CN105633469B - A kind of nonaqueous electrolytic solution - Google Patents
A kind of nonaqueous electrolytic solution Download PDFInfo
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- CN105633469B CN105633469B CN201610003389.4A CN201610003389A CN105633469B CN 105633469 B CN105633469 B CN 105633469B CN 201610003389 A CN201610003389 A CN 201610003389A CN 105633469 B CN105633469 B CN 105633469B
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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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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 invention discloses a kind of nonaqueous electrolytic solutions, according to mass fraction, consisting of: 10-20 parts of compound that structural formula (I) indicates, 5-12 parts of other lithium salts, 1, 2-5 parts of 4- butanediol sulfuric ester, 10-12 parts of adiponitrile, 15-25 parts of pimelic dinitrile, 10-15 parts of hexamethylene dicyanide, 8-20 parts of sebacic dinitrile, 4- fluoro- 1, 20-40 parts of 3- dioxolan-2-one, 5-10 parts of ethylene carbonate, 3-5 parts of propene carbonate, 5-12 parts of fluorinated ethylene carbonate, 4-8 parts of alkene ester of carbonic acid hydroxy benzenes, 3-5 parts of anti-overshoot additive, 0.5-1.5 part of fire retardant, hexamethyldisilazane or 1-2 parts of triphenyl phosphite；Lithium salts containing oxalate group can also form solid electrolyte membrane in positive electrode surface, and the high voltage withstanding performance of battery can be improved；Lithium salts containing oxalate group is environmentally friendly, and battery dismantling will not cause the pollution of environment due to the problem of electrolyte when recycling.
Description
Technical field
The invention belongs to new materials and electrochemical technology field, and in particular to a kind of nonaqueous electrolytic solution.
Background technique
High, pollution-free, memory-less effect, service life are long and famous with its specific energy for lithium ion battery.In recent years, lithium-ion electric
Pond has attracted much attention, and obtains promotion and application.It is small to arrive electronic watch, mobile phone, electric bicycle, automobile are arrived greatly, it is very popular, even
In fields such as military aerospaces, lithium ion battery is also increasingly to be favored.Lithium ion battery has profoundly affected the day of people
Normal life and work.
The positive and negative anodes of lithium ion battery activity all with higher, to the lithium ion battery of Charging state, cathode has height
Reproducibility, anode has high oxidative, if the protection without film for additive, common carbonate solvent is easy to occur with positive and negative anodes secondary
Reaction.In actual use, the lasting of electronic product (such as laptop) is increased using fever, battery use environment temperature
Factors such as (such as summer outdoor temperature are close to 40 DEG C, and closing inside the closed car of air-conditioning even can up to 60 DEG C) may all make
At battery at high operating temperatures.At high temperature, the reactivity of the positive and negative anodes of battery further enhances, the pair of electrolyte and electrode
Reaction speed is accelerated, and causes electrolyte decomposition to generate bulk gas, so that cell expansion deforms and leads to the damage of electrical appliance.Sternly
When weight, flammable electrolyte is caused to be let out since cell expansion deformation causes inside battery generation short circuit or battery packages to be burst
Dew has the risk for causing the safety accidents such as fire.
Summary of the invention
The technical problems to be solved by the present invention are: providing, a kind of compatibility is good, lithium salts dissolubility is good, has ideal high temperature
The lithium ion battery nonaqueous electrolytic solution of storage performance.
In order to solve the above technical problems, the technical scheme adopted by the invention is as follows: a kind of nonaqueous electrolytic solution, according to mass parts
Number, consisting of: 10-20 parts of compound, 5-1 2 parts of other lithium salts, 1,4-butanediol sulfuric ester 2-5 that structural formula (I) indicates
Part, 10-12 parts of adiponitrile, 15-25 parts of pimelic dinitrile, 10-15 parts of hexamethylene dicyanide, 8-20 parts of sebacic dinitrile, the fluoro- 1,3-dioxolane-of 4-
2 0-40 parts of 2- ketone (also known as fluorinated ethylene carbonate), 5-10 parts of ethylene carbonate (EC), 3-5 parts of propene carbonate (PC), fluorine
For 5-12 parts of ethylene carbonate (FEC), 4-8 parts of carbonic acid hydroxy benzenes alkene ester, 3-5 parts of anti-overshoot additive, fire retardant 0.5-
1.5 parts, hexamethyldisilazane or 1-2 parts of triphenyl phosphite；
The compound that the structural formula (I) indicates are as follows:
Wherein, Rf=CF3O(CF2CF2)n、HCF2O(CF2CF2)nOr ICF2O(CF2CF2)n, n be 1~6 integer；
Other described lithium salts are di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), difluoro dioxalic acid phosphorus
Sour lithium (LiDFOP), tetrafluoro oxalic acid lithium phosphate (LiTFOP), [N (SO2OCH2CF3)2] Li、N[SO2OCH(CF3)2]2Li、LiN
(SO2RF)2、LiN(SO2F)(SO2RF) one of or two kinds or more of combination, wherein substituent RF=CnF2n+1, n is 1 to 10
Integer.
The carbonic acid hydroxy benzenes alkene ester is carbonic acid dihydroxy benzenes vinyl acetate and/or carbonic acid monohydroxy styrene esters.
The fire retardant is trimethyl phosphate, in triethyl phosphate, triphenyl phosphate, tributyl phosphate, hexamethyl phosphonitrile
One or two or more kinds of mixtures.
Innovative point of the present invention is: the electrolyte and lithium ion battery electrode material have preferable compatibility, compared with
The features such as high thermal stability, resistance to oxidation reducing power is strong, and conductivity is high.Lithium salts containing oxalate group can also in positive electrode surface
To form solid electrolyte membrane, the high voltage withstanding performance of battery can be improved；Lithium salts containing oxalate group is environmentally friendly, electricity
The pollution of environment will not be caused when the dismantling recycling of pond due to the problem of electrolyte.
Specific embodiment
The specific embodiment being set forth below is that the present invention is described in further detail, these embodiments are only used for
The bright purpose of the present invention does not limit the invention in any way the range of included content.
Embodiment 1
1) positive production: by LiCoO2Powder, carbon black (granularity 1000nm), Kynoar (PVDF) and N, N-
Dimethyl pyrrolidone (NMP) is mixed and made into uniform slurry, by slurry even application on aluminium foil (15 μm) collector, then
It is dried, rolls, obtain LiCoO2Positive electrode.It is dried 12 hours at 120 DEG C, in the pole piece after drying, LiCoO2Zhan is always applied
The 94% of application, binder account for 4%, and carbon black accounts for 2%.Then gained pole piece is cut into diameter is 12mm disk as anode.
2) production of cathode: by artificial graphite, Kynoar (PVDF) and N, N- dimethyl pyrrolidone (NMP) mixing
Uniform slurry is made, by slurry even application on copper foil (15 μm) collector, is then dried, rolls, it is negative to obtain carbon
Pole material.It is dried 12 hours at 120 DEG C, in the pole piece after drying, the 96.4% of the total coating of graphite Zhan, binder accounts for 3.6%,
Then gained pole piece is cut into diameter is 12mm disk as cathode.
3) preparation of electrolyte:
13 parts, 5 parts of tetrafluoro oxalic acid lithium phosphate, [N (SO2OCH2CF3)2] 6 parts of L i, 1,
5 parts of 4- butanediol sulfuric ester, 11 parts of adiponitrile, 15 parts of pimelic dinitrile, 13 parts of hexamethylene dicyanide, 12 parts of sebacic dinitrile, fluoro- 1, the 3- dioxy penta of 4-
37 parts of ring -2- ketone, 8 parts of ethylene carbonate (EC), 3 parts of propene carbonate (PC), 8 parts of carbonic acid dihydroxy benzenes vinyl acetate, anti-overshoot
4 parts of additive, 0. 8 parts of triethyl phosphate, hexamethyldisilazane or 1.5 parts of triphenyl phosphite；
By conductive saltTetrafluoro oxalic acid lithium phosphate, [N (SO2OCH2CF3)2] Li vacuum is dry
It is transferred to glove box after dry, is slowly added in organic solvent, is configured to electrolyte, sealing is stand-by.
4) battery diaphragm the composition and performance evaluation of CR2032 fastening lithium ionic cell: is placed on above-mentioned steps 1) and 2)
In between prepared positive/negative plate, above-mentioned steps 3 are added dropwise) in the prepared nonaqueous electrolytic solution of institute, be assembled into the button of CR2032
Formula battery.
The cycle performance test of battery is carried out on micro-processor controlled automatic inflatable instrument (Land, CT2001A).Test-strips
Part: temperature is 25 DEG C, and blanking voltage is 4.2~2.75V, rate of charge 0.5C, discharge-rate 0.2C.The survey of the present embodiment
Data are tried referring to table 1.
Embodiment 2
Comparative example 1,18 parts, 6 parts of dioxalic acid lithium phosphate (LiDFOP), N
[SO2OCH(CF3)2]2Li6 parts, 4 parts of 1,4-butanediol sulfuric ester, 11 parts of adiponitrile, 20 parts of pimelic dinitrile, 11 parts of hexamethylene dicyanide, the last of the ten Heavenly stems two
18 parts of nitrile, 44 parts of 4- fluoro-1,3-dioxolan-2-one, 8 parts of ethylene carbonate (EC), 4 parts of propene carbonate (PC), carbonic acid one
6 parts of hydroxy styrenes ester, anti-4 parts of overshoot additive, 0.8 part of triphenyl phosphate, hexamethyldisilazane or triphenyl phosphite
1.5 part；
By step 1)~4 in embodiment 1) operation, assembling and evaluation battery.The test data of the present embodiment is referring to table 1.
Embodiment 3
12 parts, 7 parts of dioxalic acid lithium phosphate, LiN (SO2RF)25 parts, Isosorbide-5-Nitrae-fourth two
4 parts of alcohol sulfuric ester, 11 parts of adiponitrile, 20 parts of pimelic dinitrile, 13 parts of hexamethylene dicyanide, 16 parts of sebacic dinitrile, the fluoro- 1,3-dioxolane -2- of 4-
51 parts of ketone, 8 parts of ethylene carbonate (EC), 5 parts of propene carbonate (PC), 5 parts of carbonic acid dihydroxy benzenes vinyl acetate, carbonic acid monohydroxy
7 parts of styrene esters, anti-4 parts of overshoot additive, 1.3 parts of tributyl phosphate, hexamethyldisilazane or 2 parts of triphenyl phosphite；
The battery being assembled into as embodiment 1 carries out high temperature cyclic performance test.Test condition: assembled battery
Constant temperature experiment directly at 60 DEG C carries out high temperature circulation test, and blanking voltage is 4.2-2.75V.Rate of charge is 0.5C, is put
Electric multiplying power is 0.2C.The test data of the present embodiment is referring to table 1.
The electrolyte composition and battery performance test data of embodiment 1-3 are shown in Table 1.
Electrification of the composition and its lithium ion battery of 1. nonaqueous electrolytic solution of table before and after 60 DEG C or 85 DEG C of high temperature storage experiments
Learn performance data.
Claims (3)
1. a kind of nonaqueous electrolytic solution, according to mass fraction, consisting of: structural formula (I) indicate 10-20 parts of compound, other
5-12 parts of lithium salts, 2-5 parts of 1,4-butanediol sulfuric ester, 10-12 parts of adiponitrile, 15-25 parts of pimelic dinitrile, 10-15 parts of hexamethylene dicyanide, the last of the ten Heavenly stems
8-20 parts of dintrile, 37-51 parts of 4- fluoro-1,3-dioxolan-2-one, 5-10 parts of ethylene carbonate, 3-5 parts of propene carbonate, carbon
4-8 parts of sour hydroxy benzenes alkene ester, 3-5 parts of anti-over-charging additive, 0.5-1.5 part of fire retardant, hexamethyldisilazane or phosphorous acid
1-2 parts of triphenylmethyl methacrylate；
The compound that the structural formula (I) indicates are as follows:
Wherein, Rf=CF3O(CF2CF2)n、HCF2O(CF2CF2)nOr ICF2O(CF2CF2)n, n be 1~6 integer；
Other described lithium salts are di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, difluoro dioxalic acid lithium phosphate, tetrafluoro oxalic acid phosphoric acid
Lithium, [N (SO2OCH2CF3)2]Li、N[SO2OCH(CF3)2]2Li、LiN(SO2RF)2、LiN(SO2F)(SO2RF) one of or two
Kind or more combination, wherein substituent RF=CnF2n+1, n is integer of 1 to 10.
2. a kind of nonaqueous electrolytic solution according to claim 1, it is characterised in that: the carbonic acid hydroxy benzenes alkene ester is carbonic acid two
Hydroxy styrenes ester and/or carbonic acid monohydroxy styrene esters.
3. a kind of nonaqueous electrolytic solution according to claim 1, it is characterised in that: the fire retardant is trimethyl phosphate, phosphoric acid
One of triethyl, triphenyl phosphate, tributyl phosphate, hexamethyl phosphonitrile or two kinds or more of mixture.
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| CN110556578B (en) * | 2019-09-06 | 2021-02-12 | 中国科学院福建物质结构研究所 | Electrolyte additive, electrolyte containing electrolyte additive and application of electrolyte in lithium ion battery |
| CN110556579B (en) * | 2019-09-06 | 2021-02-12 | 中国科学院福建物质结构研究所 | Electrolyte and lithium ion battery containing same |
| CN111628219A (en) * | 2020-06-05 | 2020-09-04 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device containing electrolyte solution, and electronic device |
Citations (3)
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| CN102412417A (en) * | 2010-09-20 | 2012-04-11 | 华中科技大学 | Non-aqueous electrolyte for improving high-temperature electrochemical performance of lithium ion battery and application thereof |
| CN103682439A (en) * | 2013-11-18 | 2014-03-26 | 中国科学院物理研究所 | High-voltage non-aqueous electrolyte and high-voltage non-aqueous electrolyte secondary battery |
| CN104604016A (en) * | 2012-09-07 | 2015-05-06 | 丰田自动车株式会社 | Method for producing nonaqueous electrolyte secondary battery |
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| CN102074734A (en) * | 2010-09-30 | 2011-05-25 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte solution of fluorine-containing lithium sulfonimide salt and application thereof |
| CN103515650A (en) * | 2012-06-26 | 2014-01-15 | 华中科技大学 | Non-aqueous electrolyte for lithium ion battery, and application thereof |
| CN103794819A (en) * | 2014-01-17 | 2014-05-14 | 苏州氟特电池材料有限公司 | Nonaqueous electrolyte containing sulfonyl fluoride imidogen lithium salt as well as application of electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102412417A (en) * | 2010-09-20 | 2012-04-11 | 华中科技大学 | Non-aqueous electrolyte for improving high-temperature electrochemical performance of lithium ion battery and application thereof |
| CN104604016A (en) * | 2012-09-07 | 2015-05-06 | 丰田自动车株式会社 | Method for producing nonaqueous electrolyte secondary battery |
| CN103682439A (en) * | 2013-11-18 | 2014-03-26 | 中国科学院物理研究所 | High-voltage non-aqueous electrolyte and high-voltage non-aqueous electrolyte secondary battery |
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Effective date of registration: 20210512 Address after: 215600 Room 301, building 3, Yuanyuan East Village, yangshe Town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee after: Zhang Keqi Address before: 215634 Suzhou Fute battery materials Co., Ltd., on the west side of the second floor of Building D, No.7 Guangdong Road, Zhangjiagang Free Trade Zone, Suzhou City, Jiangsu Province Patentee before: SUZHOU FLUOLYTE Co.,Ltd. |
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Effective date of registration: 20230117 Address after: 430070 Room 01-01, Floor 8, Unit C, CRO Building, CRO Office Area, No. 666, Gaoxin Avenue, Donghu New Technology Development Zone, Wuhan, Hubei Province Patentee after: Wuhan Ruihua New Energy Technology Co.,Ltd. Address before: 215600 Room 301, building 3, Yuanyuan East Village, yangshe Town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee before: Zhang Keqi |