燃料电池用新型磺化聚(醚酮苯并咪唑)共聚物的合成与性能  

Preparation and Properties of Novel Sulfonated Poly(ether ketone benzimidazole)Copolymers for Fuel Cells

作　　者：郭玉飞 郭志海 张崇印 王文彬 刘飞跃 郭晓霞[1] 房建华[1] GUO Yufei;GUO Zhihai;ZHANG Chongyin;WANG Wenbin;LIU Feiyue;GUO Xiaoxia;FANG Jianhua(School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China;Shanghai Aerospace Systems Engineering Institute,Shanghai 201109,China;Shanghai Aerospace Equipments Manufacturer Co.Ltd.,Shanghai Engineering Research Center of Specialized Polymer Materials for Aerospace,Shanghai 200245,China)

机构地区：[1]上海交通大学化学化工学院,上海200240 [2]上海宇航系统工程研究所,上海201109 [3]上海航天设备制造总厂有限公司,上海航天特种环境高分子功能材料工程技术研究中心,上海200245

出　　处：《功能高分子学报》2020年第5期473-482,共10页Journal of Functional Polymers

基　　金：科技部973项目(2014CB643600)。

摘　　要：通过两步反应合成了一种邻二氨基单体4-苯氧基-1,2-苯二胺(POPDA),并将它与4,4’-二苯醚二甲酸(DCDPE)、5-氨基间苯二甲酸(APA)及3,3’-二氨基联苯胺(DAB)在多聚磷酸介质中进行无规共聚,合成了一种新型聚(醚酮苯并咪唑)共聚物(PEKBI-x,x指POPDA在芳胺单体(POPDA和DAB)中的摩尔分数)。以发烟硫酸为磺化试剂,通过后磺化反应合成了相应的磺化聚(醚酮苯并咪唑)共聚物(SPEKBI-x)。利用SPEKBI-x结构中APA单元的侧氨基与交联剂1,2,7,8-二环氧辛烷结构中的环氧基团反应,制备了一系列磺化聚(醚酮苯并咪唑)共聚物交联膜(SPEKBI-x-CL)。采用热重分析、拉伸测试、Fenton实验等研究了质子交换膜的热稳定性、力学性能、离子交换容量、吸水率、溶胀率、质子电导率、抗自由基氧化稳定性及电池性能。结果表明:所制得的交联膜具有很高的离子交换容量(2.88~3.28 meq/g)、良好的力学性能和热稳定性,膜的质子电导率随着共聚物结构中POPDA单元含量的增加而增大。单电池初步测试结果表明:由SPEKBI-0.50-CL交联膜所组装的H2-O2单电池在80℃、80%相对湿度和100 kPa背压下的最大输出功率密度(PD,max)达到662 mW/cm2,高于由Nafion212所组装的H2-O2单电池在相同条件下的发电性能(PD,max=631 mW/cm2)。An ortho-diamine monomer,4-phenoxy-1,2-phenylenediamine(POPDA),was synthesized via two-step reactions.It was randomly copolymerized with 4,4’-dicarboxydiphenyl ether(DCDPE),5-aminoisophthalic acid(APA)and 3,3’-diaminobenzidine(DAB)in polyphosphoric acid to yield a new kind of high molecular weight poly(ether ketone benzimidazole)copolymers(PEKBI-x,‘x’refers to the molar fraction of POPDA in aromatic diamines(POPDA and DAB).The resultant PEKBI-x was sulfonated using fuming sulfuric acid as the sulfonating reagent to give the corresponding sulfonated poly(ether ketone benzimidazole)s(SPEKBI-x).No significant polymer degradation was observed during the process of sulfonation reaction indicating excellent chemical stability of the copolymers PEKBI-x.A series of covalently crosslinked membranes(SPEKBI-x-CL)were prepared via the solution cast method,and the cross-linking reaction occurred between the amino groups of the APA moiety of the SPEKBI-x and the epoxy groups of the cross-linker 1,2,7,8-diepoxyoctane during the process of solvent evaporation.The thermal stability,mechanical properties,water uptake,swelling ratio,proton conductivity,ion exchange capacity,radical stability,and single cell performance of the exchange proton membranes were investigated.Results showed that these cross-linked membranes exhibited very high ion exchange capacities(2.88~3.28 meq/g)and good mechanical and thermal properties.With the increase of POPDA content in the copolymers,the proton conductivity of the proton exchange membrane increased.A preliminary test of H2-O2 single cell revealed that the maximum output power density of the single cell assembled with the SPEKBI-0.50-CL membrane reached 662 mW/cm2 at 80℃,80%relative humidity and 100 kPa back pressure,which was slightly higher than that of the one assembled with Nafion212(631 mW/cm2)under the same test conditions.

关 键 词：磺化聚(醚酮苯并咪唑) 质子交换膜 交联 燃料电池 

分 类 号：O631[理学—高分子化学]