CN102382293A - Polymer anion exchange membrane and preparation method thereof - Google Patents
Polymer anion exchange membrane and preparation method thereof Download PDFInfo
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- CN102382293A CN102382293A CN2011102242567A CN201110224256A CN102382293A CN 102382293 A CN102382293 A CN 102382293A CN 2011102242567 A CN2011102242567 A CN 2011102242567A CN 201110224256 A CN201110224256 A CN 201110224256A CN 102382293 A CN102382293 A CN 102382293A
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- 0 C*1C(C)=*(CCCCCCC(CCCCCC*2=C(C)*(C)C=C2)(c2c3)c(cc(cc4)-c(cc5)ccc5OC)c4-c2ccc3-c2ccc(*)cc2)C=C1 Chemical compound C*1C(C)=*(CCCCCCC(CCCCCC*2=C(C)*(C)C=C2)(c2c3)c(cc(cc4)-c(cc5)ccc5OC)c4-c2ccc3-c2ccc(*)cc2)C=C1 0.000 description 5
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Abstract
The invention belongs to ionomer fields, are related to a kind of anion-exchange membrane that can be used for alkaline fuel cell, and the invention discloses a kind of anionic polymer, repetitive unit is as follows:
A kind of new polymers anion-exchange membrane of good performance based on imidazole salts is prepared using above-mentioned anionic polymer, overcome the poor problem of quaternary polymer anion-exchange membrane chemical stability, the use of chloromethyl ether in traditional polymer anion-exchange membrane preparation process is avoided simultaneously, reduces the harm to human body and environment.
Description
Technical field
The present invention relates to a kind of polymer anion-exchange membrane and preparation method thereof, relate in particular to a kind of anion-exchange membrane that can be used for alkaline fuel cell and preparation method thereof.
Background technology
Anion-exchange membrane has been widely used in industrial circles such as water treatment, hydrometallurgy, chemical separation and alkaline fuel cell.The preparation method of traditional quaternary polymer anion-exchange membrane will pass through chloromethylation when introducing ion-exchange group process; And to use hypertoxic carcinogenic substance chloromethyl ether in the chloromethylation process, this all has great harm to environment protection and human health.The alkaline polymer electrolyte film is one of core component of basic anion exchange film fuel battery, and the quality of its performance is the performance and the life-span of decision battery directly.The research of alkaline polymer electrolyte starts from 1994.(Fauvarque.Electrochim Acta 1998 43:1163-1170) uses PEO to form polymkeric substance as matrix mixing Pottasium Hydroxide and water to Guinot etc. first, and its room-temperature conductivity scope is 10
-3～10
-4S/cm.Thereafter, many researchists have carried out the research work of alkali solid polymer dielectric.The Watanabe seminar of Japan, domestic Wuhan University, China Science & Technology University, Chinese Academy of Sciences Changchun should be changed seminar such as institute and carry out a few thing based on quaternary ammonium salt alkaline polymer electrolyte film field.People such as Lin (Chem.Mater., 2010,22; 6718-6725) adopt the method for in-situ polymerization to prepare anion-exchange membrane based on alkali ionic liquid; This method is simple and safe, and the anion-exchange membrane of preparation has higher specific conductivity, but this film is owing to be the fats main polymer chain; The water absorption and swelling rate is higher, and dimensional stability is relatively poor relatively.Therefore, the alkaline fuel cell polymer dielectric film still exists a lot of problems to demand researchist's solution urgently:
1) traditional quaternary ammonium salt polymer is in the preparation process, and highly toxic substance chloromethyl ether one of the raw material that is absolutely necessary makes the preparation of basic anion exchange membrane to human body and environment very big harm arranged all.
2) QAS polymer is in the halomethylation process; Be difficult to accomplish accurately to control the position and the level of response of halomethylation; Can produce a lot of side reactions; The overall performance of impact polymer, and the polymers obtained anion-exchange membrane thermostability of traditional preparation process technology, poor chemical stability are particularly degraded under comparatively high temps or alkaline environment easily.Therefore developing polymer anion-exchange membrane material that synthesizing new is used for alkaline fuel cell becomes the focus of people's research.
Good alkaline polymer anion-exchange membrane outside the good thermostability and chemicalstability, also will have favorable mechanical performance and alkali resistance except possessing higher ionic conductivity.
But the anion-exchange membrane of reporting in the prior art is difficult to satisfy simultaneously above-mentioned requirements; For example: (J.Membr.Sci.2009 such as Wu; 338,51.) silicon-dioxide for preparing/gather 2,6-dimethyl--1; 4-phenylate inorganic hybridisation anion exchange membrane has the favorable mechanical performance, but specific conductivity but not high (1～8 * 10-3Scm-1).(Macromolecules such as Wang; 2010; 43; 3895) preparation the polyether sulfone basic anion exchange membrane that contains the guanidinesalt group can reach 7.4 * 10-2S cm-1 in the 60oC ionic conductivity, but this anion-exchange membrane water-intake rate up to 107%, the mechanical property of the too high destruction anion-exchange membrane of water-intake rate.
Summary of the invention
The object of the invention provides a kind of well behaved new polymers anion-exchange membrane based on imidazole salts and preparation method thereof; Overcome the relatively poor problem of quaternary polymer anion-exchange membrane chemicalstability; Avoided the use of chloromethyl ether in the conventional polymer anionresin membrane prepare process simultaneously, reduced harm human body and environment.
For reaching the foregoing invention purpose, the technical scheme that the present invention adopts is: a kind of anionic polymer, and the repeating unit of said anionic polymer is as follows:
In the formula, wherein n is 0～7 integer; R
1Alkyl for C1～C4; R
2Be methyl or H; X is selected from I, Br, Cl, SCN, BF
4, NO
3, PF
6, CF
3SO
3, N (CN)
2, [N (SO
2CF
3)
2], a kind of among the OH, Ar is selected from a kind of in the group that following structural formula representes:
In the technique scheme, the polymerization degree of said anionic polymer and molecular weight can be controlled according to the length of polymerization time.
The preparation method of above-mentioned anionic polymer may further comprise the steps:
In the presence of alkali, under the protection of inert gas atmosphere, make the monomer that contains the imidazoles functional group, the monomer that contains the Ar structure carry out nucleophilic substitution reaction, obtain anionic polymer;
The said monomeric structural formula that contains the imidazoles functional group is:
Wherein Ar structure containing monomer is selected from:
In the technique scheme, said alkali is a kind of in yellow soda ash, salt of wormwood or the cesium carbonate.
In the technique scheme, the preparation method of said anionic polymer is characterized in that, specifically may further comprise the steps:
(1) will contain the monomer of imidazoles functional group, the monomer that contains the Ar structure, toluene, alkali and be dissolved in solvent, in 110～130 ℃ of back flow reaction 4～8 hours, the water azeotropic removal of water that generates in toluene and the reaction system; Said high boiling solvent is selected from: N, a kind of in dinethylformamide (149～156 ℃ of boiling points), methyl-sulphoxide (189 ℃ of boiling points), the N-Methyl pyrrolidone (203 ℃ of boiling points);
(2) promote temperature of reaction to 140～170 ℃, and temperature of reaction is not higher than solvent boiling point, reacted 4～30 hours, prepare anionic polymer.
Further in the technical scheme, above-mentioned anionic polymer is dissolved in the solvent, the method through solution-cast prepares anion-exchange membrane, and anion-exchange membrane is soaked in basic soln (Pottasium Hydroxide or sodium hydroxide solution), and can get negatively charged ion is OH
-The basic anion exchange membrane.
The present invention requires the polymer anion-exchange membrane based on imidazole salts of protecting method for preparing to obtain simultaneously, and described basic anion exchange membrane can be applied to the alkaline fuel cell field.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. the present invention is prepared into anion-exchange membrane with imidazole salts, compares with traditional quaternary ammonium salt anion-exchange membrane, and the anion-exchange membrane based on imidazole salts of the present invention's preparation has better thermostability and alkali resistance;
2. to prepare the basic anion exchange membrane be main polymer chain with the aromatic ring in the present invention, makes the polymer anion film have better mechanical property and dimensional stability;
3. the present invention adopts the method for simple anionresin to prepare the basic anion exchange membrane, has avoided traditional quaternary anionic membrane to prepare the use of carcinogenic substance chloromethyl ether in the process, and the preparation process is simple and safe relatively;
4. the present invention earlier carries out polymerization again with the polymerization single polymerization monomer functionalization and obtains functional polymer, has overcome the position of difficult accurately control halomethylation in traditional anionresin membrane prepare process and the defective of level of response;
5. the polymer anion-exchange membrane of the present invention's design can change different negatively charged ion according to actual needs, and the anion-exchange membrane that obtains having different anions is immersed in and obtains the basic anion exchange membrane in the alkali lye.This polymer film has remarkable alkali resistance, can be used for alkaline fuel cell.
Description of drawings
Fig. 1 is the IR Characterization figure as a result of embodiment two gained anion-exchange membranes;
Fig. 2 is the alkali resistance test result figure among the embodiment eight.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Embodiment one:
Preparation contains monomer
(reference: the Macromolecules 2010 of imidazoles functional group; 43,10196-10200).
1) in three-necked bottle, add 2,7-two bromo-9,9-two (6 '-bromohexane base) fluorenes (5.0g, 7.7mmol), para hydroxybenzene boric acid (1.2g, 8.5mmol), 40ml THF and 30ml 2M K
2CO
3Solution, nitrogen protection adds catalyst P dCl
2(dppf) 160mg, slowly elevated temperature to 70 ℃ reacted 24 hours.Crude product through the extraction, column chromatography purify light yellow crystal 2,7-two (4 '-hydroxy phenyl)-9,9-two (6 '-bromohexane) fluorenes 3.46g, productive rate 66.2%.
2) in three-necked bottle, add 2,7-two (4 '-hydroxy phenyl)-9,9-two (6 '-bromohexane) fluorenes (2.0g, 2.96mmol), DMIZ 1,2 dimethylimidazole (1ml, 12.5mmol), the 20ml acetonitrile, nitrogen protection was reacted 12 hours down at 70 ℃.Crude product obtains faint yellow solid 2.45g, productive rate 95.3% after anhydrous diethyl ether, washed with dichloromethane.
Other monomeric preparations that contain the imidazoles functional group also can be referring to above-mentioned preparation method.
Embodiment two:
In three-necked flask, add 0.005mol
0.005mol
0.011mol Cs
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 8 hours.The polymkeric substance that obtains is separated out with the deionized water deposition, uses deionized water, washing with alcohol then repeatedly, drying for standby.The 0.1g resulting polymers fully is dissolved into N, in the dinethylformamide after, polymers soln is dripped on the polyfluortetraethylene plate, 70 ℃ dry 2 hours down, prepare Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is placed 1M KOH solution, soaked 24 hours down, treat Br at 60 ℃
-Be exchanged into OH fully
-After, obtain OH
-The type anion-exchange membrane.
Employing FT-IR Varian CP-3800spectrometer carries out the infrared structure sign to two types anion-exchange membrane.Measurement range is 4000-400cm
-1Its result is as shown in Figure 1, and wherein A is the infrared spectrogram of Br-type anion-exchange membrane, and B is OH
-The infrared spectrogram of type anion-exchange membrane.C is OH
-The type anion-exchange membrane soaks the infrared spectrogram after 108 hours in 60 ℃ 1M KOH solution.Wherein, 1586cm
-1And 744cm
-1Be the infrared signature absorption of imidazole ring, 2935,2856cm
-1The place is-CH
2-charateristic avsorption band, 465-1637cm
-1. about be the charateristic avsorption band of phenyl ring.3421cm
-1. the broad peak of locating is O-H, the characteristic absorption band of N-H, and this proves that also this material has good hydrophilicity 1317 and 1151cm
-1Be the absorption peak of sulfoxide, 1245cm
-1The absorption peak proof aryl oxide (O-) existence of structure at place.Comprehensive above the analysis knows that this anion-exchange membrane is title product, contains the polymkeric substance of imidazoles functional group.C compares with B, does not have significantly to absorb the variation of position, explains that this polymkeric substance can keep Stability Analysis of Structures in basic soln, have good alkali resistance.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 1.01mmol/g, and ionic conductance is 2.54 * 10 under the room temperature
-2S cm
-1, 90 ℃ of following ionic conductances are 5.63 * 10
-2S cm
-1Tensile strength is 50.41MPa, and Young's modulus is 1.52GPa, and elongation at break is 12.65%.
Embodiment three:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 16 hours.The polymkeric substance that obtains is separated out with the deionized water deposition, uses deionized water, washing with alcohol then repeatedly, drying for standby.After fully being dissolved into the 0.1g resulting polymers in the methyl-sulphoxide, polymers soln is dripped on the polyfluortetraethylene plate, drying is 6 hours under 70 ℃, prepares Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, soaked 24 hours down, treat Br at 60 ℃
-Be exchanged into OH fully
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 1.12mmol/g, and ionic conductance is 1.37 * 10 under the room temperature
-2S cm
-1, 90 ℃ of following ionic conductances are 6.02 * 10
-2S cm
-1Tensile strength is 44.67MPa, and Young's modulus is 1.45GPa, and elongation at break is 9.65%.
Embodiment four:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 160 ℃, back flow reaction 8 hours.The polymkeric substance that obtains is separated out with the deionized water deposition, uses deionized water, washing with alcohol then repeatedly, drying for standby.After fully being dissolved into the 0.1g resulting polymers in the methyl-sulphoxide, polymers soln is dripped on the polyfluortetraethylene plate, drying is 6 hours under 70 ℃, prepares Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, soaked 24 hours down, treat Br at 60 ℃
-Be exchanged into OH fully
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 0.87mmol/g, and ionic conductance is 0.91 * 10 under the room temperature
-2S cm
-1, 90 ℃ of following ionic conductances are 3.23 * 10
-2S cm
-1Tensile strength is 47.50MPa, and Young's modulus is 1.29GPa, and elongation at break is 11.61%.
Embodiment five:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 20 hours.The polymkeric substance that obtains is separated out with the deionized water deposition, uses deionized water, washing with alcohol then repeatedly, drying for standby.The 0.1g resulting polymers fully is dissolved into N, in the dinethylformamide after, polymers soln is dripped on the polyfluortetraethylene plate, 70 ℃ dry 2 hours down, prepare Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, soaked 24 hours down, treat Br at 60 ℃
-Be exchanged into OH fully
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 0.73mmol/g, and ionic conductance is 0.65 * 10 under the room temperature
-2S cm
-1, 90 ℃ of following ionic conductances are 2.51 * 10
-2S cm
-1Tensile strength is 38.52MPa, and Young's modulus is 1.76GPa, and elongation at break is 15.52%.
Embodiment six:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 20 hours.The polymkeric substance that obtains is separated out with the deionized water deposition, uses deionized water, washing with alcohol then repeatedly, drying for standby.The 0.1g resulting polymers fully is dissolved into N, in the dinethylformamide after, polymers soln is dripped on the polyfluortetraethylene plate, 70 ℃ dry 2 hours down, prepare Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, soaked 24 hours down, treat Br at 60 ℃
-Be exchanged into OH fully
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 0.73mmol/g, and ionic conductance is 0.65 * 10 under the room temperature
-2S cm
-1, 90 ℃ of following ionic conductances are 2.51 * 10
-2S cm
-1Tensile strength is 53.87MPa, and Young's modulus is 1.88GPa, and elongation at break is 10.43%.
Embodiment seven:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 8 hours.The polymkeric substance that obtains is separated out with the deionized water deposition, uses deionized water, washing with alcohol then repeatedly, drying for standby.After fully being dissolved into the 0.1g resulting polymers in the methyl-sulphoxide, polymers soln is dripped on the polyfluortetraethylene plate, drying is 6 hours under 70 ℃, prepares Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, soaked 24 hours down, treat Br at 60 ℃
-Be exchanged into OH fully
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 0.89mmol/g, and ionic conductance is 1.08 * 10 under the room temperature
-2S cm
-1, 90 ℃ of following ionic conductances are 4.32 * 10
-2S cm
-1Tensile strength is 38.66MPa, and Young's modulus is 1.21GPa, and elongation at break is 16.44%.
Embodiment eight:
OH with the preparation of ratio described in the instance two
-The type anion-exchange membrane is a sample, carries out the alkali resistance test based on the polymer anion-exchange membrane of imidazole salts, and (Macromolecules 2010 with reference to literary composition in the alkaline resistance properties test of anion-exchange membrane; 43,3890-3896) said method is dipped into anion-exchange membrane in 60 ℃ the 1M KOH solution; Take out film at regular intervals; Be immersed in the deionized water KOH residual in the Ex-all film, adopt AC impedence method to survey the specific conductivity of anion-exchange membrane, Range of measuring temp is 30 ℃～90 ℃.Test result is as shown in Figure 2, and the result shows the increase along with soak time in alkali lye, and the specific conductivity of anion-exchange membrane downward trend do not occur as traditional quaternary ammonium salt anion-exchange membrane.What the present invention of experiment proof prepared has good alkali resistance based on ion liquid polymer anion-exchange membrane.
Claims (5)
1. an anionic polymer is characterized in that, the repeating unit of said anionic polymer is as follows:
In the formula, wherein n is 0～7 integer R
1Alkyl R for C1～C4
2Be methyl or H; X is selected from I, Br, Cl, SCN, BF
4, NO
3, PF
6, CF
3SO
3, N (CN)
2, [N (SO
2CF
3)
2], a kind of among the OH, Ar is selected from a kind of in the group that following structural formula representes:
2. the preparation method of the said anionic polymer of claim 1 is characterized in that, may further comprise the steps:
In the presence of alkali, under the protection of inert gas atmosphere, make the monomer that contains the imidazoles functional group, the monomer that contains the Ar structure carry out nucleophilic substitution reaction, obtain anionic polymer;
The said monomeric structural formula that contains the imidazoles functional group is:
Wherein Ar structure containing monomer is selected from:
3. according to the preparation method of the said anionic polymer of claim 2, it is characterized in that said alkali is a kind of in yellow soda ash, salt of wormwood or the cesium carbonate.
4. according to the preparation method of the said anionic polymer of claim 3, it is characterized in that, specifically may further comprise the steps:
(1) will contain the monomer of imidazoles functional group, the monomer that contains the Ar structure, toluene, alkali and be dissolved in solvent, in 110～130 ℃ of back flow reaction 4～8 hours, the water azeotropic removal of water that generates in toluene and the reaction system; Said solvent is selected from: N, a kind of in dinethylformamide, methyl-sulphoxide, the N-Methyl pyrrolidone;
(2) promote temperature of reaction to 140～170 ℃, and temperature of reaction is not higher than solvent boiling point, reacted 4～30 hours, prepare anionic polymer.
5. polymer anion-exchange membrane that adopts the preparation of the said anionic polymer of claim 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694078A (en) * | 2016-01-29 | 2016-06-22 | 佛山市聚成生化技术研发有限公司 | Anion-exchange membrane for fuel cells and preparation method thereof, and fuel cell using anion-exchange membrane |
| CN110862533A (en) * | 2019-11-25 | 2020-03-06 | 九江天赐高新材料有限公司 | Preparation method of polyion liquid for lithium battery polymer solid electrolyte |
| CN111225939A (en) * | 2017-10-17 | 2020-06-02 | 赢创运营有限公司 | Polymeric anion conducting membranes |
| CN112619441A (en) * | 2021-01-15 | 2021-04-09 | 福州大学 | Anion exchange membrane and solvent-free preparation method thereof |
| CN113416297A (en) * | 2021-06-08 | 2021-09-21 | 苏州大学 | Ultra-high molecular weight anion exchange membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113166335B (en) | 2018-12-11 | 2023-09-29 | 3M创新有限公司 | Copolymers having cationic nitrogen-containing groups and anion exchange membranes made therefrom |
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| CN101831023A (en) * | 2010-03-18 | 2010-09-15 | 苏州大学 | Fuel cell proton exchange membranes and preparation method thereof |
| CN102050911A (en) * | 2010-11-23 | 2011-05-11 | 苏州大学 | Polymer anion exchange membrane and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101831023A (en) * | 2010-03-18 | 2010-09-15 | 苏州大学 | Fuel cell proton exchange membranes and preparation method thereof |
| CN102050911A (en) * | 2010-11-23 | 2011-05-11 | 苏州大学 | Polymer anion exchange membrane and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694078A (en) * | 2016-01-29 | 2016-06-22 | 佛山市聚成生化技术研发有限公司 | Anion-exchange membrane for fuel cells and preparation method thereof, and fuel cell using anion-exchange membrane |
| CN105694078B (en) * | 2016-01-29 | 2018-08-24 | 深圳市晓龙新能源科技有限公司 | A kind of fuel cell of fuel cell anion-exchange membrane and its preparation method and application the anion exchange |
| CN111225939A (en) * | 2017-10-17 | 2020-06-02 | 赢创运营有限公司 | Polymeric anion conducting membranes |
| CN111225939B (en) * | 2017-10-17 | 2022-12-20 | 赢创运营有限公司 | Polymeric anion conducting membranes |
| CN110862533A (en) * | 2019-11-25 | 2020-03-06 | 九江天赐高新材料有限公司 | Preparation method of polyion liquid for lithium battery polymer solid electrolyte |
| CN110862533B (en) * | 2019-11-25 | 2022-06-17 | 九江天赐高新材料有限公司 | Preparation method of polyion liquid for lithium battery polymer solid electrolyte |
| CN112619441A (en) * | 2021-01-15 | 2021-04-09 | 福州大学 | Anion exchange membrane and solvent-free preparation method thereof |
| CN113416297A (en) * | 2021-06-08 | 2021-09-21 | 苏州大学 | Ultra-high molecular weight anion exchange membrane and preparation method and application thereof |
| CN113416297B (en) * | 2021-06-08 | 2022-06-24 | 苏州大学 | Ultra-high molecular weight anion exchange membrane and preparation method and application thereof |
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