CN102064344A - Novel electrolyte for power battery - Google Patents
Novel electrolyte for power battery Download PDFInfo
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- CN102064344A CN102064344A CN2010105987261A CN201010598726A CN102064344A CN 102064344 A CN102064344 A CN 102064344A CN 2010105987261 A CN2010105987261 A CN 2010105987261A CN 201010598726 A CN201010598726 A CN 201010598726A CN 102064344 A CN102064344 A CN 102064344A
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- carbonate
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- power battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of battery electrolytes, and in particular discloses a novel electrolyte for a power battery, which comprises the following raw materials in percent by weight: 8-15 percent of conductive lithium salt as a component A, 73-90 percent of organic solvent as a component B and 1-10 percent of additive as a component C. A sulphonate organic compound as the additive is added in the electrolyte of the common lithium ion battery, the addition of the sulphonate organic compound accounts for 1-10 percent of the weight of the electrolyte of the lithium ion power battery and is chemically compounded with 8-15 percent of conductive lithium and 75-90 percent of organic solvent to prepare the novel electrolyte for the power battery, which has better high-temperature circulating performance and is suitable for the power battery. A power battery especially using lithium manganese oxide as a cathode material can prevent Mn smelted at high temperature from being attracted on the surface of the cathode, thereby inhibiting the impedance rise, effectively improving the circulating periodicity and greatly prolonging the circulating service life.
Description
Technical field
The present invention relates to the battery electrolyte technical field, specifically disclose a kind of new type power battery electrolytic solution.
Background technology
Since the nineties in 0th century, as a new technology, the exploitation of hybrid vehicle has obtained many developed countries and regional great attentions such as the U.S., Japan and West Europe, and has obtained some great achievement and progress.China in 2004 has surpassed Germany becomes the 3rd automobile superpower in the world, estimate that the interior China of 3-5 can suddenly become the second in the world automobile superpower from now on, as not taking measures, the energy problem of thing followed China, environmental problem, traffic problems and health problem will be more than now serious.Therefore constantly improve power lithium-ion battery and electrokinetic technique and all will have important society and strategic importance the energy and environment problem of alleviating the China and the whole world.
At present, the various characteristics of electric automobile mainly depends on battery, and battery is had following requirement:
(1) high volume energy density, high weight energy density;
(2) output density of high output density, particularly Unit Weight;
(3) good cycle characteristics.
But existing lithium rechargeable battery still can not fully satisfy these requirements, and the task of top priority is the high performance large-scale lithium rechargeable battery of exploitation.Existing lithium-ion battery electrolytes all is to be mixed by following several carbonates organic solvents, as: ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), vinylene carbonate (VC), fluorinated ethylene carbonate (FEC), ethyl acetate (EA), fluorobenzene (FB) etc., every kind of solvent all has pluses and minuses, and irrational solvent formula and proportioning can influence the serviceability temperature of lithium-ion battery electrolytes.
Summary of the invention
The objective of the invention is to overcome the prior art deficiency, in existing formula system, add one or more new additives, solve lithium-ion-power cell bad problem of cycle performance under hot conditions.
The object of the present invention is achieved like this:
1, the new type power battery electrolytic solution comprises following raw materials by weight percent:
Component A electric conducting lithium salt 8-15%
Effect: as the electric conducting lithium salt of lithium-ion battery electrolytes, lithium salts is a source of supplying with lithium ion, can be lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), di-oxalate lithium borate (LiBOB), three (trifluoromethyl sulphonyl) lithium methide (LiC(SO
2CF
3)
3), trifluoromethyl sulfonic acid lithium (LiCF
3SO
3) wait one or more.
B component organic solvent 75-90%
Effect:, can be any one or a few of ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), ethyl acetate (EA), fluorobenzene (FB), fluorinated ethylene carbonate (FEC), chlorocarbonic acid vinyl acetate (ClEC) ethyl acetoacetate, carbonic acid first propyl ester (MPC), oxolane (THF), ethyl butyl carbonate (BEC), gamma-butyrolacton (GBL) as the organic solvent of lithium-ion battery electrolytes.
Component C additive 1-10%
Effect: additive has the outstanding feature of " consumption few (general volume ratio of single use or mass ratio are no more than 5%), instant effect ", under the condition that does not increase the battery cost, can significantly improve some macro property of lithium ion battery.
Additive generally has following characteristics: (1) less consumption can improve one or more performances of battery; (2) battery performance is had no side effect, not with battery in other material generation side reaction; (3) with organic solvent intermiscibility is preferably arranged, have in addition can be dissolved in fully wherein; (4) price is relatively low; (5) avirulence or toxicity are less.
Wherein, additive can be vinylene carbonate (VC), fluorinated ethylene carbonate (FEC), vinylethylene carbonate (VEC), ethyl acetate (EA), fluorobenzene (FB), 1,3-N-morpholinopropanesulfonic acid lactone (1,3-PS), cyclohexyl benzene (CHB), methane-disulfonic acid methylene ester (MMDS), triphenyl phosphite (TTPi), three (2,2,2-trifluoroethyl) any one of phosphite ester (TTFP).
Preferably; The new type power battery electrolytic solution comprises following raw materials by weight percent:
Component A electric conducting lithium salt 10 ~ 13%
B component organic solvent 80 ~ 86%
Component C additive 3 ~ 9%
More preferably; The new type power battery electrolytic solution comprises following raw materials by weight percent:
Component A electric conducting lithium salt 12%
B component organic solvent 80 ~ 85%
Component C additive 3 ~ 5%
2, technological process:
Preparation electrolyte: (preparation lithium-ion battery electrolytes among the moisture＜10ppm, oxygen part＜10ppm) in the glove box of applying argon gas, high-purity organic solvent is reached proportioning in order evenly to be mixed, with magnetic stirrer 5 ~ 15 minutes, add the additive that needs to improve high-temperature behavior, add electric conducting lithium salt in the mixed solution slowly again, stirred 5 ~ 15 minutes, the electrolyte for preparing is inserted (steel cylinder vacuumizes displacement three times with filling high-purity argon gas) in the stainless steel cylinder, promptly obtain new type lithium ion power battery electrolyte of the present invention.
Advantage of the present invention and beneficial effect are: add the additive of the organic compound of sulfonic acid methylene ester class as lithium-ion battery electrolytes in common lithium-ion battery electrolytes, addition is 1%～10% of a lithium-ion battery electrolytes weight, make and can satisfy lithium-ion battery electrolytes of the present invention lithium ion battery and have good high temperature cyclic performance.Be applicable to electrokinetic cell, particularly LiMn2O4 is done the electrokinetic cell of positive electrode, can prevent that the Mn that melts under the high temperature is adsorbed on negative terminal surface, has suppressed the impedance rising, has effectively improved cyclic periodicity, can increase its cycle life greatly.
Embodiment
The present invention is further illustrated with specific embodiment below, but the present invention is not subjected to the qualification of following embodiment.
Embodiment 1
(moisture＜10ppm in the glove box of applying argon gas, in oxygen part＜10ppm), respectively by the EC:DMC:EMC=10:30:35(weight ratio) take by weighing each high-purity organic solvent, organic solvent accounts for 80% of total weight, stirs to add additive after 10 minutes, be vinylene carbonate (VC), account for 2% of total weight, cyclohexyl benzene (CHB) accounts for 3% of total weight, methane-disulfonic acid methylene ester (MMDS) accounts for 1% of total weight and add 14% lithium hexafluoro phosphate LiPF then in mixed solution
6(concentration of lithium salts is 1mol/L) stirred and promptly obtained the novel electrokinetic cell electrolyte of the present invention in 8 minutes.
Embodiment 2
(moisture＜10ppm in the glove box of applying argon gas, in oxygen part＜10ppm), respectively by the EC:DEC:PC=10:30:45(weight ratio) take by weighing each high-purity organic solvent, organic solvent accounts for 80% of total weight, stir and add additive after 10 minutes, be vinylene carbonate (VC), account for 1% of total weight, biphenyl (BP) accounts for 2% of total weight, methane-disulfonic acid methylene ester (MMDS), account for 2% of total weight, triphenyl phosphite (TPPi) accounts for 1% of total weight, adds 12% lithium hexafluoro phosphate (LiPF then in mixed solution
6) and 2% LiBF4 (LiBF
4), stir again and promptly obtained the novel electrokinetic cell electrolyte of the present invention in 13 minutes.
Embodiment 3
(moisture＜10ppm in the glove box of applying argon gas, in oxygen part＜10ppm), respectively by EC:DEC=10:20(weight ratio) take by weighing each high-purity organic solvent, organic solvent accounts for 78% of total weight, stir and add additive after 10 minutes, fluorinated ethylene carbonate (FEC) accounts for 2% of total weight, 1, the 3-N-morpholinopropanesulfonic acid lactone (1,3-PS), account for 3% of total weight, methane-disulfonic acid methylene ester (MMDS), account for 2% of total weight, three (2,2, the 2-trifluoroethyl) phosphite ester (TTFP), account for 2% of total weight, in mixed solution, add 12% lithium hexafluoro phosphate (LiPF then
6) and 1% trifluoromethyl sulfonic acid lithium (LiCF
3SO
3), stir again and promptly obtained the novel electrokinetic cell electrolyte of the present invention in 10 minutes.
Embodiment 4
(moisture＜10ppm in the glove box of applying argon gas, in oxygen part＜10ppm), respectively by EC:DMC: the EMC:FEC=10:40:30:10(weight ratio) take by weighing each high-purity organic solvent, organic solvent accounts for 78% of total weight, stir and add additive after 10 minutes, vinylethylene carbonate (VEC), account for 2% of total weight, 1, the 3-N-morpholinopropanesulfonic acid lactone (1,3-PS), account for 2% of total weight, methane-disulfonic acid methylene ester (MMDS), account for 3% of total weight, in mixed solution, add 13% lithium hexafluoro phosphate (LiPF then
6) and 2% di-oxalate lithium borate (LiBOB), stir again and promptly obtained the novel electrokinetic cell electrolyte of the present invention in 15 minutes.
The performance test of final products
Prepare 2 kinds of different electrolytes sample A/B respectively, do not contain additive methane-disulfonic acid methylene ester (MMDS) organic compound in the A sample, the B sample contains 2% methane-disulfonic acid methylene ester (MMDS) organic compound, make the box hat battery according to certain operational procedure, wherein positive electrode is a LiMn2O4, negative material is a Delanium, through changing into, after partial volume, high-temperature storage and the cycle performance test, obtaining correction data as follows:
The comparison of 300 all circulation volume conservation rates that two kinds of electrolyte of table 1 are measured
Two kinds of electrolyte of table 2 are through the comparison of residual capacity after 85 ℃/4 hours high-temperature storage
The comparison of two kinds of electrolyte of table 3 through recovering capacity after the high-temperature storage in 85 ℃/4 hours
From table 1,2,3 as can be seen, novel electrokinetic cell of the present invention electrolyte and conventional electrolysis liquid phase ratio, the chemical property of test battery under hot conditions has good high-temperature storge quality and long cycle performance, and each chemical property index is significantly better than conventional electrolysis liquid.This illustrates that electrolyte of the present invention has good high temperature cyclic performance.
The above only is a better embodiment of the present invention, so all equivalences of doing according to the described structure of patent claim of the present invention, feature and principle change or modify, is included in the patent claim of the present invention.
Claims (9)
1. new type power battery electrolytic solution is characterized in that: comprise following raw materials by weight percent:
Component A electric conducting lithium salt 8-15%
B component organic solvent 75-90%
Component C additive 1-10%
Wherein, electric conducting lithium salt is one or more of lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, three (trifluoromethyl sulphonyl) lithium methide, trifluoromethyl sulfonic acid lithium;
Wherein, organic solvent be ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, fluorobenzene, fluorinated ethylene carbonate, chlorocarbonic acid vinyl acetate ethyl acetoacetate, carbonic acid first propyl ester, oxolane, ethyl butyl carbonate, gamma-butyrolacton any one or a few, mix with arbitrary proportion;
Wherein, additive is vinylene carbonate, fluorinated ethylene carbonate, vinylethylene carbonate, ethyl acetate, fluorobenzene, 1,3-N-morpholinopropanesulfonic acid lactone, cyclohexyl benzene, methane-disulfonic acid methylene ester, triphenyl phosphite, three (2,2,2-trifluoroethyl) any one or a few of phosphite ester.
2. a kind of new type power battery electrolytic solution according to claim 1 is characterized in that: the methane-disulfonic acid methylene ester in the described additive is white or off-white color crystal or crystalline powder.
3. a kind of new type power battery electrolytic solution according to claim 1 is characterized in that: comprise following raw materials by weight percent:
Component A electric conducting lithium salt lithium hexafluoro phosphate and di-oxalate lithium borate amount to 8 ~ 15%
B component organic solvent ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate and ethyl acetoacetate amount to 75-85% for four kinds
Component C additive methane-disulfonic acid methylene ester 1 ~ 5%.
4. a kind of new type power battery electrolytic solution according to claim 1 is characterized in that: wherein, additive is: vinylene carbonate, account for 2% of total weight, and cyclohexyl benzene accounts for 3% of total weight, and methane-disulfonic acid methylene ester accounts for 1% of total weight.
5. a kind of new type power battery electrolytic solution according to claim 1 is characterized in that: wherein, additive is: be vinylene carbonate, account for 1% of total weight, biphenyl accounts for 2% of total weight, methane-disulfonic acid methylene ester, account for 2% of total weight, triphenyl phosphite accounts for 1% of total weight.
6. a kind of new type power battery electrolytic solution according to claim 1, it is characterized in that: wherein, additive is: fluorinated ethylene carbonate accounts for 2% of total weight, 1, the 3-N-morpholinopropanesulfonic acid lactone, account for 3% of total weight, methane-disulfonic acid methylene ester accounts for 2% of total weight, three (2,2, the 2-trifluoroethyl) phosphite ester, account for 2% of total weight.
7. a kind of novel lithium-ion battery electrolytes according to claim 1 is characterized in that: wherein, additive is: vinylethylene carbonate, account for 2%, 1 of total weight, the 3-N-morpholinopropanesulfonic acid lactone, account for 2% of total weight, methane-disulfonic acid methylene ester accounts for 3% of total weight.
8. a kind of new type power battery electrolytic solution according to claim 1, it is characterized in that: its preparation method is as follows: preparation electrolyte: (moisture＜10ppm in the glove box of applying argon gas, preparation lithium-ion battery electrolytes in oxygen part＜10ppm), above-mentioned high-purity organic solvent is reached proportioning in order evenly to be mixed, with magnetic stirrer 5 ~ 15 minutes, in mixed solution, be sequentially added into additive then, add electric conducting lithium salt in the mixed solution slowly again, stirred 5 ~ 15 minutes, the electrolyte for preparing is inserted in the stainless steel cylinder, described steel cylinder vacuumizes displacement three times with filling high-purity argon gas, promptly obtains new type lithium ion battery electrolyte of the present invention.
9. a kind of novel electrokinetic cell electrolyte according to claim 1 is characterized in that:
The preparation method is as follows: (preparation lithium-ion battery electrolytes among the moisture＜10ppm, oxygen part＜10ppm) in the glove box of applying argon gas, above-mentioned high-purity organic solvent is reached proportioning in order evenly to be mixed, with magnetic stirrer 8 minutes, in mixed solution, be sequentially added into additive then, add electric conducting lithium salt in the mixed solution slowly again, stirred 5 minutes, the electrolyte for preparing is inserted (steel cylinder vacuumizes displacement three times with filling high-purity argon gas) in the stainless steel cylinder, promptly obtain new type lithium ion battery electrolyte of the present invention.
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|---|---|---|---|
| CN2010105987261A CN102064344A (en) | 2010-12-21 | 2010-12-21 | Novel electrolyte for power battery |
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|---|---|---|---|
| CN2010105987261A CN102064344A (en) | 2010-12-21 | 2010-12-21 | Novel electrolyte for power battery |
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| CN103413971A (en) * | 2013-08-23 | 2013-11-27 | 轻工业化学电源研究所 | Lithium-ion battery electrolyte |
| CN103427114A (en) * | 2013-08-29 | 2013-12-04 | 嘉德力电源科技（苏州）有限公司 | Multifunctional lithium-ion battery electrolytic solution and preparing method thereof |
| CN103474708A (en) * | 2013-09-29 | 2013-12-25 | 天津力神电池股份有限公司 | Lithium ion battery comprising electrolyte solutions with improved safety and storage performance |
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