CN104733779A - High-voltage lithium ion battery electrolyte and lithium battery - Google Patents
High-voltage lithium ion battery electrolyte and lithium battery Download PDFInfo
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- CN104733779A CN104733779A CN201510138211.6A CN201510138211A CN104733779A CN 104733779 A CN104733779 A CN 104733779A CN 201510138211 A CN201510138211 A CN 201510138211A CN 104733779 A CN104733779 A CN 104733779A
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- lithium
- ion battery
- carbonate
- electrolyte
- battery electrolytes
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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 high-voltage lithium ion battery electrolyte and a lithium battery. The high-voltage lithium ion battery electrolyte comprises non-aqueous organic solvent, lithium salt and an additive. The electrolyte additive is organic sulfone with two cyanogen radicals, and the content of the additive in the electrolyte is 0.2 to 1.0 percent by mass. In the high-voltage lithium ion battery electrolyte, the organic sulfone with two cyanogens radicals can effectively improve the cycling property of the lithium ion battery under a high voltage environment.
Description
Technical field
The invention belongs to lithium-ion battery electrolytes field, be specifically related to a kind of high-pressure type lithium-ion battery electrolytes and lithium battery thereof.
Background technology
In recent years along with variation and the intellectuality of electronic equipment development, consumer is also more and more higher for the capacity requirement of electric device battery.Wideling popularize along with electric tool simultaneously, people are also more and more urgent for the demand of the lithium ion battery of high-energy-density.
By energy theorem
known, the raising gram volume of battery material and the operating voltage of battery effectively can improve energy density.Along with the continuous effort of technical staff, the high-voltage anode material of (4.35 ~ 5V) under having occurred can be used for high voltage condition at present.But existing electrolyte is mainly based on the carbonate group electrolyte of ethylene carbonate (EC), and this electrolyte between 4.35 ~ 5.0V higher-pressure region under when carrying out discharge and recharge, can oxidation Decomposition be there is, thus cause the severe exacerbation of battery performance.Therefore a kind of high-pressure type lithium-ion battery electrolytes of applicable high voltage material must be developed.
By using some additives, electrolyte oxidation Decomposition under high pressure effectively can be suppressed.Based on above problem, do not changing on the basis that electrolyte fills a prescription substantially, by some novel electrolysis additives of exploitation, can effectively can improve electrolyte serviceability under high pressure, the chemical property of final raising high voltage material in high-voltage charge and discharge interval.
Summary of the invention
The object of the invention is to: provide a kind of lithium-ion battery electrolytes, it effectively can improve the cycle performance of lithium ion battery under high voltage condition.
The object of the invention is to realize in the following way.
A kind of high-voltage lithium-ion battery electrolyte, it comprises non-aqueous organic solvent, lithium salts and electrolysis additive, and described electrolysis additive is the organic sulfoxide compound with dicyanogen methyl isophorone.
According to the present invention, described electrolysis additive is the organic sulfoxide compound with two end cyano group.
According to the present invention, described electrolysis additive for having the organic sulfoxide compound with two cyano group shown in formula (1),
NC-R
1-SO
2-R
2-CN formula (1)
Wherein, R
1, R
2can be the same or different, independently selected from C
1-8the C that alkylidene or halogen (such as fluorine) replace
1-8alkylidene.
Preferably, described C
1-8alkylidene is straight or branched alkylidene, such as, and methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, the sub-tert-butyl group, pentylidene, hexylidene etc.
Preferably, described halogen is fluorine, chlorine or bromine.
According to the present invention, the content of described electrolysis additive is 0.1 ~ 1.0% (mass ratio), preferably 0.2 ~ 0.8%, or 0.3 ~ 0.5%, more preferably 0.2 ~ 0.5%.
As a kind of optimal way of lithium-ion battery electrolytes of the present invention, described electrolysis additive is sulfonyl diacetonitrile (SO
2(CH
2cN)
2), sulfonyl two propionitrile, sulfonyl dibutyronitrile, the own nitrile of sulfonyl two.More preferably sulfonyl two propionitrile.
According to the present invention, described anhydrous organic solvent comprise in ethylene carbonate, ethylene propylene, diethyl carbonate, methyl propyl carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate any one or multiple, in preferred above-mentioned organic solvent two or three.Particularly preferred is the two mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC), the two mixture of dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), or ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) three mixture.
As a kind of optimal way of lithium-ion battery electrolytes of the present invention, described lithium salts comprises LiPF
6, LiBF
4, LiClO
4, LiAsF
6, in LiBOB any one or multiple.
According to the present invention, described electrolyte can be applied to maximum operating voltage in the lithium ion battery of 4.35 ~ 4.6V.
The present invention also provides a kind of method preparing lithium-ion battery electrolytes, comprising: non-aqueous organic solvent, lithium salts and the electrolysis additive with the organic sulfoxide compound of two cyano group are mixed.
According to the present invention, described electrolysis additive is NC-R
1-SO
2-R
2-CN, wherein, R
1, R
2can be the same or different, be independently selected from C
1-8the C that alkylidene or halogen (such as fluorine) replace
1-8alkylidene.
Present invention also offers a kind of purposes of above-mentioned lithium-ion battery electrolytes, it is for lithium ion battery.
In addition, present invention also offers a kind of lithium ion battery, it comprises positive plate, negative plate, barrier film, and electrolyte, and wherein, described electrolyte is lithium-ion battery electrolytes of the present invention.
The present invention has following advantage and effect relative to prior art: the invention provides the high-voltage lithium-ion battery electrolyte that a class has superperformance; this electrolyte is the organic sulfoxide compound with two cyano group; it can at cathode filming; protection negative electrode; reduce the generation of side reaction between negative electrode and electrolyte; thus improve cell interface impedance, effectively improve lithium ion battery high-voltage performance.The battery capacity conservation rate of circulating battery after 100 weeks can be improved more than 20% by it.
Accompanying drawing explanation
Fig. 1 is that under embodiment 1 and comparative example 1 condition, lithium ion battery charges to 4.6V at normal temperature circulation 0.2C, and then constant voltage is to 0.02C, then cycle performance figure during 0.2C electric discharge.
Embodiment
In order to make goal of the invention of the present invention, technical scheme and technique effect more clear, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be understood that, the embodiment described in this specification is just in order to explain the present invention, and non-limiting the present invention.
Embodiment 1
The preparation of electrolyte: be full of glove box (the moisture <10ppm of argon gas, oxygen divides <10ppm) in, by the 1:1:1 mixing in mass ratio of ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), be made into the LiPF of 1mol/L
6electrolyte, then adds sulfonyl two propionitrile accounting for electrolyte quality than being 0.2%, obtains the lithium-ion battery electrolytes of embodiment 1 after stirring.
The preparation of positive plate: by positive active material nickel-cobalt-manganese ternary material LiNi
1/3co
1/3mn
1/3o
2, conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF) in mass ratio 95:3:2 be fully uniformly mixed in 1-METHYLPYRROLIDONE system, be coated on plus plate current-collecting body Al paper tinsel, after drying compressing tablet, obtain positive plate.
The preparation of negative plate: after 96:2:1.2:0.8 is fully uniformly mixed in deionized water solvent system in mass ratio by negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickener sodium carboxymethylcellulose (CMC), be coated on negative current collector Cu paper tinsel, after drying and compressing tablet, obtain negative plate.
The preparation of barrier film: using PE porous polymer film as barrier film.
The preparation of lithium ion battery: the positive plate obtained, negative plate are placed in baking oven and move into glove box after uniform temperature is dried.Then the positive plate handled well, barrier film, negative plate are put well in order, dressed up CR2025 button cell, and inject above-mentioned preparation electrolyte.
Embodiment 2
The preparation of electrolyte: be full of glove box (the moisture <10ppm of argon gas, oxygen divides <10ppm) in, by the 1:1:1 mixing in mass ratio of ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), be made into the LiPF of 1mol/L
6electrolyte, then adds and accounts for electrolyte quality than the sulfonyl dibutyronitrile being 0.5%, obtains the lithium-ion battery electrolytes of embodiment 2 after stirring.
In embodiment 2, the preparation of the preparation of positive plate, the preparation of negative plate, barrier film, and the preparation of lithium ion battery is all substantially the same manner as Example 1, repeats no more.
Embodiment 3
The preparation of electrolyte: be full of glove box (the moisture <10ppm of argon gas, oxygen divides <10ppm) in, by the 1:1:1 mixing in mass ratio of ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), be made into the LiPF of 1mol/L
6electrolyte, then adds and accounts for electrolyte quality nitrile more own than the sulfonyl two being 1.0%, obtain the lithium-ion battery electrolytes of embodiment 3 after stirring.
In embodiment 3, the preparation of the preparation of positive plate, the preparation of negative plate, barrier film, and the preparation of lithium ion battery is all substantially the same manner as Example 1, repeats no more.
Comparative example 1
The preparation of electrolyte: be full of glove box (the moisture <10ppm of argon gas, oxygen divides <10ppm) in, by the 1:1:1 mixing in mass ratio of ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), be made into the LiPF of 1mol/L
6electrolyte.
In comparative example 1, the preparation of the preparation of positive plate, the preparation of negative plate, barrier film, and the preparation of lithium ion battery is all substantially the same manner as Example 1, repeats no more.
Electrochemical property test is carried out after above-described embodiment 1, embodiment 2, embodiment 3 and comparative example 1 battery normal temperature are left standstill one day.
Embodiment 1 and comparative example 1 are at 3.0 ~ 4.6V with 0.2C circulation 100 weeks, and its cycle performance result as shown in Figure 1.As can be seen from the figure, lithium battery cycle performance is under high pressure significantly improved adding of sulfonyl two propionitrile.
The above is only better embodiment of the present invention, and those skilled in the art of the invention can also suitably change above execution mode and revise, and such as, solvent also comprises propene carbonate, diethyl carbonate etc.; Lithium salt can be 0.3 ~ 1.2M; Positive electrode can be LiCoO
2, LiMn
2o
4, LiNi
0.5co
0.2mn
0.3o
2, LiNi
0.4co
0.4mn
0.2o
2deng; Therefore the present invention is not limited to above-mentioned put forward embodiment, and all some modifications and changes according to the structure described in patent claim of the present invention all should fall in the protection range of the claims in the present invention.
Claims (9)
1. a lithium-ion battery electrolytes, it comprises non-aqueous organic solvent, lithium salts and electrolysis additive, and wherein, described electrolysis additive is the organic sulfoxide compound with two cyano group; Preferably, described electrolysis additive is the organic sulfoxide compound with two end cyano group.
2. lithium-ion battery electrolytes according to claim 1, wherein, described electrolysis additive for having the organic sulfoxide compound with two cyano group of structure shown in formula (1),
NC-R
1-SO
2-R
2-CN formula (1)
Wherein, R
1, R
2can be the same or different, be independently selected from C
1-8the C that alkylidene or halogen (such as fluorine) replace
1-8alkylidene.
Preferably, described C
1-8alkylidene is straight or branched alkylidene, and such as, methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, the sub-tert-butyl group, pentylidene, hexylidene etc., preferably, described halogen is fluorine, chlorine or bromine.
3. lithium-ion battery electrolytes according to claim 1 and 2, wherein, described electrolysis additive content range is in the electrolytic solution 0.1 ~ 1.0% (mass ratio), preferably 0.2 ~ 0.8%, or 0.3 ~ 0.5%, more preferably 0.2 ~ 0.5%.
4. the lithium-ion battery electrolytes according to any one of claim 1-3, wherein, described electrolysis additive is sulfonyl diacetonitrile, sulfonyl two propionitrile, sulfonyl dibutyronitrile, the own nitrile of sulfonyl two, is more preferably sulfonyl two propionitrile.
5. the lithium-ion battery electrolytes according to any one of claim 1-4, wherein, described anhydrous organic solvent comprise in ethylene carbonate, ethyl propyl carbonic acid ester, diethyl carbonate, methyl propyl carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate one or more, preferably, described anhydrous organic solvent is any two or three in above-mentioned solvent; Be more preferably the two mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC), the two mixture of dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), or ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) three mixture.
6. the lithium-ion battery electrolytes according to any one of claim 1-5, wherein, described lithium salts comprises LiPF
6, LiBF
4, LiClO
4, LiAsF
6, in LiBOB any one or multiple.
7. the preparation method of the lithium-ion battery electrolytes according to any one of claim 1-6, comprising: mixed by non-aqueous organic solvent, lithium salts and the electrolysis additive described in any one of claim 1-6.
8. the purposes of the lithium-ion battery electrolytes according to any one of claim 1-6, it is for lithium ion battery, and preferably, described battery electrolyte is applied to the lithium ion battery of maximum operating voltage at 4.35 ~ 4.6V.
9. a lithium ion battery, comprises positive plate, negative plate, barrier film, and electrolyte, wherein, and the lithium-ion battery electrolytes of described electrolyte according to any one of claim 1-6.
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|---|---|---|---|
| CN201510138211.6A CN104733779A (en) | 2015-03-27 | 2015-03-27 | High-voltage lithium ion battery electrolyte and lithium battery |
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|---|---|---|---|
| CN201510138211.6A CN104733779A (en) | 2015-03-27 | 2015-03-27 | High-voltage lithium ion battery electrolyte and lithium battery |
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| CN104733779A true CN104733779A (en) | 2015-06-24 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845977A (en) * | 2016-05-26 | 2016-08-10 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery comprising same |
| CN111740147A (en) * | 2020-06-29 | 2020-10-02 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device comprising the same |
Citations (2)
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|---|---|---|---|---|
| US20040048163A1 (en) * | 2002-09-06 | 2004-03-11 | Yong-Chul Park | Electrolyte for a lithium battery and a lithium battery and a lithium battery comprising the same |
| CN101442143A (en) * | 2008-12-17 | 2009-05-27 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolytic solution and lithium ion battery |
-
2015
- 2015-03-27 CN CN201510138211.6A patent/CN104733779A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040048163A1 (en) * | 2002-09-06 | 2004-03-11 | Yong-Chul Park | Electrolyte for a lithium battery and a lithium battery and a lithium battery comprising the same |
| CN101442143A (en) * | 2008-12-17 | 2009-05-27 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolytic solution and lithium ion battery |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845977A (en) * | 2016-05-26 | 2016-08-10 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery comprising same |
| CN105845977B (en) * | 2016-05-26 | 2018-12-21 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery comprising same |
| US10381681B2 (en) * | 2016-05-26 | 2019-08-13 | Contemporary Amperex Technology Co., Limited | Electrolyte and lithium-ion battery containing the same |
| CN111740147A (en) * | 2020-06-29 | 2020-10-02 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device comprising the same |
| WO2022001777A1 (en) * | 2020-06-29 | 2022-01-06 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device containing electrolyte |
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Application publication date: 20150624 |
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