本文選題：質(zhì)子交換膜燃料電池 + 介孔材料　； 參考：《南京大學(xué)》2017年碩士論文

【摘要】：伴隨著對(duì)清潔可再生能源的需求,燃料電池在交通、發(fā)電等領(lǐng)域得到廣泛的研究和應(yīng)用。作為質(zhì)子交換膜燃料電池的關(guān)鍵部件,質(zhì)子交換膜現(xiàn)階段的性能和成本限制了質(zhì)子交換膜燃料電池的商業(yè)化。全氟磺酸膜中添加微米級(jí)高比表面積的多孔材料是降低成本研究中的一個(gè)重要的方向。本文采用硫酸銨和氯氧化鋯為前驅(qū)體制備了可調(diào)控比表面積的介孔磺酸化氧化鋯(S-Zr02)。S-Zr02引入到Nafion溶液中后制備的混合膜的質(zhì)子傳導(dǎo)率得到了大大提高。該復(fù)合膜有望能作為低成本和高性能的質(zhì)子交換膜應(yīng)用在商業(yè)燃料電池中。氧化鋯材料是一種常見(jiàn)的固體超酸,其磺酸基團(tuán)具有傳導(dǎo)質(zhì)子的潛力。但傳統(tǒng)的氧化鋯的比表面積較小且表面官能化程度不高。本文提出新型的合成方法,采用硫酸銨和氯氧化鋯為前驅(qū)體,以碳黑BP2000為模板,通過(guò)高溫煅燒制備出S-Zr02。X射線衍射表征表明,當(dāng)溫度在600℃和650℃之間時(shí),生成的S-Zr02是有利于質(zhì)子傳導(dǎo)的四方晶型。傅里葉紅外光譜分析說(shuō)明其中含有大量有利于質(zhì)子傳導(dǎo)的磺酸基團(tuán)。掃描電子顯微鏡(SEM)、透射電子顯微鏡(TEM)表征發(fā)現(xiàn),S-Zr02粉末是由平均粒徑約為8 nm的納米晶體聚集而成,納米晶體之間的界限以及幾個(gè)納米尺度的通孔均表明介孔材料的成功制備。BET法表征的結(jié)果表明,制備的S-Zr02粉末的比表面積很高,最高的比表面積為181 m2 g-1,遠(yuǎn)高于大部分傳統(tǒng)氧化鋯材料。滴定法測(cè)定離子交換容量(IEC)測(cè)得其最高的IEC也高達(dá)0.48μequivm-2。同時(shí),結(jié)合表征結(jié)果能夠發(fā)現(xiàn),樣品的比表面積和IEC可以通過(guò)改變BP2000和前驅(qū)體的比例來(lái)調(diào)控,并且兩者的比值是固定的。這說(shuō)明S-Zr02比表面積的變化不影響其表面的化學(xué)性質(zhì),即磺酸基團(tuán)的面密度是保持一致的。為了提高質(zhì)子交換膜的性能,我們將介孔S-Zr02引入到Nafion基質(zhì)中,制備出S-Zr02/Nafion復(fù)合膜。SEM表征發(fā)現(xiàn),復(fù)合膜的平均厚度為20.5μm。TEM表征復(fù)合膜切片表明,高密度的離子團(tuán)簇聚集在S-Zr02和Nafion之間界面,使得S-Zr02表面官能團(tuán)化提高�；撬犭x子簇聚集到S-Zr02的介孔的表面,能夠有效地構(gòu)建平均直徑約為10nm的離子通道,確保通過(guò)整個(gè)膜的高效長(zhǎng)程質(zhì)子傳輸。實(shí)驗(yàn)分析發(fā)現(xiàn),制備的S-ZrO2/Nafion復(fù)合膜的質(zhì)子傳導(dǎo)率最高達(dá)到0.83Scm-1,約為商業(yè)Nafion 211的7倍。在80℃、20～100%相對(duì)濕度的濕度范圍內(nèi),S-ZrOa/Nafion復(fù)合膜的質(zhì)子傳導(dǎo)率均明顯高于商業(yè)Nafion211膜,這得益于膜的高含水率。全電池測(cè)試結(jié)果表明,S-ZrOa/Nafion復(fù)合膜在0.6 V時(shí)最高電流密度和功率密度分別為1310 mAcm-2和786 mW cm-2,遠(yuǎn)高于商業(yè)Nafion211膜。復(fù)合膜的最高功率密度為988 mW cm-2,大大高于商業(yè)Nafion211膜。在低濕條件下,制備的S-ZrO2/Nafion復(fù)合膜功率密度也高于商業(yè)的Nafion211膜,這證明S-ZrO2/Nafion復(fù)合膜全電池性能優(yōu)異,并能適應(yīng)不同的濕度操作條件,大大優(yōu)于目前商業(yè)的Nafion 膜。
[Abstract]:With the demand for clean and renewable energy, fuel cells have been widely studied and applied in transportation, power generation and other fields. As a key component of proton exchange membrane fuel cell, the performance and cost of proton exchange membrane at present limit the commercialization of proton exchange membrane fuel cell. The application of porous materials with high specific surface area in perfluorinated sulfonic acid membrane is an important research direction in cost reduction. In this paper, the proton conductivity of the mixed membranes with adjustable specific surface area of mesoporous zirconia (S-Zr02U. S-Zr02) was prepared by using ammonium sulfate and zirconium chloride as precursors. The proton conductivity of the mixed membranes was greatly improved after the introduction of S-Zr02U. S-Zr02 into Nafion solution. The composite membrane is expected to be used as a low-cost and high-performance proton exchange membrane in commercial fuel cells. Zirconia is a common solid superacid whose sulfonic group has the potential to conduct protons. However, the specific surface area of traditional zirconia is small and the degree of surface functionalization is not high. In this paper, a new synthesis method was proposed. The S-Zr02.X ray diffraction characterization was prepared with ammonium sulfate and zirconium chloride as precursors, carbon black BP2000 as template, and calcined at high temperature. The results showed that the temperature was between 600 鈩，

本文編號(hào)：1877715