CN106654365A - Solid polymer electrolyte-based composite gel polymer electrolyte and preparation method and application thereof - Google Patents
Solid polymer electrolyte-based composite gel polymer electrolyte and preparation method and application thereof 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
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- H01M2300/0017—Non-aqueous electrolytes
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Abstract
The invention belongs to the technical field of a lithium ion battery, and specifically relates to a composite gel polymer electrolyte and a preparation method and an application thereof. The composite gel polymer electrolyte consists of a composite electrolyte film and a liquid electrolyte, wherein the composite electrolyte film comprises two or more layers; at least one layer of the composite electrolyte film is solid polymer electrolyte capable of transferring lithium ions; and at least one layer of the composite electrolyte film is a high molecular material different from the solid polymer electrolyte. The composite gel polymer electrolyte is high in conductivity, high in lithium ion transport coefficient, high in safety and can be applied to a high-capacity, high-power and high-energy-density lithium secondary battery.
Description
The application is the Application No. 201310025675.7, applying date on January 23rd, 2013, entitled " is based on
The division Shen of the patent application of composite gel polymer electrolyte of solid polymer electrolyte and preparation method and application "
Please.
Technical field
The invention belongs to technical field of lithium ion, and in particular to a class composite gel polymer electrolyte and its preparation
Method and application.
Background technology
Lithium secondary battery especially lithium ion battery therein as a kind of mechanism of new electrochemical power sources, with energy density it is high,
The advantages of environmental friendliness, memory-less effect, notebook computer, digital camera, mobile phone have been widely used to since its commercialization
In etc. various portable electric appts, while it is also mixed power electric car (HEV), plug-in hybrid electric automobile
(PHEV), one of preferable energy storage device of pure electric automobile (EV) and small intelligent electrical network.However, due to LiPF6It is Organic Electricity
The extensive application of solution liquid (inflammable to moisture sensitivity, easily to set off an explosion) causes the security and reliability of high capacity lithium ion battery
Property is under suspicion.In order to solve traditional lithium-ion battery safety issue, polymer Li-ion battery (Polymer lithium
Ion batteries) it has been increasingly becoming study hotspot.The positive and negative electrode material of such battery is identical with traditional lithium-ion battery, only
It is to employ solid polymer to replace organic bath and barrier film.The polymer of most study mainly has following a few classes：Polyethers
Class (mainly PEO), polyacrylonitrile (PAN) class, polymethacrylates (PMMA) class and Kynoar (PVDF) class etc..It is poly-
Compound lithium ion battery solves the problems, such as that conventional lithium ion battery easily occurs leakage and leakage current is big, and security is significantly carried
It is high；In addition, polymeric material plasticity is strong, thus such battery have can thin type, arbitrary areaization it is excellent with arbitrary shape etc.
Point, such that it is able to significantly improve the specific capacity of battery.Polymer for electrolyte can be pure solid-state (solid polymer electrolytic
Matter, solid polymer electrolytes, SPEs), or add plasticizer gelinite (gel polymer electrolyte
Matter, gel polymer electrolytes, GPEs).But the electrical conductivity of solid polymer electrolyte it is low (<10-4S cm-1),
The level of practical application is reached far away；Gel polymer electrolyte has the double properties of solid and liquid electrolyte, electrical conductivity
It is suitable with liquid organic electrolyte, and electrochemical window is wider, and heat endurance is good, receives significant attention.But, gel polymerisation
Electrolyte bad mechanical strength, production cost is high, greatly limit its application in high-capacity high-power lithium ion battery；Simultaneously
The transport coefficient of anion is high in general gel polymer electrolyte, it is big to polarize, and limits the power density of lithium ion battery
Or high current charge-discharge ability.
The content of the invention
It is an object of the invention to overcome existing gel polymer electrolyte bad mechanical strength, production cost height, anion
Transport coefficient is high, polarization is big, it is extremely difficult to be used widely in Large Copacity, high power, lithium ion battery with high energy density
Shortcoming, there is provided a class high conductivity, macroion transport number, good mechanical property, security performance height, stable chemical performance, produce into
This low, good with common electrodes match materials composite gel polymer electrolyte based on solid polymer electrolyte.
Another object of the present invention is to provide a kind of preparation method of above-mentioned composite gel polymer electrolyte.
The a further object of the present invention is to provide a kind of application of above-mentioned composite gel polymer electrolyte, i.e., for lithium two
In primary cell.
The class composite gel polymer electrolyte that the present invention is provided, described composite gel polymer electrolyte is by being combined
Dielectric film and liquid electrolyte are constituted, and wherein composite electrolyte membrane is made up of two-layer or multilayer, and it is solid that wherein at least has one layer
State polymer dielectric, at least one layer is the macromolecular materials different from the solid polymer electrolyte.
Above-mentioned solid polymer electrolyte is the polymer that can transmit lithium ion, the above-mentioned solid polymer electrolyte
Macromolecular material in addition not only includes the solid polymer electrolytes different from the solid polymer electrolyte, also including polyene
Hydrocarbon, polyamide, polyimides, poly- aramid fiber, polyarylether, polyester, while also include their copolymer, blend, while at this
Can also add suitable inorganic filler in a little polymer.
Above-mentioned polyolefin includes polyethylene, polypropylene, Kynoar, poly- (biasfluoroethylene-hexafluoropropylene), above-mentioned poly-
Ester includes poly- (ethylene glycol-terephthalate), above-mentioned inorganic filler include aluminum oxide, silica, titanium oxide, zirconium oxide,
aLi2O-bAl2O3-cTiO2-dP2O5The compound of (a, b, c, d are located at 1-100 between) composition, montmorillonite, molecular sieve or it
Both or multiple compounds mixture.
Above-mentioned liquid electrolyte includes the solution of organic compound or ionic liquid and lithium salts.
The present invention provides the preparation method of composite gel polymer electrolyte, and it is concretely comprised the following steps：
(1) solid polymer electrolyte membrane is prepared initially with solwution method or heating mixing method；
(2) and then using solwution method, heating mixing method, infusion method, casting method or Electrospinning Method, will be with above-mentioned solid polymer
Macromolecular material beyond electrolyte is compound with above-mentioned solid polymer electrolyte membrane, forms the composite membrane knot of two-layer or multilayer
Structure；
(3) above-mentioned composite membrane is placed in vacuum drying chamber, heating, vacuum is dried, removes possible trace solvent；
(4) above-mentioned dried composite membrane immersion 1 minute to 48 hours in the electrolytic solution is obtained in anhydrous and oxygen-free environment
To composite gel polymer electrolyte.
The thickness of the solid polymer electrolyte membrane described in above-mentioned steps (1) is 1-30 microns.
One layer is above-mentioned solid polymer electrolyte membrane in the structure of composite membrane of above-mentioned steps (2) two-layer, in addition one
Layer is the polymer material film beyond the solid polymer electrolyte；It is at least middle to have one in described MULTILAYER COMPOSITE membrane structure
Layer is above-mentioned solid polymer electrolyte membrane, and at least one layer is the polymer material film beyond the solid polymer electrolyte；
The thickness of described composite membrane is 5-50 microns.
The preparation of above-mentioned steps (4) composite gel polymer electrolyte can be carried out in glove box, in glove box
For argon atmospher, moisture is less than 1ppm.
Electrolyte described in above-mentioned steps (4) can be made up of lithium hexafluoro phosphate and carbonate-based solvent, lithium hexafluoro phosphate
Molar concentration between 0.5M-2M.
The present invention provides a kind of application of above-mentioned composite gel polymer electrolyte, i.e., in lithium secondary battery.
The present invention not only has that solid polymer electrolyte mechanical strength is big, production using composite gel polymer electrolyte
The characteristics of low cost, and electrical conductivity is high, and electrochemical window width, good cycle, security performance is high, can be used for Large Copacity, height
The lithium secondary battery of power, high-energy-density.
Description of the drawings
Fig. 1 (a) is the molecular structural formula of the gained solid polymer electrolyte of embodiment 2；
Fig. 1 (b) is the molecular structural formula of the gained solid polymer electrolyte of embodiment 3；
The charging and discharging curve and cycle performance of Fig. 2 embodiments 7；
The charging and discharging curve and cycle performance of Fig. 3 embodiments 8；
Fig. 4 is the charging and discharging curve and cycle performance figure of comparative example of the present invention 2.
Specific embodiment
Embodiment 1
(1) by polyethylene glycol oxide (molecular weight 100,000), LiClO4、TiO2(50 nanometers of particle diameter) is by mass percentage 8.7：
1：0.3 ratio is weighed, and 120 DEG C are heated under agitation, is changed into uniform solid solution, is then poured into corrosion resistant plate
On, it is 10 microns of solid polymer electrolyte membrane to be pressed into thickness, and is cooled to room temperature.
(2) in the molten state, the thickness by obtaining in 80 DEG C of hot-stretch is 10 um porous polyethylene films, then will
The polyethylene film is placed in above above-mentioned solid polymer electrolyte membrane, is then heated to 60 DEG C, and under 10 atmospheric pressure 1 is suppressed
Individual hour, obtains solid polymer electrolyte composite membrane.
(3) by above-mentioned composite membrane be cut into it is appropriately sized after, be placed in drying in 24 hours under the conditions of 80 DEG C of vacuum drying chamber and go
Except traces of moisture, vacuum are cooled to room temperature, anhydrous, anaerobic glove box is transferred into.Then by solid polymer electrolyte composite membrane
It is immersed in 1M LiPF6Obtain final product within 6 hours in electrolyte (LB315, purchased from Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City)
Composite gel polymer electrolyte.The test of composite gel polymer electrolyte performance：
The pick up (η) of the PEO/PVDF solid polymer electrolyte composite membranes obtained to above-described embodiment 1 is using as follows
Formula (1) is calculated：
η=(Wt–W0)/W0× 100% (1)
Wherein W0And WtRespectively composite membrane inhales 1M LiPF6Electrolyte (LIB315, Cathay of Zhangjagang City Huarong chemical industry green wood
Material Co., Ltd) before and after weight.
By composite membrane 1M LiPF6After electrolyte (LIB315) saturation, using differential scanning method, (DSC, instrument is
Perkin-Elmer TGA7/DSC7) temperature of measurement electrolyte when all volatilizing.
Electrical conductivity, Ion transfer have been carried out to the PEO/PVDF composite gel polymer electrolytes that above-described embodiment 1 is obtained
Several tests.Electrical conductivity adopts AC impedence method (CHI660C, Shanghai Chen Hua companies), and frequency range is 10Hz-100kHz, its
In two extremely stainless steels, centre is composite gel polymer electrolyte, and its area is more than stainless steel, and electrical conductivity is counted by formula (2)
Obtain：
σ=l/ (RbA)(S cm-1) (2)
Wherein, σ is electrical conductivity, RbIt is the impedance of film, l is the thickness of film, and A is pole-piece area.
Lithium ion transference number is tested using timing coulometry, wherein two extremely lithium pieces, centre is plural gel electrostrictive polymer
Xie Zhi, voltage is 10mV, and its size is calculated by formula (3)：
tLi +=Iss/I0 (3)
Wherein, IssIt is the steady-state current value obtained by timing coulometry, I0It is the initial state electricity obtained by timing coulometry
Flow valuve.
Measured result is summarized in table 1.
Embodiment 2
(1) by polyvinyl alcohol (PVA, alcoholysis degree >=98%, Mw:105000,200mg) it is dissolved in boric acid (148mg)
In 20ml dimethyl sulfoxide (DMSO) DMSO, then heat 8 hours at 80 DEG C, obtain transparent solution.It is subsequently added into 88mg Li2CO3With
300mg oxalic acid, is heated to 100 DEG C and reacts 24 hours, is cooled to room temperature.Solution is poured on glass plate, in 70 DEG C of baking ovens
Drying, removes solvent, obtains poly- (vinyl alcohol-boric acid-lithium oxalate) that thickness is 30 μm, and its structural representation is led in Fig. 1 a, ion
Electric group is similar with the structure of LiBOB.
(2) in the molten state, the thickness by obtaining in 100 DEG C of hot-stretch is 10 um porous polypropylene screens, then
The polypropylene screen is placed in above the poly- lithium borate film of above-mentioned solid-state and following, 70 DEG C is then heated to, under 10 atmospheric pressure
2 hours of compacting, obtain solid polymer electrolyte composite membrane.
(3) by above-mentioned composite membrane be cut into it is appropriately sized after, be placed in drying in 24 hours under the conditions of 80 DEG C of vacuum drying chamber and go
Except trace solvent, vacuum are cooled to room temperature, anhydrous, anaerobic glove box is transferred into.Then by solid polymer electrolyte composite membrane
It is immersed in 1M LiN (CF3SO2)2(solvent is vinyl carbonate, formic acid dimethyl ester, formic acid diethylester volume ratio 1 to electrolyte:1:1
Mixture) in obtain final product composite gel polymer electrolyte within 40 hours.
With embodiment 1, the result of gained is summarized in table 1 for the performance test of gained composite gel polymer electrolyte film.
Embodiment 3
(1) by polyacrylic acid (PAA, Mw:450000,200g), boric acid (148g), 20ml deionized waters are heated to 80 DEG C,
Obtain transparent solution.59g LiOH and 300g oxalic acid is subsequently added into, 100 DEG C is heated to and is reacted 24 hours, be cooled to room temperature.Will
Solution is poured on glass plate, in 70 DEG C of baking ovens dry, remove solvent, obtain thickness be 30 μm it is poly- (acrylic acid-boric acid-
Lithium oxalate), its structural representation is in Fig. 1 b, and ionic conduction group is similar with the structure of LiBOB.
(2) P (VDF-HFP) is dissolved in METHYLPYRROLIDONE by mass percentage for 10% ratio, then
The solution is cast in into poly- (acrylic acid-boric acid-lithium oxalate) the film surface obtained by above-mentioned (1), 100 DEG C are then heated to, is carried out
Vacuum drying, obtains solid polymer electrolyte composite membrane.
(3) by above-mentioned composite membrane be cut into it is appropriately sized after, be placed in drying in 24 hours under the conditions of 80 DEG C of vacuum drying chamber and go
Except trace solvent, vacuum are cooled to room temperature, anhydrous, anaerobic glove box is transferred into.Then by solid polymer electrolyte composite membrane
(solvent is vinyl carbonate, formic acid dimethyl ester, formic acid diethylester volume ratio 1 to be immersed in 0.8M LiBOB electrolyte:1:1 it is mixed
Compound) in obtain final product composite gel polymer electrolyte within 40 hours.
With embodiment 1, the result of gained is summarized in table 1 for the performance test of gained composite gel polymer electrolyte film.
Embodiment 4
(1) it is 1 by Lithium polyacrylate (1g) and polymethyl methacrylate (9g) mass ratio：9 mixture is added to N-
In N-methyl-2-2-pyrrolidone N (100ml) solvent, 60 DEG C of dissolvings are heated to, (average grain diameter 100 is received to be subsequently adding 0.2g silica
Rice), then mixed liquor is poured on glass plate, dry in 70 DEG C of baking ovens, solvent is removed, obtain that thickness is 15 μm poly- third
Olefin(e) acid lithium-polymethyl methacrylate dielectric film.
(2) PVDF is dissolved in METHYLPYRROLIDONE by mass percentage for 10% ratio, it is then that this is molten
Liquid carries out electrospinning under the high pressure of 30KV, is then heated to 80 DEG C, is vacuum dried, and obtains the pvdf membrane that thickness is 5 microns；
Then using above-mentioned (1) gained Lithium polyacrylate-polymethyl methacrylate dielectric film as intermediate layer, electrospinning pvdf membrane conduct
The two-layer of outside, obtains the composite membrane of " sandwich " structure.
(3) by above-mentioned composite membrane be cut into it is appropriately sized after, be placed in drying in 24 hours under the conditions of 80 DEG C of vacuum drying chamber and go
Except trace solvent, vacuum are cooled to room temperature, anhydrous, anaerobic glove box is transferred into.Then by solid polymer electrolyte composite membrane
(solvent is vinyl carbonate, formic acid dimethyl ester, formic acid diethylester volume ratio 1 to be immersed in 0.8M LiBOB electrolyte:1:1 it is mixed
Compound) in obtain final product composite gel polymer electrolyte within 40 hours.
With embodiment 1, the result of gained is summarized in table 1 for the performance test of gained composite gel polymer electrolyte film.
Embodiment 5
(1) it is by mass percentage 9 by PPOX (molecular weight 200,000), LiBOB：1 ratio is weighed, and is being stirred
Mix down and be heated to 130 DEG C, be changed into uniform solid solution, be then poured on corrosion resistant plate, be pressed into thickness and be 15 microns and consolidate
State polymer dielectric film, and it is cooled to room temperature.
(2) Nafion membrane (model 117,0.1kg) that thickness is 20 microns is soaked into stagnant in LiOH saturated solutions (2kg),
48 it is little after be washed with deionized, be dried, obtain the Nafion membrane of lithiumation；Then by the solid polymer electricity obtained by above-mentioned (1)
Solution plasma membrane is compressed on the Nafion membrane of lithiumation at 70 DEG C, under the atmospheric pressure of 20MPa, obtains composite membrane.
(3) by above-mentioned composite membrane be cut into it is appropriately sized after, be placed in drying in 24 hours under the conditions of 80 DEG C of vacuum drying chamber and go
Except trace solvent, vacuum are cooled to room temperature, anhydrous, anaerobic glove box is transferred into.Then by solid polymer electrolyte composite membrane
It is immersed in the ionic liquid of 0.8M LiBOB that (ionic liquid consists of 1- alkyl -2,3- methylimidazole trifluoromethane sulfonic acids
Salt) in obtain final product composite gel polymer electrolyte within 30 hours.
With embodiment 1, the result of gained is summarized in table 1 for the performance test of gained composite gel polymer electrolyte film.
Embodiment 6
(1) by concentration for 8wt.% polyacrylonitrile (molecular weight 150,000) in N, N '-dimethyl formamide solution is coated on
On corrosion resistant plate, after 80 DEG C of dryings, cool down, prepared thickness is 15 microns of solid polymer electrolyte membrane.
(2) by poly- (ethylene glycol-the terephthalate) (Mw of melting:600,000) obtained by fusion drawn at 140 DEG C
To thickness be 40 microns, average pore size be 100nm, poly- (ethylene glycol-terephthalate) film that porosity is 50%；Then will
Solid polymer dielectric film obtained by above-mentioned (1) is compressed on poly- (ethylene glycol-to benzene two at 70 DEG C, under the atmospheric pressure of 20MPa
Formic acid esters) above film, obtain composite membrane.
(3) by above-mentioned composite membrane be cut into it is appropriately sized after, be placed in drying in 24 hours under the conditions of 80 DEG C of vacuum drying chamber and go
Except trace solvent, vacuum are cooled to room temperature, anhydrous, anaerobic glove box is transferred into.Then by solid polymer electrolyte composite membrane
It is immersed in 0.6M LiPF6(solvent is vinyl carbonate, formic acid dimethyl ester, formic acid diethyl with the mixed solution of 0.4M LiBOB
Ester volume ratio 2:1:1 mixture) in obtain final product composite gel polymer electrolyte within 5 hours.
With embodiment 1, the result of gained is summarized in table 1 for the performance test of gained composite gel polymer electrolyte film.
Comparative example 1
After commercial li-ion battery diaphragm (Celgard 2730, PE) is cut into into appropriate size, vacuum drying chamber is placed in
Drying under reduced pressure 24 hours under the conditions of 80 DEG C, vacuum is cooled to room temperature and is transferred into glove box.Carry out needing Celgard before electro-chemical test
2730 barrier films are immersed in 1mol l-1LiPF6(model LIB315 has electrolyte purchased from Cathay of Zhangjagang City Huarong new chemical materialses
Limit company) in 6 hours.
With embodiment 1, the result of gained is summarized in table 1 for the performance test of gained barrier film.
The electrochemical property test result of embodiment 1-6 of table 1 and comparative example 1
Embodiment 7
Using the composite gel polymer electrolyte of the gained of embodiment 2 as electrolyte and barrier film, with LiFePO4, conductive charcoal
Black, adhesive PVDF (mass ratio 9:0.4:0.6) mixture as positive pole, with graphite, conductive black, adhesive PVDF (matter
Amount compares 9.2:0.3:0.5) mixture constitutes lithium ion battery as negative pole.Then carry out between 2.5-4.2V under 0.2C
Charge-discharge test, the charging of gained, discharge curve and cycle performance are illustrated in Fig. 2.
Embodiment 8
Using the composite gel polymer electrolyte of the gained of embodiment 3 as electrolyte and barrier film, with LiFePO4, conductive charcoal
Black, adhesive PVDF (mass ratio 9:0.4:0.6) mixture as positive pole, with graphite, conductive black, adhesive PVDF (matter
Amount compares 9.2:0.3:0.5) mixture constitutes lithium ion battery as negative pole.Then carry out between 2.5-4.2V under 0.2C
Charge-discharge test, the charging of gained, discharge curve and cycle performance are illustrated in Fig. 3.
Comparative example 2
By commercial li-ion battery diaphragm (Celgard 2730, PE) as barrier film, using LIB315 as electrolyte, with stone
Ink, conductive black, adhesive PVDF (mass ratio 9.2:0.3:0.5) mixture constitutes lithium ion battery as negative pole.Then
Carry out charge-discharge test between 2.5-4.2V under 0.2C, the charging of gained, discharge curve and cycle performance are illustrated in Fig. 4.
From the table 1 from the point of view of the Comparative result of embodiment 1-6 and comparative example 1, the lithium based on solid polymer electrolyte material
Ion battery gel polymer electrolyte has high ionic conductivity, high lithium ion mobility coefficient, and electrolyte is complete
The temperature of volatilization is all higher than 140 DEG C, significantly larger than the 65 of comparative example DEG C, with very excellent security performance.
From the point of view of result (Fig. 2, Fig. 3 and Fig. 4) contrast of embodiment 7,8 and comparative example 2, using plural gel electrostrictive polymer
The lithium secondary battery of solution matter, has less polarization in charge and discharge process, and capacity keeps stable, this explanation plural gel
The lithium ion battery that polymer dielectric is assembled into has higher energy efficiency.
The situation of summary comparative example and embodiment, shows composite gel polymer electrolyte for high safety performance
There is good attraction for lithium secondary battery.
Claims (20)
1. a kind of composite gel polymer electrolyte, it is characterised in that described composite gel polymer electrolyte is by combined electrolysis
Plasma membrane and liquid electrolyte are constituted, and wherein composite electrolyte membrane is made up of two-layer or multilayer, and wherein at least has one layer to gather for solid-state
Polymer electrolyte, at least one layer is the macromolecular materials different from the solid polymer electrolyte.
2. composite gel polymer electrolyte as claimed in claim 1, it is characterised in that the solid polymer electrolyte is
The polymer of lithium ion can be transmitted.
3. composite gel polymer electrolyte as claimed in claim 2, it is characterised in that described to transmit the poly- of lithium ion
Compound include polyethylene glycol oxide (PEO), PPOX (PPO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA),
Poly- borate or poly- lithium borate salt, poly-aluminium acid esters or poly-aluminium acid esters lithium salts, polysiloxanes, poly-phosphine piperazine, side chain have carboxylic acid lithium
Polymer, side chain have the polymer of Sulfonic Lithium or their copolymer, blend, also may be used simultaneously in these polymer
To add the low lithium salts of molecular weight and inorganic filler.
4. composite gel polymer electrolyte as claimed in claim 3, it is characterised in that described poly- lithium borate salt is poly- third
Olefin(e) acid, boric acid, oxalic acid and Li2CO3Either LiOH reacts resulting polymers or polyvinyl alcohol, boric acid, oxalic acid and Li2CO3Or
LiOH reacts resulting polymers.
5. composite gel polymer electrolyte as claimed in claim 3, it is characterised in that described side chain has carboxylic acid lithium
Polymer is Lithium polyacrylate.
6. composite gel polymer electrolyte as claimed in claim 3, it is characterised in that described side chain has Sulfonic Lithium
Polymer is the lithium salts of Nafion membrane.
7. the composite gel polymer electrolyte as described in any one in claim 3-6, it is characterised in that described molecule
The low lithium salts of amount is LiClO4、LiBF4、LiPF6、LiAsF6, LiBOB (di-oxalate lithium borate), LiDFBO (difluoro oxalate boric acid
Lithium), LiCF3SO3、LiN(CF3SO2)2、LiN(RfOSO2)2、LiC(SO2CF3)3Or the mixing of both or various lithium salts
Thing.
8. the composite gel polymer electrolyte as described in any one in claim 3-6, it is characterised in that described inorganic to fill out
Material includes aluminum oxide, silica, titanium oxide, zirconium oxide, aLi2O-bAl2O3-cTiO2-dP2O5(a, b, c, d be located at 1-100 it
Between) compound of composition, montmorillonite, the mixture of molecular sieve or both or multiple compounds.
9. the composite gel polymer electrolyte as described in any one in claim 1-8, it is characterised in that this described is consolidated
Macromolecular material beyond state polymer dielectric not only includes the solid polymer electricity different from the solid polymer electrolyte
Xie Zhi, also including polyolefin, polyamide, polyimides, poly- aramid fiber, polyarylether, polyester, while also include they copolymer,
Blend, it is also possible to add suitable inorganic filler.
10. composite gel polymer electrolyte as claimed in claim 9, it is characterised in that described polyolefin includes poly- second
Alkene, polypropylene, Kynoar, poly- (biasfluoroethylene-hexafluoropropylene).
11. composite gel polymer electrolytes as claimed in claim 9, it is characterised in that described polyester includes poly- (second two
Alcohol-terephthalate).
12. composite gel polymer electrolytes as described in any one in claim 1-11, it is characterised in that described liquid
Body electrolyte includes the solution of organic compound or ionic liquid and lithium salts.
A kind of 13. preparation methods of the composite gel polymer electrolyte as described in any one in claim 1-12, it is special
Levy is to concretely comprise the following steps：
(1) solid polymer electrolyte membrane is prepared initially with solwution method or heating mixing method；
(2) and then using solwution method, heating mixing method, infusion method, casting method or Electrospinning Method, will be with above-mentioned solid polymer electrolyte
Macromolecular material beyond matter is compound with above-mentioned solid polymer electrolyte membrane, forms the structure of composite membrane of two-layer or multilayer；
(3) above-mentioned composite membrane is placed in vacuum drying chamber, heating, vacuum is dried, removes possible trace solvent；
(4) above-mentioned dried composite membrane is immersed in 1 minute to 48 hours in liquid electrolyte in anhydrous and oxygen-free environment, is obtained
To lithium ion battery gel polymer electrolyte.
14. methods as claimed in claim 13, it is characterised in that the thickness of the solid polymer electrolyte membrane described in step (1)
Spend for 1-30 microns.
15. methods as described in any one in claim 13,14, it is characterised in that the two-layer composite membrane described in step (2)
One layer is above-mentioned solid polymer electrolyte membrane in structure, and in addition one layer is the macromolecule material beyond the solid polymer electrolyte
Material film.
16. methods as described in any one in claim 13,14, it is characterised in that the composite membrane of step (2) multilayer
At least middle to have one layer for above-mentioned solid polymer electrolyte membrane in structure, at least one layer is the solid polymer electrolyte
Polymer material film in addition.
17. methods as described in any one in claim 13-16, it is characterised in that the composite membrane described in step (2)
Thickness is 5-60 microns.
18. methods as described in any one in claim 13-17, it is characterised in that the anhydrous and oxygen-free ring described in step (4)
Border is glove box, is argon gas atmosphere in glove box, and moisture is less than 1ppm.
19. methods as described in any one in claim 13-17, it is characterised in that the liquid electrolyte described in step (4)
Including organic compound or the solution of ionic liquid and lithium salts.
A kind of 20. applications of the composite gel polymer electrolyte as described in any one in claim 1-19, the application is work
For the electrolyte and barrier film of a kind of secondary cell, the negative pole of the secondary cell be lithium metal, the alloy of lithium metal, material with carbon element, tin,
The alloy of the alloy, silicon or silicon of tin, just extremely LiMO2(a kind of in M '=Co, Ni, Mn, Co, two kinds of elements or two kinds with
Upper element) or LiM ' PO4(a kind of in M '=Fe, Mn, Co, two kinds or 2 kinds of elements and more than).
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