本文主要研究内容
作者侯剑秋（2019）在《面向碱性燃料电池和中性液流电池阴离子交换膜结构设计》一文中研究指出：燃料电池可以将氢能高效无污染地转化成电能。目前发展最成熟的是质子交换膜燃料电池,但由于需要贵金属Pt作为催化剂和价格昂贵的Nafion膜作为聚合物电解质,其成本制约着燃料电池的推广。相比之下,使用非贵金属催化剂和阴离子交换膜(以下简称阴膜)的碱性燃料电池更具发展潜力,但目前阴膜的碱稳定性和离子电导率还不能满足实际需求。液流电池可以将风能和太阳能转化成的电能大规模地储存起来,再并入电网,实现按需供给。目前已经应用的液流电池是钒液流电池,但由于钒储量有限而且电池需要在强酸性环境下运行,不利于可持续发展。水系有机液流电池凭借原料来源广泛、价格低廉和运行安全稳定等特性,逐渐成为了研究热点。其中,中性液流电池使用阴膜,对设备和膜稳定性要求较低,在运行和材料成本上有优势,但对阴膜的机械稳定性和氯离子电导率要求较高。为了应对阴膜在碱性燃料电池和中性液流电池中的挑战,设计性能优异的膜结构是关键科学问题。目前商业化的阴膜多为功能基团和主链直接相连的结构,由于主链易受到功能基团上正电荷的影响,并且功能基团移动性差,因此膜碱稳定性和离子电导率较低。为了解决这一问题,研究者们设计了侧长链阴膜,并证实了其优异性能,但缺少简便的合成方法。此外,为了提高阴膜的在水中的稳定性,构建聚合物网络是一种实用的方法。但共价交联后的阴膜不溶不熔,一旦出现机械损伤,修复、回收或再利用都非常困难,不利于膜材料的可持续发展。因此,本文从高分子结构和合成方法上进行创新,设计新型的阴膜结构,包括“纺锤型”和“动态共价键网络型”,以期提高阴膜的离子电导率和稳定性,并赋予阴膜可回收和自修复的特性,从而使其在碱性燃料电池和中性液流电池中更具优势。具体的研究工作如下:(1)使用条件温和、无贵金属催化剂参与的Wittig反应将不同长度的烷基链引入功能基团和主链之间,构筑“纺锤型”阴膜。由于疏水侧链的引入,功能基团移动性增加,主链受到正电荷影响减小,因此膜同时具有高电导率、高碱稳定性、低水溶胀和低甲醇渗透率。其中6C长链的膜氢氧根离子电导率最高,80 ℃达到99.5 mS/cm,而水溶胀30℃时只有2.91%。与其他文献的制备方法和结构设计相比,能使用Wittig反应制备的“纺锤型”阴膜在碱性燃料电池中的应用更具潜力。(2)利用可逆二硫键构建动态聚合物网络,制备可回收阴膜。我们首先利用一步温和的反应将硫代乙酸酯接入了阴膜侧链。将改性后的膜浸泡在碱液中,发生水解和巯基交联反应,形成动态聚合物网络。二硫键网络可以在还原剂的作用下断裂转变成线性高分子,重新溶解在有机溶剂中,进而铸造一张新的阴膜,实现回收和再利用。用二硫键交联的阴膜具有与传统阴膜相当的电导率和更低的水溶胀。虽然回收后的新膜电导率有所下降,但在65 ℃C燃料电池中最大功率密度依然能达到123 mW/cm2。(3)利用Diels-Alder(DA)反应构建动态聚合物网络,制备自修复阴膜。先将呋喃通过Willimason反应接入对氯甲基苯乙烯单体,再进行RAFT聚合,形成侧链含有呋喃和苄气的嵌段聚合物。将聚合物与三甲胺(功能化试剂)和双马来酰亚胺(DA反应交联剂)在有机溶剂中混合形成膜液,涂敷在80 ℃玻璃板上反应,形成含有动态聚合物网络的阴膜。SEM证实,膜一旦出现裂痕,由于附近的DA键在高温下可以断裂再生成,裂痕就得以愈合。我们发现膜具有较高的氯离子电导率(80 ℃,32.7 mS/cm)和受限的水溶胀(30℃,16.0%),因此将其应用在中性液流电池中,得到了稳定的循环性能(连续充放电循环100圈,库仑效率>97%,能量效率>79%)。
Abstract
ran liao dian chi ke yi jiang qing neng gao xiao mo wu ran de zhuai hua cheng dian neng 。mu qian fa zhan zui cheng shou de shi zhi zi jiao huan mo ran liao dian chi ,dan you yu xu yao gui jin shu Ptzuo wei cui hua ji he jia ge ang gui de Nafionmo zuo wei ju ge wu dian jie zhi ,ji cheng ben zhi yao zhao ran liao dian chi de tui an 。xiang bi zhi xia ,shi yong fei gui jin shu cui hua ji he yin li zi jiao huan mo (yi xia jian chen yin mo )de jian xing ran liao dian chi geng ju fa zhan qian li ,dan mu qian yin mo de jian wen ding xing he li zi dian dao lv hai bu neng man zu shi ji xu qiu 。ye liu dian chi ke yi jiang feng neng he tai yang neng zhuai hua cheng de dian neng da gui mo de chu cun qi lai ,zai bing ru dian wang ,shi xian an xu gong gei 。mu qian yi jing ying yong de ye liu dian chi shi fan ye liu dian chi ,dan you yu fan chu liang you xian er ju dian chi xu yao zai jiang suan xing huan jing xia yun hang ,bu li yu ke chi xu fa zhan 。shui ji you ji ye liu dian chi ping jie yuan liao lai yuan an fan 、jia ge di lian he yun hang an quan wen ding deng te xing ,zhu jian cheng wei le yan jiu re dian 。ji zhong ,zhong xing ye liu dian chi shi yong yin mo ,dui she bei he mo wen ding xing yao qiu jiao di ,zai yun hang he cai liao cheng ben shang you you shi ,dan dui yin mo de ji xie wen ding xing he lv li zi dian dao lv yao qiu jiao gao 。wei le ying dui yin mo zai jian xing ran liao dian chi he zhong xing ye liu dian chi zhong de tiao zhan ,she ji xing neng you yi de mo jie gou shi guan jian ke xue wen ti 。mu qian shang ye hua de yin mo duo wei gong neng ji tuan he zhu lian zhi jie xiang lian de jie gou ,you yu zhu lian yi shou dao gong neng ji tuan shang zheng dian he de ying xiang ,bing ju gong neng ji tuan yi dong xing cha ,yin ci mo jian wen ding xing he li zi dian dao lv jiao di 。wei le jie jue zhe yi wen ti ,yan jiu zhe men she ji le ce chang lian yin mo ,bing zheng shi le ji you yi xing neng ,dan que shao jian bian de ge cheng fang fa 。ci wai ,wei le di gao yin mo de zai shui zhong de wen ding xing ,gou jian ju ge wu wang lao shi yi chong shi yong de fang fa 。dan gong jia jiao lian hou de yin mo bu rong bu rong ,yi dan chu xian ji xie sun shang ,xiu fu 、hui shou huo zai li yong dou fei chang kun nan ,bu li yu mo cai liao de ke chi xu fa zhan 。yin ci ,ben wen cong gao fen zi jie gou he ge cheng fang fa shang jin hang chuang xin ,she ji xin xing de yin mo jie gou ,bao gua “fang chui xing ”he “dong tai gong jia jian wang lao xing ”,yi ji di gao yin mo de li zi dian dao lv he wen ding xing ,bing fu yu yin mo ke hui shou he zi xiu fu de te xing ,cong er shi ji zai jian xing ran liao dian chi he zhong xing ye liu dian chi zhong geng ju you shi 。ju ti de yan jiu gong zuo ru xia :(1)shi yong tiao jian wen he 、mo gui jin shu cui hua ji can yu de Wittigfan ying jiang bu tong chang du de wan ji lian yin ru gong neng ji tuan he zhu lian zhi jian ,gou zhu “fang chui xing ”yin mo 。you yu shu shui ce lian de yin ru ,gong neng ji tuan yi dong xing zeng jia ,zhu lian shou dao zheng dian he ying xiang jian xiao ,yin ci mo tong shi ju you gao dian dao lv 、gao jian wen ding xing 、di shui rong zhang he di jia chun shen tou lv 。ji zhong 6Cchang lian de mo qing yang gen li zi dian dao lv zui gao ,80 ℃da dao 99.5 mS/cm,er shui rong zhang 30℃shi zhi you 2.91%。yu ji ta wen suo de zhi bei fang fa he jie gou she ji xiang bi ,neng shi yong Wittigfan ying zhi bei de “fang chui xing ”yin mo zai jian xing ran liao dian chi zhong de ying yong geng ju qian li 。(2)li yong ke ni er liu jian gou jian dong tai ju ge wu wang lao ,zhi bei ke hui shou yin mo 。wo men shou xian li yong yi bu wen he de fan ying jiang liu dai yi suan zhi jie ru le yin mo ce lian 。jiang gai xing hou de mo jin pao zai jian ye zhong ,fa sheng shui jie he qiu ji jiao lian fan ying ,xing cheng dong tai ju ge wu wang lao 。er liu jian wang lao ke yi zai hai yuan ji de zuo yong xia duan lie zhuai bian cheng xian xing gao fen zi ,chong xin rong jie zai you ji rong ji zhong ,jin er zhu zao yi zhang xin de yin mo ,shi xian hui shou he zai li yong 。yong er liu jian jiao lian de yin mo ju you yu chuan tong yin mo xiang dang de dian dao lv he geng di de shui rong zhang 。sui ran hui shou hou de xin mo dian dao lv you suo xia jiang ,dan zai 65 ℃Cran liao dian chi zhong zui da gong lv mi du yi ran neng da dao 123 mW/cm2。(3)li yong Diels-Alder(DA)fan ying gou jian dong tai ju ge wu wang lao ,zhi bei zi xiu fu yin mo 。xian jiang fu nan tong guo Willimasonfan ying jie ru dui lv jia ji ben yi xi chan ti ,zai jin hang RAFTju ge ,xing cheng ce lian han you fu nan he bian qi de qian duan ju ge wu 。jiang ju ge wu yu san jia an (gong neng hua shi ji )he shuang ma lai xian ya an (DAfan ying jiao lian ji )zai you ji rong ji zhong hun ge xing cheng mo ye ,tu fu zai 80 ℃bo li ban shang fan ying ,xing cheng han you dong tai ju ge wu wang lao de yin mo 。SEMzheng shi ,mo yi dan chu xian lie hen ,you yu fu jin de DAjian zai gao wen xia ke yi duan lie zai sheng cheng ,lie hen jiu de yi yu ge 。wo men fa xian mo ju you jiao gao de lv li zi dian dao lv (80 ℃,32.7 mS/cm)he shou xian de shui rong zhang (30℃,16.0%),yin ci jiang ji ying yong zai zhong xing ye liu dian chi zhong ,de dao le wen ding de xun huan xing neng (lian xu chong fang dian xun huan 100juan ,ku lun xiao lv >97%,neng liang xiao lv >79%)。
论文参考文献
论文详细介绍
论文作者分别是来自中国科学技术大学的侯剑秋，发表于刊物中国科学技术大学2019-07-12论文，是一篇关于碱性燃料电池论文,中性有机液流电池论文,阴离子交换膜论文,耐碱论文,可回收论文,自修复论文,中国科学技术大学2019-07-12论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自中国科学技术大学2019-07-12论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：碱性燃料电池论文; 中性有机液流电池论文; 阴离子交换膜论文; 耐碱论文; 可回收论文; 自修复论文; 中国科学技术大学2019-07-12论文;