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Polyfluorene ether nitrile cross-linked anion exchange membrane material functionalized with cationic groups for fuel cells and preparation method thereof

A technology of anion exchange membranes and cationic groups, which is applied in fuel cells, electrochemical generators, circuits, etc., can solve the problems of poor alkali resistance stability and low anion conductivity of anion exchange membranes, and achieve excellent alkali resistance stability, Good alkali resistance stability, the effect of enhancing ion conductivity

Active Publication Date: 2019-04-02
CHANGCHUN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the alkali resistance stability of anion exchange membrane is generally poor, and its anion conductivity is small

Method used

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  • Polyfluorene ether nitrile cross-linked anion exchange membrane material functionalized with cationic groups for fuel cells and preparation method thereof
  • Polyfluorene ether nitrile cross-linked anion exchange membrane material functionalized with cationic groups for fuel cells and preparation method thereof
  • Polyfluorene ether nitrile cross-linked anion exchange membrane material functionalized with cationic groups for fuel cells and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Under nitrogen protection, add 0.04mol 9-fluorenone, 0.12mol 2,6-dimethylphenol, 0.1mL 3-mercaptopropionic acid, 10mL toluene to a 100mL three-necked flask, and add 1.5mL at 30°C with a mass fraction of 98% Concentrated sulfuric acid at 55°C for 5h, and discharged in distilled water. Suction filtration obtained a light yellow solid crude product, which weighed 15.9 g after drying. Add the crude product and 200mL of toluene into a 500mL three-necked flask, stir at 90°C for 3h, and filter under reduced pressure while hot to obtain the filtrate. After cooling and standing still, the white crystalline product is obtained by suction filtration, and dried to obtain 9,9-bis(3,5- Methyl-4-hydroxyphenyl)fluorene (DMHPF), weighing 9.1g.

Embodiment 2

[0040] Under nitrogen protection, add 0.006mol (2.439g) 9,9-bis(3,5-methyl-4-hydroxyphenyl ) fluorene (prepared according to the method of Example 1), 0.009mol (3.026g) hexafluorobisphenol A, 0.015mol (2.087g) 2,6-difluorobenzonitrile, 20mL sulfolane, 0.01875mol (2.5875g) potassium carbonate, 15mL of toluene, reflux at 128°C, carry water for 4 hours, let go of the water-carrying agent; raise the temperature to 180°C, distill the toluene, continue the reaction for 10 hours, and discharge the material in water to obtain a strip-shaped polymer. The polymer was crushed with a pounder, boiled 6 times with distilled water, filtered, and dried in a vacuum oven at 40°C for 48 hours to obtain 7.1 g of benzylmethyl-containing polyfluorene ether nitrile polymer. The benzylmethyl group accounted for 160 mole percent of the resulting polymer.

Embodiment 3

[0042] Under nitrogen protection, add 0.009mol (3.659g) 9,9-bis(3,5-methyl-4-hydroxyphenyl ) fluorene (prepared according to the method of Example 1), 0.006mol (2.017g) hexafluorobisphenol A, 0.015mol (2.087g) 2,6-difluorobenzonitrile, 20mL sulfolane, 0.01875mol (2.5875g) potassium carbonate, 15mL of toluene, reflux at 128°C, carry water for 4 hours, let go of the water-carrying agent; raise the temperature to 180°C, distill the toluene, continue the reaction for 10 hours, and discharge the material in water to obtain a strip-shaped polymer. The polymer was crushed with a masher, boiled 6 times with distilled water, and dried in a vacuum oven at 40°C for 48 hours; 7.2 g of benzylmethyl-containing polyfluorene ether nitrile copolymer was obtained. The benzylmethyl group accounted for 240 mole percent of the resulting polymer.

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Abstract

The invention discloses a poly(fluorenyl ether nitrile) crosslinked anion exchange membrane material with functionalized cationic groups for a fuel cell and a preparation method of the poly(fluorenyl ether nitrile) crosslinked anion exchange membrane material, and relates to the technical field of anion exchange membranes. According to the invention, a poly(fluorenyl ether nitrile) polymer with a benzyl methyl group is produced by a nucleophilic polycondensation reaction; then a poly(fluorenyl ether nitrile) polymer with benzyl bromide is produced by a bromination reaction; then a poly(fluorenyl ether nitrile) polymer with functionalized cationic groups is produced by a quaternization reaction; at last, through adding a crosslinked agent, the poly(fluorenyl ether nitrile) crosslinked anion exchange membrane material with functionalized cationic groups is produced by a solution blending method. At 80 DEG C, the ionic conductivity is 0.051S / cm-0.089S / cm; at 30 DEG C, the methanol permeability coefficient is 0.96x10<-7>cm<2>s<-1>-1.56x10<-7>cm<2>s<-1>. After being soaked in a NaOH solution with the concentration of 2mol / L at 60 DEG C for 10 days, the crosslinked membrane remains the ionic conductivity of 60.0-77.5%, indicating that the crosslinked anion exchange membrane has excellent stability in alkali resistance. Compared with a perfluorosulfonic acid film, the composite proton exchange membrane produced in the invention is lower in cost and easy to be industrialized and can be applied in the fuel cell field.

Description

technical field [0001] The invention belongs to the technical field of anion exchange membranes, and in particular relates to a polyfluorene ether nitrile cross-linked anion exchange membrane material functionalized with cationic groups for fuel cells and a preparation method thereof. Background technique [0002] Facing the rapid depletion of fossil energy sources such as coal, oil, and natural gas, it is urgent to develop an environmentally friendly and renewable new energy source. In recent years, great progress has been made in the development and utilization of renewable energy such as solar energy, wind energy, and tidal energy. However, due to the influence of environmental factors, geographical conditions and climate, it cannot be widely used. Therefore, it is imminent to develop a new type of energy that is efficient, portable, green, and pollution-free. A fuel cell is an energy conversion device that converts chemical energy directly into electrical energy. The ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M8/1027H01M8/1081C08G65/48C08G65/40C08J5/18
CPCC08G65/4006C08G65/48C08J5/18C08J2371/00H01M8/1027H01M8/1081Y02E60/50Y02P70/50
Inventor 王哲罗雪妍徐晶美徐达
Owner CHANGCHUN UNIV OF TECH
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