Nanometer yttrium oxide and polyphosphazene derivative dual doped modified sulfonated polyphenylene sulfide proton exchange membrane and preparation method thereof

A technology of sulfonated polyphenylene sulfide and proton exchange membrane, applied in electrochemical generators, electrical components, fuel cells, etc., can solve the problems of affecting the proton exchange membrane, not obvious two-phase separation, high water absorption and swelling degree , to achieve the effect of improving the overall performance

Inactive Publication Date: 2014-01-01
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 SPPS proton exchange membrane with low DS has good mechanical strength, alcohol resistance and thermal stability, but due to the sulfonic acid group The amount of is small, the separation of the two phases is not obvious, and its proton conductivity is not ideal, which hinders the electrochemical cycle reaction of the fuel cell
Although the SPPS proton exchange membrane with high DS has high proton conductivity, its mechanical strength is reduced, its water absorption rate and swelling are too high, and SPPS will degrade in methanol at high temperature, which seriously affects the stability of the membrane and fuel consumption. battery life
Because the degree of sulfonation has contradictory effects on the performance of proton exchange membrane materials, in the design of SPPS proton exchange membranes, it is usually necessary to comprehensively consider the degree of sulfonation and modification methods of SPPS, and it is not possible to lose sight of the other.

Method used

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Embodiment one: the composition formula and preparation process of the present embodiment are as follows:

[0022] 1. Formulation

[0023] (1). Composite membrane matrix material: DS is 70.2% SPPS material, and the mass percentage is 90%.

[0024] (2). Binary doped phase: Nano Y 2 o 3 And polyphosphazene derivatives, the mass percentage is 10%, wherein Y 2 o 3 The molar ratio of the polyphosphazene derivative sub-liquid is 1:1.

[0025] 2. Synthesis of SPPS material with DS of 70.2%: Add 20 g of polyphenylene sulfide powder and 800 ml of concentrated sulfuric acid into a 1 L three-necked flask, and mechanically stir the reaction at 60 °C for 4 h, and wait for the reaction liquid to cool to After room temperature, the reaction solution was passed through a glass funnel and poured into 4.5 L of ice-water mixture. After cooling, it was rinsed with a large amount of deionized water for 5 times, then allowed to stand overnight with 4.5 L of deionized water, and then rin...

Embodiment 2

[0029] Embodiment two: the composition formula and the preparation process of the present embodiment are as follows:

[0030] 1. Formulation

[0031] (1). Composite membrane matrix material: DS is 72.4% SPPS material, and the mass percentage is 90%.

[0032] (2). Binary doped phase: Nano Y 2 o 3 And polyphosphazene derivatives, the mass percentage is 10%, wherein Y 2 o 3 The molar ratio to polyphosphazene derivatives is 1:2.

[0033] 2. Synthesis of SPPS material with DS of 72.4%: Add 20 g of polyphenylene sulfide powder and 800 ml of concentrated sulfuric acid into a 1 L three-necked flask, mechanically stir the reaction at 70 °C for 4 h, and wait for the reaction liquid to cool to After room temperature, the reaction solution was passed through a glass funnel and poured into 4.5 L of ice-water mixture. After cooling, it was rinsed with a large amount of deionized water for 5 times, then allowed to stand overnight with 4.5 L of deionized water, and then rinsed with deion...

Embodiment 3

[0037] Embodiment three: the composition formula and the preparation process of the present embodiment are as follows:

[0038] 1. Formulation

[0039] (1). Composite membrane matrix material: DS is 74.8% SPPS material, and the mass percentage is 90%.

[0040] (2). Binary doped phase: Nano Y 2 o 3 And polyphosphazene derivatives, the mass percentage is 10%, wherein Y 2 o 3 And the molar ratio of polyphosphazene derivatives is 1:3.

[0041]2. Synthesis of SPPS material with DS of 74.8%: 20 g of polyphenylene sulfide powder and 800 ml of concentrated sulfuric acid were added to a 1 L three-necked flask, mechanically stirred at 75 °C for 7 h, and the reaction solution was cooled to After room temperature, the reaction solution was passed through a glass funnel and poured into 4.5 L of ice-water mixture. After cooling, it was rinsed with a large amount of deionized water for 5 times, then allowed to stand overnight with 4.5 L of deionized water, and then rinsed with deionized...

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Abstract

The invention relates to a nanometer yttrium oxide and polyphosphazene derivative dual doped modified sulfonated polyphenylene sulfide (SPPS) proton exchange membrane and a preparation method thereof. The proton exchange membrane comprises the following components in percentage by weight: 75-99 percent of SPPS with the sulfonation degree of 57-80 percent, and 1-25 percent of a dual doped phase composed of nanometer yttrium oxide and a polyphosphazene derivative, wherein the molar ratio of the nanometer yttrium oxide to the polyphosphazene derivative is 1:(1-4). According to the invention, the SPPS with the medium sulfonation degree is used as a base material, so as to overcome the defects that the SPPS with an extremely high sulfonation degree has an extremely high water absorption rate and stability of a composite membrane is poor, and a certain water absorption rate of the composite membrane can be ensured; through the manner that the nano-scale rare-earth metallic oxide yttrium oxide and the polyphosphazene derivative are doped so as to enable an SPPS matrix to be directly in acid-base interaction with the doped material to improve the comprehensive performance of the composite membrane.

Description

technical field [0001] The invention relates to a binary doped modified sulfonated polyphenylene sulfide SPPS proton exchange membrane and a preparation method thereof, in particular to a binary doped modified sulfonated polyphenylene sulfide of nanometer yttrium oxide and polyphosphazene derivatives Ether SPPS proton exchange membrane and its preparation method. Background technique [0002] Sulfonated polyphenylene sulfide (SPPS) materials have become the research focus of proton exchange membranes for direct methanol fuel cells because of their high mechanical strength, good thermal stability and chemical stability. Use sulfonating reagents such as concentrated sulfuric acid to sulfonate polyphenylene sulfide (PPS), and introduce sulfonic acid groups into the main chain of PPS. Due to the sulfonic acid group hydrophilic phase and the benzene ring and carbon-sulfur bonds on the polymer backbone, etc. The existence of the hydrophobic phase can make the SPPS material have a...

Claims

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Application Information

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Patent Type & AuthorityApplications(China)
IPC IPC(8): H01M8/02H01M8/1032H01M8/1081
CPCY02E60/50C08J5/2256C08J2381/02C08K3/22C08K5/5399H01M8/1051C08L81/02
Inventor郭强李夏钱君质毕宸洋张天骄陈新新
OwnerSHANGHAI UNIV