CN1339846A - Lithium secondary cell electrolyte - Google Patents
Lithium secondary cell electrolyte Download PDFInfo
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- CN1339846A CN1339846A CN01141441A CN01141441A CN1339846A CN 1339846 A CN1339846 A CN 1339846A CN 01141441 A CN01141441 A CN 01141441A CN 01141441 A CN01141441 A CN 01141441A CN 1339846 A CN1339846 A CN 1339846A
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- carbonate
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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
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Abstract
The present invention belongs to the field of lithium iron cell producing technology and the nonaqueous electrolyte liquid consists of organic carbonate as solvent in 85-90 wt% and electrolyte salt in 10-15 wt%, the solvent consists of one of vinyl carbonate and alloy carbonate and one or more of dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; and the electrolyte salt is one of LiPF6, LiAsF6, LiClO4 and LiBF4. Into the electrolyte liquid, sulfur containing compound in 0.01-10 wt% may be also added to raise the charge and discharge efficienty and circulation life of the cell. The electrolyte liquid of the present invention is well compatible with positive and negative electrode material in secondary lithium ion cell.
Description
The present invention relates to technical field of lithium-ion battery, specifically is the nonaqueous electrolytic solution of secondary lithium batteries.
Background technology
At present, lithium secondary battery is owing to operating voltage height (3.6V), and volume is little, light weight, and memory-less effect, pollution-free, self discharge is little, has extended cycle life, and obtains to use on mobile phone, video camera, notebook computer, portable electronics.This battery comprises positive pole, electrolyte, negative pole.Just very cobalt acid lithium or LiMn2O4 or lithium nickelate, electrolyte are that lithium hexafluoro phosphate is dissolved in carbonate solvent, negative pole is material with carbon element or lithium metal.
Electrolyte preparation commonly used now considers it more is the conductivity of electrolyte system, and the positive and negative electrode material is considered relative lessly with the compatibility of electrolyte.Anodal cobalt acid lithium or LiMn2O4 or the anodal boundary of lithium nickelate are in discharge regime part electrolyte generation oxidation Decomposition.Negative material uses native graphite or artificial plumbago negative pole interface in the charging stage reduction decomposition.Catabolite disturbs electrochemical reaction, discharge capacity is descended, thereby influence battery electrode cycle life and efficiency for charge-discharge.
Summary of the invention
For solving the problem and shortage that above-mentioned technology exists, the invention provides the lithium secondary battery of high performance nonaqueous electrolytic solution, improve lithium ion battery cycle life and efficiency for charge-discharge.
Electrolyte solvent for use of the present invention comprises cyclic carbonate such as propene carbonate (PC), ethylene carbonate (EC) etc., and linear carbonate comprises diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) etc.Solute is a kind of in lithium hexafluoro phosphate, lithium perchlorate, the LiBF4.
An object of the present invention is that serviceability temperature scope, battery performance according to battery requires and electrolyte system is selected in the security requirement of battery.Nonaqueous electrolytic solution contains one or both solvents and the lithium hexafluoro phosphate in a kind of and dimethyl carbonate in ethylene carbonate, the propene carbonate, diethyl carbonate, the methyl ethyl carbonate.Electrolyte system has EC/DMC, EC/DEC, EC/EMC, EC/DEC/DMC, PC/DEC/DMC.
Another object of the present invention is to select proper additive to improve some performance index of battery.
The additive that electrolyte of the present invention relates to is a sulfur-containing compound, as SO
2, SOCl
2, SO
2Cl
2Deng, addition is 0.01-10%.The adding of this compounds makes electrolyte form higher reduction potential on carbon negative pole interface.The electrode interface reduzate can significantly suppress inserting altogether and reduction decomposition of solvent molecule, thereby can increase substantially the cycle life and the efficiency for charge-discharge of battery electrode.
The present invention adopts following technical measures:
Lithium secondary cell electrolyte is made up of carbonates solvent and electrolytic salt, be characterized in that nonaqueous electrolytic solution contains one or both weight of solvent in a kind of and dimethyl carbonate in ethylene carbonate, the propene carbonate, diethyl carbonate, the methyl ethyl carbonate than 85-90%, lithium hexafluoro phosphate weight ratio 10-15%.
The method for making of above-mentioned electrolyte be in dry environment with after one or both solvent in a kind of and dimethyl carbonate in ethylene carbonate, the propene carbonate, diethyl carbonate, the methyl ethyl carbonate by weight the ratio of 85-90: 10-15 lithium hexafluoro phosphate is dissolved in organic solvent, obtain the lithium secondary battery nonaqueous electrolytic solution.
The present invention can also adopt following technical measures:
Above-mentioned electrolyte, its characteristics are that one or both weight of solvent that electrolyte consists of in a kind of and dimethyl carbonate in ethylene carbonate, the propene carbonate, diethyl carbonate, the methyl ethyl carbonate compare 80-85%, lithium hexafluoro phosphate weight ratio 10-15%, sulfur-containing additive 0.01-10%.
The method for making of above-mentioned electrolyte be in dry environment with after one or both solvent in a kind of and dimethyl carbonate in ethylene carbonate, the propene carbonate, diethyl carbonate, the methyl ethyl carbonate by weight the ratio of 80-85: 10-15: 0.01-10 lithium hexafluoro phosphate and sulfur-containing additive are dissolved in organic solvent, obtain the lithium secondary battery nonaqueous electrolytic solution.
Above-mentioned electrolyte is characterized in that sulfur-containing additive is SO
2, SOCl
2, SO
2Cl
2Deng.
It hereinafter is detailed description of the present invention.
Lithium secondary battery comprises anodal negative pole, electrolyte.Generally just very cobalt acid lithium or LiMn2O4 or lithium nickelate active material and conductive adhesion thing, negative pole is for absorbing and discharge the material with carbon element and the conductive adhesion thing of lithium ion.Electrolyte is selected to add lithium hexafluoro phosphate after several solvent according to solvent types and character.
Solvent species and character such as following table that the used electrolyte of lithium secondary battery is commonly used:
The physicochemical properties of some common solvent of table 1 (25 ℃)
According to the character of all kinds of solvents in the table, often the electrolyte system of forming has EC/DMC, EC/DEC, EC/EMC, EC/DEC/DMC, PC/DEC/DMC.
Description of drawings:
Fig. 1 is that various system electrolyte conductivity can be with the variation of temperature curve.
Fig. 2 is the change curve of various system electrolyte viscosity with temperature.
Curve among the figure:
1 is EC/DMC=1: 1
2 is EC/DEC=1: 1
3 is EC/EMC=1: 1
4 is EC/DEC/DMC=1: 1: 1
5 is PC/DEC/DMC=1: 1: 3
Advantage of the present invention and good effect: by changing among the figure as can be seen, the electrolyte of different systems will directly influence indexs such as the capacity, high temperature performance, cycle life of battery.
Generally speaking, the performance of lithium secondary battery also should be considered the compatibility of positive and negative electrode material and electrolyte except the influence of considering electrolyte system.The positive and negative electrode material of electrolyte of the present invention and lithium secondary battery has good compatibility, particularly adds a certain amount of sulfur-containing compound in nonaqueous electrolytic solution, increases substantially the cycle life and the efficiency for charge-discharge of battery.
Specific embodiment
Below in conjunction with embodiment this technology is further specified, but the present invention is not limited in this
Embodiment.
Embodiment 1
In the drying box of moisture content less than 20ppm, 1 mole of lithium hexafluoro phosphate electrolyte of preparation EC/DEC, EC/DMC, EC/DEC/DMC, EC/EMC, systems such as EC/DMC/EMC, PC/DEC/DMC.Inject the electrolyte into just very that lithium cobalt compound, negative pole are in the lithium secondary battery of carbon, this battery in room temperature (20 ℃) with constant current (1CA) charging until reaching 4.2V, the constant voltage of 4.2V then continues charging 4 hours down.Subsequently in constant current (1CA) discharge down.Continuing discharge is 2.7V until end of a period voltage.Charge and discharge cycles repeats 300 times, carries out the mensuration of charge/discharge capacity, efficient and cycle life.
The assessment result such as the table 2 of battery
Table 2
| Electrolyte system | Additive addition % | Initial discharge capacity (relative value) | Cycle-index | Discharge capacitance |
| EC/DEC | ????0 | ????0.98 | ????300 | ????84.5％ |
| EC/DMC | ????0 | ????1 | ????300 | ????85.0％ |
| EC/DEC/DMC | ????0 | ????0.98 | ????300 | ????84.3％ |
| EC/EMC | ????0 | ????1 | ????300 | ????85.2％ |
| EC/DMC/EMC | ????0 | ????1 | ????300 | ????86.1％ |
| PC/DEC/DMC | ????0 | ????0.98 | ????300 | ????85％ |
After 300 charge and discharge cycles, discharge capacity is more than 84.5% of initial discharge capacity.
In the drying box of moisture content less than 20ppm, 1 mole of lithium hexafluoro phosphate electrolyte of preparation EC/DEC, EC/DMC, EC/DEC/DMC, EC/EMC, systems such as EC/DMC/EMC, PC/DEC/DMC, the sulfur-containing compound that adds 0.01-10% respectively, injecting each electrolyte just very respectively, lithium cobalt compound, negative pole are the lithium secondary battery of carbon, this battery charges until reaching 4.2V with constant current (1CA) in room temperature (20 ℃), and the constant voltage of 4.2V then continues charging 4 hours down.Subsequently in constant current (1CA) discharge down.Continuing discharge is 2.7V until end of a period voltage.Charge and discharge cycles repeats 300 times, carries out the mensuration of charge/discharge capacity, efficient and cycle life.
The assessment result such as the table 3 of battery
Table 3
| Electrolyte system | Additive addition % | Initial discharge capacity (relative value) | Cycle-index | Discharge capacitance |
| EC/DEC | ????0.2 | ????1 | ????300 | ????90.1％ |
| EC/DMC | ????0.5 | ????1.02 | ????300 | ????91.2％ |
| EC/DEC/DMC | ????1 | ????1 | ????300 | ????92.1％ |
| EC/EMC | ????2 | ????1.03 | ????300 | ????93.5％ |
| EC/DMC/EMC | ????5 | ????1.03 | ????300 | ????94.6％ |
| PC/DEC/DMC | ????10 | ????1.03 | ????300 | ????92.9％ |
After 300 charge and discharge cycles, discharge capacity is more than 90% of initial discharge capacity.The adding sulfur-containing compound of comparing, discharge capacity is greatly improved.
Claims (3)
1, lithium secondary cell electrolyte is made up of carbonates solvent and electrolytic salt, it is characterized in that: nonaqueous electrolytic solution contains one or both weight of solvent in a kind of and dimethyl carbonate in ethylene carbonate, the propene carbonate, diethyl carbonate, the methyl ethyl carbonate than 85-90%, lithium hexafluoro phosphate weight ratio 10-15%.
2. according to the electrolyte of claim 1, it is characterized in that: one or both weight of solvent that electrolyte consists of in a kind of and dimethyl carbonate in ethylene carbonate, the propene carbonate, diethyl carbonate, the methyl ethyl carbonate compare 80-85%, lithium hexafluoro phosphate weight ratio 10-15%, sulfur-containing additive 0.01-10%.
3. according to the electrolyte of claim 2, it is characterized in that: sulfur-containing additive is SO
2, SOCl
2, SO
2Cl
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01141441A CN1339846A (en) | 2001-09-25 | 2001-09-25 | Lithium secondary cell electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01141441A CN1339846A (en) | 2001-09-25 | 2001-09-25 | Lithium secondary cell electrolyte |
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|---|---|
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|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348975C (en) * | 2004-06-21 | 2007-11-14 | 比亚迪股份有限公司 | Quantitative analysis for electrolytic liquor organic component of lithium ion battery |
| CN100444457C (en) * | 2003-09-05 | 2008-12-17 | 三星Sdi株式会社 | Organic electrolytic solution and lithium-sulfur battery comprising the same |
| CN101834315A (en) * | 2010-05-20 | 2010-09-15 | 南京双登科技发展研究院有限公司 | High-temperature electrolyte of lithium ion battery |
| CN103050733A (en) * | 2012-12-28 | 2013-04-17 | 青岛润鑫伟业科贸有限公司 | Electrolyte for battery |
| CN102134065B (en) * | 2006-08-22 | 2013-06-12 | 三菱化学株式会社 | Lithium difluorophosphate,electrolytic solution preparation and difluorophosphate nonaqueous-electrolytic-solution secondary cell employing the same |
| CN106450456A (en) * | 2016-10-31 | 2017-02-22 | 武汉美格科技股份有限公司 | High-rate lithium-ion battery electrolyte with high temperature resistance and battery containing high-rate lithium-ion battery electrolyte |
| CN110176622A (en) * | 2019-05-15 | 2019-08-27 | 华南理工大学 | A kind of lithium metal secondary battery electrolyte and the preparation method and application thereof |
| WO2020216052A1 (en) * | 2019-04-26 | 2020-10-29 | 宁德时代新能源科技股份有限公司 | Electrolyte solution, lithium-ion battery, and device containing lithium-ion battery |
| CN112397786A (en) * | 2020-12-09 | 2021-02-23 | 松山湖材料实验室 | Electrolyte and lithium ion battery |
| EP3951986A4 (en) * | 2019-04-26 | 2022-06-22 | Contemporary Amperex Technology Co., Limited | Electrolyte, lithium ion battery and device containing lithium ion battery |
-
2001
- 2001-09-25 CN CN01141441A patent/CN1339846A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100444457C (en) * | 2003-09-05 | 2008-12-17 | 三星Sdi株式会社 | Organic electrolytic solution and lithium-sulfur battery comprising the same |
| US7517612B2 (en) | 2003-09-05 | 2009-04-14 | Samsung Sdi Co., Ltd. | Organic electrolytic solution and lithium-sulfur battery comprising the same |
| CN100348975C (en) * | 2004-06-21 | 2007-11-14 | 比亚迪股份有限公司 | Quantitative analysis for electrolytic liquor organic component of lithium ion battery |
| CN102134065B (en) * | 2006-08-22 | 2013-06-12 | 三菱化学株式会社 | Lithium difluorophosphate,electrolytic solution preparation and difluorophosphate nonaqueous-electrolytic-solution secondary cell employing the same |
| CN101834315A (en) * | 2010-05-20 | 2010-09-15 | 南京双登科技发展研究院有限公司 | High-temperature electrolyte of lithium ion battery |
| CN103050733A (en) * | 2012-12-28 | 2013-04-17 | 青岛润鑫伟业科贸有限公司 | Electrolyte for battery |
| CN106450456A (en) * | 2016-10-31 | 2017-02-22 | 武汉美格科技股份有限公司 | High-rate lithium-ion battery electrolyte with high temperature resistance and battery containing high-rate lithium-ion battery electrolyte |
| WO2020216052A1 (en) * | 2019-04-26 | 2020-10-29 | 宁德时代新能源科技股份有限公司 | Electrolyte solution, lithium-ion battery, and device containing lithium-ion battery |
| CN111864261A (en) * | 2019-04-26 | 2020-10-30 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| EP3951986A4 (en) * | 2019-04-26 | 2022-06-22 | Contemporary Amperex Technology Co., Limited | Electrolyte, lithium ion battery and device containing lithium ion battery |
| CN110176622A (en) * | 2019-05-15 | 2019-08-27 | 华南理工大学 | A kind of lithium metal secondary battery electrolyte and the preparation method and application thereof |
| CN110176622B (en) * | 2019-05-15 | 2022-05-24 | 华南理工大学 | Lithium metal secondary battery electrolyte and preparation method and application thereof |
| CN112397786A (en) * | 2020-12-09 | 2021-02-23 | 松山湖材料实验室 | Electrolyte and lithium ion battery |
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