CN108878969A - A kind of fire-retardant gel polymer electrolyte and its preparation and application - Google Patents
A kind of fire-retardant gel polymer electrolyte and its preparation and application Download PDFInfo
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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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- H—ELECTRICITY
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- 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
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- H01M2300/0085—Immobilising or gelification of electrolyte
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- H—ELECTRICITY
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Abstract
The invention belongs to technical field of lithium ion, disclose a kind of high pressure gel polymer electrolyte and the preparation method and application thereof of fire-retardant butyl methacrylate analog copolymer.The present invention is prepared for TPP/P (VdF-HFP)/P (BMA-AN-St) lithium ion battery polymer film with method of electrostatic spinning, the polymer film has the advantages that TPP and P (BMA-AN-St) and P (VdF-HFP) simultaneously, the fire-retardant gel electrolyte is under the premise of guaranteeing original gel electrolyte stability, anti-flammability improves, using electrostatic spinning technique, pore-size distribution, fibre diameter tunica fibrosa of uniform size can get；And the addition of TPP further improves electrolyte electrochemical performance.
Description
Technical field
The invention belongs to technical field of lithium ion, in particular to a kind of fire-retardant butyl methacrylate analog copolymer
High pressure gel polymer electrolyte and the preparation method and application thereof.
Background technique
In recent years, mobile phone, laptop, electric car etc. are quickly grown, need of the people for safe high-energy battery
Ask more more and more intense, lithium ion battery due to its energy density is high, have extended cycle life, self discharge is small, memory-less effect, to environment
The advantages that friendly, is widely used in power and energy storage device, and is grown rapidly, and is of greatest concern at present novel green
Colour circle protects secondary cell.However, most of commercial Li-ion batteries are using liquid organic electrolyte at present, due to its sudden strain of a muscle
Point is low, and steam forces down, and mobility is strong, easily leaks, and its decomposition voltage is low, easily decomposes under high pressure, or even fire
Burn, explode etc., there are very big security risks, thus also limit its application in terms of energy storage device.
In order to solve safety problem, the lithium ion polymer battery of liquid electrolyte is replaced to answer with gel polymer electrolyte
It transports and gives birth to, it has been provided simultaneously with the advantages such as energy density is high, and processing performance is good, both realizes ionic conduction, also improves peace
Full performance, thus cause the strong interest of researcher.So far, people research and development includes polyethylene oxide
(PEO), several polymer including Kynoar (PVDF), polymethyl methacrylate (PMMA), polystyrene (PSt) etc.
Matrix, these types of polymer battery has the advantages that chemical stability is high, cycle performance is good, cyclical stability is high, but gel
It is similar to the ingredient of liquid electrolyte in the ingredient of polymer dielectric, still there is combustibility under high temperature, and fire retardant has resistance
Therefore the performance of disconnected electrolyte burning has researcher to combine the two, prepare the gel polymer electrolyte with flame retardant property
Matter further increases the security performance of battery.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of fire-retardant gel
Method for preparing polymer electrolytes.
Another object of the present invention is to provide the fire-retardant gel polymer electrolyte of above method preparation.
Still a further object of the present invention is that providing above-mentioned fire-retardant gel polymer electrolyte is preparing the application in lithium battery.
The purpose of the present invention is realized by following proposal：
A kind of fire-retardant method for preparing gel polymer electrolyte comprising following steps：
(1) by triphenyl phosphate (TPP), poly- (butyl methacrylate-acrylonitrile-styrene) (P (BMA-AN-St)) and
Poly- (biasfluoroethylene-hexafluoropropylene) (P (VdF-HFP)) is added in acetone and the mixed solution of dimethyl acetamide, and stirring is straight
It is completely molten to poly- (butyl methacrylate-acrylonitrile-styrene) (P (BMA-AN-St)) and poly- (biasfluoroethylene-hexafluoropropylene)
Solution, obtains polymer blend solution；
(2) polymer blend solution obtained in step (1) is prevented obtaining on the two sides of supporter by electrostatic spinning apparatus
It is dry to the porous septum of dual coating equivalent polymer fiber；
(3) it is poly- to get fire-retardant gel that the porous septum after will be dry in step (3) impregnates 20~60min in the electrolytic solution
Polymer electrolyte.
Poly- (butyl methacrylate-acrylonitrile-styrene) (P (BMA-AN-St)) described in step (1) specifically by with
Lower step is prepared：Emulsifier is dissolved with water, is then added together with monomer methacrylic acid butyl ester, acrylonitrile and styrene
Enter into reaction vessel, under inert atmosphere then stirring is added initiator and is reacted, instead to drain the air in reaction vessel
Be demulsified after answering to gained lotion, then filter by washing of precipitate be drying to obtain poly- (butyl methacrylate-the third
Alkene nitrile-styrene)；
In step (1), the emulsifier is lauryl sodium sulfate, dodecyl sulphate potassium or ammonium lauryl sulfate
At least one of；The initiator is at least one of sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate；
The mass ratio of monomer methacrylic acid butyl ester used in step (1), acrylonitrile and styrene is 1~4：1~2：1
~8；Preferably 1:2:1；The quality that the dosage of emulsifier described in step (1) meets emulsifier accounts for water and monomer mass summation
1~4%；The quality that the dosage of the initiator meets initiator accounts for the 0.1~0.4% of water and monomer mass summation；Step
Suddenly the quality that the dosage of water described in (1) meets water accounts for the 60~72% of water and monomer mass summation；
Reaction described in step (1), which refers to, is stirred to react 4~10h at 55~65 DEG C；The purpose wherein stirred be in order to
It is that raw material sufficiently reacts, therefore can not have to specific restriction mixing speed；Preferably 6h is reacted in 60 DEG C, 800rpm；
The Al that it is 2~5% with mass fraction that demulsification described in step (1), which refers to,2(SO4)3Aqueous solution demulsification；
Water and ethanol wash are preferably used in washing described in step (1).
Triphenyl phosphate (TPP) described in step (1), poly- (butyl methacrylate-acrylonitrile-styrene) (P
(BMA-AN-St)) meet with the dosage of poly- (biasfluoroethylene-hexafluoropropylene)：Triphenyl phosphate (TPP) and poly- (vinylidene-six
Fluoropropene) mass ratio be 1~2:1~2；Poly- (biasfluoroethylene-hexafluoropropylene) and poly- (butyl methacrylate-acrylonitrile-benzene
Ethylene) (P (BMA-AN-St)) mass ratio be 1:1~5, preferably 1:4；
Acetone described in step (1) and the mixed solvent of dimethyl acetamide are preferably that volume ratio is 7:3 acetone and
The mixed solvent of dimethyl acetamide；Acetone described in step (1) and the mixed solvent of dimethyl acetamide obtain dosage satisfaction
The mass fraction of polymer is 5%~16%, preferably 10% in polymer solution obtained in step (1), wherein polymer
Mass fraction refer to that poly- (butyl methacrylate-acrylonitrile-styrene) and poly- (biasfluoroethylene-hexafluoropropylene) account for poly- (methyl
Butyl acrylate-acrylonitrile-styrene), the ratio of the gross mass of poly- (biasfluoroethylene-hexafluoropropylene) and mixed solvent；
Supporter described in step (2) is that polyethylene is touched, polypropylene is touched, in polypropylene-ethylene-propylene sandwich diaphragm
One kind；
In electrostatic spinning apparatus described in step (2), fltting speed is 1~2mm/min, syringe needle and receiver
The distance between be 20cm, syringe needle translating stroke is 75cm, and syringe needle connect with high voltage power supply, positive high voltage 19kV；
Drying described in step (2) refers to dry 10~12h in 35~50 DEG C of drying box；
Electrolyte described in step (3) is by for lithium hexafluoro phosphate (LiPF6), ethylene carbonate (EC), methyl ethyl carbonate
(EMC) it is formed with diethyl carbonate (DEC), wherein EC：EMC：DEC mass ratio is 3：5：2, LiPF6Molar concentration be 1mol/
L。
A kind of fire-retardant gel polymer electrolyte prepared by the above method.
Above-mentioned fire-retardant gel polymer electrolyte is preparing the application in lithium ion battery.
A kind of lithium ion battery prepared by above-mentioned fire-retardant gel polymer electrolyte, is specifically prepared by the following steps
It arrives：Fire-retardant gel polymer electrolyte is placed between positive diaphragm and cathode membrane, that is, is assembled into gel polymer electrolyte
Lithium ion battery, the above operation are completed in glove box.
The active material of the positive diaphragm is cobalt acid lithium, nickel ion doped, LiMn2O4, nickle cobalt lithium manganate or ferric phosphate
Lithium；The active material of the cathode membrane is natural graphite, artificial graphite, interphase carbon ball, mesophase carbon fiber, hard carbon, soft
Carbon or metal lithium sheet；The gel polymer electrolyte lithium-ion battery is button cell.
Mechanism of the invention is：
The present invention is prepared for TPP/P (VdF-HFP)/P (BMA-AN-St) lithium ion battery polymer with method of electrostatic spinning
Film, the polymer film have the advantages that TPP and P (BMA-AN-St) and P (VdF-HFP), P (BMA-AN-St) have good simultaneously
Good chemical stability, adhesiveness, coherency, liquid retention and film forming；And its is easily modified, nontoxic and pollution-free to environment, often
As film forming agent, dispersing agent, emulsifier, thickener, adhesive, flocculant and complexing agent；It is special that its intramolecular also has
Carbonyl and cyano functional group assign P (BMA-AN-St) preferable performance, preferable to the wetting property of electrolyte, at the same time,
TPP has superior flame retardant property, has certain contribution to the security performance for improving polymer film.By the gel polymer electrolyte
After matter is assembled into battery, electro-chemical test shows：The gel polymer electrolyte stable electrochemical property, there is good anti-flammability
Energy.TPP/P (VdF-HFP)/P (BMA-AN-St) gel electrolyte is blended before guaranteeing original gel electrolyte stability
It puts, anti-flammability improves, and using electrostatic spinning technique, it is of uniform size to can get pore-size distribution, fibre diameter
Tunica fibrosa；And the addition of TPP further improves electrolyte electrochemical performance.
The present invention compared with the existing technology, has the following advantages and beneficial effect：
(1) the raw materials used in the present invention is low in cost, is easy to obtain, and synthesis technology is simple, and yield is high, produces for technology
Condition is provided, industrialization promotion and utilization are easily carried out.
(2) solvent used in the present invention is acetone and dimethyl acetamide, and low toxicity, environmental pollution is small, while also can
Reduce production cost.
(3) present invention polymer film obtained has preferable anti-flammability and electrochemical stability.
(4) fire retardant triphenyl phosphate TPP has been blended in the present invention, than no P (BMA-AN- that triphenyl phosphate TPP is blended
St)/P (VdF-HFP) polymer dielectric has higher anti-flammability, and after blending fire retardant agent triphenyl phosphate TPP, also improves
The chemical property of polymer dielectric.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the polymer film being prepared in the embodiment of the present invention 1~3 and comparative example 1；
Fig. 2 is the self-gravitation time graph for the polymer film being prepared in the embodiment of the present invention 1~3 and comparative example 1；
Fig. 3 is the cycle performance curve for the polymer film being prepared in the embodiment of the present invention 2 and comparative example 1.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
Poly- (butyl methacrylate-acrylonitrile-styrene) (P (BMA-AN-St)) in following embodiment specifically by with
Lower section method is prepared：By the emulsifier sodium lauryl sulfate for accounting for ionized water and monomer gross mass 1.5% with accounting for ion
The deionized water dissolving of water and monomer gross mass 65%, by monomer methacrylic acid butyl ester, acrylonitrile and styrene are with 1：2：1
It is added in four-neck flask after mass ratio mixing together with emulsifier, at 60 DEG C, N230min is stirred under atmosphere to hold to drain reaction
Then the 0.15% initiator sodium peroxydisulfate for accounting for ionized water and monomer gross mass is added in air in device, at 60 DEG C,
6h is reacted under the conditions of 800rpm, and gained lotion is poured into the Al that mass fraction is 3%2(SO4)3It is demulsified in solution, gained is heavy
It forms sediment by filtering, deionized water and ethanol wash are dried in vacuo for 24 hours at 60 DEG C after for several times and can be prepared by the terpolymer.
The molecular weight of P (VdF-HFP) in following embodiment is 455000, is purchased from aldrich.
Embodiment 1
(1) mass ratio is 1 by 50 DEG C of water-bath constant temperature:2:8 TPP, P (VdF-HFP) and P (BMA-AN-St) is added three
In mouth flask, it is 7 that volume ratio, which is added,:3 acetone and dimethyl acetamide (DMAC) mixed solvent, machinery continuously stir 1h and are allowed to
Sufficiently dissolution obtains the gel polymer solution that mass fraction is 10%, and wherein mixing speed is 350r/min.
(2) polymer solution that step (1) obtains is fitted into the syringe of electrostatic spinning machine propulsion device, is with PE film
Support is 1.5mm/min, voltage 19kV in fltting speed, receives in the electrostatic field that distance is 20cm and carry out spinning, obtain double
Face coat equivalent polymer fiber porous septum, be transferred in 40 DEG C of vacuum ovens and dry 12h, the film with a thickness of 30-
45μm。
(3) polymer film obtained is cut into the circular dimension that diameter is 18mm, in glove box, in electrolyte
(1mol/L LiPF6+ EC+EMC+DEC, EC：EMC：DEC mass ratio is 3：5：2) 1h is impregnated in, obtains lithium ion battery gel
Polymer dielectric.
(4) in glove box, using nickel cobalt lithium aluminate as positive electrode, using lithium piece as cathode, by gel polymer electrolyte
It is placed between anode and cathode, is assembled into button cell.
Embodiment 2
(1) mass ratio is 1 by 50 DEG C of water-bath constant temperature:1:4 TPP, P (VdF-HFP) and P (BMA-AN-St) is added three
In mouth flask, it is 7 that volume ratio, which is added,:3 acetone and dimethyl acetamide (DMAC) mixed solvent, machinery continuously stir 1h and are allowed to
Sufficiently dissolution obtains the gel polymer solution that mass fraction is 10%, and wherein mixing speed is 350r/min.
(2) polymer solution that step (1) obtains is fitted into the syringe of electrostatic spinning machine propulsion device, is with PE film
Support is 1.5mm/min, voltage 19kV in fltting speed, receives in the electrostatic field that distance is 20cm and carry out spinning, obtain double
Face coat equivalent polymer fiber porous septum, be transferred in 40 DEG C of vacuum ovens and dry 12h, the film with a thickness of 30-
45μm。
(3) it is handled by 1 step of embodiment (3).
(4) it is handled by 1 step of embodiment (4).
Embodiment 3
(1) mass ratio is 2 by 50 DEG C of water-bath constant temperature:1:4 TPP, P (VdF-HFP) and P (BMA-AN-St) is added three
In mouth flask, it is 7 that volume ratio, which is added,:3 acetone and dimethyl acetamide (DMAC) mixed solvent, machinery continuously stir 1h and are allowed to
Sufficiently dissolution obtains the gel polymer solution that mass fraction is 10%, and wherein mixing speed is 350r/min.
(2) polymer solution that step (1) obtains is fitted into the syringe of electrostatic spinning machine propulsion device, is with PE film
Support is 1.5mm/min, voltage 19kV in fltting speed, receives in the electrostatic field that distance is 20cm and carry out spinning, obtain double
Face coat equivalent polymer fiber porous septum, be transferred in 40 DEG C of vacuum ovens and dry 12h, the film with a thickness of 30-
45μm。
(3) it is handled by 1 step of embodiment (3).
(4) it is handled by 1 step of embodiment (4).
Reference examples 1
(1) mass ratio is 1 by 50 DEG C of water-bath constant temperature:Three-necked flask is added in 4 P (VdF-HFP) and P (BMA-AN-St)
In, it is 7 that volume ratio, which is added,:3 acetone and dimethyl acetamide (DMAC) mixed solvent, machinery continuously stir 1h and are allowed to sufficiently molten
Solution obtains the gel polymer solution that mass fraction is 10%, and wherein mixing speed is 350r/min.
(2) polymer solution that step (1) obtains is fitted into the syringe of electrostatic spinning machine propulsion device, is with PE film
Support is being 1.5mm/min, voltage 19kV in fltting speed, is receiving in the electrostatic field that distance is 20cm and carry out spinning, obtain
The porous septum of dual coating equivalent polymer fiber is transferred in 40 DEG C of vacuum ovens and dries 12h, the film with a thickness of
30-45μm。
(3) polymer film obtained is cut into the circular dimension that diameter is 18mm, in glove box, in electrolyte
(LiPF6+ EC+EMC+DEC, EC：EMC：DEC mass ratio is 3：5：2, LiPF6Concentration is 1mol/L) in impregnate 1h, obtain lithium from
Sub- battery gel polymer electrolyte.
(4) in glove box, using nickel cobalt lithium aluminate as positive electrode, using lithium piece as cathode, by gel polymer electrolyte
It is placed between anode and cathode, is assembled into button cell.
Fig. 1 is the scanning electron microscope (SEM) photograph for the polymer film being prepared in the embodiment of the present invention 1~3 and comparative example 1, wherein
(a) represent the scanning electron microscope (SEM) photograph of the polymer film prepared in comparative example 1, (b), (c), (d) respectively represent the preparation of embodiment 1,2,3
The scanning electron microscope (SEM) photograph of obtained polymer film.As can be seen from Figure 1 after joined TPP, polymer fiber still can be with shape
At criss-cross structure, if but be added amount it is excessive, will affect the pattern of tunica fibrosa.
Test case
1, flame retardant property is tested
The blending different proportion TPP/P (VdF-HFP) that embodiment 1-3 is prepared/P (BMA-AN-St) film and control
The P (VdF-HFP) being prepared in example 1/P (BMA-AN-St) film flame retardant property is as shown in Figure 2.Flame retardant property test is certainly
It is carried out in the confined space of system, flame retardant property test is that the polymer film in each embodiment is allowed to suck equivalent electrolyte, described
Electrolyte by for lithium hexafluoro phosphate LiPF6, ethylene carbonate EC, methyl ethyl carbonate EMC and diethyl carbonate DEC composition,
Middle EC：EMC：DEC mass ratio is 3：5：2, LiPF6Molar concentration be 1mol/L after, measure self-extinguishment after being lighted with ignition device
It goes out the time, compares the length of self-gravitation time.It can be seen that the self-gravitation time is shorter and shorter with the increase of flame retardant amount, this
Show that the addition of TPP improves the flame retardant property of electrolyte.When the mass ratio of TPP and P (VdF-HFP) increase to 1：After 1, then
The amount for increasing fire retardant can not dramatically increase the flame retardant property of polymer film.
2, cycle performance is tested
The obtained polymer film of embodiment 1-3 and reference examples 1 is assembled into button cell, structure be cathode (Li)/
Gel polymer electrolyte/anode (LiNi0.8Co0.15Al0.05O2), carry out circulating battery stability test.The survey of button cell
Strip part is：Room temperature, 0.5C electric current, (to overcome experimental error, numerical value is five times to 3.0~4.5V voltage range in embodiment
The average value of experiment).It is as shown in Figure 3 to test obtained curve.From the figure 3, it may be seen that TPP/P (VdF-HFP)/P (BMA-AN-St) is poly-
The cycle performance ratio P (VdF-HFP) of compound film/P (BMA-AN-St) polymer film is superior, this shows the addition of fire retardant not only
The flame retardant property for improving battery also improves the cycle performance of battery.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of fire-retardant method for preparing gel polymer electrolyte, it is characterised in that include the following steps：
(1) triphenyl phosphate, poly- (butyl methacrylate-acrylonitrile-styrene) and poly- (biasfluoroethylene-hexafluoropropylene) are added
Enter into acetone and the mixed solution of dimethyl acetamide, stirring until poly- (butyl methacrylate-acrylonitrile-styrene) and
Poly- (biasfluoroethylene-hexafluoropropylene) is completely dissolved, and obtains polymer blend solution；
(2) polymer blend solution obtained in step (1) is spun by electrostatic spinning apparatus on the two sides of supporter, is obtained double
Face coats the porous septum of equivalent polymer fiber, dry；
(3) will it is dry in step (3) after porous septum impregnate in the electrolytic solution 20~60min to get fire-retardant gelatin polymer
Electrolyte.
2. fire-retardant method for preparing gel polymer electrolyte according to claim 1, it is characterised in that：
Triphenyl phosphate described in step (1), poly- (butyl methacrylate-acrylonitrile-styrene) and poly- (vinylidene-
Hexafluoropropene) dosage meet：The mass ratio of triphenyl phosphate and poly- (biasfluoroethylene-hexafluoropropylene) is 1~2:1~2；It is poly-
(biasfluoroethylene-hexafluoropropylene) and poly- (butyl methacrylate-acrylonitrile-styrene) mass ratio are 1:1~5.
3. fire-retardant method for preparing gel polymer electrolyte according to claim 1, it is characterised in that：
It is 7 that acetone described in step (1) and the mixed solvent of dimethyl acetamide, which are volume ratio,:3 acetone and dimethyl second
The mixed solvent of amide；Acetone described in step (1) and the mixed solvent of dimethyl acetamide obtain dosage and meet in step (1)
The mass fraction of polymer is 5%~16% in obtained polymer solution.
4. fire-retardant method for preparing gel polymer electrolyte according to claim 1, it is characterised in that：
Poly- (butyl methacrylate-acrylonitrile-styrene) described in step (1) specifically is prepared by the following steps to obtain：It will
Emulsifier is dissolved with water, is then added in reaction vessel together with monomer methacrylic acid butyl ester, acrylonitrile and styrene, lazy
Property atmosphere under stirring to drain the air in reaction vessel, then be added initiator reacted, after reaction to gained cream
Liquid is demulsified, then filter by washing of precipitate be drying to obtain poly- (butyl methacrylate-acrylonitrile-styrene).
5. fire-retardant method for preparing gel polymer electrolyte according to claim 4, it is characterised in that：
In step (1), the emulsifier is in lauryl sodium sulfate, dodecyl sulphate potassium or ammonium lauryl sulfate
It is at least one；The initiator is at least one of sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate；
The mass ratio of monomer methacrylic acid butyl ester used in step (1), acrylonitrile and styrene is 1~4：1~2：1~8；
The dosage that the dosage of emulsifier described in step (1) meets emulsifier is the 1~4% of water and monomer gross mass；Described draws
The dosage that the dosage of hair agent meets initiator is the 0.1~0.4% of water and monomer gross mass；The quality of the dosage water of the water
For the satisfaction 60~72% of water and monomer gross mass；
Reaction described in step (1), which refers to, is stirred to react 4~10h at 55~65 DEG C；
The Al that it is 2~5% with mass fraction that demulsification described in step (1), which refers to,2(SO4)3Aqueous solution demulsification；
Washing described in step (1) refers to water and ethanol wash.
6. fire-retardant method for preparing gel polymer electrolyte according to claim 1, it is characterised in that：
Supporter described in step (2) be polyethylene is touched, polypropylene is touched, one in polypropylene-ethylene-propylene sandwich diaphragm
Kind.
7. fire-retardant method for preparing gel polymer electrolyte according to claim 1, it is characterised in that：
In electrostatic spinning apparatus described in step (2), fltting speed is 1~2mm/min, between syringe needle and receiver
Distance be 20cm, syringe needle translating stroke is 75cm, and syringe needle connect with high voltage power supply, positive high voltage 19kV；
Drying described in step (2) refers to dry 10~12h in 35~50 DEG C of drying box.
8. fire-retardant method for preparing gel polymer electrolyte according to claim 1, it is characterised in that：
Electrolyte described in step (3) is by lithium hexafluoro phosphate LiPF6, ethylene carbonate EC, methyl ethyl carbonate EMC and carbonic acid two
Ethyl ester DEC is formed, wherein EC：EMC：DEC mass ratio is 3：5：2, LiPF6Molar concentration be 1mol/L.
9. a kind of fire-retardant gel polymer electrolyte that methods described in any item according to claim 1~8 are prepared.
10. fire-retardant gel polymer electrolyte according to claim 9 is preparing the application in lithium ion battery.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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