Crosslinking type polymer anionic membrane and preparation method thereof

An anion membrane, polymer technology, applied in electrical components, circuits, fuel cell parts and other directions, can solve the problems of expensive, high conductivity, low water absorption, etc.

Inactive Publication Date: 2015-08-26
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Yan Yushan et al. prepared quaternary phosphonium anion membranes with high conductivity and good chemical stability [Yushan Yan, et al., Angewandte Chemie International Edition, 2009, 48, 6499.]; The conductivity of polyethersulfone membrane is higher than that of commercial quaternary ammonium membrane, and it is stable in 1M KOH at 60°C for 48 hours, but the membrane is very brittle and expensive [S.Gu, R.Cai, et al., Angew.Chem.~Int .Ed.,2009,48,6499.]
[0006] The room temperature conductivity of the guanidinium-salted polyarylethersulfone membrane reported by Zhang Suobo and others can reach 67mS/cm, and the ion exchange capacity remains unchanged after immersion in 1M NaOH at 60°C for 48 hours, but the membrane is easy to swell and has low water absorption [Chinese patent CN 102479962 A]; Zhu Xiuling of Dalian University of Technology

Method used

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  • Crosslinking type polymer anionic membrane and preparation method thereof
  • Crosslinking type polymer anionic membrane and preparation method thereof
  • Crosslinking type polymer anionic membrane and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Example 1 (Solvent is CH 2 Cl 2 , 55℃ ionization reaction for 4 hours, DC=0.84)

[0042] Preparation of guanidine salt: under nitrogen atmosphere, dissolve tetramethylurea in dichloromethane, add oxalyl chloride dropwise, slowly increase the temperature to 60℃ and react for 1.5 hours, remove the solvent to obtain white solid Vilsmeyer salt, (tetramethylurea : Dichloromethane: oxalyl chloride = 9.6ml: 10ml: 10.2ml);

[0043] Dissolve 1 mole fraction of guanidine salt in 5 mole fraction of acetonitrile, add 0.4 mole fraction of diaminodiphenyl ether, slowly raise the temperature to 80°C and react for 24 hours. After the reaction is completed, add the reaction mixture to the 5M NaOH solution vigorously After stirring for 6 hours, the organic phase was separated, and the organic phase and solvent were removed by distillation under reduced pressure to obtain the yellow-brown viscous ionizing reagent diguanidyl diphenyl ether.

[0044] Ionization of the polymer membrane backbone: T...

Embodiment 2

[0049] Example 2 (solvent is toluene, ionization reaction at room temperature for 12 hours, DC=0.84)

[0050] Preparation of guanidine salt: Under nitrogen atmosphere, dissolve tetramethylurea in toluene, add oxalyl chloride dropwise, slowly increase the temperature to 60°C and react for 1.5 hours, distill off the solvent to obtain a white solid, which is Vilsmeyer salt (tetramethylurea: Toluene: oxalyl chloride = 9.6ml: 20ml: 10.2ml);

[0051] Dissolve 1 mole fraction of guanidine salt in 5 mole fraction of acetonitrile, add 0.4 mole fraction of diaminodiphenyl ether, slowly raise the temperature to 80°C and react for 24 hours. After the reaction is completed, add the reaction mixture to the 5M NaOH solution vigorously After stirring for 6 hours, the organic phase was separated, and the organic phase and solvent were removed by distillation under reduced pressure to obtain the yellow-brown viscous ionizing reagent diguanidyl diphenyl ether.

[0052] Ionization of polymer membrane b...

Embodiment 3

[0057] Example 3 (Solvent is acetonitrile, ionized reaction at 55°C for 4 hours, DC=0.99)

[0058] Preparation of guanidine salt: under nitrogen atmosphere, dissolve tetramethylurea in acetonitrile, add oxalyl chloride dropwise, slowly increase the temperature to 60°C and react for 1.5 hours, distill off the solvent to obtain a white solid, which is Vilsmeyer salt (tetramethylurea: Acetonitrile: oxalyl chloride = 9.6ml: 10ml: 10.2ml);

[0059] Dissolve 1 mole fraction of guanidine salt in 5 mole fraction of acetonitrile, add 0.4 mole fraction of diaminodiphenyl ether, slowly raise the temperature to 80°C and react for 24 hours. After the reaction is completed, add the reaction mixture to the 5M NaOH solution vigorously After stirring for 6 hours, the organic phase was separated, and the organic phase and solvent were removed by distillation under reduced pressure to obtain the yellow-brown viscous ionizing reagent diguanidyl diphenyl ether.

[0060] Ionization of the polymer membran...

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Abstract

The invention discloses a crosslinking type polymer anionic membrane and a preparation method of crosslinking type polymer anionic membrane. Anionic membrane takes a polymer containing chloromethyl group as a main chain; in preparation, the chloromethylation of polymer anionic membrane and ionization of the main chain are carried out successively, a biguanide or multi-guanide structural aquogel is prepared, and the aquogel performs thermal polymerization at original site in the membrane to form a membrane; at last, through the alkali treatment, the anion-exchange membrane is obtained. The guanidine type polymer contains a lot of guanidine radicals capable of conducting anion easily, and the ion conductivity can be effectively improved; the water-retaining ability of silane can also improve the ionic conduction ability of the membrane; the ion group is free from beta-H, so that Hofmann degradation can be eliminated; the super absorbent and inflation resistance of aquogel can improve water content of membrane, reduce OH- salvation degree, lighten attack of ON- to ion base, and improve the alkali stability of the membrane; the crosslinking structure can further inhibit the membrane swelling. The prepared membrane is high in water absorbent, low in swelling rate, and able to obviously improve the alkali stability of the membrane.

Description

Technical field [0001] The invention relates to the field of battery membrane materials, in particular to a cross-linked polymer anion membrane and a preparation method thereof. Background technique [0002] Energy, life, and environment are issues of global concern in the 21st century. With the growth of human demand for energy, energy issues have become one of the major global problems. At this stage, the development of reusable, environmentally friendly and high conversion rate energy technologies has become a research hotspot. Fuel cell technology is a new type of energy technology that uses electrochemical reactions to convert chemical energy stored in fuel into electrical energy. It is one of the better solutions to energy and environmental issues. Traditional Proton Exchange Membrane Fuel Cell (PEMFC) has the advantages of high energy conversion efficiency, high energy density, and environmental friendliness, but its reliance on precious metal catalysts and perfluorosulfo...

Claims

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Application Information

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IPC IPC(8): C08J5/22C08J7/12C08L81/06H01M2/16H01M8/02
CPCY02E60/50
Inventor 张凤祥李晓亮程洁
Owner DALIAN UNIV OF TECH
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