CN101777668A - Electrolyte for lithium manganese battery - Google Patents

Electrolyte for lithium manganese battery Download PDF

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Publication number
CN101777668A
CN101777668A CN201010109084A CN201010109084A CN101777668A CN 101777668 A CN101777668 A CN 101777668A CN 201010109084 A CN201010109084 A CN 201010109084A CN 201010109084 A CN201010109084 A CN 201010109084A CN 101777668 A CN101777668 A CN 101777668A
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integer
electrolyte
carbonate
general formula
lithium manganate
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周邵云
刘建生
李永坤
张利萍
张若昕
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Jiujiang Tianci High & New Material Co Ltd
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Jiujiang Tianci High & New Material Co Ltd
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an electrolyte for a lithium manganese battery, which comprises a non-aqueous organic solvent, lithium salt, a film forming additive, an anti-overcharge additive and a stabilizing additive, and also comprises the following components by weight percent: 0.1-5% of unsaturated sultone as a high temperature additive and 0.01-1% of fluorocarbon surfactant. Based on the reasonable deign of each component, the electrolyte is added with the novel high-temperature additive and the fluorocarbon surfactant, so that the lithium manganese battery using the electrolyte has excellent cycle life and high temperature properties.

Description

A kind of lithium manganate battery electrolyte
Technical field
The present invention relates to a kind of lithium-ion battery electrolytes, relate in particular to a kind of lithium manganate battery electrolyte.
Background technology
Lithium ion battery is because its operating voltage height, energy density height, a series of advantages such as power density is big, self discharge is little, memory-less effect, good charge-discharge performance, long circulation life, environmental friendliness, be widely used in portable type electronic products such as mobile communication, digital camera, MP3 at present, and progressively use at national defence, military aspect.In recent years, along with the attention of the whole world to environmental problem, the new-energy automobile fast development, lithium ion battery is considered to the Vehicular dynamic battery of current tool potentiality development.
The positive electrode that lithium ion battery is commonly used is a cobalt acid lithium, along with wafing of cobalt valency rises and instability, people actively seek to replace the positive electrode of cobalt acid lithium, and subsequently, the binary of elements such as LiMn2O4, LiFePO4, nickel manganese cobalt aluminium or multi-element compounds obtain research and industrialization.Wherein, the compound of nickel manganese cobalt aluminium etc. is owing to contain cobalt and nickel more or less, and its price does not still have greater advantage; Though the LiFePO4 raw material are cheap, preparation needs inert gas shielding to improve its cost widely; Thereby LiMn2O4 has become the positive electrode that has advantage on price most.
Yet there is serious capacity attenuation problem in spinel lithium manganate, and its capacity attenuation reason mainly contains: the dissolving of manganese, Jahn-Teller effect and electrolyte instability etc.Particularly under hot conditions, the micro-HF of electrolyte instability generation can quicken the dissolving of manganese, thereby the performance of lithium manganate battery particularly high-temperature behavior (comprising high temperature storage and high temperature cyclic performance) has become to restrict the important factor in order of its development.Except control in the preparation process of lithium manganate material with improve the quality of LiMn2O4 and improve the lithium manganate battery performance in cell preparation process optimization technology, correlative study person has spent many energy, attempt to set about, optimize dicyandiamide solution, add particularly high-temperature behavior of performance that the new function additive improves lithium manganate battery from electrolyte.New function additive wherein mainly contains two classes: a class is to stablize the stabilization additives of moisture in the electrolyte, acidity or lithium salts, and a class is the film for additive that can form fine and close solid electrolyte film on the both positive and negative polarity surface.
What use stabilization additives is 200810218809.6 as application number, denomination of invention is the Chinese patent of " a kind of electrolyte of lithium manganate battery ", it discloses a kind of electrolyte of lithium manganate battery, this electrolyte comprises lithium salts, non-aqueous organic solvent, film for additive and stabilization additives heptamethyldisilazane, this invention improves the performance of lithium manganate battery electrolyte by the stabilization of stabilization additives heptamethyldisilazane to acidity in the electrolyte.
Application number is 200410062610.0, denomination of invention is the Chinese patent of " method that improves spinel lithium manganate cell volume and cycle performance ", a kind of method that improves spinel lithium manganate cell volume and cycle performance is disclosed, its in electrolyte, add in the oxide of zinc, aluminium, magnesium, calcium one or more mixture or aluminium or magnesium as deacidification agent, remove the free acid HF in the electrolyte, improve the performance of electrolyte and lithium manganate battery.These stabilization additives are often big to the battery negative effect when addition is big, and addition is difficult to the effect that improves significantly after a little while.
Application number is 200810030369.1, denomination of invention is the Chinese patent of " improving the electrolyte of lithium manganate lithium ion battery performance ", it discloses a kind of manganate lithium ion battery electrolyte, it adds 1 in electrolyte, 3-propane sultone (PS) or two oxalic acid borate lithiums (LiBOB) are done film for additive, performance to lithium manganate battery has certain improvement, but it is well-known, PS is extensive use of in electrolyte, though form resistant to elevated temperatures SEI film and LiBOB helps negative pole, often acidity is too high but contain the electrolyte of LiBOB, and it is limited that it improves effect.
Chinese patent application 200810026705.5 discloses a kind of novel lithium-ion battery electrolytes, has wherein used fluorinated organic compound, but it is not fluorine-containing surfactant.
Chinese patent application 01123135.1 (CN1333580A) discloses a kind of non-aqueous electrochemical device, and electrolyte wherein comprises as the saturated sultone of additive and fluorine-containing surfactant.But do not use the unsaturated sulfonic acid lactone.
Therefore, lithium manganate battery with electrolyte to improve the space also very big.
Summary of the invention
Technical problem to be solved by this invention is: a kind of lithium manganate battery electrolyte is provided, this electrolyte is because the adding of new type high temperature additive and fluorocarbon surfactant, can make the fast and effeciently wetting pole piece of electrolyte and can form fine and close high temperature resistant SEI film, use this electrolyte can effectively improve the cycle life and the high-temperature behavior of lithium manganate battery at the electrode surface of battery.
The present invention relates to a kind of lithium manganate battery nonaqueous electrolytic solution, this electrolyte comprises: non-aqueous organic solvent, lithium salts, film for additive, anti-overcharge additive, stabilization additives, also contain unsaturated sulfonic acid lactone and fluorocarbon surfactant as high temperature additive.
Specific embodiments of the present invention
In one embodiment of the invention, the present invention relates to a kind of lithium manganate battery nonaqueous electrolytic solution, this electrolyte comprises: non-aqueous organic solvent, lithium salts, film for additive, anti-overcharge additive, stabilization additives, also contain unsaturated sulfonic acid lactone and fluorocarbon surfactant as high temperature additive, wherein the unsaturated sulfonic acid lactone is selected from one or more in the compound that following general formula I represents:
Figure GSA00000029539700031
R wherein 1-R 4Be hydrogen atom, fluorine atom or have the fluorine-containing or not fluorine-containing alkyl of 1-12 carbon atom (preferred 1-4 carbon atom, more preferably 1-2 carbon atom), n is the integer of 0-3.Preferably, n is 1 or 2, most preferably n=1.Most preferably, R1-R4 is a hydrogen atom.Compound of Formula I is 1-propylene-1 particularly, the 3-sultones.
In the embodiment of present invention further optimization, the present invention relates to a kind of lithium manganate battery nonaqueous electrolytic solution, this electrolyte comprises: non-aqueous organic solvent, lithium salts, film for additive, anti-overcharge additive, stabilization additives, also contain lactone of unsaturated sulfonic acid as defined above and fluorocarbon surfactant as high temperature additive, wherein fluorocarbon surfactant is selected from one or more in the compound with general formula I I or II ':
Rf-(CH 2CH 2O) x-(CH 2CH 2CH 2O) y-H general formula I I
Rf-(CH 2CH 2O) x-(C 3H 6O) y-Rf general formula I I '
In the formula, C 3H 6O=CH 2CH (CH 3) O or CH (CH 3) CH 2O,
Rf contains the fluoro of 2-18 carbon atom or the saturated or unsaturated alkyl of perfluoro.X is 1-30, preferred 2-25, the more preferably integer of 2-20.Y is 0-20 or 1-20, preferred 0-10 or 1-10, the more preferably integer of 0-5 or 1-5.X+y is 1-30, preferred 2-25, the more preferably integer of 2-20.
Or wherein fluorocarbon surfactant is selected from one or more in the compound with general formula III or IV:
C nF 2n+1SO 2N (C mH 2m+1) CH 2CH 2O (CH 2CH 2O) 1The H general formula III
In the formula, n is the integer of 4-18; M is the integer of 1-4; The 1st, the integer of 5-25;
With
C nF 2n+1-X-(CH 2CH 2O) M '-Y general formula I V
In the formula, X is-CONH-and-SO 2NR-; R is the C1-C8 alkyl; Y is-H ,-OH ,-CH 3,-PO 3W 2Or-SO 3W; W is that alkali metal n is the integer of 3-10, and m ' is the integer of 2-100;
Or wherein fluorocarbon surfactant is selected from one or more in the compound with general formula V or VI:
Figure GSA00000029539700041
(following formula is represented the polyacrylic acid fluoroalkyl, and n is an integer, the integer of preferred n=10-50)
Figure GSA00000029539700042
In the formula, n and m are respectively integers, the integer of n+m=2～30.
Preferably, the fluorocarbon surfactant with general formula I I is selected from one or more in the compound with following structural formula:
F (CF 2CF 2) m(CH 2CH 2O) nH (the integer of m=1～9; The integer of n=1～25), or
H (CF 2CF 2) mCH 2O (CH 2CH 2O) nH (the integer of m=1～9; The integer of n=1～30),
Preferably, the fluorocarbon surfactant with general formula I I ' is selected from one or more in the compound with following structural formula:
F (CF 2CF 2) mO (CH 2CH 2O) n(CF 2CF 2) mF (the integer of m=1～9; The integer of n=1～25).
Employed 1-propylene-1 in the most preferred embodiment, the 3-sultones has following structural formula:
Figure GSA00000029539700051
CAS NO:21806-61-1
Molecular formula: C 3H 4SO 3, molecular weight: 120.
Described high temperature additive unsaturated sulfonic acid lactone accounts for 0.001～6%, 0.005～6%, 0.01～6%, 0.1%～5% of electrolyte gross mass, and is preferred 0.5%～4%, and more preferably 1%～3.5%.Preferably, the moisture of this unsaturated sulfonic acid lactone is less than 400ppm, preferably is less than 300ppm, more preferably less than 200ppm, in whole embodiment of the present invention, use moisture to be less than the unsaturated sulfonic acid lactone (preferred 1-propylene-1,3-sultones) of 200ppm.Preparation 1-propylene-1 is disclosed in Chinese patent application 200910073620.7, the method for 3-sultones, the full content of this patent application is hereby incorporated by reference.
Described fluorocarbon surfactant accounts for 0.01%～1% of electrolyte gross mass, and is preferred 0.015%～0.8%, and more preferably 0.02～0.7%, more more preferably 0.03%～0.6%, more further preferred 0.04～0.6%, preferred especially 0.05～0.6%.
Described non-aqueous organic solvent is one or more of carbonic ester, carboxylate, ether or ketone.When using two or more organic solvent, they can be according to any part by weight.Described non-aqueous organic solvent also can be sulfolane or methyl sulfolane.The consumption of organic solvent is the consumption of using always in the electrolyte of lithium ion battery in the prior art, for example is the 70-95% of electrolyte total weight, preferred 75-90%, more preferably 80-88%.
Described carbonic ester is preferably ethylene carbonate (being also referred to as carbonic acid ethylidene ester), propene carbonate (is also referred to as carbonic acid 1,2-propylidene ester), one or more of carbonic acid butylidene ester, carbonic acid ethenylidene ester, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate or carbonic acid first propyl ester, and, when using two or more carbonic ester, they can be according to any part by weight; Described carboxylate is preferably one or more of methyl formate, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, methyl butyrate or ethyl butyrate, and, when using two or more carboxylate, they can be according to any part by weight; Described ether is preferably dimethoxymethane, 1,2-dimethoxy-ethane, oxolane or 1, and one or more of 3-dioxolanes, and when using two or more ether, they can be according to any part by weight; Described ketone is gamma-butyrolacton.
Described lithium salts is preferably LiPF 6, LiBF 4, LiBOB or LiODFB one or more.The concentration of lithium salts is counted 0.7～1.5mol/L by lithium ion in electrolyte, preferred 0.7～1.4mol/L, more preferably 0.8～1.4mol/L, more preferably 0.8～1.3mol/L again.
Described film for additive is preferably vinylene carbonate, vinylethylene carbonate (or vinyl ethylidene carbonic ester), fluorinated ethylene carbonate, 1,3-sulfonic acid propiolactone or 1, one or more of 4-sulfonic acid butyrolactone, account for 0.5%～5% of electrolyte gross mass, preferred 0.7%～4.5%, more preferably 0.8%～4%, more more preferably 1.0%～4%, further more preferably 1.0%～3.5%.
Described anti-overcharge additive is preferably one or more of biphenyl, cyclohexyl benzene,toluene,xylene, methyl phenyl ethers anisole, chlorobenzene methyl ether or diphenyl ether, account for 0%～12% of electrolyte gross mass, preferred 0.2%～10%, more preferably 0.5%～8%, again more preferably 0.8%～8%, further preferred 0.8%～6%.
Described stabilization additives is one or more of organic amine or alkyl silazane class, account for 0.01%～0.5% of electrolyte gross mass, preferred 0.02%～0.5%, more preferably 0.03%～0.45%, again more preferably 0.05%～0.4%, further preferred 0.1%～0.3%.Described organic amine is the C1-C8 alkyl amine preferably, and two C1-C8 alkyl amines, or three C1-C8 alkyl amines, or alcamines preferably are as carbinolamine, monoethanolamine or Propanolamine.Described silazane class is hexamethyldisiloxane, hexaethyl disilazine or six propyl group disilazanes preferably.
Advantage of the present invention and the good effect that brings: on the basis of appropriate design higher boiling point non-aqueous organic solvent, lithium salts, film for additive, anti-overcharge additive, stabilization additives, new type high temperature additive unsaturated sulfonic acid lactone and fluorocarbon surfactant in electrolyte, have been added, thereby the wetability that makes electrolyte improves electrode polarization greatly and reduces, use the electrode surface of the battery of this electrolyte can form resistant to elevated temperatures fine and close SEI film, thereby significantly reduced corrosion and the destruction of electrolyte, improved the cycle life and the high-temperature behavior of lithium manganate battery greatly electrode.
Description of drawings
Fig. 1 is Comparative Examples 1, Comparative Examples 2, Comparative Examples 3, Comparative Examples 4 and the embodiment 1 cycle performance figure at the 1C rate charge-discharge.
Fig. 2 is Comparative Examples 1, Comparative Examples 2, Comparative Examples 3, Comparative Examples 4 and the embodiment 1 cycle performance figure at 60 ℃ of hot environment 1C rate charge-discharges.
Embodiment
Below in conjunction with embodiment the present invention is described further, enforcement of the present invention includes but not limited to down routine execution mode.
Comparative Examples 1
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtain solution, wherein LiPF 6Concentration be 1mol/L, in this solution, press the electrolyte gross mass and calculate to add 1% vinylene carbonate and 0.1% monoethanolamine, must contrast electrolyte.
Comparative Examples 2
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtain solution, wherein LiPF 6Concentration be 1mol/L, in this solution, press the electrolyte gross mass calculate to add 1% vinylene carbonate, 2% 1,3-sulfonic acid propiolactone and 0.1% monoethanolamine must contrast electrolyte.
Comparative Examples 3
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtain solution, wherein LiPF 6Concentration be 1mol/L, in this solution, press the electrolyte gross mass calculate to add 1% vinylene carbonate, 2% 1,3-sulfonic acid propiolactone, 0.1% monoethanolamine and 0.1% F (CF 2CF 2) 4(CH 2CH 2O) 10H must contrast electrolyte.
Comparative Examples 4
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtain solution, wherein LiPF 6Concentration be 1mol/L, in this solution, press the electrolyte gross mass and calculate to add 1% vinylene carbonate, 1% 1-propylene-1,3-sultones and 0.1% monoethanolamine must contrast electrolyte.
Embodiment 1
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/5/10/50) and obtain solution, wherein LiPF 6Concentration be 1mol/L, in this solution, press the electrolyte gross mass and calculate to add 1% vinylene carbonate, 1% 1-propylene-1,3-sultones, 0.1% monoethanolamine and 0.1% F (CF 2CF 2) 4(CH 2CH 2O) 10H gets electrolyte of the present invention.
Embodiment 2
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/dimethyl carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 35/10/10/45) and obtain solution, wherein LiPF 6Concentration be 1mol/L, in this solution, press the electrolyte gross mass and calculate to add 1% vinylene carbonate, 0.5% 1-propylene-1,3-sultones, 0.15% ethamine and 0.15% H (CF 2CF 2) 8CH 2O (CH 2CH 2O) 20H gets electrolyte of the present invention.
Embodiment 3
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/dimethyl carbonate/carbonic acid first propyl ester/diethyl carbonate (mass ratio is 30/10/20/40) and obtain solution, wherein LiPF 6Concentration be 0.9mol/L, in this solution, press the electrolyte gross mass and calculate to add 2% vinylethylene carbonate, 1.5% 1-propylene-1,3-sultones, 0.08% ethamine and 1% F (CF 2CF 2) 5O (CH 2CH 2O) 22(CF 2CF 2) 5F gets electrolyte of the present invention.
Embodiment 4
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/ethyl acetate/methyl ethyl carbonate/ethyl butyrate (mass ratio is 20/10/30/40) and obtain solution, wherein LiPF 6Concentration be 1.2mol/L, in this solution, press the calculating of electrolyte gross mass and add 1% fluorinated ethylene carbonate, 2% 1-propylene-1, the fluorocarbon surfactant of 3-sultones, 0.2% monoethanolamine and 0.5% following structural formula, electrolyte of the present invention.
Figure GSA00000029539700091
Embodiment 5
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/ethyl propionate/propene carbonate/ethyl butyrate (mass ratio is 30/10/10/50) and obtain solution, wherein LiPF 6Concentration be 1.5mol/L, in this solution, press the electrolyte gross mass and calculate 1 of interpolation 3%, 3-sulfonic acid propiolactone, 0.5% 1-propylene-1, the fluorocarbon surfactant of 3-sultones, 3% biphenyl, 0.3% monoethanolamine and 0.01% following structural formula, electrolyte of the present invention.
Figure GSA00000029539700092
Embodiment 6
With lithium salts LiBF 4Be dissolved in the mixed solvent of ethylene carbonate/propyl acetate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 40/20/20/20) and obtain solution, wherein LiBF 4Concentration be 0.8mol/L, in this solution, press the electrolyte gross mass calculate to add 1% 1,4-sulfonic acid butyrolactone, 3% 1-propylene-1,3-sultones, 5% cyclohexyl benzene, 0.2% ethamine and 0.3% F (CF 2CF 2) 8(CH 2CH 2O) 20H gets electrolyte of the present invention.
Embodiment 7
Lithium Salt LiBOB is dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate (mass ratio is 30/15/10/45) and obtains solution, wherein LiBF 4Concentration be 0.8mol/L, in this solution, press the electrolyte gross mass calculate to add 1% 1,4-sulfonic acid butyrolactone, 3% 1-propylene-1,3-sultones, 5% cyclohexyl benzene, 0.2% ethamine and 0.5% H (CF 2CF 2) 4CH 2O (CH 2CH 2O) 18H gets electrolyte of the present invention.
Embodiment 8
With lithium salts LiPF 6Be dissolved in the mixed solvent of ethylene carbonate/ethyl propionate/propene carbonate/ethyl butyrate (mass ratio is 30/10/10/50) and obtain solution, wherein LiPF 6Concentration be 1.1mol/L, in this solution, press the electrolyte gross mass calculate to add 1% vinylene carbonate, 1% 1,3-sulfonic acid propiolactone, 1% 1-propylene-1,3-sultones, 7% toluene, 0.5% monoethanolamine and 0.05% F (CF 2CF 2) 8O (CH 2CH 2O) 14(CF 2CF 2) 8F gets electrolyte of the present invention.
Embodiment 9
With lithium salts LiPF 6, LiBOB is dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/ethyl butyrate (mass ratio is 30/10/30/30) and obtains solution, LiPF wherein 6Concentration be 0.6mol/L, the concentration of LiBOB is 0.3mol/L, in this solution, press the electrolyte gross mass calculate to add 0.5% vinylene carbonate, 1% 1,4-sulfonic acid butyrolactone, 0.5% 1-propylene-1, the fluorocarbon surfactant of 3-sultones, 5% diphenyl ether, 0.1% hexamethyldisiloxane and 0.2% following structural formula, electrolyte of the present invention.
Figure GSA00000029539700101
Embodiment 10
With lithium salts LiPF 6, LiBF 4Be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/methyl ethyl carbonate/ethyl butyrate (mass ratio is 30/10/30/30) and obtain solution, wherein LiPF 6Concentration be 0.7mol/L, LiBF 4Concentration be 0.4mol/L, in this solution, press the calculating of electrolyte gross mass and add 1% vinylethylene carbonate, 1% fluorinated ethylene carbonate, 1% 1-propylene-1, the fluorocarbon surfactant of 3-sultones, 2% biphenyl, 3% cyclohexyl benzene, 0.1% hexamethyldisiloxane and 0.4% following structural formula, electrolyte of the present invention.
Figure GSA00000029539700111
Embodiment 11
With Lithium Salt LiBOB, LiBF 4Be dissolved in the mixed solvent of ethylene carbonate/propylene carbonate/diethyl carbonate (mass ratio is 30/10/60) and obtain solution, wherein the concentration of LiBOB is 0.6mol/L, LiBF 4Concentration be 0.3mol/L, in this solution, press the electrolyte gross mass and calculate to add 2% fluorinated ethylene carbonate, 3% 1-propylene-1,3-sultones, 6% methyl phenyl ethers anisole, 0.3% hexaethyl disilazine, 0.05% F (CF 2CF 2) 2(CH 2CH 2O) 15H and 0.1% H (CF 2CF 2) 5CH 2O (CH 2CH 2O) 15H gets electrolyte of the present invention.
Embodiment 12
With lithium salts LiPF 6, LiBOB, LiBF 4Be dissolved in ethylene carbonate/1, obtain solution in the mixed solvent of 2-dimethoxy-ethane/diethyl carbonate (mass ratio is 30/20/50), wherein LiPF 6Concentration be that the concentration of 0.6mol/L, LiBOB is 0.2mol/L, LiBF 4Concentration be 0.1mol/L, in this solution, press the electrolyte gross mass and calculate to add 1% vinylethylene carbonate, 4% 1-propylene-1,3-sultones, 0.3% hexamethyldisiloxane, 0.05% F (CF 2CF 2) 6O (CH 2CH 2O) 20(CF 2CF 2) 6The fluorocarbon surfactant of F and 0.2% following structural formula, electrolyte of the present invention.
Figure GSA00000029539700112
Embodiment 13
With lithium salts LiPF 6, LiODFB is dissolved in ethylene carbonate/propylene carbonate/1, obtains solution in the mixed solvent of 3-dioxolanes/ethyl butyrate (mass ratio is 30/10/20/40), wherein LiPF 6Concentration be 0.7mol/L, the concentration of LiODFB is 0.3mol/L, in this solution, press the calculating of electrolyte gross mass and add 1% vinylethylene carbonate, 1% fluorinated ethylene carbonate, 0.5% 1-propylene-1,3-sultones, 4% dimethylbenzene, 0.05% carbinolamine, 0.02% F (CF 2CF 2) 3(CH 2CH 2O) 18H, 0.06% F (CF 2CF 2) 7O (CH 2CH 2O) 16(CF 2CF 2) 7The fluorocarbon surfactant of F and 0.04% following structural formula, electrolyte of the present invention.
Figure GSA00000029539700121
Embodiment 14
Lithium salts LiODFB is dissolved in the mixed solvent of ethylene carbonate/gamma-butyrolacton/methyl ethyl carbonate/ethyl butyrate (mass ratio is 40/10/10/40) and obtains solution, wherein the concentration of LiODFB is 0.8mol/L, in this solution, press the calculating of electrolyte gross mass and add 1% vinylene carbonate, 2% 1-propylene-1,3-sultones and 0.1% carbinolamine, 0.02% F (CF 2CF 2) 5(CH 2CH 2O) 19H, 0.08% F (CF 2CF 2) 6(CH 2CH 2O) 24H, 0.01% F (CF 2CF 2) 7(CH 2CH 2O) 16H gets electrolyte of the present invention.
Result of the test:
1, surface tension test:
To hang sheet method (platinum sheet), adopt the surface tension of the full-automatic surface tension instrument test of the BZY-1 of Shanghai Hengping Instrument ﹠ Meter Plant type electrolyte.
Surface tension test case such as the following table of the electrolyte of all Comparative Examples and embodiment under normal temperature and high temperature:
Example Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Embodiment 1
25 ℃ of tension force (mN/m) ??30.5 ??30.4 ??23.5 ??30.2 ??23.3
60 ℃ of tension force (mN/m) ??27.8 ??27.8 ??21.1 ??27.6 ??21.3
Example Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
25 ℃ of tension force (mN/m) ??23.2 ??23.1 ??23.5 ??22.8 ??22.7
60 ℃ of tension force (mN/m) ??21.1 ??21.0 ??21.8 ??21.7 ??21.3
Example Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11
25 ℃ of tension force (mN/m) ??23.1 ??23.4 ??22.9 ??22.8 ??23.6
60 ℃ of tension force (mN/m) ??21.4 ??21.8 ??20.9 ??20.9 ??21.5
Example Embodiment 12 Embodiment 13 Embodiment 14
25 ℃ of tension force (mN/m) ??23.4 ??23.5 ??23.2
60 ℃ of tension force (mN/m) ??21.4 ??21.5 ??21.5
As seen from the above table, after the interpolation fluorocarbon surfactant, the surface tension of electrolyte descends bigger, illustrate that its wettability at inside battery improves, thereby each point soaks into the consistency raising of electrolyte on the pole piece, causes electrode polarization to reduce, and helps improving the performance of battery.
2, cycle performance test:
Adopt Guangzhou to hold up day cycle performance of the BS-8300 of company cell tester test battery.
The electrolyte of Comparative Examples 1, Comparative Examples 2, Comparative Examples 3, Comparative Examples 4 and embodiment 1 is injected the LiMn2O4 soft-package battery of batch same model together, and test battery is at the cycle performance of normal temperature environment and 60 ℃ of hot environments.
Accompanying drawing 1 is that the lithium manganate battery of electrolyte preparation of Comparative Examples 1, Comparative Examples 2, Comparative Examples 3, Comparative Examples 4 and embodiment 1 is at the cycle performance figure of 1C rate charge-discharge; Accompanying drawing 2 is that the lithium manganate battery of electrolyte preparation of Comparative Examples 1, Comparative Examples 2, Comparative Examples 3, Comparative Examples 4 and embodiment 1 is at the cycle performance figure of 60 ℃ of hot environment 1C rate charge-discharges.From figure as can be known, add 1-propylene-1,3-sultones and fluorocarbon surfactant F (CF 2CF 2) 4(CH 2CH 2O) 10The cycle performance of battery and the high-temperature behavior of the electrolyte preparation of the present invention of H obviously are better than Comparative Examples.
All Comparative Examples and embodiment contrast as following table in the data of normal temperature circulation and 60 ℃ of high temperature circulation:
Example Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Embodiment 1
Normal temperature 300 all conservation rates ??86.13％ ??87.12％ ??87.63％ ??88.63％ ??89.14％
Example Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Embodiment 1
60 ℃ of 200 all conservation rate ??64.63％ ??70.15％ ??72.54％ ??74.78％ ??76.04％
Example Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Normal temperature 300 all conservation rates ??89.18％ ??88.98％ ??88.95％ ??89.10％ ??89.25％
60 ℃ of 200 all conservation rate ??75.80％ ??75.98％ ??76.10％ ??76.15％ ??75.89％
Example Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11
Normal temperature 300 all conservation rates ??88.89％ ??90.12％ ??90.03％ ??89.40％ ??89.88％
60 ℃ of 200 all conservation rate ??75.78％ ??75.98％ ??75.78％ ??76.12％ ??76.38％
Example Embodiment 12 Embodiment 13 Embodiment 14
Normal temperature 300 all conservation rates ??89.23％ ??90.04％ ??89.87％
60 ℃ of 200 all conservation rate ??76.45％ ??76.58％ ??76.87％
Know that by last table embodiments of the invention obviously are better than Comparative Examples.

Claims (10)

1. lithium manganate battery electrolyte, this electrolyte comprises: non-aqueous organic solvent, lithium salts, film for additive, anti-overcharge additive, stabilization additives, it is characterized in that: also contain unsaturated sulfonic acid lactone and fluorocarbon surfactant as high temperature additive
Wherein the unsaturated sulfonic acid lactone is selected from one or more in the compound that following general formula I represents:
Figure FSA00000029539600011
R wherein 1-R 4Be hydrogen atom, fluorine atom or have the fluorine-containing of 1-12 carbon atom or not fluorine-containing alkyl, n is the integer of 0-3.
2. lithium manganate battery electrolyte according to claim 1 is characterized in that described high temperature additive unsaturated sulfonic acid lactone accounts for 0.1%～5% of electrolyte gross mass.
3. lithium manganate battery electrolyte according to claim 1 is characterized in that described fluorocarbon surfactant accounts for 0.01%～1% of electrolyte gross mass.
4. according to any one described lithium manganate battery electrolyte among the claim 1-3, it is characterized in that:
Fluorocarbon surfactant is selected from one or more in the compound with general formula I I or II ':
Rf-(CH 2CH 2O) x-(CH 2CH 2CH 2O) y-H general formula I I
Rf-(CH 2CH 2O) x-(C 3H 6O) y-Rf general formula I I '
In the formula, C 3H 6O=CH 2CH (CH 3) O or CH (CH 3) CH 2O,
Rf contains the fluoro of 2-18 carbon atom or the saturated or unsaturated alkyl of perfluoro,
X is the integer of 1-30, and y is the integer of 0-20, and x+y is the integer of 1-30;
Or fluorocarbon surfactant is selected from the compound with general formula III or IV one or more:
C nF 2n+1SO 2N (C mH 2m+1) CH 2CH 2O (CH 2CH 2O) 1The H general formula III
In the formula, n is the integer of 4-18; M is the integer of 1-4; The 1st, the integer of 5-25;
With
C nF 2n+1-X-(CH 2CH 2O) M '-Y general formula I V
In the formula, X is-CONH-and-SO 2NR-; R is the C1-C8 alkyl; Y is-H ,-OH ,-CH 3,-PO 3W 2Or-SO 3W; W is an alkali metal; N is the integer of 3-10, and m ' is the integer of 2-100;
Or fluorocarbon surfactant is selected from the compound with general formula V or VI one or more:
Figure FSA00000029539600021
10≤n≤300 wherein
General formula V,
N among the general formula V is an integer,
Figure FSA00000029539600022
The integer of n=1～20, the integer of m=1～20, and the integer of n+m=2～30,
General formula VI.
5. according to claim 1 or 4 described lithium manganate battery electrolyte, it is characterized in that: described fluorocarbon surfactant is selected from one or more in the compound of following structural formula:
F (CF 2CF 2) m(CH 2CH 2O) nH is m=1～9 wherein, n=1～25;
H (CF 2CF 2) mCH 2O (CH 2CH 2O) nH is m=1～9 wherein, n=1～30;
F (CF 2CF 2) mO (CH 2CH 2O) n(CF 2CF 2) mF is m=1～9 wherein, n=1～25;
Figure FSA00000029539600023
10≤n≤300 wherein;
N is an integer in the formula,
Figure FSA00000029539600031
The integer of n=1～20 wherein, the integer of m=1～20, and the integer of n+m=2～30.
6. lithium manganate battery electrolyte according to claim 1 is characterized in that: described non-aqueous organic solvent is one or more of carbonic ester, carboxylate, ether or ketone.
7. lithium manganate battery electrolyte according to claim 6 is characterized in that: described carbonic ester is one or more of ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate or carbonic acid first propyl ester; Described carboxylate is one or more of methyl formate, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, methyl butyrate or ethyl butyrate; Described ether is dimethoxymethane, 1,2-dimethoxy-ethane, oxolane or 1, one or more of 3-dioxolanes; Described ketone is gamma-butyrolacton.
8. lithium manganate battery electrolyte according to claim 1 is characterized in that: described lithium salts is LiPF 6, LiBF 4, LiBOB or LiODFB one or more, the concentration of lithium salts is counted 0.7～1.5mol/L by lithium ion in electrolyte.
9. lithium manganate battery electrolyte according to claim 1, it is characterized in that: described film for additive is vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate, 1,3-sulfonic acid propiolactone or 1, one or more of 4-sulfonic acid butyrolactone account for 0.5%～5% of electrolyte gross mass.
10. lithium manganate battery electrolyte according to claim 1, it is characterized in that: described anti-overcharge additive is one or more of biphenyl, cyclohexyl benzene,toluene,xylene, methyl phenyl ethers anisole, chlorobenzene methyl ether or diphenyl ether, accounts for 0%～12% of electrolyte gross mass; Described stabilization additives is one or more of organic amine or alkyl silazane class, accounts for 0.01%～0.5% of electrolyte gross mass.
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