CN109671977A - Flame-retardant polymer gel electrolyte and preparation method thereof, lithium battery - Google Patents
Flame-retardant polymer gel electrolyte and preparation method thereof, lithium battery Download PDFInfo
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- CN109671977A CN109671977A CN201811543127.2A CN201811543127A CN109671977A CN 109671977 A CN109671977 A CN 109671977A CN 201811543127 A CN201811543127 A CN 201811543127A CN 109671977 A CN109671977 A CN 109671977A
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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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/058—Construction or manufacture
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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
- H01M2300/0085—Immobilising or gelification of 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
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- 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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- 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
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Abstract
The invention discloses a kind of flame-retardant polymer gel electrolytes comprising in-situ polymerization: lithium salts is dissolved in basic electrolyte, methyl methacrylate and the thermal initiator of phosphate ester solvent formation.The preparation method of the flame-retardant polymer gel electrolyte is comprising steps of S10, be added to phosphate ester solvent for lithium salts and be stirred, basis of formation electrolyte；S20, methyl methacrylate is added to the basic electrolyte and is stirred, form the first solution；S30, thermal initiator is added to the first solution & stir mixing, forms the second solution；S40, to second solution carry out heat treatment make each component in-situ polymerization therein, obtain the flame-retardant polymer gel electrolyte.Flame-retardant polymer gel electrolyte provided by the invention is applied in lithium battery, can promote the flame retardant property of lithium battery, and can also effectively improve the cyclical stability of lithium battery.
Description
Technical field
The invention belongs to technical field of lithium batteries more particularly to a kind of flame-retardant polymer gel electrolyte and its preparation sides
Method further relates to the lithium battery comprising the flame-retardant polymer gel electrolyte.
Background technique
The advantages that lithium battery has operating temperature range wide, and discharging voltage balance, self-discharge rate is low, long service life,
It is widely used in various fields, especially space flight and aviation, military affairs, long-life instrument and meter, material flow tracking, automotive electronics, shifting
The fields such as dynamic digital product.
Lithium battery is usually to be made of the part such as anode, cathode, diaphragm, electrolyte, structure housing.Electrolyte, as it
One of most important components are not only responsible for the effect that ion transmits between electrode, but also decide the use of energy storage device
Voltage, cycle performance, security performance and cost etc..However, most of commercialization lithium batteries are using liquid at present
Organic bath, since its flash-point is low, steam is forced down, and mobility is strong, is easily leaked, and its decomposition voltage is low, under high pressure easily
Decompose, or even burning, explosion occurs etc., there are very big security risks, thus also limit it in energy storage device side
The application in face.
Therefore, in technical field of lithium batteries, liquid electrolyte is developed to gelation and solid state and enhances its resistance
The security performances such as combustion property are very necessary.
Summary of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of flame-retardant polymer gel electrolyte and its preparation sides
Method can promote the flame retardant property of lithium battery, and can also effectively improve the cyclical stability of lithium battery.
For achieving the above object, present invention employs following technical solutions:
A kind of flame-retardant polymer gel electrolyte comprising in-situ polymerization: lithium salts is dissolved in phosphate ester solvent and is formed
Basic electrolyte, methyl methacrylate and thermal initiator.
Specifically, in the flame-retardant polymer gel electrolyte, the mass percent of the basic electrolyte is 71.23%
~74.81%, the mass percent of the methyl methacrylate is 24.94%~28.53%, the quality of the thermal initiator
Percentage is 0.14%~0.28%.
Specifically, in the basic electrolyte, the molar fraction of the lithium salts is 3mol/L~7mol/L.
Specifically, the lithium salts is selected from bis- (fluorine sulphonyl) imine lithiums, double trifluoromethanesulfonimide lithiums and double ethanedioic acid boron
One or more of sour lithium.
Specifically, the phosphate ester solvent is selected from one or both of trimethyl phosphate and triethyl phosphate.
Specifically, the thermal initiator is selected from one or both of azodiisobutyronitrile and benzoyl peroxide.
The present invention also provides a kind of preparation methods of flame-retardant polymer gel electrolyte as described above comprising step
It is rapid:
S10, lithium salts is added to phosphate ester solvent and is stirred, basis of formation electrolyte；
S20, methyl methacrylate is added to the basic electrolyte and is stirred, form the first solution；
S30, thermal initiator is added to the first solution & stir mixing, forms the second solution；
S40, heat treatment is carried out to second solution make each component in-situ polymerization therein, obtain described fire-retardant poly-
Close object gel electrolyte.
Specifically, when lithium salts being added to phosphate ester solvent, 15 DEG C~25 DEG C at a temperature of stir 0.5~3h；By first
When base methyl acrylate is added to the basic electrolyte, 15 DEG C~25 DEG C at a temperature of stir 0.5~2h；By thermal initiator
When being added to first solution, 0 DEG C~25 DEG C at a temperature of stir 0.5~2h.
Specifically, when heating to second solution, heating temperature is 50 DEG C~70 DEG C, heating time 6
~10h.
Another aspect of the present invention is to provide a kind of lithium battery comprising anode, cathode and setting it is described anode with
Diaphragm and electrolyte between cathode, wherein the electrolyte uses flame-retardant polymer gel electrolyte as described above.
Flame-retardant polymer gel electrolyte provided in an embodiment of the present invention and preparation method thereof, by by methyl methacrylate
Ester in-situ polymerization in the phosphate ester solution of high concentration lithium salts obtains gel electrolyte, is applied in lithium battery, it is possible thereby to
The flame retardant property of lithium battery is promoted, and the cyclical stability of lithium battery can also be effectively improved.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of the flame-retardant polymer gel electrolyte of the embodiment of the present invention；
Fig. 2 is that the flame-retardant polymer gel electrolyte of the embodiment of the present invention carries out the photo illustration of combustion testing；
Fig. 3 and Fig. 4 shows the battery sample of the embodiment of the present invention charge and discharge cycles test curve figure under 0.2C multiplying power.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, with reference to the accompanying drawing to specific reality of the invention
The mode of applying is described in detail.The example of these preferred embodiments is illustrated in the accompanying drawings.Shown in attached drawing and according to
The embodiments of the present invention of attached drawing description are only exemplary, and the present invention is not limited to these embodiments.
Aiming at the problem that current lithium battery is using the security risks such as inflammable and explosive existing for liquid organic electrolyte, the present invention
Embodiment provides a kind of flame-retardant polymer gel electrolyte comprising in-situ polymerization: lithium salts is dissolved in phosphate ester solvent
Basic electrolyte, methyl methacrylate and the thermal initiator of formation.By by methyl methacrylate in high concentration lithium salts
Phosphate ester solution in in-situ polymerization obtain gel electrolyte, thus promote its flame retardant property, improve the security performance of lithium battery.
In specific technical solution, in the flame-retardant polymer gel electrolyte, the quality hundred of the basic electrolyte
Divide than being 71.23%~74.81%, the mass percent of the methyl methacrylate is 24.94%~28.53%, described
The mass percent of thermal initiator is 0.14%~0.28%.
Wherein, in the basic electrolyte, the molar fraction of the lithium salts is 3mol/L~7mol/L.
Wherein, the lithium salts is selected from bis- (fluorine sulphonyl) imine lithiums, double trifluoromethanesulfonimide lithiums and double ethanedioic acid boric acid
One or more of lithium.
Wherein, the phosphate ester solvent is selected from one or both of trimethyl phosphate and triethyl phosphate.
Wherein, the thermal initiator is selected from one or both of azodiisobutyronitrile and benzoyl peroxide.
The embodiment of the invention provides the preparation methods of flame-retardant polymer gel electrolyte as described above, as shown in Figure 1,
The preparation method comprising steps of
S10, lithium salts is added to phosphate ester solvent and is stirred, basis of formation electrolyte.
In specific scheme, when lithium salts is added to phosphate ester solvent, 15 DEG C~25 DEG C at a temperature of stirring 0.5~
3h forms the basic electrolyte of molten ratio with high salt so that lithium salts is completely dissolved.Preferably, lithium salts rubs in the basic electrolyte
Your concentration is 3~7mol/L.
S20, methyl methacrylate is added to the basic electrolyte and is stirred, form the first solution.
In specific scheme, when methyl methacrylate is added to the basic electrolyte, at 15 DEG C~25 DEG C
At a temperature of stir 0.5~2h so that methyl methacrylate is uniformly mixed into the basic electrolyte.
S30, thermal initiator is added to the first solution & stir mixing, forms the second solution.
In specific scheme, when thermal initiator is added to first solution, 0 DEG C~25 DEG C at a temperature of stir
0.5~2h, so that thermal initiator is dispersed in first solution.
S40, heat treatment is carried out to second solution make each component in-situ polymerization therein, obtain flame-retardant polymer
Gel electrolyte.
In specific scheme, it can be and second solution is coated on diaphragm, then heat treatment makes therein
Each component in-situ polymerization, thus the flame-retardant polymer gel electrolyte, which is directly prepared, is formed on diaphragm, facilitate it is subsequent into
Row battery assembly.Wherein, the diaphragm can choose for nonwoven cloth diaphragm, cellulosic separator either polypropylene diaphragm, preferably
Use nonwoven cloth diaphragm.
Wherein, when heating to second solution, heating temperature be 50 DEG C~70 DEG C, heating time be 6~
10h。
Flame-retardant polymer gel electrolyte as above, by by methyl methacrylate high concentration lithium salts phosphate ester solution
In-situ polymerization obtains gel electrolyte in (basic electrolyte), is applied in lithium battery, it is possible thereby to promote the resistance of lithium battery
Performance is fired, and the cyclical stability of lithium battery can also be effectively improved.The preparation of the flame-retardant polymer gel electrolyte
Method and process process is simple, the advantages of being easily achieved, and is suitable for large-scale industrial production.
Embodiment 1
Flame-retardant polymer gel electrolyte provided in this embodiment includes the following components according to weight ratio meter: 71.33%
Basic electrolyte, 28.53% methyl methacrylate and 0.14% azodiisobutyronitrile, by heat treatment so that
Above each component in-situ polymerization forms the flame-retardant polymer gel electrolyte.Wherein, the basic electrolyte is by bis- (fluorine
Sulphonyl) imine lithium is dissolved in the basic electrolyte of tripotassium phosphate ester solvent formation, and in the basic electrolyte, bis- (fluorine sulphonyl) is sub-
The molar fraction of amine lithium is 7mol/L.
Flame-retardant polymer gel electrolyte in the present embodiment the preparation method is as follows:
(1), bis- (fluorine sulphonyl) imine lithiums of 3.3g are dissolved in the tripotassium phosphate ester solvent of 2.5mL, 20 DEG C at a temperature of
Stirring 1h is completely dissolved the basic electrolyte to form high concentration lithium salts, the basic electrolyte to bis- (fluorine sulphonyl) imine lithiums
In, the molar concentration of bis- (fluorine sulphonyl) imine lithiums is 7mol/L.
(2), 1g methyl methacrylate is added in the basic electrolyte of the high concentration lithium salts of 2.5g, at 25 DEG C
At a temperature of stir 0.5h, until methyl methacrylate is uniformly mixed into the basic electrolyte and forms the first solution.
(3), 0.005g azodiisobutyronitrile is added in first solution, 25 DEG C at a temperature of stir 15min,
Until azodiisobutyronitrile is dispersed in first solution and forms the second solution.
(4), carrying out heat treatment to second solution makes each component in-situ polymerization therein, obtains flame-retardant polymer
Gel electrolyte.In the present embodiment, subsequent carry out battery assembly, is coated to diaphragm for second solution first for convenience
On (nonwoven cloth diaphragm), then heat treatment makes each component in-situ polymerization therein, thus the flame-retardant polymer gel electricity
Solve it is upright connect preparation and be formed on nonwoven cloth diaphragm, heating temperature is 50 DEG C, heating time 10h.
Fig. 2 is the photo illustration that the flame-retardant polymer gel electrolyte that the present embodiment prepares carries out combustion testing, warp
Overtesting, flame-retardant polymer gel electrolyte provided in this embodiment have good flame retardant property.
Embodiment 2
Flame-retardant polymer gel electrolyte provided in this embodiment includes the following components according to weight ratio meter: 71.23%
Basic electrolyte, 28.49% methyl methacrylate and 0.28% azodiisobutyronitrile, by heat treatment so that
Above each component in-situ polymerization forms the flame-retardant polymer gel electrolyte.Wherein, the basic electrolyte is by double three
Fluoromethane sulfimide lithium is dissolved in the basic electrolyte of triethyl phosphate solvent formation, in the basic electrolyte, double trifluoros
The molar fraction of sulfonyl methane imine lithium is 5mol/L.
Flame-retardant polymer gel electrolyte in the present embodiment the preparation method is as follows:
(1), the bis- trifluoromethanesulfonimide lithiums of 2.3g are dissolved in the triethyl phosphate solvent of 2.5mL, in 15 DEG C of temperature
The lower stirring 3h of degree is completely dissolved the basic electrolyte to form high concentration lithium salts, the base to double trifluoromethanesulfonimide lithiums
In plinth electrolyte, the molar concentration of double trifluoromethanesulfonimide lithiums is 5mol/L.
(2), 1g methyl methacrylate is added in the basic electrolyte of high concentration lithium salts described in 2.5g, at 20 DEG C
At a temperature of stir 1h, until methyl methacrylate is uniformly mixed into the basic electrolyte and forms the first solution.
(3), 0.010g azodiisobutyronitrile is added in first solution, 25 DEG C at a temperature of stir 0.5h,
Until azodiisobutyronitrile is dispersed in first solution and forms the second solution.
(4), carrying out heat treatment to second solution makes each component in-situ polymerization therein, obtains flame-retardant polymer
Gel electrolyte.In the present embodiment, subsequent carry out battery assembly, is coated to diaphragm for second solution first for convenience
On (nonwoven cloth diaphragm), then heat treatment makes each component in-situ polymerization therein, thus the flame-retardant polymer gel electricity
Solve it is upright connect preparation and be formed on nonwoven cloth diaphragm, heating temperature is 60 DEG C, heating time 8h.
Embodiment 3
Flame-retardant polymer gel electrolyte provided in this embodiment includes the following components according to weight ratio meter: 74.81%
Basic electrolyte, 24.94% methyl methacrylate and 0.25% thermal initiator, by heat treatment so that more than
Each component in-situ polymerization forms the flame-retardant polymer gel electrolyte.Wherein, the basic electrolyte is by double ethanedioic acids
Lithium borate is dissolved in the base that phosphate ester solvent (trimethyl phosphate and triethyl phosphate are mixed according to the ratio of volume ratio 1:1) is formed
Plinth electrolyte, in the basic electrolyte, the molar fraction of biethyl diacid lithium borate is 7mol/L；The thermal initiator is azo
Bis-isobutyronitrile and benzoyl peroxide are mixed according to the ratio of mass ratio 1:1.
Flame-retardant polymer gel electrolyte in the present embodiment the preparation method is as follows:
(1), 2.80g biethyl diacid lithium borate is dissolved in the phosphate ester solvent of 5mL (trimethyl phosphate and triethyl phosphate is pressed
According to the ratio mixing of volume ratio 1:1) in, shape is completely dissolved to the biethyl diacid lithium borate in 25 DEG C of at a temperature of stirring 0.5h
At the basic electrolyte of high concentration lithium salts, in the basic electrolyte, the molar concentration of biethyl diacid lithium borate is 3mol/L.
(2), 1g methyl methacrylate is added in the basic electrolyte of high concentration lithium salts described in 3g, in 15 DEG C of temperature
Degree is lower to stir 2h, until methyl methacrylate is uniformly mixed into the basic electrolyte and forms the first solution.
(3), by 0.010g thermal initiator (azodiisobutyronitrile and benzoyl peroxide are mixed according to the ratio of mass ratio 1:1)
Be added in first solution, 20 DEG C at a temperature of stir 1h, until to be dispersed in described first molten for thermal initiator
The second solution is formed in liquid.
(4), carrying out heat treatment to second solution makes each component in-situ polymerization therein, obtains flame-retardant polymer
Gel electrolyte.In the present embodiment, subsequent carry out battery assembly, is coated to diaphragm for second solution first for convenience
On (nonwoven cloth diaphragm), then heat treatment makes each component in-situ polymerization therein, thus the flame-retardant polymer gel electricity
Solve it is upright connect preparation and be formed on nonwoven cloth diaphragm, heating temperature is 70 DEG C, heating time 6h.
Flame-retardant polymer gel electrolyte provided above is assembled in lithium battery by the embodiment of the present invention, to carry out electrification
Test is learned, specific as follows:
Specific battery structure can use button battery comprising anode, cathode and setting it is described it is positive with it is negative
Diaphragm and electrolyte between pole.Wherein, the electricity that positive electrode slice is formed using LiFePO4 is coated in aluminum foil current collector
Pole piece, the electrode slice of cathode either coated in copper foil current collector using metal lithium electrode graphite, graphene, carbon nanotube,
The electrode slice that the negative electrode materials such as carbon nanobelts, porous carbon are formed, diaphragm and electrolyte are using above embodiments 1~3 in non-woven fabrics
Diaphragm prepares the flame-retardant polymer gel electrolyte to be formed, and prepares 2 battery samples in total and carries out electro-chemical test, obtains
Following performance parameter table (table 1).
1 electrochemical property test parameter list of table
Fig. 3 shows the battery sample P1 of the present embodiment charge and discharge cycles test curve figure under 0.2C multiplying power, can from Fig. 3
To find out, capacity retention ratio reaches 93.7% after battery sample P1 is recycled 100 times under 0.2C multiplying power, and coulombic efficiency reaches
98.6%.Fig. 4 shows the battery sample P2 of the present embodiment charge and discharge cycles test curve figure under 0.2C multiplying power, can from Fig. 4
To find out, capacity retention ratio reaches 97.3% after battery sample P2 is recycled 100 times under 0.2C multiplying power, and coulombic efficiency reaches
99.3%.
In conclusion flame-retardant polymer gel electrolyte provided in an embodiment of the present invention and preparation method thereof, by by first
Base methyl acrylate in-situ polymerization in the phosphate ester solution of high concentration lithium salts obtains gel electrolyte, is applied to lithium battery
In, it is possible thereby to promote the flame retardant property of lithium battery, and the cyclical stability of lithium battery can also be effectively improved.
The above is only the specific embodiment of the application, it is noted that for the ordinary skill people of the art
For member, under the premise of not departing from the application principle, several improvements and modifications can also be made, these improvements and modifications are also answered
It is considered as the protection scope of the application.
Claims (10)
1. a kind of flame-retardant polymer gel electrolyte, which is characterized in that including in-situ polymerization:
Lithium salts is dissolved in the basic electrolyte of phosphate ester solvent formation；
Methyl methacrylate；And
Thermal initiator.
2. flame-retardant polymer gel electrolyte according to claim 1, which is characterized in that the flame-retardant polymer gel electricity
Xie Zhizhong, the mass percent of the basic electrolyte are 71.23%~74.81%, the quality of the methyl methacrylate
Percentage is 24.94%~28.53%, and the mass percent of the thermal initiator is 0.14%~0.28%.
3. flame-retardant polymer gel electrolyte according to claim 2, which is characterized in that in the basic electrolyte, institute
The molar fraction for stating lithium salts is 3mol/L~7mol/L.
4. flame-retardant polymer gel electrolyte according to claim 1 to 3, which is characterized in that the lithium salts is selected from double
One or more of (fluorine sulphonyl) imine lithium, double trifluoromethanesulfonimide lithiums and biethyl diacid lithium borate.
5. flame-retardant polymer gel electrolyte according to claim 1 to 3, which is characterized in that the phosphate ester solvent
Selected from one or both of trimethyl phosphate and triethyl phosphate.
6. flame-retardant polymer gel electrolyte according to claim 1 to 3, which is characterized in that the thermal initiator choosing
From one or both of azodiisobutyronitrile and benzoyl peroxide.
7. a kind of preparation method of the flame-retardant polymer gel electrolyte as described in claim 1-6 is any, which is characterized in that packet
Include step:
S10, lithium salts is added to phosphate ester solvent and is stirred, basis of formation electrolyte；
S20, methyl methacrylate is added to the basic electrolyte and is stirred, form the first solution；
S30, thermal initiator is added to the first solution & stir mixing, forms the second solution；
S40, to second solution carry out heat treatment make each component in-situ polymerization therein, obtain the flame-retardant polymer
Gel electrolyte.
8. the preparation method of flame-retardant polymer gel electrolyte according to claim 7, which is characterized in that lithium salts to be added
When to phosphate ester solvent, 15 DEG C~25 DEG C at a temperature of stir 0.5~3h；Methyl methacrylate is added to the basis
When electrolyte, 15 DEG C~25 DEG C at a temperature of stir 0.5~2h；When thermal initiator is added to first solution, at 0 DEG C
0.5~2h is stirred at a temperature of~25 DEG C.
9. the preparation method of flame-retardant polymer gel electrolyte according to claim 7, which is characterized in that described second
When solution is heated, heating temperature is 50 DEG C~70 DEG C, and heating time is 6~10h.
10. a kind of lithium battery, including anode, cathode and the diaphragm and electrolyte being arranged between the positive electrode and negative electrode,
It is characterized in that, the electrolyte is using the flame-retardant polymer gel electrolyte as described in claim 1-6 is any.
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| CN201811543127.2A CN109671977A (en) | 2018-12-17 | 2018-12-17 | Flame-retardant polymer gel electrolyte and preparation method thereof, lithium battery |
| PCT/CN2019/124602 WO2020125519A1 (en) | 2018-12-17 | 2019-12-11 | Flame-retardant polymer gel electrolyte and preparation method therefor, and lithium battery |
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| CN201811543127.2A CN109671977A (en) | 2018-12-17 | 2018-12-17 | Flame-retardant polymer gel electrolyte and preparation method thereof, lithium battery |
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| CN117855614B (en) * | 2023-12-28 | 2024-09-20 | 贲安能源科技江苏有限公司 | Colloidal sodium ion battery with zero volume effect and assembly method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860638A (en) * | 2003-08-26 | 2006-11-08 | 独立行政法人宇宙航空研究开发机构 | Non-inflammable non aqueous electrolyte and lithium-ion battery containing the same |
| CN101071863A (en) * | 2007-05-31 | 2007-11-14 | 惠州亿纬电源科技有限公司 | Lithium cell electrolyte |
| US20150125759A1 (en) * | 2012-02-07 | 2015-05-07 | Battelle Memorial Institute | Solid electrolyte interphase film-suppression additives |
| CN105720300A (en) * | 2016-03-31 | 2016-06-29 | 成都国珈星际固态锂电科技有限公司 | Gel electrolyte membrane, gel polymer lithium ion battery, preparation methods thereof and electromobile |
| CN106450442A (en) * | 2016-09-27 | 2017-02-22 | 湖南杉杉能源科技股份有限公司 | Flame-retardant gel electrolyte for lithium-ion battery and preparation method of flame-retardant gel electrolyte, and preparation method of lithium-ion battery |
| CN107464950A (en) * | 2017-07-27 | 2017-12-12 | 中国科学院化学研究所 | A kind of high salt concentration solid electrolyte and application |
| CN108808085A (en) * | 2018-07-12 | 2018-11-13 | 合肥国轩高科动力能源有限公司 | Electrolyte for improving heat-resistant uncontrol performance of lithium ion battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL135078A0 (en) * | 1999-03-17 | 2001-05-20 | Noboru Oyama | Polymer electrolyte |
| CN103996869B (en) * | 2014-05-13 | 2017-03-22 | 东莞新能源科技有限公司 | Gel electrolyte and preparation method of lithium ion battery containing the gel electrolyte |
| KR102133384B1 (en) * | 2016-09-02 | 2020-07-14 | 주식회사 엘지화학 | Gel polymer electrolyte and lithium secondary battery comprising the same |
| CN108183028A (en) * | 2017-12-19 | 2018-06-19 | 中南大学 | Aluminium electrolutic capacitor flame retardant type heat cure gel polymer electrolyte and preparation method |
| CN109671977A (en) * | 2018-12-17 | 2019-04-23 | 深圳先进技术研究院 | Flame-retardant polymer gel electrolyte and preparation method thereof, lithium battery |
-
2018
- 2018-12-17 CN CN201811543127.2A patent/CN109671977A/en active Pending
-
2019
- 2019-12-11 WO PCT/CN2019/124602 patent/WO2020125519A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860638A (en) * | 2003-08-26 | 2006-11-08 | 独立行政法人宇宙航空研究开发机构 | Non-inflammable non aqueous electrolyte and lithium-ion battery containing the same |
| CN101071863A (en) * | 2007-05-31 | 2007-11-14 | 惠州亿纬电源科技有限公司 | Lithium cell electrolyte |
| US20150125759A1 (en) * | 2012-02-07 | 2015-05-07 | Battelle Memorial Institute | Solid electrolyte interphase film-suppression additives |
| CN105720300A (en) * | 2016-03-31 | 2016-06-29 | 成都国珈星际固态锂电科技有限公司 | Gel electrolyte membrane, gel polymer lithium ion battery, preparation methods thereof and electromobile |
| CN106450442A (en) * | 2016-09-27 | 2017-02-22 | 湖南杉杉能源科技股份有限公司 | Flame-retardant gel electrolyte for lithium-ion battery and preparation method of flame-retardant gel electrolyte, and preparation method of lithium-ion battery |
| CN107464950A (en) * | 2017-07-27 | 2017-12-12 | 中国科学院化学研究所 | A kind of high salt concentration solid electrolyte and application |
| CN108808085A (en) * | 2018-07-12 | 2018-11-13 | 合肥国轩高科动力能源有限公司 | Electrolyte for improving heat-resistant uncontrol performance of lithium ion battery |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020125519A1 (en) * | 2018-12-17 | 2020-06-25 | 深圳先进技术研究院 | Flame-retardant polymer gel electrolyte and preparation method therefor, and lithium battery |
| CN110911739A (en) * | 2019-11-20 | 2020-03-24 | 深圳先进技术研究院 | Solid polymer electrolyte, preparation method thereof and lithium battery |
| CN111253523B (en) * | 2020-01-19 | 2022-05-17 | 四川大学 | Non-combustible gel polymer electrolyte and preparation method and application thereof |
| CN111253523A (en) * | 2020-01-19 | 2020-06-09 | 四川大学 | Non-combustible gel polymer electrolyte and preparation method and application thereof |
| CN111786012A (en) * | 2020-07-13 | 2020-10-16 | 深圳先进技术研究院 | Non-combustible gel electrolyte precursor, modified solid electrolyte, lithium battery and preparation method thereof |
| WO2022011980A1 (en) * | 2020-07-13 | 2022-01-20 | 深圳先进技术研究院 | Non-flammable gel electrolyte precursor, modified solid-state electrolyte, lithium battery, and preparation method therefor |
| WO2022183606A1 (en) * | 2021-03-01 | 2022-09-09 | 齐鲁工业大学 | High-performance all-solid-state supercapacitor based on gel polymer electrolyte and preparation method therefor |
| CN113437352A (en) * | 2021-06-24 | 2021-09-24 | 珠海冠宇电池股份有限公司 | Battery and preparation method thereof |
| CN116072963A (en) * | 2022-05-06 | 2023-05-05 | 齐齐哈尔大学 | Preparation method of biomass-derived carbon/polymer gel electrolyte and application of biomass-derived carbon/polymer gel electrolyte in sodium-sulfur battery |
| CN116072963B (en) * | 2022-05-06 | 2023-10-10 | 齐齐哈尔大学 | Preparation method of biomass-derived carbon/polymer gel electrolyte and application of biomass-derived carbon/polymer gel electrolyte in sodium-sulfur battery |
| CN114976236A (en) * | 2022-07-08 | 2022-08-30 | 福州大学 | Flame-retardant gel electrolyte for lithium metal and preparation method and application thereof |
| CN114976236B (en) * | 2022-07-08 | 2024-07-26 | 福州大学 | Flame-retardant gel electrolyte for lithium metal and preparation method and application thereof |
| CN115954449A (en) * | 2022-12-28 | 2023-04-11 | 广东微电新能源有限公司 | Preparation method of flame-retardant gel polymer electrode material and battery |
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