CN106129473A - A kind of nonaqueous electrolytic solution of silicon-based anode lithium ion battery - Google Patents
A kind of nonaqueous electrolytic solution of silicon-based anode lithium ion battery Download PDFInfo
- Publication number
- CN106129473A CN106129473A CN201610827267.7A CN201610827267A CN106129473A CN 106129473 A CN106129473 A CN 106129473A CN 201610827267 A CN201610827267 A CN 201610827267A CN 106129473 A CN106129473 A CN 106129473A
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- CN
- China
- Prior art keywords
- electrolytic solution
- nonaqueous electrolytic
- additive
- silicon
- lithium ion
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
It is desirable to provide a kind of charge and discharge cycles and the nonaqueous electrolytic solution of the excellent silicon-based anode lithium ion battery of high-temperature storage performance.The present invention is made up of solvent, lithium salts, unsaturated siloxane class additive A and fluoro sulfimide salt additive B, and additive A is 0.1% 3% relative to the ratio of nonaqueous electrolytic solution gross weight；Additive B is 0.1% 10% relative to the ratio of nonaqueous electrolytic solution gross weight；Solvent is cyclic carbonate and/or linear carbonate, and lithium salts molar concentration in a solvent is 0.8 1.5mol/L；The nonaqueous electrolytic solution of the present invention can comprehensively promote high/low temperature and the cycle performance of silicon-based anode lithium ion battery.Present invention can apply to field of lithium ion battery.
Description
Technical field
The present invention relates to a kind of field of lithium ion battery, particularly relate to the non-aqueous solution electrolysis of a kind of silicon-based anode lithium ion battery
Liquid.
Background technology
Lithium ion battery because of its have running voltage height, energy density height, environmental friendliness, stable circulation and safety etc. excellent
Point, obtains extensively application in 3C electronic equipment, the application then rapid development in pure electronic and hybrid electric vehicle.New application
Constantly increasing the demand of capacity of lithium ion battery, silicon based anode material is one of effective way solving this problem, and it stores up lithium
The pure graphite cathode of Capacity Ratio is higher and raw material is the abundantest.
The silicon based anode material of lithium ion battery is in actual use owing to the embedding abjection of lithium is along with huge volume
Change, can cause the efflorescence of material, crack and the stripping with conductive agent, directly result in the cyclicity of silicon-based anode lithium ion battery
Can dramatic decrease.It is usually added into fluoro carbonic ester class additive carries out negative pole to promote the circulation of silicon-based anode lithium ion battery
Film forming, but this membrane structure can rupture in the circulating cycle, causes fluoro carbonic ester quickly to be disappeared during continuous film forming
Consumption.It addition, the high-temperature behavior of fluoro carbonic ester class additive is poor, easily produce after high-temperature storage gas cause cell expansion and
The capability retention of battery and capacity restoration rate decline.
Summary of the invention
The technical problem to be solved is to overcome the deficiencies in the prior art, it is provided that a kind of charge and discharge cycles and high temperature
The nonaqueous electrolytic solution of the silicon-based anode lithium ion battery that storge quality is excellent.
The technical solution adopted in the present invention is: electrolyte of the present invention is added by solvent, lithium salts, unsaturated siloxane class
Add agent A and fluoro sulfimide salt additive B composition；Described electrolysis additive A selected from structural formula as (1), (2), (3) or
(4) compound shown in,
(1)
Wherein R1～R12 selected from carbon number be the alkyl of 1-3, in R1～R12 at least one be unsaturated alkyl；
(2)
Wherein R13～R22 selected from carbon number be the alkyl of 1-3, in R13～R22 at least one be unsaturated alkyl；
(3)
Wherein R23～R30 selected from carbon number be the alkyl of 1-3, in R23～R30 at least one be unsaturated alkyl；
(4)
Wherein R31～R36 selected from carbon number be the alkyl of 1-3, in R31～R36 at least one be unsaturated alkyl；
Unsaturated siloxane class additive A is 0.1%～3% relative to the ratio of nonaqueous electrolytic solution gross weight；Described fluoro sulphonyl
Imines salt additive B is selected from trimethyl fluoride sulfonyl lithium (LiCF3SO2), difluoro lithium sulfimide (LiFN (FSO2)2), double
(trifluoromethyl sulfonyl) imide li (LiN (CF3SO2)2), double (pentafluoroethyl group sulfonyl) imide li (LiN
(C2F5SO2)2, difluoromethyl ring di-sulfonyl imides lithium (LiDMSI), the double sulfimide lithium (LiTESI) of four fluoro ethyl rings or hexafluoro
At least one in the double sulfimide lithium (LiHPSI) of propyl group ring, additive B is relative to the ratio of nonaqueous electrolytic solution gross weight
0.1%～10%；Solvent is cyclic carbonate and/or linear carbonate, and lithium salts molar concentration in a solvent is 0.8～1.
5mol/L。
Further, described nonaqueous electrolytic solution also includes conventional lithium battery electrolytes additive, with described nonaqueous electrolytic solution
Total amount be 100 parts of meters, the addition of conventional lithium battery electrolytes additive is less than or equal to 10 weight portions, that is conventional lithium electricity
The addition of pond electrolysis additive is 0～10 weight portions.
The most further, described conventional lithium battery electrolytes additive is ethylene carbonate, fluorinated ethylene carbonate, fourth two
At least one in nitrile, adiponitrile, 1,3-propane sultone, 1,4-butane sultones or 1,3-propene sultone.
Further, described cyclic carbonate is ethylene carbonate, Allyl carbonate, butylene or γ-Ding Nei
At least one in ester.
The most further, described linear carbonate is dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, carbonic acid first
At least one in propyl ester, ethyl propyl carbonic acid ester, propyl acetate, ethyl propionate or propyl propionate.
The most further, described lithium salts is LiPF6、LiBF4、LiAsF6, LiBOB, LiDFOB or LiPF4C204In
At least one.
The invention has the beneficial effects as follows: the anion of the fluoro sulfimide class salt in the present invention can be at silicon-based anode table
The rapid releasing fluoride ion in face forms passing through of high-quality lithium fluoride film, beneficially lithium ion, then by adding unsaturated silica
Alkyl compound, Si-O-Si key therein and unsaturated double-bond or three keys are combined and occur polyreaction with negative material, right
Silicon-based anode SEI film destruction in volume contraction with expansion process plays the effect filling up agent, increases the elasticity of SEI film, from
And reduce fluorion in circulation and, in the consumption of film forming procedure repeatedly, therefore can significantly improve the circulation of silicon-based anode lithium ion battery
Performance.
Detailed description of the invention
Below by way of specific embodiment, the present invention is described in detail.
Embodiment 1
Preparing silicon-based anode lithium ion nonaqueous electrolytic solution in BRAUN glove box, being full of purity in glove box is the nitrogen of 99.999%
Gas, in glove box, moisture is less than 5 ppm, and temperature is room temperature, and the proportioning of electrolyte is: ethylene carbonate (EC), Ethyl methyl carbonate
Lithium hexafluoro phosphate (the LiPF of 1mol/L is added with diethyl carbonate after mixing with mass ratio 1:1:16), add total electrolyte matter
The fluorinated ethylene carbonate of gauge 5%, four (dimethyl ethenyl siloxy) silane and 1% imidodisulfuryl fluoride lithium salts of 1%.
Being positive pole by the cobalt acid lithium that this electrolyte injects 2Ah, the silicon carbon material of 10% silicone content is in the lithium battery of negative pole,
With 0.05C constant-current charge 1h, with 0.1C constant-current charge 1h, then with the electric current constant-current constant-voltage charging of 0.2C to 4.35V, insert 55
DEG C baking oven in aging 24h, with 0.2C electric current constant-current discharge to 3V, carry out room temperature circulation, high temperature storage and low temperature the most respectively
Discharge test.
Carry out normal-temperature circulating performance test
Battery after chemical conversion drops to 0.1C with 1C constant-current charge to 4.35V then constant-voltage charge to electric current under the conditions of 25 DEG C,
Then with 1C electric current constant-current discharge to 3.0V, so circulation 100 weeks, test battery the capacity holding of the 1st week and the 100th week
Rate, by the capability retention of following formula calculating room temperature circulation:
Discharge capacity * 100% of the discharge capacity of capability retention=100th week/1st week.
High-temperature storage performance is tested
Battery after chemical conversion drops to 0.1C with 1C constant-current charge to 4.35V then constant-voltage charge to electric current under the conditions of 25 DEG C,
Measure initial discharge capacity and the cell thickness of battery, with 1C electric current constant-current discharge to 3.0V after 85 DEG C/6h of high temperature storage, record
The holding capacity of battery and recovery capacity, cell thickness and internal resistance all measure after battery is cooled to room temperature.By following formula
The high-temperature storage performance of son calculating battery:
Holding capacity/initial discharge capacity the * 100% of battery after capability retention=high-temperature storage；
Thickness swelling=(cell thickness-initial cells thickness after high-temperature storage)/initial cells thickness * 100%；
Resistance change rate=(internal resistance of cell-initial cells internal resistance after high-temperature storage)/initial cells internal resistance * 100%.
The present invention is also carried out example 2～6 and comparative example 1～7.Embodiment 2～6 and the operating process of comparative example 1～7
Same as in Example 1, different replaces four (dimethyl ethenyl siloxy) silane and 1% imidodisulfuryl fluoride lithium salt of 1%
For the additive formula in table 1, the most as shown in table 1.
Table 1
By embodiment 1～6 and the electrolyte for preparing of comparative example 1～7 be used for preparing lithium ion battery.The lithium ion battery prepared
High/low temperature and normal-temperature circulating performance are as shown in table 2.
Table 2
Knowable to the electric discharge of silicon-based anode high/low temperature shown in table 2 and loop test data, additive A is individually used to significantly improve
The high-temperature storage performance of battery, but the storage flatulence of battery and circulation can be deteriorated.Individually add additive B and can improve battery
Cycle performance and high temperature flatulence, but cryogenic property slightly reduces；When both are used in conjunction with, owing to coordinating effect is at silicon-based anode
Surface produces composite passivation film such that it is able to improve the combination property of battery.The additionally silicon in additive A-oxygen key and unsaturation
Exist while key and make silicon-based anode film strength higher and the impedance caused under high temperature storage conditions can be significantly reduced to increase,
Thus to promoting high-temperature storage performance, there is pivotal role.Dissociating of fluorine in additive B can reduce fluoro carbonic acid in circulation
The consumption of lithium ion in ester and electrolyte, thus the cycle performance of battery can be obviously improved.
Present invention can apply to field of lithium ion battery.
Claims (6)
1. the nonaqueous electrolytic solution of a silicon-based anode lithium ion battery, it is characterised in that: described electrolyte is by solvent, lithium salts, no
Saturated type siloxane additive A and fluoro sulfimide salt additive B composition；Described electrolysis additive A is selected from structural formula
Compound as shown in (1), (2), (3) or (4),
(1)
Wherein R1～R12 selected from carbon number be the alkyl of 1-3, in R1～R12 at least one be unsaturated alkyl；
(2)
Wherein R13～R22 selected from carbon number be the alkyl of 1-3, in R13～R22 at least one be unsaturated alkyl；
(3)
Wherein R23～R30 selected from carbon number be the alkyl of 1-3, in R23～R30 at least one be unsaturated alkyl；
(4)
Wherein R31～R36 selected from carbon number be the alkyl of 1-3, in R31～R36 at least one be unsaturated alkyl；
Unsaturated siloxane class additive A is 0.1%～3% relative to the ratio of nonaqueous electrolytic solution gross weight；Described fluoro sulphonyl
Imines salt additive B is selected from LiCF3SO2、LiFN(FSO2)2、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiDMSI、LiTESI
Or at least one in LiHPSI, additive B is relative to the ratio 0.1%～10% of nonaqueous electrolytic solution gross weight；Solvent is ring-type
Carbonic ester and/or linear carbonate, lithium salts molar concentration in a solvent is 0.8～1. 5mol/L.
The nonaqueous electrolytic solution of a kind of silicon-based anode lithium ion battery the most according to claim 1, it is characterised in that: described non-
Water electrolysis liquid also includes conventional lithium battery electrolytes additive, is in terms of 100 parts by the total amount of described nonaqueous electrolytic solution, conventional lithium electricity
The addition of pond electrolysis additive is less than or equal to 10 weight portions.
The nonaqueous electrolytic solution of a kind of silicon-based anode lithium ion battery the most according to claim 1, it is characterised in that: described ring
Shape carbonic ester is at least one in ethylene carbonate, Allyl carbonate, butylene or gamma-butyrolacton.
The nonaqueous electrolytic solution of a kind of silicon-based anode lithium ion battery the most according to claim 1, it is characterised in that: described chain
Shape carbonic ester be dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, propyl acetate, third
At least one in acetoacetic ester or propyl propionate.
The nonaqueous electrolytic solution of a kind of silicon-based anode lithium ion battery the most according to claim 2, it is characterised in that: described often
In rule lithium battery electrolytes additive is ethylene carbonate, fluorinated ethylene carbonate, succinonitrile, adiponitrile, 1,3-propane sulfonic acid
At least one in ester, 1,4-butane sultones or 1,3-propene sultone.
The nonaqueous electrolytic solution of a kind of silicon-based anode lithium ion battery the most according to claim 1, it is characterised in that: described lithium
Salt is LiPF6、LiBF4、LiAsF6, LiBOB, LiDFOB or LiPF4C204In at least one.
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| CN201610827267.7A CN106129473A (en) | 2016-09-18 | 2016-09-18 | A kind of nonaqueous electrolytic solution of silicon-based anode lithium ion battery |
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| CN201610827267.7A CN106129473A (en) | 2016-09-18 | 2016-09-18 | A kind of nonaqueous electrolytic solution of silicon-based anode lithium ion battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109088100A (en) * | 2018-07-13 | 2018-12-25 | 珠海市赛纬电子材料股份有限公司 | Electrolyte functional additive, nonaqueous lithium ion battery electrolyte and lithium ion battery containing the additive |
| CN109786809A (en) * | 2019-02-21 | 2019-05-21 | 欣旺达电动汽车电池有限公司 | A kind of electrolyte and secondary cell |
| CN112018446A (en) * | 2020-09-27 | 2020-12-01 | 珠海冠宇电池股份有限公司 | Electrolyte suitable for silicon-carbon system lithium ion battery |
| CN112886064A (en) * | 2021-04-27 | 2021-06-01 | 蜂巢能源科技有限公司 | Electrolyte and lithium ion battery |
| CN113161617A (en) * | 2021-03-26 | 2021-07-23 | 天津市捷威动力工业有限公司 | Low-temperature lithium ion battery electrolyte and lithium ion battery thereof |
| CN114204121A (en) * | 2021-11-01 | 2022-03-18 | 上海如鲲新材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
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| EP1202373A2 (en) * | 2000-10-30 | 2002-05-02 | Denso Corporation | Nonaqueous electrolytic solution and nonaqueous secondary battery |
| CN104900916A (en) * | 2015-06-26 | 2015-09-09 | 广州天赐高新材料股份有限公司 | Electrolyte solution for high-capacity lithium-ion battery, preparation method and lithium-ion battery |
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2016
- 2016-09-18 CN CN201610827267.7A patent/CN106129473A/en active Pending
Patent Citations (2)
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| EP1202373A2 (en) * | 2000-10-30 | 2002-05-02 | Denso Corporation | Nonaqueous electrolytic solution and nonaqueous secondary battery |
| CN104900916A (en) * | 2015-06-26 | 2015-09-09 | 广州天赐高新材料股份有限公司 | Electrolyte solution for high-capacity lithium-ion battery, preparation method and lithium-ion battery |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109088100A (en) * | 2018-07-13 | 2018-12-25 | 珠海市赛纬电子材料股份有限公司 | Electrolyte functional additive, nonaqueous lithium ion battery electrolyte and lithium ion battery containing the additive |
| CN109786809A (en) * | 2019-02-21 | 2019-05-21 | 欣旺达电动汽车电池有限公司 | A kind of electrolyte and secondary cell |
| CN109786809B (en) * | 2019-02-21 | 2023-08-15 | 欣旺达电动汽车电池有限公司 | Electrolyte and secondary battery |
| CN112018446A (en) * | 2020-09-27 | 2020-12-01 | 珠海冠宇电池股份有限公司 | Electrolyte suitable for silicon-carbon system lithium ion battery |
| CN112018446B (en) * | 2020-09-27 | 2022-07-01 | 珠海冠宇电池股份有限公司 | Electrolyte suitable for silicon-carbon system lithium ion battery |
| CN113161617A (en) * | 2021-03-26 | 2021-07-23 | 天津市捷威动力工业有限公司 | Low-temperature lithium ion battery electrolyte and lithium ion battery thereof |
| CN112886064A (en) * | 2021-04-27 | 2021-06-01 | 蜂巢能源科技有限公司 | Electrolyte and lithium ion battery |
| CN112886064B (en) * | 2021-04-27 | 2022-03-08 | 蜂巢能源科技有限公司 | Electrolyte and lithium ion battery |
| CN114204121A (en) * | 2021-11-01 | 2022-03-18 | 上海如鲲新材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
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