CN102569885A - Non-aqueous electrolyte for lithium ion battery and lithium ion secondary battery - Google Patents
Non-aqueous electrolyte for lithium ion battery and lithium ion secondary battery Download PDFInfo
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- CN102569885A CN102569885A CN2011104511322A CN201110451132A CN102569885A CN 102569885 A CN102569885 A CN 102569885A CN 2011104511322 A CN2011104511322 A CN 2011104511322A CN 201110451132 A CN201110451132 A CN 201110451132A CN 102569885 A CN102569885 A CN 102569885A
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Abstract
The invention provides non-aqueous electrolyte for a lithium ion battery and a lithium ion secondary battery prepared from the non-aqueous electrolyte. The non-aqueous electrolyte for the lithium ion battery comprises cyclic carboxylic ester and/or cyclic carbonate ester, cyclic sulfate, an electrolyte salt, fluoroether with the following structural formula: Rf1-O-Rf2, and a fluorocarbon surfactant, wherein the Rf1 is a fluorine-containing alkyl group of which the carbon atom number is 3 to 4; the Rf2 is a fluorine-containing alkyl group of which the carbon atom number is 2 to 5; the mass percentage of the fluoroether in the electrolyte is 10 to 50 percent; and the fluorocarbon surfactant is used for further improving the performances of the battery. The high temperature performance and the safety of the lithium ion secondary battery prepared from the non-aqueous electrolyte can be kept at a higher level as a whole, and the cycling performance is improved.
Description
Technical field
The lithium rechargeable battery that the present invention relates to a kind of non-aqueous electrolyte for lithium ion cell and process.
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 electrolytes 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 breakdown; Even the 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.
The flame retardant type of industry exploitation at present electrolyte mainly contains two technology paths.On the one 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.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.Attempt adopting higher boiling point on the other hand, the organic solvent of high-flash replaces low boiling, and low-flash linear carbonates kind solvent is placed performance with this security performance and high temperature that improves electrolyte, has obtained certain progress.The patent CN1577944 of Korea S Samsung SDI Co., Ltd discloses a kind of electrolyte that is used for lithium ion battery; The gamma-butyrolacton that wherein comprises higher boiling point, high-flash; Cyclic carbonate and the ester type compound with electron withdraw group, this electrolyte system has good fail safe and excellent storage characteristic.Kejha J B discloses a kind of high-performance of lithium ion battery and safer electrolyte system of being applicable in patent US2006204857 (A1), this system adopts with LiBF
4Be lithium salts, it is organic solvent that the high-flash with 10～30%, high boiling γ BL (or PC or BC) add 70～90% EC, the combustion of gained electrolyte difficult point, and chemical property can match in excellence or beauty with the conventional electrolysis liquid phase that has adopted the linear carbonates kind solvent.
In recent years, expect energetic, require battery case in light weight along with battery, thin thickness, thus make battery expand more easily.In practical application, usually corresponding with service condition, the various performance requirements of battery are also changed the high-temperature storage performance of first battery.Improve the high-temperature storage performance of battery and can use electrolyte solvent, perhaps adopt and suppress the method (CN1282272C) that nonaqueous electrolyte decomposes on the both positive and negative polarity surface with higher boiling point, low-vapor pressure.Using higher boiling point; During the solvent of low-vapor pressure; The general viscosity of solvent that all exists raises, problems such as the conductivity reduction of nonaqueous electrolyte and flash-over characteristic reduction, therefore; For the conductivity that makes nonaqueous electrolyte does not reduce, Te Kaiping (2000-235868) has proposed use high-k and high boiling gamma-butyrolacton schemes such as (GBL).But be to use GBL base electrolyte being inferior to the electrolyte that uses mixed carbonic acid ethyl and low viscosity solvent to obtain aspect electrochemistry oxidative resistance and the reducing resistance.GBL base electrolyte is loose porous at the carbon cathode film formation; Coarse; Stability is bad, when charging, on negative pole, causes the reduction decomposition reaction easily, because the effect of this decomposition product increases the sheet resistance of negative pole; The micropore that causes barrier film simultaneously stops up, and therefore when discharging and recharging repeatedly, has the significantly reduced problem of battery capacity.It is more unstable to preserve charged state GBL base electrolyte at high temperature simultaneously, and easy and both positive and negative polarity generation side reaction causes internal resistance to increase significantly, and is serious to the SEI film destroy simultaneously, causes maintenance capacity and recovery capacity to descend, and the battery bulging is severe.When using in the battery that therefore the basic electrolyte existence of GBL is negative pole with graphite, the problem that capacity attenuation is fast; The problem of aspects such as battery capacity maintenance at high temperature needs further to improve.In addition; Under the situation of the additive surplus in electrolyte; Oxidative decomposition can take place and produce gas in superfluous that part of additive on positive pole when high temperature is placed, therefore can cause the remarkable expansion of battery owing to the rising of interior pressure, and these all are the problems that exists.
Summary of the invention
The inventor attempts finding through a large amount of experiments, through adding the sulfuric ester and the wire fluorine ether of ring-type, can successfully solve the problem with γ BL base electrolyte capacity attenuation and high-temperature storage performance deterioration.
Based on above-mentioned discovery, the present invention is in order to solve the correlation technique problem that above-mentioned electrolyte exists.A kind of non-aqueous electrolyte for lithium ion cell is provided, and this electrolyte can make lithium ion battery when having high security, obtain excellent electrochemical properties, comprises remarkable high-temperature storage performance and excellent cycle performance.
This kind non-aqueous electrolyte for lithium ion cell adopts high-flash, high boiling organic solvent, the thinking that adds halogenated flame retardant (linear fluorine ether) again or further add fluorocarbon surfactant.Idea and a kind of electrolyte that helps improving the lithium ion battery cycle performance and improve the high-temperature storage performance of obtaining according to this, the capacity type battery during this electrolyte is particularly useful under the low range.
The present invention provides a kind of lithium ion battery to use nonaqueous electrolytic solution, and this electrolyte contains:
Lithium salts;
The mixture of cyclic carboxylic esters, cyclic carbonate or cyclic carboxylic esters and cyclic carbonate;
Fluorine ether shown in structural formula (I):
R
F1-O-R
F2Structural formula (I)
R in the formula
F1Be that carbon number is 3～4 the fluoroalkyl that contains, R
F2Be that carbon number is 2～5 the fluoroalkyl that contains;
Cyclic sulfates shown in structural formula (II):
Structural formula (II)
The value of n is 0 or 1 in the formula, R
1, R
2, R
3And R
4The alkyl of representing hydrogen atom or 1～5 carbon atom respectively independently.
Wherein, said cyclic carboxylic esters preferably certainly: one or more in gamma-butyrolacton, gamma-valerolactone, δ-Wu Neizhi, halo gamma-butyrolacton, nitro gamma-butyrolacton, cyanic acid gamma-butyrolacton, the α-acetyl group-gamma-butyrolacton.
Wherein, said cyclic carbonate preferably certainly: one or more in ethylene carbonate, propene carbonate, butylene or the halogenated ethylene carbonate.
Wherein, the mass percent of described fluorine ether in electrolyte is preferably 10～50%.
Wherein, the mass percent of said cyclic sulfates in electrolyte is preferably 0.01%～2%.
Preferably, said electrolyte also comprises the fluorocarbon surfactant of structural formula as shown in the formula (III):
R
F3X (CH
2CH
2O)
nR
1Or R
F3X (CHCH
3CH
2O)
nR
1Structural formula (III)
Wherein, R
F3Be that carbon number is 2～18 the fluoroalkyl that contains, X be oxygen (O-), sulphur (S-), amine oxide (
+NO
--), acid amides (CONH-) or sulfonamide (SO
2N-) functional group, R
1Be that hydrogen atom or carbon number are 1～4 alkyl, n=1～25.
Preferably, said electrolyte also contains one or more in linear carbonate, chain carboxylate or the chain sulfite.
Wherein said linear carbonate is preferably from dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, one or more in the dipropyl carbonate;
Said chain carboxylate is preferably from methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, one or more in the ethyl butyrate;
Said chain sulfite is preferably from dimethyl sulfite, one or more in sulfurous acid diethyl ester, the sulfurous acid methyl ethyl ester.
Wherein, said lithium salts preferably certainly: LiPF
6, LiBF
4, LiClO
4, LiBOB, LiODFB, LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2, LiN (SO
2F)
2In one or more, the concentration of said lithium salts in electrolyte is counted 0.6～2mol/L by lithium ion.
Preferably, said electrolyte also contains additive, and said additive is preferably from vinylene carbonate; Ethylene sulfite, fluorinated ethylene carbonate, vinylethylene carbonate; 1, one or more in the 3-propane sultone, the mass percent of said additive in electrolyte is 0.1～10%.
The present invention also provides the lithium rechargeable battery that is the basis with above-mentioned electrolyte, and it comprises positive pole, negative pole and electrolyte.
Preferably, said just having a lithium salts active material that contains transition metal oxide, and this lithium salts comprises 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
4In one or more; It is graphite that negative pole has active material, contain alloy material or the lithium titanate of Si or Sn.
This technical scheme compared with prior art has following beneficial effect:
1. higher boiling point, the low vapor pressure solvent of the mixture of cyclic carboxylic esters, cyclic carbonate or cyclic carboxylic esters and cyclic carbonate and fluorine ether composition add the film for additive that suppresses the high temperature aerogenesis, and the high-temperature storage performance is remarkable.Aerogenesis is few when therefore high-flash of the present invention, electrolyte high-temperature storage that low vapor pressure solvent is formed, helps improving the high-temperature storage performance.For cooperating this solvent, the present invention forms stable SEI film through adding the little additive cyclic sulfates on electrode, makes the decomposition of nonaqueous electrolyte on dynamics, be able to inhibition and more help improving the high-temperature storage performance.
2. through adding cyclic sulfates and the coupling of wire fluorine ether, it is unstable successfully to solve in the battery that with graphite is negative pole γ BL base electrolyte film forming, the side reaction that the basic electrolyte of PC inserts altogether and render electrical tankage attenuation problem.Fluorine ether is used as the reactivity that solvent can reduce electrolyte and electrode, has suppressed the heat production of electrode interface; The cyclic sulfates filming performance is good, and experiment finds that both couplings can suppress γ BL, high-flash such as PC, and high boiling solvent improves the high-temperature storage performance greatly in the side reaction of graphite cathode, becomes the fail safe of further raising battery and effective guarantee of battery performance.
3. high-flash, its flash-point of electrolyte and boiling point that high boiling solvent is formed are also high; Be not easy to light, fluoridize ether fire retardant in addition, fluorine ether itself contains the ignition-proof element fluorine element, and its flash-point is high, and difficult combustion is added in the electrolyte, makes inflammable organic electrolyte become difficult combustion or non-flammable electrolyte, produces effect to fire-retardant; Even under the environment of very severe, electrolyte has reached its flash point and by being lighted, and what also have fluorine ether is fire-retardant from putting out effect, than conventional electrolysis liquid many double safety guarantee, more effectively improved the security performance of battery.
4. in order further to optimize battery performance, utilize the dispersive property of fluorocarbon surfactant, help improving fluorine ether and higher boiling point, the intermiscibility of high flash solvent fluorine ether and other component solvent.Fluorocarbon surfactant is effective to the wettability height that improves solvent; Especially for higher boiling point; The high viscosity solvent system that high flash solvent is formed, the adding of surfactant 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.
Therefore, through with high-flash, the solvent of higher boiling point ring-type replaces low-flash linear carbonates or carboxylate; Add the technical scheme of cyclic sulfates and halogenated flame retardant fluorine ether again, and obtain anti-flammability and the double excellent electrolyte for lithium secondary batteries of battery behavior (high-temperature storage performance, cycle performance).
Embodiment
By specifying technology contents of the present invention, structural feature, realized purpose and effect, give explanation below in conjunction with execution mode is detailed.
One. the preparation method of embodiment electrolyte
(H in the glove box of applying argon gas
2O＜10ppm), the electrolyte quality ratio that cyclic carbonate, cyclic carboxylic esters, wire fluorine ether, lithium salts, cyclic sulfates, 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 C under the record normal temperature
1, with the 1C constant current constant voltage battery is full of electricity again, the thickness D of battery under the test full power state
1, the battery of full power state is carried out high temperature preservation test.Treat battery cool off fully after the thickness D of test battery once more
2The 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 C
2
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 C
3
High temperature is preserved back capability retention=C
2/ C
1* 100%, capacity restoration rate=C
3/ C
1* 100%,
Thickness swelling=(D
2-D
1)/D
1* 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
S
7Be (CH
2F)
2CHOC (CF
3)
3
2. the cyclic sulfates among each embodiment:
A
1Be glycol sulfate
A
2Be 1,2-propane diols sulfuric ester
A
3Be 1,2-butanediol sulfuric ester
A
4Be 1,3-butanediol sulfuric ester
A
5Be 2,3-butanediol sulfuric ester
A
6Be 1,2-heptandiol sulfuric ester
A
7For
3. the fluorocarbon surfactant among each embodiment:
a
1Be CF
3(CF
2)
4CH
2O (CH
2CH
2O)
3H,
a
2Be C
6F
13CH
2CH
2S (CH
2CH
2O)
3H,
a
3Be C
8F
17CH
2CH
2SO
2N (CH
3) CH
2CH
2OH,
a
4Be CF
3CHFCF
2CH
2O [CH (CH
3) CH
2O]
2H
a
5Be CF
3CH
2NO (CH
2CHO)
25CH
3
a
6Be CH
2F (CH
2)
16CH
2CONH (CH (CH
3) CH
2O)
10(CH
2)
3CH
3
4. other organic component code name explanation
| PC： | Propene carbonate | ?GBL： | Gamma-butyrolacton |
| VC： | Vinylene carbonate | ?EC： | Ethylene carbonate |
| EMC： | Methyl ethyl carbonate | ?EB： | Ethyl butyrate |
| DMS： | Dimethyl sulfite | ?ES： | Ethylene sulfite |
| 1，3-PS： | 1,3-propane sultone | ?BC | Butylene |
| DMC： | Dimethyl carbonate | ?FEC： | Fluorinated ethylene carbonate |
| DEC： | Diethyl carbonate | ?MPC： | Methylpropyl carbonate |
| DVL： | δ-Wu Neizhi | ?DES： | Sulfurous acid diethyl ester |
| BA： | Methyl butyrate | ?VEC： | Vinylethylene carbonate |
| ?MES： | The sulfurous acid methyl ethyl 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 cyclic sulfates A
1, account for 1% of electrolyte 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 normal temperature the 100th all capability retentions that circulate; 60 ℃ store 30 days after its capability retention, capacity restoration rate and thickness swelling be shown in table 1.
Embodiment 2:
Identical with the technology of embodiment 1, difference is that fluorine ether is S
2, cyclic sulfates is A
2
Embodiment 3:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: GBL: S
4=1: 1: 1,1.0M LiPF
6With 0.2M LiBF
4, A
3: 1%.
Embodiment 4:
Identical with the technology of embodiment 3, difference is that fluorine ether is S
5, cyclic sulfates is A
4
Embodiment 5:
Identical with the technology of embodiment 3, difference is that fluorine ether is S
6, cyclic sulfates is A
5
Embodiment 6:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: GBL: S
3=30: 30: 10: 30,1.0M LiPF
6With 0.2M LiBF
4, A
1: 1%.
Embodiment 7:
Identical with the technology of embodiment 1, difference has been added 2% VC on the basis of embodiment 1 electrolyte ratio.
Embodiment 8:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: GBL: MB: S
6=30: 40: 10: 20,0.8M LiBF
4With 0.2M LiN (SO
2CF
3)
2, VC:1%, A
5: 2%.
Embodiment 9:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: PC: S
2=60: 40,1.2M LiPF
6With 0.2M LiBOB, VC:1%, A
2: 0.8%.
Embodiment 10:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: GBL: S
1=50: 50,1.4M LiBF
4, VC:1%, A
4: 0.8%.
Embodiment 11:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: PC: S
2=60: 40,1.2M LiPF
6With 0.2M LiBOB, VC:1%, ES:2%, A
2: 0.8%.
Embodiment 12:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: GBL: S
1=50: 50,1.4M LiBF
4, VC:1%, 1,3-PS:2%, A
4: 0.8%.
Embodiment 13:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S
1=30: 20: 10: 40,1.2M LiPF
6, A
5: 0.6%.
Embodiment 14:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S
1=30: 20: 10: 40,1.2M LiPF
6, VC:1%, A
5: 0.6%.
Embodiment 15:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S
1=30: 20: 10: 40,1.2M LiPF
6, VC:1%, A
5: 0.6%, a
1: 0.1%.
Embodiment 16:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: DMS: S
3=20: 20: 20: 40,1.2M LiPF
6, VC:1%, A
1: 1%.
Embodiment 17:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: DMS: S
3=20: 20: 20: 40,1.2M LiPF
6, VC:1%, A
1: 1%, a
2: 0.1%.
Embodiment 18:
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: 1.5%.
Embodiment 19:
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: 1.5%,, a
3: 0.1%.
Embodiment 20:
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%, A
2: 1.5%,, a
4: 0.1%.
Embodiment 21:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: BC: DEC: MPC: DES: S
7=20: 10: 10: 10: 50; LiClO
4: 0.6M; A
6: 0.01%; FEC:0.1%; a
5: 0.2%.
Embodiment 22:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: FEC: DVL: BA: MES: S
1=25: 10: 20: 15: 30; LiN (SO
2F)
2: 2.0M; A
7: 2%; VEC:10%; a
6: 0.02%.
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%.
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%, a
4: 0.1%.
Comparative Examples 3:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: PC: EMC: S
1=30: 20: 10: 40,1.2M LiPF
6, VC:1%.
Comparative Examples 4:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: EC: GBL: DMC=1: 1: 1, and 1.2M LiPF
6, VC:1%, A
1: 1%.
Comparative Examples 5:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: PC: DMC=60: 40, and 1.2M LiPF
6With 0.2M LiBOB, A
2: 0.8%.
Comparative Examples 6:
Identical with the technology of embodiment 1, difference is that electrolyte ratio is: GBL: S
1=50: 50,1.4M LiBF
4, VC:1%, 1,3-PS:2%.
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.Wherein do not contain low-flash linear carbonates or carboxylate or sulfite among embodiment 1～7, the embodiment 9～12, electrolyte is difficult in the short time light, and explains that its flame retardant effect is better.
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), and thickness swelling is starkly lower than benchmark appearance (Comparative Examples 1).The embodiment 1 that relatively replaces DMC in the Comparative Examples 4 with fluorine ether; The capability retention of Comparative Examples 4 and recovery rate are lower than embodiment 1, and the thickness swelling of embodiment 1 is starkly lower than Comparative Examples 4 simultaneously, and the existence of fluorine ether is described; Can suppress the heat production between electrode and electrolyte interface, favourable to high-temperature storage.Further relatively have the Comparative Examples 2 and embodiment 20, Comparative Examples 3 and embodiment 14 of same solvent proportioning, wherein be added with cyclic sulfates A in embodiment 20 (or embodiment 14) electrolyte
2(or A
5); 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 cyclic sulfates helps improving the high-temperature storage performance of battery, can suppress battery aerogenesis when high-temperature storage.Place performance through using the cyclic sulfates compound can improve high temperature; Although its reason is also indeterminate; But can infer owing to have sulfuric ester and on the surface of electrode material, form good SEI film; Thereby suppressed the reduction decomposition of solvent on lip-deep oxidation of positive pole and negative terminal surface, and caused the generation of gas.
Can know that by table embodiment 7, embodiment 14, and embodiment 15, and embodiment 17 and embodiment 19 normal temperature circulate that the capability retention in the 100th week is higher than or be suitable with conventional electrolysis liquid (Comparative Examples 1).Comparing embodiment 1 and Comparative Examples 4; Embodiment 9 can know with Comparative Examples 5, and the embodiment 1 of fluorine-containing ether and embodiment 9 capability retentions are far above the not Comparative Examples 4 and Comparative Examples 5 of fluorine-containing ether.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 100 all its capability retentions afterwards are more than 80%.Further relatively have the Comparative Examples 2 and embodiment 20, Comparative Examples 3 and embodiment 14, Comparative Examples 6 and embodiment 12 of same solvent proportioning, wherein be added with cyclic sulfates A in the electrolyte of embodiment 20, embodiment 14 and embodiment 12
2, A
5And A
4, its normal temperature the 100th all capability retentions that circulate are higher than Comparative Examples 2, Comparative Examples 3 and Comparative Examples 6, and the adding that cyclic sulfates is described removes and can improve the high-temperature storage performance, also helps the normal-temperature circulating performance of improving battery.
Can know from table 1; The embodiment 15, embodiment 17, embodiment 19, the embodiment 20 that contain surfactant; Its capability retention is higher than embodiment 14, the embodiment 16 with same solvent composition, and embodiment 18, explain that the adding of small amount of fluorine carbon surface active agent can improve the cycle performance of battery; On the basis of embodiment 1, add the embodiment 7 of 2%VC; Embodiment 14 cycle performances that add VC on the basis of embodiment 13 improve; On the basis of embodiment 9 and embodiment 10, add the embodiment 11 of ES; Add 1, the circulate capability retention in the 100th week of embodiment 12 normal temperature of 3-PS all increases, and the high-temperature storage performance also further improves.It is thus clear that, in electrolyte of the present invention, adding film for additive, battery performance can also further be optimized.
Each embodiment of table 1 and Comparative Examples electrolyte ratio, its capability retention after flammable performance and 100 all back capability retentions and the high-temperature storage, capacity restoration rate, thickness swelling test result
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (12)
1. a lithium ion battery is used nonaqueous electrolytic solution, it is characterized in that, this electrolyte contains:
Lithium salts;
The mixture of cyclic carboxylic esters, cyclic carbonate or cyclic carboxylic esters and cyclic carbonate;
Fluorine ether shown in structural formula (I):
R
F1-O-R
F2Structural formula (I)
R in the formula
F1Be that carbon number is 3～4 the fluoroalkyl that contains, R
F2Be that carbon number is 2～5 the fluoroalkyl that contains;
Cyclic sulfates shown in structural formula (II):
Structural formula (II)
The value of n is 0 or 1 in the formula, R
1, R
2, R
3And R
4The alkyl of representing hydrogen atom or 1～5 carbon atom respectively independently.
2. lithium ion battery according to claim 1 is used nonaqueous electrolytic solution; It is characterized in that said cyclic carboxylic esters is selected from: one or more in gamma-butyrolacton, gamma-valerolactone, δ-Wu Neizhi, halo gamma-butyrolacton, nitro gamma-butyrolacton, cyanic acid gamma-butyrolacton, the α-acetyl group-gamma-butyrolacton.
3. lithium ion battery according to claim 1 is used nonaqueous electrolytic solution, it is characterized in that, said cyclic carbonate is selected from: one or more in ethylene carbonate, propene carbonate, butylene or the halogenated ethylene carbonate.
4. lithium ion battery according to claim 1 is used nonaqueous electrolytic solution, it is characterized in that, the mass percent of described fluorine ether in electrolyte is 10～50%.
5. lithium ion battery as claimed in claim 1 is used nonaqueous electrolytic solution, it is characterized in that, the mass percent of said cyclic sulfates in electrolyte is 0.01%～2%.
6. lithium ion battery as claimed in claim 1 is used nonaqueous electrolytic solution, it is characterized in that, said electrolyte also comprises the fluorocarbon surfactant of structural formula as shown in the formula (III):
R
F3X (CH
2CH
2O)
nR
1Or R
F3X (CHCH
3CH
2O)
nR
1Structural formula
(III)
Wherein, R
F3Be that carbon number is 2～18 the fluoroalkyl that contains, X be oxygen (O-), sulphur (S-), amine oxide (
+NO
--), acid amides (CONH-) or sulfonamide (SO
2N-) functional group, R
1Be that hydrogen atom or carbon number are 1～4 alkyl, n=1～25.
7. lithium ion battery according to claim 1 is used nonaqueous electrolytic solution, it is characterized in that, said electrolyte also contains one or more in linear carbonate, chain carboxylate or the chain sulfite.
8. lithium ion battery according to claim 7 is used nonaqueous electrolytic solution, it is characterized in that,
Said linear carbonate is selected from: dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, one or more in the dipropyl carbonate;
Said chain carboxylate is selected from: methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, one or more in the ethyl butyrate;
Said chain sulfite is selected from: dimethyl sulfite, one or more in sulfurous acid diethyl ester, the sulfurous acid methyl ethyl ester.
9. non-aqueous electrolyte for lithium ion cell as claimed in claim 1 is characterized in that said lithium salts is selected from: LiPF
6, LiBF
4, LiClO
4, LiBOB, LiODFB, LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2, LiN (SO
2F)
2In one or more, the concentration of said lithium salts in electrolyte is counted 0.6～2mol/L by lithium ion.
10. use nonaqueous electrolytic solution like any described lithium ion battery of claim 1～9, it is characterized in that said electrolyte also contains additive; Said additive is selected from: vinylene carbonate, ethylene sulfite, fluorinated ethylene carbonate; Vinylethylene carbonate; 1, one or more in the 3-propane sultone, the mass percent of said additive in electrolyte is 0.1～10%.
11. a lithium rechargeable battery, it comprises positive pole, negative pole and electrolyte, it is characterized in that, said electrolyte is that each described lithium ion battery is used nonaqueous electrolytic solution in the claim 1～10.
12. lithium rechargeable battery according to claim 11 is characterized in that: said just having a lithium salts active material that contains transition metal oxide, and this lithium salts comprises 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
4In one or more; It is graphite that negative pole has active material, contain alloy material or the lithium titanate of Si or Sn.
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