含朝格尔碱基聚酰亚胺-聚苯并咪唑宽温域复合质子交换膜的制备和性能  

Preparation and Properties of Composite Proton Exchange Membranes from Tröger’s Base-based Polyimides/Polybenzimidazoles for Fuel Cells Operating in a Wide Temperature Range

作　　者：钟建铭 代俊明 张宇 赵庆美[1] 张旭[1] 庄永兵 Jian-ming Zhong;Jun-ming Dai;Yu Zhang;Qing-mei Zhao;Xu Zhang;Yong-bing Zhuang(Chemistry and Environmental Engineering,Yangtze University,Jingzhou 434023;State Key Laboratory of Biochemical Engineering,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190;School of Chemical Engineering,University of Chinese Academy of Sciences,Beijing 100049)

机构地区：[1]长江大学化学与环境工程学院,荆州434023 [2]中国科学院过程工程研究所生化工程国家重点实验室,北京100190 [3]中国科学院大学化学工程学院,北京100049

出　　处：《高分子学报》2024年第4期452-461,共10页Acta Polymerica Sinica

基　　金：国家自然科学基金面上项目(基金号52173210);江苏冰城氢能科技有限公司企业委托项目资助。

摘　　要：针对氢燃料电池对宽温域质子交换膜材料的迫切应用需求,合成了新型含Tr?ger’s base(TB)结构的聚苯并咪唑(TB-PBI-N),并以之为填料与含TB基聚酰亚胺(PI-TB-N)共混,制备了5种不同比例的磷酸掺杂复合质子交换膜.通过傅里叶红外光谱(FTIR)、核磁氢谱(^(1)H-NMR)、热失重分析(TGA)和拉伸试验等表征了质子交换膜的结构、机械性能、热及氧化稳定性、酸吸收、溶胀度、质子电导率(σ)及氢/空燃料单电池的功率密度(PD),探究了TB-PBI-N填料的添加对复合膜性能的影响.结果表明:磷酸掺杂前复合膜的拉伸强度为87.3~129.5 MPa,掺杂后膜的拉伸强度为3.7~9.5 MPa,磷酸吸收率为235.3%~288.7%,溶胀率为13.9%~25.0%,可在30~160℃传导质子,σ和PD最高分别可达94.3 mS/cm和334.6 mW/cm^(2).TBPBI-N填料的添加改善了复合膜的机械性能及磷酸掺杂膜的尺寸稳定性.另外,填料TB-PBI-N的TB结构具有额外的碱基位点,可提供一定的酸吸附能力,从而提升了σ.其中,复合膜TB-PI-5PBI的拉伸强度为116.8 MPa,磷酸掺杂后膜的σ=67.7 mS/cm(160℃、0%RH),在30、80和160℃下,电池的功率密度分别达到58.9、224.7和334.6 mW/cm^(2),具有无湿度环境宽温域范围应用前景.For proton exchange membranes used in fuel cells,it is critical to develop materials that can withstand a wide range of industrially relevant temperatures.In this work,novel polybenzimidazole(TB-PBI-N)containing Tröger’s base(TB)units was synthesized and used as a filler to be blended with TB-based polyimide(PI-TB-N)for five types of phosphoric acid-doped composite proton exchange membranes.The chemical structures,mechanical properties,thermal and oxidative stability,acid adsorption,swelling ratios,proton conductivity(σ)and power density of H_(2)O/air fuel cells(PD)of the composite membranes were characterized by Fourier transform infrared spectroscopy(FTIR),magnetic resonance spectroscopy(1H-NMR),thermogravimetric analysis(TGA),and tensile tests.The effect of incorporated TB-PBI-N filler on the properties of the composite membranes were investigated in details.The results showed that the tensile strength of the composite membranes without phosphoric acid doping were 87.3-129.5 MPa,and 3.7-9.5 MPa for the acid doped membranes.The phosphonic acid uptake were 235.3%-288.7%after doping with the swelling ratios ranging between 13.9%-25.0%,and the composite membranes can conduct protons at wide temperature range from 30℃to 160℃.The maximumσand PD of the composite membranes reached up to 94.3 mS/cm and 334.6 mW/cm^(2),respectively.Furthermore,it was found that the introduction of TB-PBI-N filler improved the mechanical properties and the dimensional stability for the phosphoric acid doped membranes.In addition,the TB units in TB-PBI-N have additional base sites,which enhanced acid adsorption capacity and greatly improved theσvalues of the membranes.Among the five membrane types,the TB-PI-5PBI membrane showed a tensile strength of 116.8 MPa,proton conductivity of 67.7 mS/cm(160℃,0%RH).More importantly,the PD values of the fuel cells reached 58.9,224.7 and 334.6 mW/cm^(2) at 30,80 and 160℃,respectively,indicating excellent application prospect in a wide temperature range under non-humidity environment.

关 键 词：聚酰亚胺 聚苯并咪唑 朝格尔碱基 质子交换膜 复合膜 

分 类 号：TB383.2[一般工业技术—材料科学与工程] TM911.4[电气工程—电力电子与电力传动]