CN106785037B - A kind of lithium-ion battery electrolytes for ternary material battery - Google Patents
A kind of lithium-ion battery electrolytes for ternary material battery Download PDFInfo
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- CN106785037B CN106785037B CN201611217436.1A CN201611217436A CN106785037B CN 106785037 B CN106785037 B CN 106785037B CN 201611217436 A CN201611217436 A CN 201611217436A CN 106785037 B CN106785037 B CN 106785037B
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- lithium
- ion battery
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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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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 discloses a kind of lithium-ion battery electrolytes for ternary material battery, belong to lithium-ion battery electrolytes technical field.Technical solution of the present invention main points are as follows: a kind of lithium-ion battery electrolytes for ternary material battery, including organic solvent, lithium salts and additive, wherein the mass ratio of organic solvent, lithium salts and additive is 80-87:10.9-14:1.9-2.5.It is added in lithium-ion battery electrolytes of the invention in cyclohexyl benzene, double fluorine sulfimides and di-oxalate lithium borate, battery stores and overcharge performance in test in normal temperature circulation, high temperature circulation, full electricity and significantly improve.
Description
Technical field
The invention belongs to lithium-ion battery electrolytes technical fields, and in particular to a kind of lithium for ternary material battery from
Sub- battery electrolyte.
Background technique
In recent years, increasing due to haze, China pays high attention to energy and environmental problem at present, in the energy and environmental protection pressure
Under power, national urgent need low-carbon, environmental protection, the exploitation of renewable resource and implementation, the Chinese government are being increased to new energy vapour
The support dynamics of vehicle, New Energy Sources In China automobile market have a high potential.And China's automobile power lithium TV university at present mostly uses ferric phosphate
Lithium route, but the specific capacity due to LiFePO4, tap density, compacted density and current potential is all lower and limitation of consistency, closely
Development in pluralism is presented in the China Nian Lai lithium battery technology route, and especially ternary material battery has good development prospect.City at present
Battery Frequent Accidents on field, the safety of battery, which just seems, to be even more important, but current tertiary cathode material power battery presence follows
The defects of ring performance difference and poor safety.
Summary of the invention
The present invention is provided for the defect of ternary material battery poor circulation and poor safety performance currently on the market
A kind of lithium-ion battery electrolytes for ternary material battery.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of lithium ion for ternary material battery
Battery electrolyte, it is characterised in that the lithium-ion battery electrolytes include organic solvent, lithium salts and additive, wherein organic molten
The mass ratio of agent, lithium salts and additive is 80-87:10.9-14:1.9-2.5, and the organic solvent is by ethylene carbonate, carbonic acid
Acrylic ester, diethyl carbonate and methyl ethyl carbonate composition, the lithium salts is by lithium hexafluoro phosphate, double fluorine sulfimide lithiums and double oxalic acid
Lithium borate composition, the additive are made of vinylene carbonate, 1,3-propane sultone and cyclohexyl benzene.
Further preferably, the mass ratio of organic solvent, lithium salts and additive is in the lithium-ion battery electrolytes
81.7-85:11.4-13.2:2.5-5.9。
Further preferably, ethylene carbonate, propene carbonate, diethyl carbonate and methyl ethyl carbonate in the organic solvent
The mass ratio of ester is 26-32:5-8:20.6-28:20-25.
Further preferably, lithium hexafluoro phosphate in the lithium salts, double fluorine sulfimide lithiums and di-oxalate lithium borate quality
Than for 11-13:0.1-0.9:0.1-0.5.
Further preferably, vinylene carbonate in the additive, 1,3-propane sultone and cyclohexyl benzene quality
Than for 0.5-0.7:1-1.2:1-4.
Compared with the prior art, the present invention has the following advantages: double fluorine sulfimide lithiums (LiFSI) are ternarys in the present invention
Very crucial one of lithium carbonate in material cell very effective can improve the property such as its circulation and high/low temperature, and
LiFSI can greatly improve electrolyte high temperature resistant and high-voltage performance；Without containing F member in di-oxalate lithium borate (LiBOB) molecular structure
Element, and there is good thermal stability and very unique filming performance.Both lithium carbonates are added on a small quantity, can be significantly
Improve the cycle performance of battery, especially high temperature cyclic performance.Present invention adds 1,3- propane sultone (PS) and carbonic acid are sub-
Vinyl acetate (VC) synergistic effect, forms stable SEI film, reduces impedance, improves the cycle performance of battery.In addition the present invention also adds
Cyclohexyl benzene additive is entered.Battery during the charging process, voltage be more than additive electropolymerization voltage when, cyclohexyl benzene monomer
Polymerization reaction occurs, generates atrament polycyclic hexyl benzene, forms barrier layer in electrode surface, increases rapidly the internal resistance of cell,
To slow down or prevent the further decomposition of electrolyte, gas and the heat of generation are significantly reduced, and prevent thermal runaway, keep battery
It is in a safe condition.The preferred solvent ratios of the present invention, keep the electrolyte property more excellent.
Detailed description of the invention
Fig. 1 is the over-charging of battery test curve that lithium-ion battery electrolytes made from the embodiment of the present invention 1 are formed；
Fig. 2 is the over-charging of battery test curve that lithium-ion battery electrolytes made from comparative example 1 of the present invention are formed.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
By 0.7g vinylene carbonate, 1.2g 1,3- propane sultone, 4g cyclohexyl benzene, the bis- fluorine sulfimide lithiums of 0.9g,
0.5g di-oxalate lithium borate and 11g lithium hexafluoro phosphate are dissolved in 81.7g organic solvent (wherein 32g ethylene carbonate, 7g carbonic acid third
Enester, 20.6g diethyl carbonate and 22.1g methyl ethyl carbonate) in, it is uniformly mixed obtained lithium-ion battery electrolytes.
Embodiment 2
By 0.7g vinylene carbonate, 1.2g 1,3- propane sultone, 3.4g cyclohexyl benzene, the bis- fluorine sulfimides of 0.4g
Lithium, 0.4g di-oxalate lithium borate and 11g lithium hexafluoro phosphate are dissolved in 82.9g organic solvent (wherein 31g ethylene carbonate, 7g carbon
Acid propylene ester, 21g diethyl carbonate and 23.9g methyl ethyl carbonate) in, it is uniformly mixed obtained lithium-ion battery electrolytes.
Embodiment 3
By 0.7g vinylene carbonate, 1.2g 1,3- propane sultone, 3.4g cyclohexyl benzene, the bis- fluorine sulfimides of 0.4g
Lithium, 0.4g di-oxalate lithium borate and 11g lithium hexafluoro phosphate are dissolved in 82.9 organic solvents (wherein 26g ethylene carbonate, 6g carbonic acid
Acrylic ester, 25.9g diethyl carbonate, 25g methyl ethyl carbonate) in, it is uniformly mixed obtained lithium-ion battery electrolytes.
Embodiment 4
By 0.6g vinylene carbonate, 1g 1,3- propane sultone, 2g cyclohexyl benzene, the bis- fluorine sulfimide lithiums of 0.3g,
0.3g di-oxalate lithium borate and 12g lithium hexafluoro phosphate are dissolved in 83.8g organic solvent (wherein 27.3g ethylene carbonate, 6g carbonic acid
Acrylic ester, 25g diethyl carbonate and 24.5g methyl ethyl carbonate) in, it is uniformly mixed obtained lithium-ion battery electrolytes.
Embodiment 5
By 0.6g vinylene carbonate, 1g 1,3- propane sultone, 2g cyclohexyl benzene, the bis- fluorine sulfimide lithiums of 0.2g,
0.2g di-oxalate lithium borate and 11g lithium hexafluoro phosphate are dissolved in 85g organic solvent (wherein 30g ethylene carbonate, 5g propylene carbonate
Ester, 28g diethyl carbonate and 22g methyl ethyl carbonate) in, it is uniformly mixed obtained lithium-ion battery electrolytes.
Embodiment 6
By 0.5g vinylene carbonate, 1g 1,3- propane sultone, 1g cyclohexyl benzene, the bis- fluorine sulfimide lithiums of 0.1g,
0.1g di-oxalate lithium borate and 13g lithium hexafluoro phosphate are dissolved in 84.3g organic solvent (wherein 30.3g ethylene carbonate, 8g carbonic acid
Acrylic ester, 26g diethyl carbonate and 20g methyl ethyl carbonate) in, it is uniformly mixed obtained lithium-ion battery electrolytes.
Comparative example 1
0.1g di-oxalate lithium borate and 13g lithium hexafluoro phosphate are dissolved in 86.9g organic solvent (wherein 32g ethylene carbonate
Ester, 7g propene carbonate, 26.4g diethyl carbonate and 21.5g methyl ethyl carbonate) in, it is uniformly mixed obtained lithium ion battery battery
Solve liquid.
Comparative example 2
By 0.5g vinylene carbonate, 1g 1,3- propane sultone, 1g cyclohexyl benzene, 0.1g di-oxalate lithium borate and 13g
Lithium hexafluoro phosphate is dissolved in 84.4g organic solvent (wherein 27.4g ethylene carbonate, 7g propene carbonate, 30g diethyl carbonate
With 20g methyl ethyl carbonate) in, it is uniformly mixed obtained lithium-ion battery electrolytes.
Comparative example 3
By 0.5g vinylene carbonate, 1g cyclohexyl benzene, the bis- fluorine sulfimide lithiums of 0.4g, 0.1g di-oxalate lithium borate and
13g lithium hexafluoro phosphate be dissolved in 85g organic solvent (wherein 16g ethylene carbonate, 7g propene carbonate, 42g diethyl carbonate and
20g methyl ethyl carbonate) in, it is uniformly mixed obtained lithium-ion battery electrolytes.
It is soft that above-described embodiment 1-6 and comparative example 1-3 lithium-ion battery electrolytes prepared are added separately to 20Ah monomer
On packet battery, room temperature 1C charge-discharge cycle, 55 DEG C of 0.5C charge-discharge cycles, 60 DEG C of full electricity are tested respectively and stores 7 days, overcharge test.By
Cyclohexyl benzene, double fluorine sulfimide lithiums and double oxalic acid boric acid is added known to following table in lithium-ion battery electrolytes produced by the present invention
Lithium, battery store and overcharge performance in test in normal temperature circulation, high temperature circulation, full electricity and significantly improve.
Specific testing result is as shown in the table:
| 500 weeks usually warm circulation volume conservation rate % | 55 degree of high temperature circulations, 300 weeks capacity retention ratio % | 60 degree of full electricity storages, 7 days capacity retention ratio % | 60 degree of 7 days thickness change % | It overcharges | |
| Embodiment 1 | 95% | 85% | 94.20% | 2.30% | 3C10V passes through |
| Embodiment 2 | 94.62% | 82.00% | 92.30% | 2.25% | 3C10V passes through |
| Embodiment 3 | 94.10% | 80.70% | 92.20% | 2.43% | 3C10V passes through |
| Embodiment 4 | 93.80% | 79.60% | 90.60% | 3.30% | 3C8.4V passing through |
| Embodiment 5 | 93.6 | 79.50% | 89.90% | 3.28% | 3C6.3V passing through |
| Embodiment 6 | 92.90% | 78.50% | 86.73% | 3.56% | 1C5.5V passing through |
| Comparative example 1 | 70.20% | 55.80% | 60.20% | 5.63% | Explosion on fire |
| Comparative example 2 | 80.20% | 58.90% | 63.08% | 6.00% | Explosion on fire |
| Comparative example 3 | 77.80% | 56.20% | 61.20% | 5.10% | Explosion on fire |
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (4)
1. a kind of lithium-ion battery electrolytes for ternary material battery, it is characterised in that the lithium-ion battery electrolytes include
Organic solvent, lithium salts and additive, wherein the mass ratio of organic solvent, lithium salts and additive is 80-87:10.9-14:1.9-
2.5, the organic solvent is made of ethylene carbonate, propene carbonate, diethyl carbonate and methyl ethyl carbonate, the lithium salts by
Lithium hexafluoro phosphate, double fluorine sulfimide lithiums and di-oxalate lithium borate composition, the additive is by vinylene carbonate, 1,3- propane
Sultone and cyclohexyl benzene composition；The matter of lithium hexafluoro phosphate in the lithium salts, double fluorine sulfimide lithiums and di-oxalate lithium borate
Amount is than being 11-13:0.1-0.9:0.1-0.5.
2. the lithium-ion battery electrolytes according to claim 1 for ternary material battery, it is characterised in that: described
The mass ratio of organic solvent, lithium salts and additive is 81.7-85:11.4- in lithium-ion battery electrolytes
13.2:2.5-5.9。
3. the lithium-ion battery electrolytes according to claim 1 or 2 for ternary material battery, it is characterised in that: institute
Ethylene carbonate in the organic solvent stated, propene carbonate, diethyl carbonate and methyl ethyl carbonate mass ratio be 26-32:5-
8:20.6-28:20-25。
4. the lithium-ion battery electrolytes according to claim 1 or 2 for ternary material battery, it is characterised in that: institute
The mass ratio of vinylene carbonate, 1,3- propane sultone and cyclohexyl benzene is 0.5- in the additive stated
0.7:1-1.2:1-4。
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| CN107742727A (en) * | 2017-10-13 | 2018-02-27 | 江苏海四达电源股份有限公司 | Lithium cell cathode material, cathode of lithium battery and preparation method thereof and lithium battery |
| CN111463487B (en) * | 2018-12-20 | 2023-05-30 | 安徽巡鹰新材料科技有限公司 | Processing technology of lithium ion battery electrolyte |
| CN112436190A (en) * | 2019-08-25 | 2021-03-02 | 深圳格林德能源集团有限公司 | Lithium ion battery electrolyte and lithium ion battery thereof |
| CN111430803A (en) * | 2020-01-17 | 2020-07-17 | 蜂巢能源科技有限公司 | Flame-retardant electrolyte, lithium battery and vehicle |
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| CN102082297A (en) * | 2010-12-30 | 2011-06-01 | 东莞市杉杉电池材料有限公司 | Electrolyte for lithium iron phosphate power lithium ion battery |
| CN103985903A (en) * | 2014-04-22 | 2014-08-13 | 中南大学 | Electrolyte for improving high temperature performance of lithium manganate power battery and lithium manganate power battery |
| CN104425840A (en) * | 2013-08-28 | 2015-03-18 | 张家港骏博新材料有限公司 | High-temperature electrolyte of power battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101093901A (en) * | 2007-08-14 | 2007-12-26 | 深圳市海盈科技有限公司 | Constituents of electrolyte of lithium ion battery possessing function of guarding against over charge, and gaseous distention |
| CN102082297A (en) * | 2010-12-30 | 2011-06-01 | 东莞市杉杉电池材料有限公司 | Electrolyte for lithium iron phosphate power lithium ion battery |
| CN104425840A (en) * | 2013-08-28 | 2015-03-18 | 张家港骏博新材料有限公司 | High-temperature electrolyte of power battery |
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Address after: 453000 Xinxiang Xiaodian Industrial Park, Henan Province Applicant after: HENAN HUARUI ADVANCED MATERIALS CO.,LTD. Address before: 453000 Xinxiang Xiaodian Industrial Park, Henan Province Applicant before: HENAN HUARUI HIGH - TECH MATERIAL TECHNOLOGY CO.,LTD. |
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Effective date of registration: 20210119 Address after: Floor 11, E-Valley, Zhongguancun, Jingba Road, Xinxiang economic and Technological Development Zone, Xinxiang City, Henan Province Patentee after: Xinxiang Huarui lithium new energy Co.,Ltd. Address before: 453000 Xinxiang Xiaodian Industrial Park, Henan Province Patentee before: HENAN HUARUI ADVANCED MATERIALS Co.,Ltd. |
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Address after: 453000 north of the road 30 meters west of the intersection of Guangda road and Guang'an Street in Xinxiang economic and Technological Development Zone, Henan Province Patentee after: Xinxiang Huarui lithium new energy Co.,Ltd. Address before: Floor 11, E-Valley, Zhongguancun, Jingba Road, Xinxiang economic and Technological Development Zone, Xinxiang City, Henan Province Patentee before: Xinxiang Huarui lithium new energy Co.,Ltd. |