CN103390501B - Gel polymer electrolyte film and preparation method thereof - Google Patents
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Abstract
A kind of gel polymer electrolyte film, comprises polymeric substrates and the ionic liquid being mixed in polymeric substrates, and polymeric substrates and ionic liquid mass ratio are 10: 3 ~ 2: 1；Wherein, polymeric substrates is polymethyl methacrylate；Ionic liquid has following structural formula,Wherein, R is methoxy ethyl；Y‑For BF4 ‑、PF6 ‑、(CF3SO2)2N‑Or CF3SO3 ‑.State that the safety of gel polymer electrolyte film is higher and environmental friendliness, can be applicable to ultracapacitor.Additionally, also provide the preparation method of a kind of gel polymer electrolyte film.
Description
[technical field]
The present invention relates to the electrolyte field of ultracapacitor, particularly to a kind of gel polymer electrolyte film
And its preparation method.
[background technology]
Ultracapacitor is a kind of novel energy storage component between rechargeable battery and capacitor, has volume
Little, capacity is big, charging rate is fast, have extended cycle life, discharging efficiency height, operating temperature range width, reliable
Property the advantage such as good and contaminant-free maintenance-free, be a kind of novel, efficient, practical energy accumulating device, thus
It is widely used in the AC-battery power source etc. of military field, device for mobile communication, computer and electric automobile.
Ultracapacitor working electrolyte is divided into aqueous electrolyte, organic liquid electrolyte and polymer dielectric.
The decomposition voltage of aqueous electrolyte is low, thus studies less.At present, widely used liquid electrolyte has
The advantage that electrical conductivity is high, but owing to it contains organic solvent inflammable, volatile, it is at charge and discharge process
In discharge fuel gas, particularly (such as high-power discharge and recharge, overcharge under some unconventional working condition
Cross and put) produce big calorimetric and can accelerate the generation of gas, cause inner pressure of battery to increase, gas leaks, even
Blast on fire, thus there is serious potential safety hazard.Polymer dielectric ultracapacitor and polymer electrolytic
Matter lithium ion battery is because having the advantages such as safety, No leakage, leakage current be little and studied persons are paid attention to.Gu
Electrical conductivity relatively low (10 under state polymer dielectric room temperature-5~10-4S/cm) so that it is application is restricted, thus solidifying
Xanthan polymer electrolyte becomes research emphasis.But liquid organic electrolyte is inflammable, volatile, heat stability
, there is potential safety hazard in the shortcoming such as bad.
[summary of the invention]
Based on this, it is necessary to provide a kind of safety gel polymer electrolyte film higher, eco-friendly and
Its preparation method.
A kind of gel polymer electrolyte film, comprises polymeric substrates and and is mixed in described polymeric substrates
Ionic liquid, described polymeric substrates and described ionic liquid mass ratio are 10: 3 ~ 2: 1；Wherein, described poly-
Polymer substrates is polymethyl methacrylate；Described ionic liquid has following structural formula,
Wherein, R is methoxy ethyl；Y-For BF4 -、PF6 -、(CF3SO2)2N-Or CF3SO3 -。
Wherein in an embodiment, the relative molecular mass of described polymethyl methacrylate is 50,000 ~ 100
Ten thousand.
The preparation method of a kind of gel polymer electrolyte film, comprises the steps:
Step one: provide or prepare 3-Methylimidazole. and compound A that formula is RX；Wherein, R is methoxy
Base ethyl；X is halogens chlorine, bromine, iodine；
Step 2: be to mix at 1: 1.05 ~ 1: 1.2 according to mol ratio by 3-Methylimidazole. and described compound A,
Being heated to 60 DEG C ~ 80 DEG C under oxygen free condition, stir 24 hours ~ 72 hours, there is synthetic reaction in stirring,
To having the compound B that following structural formula represents,
Step 3: be M by described compound B and formula+Y-Salt according to mol ratio be 1: 1 ~ 1: 1.1 mixing,
Add deionized water, stir 5 hours ~ 24 hours in temperature is 20 DEG C ~ 40 DEG C, ion-exchange reactions occurs,
Obtain that there is the ionic liquid C that following structural formula represents,
Wherein, M+For Na+、K+Or NH4 +；Y-For BF4 -、PF6 -、(CF3SO2)2N-Or CF3SO3 -；
Step 4: be to mix at 3: 10 ~ 1: 2 according to mass ratio by described ionic liquid C and polymethyl methacrylate
Close, add organic solvent, in the environment of anhydrous and anaerobic, be heated to 40 DEG C ~ 60 DEG C, and stir formation all
Even solution；And
Step 5: be cast on substrate by described homogeneous solution, in vacuum atmosphere, 80 DEG C ~ 100 DEG C are dried
24 hours ~ 48 hours, peel off and obtain described gel polymer electrolyte film.
Wherein in an embodiment, after step 2, also include the purification step to described compound B: first
Wash by ethyl acetate after first the reactant liquor of described synthetic reaction being stood cooling, then by the product after washing
Vacuum drying, obtains the described compound B of purification.
Wherein in an embodiment, in step 3, described deionized water and the mass ratio of described compound B
It is 1: 1 ~ 3: 1.
Wherein in an embodiment, after step 3, also include the purification step to described ionic liquid C:
Dichloromethane is used extract to be obtained by extraction, then by described extraction the mixed liquor after described ion-exchange reactions
Take liquid and use deionized water back extraction, until with saturated AgNO3Aqueous solution titration produces without precipitation, then
Described extract evaporation and concentration final vacuum is dried, obtains the described ionic liquid C of purification.
Wherein in an embodiment, in step 4, described organic solvent is oxolane, acetonitrile or N-first
Base ketopyrrolidine；Wherein, described organic solvent is 1: 5 ~ 3: 10 with the mass ratio of described polymethyl methacrylate.
Above-mentioned gel polymer electrolyte film include polymeric substrates polymethyl methacrylate (PMMA) with
And it is mixed in the ionic liquid in polymethyl methacrylate (PMMA), due to having of this ionic liquid
Electrical conductivity high (about 10ms/cm), fusing point low (about-60 DEG C), electrochemical window width (about 4V),
Good stability, the most volatile and nonflammable feature, polymeric substrates polymethyl methacrylate
(PMMA), after being combined with this ionic liquid, the content of organic solvent in dielectric film is not only reduced,
Improve the safety of gel polymer electrolyte film, reduce its inflammability and volatility, improve electrolysis
The stability of plasma membrane, but also improve the film property of polymethyl methacrylate, therefore, above-mentioned gel gathers
The safety of polymer electrolyte membrane is higher and environmental friendliness, can be applicable to ultracapacitor.And above-mentioned gel gathers
The preparation method of polymer electrolyte membrane is simple and simple to operate, is conducive to extensive preparation.
[accompanying drawing explanation]
Fig. 1 is the preparation method flow chart of the gel polymer electrolyte film of an embodiment.
[detailed description of the invention]
Below mainly in combination with drawings and the specific embodiments gel polymer electrolyte film and preparation method thereof made into
One step detailed description.
The gel polymer electrolyte film of one embodiment, comprises polymeric substrates and is mixed in polymeric substrates
In ionic liquid, polymeric substrates and ionic liquid mass ratio are 10: 3 ~ 2: 1；Wherein, polymeric substrates is
Polymethyl methacrylate (PMMA)；Ionic liquid has following structural formula,
Wherein, R is methoxy ethyl；Y-For BF4 -、PF6 -、(CF3SO2)2N-Or CF3SO3 -。
Wherein in an embodiment, the relative molecular mass of polymethyl methacrylate is 50,000 ~ 1,000,000.
Above-mentioned gel polymer electrolyte film include polymeric substrates polymethyl methacrylate (PMMA) with
And it is mixed in the ionic liquid in polymeric substrates polymethyl methacrylate (PMMA), due to this ion
Liquid has electrical conductivity high (about 10ms/cm), fusing point low (about-60 DEG C), electrochemical window width (4V
Left and right), good stability, the most volatile and nonflammable feature, polymeric substrates poly-methyl methacrylate
After ester (PMMA) is combined with this ionic liquid, not only reduce the content of organic solvent in dielectric film,
Improve the safety of gel polymer electrolyte film, reduce its inflammability and volatility, improve electrolysis
The stability of plasma membrane, but also improve the film property of polymethyl methacrylate, therefore, above-mentioned gel gathers
The safety of polymer electrolyte membrane is higher and environmental friendliness, can be applicable to ultracapacitor.
As it is shown in figure 1, the preparation method of the gel polymer electrolyte film of an embodiment, including walking as follows
Rapid:
Step S210: provide or prepare 3-Methylimidazole. and compound A that formula is RX；Wherein, R is
Methoxy ethyl；X is chlorine, bromine or iodine.
Step S220: be to mix at 1: 1.05 ~ 1: 1.2 according to mol ratio by 3-Methylimidazole. and compound A,
It is heated to 60 DEG C ~ 80 DEG C under oxygen free condition, stirs 24 hours ~ 72 hours, synthetic reaction occurs, is had
Following structural formula is had to represent B,
Wherein in an embodiment, also include the purification step to compound B after step S220: first
Wash by ethyl acetate after the reactant liquor of synthetic reaction is stood cooling, then the product vacuum after washing is done
Dry, obtain the compound B of purification.Wherein, the reactant liquor of synthetic reaction ethyl acetate is washed three times；Vacuum
The temperature being dried is 80 DEG C.
It is pointed out that the oxygen free condition in present embodiment refers at N2Or atmosphere of inert gases is inferior.
Step S230: be M by compound B and formula+Y-Salt according to mol ratio be 1: 1 ~ 1: 1.1 mixing,
Add deionized water, stir 5 hours ~ 24 hours in temperature is 20 DEG C ~ 40 DEG C, ion-exchange reactions occurs,
Obtain that there is the ionic liquid C that following structural formula represents,
Wherein, M+For Na+、K+Or NH4 +；Y-For BF4 -、PF6 -、(CF3SO2)2N-Or CF3SO3 -。
Wherein in an embodiment, in step S230, deionized water with the mass ratio of compound B is
1∶1~3∶1。
Wherein in an embodiment, after step S230, also include the purification step to ionic liquid C: will
Mixed liquor after ion-exchange reactions uses dichloromethane that extract is obtained by extraction, and is then used by extract and goes
Ionized water back extraction, until with saturated AgNO3Aqueous solution titration produces without precipitation, is then steamed by extract
Send out concentration final vacuum to be dried, obtain the ionic liquid C of purification.
The synthetic route synthesizing above-mentioned ionic liquid C is as follows:
Step S240: be to mix at 3: 10 ~ 1: 2 according to mass ratio by ionic liquid C and polymethyl methacrylate,
Add organic solvent, in the environment of anhydrous and anaerobic, be heated to 40 DEG C ~ 60 DEG C, and it is the most molten to stir formation
Liquid.
Wherein in an embodiment, in step S240, organic solvent is oxolane (THF), acetonitrile (AN)
Or N-Methyl pyrrolidone (NMP).Organic solvent itself is also a kind of plasticizer, simultaneously works as solvent and increasing
Mould the effect of agent.Organic solvent is 1: 5 ~ 3: 10 with the mass ratio of polymethyl methacrylate (PMMA).
Step S250: be cast on substrate by homogeneous solution, in vacuum atmosphere, 80 DEG C ~ 100 DEG C are dried 24
Hour ~ 48 hours, peel off and obtain gel polymer electrolyte film.In the present embodiment, substrate is sheet glass.
The preparation method of above-mentioned gel polymer electrolyte film is simple and simple to operate, is conducive to extensive preparation.
It is below specific embodiment part:
Embodiment 1
Preparation 1-methoxy ethyl-3-methyl imidazolium tetrafluoroborate/PMMA gel polymer electrolyte film
(1) synthesis 1-methoxy ethyl-3-Methylimidazole. villaumite
3-Methylimidazole. (83g, 1mol) and methoxyl group ethyl chloride it is separately added in the flask of 250mL
(103.4g, 1.1mol) mixes；Then at N2Under atmosphere protection, being heated to 60 DEG C, stirring occurs synthesis anti-
Answer 72 hours；Stand cooling subsequently, wash product 3 times by ethyl acetate, and be vacuum dried at 80 DEG C,
Obtaining lurid 1-methoxy ethyl-3-Methylimidazole. villaumite, yield is 71%.
(2) synthesis ionic liquid 1-methoxy ethyl-3-methyl imidazolium tetrafluoroborate
By above-mentioned prepared 1-methoxy ethyl-3-Methylimidazole. villaumite (88.5g, 0.5mol), NaBF4(55g,
0.5mol) add in the flask of 500mL with 100mL deionized water, there is ion exchange in stirring at 30 DEG C
React 10 hours；After having reacted, it is thus achieved that mixed liquor；Then, mixed liquor 250mL dichloromethane extracts
3 times, combining extraction liquid；Then extract is used every time 60mL deionized water back extraction, until with saturated
AgNO3Aqueous solution titration produces without precipitation；After dichloromethane concentrates with Rotary Evaporators, 80 DEG C of vacuum
It is dried and obtains colourless liquid in 48 hours, be ionic liquid 1-methoxy ethyl-3-Methylimidazole. Tetrafluoroboric acid
Ionic liquid.
The synthetic reaction formula of ionic liquid 1-methoxy ethyl-3-methyl imidazolium tetrafluoroborate is as follows:
The nuclear magnetic resoance spectrum diagram data of ionic liquid 1-methoxy ethyl-3-methyl imidazolium tetrafluoroborate is as follows:
1H NMR(CDCl3,400MHz,ppm):9.12(s,1H),7.78(s,1H),7.72(s,1H),4.61
(t,2H),4.35(t,2H),3.87(s,3H),3.83(s,3H)。
(3) 1-methoxy ethyl-3-methyl imidazolium tetrafluoroborate/PMMA gel polymer electrolyte is prepared
Film
Being sequentially added into 100gPMMA(relative molecular mass in the there-necked flask of 500mL is 50,000), 50g
1-methoxy ethyl-3-methyl imidazolium tetrafluoroborate and 20g THF.At dry noble gas N2Protection
Under, it is warmed up to 40 DEG C, and stirring allows PMMA dissolve, and makes system become homogeneous solution.By above-mentioned the most molten
Liquid casts on the sheet glass of cleaning, is transferred quickly in vacuum drying oven, is dried 24 hours at 80 DEG C,
Slough solvent, after being cooled to room temperature, at full noble gas N2Glove box in separate on sheet glass transparent
Elastica be 1-methoxy ethyl-3-methyl imidazolium tetrafluoroborate/PMMA gel polymer electrolyte
Film.
Embodiment 2
Preparation 1-methoxy ethyl-3-Methylimidazole. hexafluorophosphate/PMMA gel polymer electrolyte film
(1) synthesis 1-methoxy ethyl-3-Methylimidazole. bromide
3-Methylimidazole. (83g, 1mol) and methoxyl group bromoethane it is separately added in the flask of 250mL
(166.8g, 1.2mol) mixes；Then at Ar2Under atmosphere protection, being heated to 80 DEG C, stirring occurs synthesis anti-
Answer 48 hours；Stand cooling subsequently, wash product 3 times by ethyl acetate, and be vacuum dried at 80 DEG C,
Obtaining lurid 1-methoxy ethyl-3-Methylimidazole. bromide, yield is 74%.
(2) synthesis ionic liquid 1-methoxy ethyl methoxy ethyl-3-Methylimidazole. hexafluorophosphate
By above-mentioned prepared 1-methoxy ethyl-3-Methylimidazole. bromide (110.5g, 0.5mol), KPF6(92g,
0.5mol) add in the flask of 500mL with 150mL deionized water, there is ion exchange in stirring at 20 DEG C
React 24 hours；After having reacted, it is thus achieved that mixed liquor；Then, mixed liquor 250mL dichloromethane extracts
3 times, combining extraction liquid；Then extract is used every time 60mL deionized water back extraction, until with saturated
AgNO3Aqueous solution titration produces without precipitation；After dichloromethane concentrates with Rotary Evaporators, 80 DEG C of vacuum
It is dried and obtains colourless liquid in 48 hours, be ionic liquid 1-methoxy ethyl-3-Methylimidazole. hexafluorophosphoric acid
Salt.
The synthetic reaction formula of ionic liquid 1-methoxy ethyl-3-Methylimidazole. hexafluorophosphate is as follows:
The nuclear magnetic resoance spectrum diagram data of ionic liquid 1-methoxy ethyl-3-Methylimidazole. hexafluorophosphate is as follows:.
1H NMR(CDCl3,400MHz,ppm):9.14(s,1H),7.78(s,1H),7.72(s,1H),4.62
(t,2H),4.37(t,2H),3.88(s,3H),3.85(s,3H)。
(3) 1-methoxy ethyl-3-Methylimidazole. hexafluorophosphate/PMMA gel polymer electrolyte is prepared
Film
Being sequentially added into 100gPMMA(relative molecular mass in the there-necked flask of 500mL is 1,000,000),
30g 1-methoxy ethyl-3-Methylimidazole. hexafluorophosphate and 30g AN.At dry noble gas N2Guarantor
Protect down, be warmed up to 50 DEG C, and stirring allows PMMA dissolve, and makes system become homogeneous solution.By above-mentioned uniformly
Solution-cast, on clean sheet glass, is transferred quickly in vacuum drying oven, is dried 48 hours at 80 DEG C,
Slough solvent, after being cooled to room temperature, separate on sheet glass transparent in the glove box of full noble gas Ar
Elastica be 1-methoxy ethyl-3-Methylimidazole. hexafluorophosphate/PMMA gel polymer electrolyte
Film.
Embodiment 3
Double (fluoroform sulphonyl) inferior amine salt of preparation 1-methoxy ethyl-3-Methylimidazole ./PMMA gelatin polymer electricity
Solve plasma membrane
(1) synthesis 1-methoxy ethyl-3-Methylimidazole. iodine salt
3-Methylimidazole. (83g, 1mol) and methoxyl group iodoethane it is separately added in the flask of 250mL
(204.6g, 1.1mol) mixes；Then at N2Under atmosphere protection, being heated to 65 DEG C, stirring occurs synthesis anti-
Answer 60 hours；Stand cooling subsequently, wash product 3 times by ethyl acetate, and be vacuum dried at 80 DEG C,
Obtaining lurid 1-methoxy ethyl-3-Methylimidazole. iodine salt, yield is 78%.
(2) double (fluoroform sulphonyl) inferior amine salt of synthesis ionic liquid 1-methoxy ethyl-3-Methylimidazole.
By above-mentioned prepared 1-methoxy ethyl-3-Methylimidazole. iodine salt (134g, 0.5mol), fluoroform sulphonyl Asia
Amine potassium (CF3SO2)2NK (159.5g, 0.5mol) and 134mL deionized water add in the flask of 500mL,
At 30 DEG C there is ion-exchange reactions 12 hours in stirring；After having reacted, it is thus achieved that mixed liquor；Then, mixing
Liquid 250mL dichloromethane extracts 3 times, combining extraction liquid；Then extract use 60mL go every time
Ionized water back extraction, until with saturated AgNO3Aqueous solution titration produces without precipitation；Dichloromethane is mutually with rotation
After turning evaporimeter concentration, 80 DEG C of vacuum drying obtain colourless liquid in 48 hours, are ionic liquid 1-methoxy
Double (fluoroform sulphonyl) the inferior amine salt ionic liquid of base ethyl-3-methylimidazole.
The synthetic reaction formula of double (fluoroform sulphonyl) inferior amine salt of ionic liquid 1-methoxy ethyl-3-Methylimidazole. is such as
Under:
The nmr spectrum of double (fluoroform sulphonyl) inferior amine salt of ionic liquid 1-methoxy ethyl-3-Methylimidazole.
Data are as follows:
1H NMR(CDCl3,400MHz,ppm):9.15(s,1H),7.79(s,1H),7.72(s,1H),4.63
(t,2H),4.39(t,2H),3.88(s,3H),3.85(s,3H)。
(3) prepare double (fluoroform sulphonyl) inferior amine salt/PMMA gel of 1-methoxy ethyl-3-Methylimidazole. to gather
Polymer electrolyte membrane
Being sequentially added into 100gPMMA(relative molecular mass in the there-necked flask of 500mL is 500,000), 45g
Double (fluoroform sulphonyl) inferior amine salt of 1-methoxy ethyl-3-Methylimidazole. and 25g NMP.At dry indifferent gas
Body N2Protection under, be warmed up to 50 DEG C, and stir allow PMMA dissolve, make system become homogeneous solution.
Above-mentioned homogeneous solution is cast on the sheet glass of cleaning, be transferred quickly in vacuum drying oven, at 100 DEG C
It is dried 24 hours, sloughs solvent, after being cooled to room temperature, at full noble gas N2Glove box in peel off
Go out elastica transparent on sheet glass and be double (fluoroform sulphonyl) inferior amine salt of 1-methoxy ethyl-3-Methylimidazole.
/ PMMA gel polymer electrolyte film.
Embodiment 4
Preparation 1-methoxy ethyl-3-Methylimidazole. fluoroform sulphonate/PMMA gel polymer electrolyte film:
(1) synthesis 1-methoxy ethyl-3-Methylimidazole. villaumite
3-Methylimidazole. (83g, 1mol) and methoxyl group ethyl chloride (99.2 it is separately added in the flask of 250mL
G, 1.05mol) mixing；Then at N2Under atmosphere protection, being heated to 70 DEG C, there is synthetic reaction 24 in stirring
Hour；Stand cooling subsequently, wash product 3 times by ethyl acetate, and be vacuum dried at 80 DEG C,
To lurid 1-methoxy ethyl-3-Methylimidazole. villaumite, yield is 72%.
(2) synthesis 1-methoxy ethyl-3-Methylimidazole. fluoroform sulphonate
By above-mentioned prepared 1-methoxy ethyl-3-Methylimidazole. villaumite (88.5g, 0.5mol), CF3SO3NH4(92
G, 0.55mol) and 265mL deionized water add 500mL flask in, at 40 DEG C stirring occur ion
Exchange reaction 5 hours；After having reacted, it is thus achieved that mixed liquor；Then, mixed liquor 250mL dichloromethane
Extract 3 times, combining extraction liquid；Then extract is used every time 60mL deionized water back extraction, until using
Saturated AgNO3Aqueous solution titration produces without precipitation；After dichloromethane concentrates with Rotary Evaporators, 80 DEG C
It is vacuum dried and obtains colourless liquid in 48 hours, be 1-methoxy ethyl-3-Methylimidazole. fluoroform sulphonate
Ionic liquid.
The synthetic reaction formula of ionic liquid 1-methoxy ethyl-3-Methylimidazole. fluoroform sulphonate is as follows:
The nuclear magnetic resoance spectrum diagram data of ionic liquid 1-methoxy ethyl-3-Methylimidazole. fluoroform sulphonate is such as
Under:
1H NMR(CDCl3,400MHz,ppm):9.13(s,1H),7.79(s,1H),7.72(s,1H),4.63
(t,2H),4.39(t,2H),3.88(s,3H),3.85(s,3H)。
(3) 1-methoxy ethyl-3-Methylimidazole. fluoroform sulphonate/PMMA gel polymer electrolyte is prepared
Plasma membrane
Being sequentially added into 100gPMMA(relative molecular mass in the there-necked flask of 500mL is 500,000),
50g1-methoxy ethyl-3-Methylimidazole. fluoroform sulphonate and 20g THF.At dry noble gas N2
Protection under, be warmed up to 60 DEG C, and stir allow PMMA dissolve, make system become homogeneous solution.By above-mentioned
Homogeneous solution casts on the sheet glass of cleaning, is transferred quickly in vacuum drying oven, is dried 36 at 90 DEG C
Hour, slough solvent, after being cooled to room temperature, at full noble gas N2Glove box in separate sheet glass
Upper transparent elastica is 1-methoxy ethyl-3-Methylimidazole. fluoroform sulphonate/PMMA gel polymerisation
Thing dielectric film.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed,
But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for this area
Those of ordinary skill for, without departing from the inventive concept of the premise, it is also possible to make some deformation and
Improving, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended
Claim is as the criterion.
Claims (5)
1. the preparation method of a gel polymer electrolyte film, it is characterised in that comprise the steps:
Step one: provide or prepare 3-Methylimidazole. and compound A that formula is RX；Wherein, R is methoxy
Base ethyl；X is chlorine, bromine or iodine；
Step 2: be that 1:1.05～1:1.2 mixes with described compound A according to mol ratio by described 3-Methylimidazole.,
It is heated to 60 DEG C～80 DEG C under anaerobic, stirs 24 hours～72 hours, synthetic reaction occurs, obtains
There is the compound B that following structural formula represents,
Step 3: be M by described compound B and formula+Y-Salt be 1:1 according to mol ratio～1:1.1 mixing,
Add deionized water, stir 5 hours～24 hours in temperature is 20 DEG C～40 DEG C, ion-exchange reactions occurs,
Obtain that there is the ionic liquid C that following structural formula represents,
Wherein, M+For Na+、K+Or NH4 +；Y-For BF4 -、PF6 -、(CF3SO2)2N-Or CF3SO3 -；
Step 4: be that 3:10～1:2 mixes with polymethyl methacrylate according to mass ratio by described ionic liquid C
Close, add organic solvent, in the environment of anhydrous and anaerobic, be heated to 40 DEG C～60 DEG C, and stir formation all
Even solution；And
Step 5: be cast on substrate by described homogeneous solution, in vacuum atmosphere, 80 DEG C～100 DEG C are dried
24 hours～48 hours, peel off and obtain described gel polymer electrolyte film.
The preparation method of gel polymer electrolyte film the most according to claim 1, it is characterised in that
The purification step to described compound B is also included: first by the reactant liquor of described synthetic reaction after step 2
Wash by ethyl acetate after standing cooling, then the product vacuum after washing is dried, obtains the described of purification
Compound B.
The preparation method of gel polymer electrolyte film the most according to claim 1, it is characterised in that
In step 3, described deionized water is 1:1～3:1 with the mass ratio of described compound B.
The preparation method of gel polymer electrolyte film the most according to claim 1, it is characterised in that
The purification step to described ionic liquid C is also included: by mixing after described ion-exchange reactions after step 3
Closing liquid uses dichloromethane that extract is obtained by extraction, and then described extract is used deionized water back extraction,
Until with saturated AgNO3Aqueous solution titration produces without precipitation, then by true after described extract evaporation and concentration
Empty dry, obtain the described ionic liquid C of purification.
The preparation method of gel polymer electrolyte film the most according to claim 1, it is characterised in that
In step 4, described organic solvent is oxolane, acetonitrile or N-Methyl pyrrolidone；Wherein, have described in
Machine solvent is 1:5～3:10 with the mass ratio of described polymethyl methacrylate.
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| CN1367276A (en) * | 2001-01-26 | 2002-09-04 | 韩国科学技术研究院 | Method for producing fine fibrous polymer fabric |
| CN101440188A (en) * | 2008-12-30 | 2009-05-27 | 哈尔滨工业大学 | Lithium ionic cell gel type ion liquid / polymer electrolyte and preparation thereof |
| CN102299376A (en) * | 2011-06-24 | 2011-12-28 | 中国科学院宁波材料技术与工程研究所 | Polymer solid electrolyte membrane and preparation method thereof |
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