success in the high-energy battery field, emerge but the consumer still expects the higher battery of combination property, and this depends on the research and development to new electrode material and electrolyte system.The lithium ion battery electrolyte system is the essential critical material of lithium ion battery as the lithium ion battery important component part, and its performance quality is greatly to restrict to the development of lithium ion battery.At present the electrolyte of lithium ion battery is made up of inflammable organic solvent and lithium salts, when lithium rechargeable battery is is excessively discharging and recharging, under short circuit and electric current works long hours greatly the situation; Emit a large amount of heat, these heats cause the battery system internal temperature too high, become the potential safety hazard of inflammable electrolyte; Possibly cause calamitous thermal runaway; Even battery explosion [Zheng Honghe. lithium ion battery electrolyte [M]. Beijing: Chemical Industry Press, 2006,134.].Therefore, safety issue has become the important prerequisite of lithium ion battery market innovation, particularly the fail safe of battery has been proposed in the application in the power lithium-ion battery field of electric automobile (EV) and hybrid vehicle (HEV) higher, the requirement of renewal.
Colleges and universities and enterprise for being engaged in the electrolyte research and development and producing invest and develop safer lithium ion battery electrolyte energetically, and the application that enlarges lithium ion battery is significant, and its market prospects are also boundless.Wherein flame retardant type electrolyte is to solve the most economical effective measures of lithium ion battery security at present, especially receives the attention of industrial circle.The flame retardant type of industry exploitation at present electrolyte mainly contains two technology paths.Attempt adopting higher boiling point on the one hand, the organic solvent of high-flash replaces low boiling, and low-flash linear carbonates kind solvent improves the security performance of electrolyte with this, and has obtained certain progress.On the other hand through adding phosphorus flame retardant; Halogenated flame retardant; Composite flame-retardant agent and other BACN can make inflammable organic electrolyte become difficult combustion or non-flammable electrolyte in conventional electrolysis liquid, reduce battery heat release value and battery self-heating rate; Increase the thermal stability of electrolyte self, thereby avoid burning or the blast of battery under overheated condition.
The blast means that prevent as electrolyte; Japanese patent laid-open 11-283669 communique; Japanese patent laid-open 11-233141 communique; Japanese patent laid-open 2002-280061 communique and japanese patent laid-open 09-293533 communique have proposed in electrolyte, to cooperate fluoroalkane, phosphate, and phosphides etc. are as the motion of additive.But in adding the system of fluoroalkane and since fluoroalkane self with mix hardly as the necessary carbonates of bath composition, so can separate by genetic horizon, battery performance is worsened.Kang Xu is in its summary (Chemical Reviews, 2004,104 (10); 4400-4405.) in summarized and adding phosphate; In the electrolyte system of phosphide, though suppressed the flammability of electrolyte, because viscosity increased; Conductivity descends, and causes that easily the battery performance that is produced by charge and discharge cycles worsens.Playing under the fire-retardant condition, reducing the chemical property (for example cycle performance and initial capacity) of battery to a certain extent.
In order not reduce the performance as electrolyte, and improve its anti-flammability, Daikin Co., Ltd. is at Chinese patents CN101490893A, and CN101584075A has proposed to add the scheme of fluorine-containing ether.But for lower boiling fluorine ether, intermiscibility general and other solvent is low, and low to the dissolubility of electrolytic salt, and then reduces the performance of battery.Also be mentioned among the patent CN101584075A and contain the relatively all surfactant of solvent below 5%, but the surfactant of its use is limited to fluorine-containing carboxylate (RfCOO -M +) and sulfonic fluoropolymer salt (RfSO 3 -M +), electrolyte property still has the leeway of further optimization and improvement.
In the application aspect the lithium ion battery, many patent reports have been arranged about fluorocarbon surfactant.At Chinese patents CN1333580A a kind of non-aqueous electrochemical device is disclosed like Matsushita Electric Ind. Co., Ltd.; Electrolyte wherein comprises the fluorine-containing surfactant as additive; Improved between nonaqueous electrolytic solution and the electrode wetability and in the ions diffusion property at this interface, obtain the good lithium rechargeable battery of charge-discharge characteristic and cycle life.Chinese patent CN101777668A discloses a kind of lithium manganate battery and has used electrolyte; This electrolyte adopts the lithium manganate battery of this electrolyte to have good cycle life and high-temperature behavior through adding new type high temperature additive unsaturated sulfonic acid lactone and fluorocarbon surfactant, making.Chinese patent CN101667662A discloses a kind of electrolyte of lithium-ion secondary battery that contains fluorocarbon surfactant; This surfactant can reduce the surface tension of liquid lithium ion secondary cell electrolyte; Optimize the wetting property of electrolyte and positive and negative pole material and barrier film, optimize the chemical property of integral battery door.Above-mentioned all technical schemes effectively do not solve the inflammability problem of lithium ion battery.
Summary of the invention
This is in order to solve the correlation technique problem that above-mentioned electrolyte exists.Providing a kind of has fire-retardant even the flame-retardant lithium ion battery electrolyte of combustion function not fully; And this electrolyte can make lithium ion battery when having high security, obtain excellent electrochemical properties, comprises good cycle performance and high-temperature storage performance.
This flame retardant type nonaqueous electrolytic solution, it comprises electrolytic salt, nonaqueous solvents, fire retardant and surfactant, wherein, said nonaqueous solvents comprises cyclic carbonate and/or cyclic carboxylic esters; Said fire retardant comprises that structure is R F1-O-R F2Fluorine ethers organic substance, R wherein F1Be that carbon number is 3～4 the fluoroalkyl that contains, R F2Be that carbon number is 2～5 the fluoroalkyl that contains; Said surfactant comprises that structure is R F3X (CH 2CH 2O) nR 1Or R F3X (CHCH 3CH 2O) nR 1Fluorocarbon surfactant, R wherein F3Be carbon number be 2～18 contain fluoroalkyl (perfluoroalkyl or the substituted alkyl of part fluorine), X be oxygen (O-), sulphur (S-), amine oxide ( +NO --), acid amides (CONH-) or sulfonamide (SO 2N-), R 1Be that hydrogen atom or carbon number are 1～4 alkyl, n=1～25.
Preferably, the quality percentage composition of said fire retardant is 10～50%, and is more excellent, and its content is 20%～40%.
Preferably, the quality percentage composition of said surfactant is 0.001%～2%, and is more excellent, and its content is 0.01%～1.5%.
Preferably, said cyclic carbonate comprises a kind of in ethylene carbonate, propene carbonate, butylene or the halogenated ethylene carbonate at least.
Preferably, said cyclic carboxylic esters comprises a kind of in gamma-butyrolacton, gamma-valerolactone, fluoro gamma-butyrolacton, two fluoro gamma-butyrolactons, chloro gamma-butyrolacton, dichloro-gamma-butyrolacton, bromo gamma-butyrolacton, dibrominated gamma-butyrolacton, nitro gamma-butyrolacton, cyanic acid gamma-butyrolacton or the α-acetyl group-gamma-butyrolacton at least.
Preferably, said nonaqueous solvents also comprises the linear carbonate and/or the chain carboxylate of mass percent＜30%.
Further, said linear carbonate comprises a kind of in dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate or the dipropyl carbonate at least.
Further, said chain carboxylate comprises a kind of in methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate or the ethyl butyrate at least.
Preferably, said electrolytic salt comprises LiPF at least 6, LiBF 4, LiClO 4, LiBOB, LiODFB, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2Or LiN (SO 2F) 2In a kind of, and its content is counted 0.6～2mol/L by lithium ion.
Preferably, said electrolyte also comprises vinylene carbonate, fluorinated ethylene carbonate, vinylethylene carbonate or 1 at least, a kind of additive in the 3-propane sultone, and the mass percent of every kind of additive in electrolyte is 0.1～10%.
Preferably, said fire retardant comprises that also the quality percentage composition is the fluoro phosphoric acid ester fire retardant below 15%.
Another object of the present invention also provides a kind of lithium ion battery, and its electrolyte is above-mentioned flame retardant type nonaqueous electrolytic solution.This battery just have a lithium salts active material that contains transition metal oxide, this lithium salts comprises LiCoO 2, LiMn 2O 4, LiNi 1-x-yCo xMn yO 2, LiNi 1-xCo xO 2Or LiFePO 4In one or more, 0＜x＜1,0＜y＜1 wherein; Negative pole has active material graphite or contains alloy material or the lithium titanate of Si or Sn.
This technical scheme compared with prior art has following beneficial effect:
Through in lithium ion battery, using flame retardant type nonaqueous electrolytic solution of the present invention, can improve the security performance of lithium ion battery greatly; To the chemical property such as the cycle performance of lithium ion battery, the high temperature retention has clear improvement simultaneously.In depth discover and use the electrolyte of flame retardant type nonaqueous electrolytic solution of the present invention, have following four aspect advantages than routine:
1. utilize the dispersive property of nonionic fluorocarbon surfactant, help improving the intermiscibility of low boiling fluorine ether and other solvent fluorine ether.
2. nonionic fluorocarbon surfactant and fluorine ether itself contain the ignition-proof element fluorine, and its flash-point is high, and difficult combustion is added in the electrolyte, make inflammable organic electrolyte become difficult combustion or non-flammable electrolyte, to fire-retardant obvious effects are arranged.
3. the nonionic fluorocarbon surfactant is effective to the wettability height of solvent; So can improve between nonaqueous electrolytic solution and the electrode wetability and in the ions diffusion property at this interface; Under the prerequisite of guaranteeing the difficult combustion of electrolyte or not firing, has good battery behavior simultaneously.
4. fluorine ether is used as the reactivity that solvent has reduced electrolyte and electrode, has suppressed the heat production of electrode interface, becomes effective guarantee of further raising battery security, is used for its security performance of lithium ion battery and improves greatly.Therefore, through the technical scheme of interpolation fluorine ether and the coupling of nonionic fluorocarbon surfactant, and obtain anti-flammability and the double excellent electrolyte for lithium secondary batteries of battery behavior (cycle performance, high-temperature storage performance).
Description of drawings
Fig. 1 is the embodiment of the invention 5 and Comparative Examples 1 (benchmark appearance) the normal temperature 150 all discharge capacity curve charts that circulate.
Fig. 2 is the capability retention figure in the embodiment of the invention 5 and 150 weeks of Comparative Examples 1 normal temperature circulation.
Specific embodiment
The embodiments described below only are a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
One. the preparation method of embodiment electrolyte
(H in the glove box of applying argon gas 2O＜10ppm), with cyclic carbonate, cyclic carboxylic esters, wire fluorine ether, lithium salts, the electrolyte quality ratio that film for additive and fluorocarbon surfactant are listed by each embodiment of table 1 and Comparative Examples is prepared.Above-mentioned each raw material is added successively, stir, promptly obtain lithium-ion battery electrolytes of the present invention, be used for flammable performance test and battery performance test.
Two. the manufacture method of embodiment lithium ion battery
Nonaqueous electrolytic solution secondary battery of the present invention is by above-mentioned nonaqueous electrolytic solution, and negative pole constitutes with anodal.
Constituting anodal active material can be LiCoO 2, LiMn 2O 4, LiNi 1-x-yCo xMn yO 2(0＜x＜1,0＜y＜1), LiNi 1-xCo xO 2(0＜x＜1), LiFePO 4Deng.
The active material that constitutes negative pole can be graphite, contain alloy material or the lithium titanate of Si or Sn etc.
With LiCoO 2, conductive agent acetylene black and Kynoar mix by 8: 1: 1 weight ratio, add 1-Methyl-2-Pyrrolidone subsequently and form slurry, then it are coated on the aluminium foil, and dry afterwards and mold pressing forms negative electrode.
With native graphite, Kynoar mixes by 9: 1 weight ratio, adds 1-Methyl-2-Pyrrolidone subsequently and forms slurry, then it is coated on the Copper Foil, and dry afterwards, mold pressing and heat treatment form anode.Use polypropylene porous film to be barrier film, after with anode strip, cathode sheets and membrane coil are around forming coiling body, or lamination poling group, and said modules is encapsulated in the metal shell with the electrolyte of above-mentioned preparation and processes rectangular lithium ion battery.
Three. changing into and method of testing of embodiment lithium ion battery:
The present invention adopts changes into work step: once change into condition: 0.05C, 3min; 0.2C, 5min; 0.5C, 25min.After-teeming liquid and shaping are sealed then, and secondary changes into the 0.2C constant current and is charged to 4.2V, and aged at room temperature 24h again replenishes with 0.2C constant current constant voltage (4.2V) then, again with the 0.2C constant-current discharge to 3.0V.
The present invention estimates the lithium-ion battery electrolytes charge-discharge performance: the aluminum hull square LiCoO that the lithium-ion battery electrolytes of being prepared is injected into 1000mAh 2In the battery, voltage range carries out the charge and discharge cycles test at 3.0～4.2V under the 1C condition.
The present invention is to lithium-ion battery electrolytes high-temperature storage performance method of testing:
At first battery is discharged and recharged once with 1C under normal temperature (25 ℃ ± 2 ℃) state, discharge capacity is C1 under the record normal temperature, with the 1C constant current constant voltage battery is full of electricity again, and the thickness D1 of battery under the test full power state carries out high temperature with the battery of full power state and preserves test.Treat battery cool off fully after the thickness D2 of test battery once more; The battery that takes out is discharged and recharged by following mode:
A, 1C constant-current discharge are to final voltage 2.75V, and discharge capacity is designated as C2.
B, shelve 5min.
C, 1C constant-current constant-voltage charging be to 4.2V, cut-off current 0.02C.
D, shelve 5min.
E, 1C constant-current discharge are to final voltage 2.75V, and discharge capacity is designated as C3.
High temperature is preserved back capability retention=C2/C1 * 100%, capacity restoration rate=C3/C1 * 100%, and thickness swelling=(D2-D1)/D1 * 100%.
The present invention is to the method for testing of the fire resistance of lithium battery electrolytes: with long 50mm; Wide 5mm; The vacuolar membrane nickel of thick 1.65mm is dipped in the electrolyte of embodiment that the present invention mentions or Comparative Examples, takes out with tweezers then, near igniter flame; Stop 2s, remove the flame observe phenomena again and write down self-extinguishing time.
Four. organic substance code name explanation among the embodiment
1, the fluorine ether among each embodiment:
S 1Be HCF 2CF 2CH 2OCF 2CF 2H,
S 2Be HCF 2CF 2CH 2OCF 2CFHCF 3
S 3Be CF 3CF 2CH 2OCF 2CFHCF 3
S 4Be CF 3CF 2CH 2OCF 2CF 2CF 2CF 2H
S 5Be HCF 2CF 2CF 2CH 2OCH 2CF 2CF 2CF 2CF 2H
S 6Be HCF 2CF 2CF 2CH 2OCF 2CF 2H
2, the fluorocarbon surfactant among each embodiment:
(II)R f3X(CH 2CH 2O) nR 1
X be oxygen (O-)
A 1.1Be CF 3(CF 2) 4CH 2O (CH 2CH 2O) 3H
A 1.2Be CF 3(CF 2) 16CH 2O (CH 2CH 2O) 10CH 2CH 2CH 3
A 1.3Be CF 3CF 2O (CH 2CH 2O) 25CH 2CH 2CH 2CH 3
X be sulphur (S-)
A 2.1And A 2Be C 6F 13CH 2CH 2S (CH 2CH 2O) 3H,
A 2.2Be CF 3CF 2S CH 2CH 2O CH 2CH 2CH 2CH 3
A 2.3Be CF 3(CF 2) 16CH 2S (CH 2CH 2O) 25CH 2CH 2CH 3
Amine oxide ( +NO --)
A 3.1Be CF 3(CF 2) 16CH 2 +NO -(CH 2CH 2O) 10CH 2CH 3
A 3.2Be CF 3(CF 2) 4CH 2 +NO -(CH 2CH 2O) 25CH 2CH 2CH 2CH 3
A 3.3Be CF 3CF 2 +NO -CH 2CH 2O H
Acid amides (CONH-)
A 4.1Be CF 3CF 2CONH CH 2CH 2O CH 2CH 2CH 2CH 3
A 4.2Be CF 3(CF 2) 6CH 2CONH (CH 2CH 2O) 25CH 3
A 4.3Be CF 3(CF 2) 16CH 2CONH (CH 2CH 2O) 10CH 2CH 3
Sulfonamide (SO 2N-)
A 5.1And A 3Be C 8F 17CH 2CH 2SO 2N (CH 3) CH 2CH 2OH,
A 5.2Be CF 3CF 2SO 2N (CH 3) (CH 2CH 2O) 11CH 3,
A 5.3Be CF 3(CF 2) 16CH 2SO 2N (CH 3) (CH 2CH 2O) 25CH 2CH 2CH 3
(II) or R F3X (CHCH 3CH 2O) nR 1
A 6.1Be CF 3CHFCF 2CH 2O [CH (CH 3) CH 2O] 2H
A 6.2Be CF 3(CF 2) 6CH 2S [CH (CH 3) CH 2O] 10CH 3
A 6.3Be CF 3(CF 2) 8CH 2 +NO -[CH (CH 3) CH 2O] 2H
A 6.4Be CF 3(CF 2) 16CH 2CONH [CH (CH 3) CH 2O] 25H
A 6.5Be CF 3CHFCF 2CH 2SO 2N [CH (CH 3) CH 2O] 2H
3, organic component code name explanation
FEC: fluorinated ethylene carbonate PC: propene carbonate
VEC: vinylethylene carbonate DMC: dimethyl carbonate
VC: vinylene carbonate EC: ethylene carbonate
EMC: methyl ethyl carbonate EB: ethyl butyrate
MB: methyl butyrate GBL: gamma-butyrolacton
TFEP: three (2,2, the 2-trifluoroethyl)
Phosphite ester
Embodiment 1:
(H in the glove box of applying argon gas 2O＜10ppm), be EC: GBL: S by mass ratio with organic solvent 1=1: with lithium hexafluoro phosphate (1.2M) mix at 1: 1, additive is fluorocarbon surfactant A 1.1, account for 0.5% of total weight.Above-mentioned each raw material is added successively, stir, promptly obtain lithium-ion battery electrolytes of the present invention (free acid＜30ppm, moisture＜10ppm).Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 2:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: S 1=1: 1: 1,1.2M LiPF 6, A 1.1: 0.5%.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 3:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: GBL: S 1=30: 15: 15: 40,1.2M LiPF 6, A 1.1: 0.5%.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 4:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S 1=20: 20: 20: 40,1.2M LiPF 6, A 1.1: 0.5%.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 5:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S 1=20: 20: 20: 40,1.2M LiPF 6, VC:1%, A 1.1: 0.5%.The discharge capacity and the capability retention curve chart in its 150 weeks of normal temperature circulation are seen Fig. 1 and Fig. 2.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 6:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S 2=20: 20: 20: 40,1.2M LiPF 6, VC:1%, A 1.2: 0.5%.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 7:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S 3=20: 20: 20: 40,1.2M LiPF 6, VC:1%, A 1.3: 0.5%.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 8:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EB: S 2=30: 20: 20: 30,1.2M LiPF 6, VC:1%, A 2.1: 1%, TFEP:5%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 9:
Identical with the technology of embodiment 8, difference is that fluorocarbon surfactant is A 2.2Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 10:
Identical with the technology of embodiment 8, difference is that fluorine ether is S 4, fluorocarbon surfactant is A 2.3Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 11:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S 5=40: 5: 15: 40,1.4M LiPF 6, VC:1%, VEC:2%, A 2: 0.5%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 12:
Identical with the technology of embodiment 5, difference is that fluorocarbon surfactant is A 3.1Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 13:
Identical with the technology of embodiment 5, difference is that fluorine ether is S 5, fluorocarbon surfactant is A 3.2Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 14:
Identical with the technology of embodiment 5, difference is that fluorine ether is S 6, fluorocarbon surfactant is A 3.3Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 15:
Identical with the technology of embodiment 5, difference is that fluorine ether is S 2, fluorocarbon surfactant is A 4.1Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 16:
Identical with the technology of embodiment 5, difference is that fluorine ether is S 3, fluorocarbon surfactant is A 4.2Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 17:
Identical with the technology of embodiment 1, difference is that fluorine ether is S 4, fluorocarbon surfactant is A 4.3Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 18:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: DMC: S 6: TFEP=40: 5: 25: 20: 10,1.4M LiPF 6, VC:1%, 1,3-PS:2%, A 5.1: 0.2%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 19:
Identical with the technology of embodiment 18, difference is that fluorine ether is S 3, fluorocarbon surfactant is A 5.2Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 20:
Identical with the technology of embodiment 18, difference is that fluorine ether is S 5, fluorocarbon surfactant is A 5.3Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 21:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: GBL: S 6=1: 1: 1,0.8M LiPF 6With 0.4M LiBF 4, VC:1%, A 4.1: 0.3%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 22:
Identical with the technology of embodiment 21, difference is that fluorine ether is S 1Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 23:
Identical with the technology of embodiment 21, difference is that fluorine ether is S 3Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention after the high-temperature storage, the capacity restoration rate, thickness swelling is shown in table 1.
Embodiment 24:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: GBL: S 4=30: 30: 10: 30,0.8M LiPF 6With 0.4M LiBF 4, VC:1%, A 4.1: 0.3%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 25:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: GBL: MB: S 5=30: 40: 10: 20,0.8M LiBF 4With 0.2M LiN (SO 2CF 3) 2, VC:1%, A 4.1: 0.02%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 26:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: PC: S 2=60: 40,1.3MLiPF 6, A 5.2: 0.06%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 27:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: GBL: S 1=50: 50,1.5MLiBF 4, A 2.2: 0.5%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 28:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: PC: S 2=60: 40,1.3MLiPF 6, VC:1%, FEC:2%, A 5.2: 0.06%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 29:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: GBL: S 1=50: 50,1.5MLiBF 4, VC:1%, 1,3-PS:2%, A 2.2: 0.5%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 30:
Identical with the technology of embodiment 5, difference is that fluorine ether is S 2, fluorocarbon surfactant is 0.2% A 6.1Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 31:
Identical with the technology of embodiment 5, difference is that fluorine ether is S 3, fluorocarbon surfactant is 0.1% A 6.2Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 32:
Identical with the technology of embodiment 5, difference is that fluorine ether is S 4, fluorocarbon surfactant is 0.01% A 6.3Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 33:
Identical with the technology of embodiment 5, difference is that fluorine ether is S 5, fluorocarbon surfactant is 0.08% A 6.4Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Embodiment 34:
Identical with the technology of embodiment 5, difference is that fluorine ether is S 6, fluorocarbon surfactant is 1.0% A 6.5Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Comparative Examples 1 (benchmark appearance):
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: DMC=40: 5: 55, and 1.2M LiPF 6, VC:2%.Used for electrolyte is in flammable performance and battery performance test; The discharge capacity and the capability retention curve chart in its 150 weeks of normal temperature circulation are seen Fig. 1 and Fig. 2.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Comparative Examples 2:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S 5=40: 5: 15: 40,1.4M LiPF 6, VC:1%, VEC:2%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Comparative Examples 3:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S 1=20: 20: 20: 40,1.2M LiPF 6, VC:1%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Comparative Examples 4:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: GBL: DMC=1: 1: 1, and 0.8M LiPF 6With 0.4M LiBF 4, VC:1%, A 4.1: 0.3%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention, capacity restoration rate and thickness swelling are shown in table 1 after the high-temperature storage.
Comparative Examples 5:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: PC: DMC=60: 40, and 1.3M LiPF 6, A 5.2: 0.3%.Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention after the high-temperature storage, the capacity restoration rate, thickness swelling is shown in table 1.
Comparative Examples 6:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: GBL: S 1=50: 50,1.5MLiBF 4Used for electrolyte is in flammable performance test and battery performance test.Flammable The performance test results and the normal temperature 150 all capability retentions that circulate; Its capability retention after the high-temperature storage, the capacity restoration rate, thickness swelling is shown in table 1.
Five. the beneficial effect analysis:
The flammable performance table with test results 1 of electrolyte is analyzed and learnt from each embodiment and Comparative Examples: Comparative Examples 1, Comparative Examples 4 and Comparative Examples 5 are owing to contain a large amount of low-flash DMC; Electrolyte is flammable, and other each embodiment and Comparative Examples be because contain fluorine ether, all shows to a certain degree fire-retardant from putting out effect; Particularly embodiment 1～34; Owing to contain fluorine ether and fluorocarbon surfactant simultaneously, self-extinguishing time is short, and flame retardant effect is better with Comparative Examples 3 than the Comparative Examples 2 of fluorine-containing ether only; Wherein do not contain low-flash linear carbonates or carboxylate in embodiment 1, embodiment 2, embodiment 3, embodiment 21, embodiment 22, embodiment 23, embodiment 24, embodiment 26, embodiment 27, embodiment 28 and embodiment 29 electrolyte; Electrolyte is difficult in the short time light, and explains that its flame retardant effect is better.Wherein Comparative Examples 2 contains fluorine ether and does not have fluorocarbon surfactant with Comparative Examples 3; Show certain fire-retardant from putting out effect; Can know relatively that with embodiment that same solvent composition is arranged 11 and embodiment 5 self-extinguishing time of embodiment 11 and embodiment 5 is shorter, fire resistance further is improved.Explain that an amount of fluorocarbon surfactant is to fire-retardant effective.The embodiment 8, embodiment 9, embodiment 10, embodiment 18, embodiment 19 and embodiment 20 self-extinguishing times that are added with flame-retardant additive TFEP shorten, and fire resistance is further enhanced.
Can know from each embodiment of table 1 and Comparative Examples high-temperature storage performance parameter: the capability retention of each embodiment, capacity restoration rate all are higher than benchmark appearance (Comparative Examples 1) or suitable with benchmark appearance, and thickness swelling is starkly lower than benchmark appearance (Comparative Examples 1).Relatively with fluorine ether (S 6, S 1, S 3) replace the embodiment 21 of DMC in the Comparative Examples 4; Embodiment 22 and embodiment 23, both capability retentions and recovery rate are suitable, but embodiment 21; The thickness swelling of embodiment 22 and embodiment 23 is starkly lower than Comparative Examples 4; The existence of fluorine ether is described, can be suppressed the heat production between electrode and electrolyte interface, favourable to high-temperature storage.The Comparative Examples 2 and embodiment 11 (or Comparative Examples 3 and embodiment 5) that further relatively have the same solvent proportioning wherein are added with 0.5% fluorocarbon surfactant A in embodiment 11 (or embodiment 5) electrolyte 2.1(or A 1.1); Its capability retention and capacity restoration rate all are higher than Comparative Examples 2 (or Comparative Examples 3); Thickness swelling is lower than Comparative Examples 2 (or Comparative Examples 3), explains that the adding of fluorocarbon surfactant helps improving the high-temperature storage performance of battery, can suppress battery aerogenesis when high-temperature storage.The technical scheme of fluorocarbon surfactant and the coupling of fluorine ether is described thus, can be improved the battery high-temperature storge quality.
Can know that from table 1 except embodiment 26, embodiment 27, embodiment 28 and embodiment 29, other each embodiment circulates 150 its capability retentions of all backs more than 90% at 1C normal temperature.The Comparative Examples 2, Comparative Examples 3 and the Comparative Examples 6 that do not contain surfactant, its capability retention are lower than embodiment 11, embodiment 5 and the embodiment 27 with same solvent composition, explain that the adding of small amount of fluorine carbon surface active agent can improve the cycle performance of battery; Comparing embodiment 21, embodiment 22, embodiment 23 and Comparative Examples 4; Comparing embodiment 26 can know that with Comparative Examples 5 embodiment 21 of fluorine-containing ether, embodiment 22, embodiment 23 and embodiment 26 capability retentions are far above not fluorine-containing ether Comparative Examples 4 and Comparative Examples 5.It is thus clear that the existence of fluorine ether has certain inhibitory action to the common insertion and the side reaction that GBL base electrolyte film forming poor stability causes of PC base, helps improving cycle performance of battery, so 150 all its capability retentions afterwards are more than 80%.
The embodiment 4 that further comparative analysis has the same solvent component, embodiment 5 and Comparative Examples 3, the capability retention in its 150 weeks is respectively 92.8%, 94.5%, 87.2%.On embodiment 4 bases, add the embodiment 5 of 1%VC, its capability retention increases; Be added with 1% VC and do not contain surfactant A 1.13 kinds of its capacity of Comparative Examples keep below implement 4 with embodiment 5.On embodiment 26 and embodiment 27 bases, further add film for additive VC+FEC or VC+1, the embodiment 28 of 3-PS, embodiment 29 cycle performances are further improved.It is thus clear that, in electrolyte of the present invention, adding film for additive, battery performance can also further be optimized.
Fig. 1 for embodiment 5 and Comparative Examples 1 (benchmark appearance) at the circulate curve chart of 150 all discharge capacities of 1C normal temperature; Wherein the discharge capacity of embodiment 5 is lower than Comparative Examples 1 (benchmark appearance) slightly; Because embodiment 5 contains than Polyfluoroether; The existence of fluorine ether has reduced the conductivity of system, and containing than the electrolyte system of Polyfluoroether has certain inhibition to the migration of lithium ion; When discharging with 1C, the anodal lithium ion of deviating from from negative pole of lithium ion embedding is less than the Comparative Examples 1 (benchmark appearance) that contains a large amount of linear carbonates solvents, so the discharge capacity of its 1C is lower than benchmark appearance (Comparative Examples 1); But can know that from Fig. 2 the capability retention of embodiment 5 is higher than benchmark appearance (Comparative Examples 1), the discharge capacity of embodiment 5 is 94.5% of an initial capacity after 150 weeks, shows excellent cycle performance, has reached realistic scale.Further illustrate the cycle performance that fluorocarbon surfactant and the coupling of fluorine ether can improve battery.
Each embodiment of table 1 and Comparative Examples electrolyte ratio, its capability retention after flammable performance and 150 all back capability retentions and the high-temperature storage, capacity restoration rate, thickness swelling test result
Figure BDA0000083933690000191
Figure BDA0000083933690000201
Figure BDA0000083933690000211
Above disclosedly be merely a kind of preferred embodiment of the present invention, can not limit the present invention's interest field certainly with this, the equivalent variations of therefore doing according to claim of the present invention still belongs to the scope that the present invention is contained.

Claims (13)

1.一种阻燃型非水电解液，其包括电解质盐、非水溶剂、阻燃剂以及表面活性剂，其特征在于：所述非水溶剂包括环状碳酸酯和/或环状羧酸酯；所述阻燃剂包括结构是Rf1-O-Rf2的氟醚类有机物，其中Rf1是碳原子数为3～4的含氟烷基，Rf2是碳原子数为2～5的含氟烷基；所述表面活性剂包括结构是Rf3X(CH2CH2O)nR1或Rf3X(CHCH3CH2O)nR1的氟碳表面活性剂，其中Rf3是碳原子数为2～18的含氟烷基，X是氧(-O-)、硫(-S-)、氧化胺(-+NO--)、酰胺(-CONH-)或磺酰胺(-SO2N-)，R1是氢原子或者碳原子数为1～4的烷基，n＝1～25。1. A flame-retardant non-aqueous electrolytic solution comprising electrolyte salt, non-aqueous solvent, fire retardant and surfactant, characterized in that: said non-aqueous solvent comprises cyclic carbonate and/or cyclic carboxylic acid ester; the flame retardant includes fluoroether organic compounds with the structure R f1 -OR f2 , wherein R f1 is a fluorine-containing alkyl group with 3 to 4 carbon atoms, and R f2 is a fluorine-containing alkyl group with 2 to 5 carbon atoms Fluoroalkyl; said surfactant includes the structure is R f3 X (CH 2 CH 2 O) n R 1 or R f3 X (CHCH 3 CH 2 O) n R 1 fluorocarbon surfactant, wherein R f3 is A fluorine-containing alkyl group with 2 to 18 carbon atoms, X is oxygen (-O-), sulfur (-S-), amine oxide (-+NO - -), amide (-CONH-) or sulfonamide (- SO 2 N-), R 1 is a hydrogen atom or an alkyl group with 1-4 carbon atoms, n=1-25. 2.如权利要求1所述的阻燃型非水电解液，其特征在于，所述阻燃剂的质量百分含量为10～50％。2. The flame-retardant non-aqueous electrolyte according to claim 1, characterized in that the mass percentage of the flame retardant is 10-50%. 3.如权利要求1所述的阻燃型非水电解液，其特征在于，所述表面活性剂的质量百分含量为0.001％～2％。3. The flame-retardant non-aqueous electrolyte solution according to claim 1, characterized in that the mass percentage of the surfactant is 0.001%-2%. 4.如权利要求1所述的阻燃型非水电解液，其特征在于，所述环状碳酸酯至少包括碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯或卤代碳酸乙烯酯中的一种。4. flame retardant type non-aqueous electrolytic solution as claimed in claim 1, is characterized in that, described cyclic carbonate at least comprises one in ethylene carbonate, propylene carbonate, butylene carbonate or halogenated ethylene carbonate kind. 5.如权利要求1所述的阻燃型非水电解液，其特征在于，所述环状羧酸酯至少包括γ-丁内酯、γ-戊内酯、氟代γ-丁内酯、二氟代γ-丁内酯、氯代γ-丁内酯、二氯代γ-丁内酯、溴代γ-丁内酯、二溴代γ-丁内酯、硝基γ-丁内酯、氰基γ-丁内酯或α-乙酰基-γ-丁内酯中的一种。5. flame retardant type non-aqueous electrolytic solution as claimed in claim 1, is characterized in that, described cyclic carboxylate comprises gamma-butyrolactone, gamma-valerolactone, fluorinated gamma-butyrolactone, Difluoro γ-butyrolactone, Chlorinated γ-butyrolactone, Dichloro γ-butyrolactone, Bromo γ-butyrolactone, Dibromo γ-butyrolactone, Nitro γ-butyrolactone , cyano γ-butyrolactone or α-acetyl-γ-butyrolactone. 6.如权利要求1所述的阻燃型非水电解液，其特征在于，所述非水溶剂还包括质量百分比＜30％的链状碳酸酯和/或链状羧酸酯。6 . The flame-retardant non-aqueous electrolyte according to claim 1 , wherein the non-aqueous solvent further comprises chain carbonates and/or chain carboxylates with a mass percentage of <30%. 7.如权利要求6所述的阻燃型非水电解液，其特征在于，所述链状碳酸酯至少包括碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、碳酸甲基丙基酯、碳酸乙基丙基酯或碳酸二丙酯中的一种。7. flame retardant type non-aqueous electrolytic solution as claimed in claim 6, is characterized in that, described chain carbonate at least comprises dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate , ethyl propyl carbonate or dipropyl carbonate. 8.如权利要求6所述的阻燃型非水电解液，其特征在于，所述链状羧酸酯至少包括乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯或丁酸乙酯中的一种。8. flame retardant type non-aqueous electrolytic solution as claimed in claim 6, is characterized in that, described chain carboxylate comprises methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate at least One of ester, propyl propionate, methyl butyrate or ethyl butyrate. 9.如权利要求1所述的阻燃型非水电解液，其特征在于，所述电解质盐至少包括LiPF6、LiBF4、LiClO4、LiBOB、LiODFB、LiN(SO2CF3)2、LiN(SO2C2F5)2或LiN(SO2F)2中的一种，且其含量按锂离子计为0.6～2mol/L。9. The flame-retardant non-aqueous electrolyte according to claim 1, wherein the electrolyte salt includes at least LiPF 6 , LiBF 4 , LiClO 4 , LiBOB, LiODFB, LiN(SO 2 CF 3 ) 2 , LiN One of (SO 2 C 2 F 5 ) 2 or LiN(SO 2 F) 2 , and its content is 0.6-2 mol/L in terms of lithium ions. 10.如权利要求1所述的阻燃型非水电解液，其特征在于，所述电解液还至少包括碳酸亚乙烯酯、氟代碳酸乙烯酯、碳酸乙烯亚乙酯或1，3-丙烷磺内酯的一种添加剂，且每种添加剂在电解液中的质量百分比为0.1～10％。10. flame retardant type non-aqueous electrolytic solution as claimed in claim 1, is characterized in that, described electrolytic solution also comprises at least vinylene carbonate, fluoroethylene carbonate, ethylene carbonate or 1,3-propane An additive of sultone, and the mass percentage of each additive in the electrolyte is 0.1-10%. 11.如权利要求1所述的阻燃型非水电解液，其特征在于，所述阻燃剂还包括质量百分含量为15％以下的氟代磷酸酯类阻燃剂。11. The flame-retardant non-aqueous electrolyte according to claim 1, wherein the flame retardant further comprises a fluorophosphate flame retardant with a mass percentage of 15% or less. 12.一种锂离子电池，其包括电池正极、负极以及电解液，其特征在于，所述电解液是权利要求1～11中任一项所述的锂离子电池非水电解液。12. A lithium-ion battery, comprising a battery positive pole, a negative pole, and an electrolyte, characterized in that the electrolyte is the non-aqueous electrolyte for a lithium-ion battery according to any one of claims 1-11. 13.如权利要求12所述的锂离子电池，其特征在于：所述电池正极具有含过渡金属氧化物的锂盐活性物质，该锂盐包括LiCoO2、LiMn2O4、LiNi1-x-yCoxMnyO2、LiNi1-xCoxO2或LiFePO4中的一种或几种，其中0＜x＜1，0＜y＜1；负极具有活性物质石墨、含Si或Sn的合金材料或者钛酸锂。13. The lithium-ion battery according to claim 12, wherein the positive electrode of the battery has a lithium salt active material containing a transition metal oxide, and the lithium salt includes LiCoO 2 , LiMn 2 O 4 , LiNi 1-xy Co One or more of x Mny O 2 , LiNi 1-x Co x O 2 or LiFePO 4 , where 0<x<1, 0<y<1; the negative electrode has active material graphite, alloy containing Si or Sn material or lithium titanate.
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