CN105895954A - High-stability power battery electrolyte - Google Patents
High-stability power battery electrolyte Download PDFInfo
- Publication number
- CN105895954A CN105895954A CN201610297540.XA CN201610297540A CN105895954A CN 105895954 A CN105895954 A CN 105895954A CN 201610297540 A CN201610297540 A CN 201610297540A CN 105895954 A CN105895954 A CN 105895954A
- Authority
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- China
- Prior art keywords
- electrolyte
- power battery
- high stability
- stabilizer
- stability power
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Classifications
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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
-
- 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
-
- 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 a high-stability power battery electrolyte. The high-stability power battery electrolyte comprises lithium hexafluorophate, a non-aqueous solvent, an additive and an electrolyte stabilizer, wherein the electrolyte stabilizer is combination of a phosphite ester compound and a carbodiimide compound. The phosphite ester stabilizer of the electrolyte provided by the invention and PF5 can form a complex of a sexadentale body, the reaction activity of the PF5 is reduced, side reaction of impurity in the PF5 and the electrolyte is reduced, and the acidity and the chromaticity of the electrolyte in a high-temperature condition are prevented from rapidly rising; and meanwhile, the carbodiimide stabilizer can generate slow hydrolysis reaction in the electrolyte, the slight amount of HF in the electrolyte can be effectively captured by an alkali hydrolysis product, thus, the moisture content in the electrolyte is effectively reduced, and the acidity of the electrolyte is prevented from rising. With the adoption of a power battery prepared from the electrolyte provided by the invention, the comprehensive performance of the battery is excellent, and the high-temperature cycle performance at 60 DEG C is excellent.
Description
Technical field
The present invention relates to lithium ion battery preparing technical field, be specifically related to a kind of high stability power battery electrolyte.
Background technology
The advantages such as lithium ion battery has that specific energy is high, voltage high, has extended cycle life, environmental friendliness, be widely used in number,
The fields such as energy storage, power, militay space flight and communication apparatus.
Electrolyte, as the important component part of lithium ion battery, plays the effect of transmission electric charge, to battery between battery plus-negative plate
Capacity play performance, cycle performance and high temperature performance most important.Electrolyte product is by its material purity, production preparation work
The impact of skill, is inevitably present following trace impurity: H2The materials such as O, HF, alcohol, aldehyde, ketone and amine.Above-mentioned trace is miscellaneous
Matter and the catabolite PF of lithium hexafluoro phosphate5When coexisting, being susceptible to reaction, its product directly results in electrolyte colourity and acidity is fast
Speed rises, deterioration electrolyte quality, reduction battery capacity and cycle life.
The phosphite ester compounds such as triphenyl phosphite have antioxidant effect, are widely used in chemical industry as antioxidant
In.Research shows, adds the triphenyl phosphite of 300ppm-500ppm in the electrolytic solution, can effectively slow down the storage of electrolyte room temperature
Colourity during depositing rises, but below 500ppm addition is for the electrolyte colourity during suppression 60 DEG C storage, acid
On degree, ascending effect is the most notable；Meanwhile, phosphite-type stabilisers zest is relatively strong, addition more than 300ppm to liquid-filling cart
Between the healthy injury of employee bigger.
In terms of electrolyte deacidification additive, what present stage was commonly used is concentrated mainly on hexamethyldisiloxane, seven methyl two silicon
The silicon nitrogen silane compound such as azane, TMSDEA, it has preferably work to the moisture in suppression electrolyte and acidity
With.But, this type of stabilizer cannot suppress colourity to rise, and is easily producing white sinking in electrolyte prolonged storage
Shallow lake thing, although solve electrolyte moisture, acidity problem, but creates new quality problem, when serious curtailment electrolyte stores
Between.
In consideration of it, be badly in need of a kind of electrolyte stabilizer of exploitation or a combination thereof, with electrolyte colourity, acid under effectively suppression hot conditions
Degree rises, and electrolyte quality, battery performance aspect will not be brought new problem again simultaneously.
Summary of the invention
For not enough present in background above technology, the invention provides a kind of high stability power battery electrolyte.
A kind of high stability power battery electrolyte, including lithium hexafluoro phosphate, nonaqueous solvent, additive and electrolyte stabilizer；
Described electrolyte stabilizer is the combination of bi-ester of phosphite and carbodiimide compound.
The combination that described electrolyte stabilizer is bi-ester of phosphite and carbodiimide compound is 1:0.1-10 in mass ratio.
Described electrolyte stabilizer is the combination that bi-ester of phosphite and carbodiimide compound are preferably 1:0.5-5 in mass ratio.
Described bi-ester of phosphite be in NSC 6513, NSC 5284, triphenyl phosphite any one or
Two or more mixture in any proportion.
Described carbodiimide compound be in N, N'-DIC, N, N'-dicyclohexylcarbodiimide any one or
Two kinds of mixture in any proportion of person.
Two or more in the following component of described nonaqueous solvent: ethylene carbonate, Allyl carbonate, carbonic acid diformazan
Ester, diethyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, gamma-butyrolacton, propyl acetate, ethyl propionate, propyl propionate.
Described additive is one or more in following component: vinylene carbonate, fluorinated ethylene carbonate, 1,3-propane sulfonic acid
Lactone, sulfuric acid vinyl ester, methane-disulfonic acid methylene ester, double fluorine sulfimide lithium, double trifluoromethanesulfonimide lithium.
Described additive addition accounts for the 1.0%～15.0% of lithium-ion battery electrolytes gross mass.
A kind of lithium ion battery, have employed the high stability power battery electrolyte of the present invention.
It is an advantage of the current invention that:
1, the electrolyte phosphite ester stabilizer in the present invention, energy and PF5Form the coordination compound of sexadentate, reduce PF5Reaction
Activity, reduces PF5With impurity generation side reaction in electrolyte, suppression electrolyte acidity under the high temperature conditions, colourity quickly on
Rise.
2, the carbodiimide stabilizer in the present invention can occur slow hydrolysis in the electrolytic solution, and its alkaline hydrolysis products can be effective
Catch the trace HF in electrolyte, thus effectively reduce electrolyte moisture and suppress its acidity to rise.
3, the combination of stabilizers mode that the present invention uses, solves existing stabilizer and cannot effectively suppress color under electrolyte hot environment
Degree and the zooming problem of acidity, it also avoid zest problem and white depositions problem that electrolyte stabilizer brings simultaneously.
4, the high stability power battery electrolyte that the present invention provides, not only during high-temperature storage, acidity, colourity are able to maintain that
At normal level, effectively extend electrolyte and store the time；More importantly, use electrokinetic cell prepared by electrolyte of the present invention,
60 DEG C of high temperature cyclic performances are the most excellent.
Accompanying drawing illustrates:
Accompanying drawing 1 is that electrokinetic cell 300 cycle of the embodiment of the present invention 1 circulates forward and backward charging and discharging curve figure.
Detailed description of the invention
Below by exemplary embodiment, the present invention will be further elaborated；But the scope of the present invention should not be limited to implement
The scope of example, any change without departing from present subject matter or change can be understood by the person skilled in the art, all at this
Within bright protection domain.
Embodiment 1
Electrolyte quota step: in the glove box of full argon, presses ethylene carbonate, Ethyl methyl carbonate and diethyl carbonate
Mass ratio is that EC:EMC:DEC=3:5:2 mixes, and being then slowly added to concentration to mixed solution is 1.0mol/L's
Lithium hexafluoro phosphate, is eventually adding vinylene carbonate based on electrolyte gross weight 2wt% (VC), 300ppm triphenyl phosphite
(TPPi), 300ppm N, N'-dicyclohexylcarbodiimide (DCC), obtain the lithium ion battery battery of embodiment 1 after stirring
Solve liquid.
60 DEG C of loop tests of lithium iron phosphate dynamic battery 0.5C@:
Lithium-ion battery electrolytes above-mentioned steps prepared injects the graphite/LiFePO through being fully dried4Square power battery
In, battery is shelved, is melted into through 45 DEG C, fixture shaping, after secondary sealing and conventional partial volume, carry out 0.5C@60 DEG C circulation and survey
Examination: at 60 DEG C, the battery after partial volume is charged to 3.65V, cut-off current 0.02C by 0.5C constant current constant voltage, then presses 0.5C
Constant-current discharge is to 2.50V, and circulation volume conservation rate computing formula is as follows: the 300th circulation volume conservation rate (%)=the (the 300th
The cyclic discharge capacity of secondary cyclic discharge capacity/first) × 100%, test result is as shown in table 1.
Embodiment 2～9 and comparative example 1～6
Embodiment 2～9, with comparative example 1～6, forms except electrolyte solvent, additive and stabilizer and content is as shown in table 1
Outside interpolation, other is the most same as in Example 1.
In above-mentioned table 1, it is as follows that corresponding title write a Chinese character in simplified form in each chemical substance letter:
EC (ethylene carbonate), PC (Allyl carbonate), DEC (diethyl carbonate), EMC (Ethyl methyl carbonate), VC (carbonic acid
Vinylene), LiFSi (double fluorine sulfimide lithium), DTD (sulfuric acid vinyl ester), MMDS (methane-disulfonic acid methylene ester),
TPPi (triphenyl phosphite), TMPi (NSC 6513), DCC (N, N'-dicyclohexylcarbodiimide), DIC (N, N'-
DIC), HMDS (hexamethyldisiloxane).
Electrolyte storage colourity, acidity test:
In glove box, the lithium-ion battery electrolytes that above-mentioned steps is prepared being installed to import seal in Aluminum Bottle, Aluminum Bottle aluminum plastic film is taken out
Vacuum Package, is placed in the calorstat that design temperature is 60 DEG C storage by electrolyte sample, the most before storage with storage 50 days
After in glove box sampling detection electrolyte colourity (Hazen), acidity (ppm), outward appearance, determination of colority method use platinum-cobalt
Colorimetry, acidity assaying method uses acid-base titrations, and testing result is as shown in table 2.
Above table 1 understands with table 2 result:
Comparative example 1～3 compares with each embodiment, time in comparative example electrolyte without carbodiimide compound, and phosphite ester chemical combination
Thing content is the highest, and electrolyte colourity, acidity rise the slowest, and 500ppm TPPi can suppress 60 DEG C to store in colourity substantially
Rise, but suppression acidity is risen the most prominent；700ppm can reach the effect of stable colourity, acidity the most substantially, but TPPi
After addition is more than 300ppm, electrolyte zest is too strong, and power battery at high temperature cycle performance is not ideal enough.
Comparative example 4,5 compares with each embodiment, individually adds carbodiimide compound, even if addition reaches in electrolyte
700ppm also cannot suppress electrolyte colourity to rise；Suppression electrolyte acidity is risen and then has certain effect, but still
The most prominent, power battery at high temperature cycle performance is the most poor.
Comparative example 6 adds phosphite ester and each 300ppm of silazane, after electrolyte stores 50 days in 60 DEG C of environment, acid
Degree rises slowly, and chromatic value is relatively low；But silazane additive is easily caused in electrolyte precipitation white depositions,
Affect electrolyte quality, simultaneously prepared by power battery at high temperature cycle performance the most general.
And in embodiment 1～9, interpolation bi-ester of phosphite and carbodiimide compound are as electrolyte stabilizer simultaneously,
In the effective deacidification of carbodiimide compound except, under water effect, bi-ester of phosphite only needs the consumption of 300ppm i.e. to can reach
The effect that effect suppression electrolyte acidity and colourity rise, it is to avoid phosphorous acid esters too high levels and to injure employee healthy.
To sum up: the combination of stabilizers mode that the present invention uses, solve existing stabilizer and cannot effectively suppress electrolyte hot environment
Lower colourity and the zooming problem of acidity, it also avoid zest problem and white depositions that electrolyte stabilizer brings simultaneously
Problem；Using electrokinetic cell prepared by electrolyte of the present invention, 60 DEG C of high temperature cyclic performances are the most excellent.
Be above illustrating of the section Example for the present invention, be not intended to limit the scope of the claims of the present invention, all not
Depart from change or the replacement of present invention, all should be within protection scope of the present invention.
Claims (9)
1. a high stability power battery electrolyte, including lithium hexafluoro phosphate, nonaqueous solvent, additive and electrolyte stabilizer；Described electrolyte stabilizer is the combination of bi-ester of phosphite and carbodiimide compound.
High stability power battery electrolyte the most according to claim 1, the combination that described electrolyte stabilizer is bi-ester of phosphite and carbodiimide compound is 1:0.1-10 in mass ratio.
High stability power battery electrolyte the most according to claim 2, the combination that described electrolyte stabilizer is bi-ester of phosphite and carbodiimide compound is 1:0.5-5 in mass ratio.
High stability power battery electrolyte the most according to claim 1, described bi-ester of phosphite is any one or two or more mixture in any proportion in NSC 6513, NSC 5284, triphenyl phosphite.
High stability power battery electrolyte the most according to claim 1, described carbodiimide compound is any one or two kinds of mixture in any proportion in N, N'-DIC, N, N'-dicyclohexylcarbodiimide.
High stability power battery electrolyte the most according to claim 1, two or more in the following component of described nonaqueous solvent: ethylene carbonate, Allyl carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, gamma-butyrolacton, propyl acetate, ethyl propionate, propyl propionate.
High stability power battery electrolyte the most according to claim 1, described additive is one or more in following component: vinylene carbonate, fluorinated ethylene carbonate, 1,3-propane sultone, sulfuric acid vinyl ester, methane-disulfonic acid methylene ester, double fluorine sulfimide lithium, double trifluoromethanesulfonimide lithium.
High stability power battery electrolyte the most according to claim 1, described additive addition accounts for the 1.0% ~ 15.0% of lithium-ion battery electrolytes gross mass.
9. a lithium ion battery, described lithium ion battery have employed the high stability power battery electrolyte described in any one of claim 1-8.
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| CN201610297540.XA CN105895954A (en) | 2016-05-05 | 2016-05-05 | High-stability power battery electrolyte |
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| CN201610297540.XA CN105895954A (en) | 2016-05-05 | 2016-05-05 | High-stability power battery electrolyte |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106596772A (en) * | 2016-12-14 | 2017-04-26 | 东莞市凯欣电池材料有限公司 | Method for detecting aggregated double-bone compounds in lithium hexafluorophosphate electrolyte solution |
| CN106784994A (en) * | 2017-01-09 | 2017-05-31 | 洪泽宇 | A kind of smart home lithium-ion battery electrolytes and battery |
| CN107887647A (en) * | 2017-10-26 | 2018-04-06 | 广州天赐高新材料股份有限公司 | A kind of 5V high voltages electrolyte for lithium secondary batteries and the lithium secondary battery containing the electrolyte |
| CN108242566A (en) * | 2016-12-26 | 2018-07-03 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN108511798A (en) * | 2017-04-27 | 2018-09-07 | 万向二三股份公司 | A kind of high-temperature lithium ion battery long circulating electrolyte |
| CN108649265A (en) * | 2018-05-10 | 2018-10-12 | 桑德集团有限公司 | Electrolysis additive, lithium battery electrolytes and lithium battery |
| 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 |
| CN112993400A (en) * | 2019-12-17 | 2021-06-18 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte for lithium battery and application thereof |
| CN113067037A (en) * | 2021-05-17 | 2021-07-02 | 湖北亿纬动力有限公司 | Electrolyte and lithium ion battery comprising same |
| CN113659205A (en) * | 2021-08-12 | 2021-11-16 | 湖州昆仑亿恩科电池材料有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN114142090A (en) * | 2021-11-20 | 2022-03-04 | 九江天赐高新材料有限公司 | Electrolyte additive composition, electrolyte and lithium secondary battery |
| CN115148500A (en) * | 2021-03-30 | 2022-10-04 | 南通新宙邦电子材料有限公司 | Preparation method of aluminum capacitor electrolyte |
| CN115148500B (en) * | 2021-03-30 | 2024-04-19 | 南通新宙邦电子材料有限公司 | Preparation method of aluminum capacitor electrolyte |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106596772A (en) * | 2016-12-14 | 2017-04-26 | 东莞市凯欣电池材料有限公司 | Method for detecting aggregated double-bone compounds in lithium hexafluorophosphate electrolyte solution |
| CN108242566A (en) * | 2016-12-26 | 2018-07-03 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| WO2018120787A1 (en) * | 2016-12-26 | 2018-07-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and secondary battery |
| CN106784994B (en) * | 2017-01-09 | 2020-08-18 | 江苏众富智能电气研究院有限公司 | Lithium ion battery electrolyte for smart home and battery |
| CN106784994A (en) * | 2017-01-09 | 2017-05-31 | 洪泽宇 | A kind of smart home lithium-ion battery electrolytes and battery |
| CN108511798A (en) * | 2017-04-27 | 2018-09-07 | 万向二三股份公司 | A kind of high-temperature lithium ion battery long circulating electrolyte |
| CN107887647A (en) * | 2017-10-26 | 2018-04-06 | 广州天赐高新材料股份有限公司 | A kind of 5V high voltages electrolyte for lithium secondary batteries and the lithium secondary battery containing the electrolyte |
| CN107887647B (en) * | 2017-10-26 | 2020-08-11 | 广州天赐高新材料股份有限公司 | Electrolyte for 5V high-voltage lithium secondary battery and lithium secondary battery containing electrolyte |
| CN108649265A (en) * | 2018-05-10 | 2018-10-12 | 桑德集团有限公司 | Electrolysis additive, lithium battery electrolytes and lithium battery |
| CN112993400A (en) * | 2019-12-17 | 2021-06-18 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte for lithium battery and application thereof |
| 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 |
| CN115148500A (en) * | 2021-03-30 | 2022-10-04 | 南通新宙邦电子材料有限公司 | Preparation method of aluminum capacitor electrolyte |
| CN115148500B (en) * | 2021-03-30 | 2024-04-19 | 南通新宙邦电子材料有限公司 | Preparation method of aluminum capacitor electrolyte |
| CN113067037A (en) * | 2021-05-17 | 2021-07-02 | 湖北亿纬动力有限公司 | Electrolyte and lithium ion battery comprising same |
| CN113659205A (en) * | 2021-08-12 | 2021-11-16 | 湖州昆仑亿恩科电池材料有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN114142090A (en) * | 2021-11-20 | 2022-03-04 | 九江天赐高新材料有限公司 | Electrolyte additive composition, electrolyte and lithium secondary battery |
| WO2023087536A1 (en) * | 2021-11-20 | 2023-05-25 | 九江天赐高新材料有限公司 | Electrolyte solution additive composition, electrolyte solution and lithium secondary battery |
| CN114142090B (en) * | 2021-11-20 | 2023-10-31 | 九江天赐高新材料有限公司 | Electrolyte additive composition, electrolyte and lithium secondary battery |
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Effective date of registration: 20190401 Address after: 510000 No. 8 Kangda Road, Dongcheng District, Yunpu Industrial Zone, Huangpu District, Guangzhou City, Guangdong Province Applicant after: Guangzhou Tianci High-Tech Material Co., Ltd. Address before: 523000 Dongguan Eco-Industrial Park, Dongguan City, Guangdong Province Applicant before: Dongguan City Kai Xin battery material Co., Ltd |
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