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    郭玉飞, 郭志海, 张崇印, 王文彬, 刘飞跃, 郭晓霞, 房建华. 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[J]. 功能高分子学报, 2020, 33(5): 473-482. doi: 10.14133/j.cnki.1008-9357.20191230001
    引用本文: 郭玉飞, 郭志海, 张崇印, 王文彬, 刘飞跃, 郭晓霞, 房建华. 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[J]. 功能高分子学报, 2020, 33(5): 473-482. doi: 10.14133/j.cnki.1008-9357.20191230001
    GUO Yufei, GUO Zhihai, ZHANG Chongyin, WANG Wenbin, LIU Feiyue, GUO Xiaoxia, FANG Jianhua. Preparation and Properties of Novel Sulfonated Poly(ether ketone benzimidazole) Copolymers for Fuel Cells[J]. Journal of Functional Polymers, 2020, 33(5): 473-482. doi: 10.14133/j.cnki.1008-9357.20191230001
    Citation: GUO Yufei, GUO Zhihai, ZHANG Chongyin, WANG Wenbin, LIU Feiyue, GUO Xiaoxia, FANG Jianhua. Preparation and Properties of Novel Sulfonated Poly(ether ketone benzimidazole) Copolymers for Fuel Cells[J]. Journal of Functional Polymers, 2020, 33(5): 473-482. doi: 10.14133/j.cnki.1008-9357.20191230001

    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

    • 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-xx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)。

       

      Abstract: 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 cross-linked 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.

       

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