CN109659616A - A kind of electrolyte and lithium ion battery - Google Patents
A kind of electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN109659616A CN109659616A CN201811566568.4A CN201811566568A CN109659616A CN 109659616 A CN109659616 A CN 109659616A CN 201811566568 A CN201811566568 A CN 201811566568A CN 109659616 A CN109659616 A CN 109659616A
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- Prior art keywords
- lithium
- ion battery
- lithium ion
- additive
- electrolyte
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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
A kind of electrolyte and lithium ion battery, belong to lithium ion battery material technical field.Additive includes 1 compound represented of structural formula, cathode film formation additive and difluorophosphate (LiPO2F2).The mass fraction of cathode film formation additive in the electrolytic solution is 0.1%~5%; the mass fraction of Furanones compound in the electrolytic solution is 0.1%~3%; the mass fraction of difluorophosphate in the electrolytic solution is 0.1%~2%; the Furanones compound has chemical structural formula shown in Formulas I: additive combination forms high-intensitive, low-impedance protective film in electrode surface; it can significantly improve the cryogenic discharging characteristic of battery, while battery high-temperature storage performance can be improved again.
Description
Technical field
The invention belongs to field of lithium ion battery material, and in particular to a kind of electrolyte and lithium ion battery.
Background technique
Lithium ion battery is since commercialization, since its specific energy is high, good cycle, be widely used in it is digital,
The fields such as energy storage, power, militay space flight and communication apparatus.With the extensive use of lithium ion battery, consumer is suitable to its environment
Answering property is put forward higher requirements.Such as in the low temp area of bad environments, it is desirable that lithium ion battery also can be normal under extreme low temperature
Work.However, lithium ion battery is at low ambient temperatures, charge-discharge performance is decreased obviously compared with will appear under normal temperature environment.
Important component of the electrolyte as lithium ion battery influences the cryogenic property of battery great.Current electrolysis
There are mainly two ways can improve the cryogenic property of lithium ion battery for liquid.First, optimization solvent composition, reduces electrolyte low temperature
Under viscosity, improve low temperature under conductivity, still, this approach usually reduces the high-temperature behavior of battery, cannot finally solve lithium from
Sub- battery in the application the problem of.Second, improving electrolyte/electrode interface property by optimization electrolysis additive, boundary is reduced
Face impedance can also improve the dynamic performance of lithium ion battery at low temperature.Therefore, it is excellent to develop a kind of high temperature performance
Electrolysis additive and lithium ion battery are necessary.
Summary of the invention
The purpose of the present invention is to solve existing lithium ion battery high temperature performances to be difficult to the problem of taking into account, and provides one
Kind electrolyte and lithium ion battery in the battery by this kind of additive application can make battery have excellent high temperature performance.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of electrolyte, including organic solvent, electric conducting lithium salt and additive, the additive contain Furanones chemical combination
Object, cathode film formation additive and difluorophosphate；The mass fraction of cathode film formation additive in the electrolytic solution is 0.1%~5%,
The mass fraction of Furanones compound in the electrolytic solution is 0.1%~3%, the mass fraction of difluorophosphate in the electrolytic solution
It is 0.1%~2%, the Furanones compound has chemical structural formula shown in Formulas I:
Wherein, R1、R2、R3It is independently selected from hydrogen, halogen, alkyl, alkyl halide alkyl, alkylene, alkynes base, silicon
Any one in alkyl, aryl radical, halogenated aromatic alkyl, alkoxy or carboxyl.
A kind of lithium ion battery containing above-mentioned electrolyte, the lithium ion battery include anode, cathode, diaphragm,
Electrolyte.
The beneficial effect of the present invention compared with the existing technology is: using Furanones compound and cathode film formation additive
It being used in mixed way, two kinds of compounds form protective film in positive and negative pole surface jointly, while reducing battery impedance using difluorophosphate,
The ionic conductivity for being conducive to increase protective film, makes the movement of lithium ion become smooth, while the protective film has preferably surely
It is qualitative, so that the high/low temperature for significantly improving battery takes into account performance.
Specific embodiment
Below with reference to embodiment, further description of the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.
Specific embodiment 1: what present embodiment recorded is a kind of electrolyte, including organic solvent, electric conducting lithium salt and add
Add agent, the additive contains Furanones compound, cathode film formation additive and difluorophosphate (LiPO2F2)；Cathode at
The mass fraction of film additive in the electrolytic solution is 0.1%~5%, and the mass fraction of Furanones compound in the electrolytic solution is
0.1%~3%, when the content of Furanones compound is lower than 0.1%, protective film cannot be effectively formed in electrode surface,
To not can effectively prevent side reaction caused by the electronics transfer between electrolyte and electrode；And when Furanones compound is big
When 3%, thicker protective film can be formed in electrolyte surface, causes lithium ion mobility resistance to increase, is unfavorable for the low of battery
Warm nature energy；The mass fraction of difluorophosphate in the electrolytic solution is 0.1%~2%, when difluorophosphate adding in the electrolytic solution
When dosage is lower than 0.1%, protective film cannot be effectively formed in electrode surface, the cryogenic property of battery is without improvement；And work as difluoro
When the content of lithium phosphate is higher than 2%, battery impedance larger impact battery cryogenic property；The Furanones compound has formula
Chemical structural formula shown in I:
Wherein, R1、R2、R3It is independently selected from hydrogen, halogen, alkyl, alkyl halide alkyl, alkylene, alkynes base, silicon
Any one in alkyl, aryl radical, halogenated aromatic alkyl, alkoxy or carboxyl.
Specific embodiment 2: a kind of lithium-ion battery electrolytes described in specific embodiment one, the cathode at
Film additive is fluorinated ethylene carbonate, 1,3- propane sultone, vinylethylene carbonate, ethyl sulfate or carbonic acid Asia second
One or more of enester.
Specific embodiment 3: a kind of lithium ion battery described in specific embodiment one, the organic solvent is carbon
Vinyl acetate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propyl acetate, n-butyl acetate, acetic acid
One or more of isobutyl ester, n-amyl acetate, isoamyl acetate, ethyl propionate, n propyl propionate, ethyl butyrate.
Specific embodiment 4: a kind of lithium ion battery described in specific embodiment one, the electric conducting lithium salt is two
Fluorine oxalic acid lithium phosphate, double fluorine sulfimide lithiums, bis trifluoromethyl sulfimide lithium, lithium hexafluoro phosphate, di-oxalate lithium borate, difluoro
One or more of Lithium bis (oxalate) borate, LiBF4, lithium perchlorate.
Specific embodiment 5: a kind of contain electrolyte described in any specific embodiment of specific embodiment one to four
Lithium ion battery, the lithium ion battery include anode, cathode, diaphragm, electrolyte.
The additive of the involved I containing structural formula in embodiment and comparative example:
Comparative example 1
Solvent ethylene carbonate/propyl propionate/diethyl carbonate/ethyl acetate 3:4:1:2 in mass ratio is mixed, by electricity
The T1 that liquid gross mass calculates the addition 0.5% inside mixed liquor is solved, 1% VC is eventually adding 14% hexafluoro phosphorus as additive
Sour lithium obtains 1 electrolyte of comparative example.It injects the electrolyte into the battery core of the non-fluid injection comprising positive plate, negative electrode tab and diaphragm, system
At lithium ion battery, 1 battery of comparative example is obtained.
Comparative example 2
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 1%
The LiPO2F2 of T2 and 0.5%.
Comparative example 3
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 1%
The LiPO2F2 of PS and 1%.
Embodiment 1
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 0.5%
VEC, 1% LiPO2F2 and 0.8% T1.
Embodiment 2
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 7%
FEC, 1.5% LiPO2F2 and 1.5% T2.
Embodiment 3
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 3%
PS, 0.5% LiPO2F2 and 2% T3.
Embodiment 4
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 1%
DTD, 2% LiPO2F2 and 0.5% T4.
Embodiment 5
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 2%
VC, 0.3% LiPO2F2 and 2.5% T5.
Embodiment 6
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 1%
The T6 of VC, 1% DTD, 0.5% LiPO2F2 and 0.5%.
Embodiment 7
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 2%
The T7 of PS, 1% DTD, 0.5% LiPO2F2 and 3%.
Embodiment 8
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 5%
The T8 of FEC, 3% PS, 0.2% LiPO2F2 and 1.5%.
Embodiment 9
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 4%
FEC, 1% VEC, 0.5% LiPO2F2,2% T1 and 0.2% T4.
Embodiment 10
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 3%
VC, 2% PS, 1% LiPO2F2,1% T3 and 0.5% T7.
Embodiment 11
Using lithium ion battery used in comparative example 1.The difference is that the additive being added is to account for electrolyte total weight 0.5%
VEC, 0.5% LiPO2F2,0.2% T5 and 0.5% T2.
Electrochemical property test is carried out to the above comparative example and the resulting lithium ion battery of embodiment
High temperature storage experiment: by embodiment 1~11 and 1~3 gained battery of comparative example at room temperature with the charge and discharge of 1.2C
Multiplying power carries out 10 charge and discharge cycles tests, and then 1.2C multiplying power is charged to full power state.1.2C capacity Q is recorded respectively and battery is thick
Spend T.The battery of full power state is stored 21 days at 60 DEG C, records cell thickness T0With 1.2C discharge capacity Q1, then by battery
At room temperature with the multiplying power charge and discharge of 1.2C 10 weeks, 1.2C discharge capacity Q is recorded2, the holding of battery high-temperature memory capacity is calculated
The experimental datas such as rate, capacity restoration rate and thickness change record result such as table 1.
The calculation formula wherein used is as follows:
Low temperature discharge experiment: by embodiment 1~11 and 1~3 gained battery of comparative example at room temperature with the progress of 1.2C multiplying power
Then 10 charge and discharge cycles are charged to full power state with 1.2C multiplying power, record 1.2C capacity Q0.By the battery under full power state
After shelving 4h at -20 DEG C, with 0.25C multiplying power discharging to 3V, discharge capacity Q is recorded3, can be calculated low temperature discharge capacity holding
Rate records result such as table 1.
Low temperature discharge capacity conservation rate calculation is following formula:
The comparison of 1 embodiment and comparative example experimental result of table
As can be seen from Table 1: taking into account performance using the high/low temperature of the lithium ion battery of electrolyte of the present invention and obviously changed
It is kind.The above embodiment is a preferred embodiment of the present invention, but embodiment of the present invention are not limited by the above embodiments,
It is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify, should all
For equivalent substitute mode, it is included within the scope of the present invention.
Claims (5)
1. a kind of electrolyte, including organic solvent, electric conducting lithium salt and additive, it is characterised in that: the additive contains furan
It mutters ketone compounds, cathode film formation additive and difluorophosphate；The mass fraction of cathode film formation additive in the electrolytic solution is
0.1%~5%, the mass fraction of Furanones compound in the electrolytic solution is 0.1%~3%, and difluorophosphate is in electrolyte
In mass fraction be 0.1%~2%, the Furanones compound have Formulas I shown in chemical structural formula:
Wherein, R1、R2、R3Be independently selected from hydrogen, halogen, alkyl, alkyl halide alkyl, alkylene, alkynes base,
Any one in silylation, aryl radical, halogenated aromatic alkyl, alkoxy or carboxyl.
2. a kind of lithium-ion battery electrolytes according to claim 1, it is characterised in that: the cathode film formation additive
For in fluorinated ethylene carbonate, 1,3- propane sultone, vinylethylene carbonate, ethyl sulfate or vinylene carbonate
It is one or more of.
3. a kind of lithium ion battery according to claim 1, it is characterised in that: the organic solvent is ethylene carbonate
Ester, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propyl acetate, n-butyl acetate, Sucrose Acetate
One or more of ester, n-amyl acetate, isoamyl acetate, ethyl propionate, n propyl propionate, ethyl butyrate.
4. a kind of lithium ion battery according to claim 1, it is characterised in that: the electric conducting lithium salt is difluoro oxalate phosphorus
Sour lithium, double fluorine sulfimide lithiums, bis trifluoromethyl sulfimide lithium, lithium hexafluoro phosphate, di-oxalate lithium borate, difluoro oxalate boric acid
One or more of lithium, LiBF4, lithium perchlorate.
5. a kind of lithium ion battery containing electrolyte described in Claims 1 to 4 any claim, it is characterised in that: institute
The lithium ion battery stated includes anode, cathode, diaphragm, electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811566568.4A CN109659616A (en) | 2018-12-19 | 2018-12-19 | A kind of electrolyte and lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811566568.4A CN109659616A (en) | 2018-12-19 | 2018-12-19 | A kind of electrolyte and lithium ion battery |
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| CN201811566568.4A Pending CN109659616A (en) | 2018-12-19 | 2018-12-19 | A kind of electrolyte and lithium ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110233291A (en) * | 2019-05-31 | 2019-09-13 | 骆驼集团新能源电池有限公司 | A kind of wide temperate zone lithium battery electrolytes of 12V start and stop balancing high/low temperature |
| CN111952584A (en) * | 2020-07-13 | 2020-11-17 | 深圳市秸川材料科技有限公司 | Lithium battery |
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| JP2005340151A (en) * | 2004-04-28 | 2005-12-08 | Mitsubishi Chemicals Corp | Lithium secondary battery |
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| KR20080065561A (en) * | 2007-01-09 | 2008-07-14 | 주식회사 엘지화학 | Non-aqueous electrolyte and secondary battery comprising the same |
| CN103367800A (en) * | 2012-04-09 | 2013-10-23 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte used for layered manganese acid lithium battery |
| CN107369849A (en) * | 2017-08-04 | 2017-11-21 | 广州天赐高新材料股份有限公司 | A kind of lithium secondary cell electrolyte and lithium secondary battery |
| CN108496272A (en) * | 2015-10-26 | 2018-09-04 | 索尔维公司 | Include the non-aqueous electrolyte composition of fluorated solvent and 2- furanones |
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2018
- 2018-12-19 CN CN201811566568.4A patent/CN109659616A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11273725A (en) * | 1998-03-20 | 1999-10-08 | Ube Ind Ltd | Electrolytic solution for lithium secondary battery and lithium secondary battery using it |
| CN1479400A (en) * | 2002-08-31 | 2004-03-03 | 三星Sdi株式会社 | Organic electrolyte and lithium cell using it |
| JP2005340151A (en) * | 2004-04-28 | 2005-12-08 | Mitsubishi Chemicals Corp | Lithium secondary battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110233291A (en) * | 2019-05-31 | 2019-09-13 | 骆驼集团新能源电池有限公司 | A kind of wide temperate zone lithium battery electrolytes of 12V start and stop balancing high/low temperature |
| CN111952584A (en) * | 2020-07-13 | 2020-11-17 | 深圳市秸川材料科技有限公司 | Lithium battery |
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| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant after: Zhuhai Guanyu Battery Co., Ltd. Address before: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant before: Zhuhai Coslight Battery Co., Ltd. |
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Address after: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant after: Zhuhai Guanyu Battery Co., Ltd Address before: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
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| RJ01 | Rejection of invention patent application after publication | ||
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Application publication date: 20190419 |