本文選題：雜多酸 + 質子交換膜　； 參考：《安徽理工大學》2014年碩士論文

【摘要】：全氟磺酸質子交換膜是聚合物質子交換膜燃料電池的核心部件,它可以讓質子穿過、而水分和氣體無法透過。膜的機械強度、耐高溫性、耐化學藥品性等對于膜的使用壽命具有重要影響。摻雜無機親水粒子、無機質子導體的質子膜改性對于提高膜的熱穩(wěn)定性和高溫保水性等,具有重要意義。 以國產東岳集團生產的全氟磺酸離子膜為基體,分別摻雜磷鉬酸和硅鎢酸、硅鎢酸以及二氧化鈦、二氧化硅顆粒,利用溶膠-凝膠法和交聯法,制備用于燃料電池的磷鉬酸/硅鎢酸、硅鎢酸、TiO2/SiO2復合質子交換膜。分別測定其室溫(20℃)、30℃～90℃以及低溫-30℃～0℃下的阻抗譜,進而求得不同溫度下各復合膜對應的電導率。可以發(fā)現,改性之后的復合膜其電導率明顯高于原膜。如在90℃時,磷鉬酸/硅鎢酸復合膜及原膜的電導率分別為27.5×10-6·cm-1和2.70×10-6S·cm-1。且隨著溫度的升高原膜與復合膜的電導率均呈增大的趨勢。如,20℃升到90℃時,二氧化鈦/二氧化硅復合膜的電導率從31.2×10-7S·cm-1增加到約為20℃時電導率的4倍。測定擾動電壓分別為5mV、10mV、20mV和l00mV時,其對原膜和磷鉬酸/硅鎢酸復合膜阻抗譜的影響,但發(fā)現其變化對阻抗譜的高頻半圓影響不大。 使用熱失重法考察制備的每種復合膜的熱穩(wěn)定性。對于磷鉬酸/硅鎢酸復合膜,使用Kissinger法、Flynn-Wall-Ozawa法研究其熱降解動力學,得到表觀活化能E、相關系數r等動力學參數；比較了改性前后質子膜熱穩(wěn)定性的變化,發(fā)現當溫度超過363.3℃時,復合膜的熱穩(wěn)定性優(yōu)于原膜,當溫度低于363.3℃時,復合膜耐溫性能不及原膜。對于硅鎢酸、二氧化鈦/二氧化硅復合膜,使用Kissinger、 Flynn-Wall-Ozawa、Starink和Friedman法研究其熱降解動力學,并使用Achar-Brindley-Sharp、Coats-Redfern以及α-Z(α)法推導出了其可能的熱降解機理。硅鎢酸復合膜第一階段的熱降解機理為Mampel Power (R1)法則：微分式f(α)=1,積分式g(α)=α。第二階段的機理函數：f(a)=(1-α)2, g(α)=(1-α)-1;二氧化鈦/二氧化硅復合膜的熱降解機理亦為二級反應、F2機理。
[Abstract]:Perfluorosulfonic acid proton exchange membrane is the core component of the polymer proton exchange membrane fuel cell. It can let protons pass through, and the water and gas can not be permeated. The mechanical strength, high temperature resistance and chemical resistance of the membrane have an important influence on the life of the membrane. It is of great significance to improve the thermal stability and high temperature water retention of the membrane.
The perfluoro sulfonic acid ion membrane produced by the domestic Dongyue Group was used as the matrix, doped phosphotungstic acid and silicotungstic acid, silicotungstic acid and titanium dioxide, silica particles. The phospho molybdic acid / silicotungstic acid, silicotungstic acid and TiO2/ SiO2 composite proton exchange membrane used in fuel cell were prepared by the sol-gel method and crosslinking method. The room temperature (20 C) and 30 C were measured respectively. The electrical conductivity of the composite films at different temperatures was obtained at 90 C and at low temperature -30 to 0 C. It was found that the conductivity of the modified composite films was significantly higher than that of the original film. At 90, the conductivity of the phospho molybdic acid / silicotungstic acid composite film and the original film were 27.5 * 10-6. Cm-1 and 2.70 x 10-6S. The conductivity of the original film and the composite film increased. For example, the conductivity of the titanium dioxide / silica composite film increased from 31.2 x 10-7S. Cm-1 to about 4 times at about 20 C. The impedance spectra of the membrane and phosphotungstic acid / silicotungstic acid composite membrane were measured at 5mV, 10mV, 20mV and l00mV, respectively. But the change of impedance has little effect on the high frequency semicircle of impedance spectrum.
Thermal stability of each composite membrane prepared by thermal weight loss was investigated. For phospho Molybdate / silicotungstic acid composite membrane, the thermal degradation kinetics was studied by Kissinger method and Flynn-Wall-Ozawa method. The kinetic parameters such as apparent activation energy E, correlation coefficient r were obtained, and the thermal stability of the membrane was compared before and after the modification, and it was found that the temperature was over 363.. At 3 C, the thermal stability of the composite film is better than that of the original film. When the temperature is below 363.3, the temperature resistance of the composite film is less than that of the original film. For silicotungstic acid, titanium dioxide / silica composite membrane, the thermal degradation kinetics of the composite film is studied by Kissinger, Flynn-Wall-Ozawa, Starink and Friedman, and Achar-Brindley-Sharp, Coats-Redfern and alpha -Z (alpha) are used. The mechanism of thermal degradation is deduced by method. The thermal degradation mechanism of the first phase of the composite membrane of silicotungstate is Mampel Power (R1) rule: differential f (alpha) =1, integral g (alpha) = Alpha. The mechanism function of the second stage: F (a) = (1- a) 2, G (alpha) = (1- alpha) -1, and the thermal degradation mechanism of the two oxygen titanium / silica composite membrane is also the two order reaction mechanism.

【學位授予單位】：安徽理工大學
【學位級別】：碩士
【學位授予年份】：2014
【分類號】：TM911.4

【參考文獻】

相關期刊論文 前2條

1 ;Synthesis and Water Uptake of Sulfonated Poly (phthalazinone ether sulfone ketone)/Polyacrylic Acid Proton Exchange Membranes[J];Chinese Chemical Letters;2006年07期

2 榮倩;顧爽;賀高紅;吳雪梅;胡正文;焉曉明;;SPEEK/P4VP酸堿復合質子交換膜的制備與性能[J];高分子材料科學與工程;2009年08期

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本文編號：1781216