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Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof

A technology of sulfonated polyether ether ketone and proton exchange membrane, applied in electrical components, electrochemical generators, fuel cells, etc., can solve the problem of low proton conductivity, reduced mechanical strength, water absorption and swelling degree, and two-phase separation Not obvious and other problems, to achieve the effect of improving the overall performance

Inactive Publication Date: 2012-06-13
SHANGHAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the sulfonation degree (DS) of this material will directly affect the performance of the proton exchange membrane in all aspects. The SPEEK proton exchange membrane with low DS has good mechanical strength, alcohol resistance and thermochemical stability, but due to the sulfonic acid group The amount of the material is small, the separation of the two phases is not obvious, and its proton conductivity is not high, which hinders the realization of the electrochemical cycle reaction of the fuel cell and the efficiency of the fuel cell. Although the SPEEK proton exchange membrane with high DS has a high proton conductivity , but its mechanical strength is reduced, water absorption and swelling are too high, SPEEK will degrade in methanol at high temperature, which seriously affects the stability of the membrane and the life of the fuel cell

Method used

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  • Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof
  • Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof
  • Binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and preparation method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Embodiment one: the composition formula and preparation process of the present embodiment are as follows:

[0028] 1. Formulation

[0029] A. Composite membrane matrix material: DS is 68.02% SPEEK material, and the mass percentage is 90%.

[0030] B. Binary doped solid: nano-CeO 2 、H 3 PW 12 o 40 , the mass percentage is 10%, where CeO 2 and H 3 PW 12 o 40 The molar ratio is 1:1.

[0031] 2. Synthesis of SPEEK material with DS of 68.02%: Add 20g of PEEK powder and 800ml of concentrated sulfuric acid into a 1L three-necked flask, and stir the reaction at 60°C for 9 hours. After the reaction solution is cooled to room temperature, pass the reaction solution through the glass Pour the funnel into 4.5L of ice-water mixture, after cooling, rinse with a large amount of deionized water for 6 times, then let it stand overnight with 4.5L of deionized water, then rinse with deionized water for 3 times, and filter out the pink A colored SPEEK solid was obtained, and the ...

Embodiment 2

[0035] Embodiment two: the composition formula and the preparation process of the present embodiment are as follows:

[0036] 1. Formulation

[0037] A. Composite membrane matrix material: DS is 61.79% SPEEK material, and the mass percentage is 85%.

[0038] B. Binary Doped Solid: Nano Y2 o 3 、H 3 PW 12 o 40 , the mass percentage is 15%, where Y 2 o 3 and H 3 PW 12 o 40 The molar ratio is 1:1.

[0039] 2. Synthesis of SPEEK: Add 25g of PEEK powder and 500ml of concentrated sulfuric acid into a 1L three-necked flask, and mechanically stir the reaction at 60°C for 6h. After the reaction solution is cooled to room temperature, pour the reaction solution through a glass funnel into 4.5L After cooling, rinse with a large amount of deionized water for 6 times, then let it stand overnight with 4.5L of deionized water, then rinse with deionized water for 3 times, filter out the pink SPEEK solid, and put The product was dried under vacuum at 100 °C for 24 h.

[0040] 3. Pre...

Embodiment 3

[0043] Embodiment three: the composition formula and the preparation process of the present embodiment are as follows:

[0044] 1. Formulation

[0045] A. Composite membrane matrix material: DS is 61.79% SPEEK material, and the mass percentage is 90%.

[0046] B. Binary Doped Solid: Nano Y 2 o 3 、H 3 PW 12 o 40 , the mass percentage is 10%, where Y 2 o 3 and H 3 PW 12 o 40 The molar ratio is 1:2.

[0047] 2. Synthesis of SPEEK: Add 25g of polyetheretherketone PEEK powder and 500ml of concentrated sulfuric acid into a 1L three-necked flask, and mechanically stir the reaction at 60°C for 6h. After the reaction solution is cooled to room temperature, pass the reaction solution through a glass funnel. Pour into 4.5L of ice-water mixture, after cooling, rinse with a large amount of deionized water for 6 times, then let it stand overnight with 4.5L of deionized water, then rinse with deionized water for 3 times, and filter out the pink SPEEK was solid, and the product wa...

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Abstract

The invention relates to a binary doped modified sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) and a preparation method thereof. The PEM comprises the following components in percentage by weight: 80-99% of SPEEK with the vulcanization degree being 40-80%: and 1-20% of binary doped solid:, wherein the binary doped solid comprises cerium oxide or yttrium oxide and phosphotungstic acid in a mol rate of 1:(1-3).

Description

[0001] technology neighborhood [0002] The invention relates to a binary doped modified sulfonated polyether ether ketone SPEEK proton exchange membrane and a preparation method thereof, in particular to a binary doped modified sulfonated polyetheretherketone SPEEK of cerium oxide or yttrium oxide and phosphotungstic acid Proton exchange membrane and its preparation method. Background technique [0003] Polyetheretherketone (SPEEK) material has become a key research material for proton exchange membranes in direct methanol fuel cells because of its high mechanical strength, good thermal stability and chemical stability. Sulfonate PEEK with sulfonating reagents such as concentrated sulfuric acid, and introduce sulfonic acid groups into the main chain of PEEK. Due to the presence of sulfonic acid group hydrophilic phase and hydrophobic phases such as benzene rings and ether bonds on the polymer backbone, it can make SPEEK material has a certain proton conductivity, and the rel...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M8/02H01M2/16C08L71/08C08K3/22C08K3/32C08J5/22H01M8/1025H01M8/1081
CPCY02E60/12Y02E60/50
Inventor 郭强赵娟王娴娴童菊英李夏蔡京晶罗德刚
Owner SHANGHAI UNIV
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