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Composite type high-temperature proton exchange membrane (PEM) based on sulfonated aryl ether type polybenzimidazole (PBI) and sulfonated polysilsesquioxane and preparation method of composite type high-temperature proton exchange membrane

A technology of polybenzimidazole and silsesquioxane, which is applied in the manufacture of final products, electrochemical generators, sustainable manufacturing/processing, etc., can solve problems such as difficult separation, impurities, and low efficiency, and achieve low cost , reduce the swelling rate, improve the effect of adsorption level

Active Publication Date: 2019-07-23
JILIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In most cases, the sulfonic acid groups on the polymer are connected to the main chain of the polymer by post-sulfonation, which is inefficient and contains impurities, which are not easy to separate

Method used

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  • Composite type high-temperature proton exchange membrane (PEM) based on sulfonated aryl ether type polybenzimidazole (PBI) and sulfonated polysilsesquioxane and preparation method of composite type high-temperature proton exchange membrane
  • Composite type high-temperature proton exchange membrane (PEM) based on sulfonated aryl ether type polybenzimidazole (PBI) and sulfonated polysilsesquioxane and preparation method of composite type high-temperature proton exchange membrane
  • Composite type high-temperature proton exchange membrane (PEM) based on sulfonated aryl ether type polybenzimidazole (PBI) and sulfonated polysilsesquioxane and preparation method of composite type high-temperature proton exchange membrane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] 1) Synthesis of diacid monomer

[0039] Put 0.1mol of potassium 2,5-dihydroxybenzenesulfonate and 0.21mol of potassium carbonate in a three-neck flask, add 200mL of N,N-dimethylacetamide and 40mL of toluene into the three-necked flask, and use nitrogen as a protection gas. Under mechanical stirring, heat the reaction system to 150°C to make it evenly reflux, remove the water generated by the reaction in the system by azeotroping, and use an oil-water separator to keep the system in this state for 3.5 hours. After fully removing water, release the excess water in the system. toluene. Add 0.21 mol p-fluorobenzonitrile solid to the system, and raise the temperature to 160°C. After reacting for 7 hours, pour the reaction solution into cold water, and obtain a solid product after suction filtration, and wash with ethanol several times to obtain a white solid.

[0040]Add the white solid obtained above and 4 mol of potassium hydroxide solid into a three-necked flask, and ad...

Embodiment 2

[0050] 1) Dissolve 0.2850 g of sulfonated polybenzimidazole polymer with a sulfonation degree of 30% in 7 mL of DMAc to obtain a polymer solution; Propanesulfonic acid aqueous solution was added to 1mL of DMAc, and then 0.1mL of ammonia water with a mass fraction of 25% was added to obtain a mixed solution. While the polymer solution was constantly stirring, the mixed solution was added to make it evenly mixed, and then poured on a clean glass plate In the oven, dry at 80°C for 24h, at 100°C for 12h, at 120°C for 12h, and finally keep at 120°C for 12h in vacuum, so that the hydrophilic sulfonated aryl ether type polybenzimidazole and sulfonate can be obtained on the glass plate. film of polysilsesquioxane.

[0051] 2) Soak the obtained film based on hydrophilic sulfonated aryl ether polybenzimidazole and sulfonated polysilsesquioxane at 120°C in an aqueous solution of phosphoric acid with a mass fraction of 85% for 48 hours, then take it out and dry it at 120°C After 12 hours...

Embodiment 3

[0054] 1) Dissolve 0.2760 g of sulfonated polybenzimidazole polymer with a sulfonation degree of 30% in 7 mL of DMAc to obtain a polymer solution; then 57 uL of 3-(trihydroxysilyl)- Propanesulfonic acid aqueous solution was added to 1mL of DMAc, and then 0.1mL of ammonia water with a mass fraction of 25% was added to obtain a mixed solution. While the polymer solution was constantly stirring, the mixed solution was added to make it evenly mixed, and then poured on a clean glass plate In the oven, dry at 80°C for 24h, at 100°C for 12h, at 120°C for 12h, and finally keep at 120°C for 12h in vacuum, so that the hydrophilic sulfonated aryl ether type polybenzimidazole and sulfonate can be obtained on the glass plate. film of polysilsesquioxane.

[0055] 2) Soak the obtained film based on hydrophilic sulfonated aryl ether polybenzimidazole and sulfonated polysilsesquioxane at 120°C in an aqueous solution of phosphoric acid with a mass fraction of 85% for 48 hours, then take it out ...

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Abstract

The invention relates to a composite type high-temperature proton exchange membrane (PEM) based on hydrophilic sulfonated aryl ether type polybenzimidazole (PBI) and sulfonated polysilsesquioxane anda preparation method of the composite type high-temperature proton exchange membrane, and belongs to the technical field of fuel cells. The preparation method comprises the following steps: first, dissolving a sulfonated polybenzimidazole polymer in an organic solution, then sufficiently mixing with an additive solution, casting an obtained mixed solution into a membrane, then soaking the membranein phosphoric acid, taking out the soaked membrane, and drying to obtain the exchange membrane. The presence of a sulfonic acid group in the sulfonated polybenzimidazole polymer greatly enhances thehydrophilicity, and the problem of precipitation at the presence of water during the addition of a 3-(trihydroxysilyl)-1-propanesulfonic acid additive aqueous solution is solved. Further, a sulfonatedpolysilsesquioxane skeleton with a cage structure is formed in the film, and the skeleton has hydrophobicity and has the sulfonic acid group, so that the overall hydrophilic and acidophilic properties are enhanced. After sulfonated polysilsesquioxane is introduced into the composite membrane, the swelling ratio of the proton exchange membrane can also be reduced to a certain extent and the mechanical properties of the proton exchange membrane are enhanced.

Description

technical field [0001] The invention belongs to the technical field of fuel cells, and specifically relates to a composite high-temperature proton exchange membrane based on hydrophilic sulfonated aryl ether polybenzimidazole and sulfonated polysilsesquioxane and a preparation method thereof. Background technique [0002] Proton exchange membrane fuel cell (PEMFC) has many advantages, such as high specific power, high specific energy, fast cold start and environmental friendliness. It is because of its distinctive features that it is widely used in many fields such as power generation and cogeneration. This arouses the research interest of scientists. In a proton exchange membrane fuel cell, the core component is the proton exchange membrane (PEM), which not only conducts protons, but also prevents cross-permeation of oxygen from the cathode and hydrogen from the anode. At present, most of the perfluorosulfonic acid membranes are used in the market, but it also has disadvan...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08J7/14C08J5/22C08L79/04C08L83/08C08G73/18H01M8/1072
CPCC08G73/18C08J5/22C08J7/14C08J2379/04C08J2483/08H01M8/1074Y02E60/50Y02P70/50
Inventor 刘佰军李天洋王鹏石埕荧
Owner JILIN UNIV
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