Method for preparing high-temperature proton exchange membrane

Abstract

The invention discloses a method for preparing a high-temperature proton exchange membrane. The method is characterized by comprising the following steps: introducing a precursor composition with a metal organic frame into oxidized graphene to form a coexisting body of the oxidized graphene and the metal organic frame, subsequently adding the coexisting body together with a sodium hydroxide solution into an N-methyl pyrrolidone solution of sulfonyl chlorination polyphenyl ether to perform Hinsberg reaction to obtain polymer membrane casting liquid with the coexisting body, coating and drying so as to obtain the high-temperature proton exchange membrane. According to the method, the metal organic frame is introduced into the oxidized graphene by using a hydrothermal method to form the coexisting body, and is further prepared into the high-temperature proton exchange membrane together with sulfonated polyphenyl ether in a chemical bond mode, the membrane is good in mechanical strength, thermal stability and excellent high-temperature proton conductivity and oxidative resistance, and can be applied to high-temperature proton exchange membrane fuel batteries.

Description

technical field

[0001] The invention belongs to the technical field of high-temperature proton exchange membranes, and in particular relates to a preparation method of a novel graphene oxide-metal organic framework-based high-temperature proton exchange membrane. Background technique

[0002] Increasing the working temperature of the fuel cell is one of the effective measures to solve the complex water heat management of the battery and the poisoning of the catalyst; at the same time, it can also improve the kinetics of the oxygen reduction reaction at the anode and cathode of the battery, especially the cathode, thereby improving the working efficiency of the battery. Therefore, high-temperature proton exchange membrane fuel cell technology has become the main direction of fuel cell development today.

[0003] As one of the key materials of proton exchange membrane fuel cell, the working temperature of proton exchange membrane determines the working temperature of fuel cell...

Examples

Embodiment 1

[0034] This embodiment prepares the high temperature proton exchange membrane according to the following steps:

[0035] (1) Preparation of graphene oxide-metal organic framework: Ultrasonic dispersion of 0.03 g graphene oxide in 10 mL of water-ethanol mixture (volume ratio of water and ethanol is 1:1) to obtain mixture A, and then metal organic framework The precursor synthesis of the framework (0.1g basic zinc carbonate, 0.1g oxalic acid and 0.4g 3-amino-1,2,4-triazole) was ultrasonically dispersed in the obtained mixture A, and reacted for 72 hours at 180°C to obtain the product Wash with water and ethanol three times respectively, and then dry at 60° C. (dry for 4 hours) to obtain a brown-black graphene oxide-metal-organic framework coexistence body.

[0036] (2) Preparation of N-methylpyrrolidone solution of sulfonylchlorinated polyphenylene ether: Dissolve 0.2g of sulfonated polyphenylene ether in 1mL (0.9445g) of N,N-dimethylformamide, and slowly Add 0.5mL (0.838g) of ...

Embodiment 2

[0043] This embodiment prepares the high temperature proton exchange membrane according to the following steps:

[0044] (1) Preparation of graphene oxide-metal organic framework: Ultrasonic dispersion of 0.06 g graphene oxide in 10 mL of water-ethanol mixture (volume ratio of water and ethanol is 1:1) to obtain mixture A, and then metal organic framework The precursor synthesis of the framework (0.1g basic zinc carbonate, 0.1g oxalic acid and 0.4g 3-amino-1,2,4-triazole) was ultrasonically dispersed in the obtained mixture A, and reacted for 72 hours at 180°C to obtain the product Wash with water and ethanol three times respectively, and dry at 60°C (dry for 4 hours) to obtain a brown-black graphene oxide-metal organic framework coexistence body.

[0045] (2) Preparation of N-methylpyrrolidone solution of sulfonylchlorinated polyphenylene ether: Dissolve 0.2g of sulfonated polyphenylene ether in 1mL (0.9445g) of N,N-dimethylformamide, and slowly Add 0.5mL (0.838g) of thionyl...

Embodiment 3

[0052] (1) Preparation of graphene oxide-metal organic framework: Ultrasonic dispersion of 0.09 g graphene oxide in 10 mL of water-ethanol mixture (volume ratio of water and ethanol is 1:1) to obtain mixture A, and then metal organic framework The precursor synthesis of the framework (0.1g basic zinc carbonate, 0.1g oxalic acid and 0.4g 3-amino-1,2,4-triazole) was ultrasonically dispersed in the obtained mixture A, and reacted for 72 hours at 180°C to obtain the product Wash with water and ethanol three times respectively, and then dry at 60° C. (dry for 4 hours) to obtain a brown-black graphene oxide-metal-organic framework coexistence body.

[0053] (2) Preparation of N-methylpyrrolidone solution of sulfonylchlorinated polyphenylene ether: Dissolve 0.2g of sulfonated polyphenylene ether in 1mL (0.9445g) of N,N-dimethylformamide, and slowly Add 0.5mL (0.838g) of thionyl chloride dropwise, a white precipitate is formed, wash and filter with water, and dry at 60°C (dry for 2 ho...

technical field

[0001] The invention belongs to the technical field of high-temperature proton exchange membranes, and in particular relates to a preparation method of a novel graphene oxide-metal organic framework-based high-temperature proton exchange membrane. Background technique

[0002] Increasing the working temperature of the fuel cell is one of the effective measures to solve the complex water heat management of the battery and the poisoning of the catalyst; at the same time, it can also improve the kinetics of the oxygen reduction reaction at the anode and cathode of the battery, especially the cathode, thereby improving the working efficiency of the battery. Therefore, high-temperature proton exchange membrane fuel cell technology has become the main direction of fuel cell development today.

[0003] As one of the key materials of proton exchange membrane fuel cell, the working temperature of proton exchange membrane determines the working temperature of fuel cell...

Examples

Embodiment 1

[0034] This embodiment prepares the high temperature proton exchange membrane according to the following steps:

[0035] (1) Preparation of graphene oxide-metal organic framework: Ultrasonic dispersion of 0.03 g graphene oxide in 10 mL of water-ethanol mixture (volume ratio of water and ethanol is 1:1) to obtain mixture A, and then metal organic framework The precursor synthesis of the framework (0.1g basic zinc carbonate, 0.1g oxalic acid and 0.4g 3-amino-1,2,4-triazole) was ultrasonically dispersed in the obtained mixture A, and reacted for 72 hours at 180°C to obtain the product Wash with water and ethanol three times respectively, and then dry at 60° C. (dry for 4 hours) to obtain a brown-black graphene oxide-metal-organic framework coexistence body.

[0036] (2) Preparation of N-methylpyrrolidone solution of sulfonylchlorinated polyphenylene ether: Dissolve 0.2g of sulfonated polyphenylene ether in 1mL (0.9445g) of N,N-dimethylformamide, and slowly Add 0.5mL (0.838g) of ...

Embodiment 2

[0043] This embodiment prepares the high temperature proton exchange membrane according to the following steps:

[0044] (1) Preparation of graphene oxide-metal organic framework: Ultrasonic dispersion of 0.06 g graphene oxide in 10 mL of water-ethanol mixture (volume ratio of water and ethanol is 1:1) to obtain mixture A, and then metal organic framework The precursor synthesis of the framework (0.1g basic zinc carbonate, 0.1g oxalic acid and 0.4g 3-amino-1,2,4-triazole) was ultrasonically dispersed in the obtained mixture A, and reacted for 72 hours at 180°C to obtain the product Wash with water and ethanol three times respectively, and dry at 60°C (dry for 4 hours) to obtain a brown-black graphene oxide-metal organic framework coexistence body.

[0045] (2) Preparation of N-methylpyrrolidone solution of sulfonylchlorinated polyphenylene ether: Dissolve 0.2g of sulfonated polyphenylene ether in 1mL (0.9445g) of N,N-dimethylformamide, and slowly Add 0.5mL (0.838g) of thionyl...

Embodiment 3

[0052] (1) Preparation of graphene oxide-metal organic framework: Ultrasonic dispersion of 0.09 g graphene oxide in 10 mL of water-ethanol mixture (volume ratio of water and ethanol is 1:1) to obtain mixture A, and then metal organic framework The precursor synthesis of the framework (0.1g basic zinc carbonate, 0.1g oxalic acid and 0.4g 3-amino-1,2,4-triazole) was ultrasonically dispersed in the obtained mixture A, and reacted for 72 hours at 180°C to obtain the product Wash with water and ethanol three times respectively, and then dry at 60° C. (dry for 4 hours) to obtain a brown-black graphene oxide-metal-organic framework coexistence body.

[0053] (2) Preparation of N-methylpyrrolidone solution of sulfonylchlorinated polyphenylene ether: Dissolve 0.2g of sulfonated polyphenylene ether in 1mL (0.9445g) of N,N-dimethylformamide, and slowly Add 0.5mL (0.838g) of thionyl chloride dropwise, a white precipitate is formed, wash and filter with water, and dry at 60°C (dry for 2 ho...

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