POSS (Polyhedral Oligomeric Silsesquioxane) crosslinking type sulfonated polyimide proton exchange membrane as well as preparation method thereof

A technology of sulfonated polyimide and proton exchange membrane, which is applied in the field of functional polymer materials and electrochemistry, and can solve proton conduction hindrance, poor stability against free radical oxidation, and low proton conductivity of sulfonated polybenzimidazole membrane And other issues

Inactive Publication Date: 2014-02-05
TONGJI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, with Nafion ? Compared with sulfonated hydrocarbon polymer membranes, the stability against free radical oxidation is relatively poor, thus affecting the service life of fuel cells
[0004] Sulfonated polybenzimidazole has excellent resistance to free radical oxidation, but proton conduction is hindered due to the strong interaction between the basic imidazole group and the acidic sulfonic acid group, making the proton conduction of the sulfonated polybenzimidazole membrane very low rate

Method used

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  • POSS (Polyhedral Oligomeric Silsesquioxane) crosslinking type sulfonated polyimide proton exchange membrane as well as preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] The ratio of raw materials used is as follows:

[0033] 1 part of SPIBI-100 (number of moles of repeating units)

[0034] Octaepoxy polyhedral oligomeric silsesquioxane (POSS) 0.025 parts (accounting for the mass number of SPIBI-100)

[0035] Dimethylsulfoxide 160 parts (moles)

[0036] (1) Soak 0.6g SPIBI-100 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolved in 13 mL of dimethyl sulfoxide (DMSO) at 100 °C to form a homogeneous solution.

[0037] (2) Dissolve 0.015g octaepoxy-substituted POSS in 1mL DMSO solution at room temperature, and stir until a homogeneous solution. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

[0038] (3) The mixture obtained in step (2) was poured on a 10 cm×10 cm glass plate, and dried in a vacuum oven at 80 °C for 6 h, and the solvent was completely evaporated. Raise the temperature to 150 °C and continue heating for 10 h to complete the cross-linking react...

Embodiment 2

[0043] The ratio of raw materials used is as follows:

[0044] 1 part of SPIBI-10 (number of moles of repeating units)

[0045] 0.15 parts of octaepoxy polyhedral oligomeric silsesquioxane (POSS) (accounting for the mass number of SPIBI-10)

[0046]400 parts of dimethyl sulfoxide (number of moles)

[0047] (1) Soak 0.6g SPIBI-100 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolved in 30 mL dimethyl sulfoxide (DMSO) at 100 °C to form a homogeneous solution.

[0048] (2) Dissolve 0.015g octaepoxy-substituted POSS in 4mL DMSO solution at room temperature, and stir until a homogeneous solution is obtained. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

[0049] (3) The mixture obtained in step (2) was poured on a 10 cm×10 cm glass plate, and dried in a vacuum oven at 80 °C for 6 h, and the solvent was completely evaporated. Raise the temperature to 150°C and continue heating for 12 hours to complet...

Embodiment 3

[0052] The ratio of raw materials used is as follows:

[0053] 1 part of SPIBI-190 (number of moles of repeating unit)

[0054] Octaepoxy polyhedral oligomeric silsesquioxane (POSS) 0.50 parts (mass ratio to SPIBI-190)

[0055] N-Methylpyrrolidone (NMP) 500 parts (moles)

[0056] (1) Soak 0.6g SPIBI-190 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolve in 30 mL of N-methylpyrrolidone (NMP) at 100 °C to form a homogeneous solution.

[0057] (2) Dissolve 0.3g of octaepoxy-substituted POSS in 10mL of NMP solution at room temperature, and stir until a homogeneous solution is obtained. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

[0058] (3) The mixture obtained in step (2) was poured on a 10 cm×10 cm glass plate, and dried in a vacuum oven at 80 °C for 6 h, and the solvent was completely evaporated. Raise the temperature to 150°C and continue heating for 8 hours to complete the crosslinking rea...

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Abstract

The invention belongs to the technical field of functional high molecular materials and electrochemistry, and specifically relates to a POSS (Polyhedral Oligomeric Silsesquioxane) crosslinking type sulfonated polyimide proton exchange membrane as well as a preparation method thereof. The preparation method comprises the following steps: firstly, synthesizing a sulfonated polyimide polymer with a crosslinkable group imidazole group on a main chain, wherein the degree of sulfonation is controlled within 10-190%; and preparing a membrane forming liquid, adding a functional POSS crosslinking agent, carrying out reaction with the imidazole group, crosslinking the sulfonated polyimide polymer in a membrane forming process to form the crosslinking type sulfonated polyimide proton exchange membrane. The crosslinking membrane is endowed with good mechanical property and has higher hydrolytic stability and anti-oxidation stability. The method disclosed by the invention is good in controllability of the preparation process. Compared with conventional sulfonated polyimide membranes, the crosslinking type sulfonated polyimide proton exchange membrane is high in mechanical strength, strong in hydrolytic resistance and oxidation resistance, and good in dimensional stability, and has a broad application prospect in polymer electrolyte membrane fuel cells.

Description

technical field [0001] The invention belongs to the technical field of functional polymer materials and electrochemistry, and in particular relates to a POSS cross-linked sulfonated polyimide proton exchange membrane and a preparation method thereof. Background technique [0002] Proton exchange membrane fuel cells (PEMFCs) are currently the most mature technology in the world that can convert hydrogen and oxygen in the air into clean water and release electricity. It has the advantages of high energy efficiency, low emissions and environmental friendliness. The proton exchange membrane is the core component of PEMFC, which determines the performance and service life of the entire battery. At present, the main application in PEMFC is perfluorosulfonic acid membrane (such as Nafion ? ), but the disadvantages of high price, low mechanical strength, poor dimensional stability and high permeability limit its wide application. [0003] The sulfonated polyimide proton membrane h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M8/02H01M8/10C08J5/22C08L79/08C08K5/549
CPCY02E60/523C08J5/2262C08J2379/08C08K5/549C08L2203/16H01M8/103C08L79/08Y02E60/50
Inventor 潘海燕张媛媛浦鸿汀常志宏
Owner TONGJI UNIV
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