CN1330107A - Optically triggered polymerization process for preparing electrolyte film of gel-state lithium ion polymer - Google Patents

Optically triggered polymerization process for preparing electrolyte film of gel-state lithium ion polymer Download PDF

Info

Publication number
CN1330107A
CN1330107A CN 01126112 CN01126112A CN1330107A CN 1330107 A CN1330107 A CN 1330107A CN 01126112 CN01126112 CN 01126112 CN 01126112 A CN01126112 A CN 01126112A CN 1330107 A CN1330107 A CN 1330107A
Authority
CN
China
Prior art keywords
gel
lithium ion
ion polymer
state lithium
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 01126112
Other languages
Chinese (zh)
Inventor
付延鲍
马晓华
杨清河
宗祥福
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fudan University
Original Assignee
Fudan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fudan University filed Critical Fudan University
Priority to CN 01126112 priority Critical patent/CN1330107A/en
Publication of CN1330107A publication Critical patent/CN1330107A/en
Pending legal-status Critical Current

Links

Landscapes

  • Secondary Cells (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

An optically triggering process for preparing gel-state Li-ion polymer electrolyte film used as solid electrolyte of li-ion battery or other electrochemical elements features that acrylate derivatives are used as monomer, the multi-function-radical substance is used as cross-linking agent, and the ultraviolet ray is used to trigger polymerization. Its advantages are simple process, one-step filming forming and stable performance of film.

Description

The optically triggered polymerization process for preparing of electrolyte film of gel-state lithium ion polymer
Technical field the invention belongs to the optically triggered polymerization process for preparing of electrolytic membrane of lithium-ion battery.
The background technology lithium ion battery is the mechanism of new electrochemical power sources that grows up after lead-acid cell, nickel-cadmium cell and nickel-hydrogen cell, characteristics such as specific storage is big, memory-less effect, environmental friendliness that it has.Being widely used in now in the various portable electric appts is the liquid electrolyte lithium ion battery, releases market in 1991 by Japanese Sony Corporation at first.The liquid electrolyte lithium ion battery adopts liquid electrolyte solution, and its composition is mainly by ethyl-carbonate (ethylenecarbonate (EC), C 3H 4O 3), diethyl carbonate (diethyl carbonate (DEC), C 5H 10O 3), methylcarbonate (dimethyl carbonate (DMC), C 3H 6O 3), propyl carbonate (propylene carbonate (PC), C 4H 6O 3) wait organic solvent and various inorganic lithium salt such as LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiCF 3SO 3And LiN (CF 3SO 2) 2The lithium salt solution that is mixed with is an electrolyte solution.These lithium salt solutions provide specific conductivity greater than 10 for lithium ion battery -3The electrolyte solution of S/cm has satisfied the requirement of the low internal resistance of lithium ion battery, high charge-discharge speed.The weak point of liquid lithium ionic cell is to have adopted organic solution easily mobile, easy to leak, in use, be easy to generate danger such as leakage, corrosion and burning, thereby its security is relatively poor.
In order to improve the performance of liquid electrolyte lithium ion battery, the investigator by with polymer blend method, make the liquid electrolyte solid state, produced a kind of new lithium ion battery-polymer electrolyte lithium-ion battery.The preparation of polymer dielectric film material is the gordian technique of polymer Li-ion battery.Typical case's representative of this respect is invention (the US Patent5 of Bellcore company, 540,741) be the porous-film technology of parent and by the film forming gel polymer electrolyte membrane technique of teeming practice based on vinylidene-R 1216 (PVDF-HFP) multipolymer, these technology are included in liquid electrolyte in the polymeric matrix network, solve the safety problems such as leakage, corrosion and burning that exist in the liquid electrolyte lithium ion battery.But be based on the porous polymer dielectric film of Bellcore technology and the gel polymer electrolyte film that teeming practice forms, its formed polymer network structure, it is physical crosslinking structure interior by polymer molecular chain or that the effect of molecule interchain Van der Waals force forms, this physical crosslinking structure is externally during condition changing, cross-linking set disconnects easily, thereby liquid electrolyte easily from network dialysis cause performance decrease to the film surface; Bellcore porous-film technology complicated process of preparation will be through processes such as dissolving, mixing, system film, extraction, immersions, and cost is higher.
Summary of the invention the objective of the invention is to develop the preparation method of simple, the constitutionally stable three-dimensional network shape of a kind of technology electrolyte film of gel-state lithium ion polymer.The present invention adopts the preparation method of uv-light polymerization.
The present invention is a monomer with the series of acrylate derivative, containing the polyfunctional group alkene derivatives is linking agent, by UV-irradiation initiated polymerization method, make liquid lithium ion electrolyte solution and acrylic ester polymer form three-dimensional network shape electrolyte film of gel-state lithium ion polymer.Ultraviolet lamp (high voltage mercury lamp) power is 20～100W/cm, and polymerization time is 0.5～5 minute, and atmosphere temperature is 10～70 ℃.The polymkeric substance that final photopolymerization forms is a three-dimensional net structure, as the gel polymer electrolyte system of parent big liquid electrolyte containing ability and good structural stability is arranged.The gained gelling system has big electrolyte solution containing ability and temperature profile well.Gained gel polymer electrolyte film ionic conductivity is near 10 -3Scm -1The order of magnitude, no obvious pyrolysis in 0～100 ℃ of scope.
The series of acrylate derivatives monomer structural formula that the present invention adopts is: CH 2=C (R 1) CO 2(CH 2CH 2O) nR 2, R wherein 1The structure of group is H or CH 3The value of n is between 0-10; R 2Structure is C mH 2m+1, m=1～6 wherein, or-C 6H 5,-CH 2CF 3,-CH 2CF 2CF 2CF 3,-CH 2CF 2CHFCH 3,-CH (CF 3) 2,-Si (OCH 3) 3And-Si (CH 3) 3Deng.It is 5%-30% that acrylate monomer weight accounts for the mixed solution gross weight.
Multi-group crosslink agent: the alkene derivatives that comprises bifunctional, trifunctional and four-functional group.
Bifunctional crosslinking agent's structural formula is: CH 2=C (R 1)-R 2-C (R 1)=CH 2, R wherein 1Be H or CH 3, R 2Structure is :-COO (CH 2CH 2O) xCO-, x=1～12 wherein ,-COO-(CH 2CH 2O) yCOArCOO (CH 2CH 2O) yCO, y=1～10 wherein, or-CH 2COO-Ar-COOCH 2-etc.;
Trifunctional group cross-linking agent's structural formula is: (CH 2=C (R 1) CO 2(CH 2CH 2O) nCH 2) 3CR, its R 1Be H or CH 3, n=0～10, R is-CH 3Or-C 2H 5
Four-functional group linking agent structural formula is: (CH 2=C (R 1) COO (CH 2CH 2O) nCH 2) 4C, wherein R 1Be H or-CH, n=0～10.
The ratio that linking agent weight accounts for the mixed solution gross weight is 2%-30%.
Monomer of the present invention is as CH 2=C (CH 3) COOCH 3, CH 2=CHCOOCH 2CH 2OSi (CH 3) 3, CH 2=C (CH 3) COOCH 2CH 2OCH 2CH 3, CH 2=CHCOOCH 2(CF 2) 2CF 3Deng.
Linking agent of the present invention is as CH 2=CHCOO (CH 2CH 2O) 10OCCH=CH 2, CH 2=CHCOO (CH 2CH 2O) 3OCCH=CH 2, C 6H 4(CO (OCH 2CH 2) 2OCOCH=CH 2) 2, (CH 2=CHCOOCH 2) 3CCH 2CH 3Deng.
When preparing network-like gel polymer film, be used for the light trigger of uv-light polymerization reaction, can be: hydroxyl cyclohexyl phenyl ketone (C 6H 5-CO-C 6H 11(OH)), diethoxy acetophenone (C 6H 5-CO-CH (OC 2H 5) 2), 2,2-dimethyl-Alpha-hydroxy methyl phenyl ketone (C 6H 5-CO-C (CH 3) 2OH), benzophenone+triethylamine (C 6H 5-CO-C 6H 5+ (CH 3CH 2) 3N) etc., light trigger weight accounts for the 0.1%-2% of liquid gross weight.
The liquid lithium ion electrolyte salt solution is: 1M LiPF 6, EC/DEC=1/1 (w/w); 1MLiPF 6, EC/DMC=1/1 (w/w); 1M LiPF 6, EC/PC=1/1 (w/w); 1M LiPF 6, EC/DEC/PC=1/1/1 (w/w/w); 1M LiPF 6, EC/DEC/DMC=1/1/1 (w/w/w).It is 50%-90% that liquid lithium ion electrolyte salt solution weight accounts for the mixed solution gross weight.
It is monomer that the present invention adopts the series of acrylate derivative, form mixed solution with linking agent lithium-ion electrolyte liquid and initiator, this mixed solution at room temperature has good flowability, can be applied to non-woven fabrics or porous diaphragm material or battery plus-negative plate surface in advance, use UV-irradiation, initiated polymerization becomes three-dimensional netted gel state electrolyte film.Ultraviolet lamp power is 20～100W/cm, and irradiation time is 0.5～5 minute.
Acrylate and derivatives monomer structural formula thereof that the present invention adopts are CH 2=C (R 1) CO 2(CH 2CH 2O) nR 2, wherein n=0～3 are better, R 2Be C mH 2m+1, wherein m=1～3 are better, and raw material is cheap and easy to get, for example: CH 2=C (CH 3) COOCH 3CH 2=C (CH 3) COOCH 2CH 2OCH 2CH 3Deng.
Bifunctional crosslinking agent's structural formula that the present invention adopts is: CH 2=C (R 1)-R 2-C (R 1)=CH 2, wherein-R 2-structural formula is-COO (CH 2CH 2O) xCO-or-COO (CH 2CH 2O) xCO-Ar-COO (CH 2CH 2O) xCO-or-CH 2-O-CO-Ar-CO-O-CH 2-, wherein x=2～10 are better, and raw material is cheap and easy to get, for example: CH 2=CHCOO (CH 2CH 2O) 3OCCH=CH 2, C 6H 4(CO (OCH 2CH 2) 2OCOCH=CH 2) 2Deng.
The linking agent structural formula of trifunctional is: (CH 2=C (R 1) CO 2(CH 2CH 2O) nCH 2) 3CR, wherein n=0～6 are better, and raw material is cheap and easy to get, for example: (CH 2=CHCOOCH 2) 3CCH 2CH 3, (CH 2=CHCOOCH 2CH 2O) 3CCH 2CH 3Deng.
The four-functional group linking agent that the present invention adopts is: (CH 2=C (R 1)-COO-(CH 2CH 2O) n-CH 2) 4C, wherein n=1～6 are better, and raw material is easy to get, and good fluidity, for example (CH 2=CH-COO-CH 2) 4C.
Above-mentioned reactant feed, i.e. monomer, linking agent, initiator, each components contents of lithium-ion electrolyte solution mixed solution following (wt%):
Monomer: 6～25;
Linking agent: 3～25;
Light trigger: 0.5～2;
Lithium-ion electrolyte solution: 65～85.
The gel lattice polymer dielectric film performance that forms after the mixed solution photopolymerization of above-mentioned content is more stable and good.
Ultraviolet lamp power is better in 30～70W/cm scope, and rate of polymerization is fast, exceeds the ground consumes energy again, and guarantees to have guaranteed the performance of product a little less than the photodegradation reaction.
The polymerization atmosphere temperature is better in 20～60 ℃ of scopes, and trigger rate is fast.
The product that the present invention makes can be widely used in the electrochemical devices such as polymer Li-ion battery, transmitter, electrical condenser, has good performance.
The present invention utilizes the uv-light polymerization single stage method to prepare lithium ion gel polymer electrolyte film material.The inventive method is to utilize the UV curing method of technology maturation, have technology simply, efficiently quick, free of contamination characteristics; Monomer that the present invention selects for use and linking agent photopolymerization performance are good, behind the polymerization film formation, polymeric matrix group and lithium-ion electrolyte solution have consistency preferably, can contain a large amount of liquid electrolytes, help to improve ionic conductivity, and make chemical property keep stable; The present invention forms three-dimensional network shaped polymer dielectric film by chemical crosslink technique, and membrane structure is stable, and good mechanical property is convenient to assemble in various electrochemical devices.
Specific embodiment example 1 electrolyte film of gel-state lithium ion polymer material prepares 1 methyl methacrylate (CH2＝C(CH 3)CO 2CH 3, MMA): 20.5wt% triethylene glycol diacrylate (CH2＝CHCOO(CH 2CH 2O) 3OCCH＝CH 2, TEGDA): 5.7wt% hydroxyl cyclohexyl phenyl ketone (C6H 5-CO-C 6H 11(OH)): 1.4wt% electrolyte solution, 1M liClO4，EC/PC＝1/1(w/w)：72.4wt％
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 30W/cm, 28 ℃ of atmosphere temperatures, irradiation time 2 minutes), just obtain the transparence gel polymer electrolyte Film. Comparative example 1 Methyl methacrylate (CH2＝C(CH 3)CO 2CH 3, MMA): 26wt%; Hydroxyl cyclohexyl phenyl ketone (C6H 5-CO-C 6H 11(OH)): 1.7wt%; Electrolyte solution, 1M 1iClO4EC/PC＝1/l(w/w)：72.3wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate) draws under uviol lamp. a polymerization (power 30W/cm, 28 ℃ of atmosphere temperatures, irradiation time 5 minutes), the energy polymerization film formation, but owing to do not contain in the mixed liquor Cross-linking monomer, so polymerization time is long, and the film bad mechanical property. Example 2 electrolyte film of gel-state lithium ion polymer materials prepare 2 Trifluoroethyl methacrylate (CH2＝C(CH 3)CO 2CH 2CF 3, TFEMA): 9.8wt%; Glycol diacrylate oligomer (CH2＝CHCOO(CH 2CH 2O) 10OCCH＝CH 2, OEGDA): 22.1wt%; Hydroxyl cyclohexyl phenyl ketone (C6H 5-CO-C 6H 11(OH)): 1.2wt%; Electrolyte solution, 1M liClO6，EC/PC＝1/1(w/w)：66.9wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 35W/cm, 40 ℃ of atmosphere temperatures, irradiation time 0.5 minute), just obtain the electrolysis of transparence gel polymer Plasma membrane. Comparative example 2 Trifluoroethyl methacrylate (CH2＝C(CH 3)CO 2CH 3, TFEMA): 16.2wt%; Glycol diacrylate oligomer (CH2＝CHCOO(CH 2CH 2O) 10OCCH＝CH 2, OEGDA): 37.3wt%; Hydroxyl cyclohexyl phenyl ketone (C6H 5-CO-C 6H 11(OH)): 1.1wt%; Electrolyte solution, 1M liClO6，EC/PC＝1/l(w/w)：45.3wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 35W/cm, 28 ℃ of atmosphere temperatures, irradiation time 1 minute), can obtain the transparence gel polymer electrolyte Film, but be higher than 25% owing to electrolyte solution content is lower than 50%, two functional group's cross-linking monomer content, So the ionic conductivity of dielectric film is low, and film fragility is bigger. Example 3 electrolyte film of gel-state lithium ion polymer materials prepare 3 Methyl methacrylate (CH2＝C(CH 3)CO 2CH 3, MMA): 16.5wt%; PDDA (C6H 4(CO(OCH 2CH 2) 2OCOCH＝CH 2) 2, PDDA): 13.3wt%; Hydroxyl cyclohexyl phenyl ketone (C6H 5-CO-C 6H 11(OH)): 1.2wt%; Electrolyte solution, 1M liClO4，EC/PC＝1/1(w/w)：69wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 40W/cm, 30 ℃ of atmosphere temperatures, irradiation time 2 minutes), just obtain the transparence gel polymer electrolyte Film. Example 4 electrolyte film of gel-state lithium ion polymer materials prepare 4 Ethyl acrylate (CH2＝CHCO 2CH 2CH 3, EA): 15.5wt%; Triethylene glycol diacrylate (CH2＝CHCOO(CH 2CH 2O) 3OCCH＝CH 2, TEGDA): 5.3wt%; Hydroxyl cyclohexyl phenyl ketone (C6H 5-CO-C 6H 11(OH)): 0.8wt%; Electrolyte solution, 1M liPF6，EC/DMC＝1/1(w/w)：79.4wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 40W/cm, 50 ℃ of atmosphere temperatures, irradiation time 4 minutes), just obtain the transparence gel polymer electrolyte Film. Comparative example 3 Ethyl acrylate (CH2＝C(CH 3)CO 2CH 3, EA): 15.5wt%; Triethylene glycol diacrylate (CH2＝CHCOO(CH 2CH 2O) 3OCCH＝CH 2, TEGDA): 5.3wt%; Hydroxyl cyclohexyl phenyl ketone (C6H 5-CO-C 6H 11(OH)): 0.8wt%; Electrolyte solution, 1M liPF6，EC/DMC＝1/1(w/w)：79.4wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 18W/cm, 50 ℃ of atmosphere temperatures, irradiation time 10 minutes), can polymerization film formation, but because ultraviolet light spoke Penetrate power and be lower than 20W/cm, so polymerization time is long, and polymerization is incomplete, the film bad mechanical property. Example 5 electrolyte film of gel-state lithium ion polymer materials prepare 5 Methacrylic acid ethoxy ethyl ester (CH2＝C(CH 3)CO 2CH 2CH 2OC 2H 5, EMA): 6.1wt%; Triethylene glycol diacrylate (CH2＝CHCOO(CH 2CH 2O) 3OCCH＝CH 2, TEGDA): 9.9wt%; Hydroxyl cyclohexyl phenyl ketone (C6H 5-CO-C 6H 11(OH)): 0.5wt%; Electrolyte solution, 1M 1iPF6，EC/DEC＝1/1(w/w/)：83.5wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 40W/cm, 40 ℃ of atmosphere temperatures, irradiation time 2 minutes), just obtain the transparence gel polymer electrolyte Film. Example 6 electrolyte film of gel-state lithium ion polymer materials prepare 6 Ethyl acrylate (CH2＝CHCO 2CH 2CH 3, EA): 21.4wt%; Diallyl phthalate (C6H 4(COOCH 2CH＝CH 2) 2, PDPDA): 11.5wt%; Benzophenone+triethylamine (C6H 5CO C 6H 5＋(CH 3CH 2) 3N): 2wt%; Electrolyte solution, 1M liPF6，EC/DMC＝1/1(w/w/)：65.1wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 35W/cm, 30 ℃ of atmosphere temperatures, irradiation time 4 minutes), just obtain the transparence gel polymer electrolyte Film. Example 7 electrolyte film of gel-state lithium ion polymer materials prepare 7 Butyl acrylate (CH2＝CHCO 2CH 2CH 2CH 2CH 3, BA): 10.2wt%; Trimethylolpropane ethyoxyl triacrylate ((CH2＝CHCOOCH 2CH 2O) 3CCH 2CH 3, PMPEOTA): 14.2wt%; 2-hydroxy-2-methyl-1-phenyl-1-acetone (C6H 5COCH(OH)(CH 3), Darocure1173): 1.9wt%; Electrolyte solution, 1M liClO4，EC/PC＝1/1(w/w/)：73.7wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 65W/cm, 25 ℃ of atmosphere temperatures, irradiation time 1 minute), just obtain the transparence gel polymer electrolyte Film. Example 8 electrolyte film of gel-state lithium ion polymer materials prepare 8 Methacrylic acid ethylene glycol ethyl carbonic ester (CH2＝C(CH 3)CO 2CH 2CH 2OCOC 2H 5, EGECM): 20.8wt%; Triethylene glycol diacrylate (CH2＝CHCOO(CH 2CH 2O) 3OCCH＝CH 2, TEGDA): 8.9wt%; Hydroxyl cyclohexyl phenyl ketone (C6H 5-CO-C 6H 11(OH)): 1.0wt%; Electrolyte solution, 1M liPF6，EC/DMC＝1/1(w/w/)：69.3wt％。
In dry environment and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor. Mixed liquor Should become transparence and good flowability is arranged, quantitative mixed liquor is coated in the nonwoven of certain area Upper (nonwoven places on the PTFE substrate), initiated polymerization under uviol lamp (power 30W/cm, 68 ℃ of atmosphere temperatures, irradiation time 2 minutes), just obtain the transparence gel polymer electrolyte Film.

Claims (9)

1, a kind of preparation method of gel-state lithium ion polymer electrolyte, it is characterized in that in order to acrylate and derivative thereof be monomer, to contain multi-functional alkene derivatives is linking agent, makes liquid lithium ion electrolyte solution and acrylate monomer and linking agent polymerization form electrolyte film of gel-state lithium ion polymer by UV-light (high voltage mercury lamp) radiation crosslinking.
Photopolymerization ultraviolet lamp power is 20-100W/cm, and atmosphere temperature is 10～70 ℃, polymerization time 0.5～5 minute, wherein:
The acrylate monomer structural formula is: CH 2=C (R 1) CO 2(CH 2CH 2O) nR 2, R wherein 1Be H or CH 3, n=0～10; R 2Be in the following structure any, C mH 2m+1, m=1～6 wherein, or-C 6H 5,-CH 2-CF 3,-CH 2-CF 2-CF 2-CF 3,-CH 2-CF 2-CHFCH 3,-CH (CF 3) 2,-Si (OCH 3) 3And-Si (CH 3) 3
Bifunctional crosslinking agent's structural formula is: CH 2=C (R 1)-R 2-C (R 1)=CH 2, R wherein 1Be H or CH 3, R 2Structure is :-COO (CH 2CH 2O) xCO-, x=1～12 wherein ,-COO-(CH 2CH 2O) yCOArCOO (CH 2CH 2O) yCO, y=1～10 wherein, or-CH 2COO-Ar-COOCH 2-;
Trifunctional group cross-linking agent's structural formula is: (CH 2=C (R 1) CO 2(CH 2CH 2O) nCH 2) 3CR, its R 1Be H or CH 3, n=0～10, R is-CH 3Or-C 2H 5
Four-functional group linking agent structural formula is: (CH 2=C (R 1) COO (CH 2CH 2O) nCH 2) 4C, wherein R 1Be H or-CH, n=0～10.
Above-mentioned mixed solution content is (wt%): monomer: 5～30%; Linking agent: 2～30%; Light trigger: 0.1～2%; Lithium-ion electrolyte solution: 50～90%.
2, electrolyte film of gel-state lithium ion polymer preparation methods according to claim 1 is characterized in that n=0～6 in acrylate and the derivatives monomer structure thereof, m=1～3.
3, the preparation method of gel-state lithium ion polymer electrolyte according to claim 1 is characterized in that x=2～10 in bifunctional crosslinking agent's structure, y=1～6.
4, the preparation method of gel-state lithium ion polymer electrolyte according to claim 1 is characterized in that n=0～6 in trifunctional group cross-linking agent's structure.
5, the preparation method of gel-state lithium ion polymer electrolyte according to claim 1 is characterized in that n=1～6 in the four-functional group linking agent structure.
6, electrolyte film of gel-state lithium ion polymer preparation methods according to claim 1 is characterized in that each components contents of mixed solution is (wt%):
Monomer: 6～25;
Linking agent: 3～25;
Light trigger: 0.5～2;
Lithium-ion electrolyte solution: 65～85.
7, electrolyte film of gel-state lithium ion polymer preparation methods according to claim 1 is characterized in that ultraviolet lamp power is 30～70W/cm.
8, electrolyte film of gel-state lithium ion polymer preparation methods according to claim 1 is characterized in that the uv-light polymerization atmosphere temperature is 20～60 ℃.
9, electrolyte film of gel-state lithium ion polymer preparation methods according to claim 1 is characterized in that this product is used for electrochemical device.
CN 01126112 2001-07-12 2001-07-12 Optically triggered polymerization process for preparing electrolyte film of gel-state lithium ion polymer Pending CN1330107A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 01126112 CN1330107A (en) 2001-07-12 2001-07-12 Optically triggered polymerization process for preparing electrolyte film of gel-state lithium ion polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 01126112 CN1330107A (en) 2001-07-12 2001-07-12 Optically triggered polymerization process for preparing electrolyte film of gel-state lithium ion polymer

Publications (1)

Publication Number Publication Date
CN1330107A true CN1330107A (en) 2002-01-09

Family

ID=4666180

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 01126112 Pending CN1330107A (en) 2001-07-12 2001-07-12 Optically triggered polymerization process for preparing electrolyte film of gel-state lithium ion polymer

Country Status (1)

Country Link
CN (1) CN1330107A (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992434A (en) * 2014-04-23 2014-08-20 宁波祢若电子科技有限公司 Ultraviolet-curable electrolyte gel and its application in electrochromic device
CN105590759A (en) * 2014-10-23 2016-05-18 同济大学 Method of preparing ionic liquid gel electrolyte by semiconductor through self-initiated polymerization
CN106098382A (en) * 2016-08-31 2016-11-09 湖南艾华集团股份有限公司 A kind of high pressure stacked aluminum electrolytic capacitor and preparation method thereof
CN106252087A (en) * 2016-09-21 2016-12-21 中山大学 A kind of photocuring gel electrolyte and its preparation method and application
CN106252078A (en) * 2016-08-31 2016-12-21 湖南艾华集团股份有限公司 A kind of electrolyte of photocuring gel state aluminium electrolutic capacitor and preparation method thereof
CN106409516A (en) * 2016-08-31 2017-02-15 湖南艾华集团股份有限公司 Ultra-thin high-capacity laminated aluminum electrolytic capacitor and preparation method thereof
CN106409513A (en) * 2016-08-31 2017-02-15 湖南艾华集团股份有限公司 Square aluminum electrolytic capacitor based on gel electrolyte and preparation method thereof
CN106449112A (en) * 2016-08-31 2017-02-22 湖南艾华集团股份有限公司 Photopolymerization gel electrolyte-based aluminum electrolytic capacitor and preparation method thereof
CN106449114A (en) * 2016-08-31 2017-02-22 湖南艾华集团股份有限公司 High-capacity laminated type aluminium electrolytic capacitor and preparation method therefor
CN109509913A (en) * 2018-10-19 2019-03-22 安徽正熹标王新能源有限公司 A kind of preparation method of lithium battery gel electrolyte
CN110071324A (en) * 2019-04-08 2019-07-30 西安交通大学 A kind of application of multi-functional organogel in lithium ion battery
CN110854344A (en) * 2019-11-28 2020-02-28 厦门大学 High-molecular polymer modified diaphragm, preparation method and application
CN112736283A (en) * 2021-02-04 2021-04-30 昆山博益鑫成高分子材料有限公司 Preparation method and application of gel polyelectrolyte membrane
CN113701924A (en) * 2021-08-24 2021-11-26 南京工业大学 Porous solid-state ionic gel electrode and preparation method and application thereof

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992434A (en) * 2014-04-23 2014-08-20 宁波祢若电子科技有限公司 Ultraviolet-curable electrolyte gel and its application in electrochromic device
CN105590759A (en) * 2014-10-23 2016-05-18 同济大学 Method of preparing ionic liquid gel electrolyte by semiconductor through self-initiated polymerization
CN105590759B (en) * 2014-10-23 2018-06-26 同济大学 A kind of method that semiconductor self-initiating polymerization prepares ionic liquid gel electrolyte
CN106449114A (en) * 2016-08-31 2017-02-22 湖南艾华集团股份有限公司 High-capacity laminated type aluminium electrolytic capacitor and preparation method therefor
CN106252078A (en) * 2016-08-31 2016-12-21 湖南艾华集团股份有限公司 A kind of electrolyte of photocuring gel state aluminium electrolutic capacitor and preparation method thereof
CN106409516A (en) * 2016-08-31 2017-02-15 湖南艾华集团股份有限公司 Ultra-thin high-capacity laminated aluminum electrolytic capacitor and preparation method thereof
CN106409513A (en) * 2016-08-31 2017-02-15 湖南艾华集团股份有限公司 Square aluminum electrolytic capacitor based on gel electrolyte and preparation method thereof
CN106449112A (en) * 2016-08-31 2017-02-22 湖南艾华集团股份有限公司 Photopolymerization gel electrolyte-based aluminum electrolytic capacitor and preparation method thereof
CN106098382A (en) * 2016-08-31 2016-11-09 湖南艾华集团股份有限公司 A kind of high pressure stacked aluminum electrolytic capacitor and preparation method thereof
CN106252087A (en) * 2016-09-21 2016-12-21 中山大学 A kind of photocuring gel electrolyte and its preparation method and application
CN106252087B (en) * 2016-09-21 2018-09-04 中山大学 A kind of photocuring gel electrolyte and its preparation method and application
CN109509913A (en) * 2018-10-19 2019-03-22 安徽正熹标王新能源有限公司 A kind of preparation method of lithium battery gel electrolyte
CN110071324A (en) * 2019-04-08 2019-07-30 西安交通大学 A kind of application of multi-functional organogel in lithium ion battery
CN110854344A (en) * 2019-11-28 2020-02-28 厦门大学 High-molecular polymer modified diaphragm, preparation method and application
CN112736283A (en) * 2021-02-04 2021-04-30 昆山博益鑫成高分子材料有限公司 Preparation method and application of gel polyelectrolyte membrane
CN113701924A (en) * 2021-08-24 2021-11-26 南京工业大学 Porous solid-state ionic gel electrode and preparation method and application thereof

Similar Documents

Publication Publication Date Title
KR100261252B1 (en) Polymer solid electrolyte and lithium secondary cell adopting the same
CN1330107A (en) Optically triggered polymerization process for preparing electrolyte film of gel-state lithium ion polymer
JP3974371B2 (en) Polymer gel electrolyte composition and method for producing the same
CN1152086C (en) Process for preparing gel-state lithium ion polymer as electrolyte and bettery
CN111533851A (en) Preparation method of polymer electrolyte and application of polymer electrolyte in all-solid-state battery
CN1301565C (en) Lithium ion cell gel liquor formula and method for preparing gel electrolytic liquor using same
JP2896361B2 (en) Polymer solid electrolyte, method for producing the same, and lithium secondary battery employing the polymer solid electrolyte
CN101814628A (en) Hyperbranched polyester lithium ion battery gel electrolyte and preparation method thereof
CN113451642A (en) Chemical crosslinking gradient-block copolymer membrane for preparing polymer gel electrolyte and preparation method thereof
CN104558390A (en) Polymer for gel polymer electrolyte, preparation method of polymer, gel polymer electrolyte and preparation method of gel polymer electrolyte
CN114373986A (en) Polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery
JP2003303739A (en) Electric double layered capacitor that uses uv-curing gel polymer electrolyte
CN104157904A (en) Polymer for gel polymer electrolyte, gel polymer electrolyte and preparation method of polymer
CN111883824A (en) Preparation method of in-situ polymerized solid electrolyte
Longo et al. Gelatine based gel polymer electrolyte towards more sustainable Lithium-Oxygen batteries
CN1558463A (en) In-situ heat cross bonding process for preparing fluorine containing gel state electrolyte material and process for making polymeric lithium ion cell
CN104031289A (en) Polyolefin composite membrane and preparation method thereof, and lithium ion battery
CN108767313B (en) All-solid-state polymer electrolyte with spectrum plasticizing effect and preparation method and application thereof
CN101200568B (en) Gel polymer electrolytes and preparation method thereof
KR20170092933A (en) Uv curable gel polymer electrolyte composition containing eco-friendly polymer and manufacturing method
CN113964380B (en) Self-repairing polymer electrolyte capable of in-situ thermal polymerization and preparation method thereof
CN115566268A (en) Nitrile polymer solid electrolyte and preparation method and application thereof
JP3843505B2 (en) Polymer electrolyte and battery
JPH10223044A (en) Polymer solid electrolyte gel
KR20180072111A (en) Composite electolyte, method for manufacturing the same, and rechargeable battery comprising the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication