CN107799823A - A kind of electrolysis additive and electrolyte and lithium secondary battery containing the additive - Google Patents
A kind of electrolysis additive and electrolyte and lithium secondary battery containing the additive Download PDFInfo
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- CN107799823A CN107799823A CN201710990584.5A CN201710990584A CN107799823A CN 107799823 A CN107799823 A CN 107799823A CN 201710990584 A CN201710990584 A CN 201710990584A CN 107799823 A CN107799823 A CN 107799823A
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- lithium
- electrolyte
- additive
- carbonate
- electrolytic liquid
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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
-
- 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 belongs to field of lithium ion battery material, discloses a kind of electrolysis additive and electrolyte and lithium secondary battery containing the additive.The electrolysis additive is 4 methyl N tosyl benzsulfamides.Cyclic carbonate solvents and linear carbonate solvent are mixed, clarification, water removal, add electric conducting lithium salt at ambient temperature, obtain general electrolytic liquid, then the additive equivalent to general electrolytic liquid quality 0.5~3.0% is added in general electrolytic liquid, obtains final electrolyte.The present invention uses additive of the 4 methyl N tosyl benzsulfamides as lithium re-electrolysis liquid, is improved the cycle performance of lithium secondary battery under high pressure.
Description
Technical field
The invention belongs to field of lithium ion battery material, and in particular to a kind of electrolysis additive and contain the additive
Electrolyte and lithium secondary battery.
Background technology
In existing commercialization secondary cell, lithium secondary battery it is more best than energy highest, cycle performance, and because of it
The diversity of electrode material selection, has vast potential for future development as energy-storage battery.
With science and technology progress and market continuous development, lifted lithium secondary battery energy density increasingly seem it is important and
Urgently.Therefore lifting lithium secondary battery so as to improve the energy density of battery is the emphasis studied at present using voltage.But
Conventional commercial electrolyte liquid is under high pressure easily in electrode surface oxidation Decomposition, and the oxidative decomposition of electrolyte itself is simultaneously
The pernicious reactions such as the change of positive electrode pattern, structure collapses can be promoted.
Therefore, it is necessary to develop a kind of electrolyte, lithium secondary battery cycle performance under high pressure can be improved, and then realize lithium two
The excellent performance of primary cell electrical property, improve lithium secondary battery cycle life.By in the lithium secondary cell electrolyte of routine
It is the most economical method of most convenient for improving lithium secondary battery performance to add a small amount of electrolysis additive.
The content of the invention
In place of shortcoming and defect existing for above prior art, primary and foremost purpose of the invention is to provide a kind of electrolysis
Solution additive.
Another object of the present invention is to provide a kind of electrolyte containing above-mentioned additive.
It is still another object of the present invention to provide the preparation method of above-mentioned electrolyte.
A further object of the present invention is to provide the application of above-mentioned electrolyte in the lithium secondary battery.
The object of the invention is achieved through the following technical solutions:
A kind of electrolysis additive, the electrolysis additive have the structural formula shown in formula (1),
A kind of electrolyte containing above-mentioned additive, by general electrolytic liquid and equivalent to general electrolytic liquid quality 0.5~3%
Additive form;The general electrolytic liquid includes cyclic carbonate solvents, linear carbonate solvent and electric conducting lithium salt.
Preferably, the cyclic carbonate solvents are ethylene carbonate (EC).
Preferably, the linear carbonate solvent includes dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), carbonic acid two
At least one of ethyl ester (DEC) and methyl propyl carbonate (MPC).
Preferably, the mass ratio of the cyclic carbonate solvents and linear carbonate solvent is 1:3~2:3.
Preferably, the electric conducting lithium salt is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), dioxalic acid boron
Sour lithium (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), trifluoromethyl sulfonic acid lithium (LiSO3CF3), lithium perchlorate (LiClO4)、
Hexafluoroarsenate lithium (LiAsF6), bis trifluoromethyl sulfimide lithium (Li (CF3SO2)2) and per-fluoroalkyl sulfonyl lithium methide (LiC N
(CF3SO2)3At least one of).
Preferably, concentration of the electric conducting lithium salt in final electrolyte is 1.0mol/L.
The preparation method of above-mentioned electrolyte, comprises the following steps:
(1) cyclic carbonate solvents and linear carbonate solvent are mixed, clarification, water removal;
(2) at ambient temperature, by the solvent obtained by electric conducting lithium salt addition step (1), general electrolytic liquid is obtained;
(3) adding equivalent to general electrolytic liquid quality 0.5~3.0% is added in the general electrolytic liquid that step (2) obtains
Add agent, obtain the electrolyte.
Preferably, the clarification, water removal described in step (1) refer to by molecular sieve, activated carbon, calcium hydride, hydrogen
Change at least one of lithium, anhydrous calcium oxide, calcium chloride, phosphorus pentoxide, alkali metal or alkaline-earth metal to be handled.
Described molecular sieve can useType,Type orType, preferably selectType orType.
The application of above-mentioned electrolyte in the lithium secondary battery, obtained lithium secondary battery have good charge-discharge performance.
The invention has the advantages that and beneficial effect:
The present invention uses additive of the 4- methyl-N- tosyls benzsulfamides as lithium re-electrolysis liquid, due to this
Additive has relatively low oxidizing potential and higher reduction potential, can be in positive pole and negative pole table during first charge-discharge
Face forms one layer of densification, stable SEI films, optimizes both positive and negative polarity skin covering of the surface, suppresses the surface-active of electrode, so as to guard electrode
Material, and further contacting for electrolyte and electrode active material can be suppressed, electrolyte bulk solvent is reduced in electrode surface
Oxidation Decomposition, improved the cycle performance of lithium secondary battery under high pressure.
Brief description of the drawings
The final electrolyte of the gained of Fig. 1 embodiment of the present invention 1 and general electrolytic liquid are used for LiNi0.6Co0.2Mn0.2O2/ graphite is soft
The cycle performance result figure of bag battery.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) by cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) and
Diethyl carbonate (DEC) EC in mass ratio:EMC:DEC=3:5:2 mixing, and using molecular sieve, calcium hydride, lithium hydride purifying
Removal of impurities, water removal;
(2) at ambient temperature, by electric conducting lithium salt LiPF6It is dissolved in the solvent that step (1) obtains, the end of electric conducting lithium salt
Concentration is 1.0mol/L, is stirred, and obtains general electrolytic liquid;
(3) added in general electrolytic liquid prepared by step (2) 4- methyl-N- tosyls benzsulfamides (buy in
TCI), dosage is the 0.5% of general electrolytic liquid quality, obtains final electrolyte.
Final electrolyte obtained by the present embodiment and the general electrolytic liquid of step (2) are used for LiNi0.6Co0.2Mn0.2O2/ stone
Black soft-package battery carries out cycle performance comparison, as a result as shown in Figure 1.As seen from Figure 1,4- methyl-N- tosyls are added
Base benzsulfamide prepare final electrolyte, under 3~4.35V carry out 150 circle after can also keep 86.1% capability retention,
And 41.7% capability retention can only be kept after the circle of general electrolytic liquid progress 150.From the results, it was seen that addition 4- methyl-
The electrolyte of N- tosyl benzsulfamides, which is used for lithium secondary battery, can improve its cycle performance.
Embodiment 2
(1) by cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) and
Dimethyl carbonate (DMC) EC in mass ratio:EMC:DMC=3:5:2 mixing, and using molecular sieve, calcium hydride, lithium hydride purifying
Removal of impurities, water removal;
(2) at ambient temperature, by electric conducting lithium salt LiPF6It is dissolved in the solvent that step (1) obtains, the end of electric conducting lithium salt
Concentration is 1.0mol/L, is stirred, and obtains general electrolytic liquid;
(3) 4- methyl-N- tosyl benzsulfamides are added in general electrolytic liquid prepared by step (2), dosage is
The 1.0% of general electrolytic liquid quality, obtains final electrolyte.
Embodiment 3
(1) by cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) and
Dimethyl carbonate (DMC) EC in mass ratio:EMC:DMC=3:5:2 mixing, and using molecular sieve, calcium hydride, lithium hydride purifying
Removal of impurities, water removal;
(2) at ambient temperature, by electric conducting lithium salt LiPF6It is dissolved in the solvent that step (1) obtains, the end of electric conducting lithium salt
Concentration is 1.0mol/L, is stirred, and obtains general electrolytic liquid;
(3) 4- methyl-N- tosyl benzsulfamides are added in general electrolytic liquid prepared by step (2), dosage is
The 3.0% of general electrolytic liquid quality, obtains final electrolyte.
Embodiment 4
(1) by cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) and
Dimethyl carbonate (DMC) EC in mass ratio:EMC:DMC=3:5:2 mixing, and using molecular sieve, calcium hydride, lithium hydride purifying
Removal of impurities, water removal;
(2) at ambient temperature, by electric conducting lithium salt LiAsF6It is dissolved in the solvent that step (1) obtains, electric conducting lithium salt
Final concentration of 1.0mol/L, stirs, and obtains general electrolytic liquid;
(3) 4- methyl-N- tosyl benzsulfamides are added in general electrolytic liquid prepared by step (2), dosage is
The 1.0% of general electrolytic liquid quality, obtains final electrolyte.
Embodiment 5
(1) by cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) and
Dimethyl carbonate (DMC) EC in mass ratio:EMC:DMC=1:1:1 mixing, and using molecular sieve, calcium hydride, lithium hydride purifying
Removal of impurities, water removal;
(2) at ambient temperature, by electric conducting lithium salt Li (CF3SO2)2N is dissolved in the solvent that step (1) obtains, conductive lithium
The final concentration of 1.0mol/L of salt, stirs, and obtains general electrolytic liquid;
(3) 4- methyl-N- tosyl benzsulfamides are added in general electrolytic liquid prepared by step (2), dosage is
The 1.0% of general electrolytic liquid quality, obtains final electrolyte.
Embodiment 6
(1) cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) are pressed into matter
Amount compares EC:EMC=1:2 mixing, and using molecular sieve, calcium hydride, lithium hydride clarification, water removal;
(2) at ambient temperature, by electric conducting lithium salt LiC (CF3SO2)3It is dissolved in the solvent that step (1) obtains, conductive lithium
The final concentration of 1.0mol/L of salt, stirs, and obtains general electrolytic liquid;
(3) 4- methyl-N- tosyl benzsulfamides are added in general electrolytic liquid prepared by step (2), dosage is
The 1.0% of general electrolytic liquid quality, obtains final electrolyte.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
- A kind of 1. electrolysis additive, it is characterised in that the electrolysis additive has the structural formula shown in formula (1),
- A kind of 2. electrolyte containing additive described in claim 1, it is characterised in that:By general electrolytic liquid and equivalent to common The additive of electrolyte quality 0.5~3% is formed;It is molten that the general electrolytic liquid includes cyclic carbonate solvents, linear carbonate Agent and electric conducting lithium salt.
- 3. electrolyte according to claim 2, it is characterised in that:The cyclic carbonate solvents are ethylene carbonate.
- 4. electrolyte according to claim 2, it is characterised in that:The linear carbonate solvent include dimethyl carbonate, At least one of methyl ethyl carbonate, diethyl carbonate and methyl propyl carbonate.
- 5. electrolyte according to claim 2, it is characterised in that:The cyclic carbonate solvents and linear carbonate solvent Mass ratio be 1:3~2:3.
- 6. electrolyte according to claim 2, it is characterised in that:The electric conducting lithium salt is selected from lithium hexafluoro phosphate, tetrafluoro boron Sour lithium, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, trifluoromethyl sulfonic acid lithium, lithium perchlorate, hexafluoroarsenate lithium, double fluoroforms At least one of base sulfimide lithium and per-fluoroalkyl sulfonyl lithium methide.
- 7. electrolyte according to claim 2, it is characterised in that:Concentration of the electric conducting lithium salt in final electrolyte is 1.0mol/L。
- 8. the preparation method of a kind of electrolyte described in any one of claim 2~7, it is characterised in that comprise the following steps:(1) cyclic carbonate solvents and linear carbonate solvent are mixed, clarification, water removal;(2) at ambient temperature, by the solvent obtained by electric conducting lithium salt addition step (1), general electrolytic liquid is obtained;(3) additive equivalent to general electrolytic liquid quality 0.5~3.0% is added in the general electrolytic liquid that step (2) obtains, Obtain the electrolyte.
- A kind of 9. preparation method of electrolyte according to claim 8, it is characterised in that:Purifying described in step (1) Removal of impurities, water removal refer to by molecular sieve, activated carbon, calcium hydride, lithium hydride, anhydrous calcium oxide, calcium chloride, phosphorus pentoxide, alkali At least one of metal or alkaline-earth metal are handled.
- 10. the application of electrolyte in the lithium secondary battery described in any one of claim 2~7.
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Cited By (5)
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CN110190330A (en) * | 2019-06-04 | 2019-08-30 | 华南师范大学 | The preparation method of lithium battery and its electrolyte, electrolyte |
CN111740177A (en) * | 2019-07-26 | 2020-10-02 | 瑞新材料科技(香港)有限公司 | Positive electrode material, positive electrode, battery, and battery pack |
CN111934013A (en) * | 2020-08-19 | 2020-11-13 | 四川虹微技术有限公司 | Lithium ion battery electrolyte with wide temperature range |
CN114865083A (en) * | 2022-05-18 | 2022-08-05 | 湖南大学 | Electrolyte with diphenylsulfonimide as additive and lithium battery thereof |
CN116600613A (en) * | 2023-07-17 | 2023-08-15 | 四川京龙光电科技有限公司 | Perovskite flexible display device preparation method and flexible display device |
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Cited By (9)
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CN110190330A (en) * | 2019-06-04 | 2019-08-30 | 华南师范大学 | The preparation method of lithium battery and its electrolyte, electrolyte |
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CN111740177A (en) * | 2019-07-26 | 2020-10-02 | 瑞新材料科技(香港)有限公司 | Positive electrode material, positive electrode, battery, and battery pack |
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CN111934013B (en) * | 2020-08-19 | 2021-09-28 | 四川虹微技术有限公司 | Lithium ion battery electrolyte with wide temperature range |
CN114865083A (en) * | 2022-05-18 | 2022-08-05 | 湖南大学 | Electrolyte with diphenylsulfonimide as additive and lithium battery thereof |
CN116600613A (en) * | 2023-07-17 | 2023-08-15 | 四川京龙光电科技有限公司 | Perovskite flexible display device preparation method and flexible display device |
CN116600613B (en) * | 2023-07-17 | 2023-09-26 | 四川京龙光电科技有限公司 | Perovskite flexible display device preparation method and flexible display device |
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