CN106748882A - A kind of lithium battery electrolytes high temperature flame-proof additive - Google Patents
A kind of lithium battery electrolytes high temperature flame-proof additive Download PDFInfo
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- CN106748882A CN106748882A CN201611015000.4A CN201611015000A CN106748882A CN 106748882 A CN106748882 A CN 106748882A CN 201611015000 A CN201611015000 A CN 201611015000A CN 106748882 A CN106748882 A CN 106748882A
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- lithium battery
- itrile group
- flame
- carboxylic acid
- ester
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
-
- 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 present invention provides a kind of lithium battery electrolytes high temperature flame-proof additive, and, as fertile material, be introduced into itrile group in carboxylate first by the additive using carboxylate, then using SF4Carboxylate is fluorinated, so as to obtain flame-retardant additive.The flame-retardant additive can form tight structure layer in the electrolytic solution, and because itrile group has electrophilic sub-feature higher, promotion forms high connductivity additive, improves stability, uniformity, the electrical conductance of electrode and electrolysis liquid interface film, and electrolyte can be prevented further to decompose.The above method that the present invention is provided, overcome low temperature viscosity increase and the burning risk of high-temperature electrolyte of electrolyte in the prior art, with high-temperature stability, and for electric charge fast transferring provides passage, so as to increased lithium ion battery cycle charge discharge electrical property at ambient and elevated temperatures and stability, the promotion and application of lithium ion battery are further expanded.
Description
Technical field
The present invention relates to nonaqueous electrolytic solution high temperature flame-proof additive, more particularly to a kind of lithium battery electrolytes high temperature flame-proof adds
Plus agent.
Background technology
Used as a kind of new chemical energy source, it has energy density big to lithium secondary battery, and operating voltage is high, cycle life
Long, and environmentally friendly the features such as, it has been widely used in the production and living of people, has such as been applied to mobile phone, notebook electricity
It is also following electric automobile and the preferred electrical source of power of mixed type electric automobile in the portable electric appts such as brain, video camera,
Have broad application prospects and huge economic benefit.As lithium battery is more used for electrokinetic cell, in quick charge and discharge
The change of temperature is easily produced when electric, destabilizing factor has been thus resulted in.Lithium rechargeable battery excessive discharge and recharge, short circuit and
High current releases a large amount of Joule heats in the case of working long hours, these heats turn into the potential safety hazard of inflammable electrolyte, may
Cause catastrophic thermal breakdown even battery explosion.Add fire retardant to overcome the defect at present.
Chinese invention patent application number 201010003004.7 disclose a kind of flame-retardant electrolyte, lithium rechargeable battery and
Its manufacture method.The method be by lithium salts, linear carbonate class solvent, at least one ammonium cation, phosphoric acid class solvent and comprising
The additive of oxalic acid borate is used as flame retardant electrolyte solution.The invention has the advantages that process is simple, low cost, it is easy to accomplish
Large-scale production.However, the invention is mainly or by the use of lithium ion salt as the raw material of fire retardant, in battery charge and discharge process
Can be consumed, secondly Ammonium Salt Ionic therein is very likely to be released ammonia in charge and discharge process, causes battery volume
Expand and burst.
Chinese invention patent application number 201010597448.8 discloses a kind of combined electrolysis for improving battery high-temperature behavior
Solution additive, can effectively improve battery security at high operating temperatures, fire-retardant, prevent battery from causing electrolyte because of overheat
Burning is so that blast.The invention is constituted using the carbonic ester and alkyl phosphate that are replaced by fluorine.Both it was effectively guaranteed
Battery security at high operating temperatures, has the electrical property not on battery to produce influence, can well meet consumer to electricity
The demand of pond high security.But the technology is actually to mix the carbonic ester and alkyl phosphate of fluorine substitution in any proportion
Close, the method for this mechanical mixture, solution problems of excessive heat that can only be limited, and its fire retardant viscosity and electrolyte difference compared with
Greatly, cause the separation of electrolyte uneven.
Chinese invention patent application number 201310516767.5 discloses a kind of electrolyte flame-retardant additive and flame retardant type
Lithium-ion battery electrolytes.The invention is the addition halo sulfonyl based flame retardant additives in conventional electrolysis liquid, flame-retardant additive
Electrolyte has low viscosity, low toxicity, electrochemical window wider and temperature range, while having highly effective flame-retardant effect.But
It is, the internal resistance that has transported inhibition, addition after can increase electrolyte of this additive to ion in the battery, so as to lead
Cause, the internal resistance of cell increases, more electric energy are consumed in internal resistance.
According to above-mentioned analysis, although existing fire retardant has preferable function at fire-retardant aspect, due to fire retardant and electricity
There is larger difference in solution liquid, therefore can influence the viscosity of electrolyte, and also improve the internal resistance destruction of battery to a certain extent
Battery cycle performance at high temperature.So as to such case can bring more negative effect, lithium ion battery is seriously restricted
Further genralrlization and application.Inspired by fluorination fire retardant, if being further introduced into one on the basis of fire retardant is fluorinated
The group of a little electrophilic subbases, will effectively solve the above problems.
The content of the invention
Although solving battery temperature to a certain extent after being added for lithium ion battery fire retardant conventional at present
The unstable and spontaneous combustion problems that rising is caused, improve the lithium ion battery safety that battery is used in long-time charge and discharge process
Property, but there is uneven, or fire retardant sheet in the general viscosity of this flame-retardant electrolyte and the viscosity differences of electrolyte
Body has resistance higher, and the internal resistance which improves battery destroys cycle performance under battery high-temperature environment, serious shadow
Further genralrlization and the application of lithium ion battery are rung.Therefore the present invention proposes a kind of lithium battery electrolytes high temperature flame-proof addition
Agent, the additive is itrile group fluorinated carboxylic ester flame-retardant additive, is, as fertile material, first to draw itrile group using carboxylate
In entering carboxylate, then using SF4Carboxylate is fluorinated, so as to obtain flame-retardant additive.Because itrile group is a kind of electrophilic group,
And with electrophilic characteristic high, promote electric charge transmission, improve heat endurance, uniformity, the electrical conductance of electrolyte.So as to, gram
Low temperature viscosity increase and the burning risk of high-temperature electrolyte of electrolyte in the prior art are taken, with high-temperature stability, and has been
Electric charge fast transferring provides passage, so as to increased lithium ion battery cycle charge discharge electrical property at ambient and elevated temperatures and stabilization
Property, the promotion and application of lithium ion battery are further expanded, with commercial application value very high.
The present invention provides a kind of lithium battery electrolytes high temperature flame-proof additive, using carboxylate as fertile material, first
Itrile group is introduced into carboxylate, then using SF4Carboxylate is fluorinated, so as to obtain flame-retardant additive, is comprised the following steps：
（1）By KHSO3With KCN blendings, it is put into solvent, wherein KHSO3, KCN and solvent mass ratio be：1:0.2-1.1:
2.0-4.0, after 10-30min is stirred at room temperature, obtains KHSO3With the mixed solution of KCN；
（2）Under water bath, by step（1）The mixed solution of acquisition mixes with alkenyl carboxylate, wherein mixed solution and alkene
The mass ratio of yl carboxylic acid ester is 1:1.5-50, stirs 24-90 hours, cyanogenation occurs due to there is alkenyl, above alkenyl
Side chain cyaniding, obtain grafting itrile group alkene-carboxylic acid's ester solution；
（3）By alkene-carboxylic acid's ester solution and SF of the grafting itrile group4With HF solution blendings, controlling reaction temperature is 20-80 DEG C,
Itrile group fluorinated carboxylic ester flame-retardant additive is obtained.
Preferably, the solvent is ethanol, ether, dichloromethane, ethyl acetate, toluene, acetonitrile, dimethyl sulfoxide, N, N-
One or more in dimethylformamide, acetone etc..
Preferably, the bath temperature is 0-10 DEG C.
Preferably, the alkenyl carboxylate may be selected from chloroethylenes carboxylic acid to hydroxyl first for haloalkenyl group carboxylic hydroxy group's ester
Ester, 2- chloroethylenes carboxylic acid are to hydroxy methacrylate, 3- bromo propylene carboxylic acids to hydroxy methyl, 2- chloropropenes carboxylic acid to hydroxyl third
Ester, 1,2- dichloro- propylene carboxylic acids are to hydroxy methyl, the chloro- 2- bromos propylene carboxylic acids of 1- to one kind in hydroxy methyl etc. or several
Kind.
Preferably, alkene-carboxylic acid's ester solution and SF of the grafting itrile group4It is 1 with the weight ratio of HF solution blendings:1:
1-2。
Preferably, the SF4In the grafting itrile group course of reaction, the first step first uses 20-30 DEG C, reacts 3 hours,
Generate covalent intermediate ROSF3By 40-80 DEG C, the reaction of 4 hours obtains the itrile group fluorinated carboxylic ester.
The present invention also provides a kind of lithium battery electrolytes, and ethene carbonic ether, carbovinate fat, dimethyl carbonic ether are pressed
Volume ratio 1:1:1 ratio is hybridly prepared into solute for lithium hexafluoro phosphate, and concentration is the electrolyte of 1-1.5mol/L, takes the electricity
100 grams of liquid of solution, is added thereto to the itrile group fluorinated carboxylic ester 0.5-2g as described in right wants 1-5 and is dissolved, and prepares described
Lithium battery electrolytes.
By the present invention prepare a kind of lithium battery electrolytes special-purpose anti-flaming additive lithium ion battery with before being not added with
Performance of lithium ion battery is more as shown in table 1.
Table 1
| Performance indications | The internal resistance of cell（Ohm） | 80 DEG C of cycle lives（Ten thousand hours） | The upper limit temperature of heat tolerance |
| It is not added with | 2.1 | 0.01 | 80℃ |
| Addition additive of the present invention | 0.02 | 3.2 | 125℃ |
A kind of lithium battery electrolytes high temperature flame-proof additive, compared with prior art, its protrusion the characteristics of and excellent effect exist
In：
1st, the itrile group fluorinated carboxylic ester flame-retardant additive that the present invention is used, heat endurance is high, after mixing electrolyte, is electrolysed fluid viscosity
Change is little, and electrolyte remains in that homogeneity higher, and eliminates the risk of high-temp combustion.
2nd, the present invention provide itrile group fluorinated carboxylic ester flame-retardant additive, with electrophilicity higher, be conducive to lithium from
Electric charge transfer in sub- battery, will not increase the internal resistance of cell after incorporation.
3rd, the raw material that the present invention is used is conventional industrial chemicals, and input is small, and yield is high, can significantly reduce cost, tool
There is significant market application value.
4th, the present invention uses simple production technology, significantly reduces the production cost of flame-retardant additive, can carry out scale
Change and streaming production.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as into the present invention
Scope be only limitted to following example.In the case where above method thought of the present invention is not departed from, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）By KHSO3With KCN blendings, it is put into solvent, wherein KHSO3, KCN and absolute ethyl alcohol mass ratio be：1:0.2:
2.0, after 10min is stirred at room temperature, obtain KHSO3With the mixed solution of KCN；
（2）Under 0 DEG C of environment of water-bath, by step（1）The mixed solution of acquisition mixes with chloroethylenes carboxylic acid to hydroxy methyl, its
Middle mixed solution is 1 to the mass ratio of hydroxy methyl with chloroethylenes carboxylic acid:1.5, stir 24 hours, occur due to there is alkenyl
Cyanogenation, by the side chain cyaniding above alkenyl, obtains itrile group vinylcarboxylic acid to hydroxy methyl solution；
（3）By the itrile group vinylcarboxylic acid to hydroxy methyl solution and SF4With HF solution blendings, the itrile group vinylcarboxylic acid is to hydroxyl
Base methyl esters and SF4It is 1 with the weight ratio of HF solution blendings:1:1, the SF4In the grafting itrile group course of reaction, first
Step first uses 20 DEG C, reacts 3 hours, generates covalent intermediate ROSF3By 40 DEG C, the reaction of 4 hours obtains itrile group fluorination
Carboxylate methyl ester flame-retardant additive.
The lithium battery electrolytes prepared by method in embodiment 1 are applied in lithium battery, by testing lithium battery
Parameter can be obtained as shown in table 2.
Embodiment 2
（1）By KHSO3With KCN blendings, it is put into solvent, wherein KHSO3, KCN and absolute ethyl alcohol mass ratio be：1:0.4:
2.2, after 15min is stirred at room temperature, obtain KHSO3With the mixed solution of KCN；
（2）Under 3 DEG C of environment of water-bath, by step（1）The mixed solution of acquisition mixes with 2- chloroethylenes carboxylic acids to hydroxy methyl,
Wherein mixed solution is 1 to the mass ratio of hydroxy methyl with 2- chloroethylenes carboxylic acid:2.0, stir 36 hours, due to there is alkenyl
Generation cyanogenation, by the side chain cyaniding above alkenyl, obtains 2- itrile groups vinylcarboxylic acid to hydroxy methyl solution；
（3）By the 2- itrile groups vinylcarboxylic acid to hydroxy methyl solution and SF4With HF solution blendings, the 2- itrile groups vinylcarboxylic acid
To hydroxy methyl and SF4It is 1 with the weight ratio of HF solution blendings:1:1.5, the SF4With the grafting itrile group course of reaction
In, the first step first uses 25 DEG C, reacts 3 hours, generates covalent intermediate ROSF3By 45 DEG C, the reaction of 5 hours obtains 2-
Itrile group fluorinated carboxylic methyl esters flame-retardant additive.
The lithium battery electrolytes prepared by method in embodiment 2 are applied in lithium battery, by testing lithium battery
Parameter can be obtained as shown in table 2.
Embodiment 3
（1）By KHSO3With KCN blendings, it is put into solvent, wherein KHSO3, KCN and ether mass ratio be：1:0.5:2.5, room
After temperature stirring 25min, KHSO is obtained3With the mixed solution of KCN；
（2）Under 5 DEG C of environment of water-bath, by step（1）The mixed solution of acquisition mixes with 2- chloroethylenes carboxylic acids to hydroxy methyl,
Wherein mixed solution is 1 to the mass ratio of hydroxy methyl with 3- bromo propylene carboxylic acids:3.0, stir 36 hours, due to there is alkenyl
Generation cyanogenation, by the side chain cyaniding above alkenyl, obtains 3- itrile group propylene carboxylic acids to hydroxy methyl solution；
（3）By the 3- itrile groups propylene carboxylic acid to hydroxy methyl solution and SF4With HF solution blendings, the 3- itrile groups propylene carboxylic acid
To hydroxy methyl and SF4It is 1 with the weight ratio of HF solution blendings:1:1.7, the SF4With the grafting itrile group course of reaction
In, the first step first uses 30 DEG C, reacts 3 hours, generates covalent intermediate ROSF3By 50 DEG C, the reaction of 7 hours obtains 3-
Itrile group propylene carboxylic acid is to hydroxy methyl flame-retardant additive.
The lithium battery electrolytes prepared by method in embodiment 3 are applied in lithium battery, by testing lithium battery
Parameter can be obtained as shown in table 2.
Embodiment 4
（1）By KHSO3With KCN blendings, it is put into solvent, wherein KHSO3, KCN and ethyl acetate mass ratio be：1:0.7:
3.0, after 20min is stirred at room temperature, obtain KHSO3With the mixed solution of KCN；
（2）Under 7 DEG C of environment of water-bath, by step（1）The mixed solution of acquisition mixes with chloroethylenes carboxylic acid to hydroxy methyl, its
Middle mixed solution is 1 to the mass ratio of hydroxy methyl with chloroethylenes carboxylic acid:1.8, stir 72 hours, occur due to there is alkenyl
Cyanogenation, by the side chain cyaniding above alkenyl, obtains itrile group vinylcarboxylic acid to hydroxy methyl solution；
（3）By the itrile group vinylcarboxylic acid to hydroxy methyl solution and SF4With HF solution blendings, the itrile group vinylcarboxylic acid is to hydroxyl
Base methyl esters and SF4It is 1 with the weight ratio of HF solution blendings:1:20, the SF4In the grafting itrile group course of reaction, first
Step first uses 30 DEG C, reacts 3 hours, generates covalent intermediate ROSF3By 60 DEG C, the reaction of 4 hours obtains itrile group fluorination
Carboxylate methyl ester flame-retardant additive.
The lithium battery electrolytes prepared by method in embodiment 4 are applied in lithium battery, by testing lithium battery
Parameter can be obtained as shown in table 2.
Embodiment 5
（1）By KHSO3With KCN blendings, it is put into solvent, wherein KHSO3, KCN and absolute ethyl alcohol mass ratio be：1:1:4, room
After temperature stirring 30min, KHSO is obtained3With the mixed solution of KCN；
（2）Under 10 DEG C of environment of water-bath, by step（1）The mixed solution of acquisition is with the chloro- 2- bromos propylene carboxylic acids of 1- to hydroxyl first
Ester mixes, and wherein mixed solution is 1 to the mass ratio of hydroxy methyl with the chloro- 2- bromos propylene carboxylic acids of 1-:2, stir 90 hours, by
There is cyanogenation in there is alkenyl, by the side chain cyaniding above alkenyl, obtaining 1- itrile group -2- bromo propylene carboxylic acids to hydroxyl first
Ester solution；
（3）By the 1- itrile groups -2- bromo propylene carboxylic acids to hydroxy methyl solution and SF4With HF solution blendings, the 1- itrile groups-
2- bromo propylene carboxylic acids are to hydroxy methyl and SF4It is 1 with the weight ratio of HF solution blendings:1:50, the SF4With the grafting
In itrile group course of reaction, the first step first uses 30 DEG C, reacts 3 hours, generates covalent intermediate ROSF3By 80 DEG C, 4 hours
Reaction obtain 1- itrile group fluorinated carboxylic methyl esters flame-retardant additives.
The lithium battery electrolytes prepared by method in embodiment 5 are applied in lithium battery, by testing lithium battery
Parameter can be obtained as shown in table 2.
Table 2
| Performance indications | The internal resistance of cell（Ohm） | 80 DEG C of cycle lives（Ten thousand hours） | The upper limit temperature of heat tolerance |
| Embodiment 1 | 0.10 | 0.9 | 85℃ |
| Embodiment 2 | 0.07 | 0.8 | 125℃ |
| Embodiment 3 | 0.04 | 1.2 | 115℃ |
| Embodiment 4 | 0.07 | 1.0 | 125℃ |
| Embodiment 5 | 0.11 | 1.1 | 105℃ |
Claims (7)
1. a kind of lithium battery electrolytes high temperature flame-proof additive, it is characterised in that methods described is using carboxylate as parent material
, be introduced into itrile group in carboxylate first by material, then using SF4Carboxylate is fluorinated, so as to obtain high temperature flame-proof additive；The height
Warm flame-retardant additive is prepared by the following method：
（1）By KHSO3With KCN blendings, it is put into solvent, wherein KHSO3, KCN and solvent mass ratio be：1:0.2-1.1:
2.0-4.0, after 10-30min is stirred at room temperature, obtains KHSO3With the mixed solution of KCN；
（2）Under water bath, by step（1）The mixed solution of acquisition mixes with alkenyl carboxylate, wherein mixed solution and alkene
The mass ratio of yl carboxylic acid ester is 1:1.5-50, stirs 24-90 hours, cyanogenation occurs due to there is alkenyl, above alkenyl
Side chain cyaniding, obtain grafting itrile group alkene-carboxylic acid's ester solution；
（3）By alkene-carboxylic acid's ester solution and SF of the grafting itrile group4With HF solution blendings, controlling reaction temperature is 20-80 DEG C,
Itrile group fluorinated carboxylic ester flame-retardant additive is obtained.
2. a kind of lithium battery electrolytes high temperature flame-proof additive according to claim 1, it is characterised in that：The solvent is second
One kind in alcohol, ether, dichloromethane, ethyl acetate, toluene, acetonitrile, dimethyl sulfoxide, DMF, acetone etc.
Or it is several.
3. a kind of lithium battery electrolytes high temperature flame-proof additive according to claim 1, it is characterised in that：The bath temperature
It is 0-10 DEG C.
4. a kind of lithium battery electrolytes high temperature flame-proof additive according to claim 1, the alkenyl carboxylate is haloalkene
Yl carboxylic acid hydroxy ester is selected from chloroethylenes carboxylic acid to hydroxy methyl, 2- chloroethylenes carboxylic acid to hydroxy methacrylate, 3- bromo propylene carboxylics
Acid is to hydroxy methyl, 2- chloropropenes carboxylic acid to hydroxy propyl ester, 1,2- dichloro- propylene carboxylic acids to hydroxy methyl, the chloro- 2- bromines of 1-
For propylene carboxylic acid to one or more in hydroxy methyl etc..
5. a kind of lithium battery electrolytes high temperature flame-proof additive according to claim 1, it is characterised in that：The grafting itrile group
Alkene-carboxylic acid's ester solution and SF4It is 1 with the weight ratio of HF solution blendings:1:1-2.
6. a kind of lithium battery electrolytes high temperature flame-proof additive according to claim 1, it is characterised in that：The SF4With it is described
In grafting itrile group course of reaction, the first step first uses 20-30 DEG C, reacts 3 hours, generates covalent intermediate ROSF3By 40-
80 DEG C, the reaction of 4 hours obtains the itrile group fluorinated carboxylic ester.
7. a kind of lithium battery electrolytes, it is characterised in that：Ethene carbonic ether, carbovinate fat, dimethyl carbonic ether are pressed into body
Product compares 1:1:1 ratio is hybridly prepared into solute for lithium hexafluoro phosphate, and concentration is the electrolyte of 1-1.5mol/L, takes the electrolysis
100 grams of liquid, is added thereto to the itrile group fluorinated carboxylic ester 0.5-2g as described in right wants any one of 1-6 and is dissolved, and prepares
The lithium battery electrolytes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611015000.4A CN106748882A (en) | 2016-11-18 | 2016-11-18 | A kind of lithium battery electrolytes high temperature flame-proof additive |
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| CN201611015000.4A CN106748882A (en) | 2016-11-18 | 2016-11-18 | A kind of lithium battery electrolytes high temperature flame-proof additive |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110718715A (en) * | 2019-10-23 | 2020-01-21 | 东莞维科电池有限公司 | Battery electrolyte additive, battery electrolyte and lithium ion battery |
| CN113299991A (en) * | 2021-05-12 | 2021-08-24 | 广州明美新能源股份有限公司 | High-temperature-resistant lithium ion battery electrolyte |
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| WO2002053518A2 (en) * | 2000-12-29 | 2002-07-11 | Honeywell International, Inc. | HALOGENATED-α,β-UNSATURATED-β-(SUBSTITUTED-AMINO) CARBOXYLATE ESTERS |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110718715A (en) * | 2019-10-23 | 2020-01-21 | 东莞维科电池有限公司 | Battery electrolyte additive, battery electrolyte and lithium ion battery |
| CN110718715B (en) * | 2019-10-23 | 2022-09-27 | 东莞维科电池有限公司 | Battery electrolyte additive, battery electrolyte and lithium ion battery |
| CN113299991A (en) * | 2021-05-12 | 2021-08-24 | 广州明美新能源股份有限公司 | High-temperature-resistant lithium ion battery electrolyte |
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Application publication date: 20170531 |