首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化...首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化为溴甲基;然后,通过4-羟基苯磺酸钠的SN2亲核取代制得具有不同离子交换容量的磺化聚芴醚酮(SPFEK-x);最后,通过溶液浇铸法成膜并酸化,制得新型低成本质子交换膜(PEMs)。采用^(1)HNMR、FTIR、TGA对其进行了表征,并对其性能进行了测试。结果表明,SPFEK-40膜具有较高的质子传导率及离子选择性、较低的钒离子渗透率及面电阻,综合性能优异。以SPFEK-40膜组装的全钒液流电池(VRFB)在电流密度为80 m A/cm^(2)时的能量效率为88.2%,高于以Nafion 212膜组装的VRFB的84.8%。此外,以SPFEK-40膜组装的VRFB在30次循环后放电容量保持率为84.3%,远高于以Nafion 212膜组装的VRFB(66.1%)。该合成路线的原料来源广泛,价格低廉,不涉及危险的磺化反应,易于工业放大。制得的SPFEK-x均具有良好的机械性能和氧化稳定性。展开更多
Proton conductive membrane plays a decisive role in polymer electrolyte membrane fuel cell systems. To prepare polymer electrolyte membranes for direct methanol fuel cell(DMFC), a series of novel sulfonated polyimides...Proton conductive membrane plays a decisive role in polymer electrolyte membrane fuel cell systems. To prepare polymer electrolyte membranes for direct methanol fuel cell(DMFC), a series of novel sulfonated polyimides(SPI) were synthesized from sulfonated diamine,2,5-bis(4-aminophenoxy)benzene sulfonic acid (S-TBDA) with 3,3′,4,4′- benzophenone tetracarboxylic dianhydride (BTDA) and non-sulfonated diamine(ODA) via direct polymerization in this study.The sulfonation degree of the polymers was controlled by changing the molar ratio of the monomers. The obtained SPI membrane was then characterized with FTIR and the influence of sulfonation degree on proton conductivity, methanol permeability and other properties were investigated.With the increase of sulfonation degree,the proton conductivity and methanol permeability increased gradually.The proton conductivity of the SPI membranes ranged from 3.9×10 -3 to 3.4×10 -2 S·cm -1 and the methanol permeability was less than 1×10 -7 cm2 ·s -1.The experiment result indicated the potential of such proton conductive membrane for fuel cell applications.展开更多
文摘首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化为溴甲基;然后,通过4-羟基苯磺酸钠的SN2亲核取代制得具有不同离子交换容量的磺化聚芴醚酮(SPFEK-x);最后,通过溶液浇铸法成膜并酸化,制得新型低成本质子交换膜(PEMs)。采用^(1)HNMR、FTIR、TGA对其进行了表征,并对其性能进行了测试。结果表明,SPFEK-40膜具有较高的质子传导率及离子选择性、较低的钒离子渗透率及面电阻,综合性能优异。以SPFEK-40膜组装的全钒液流电池(VRFB)在电流密度为80 m A/cm^(2)时的能量效率为88.2%,高于以Nafion 212膜组装的VRFB的84.8%。此外,以SPFEK-40膜组装的VRFB在30次循环后放电容量保持率为84.3%,远高于以Nafion 212膜组装的VRFB(66.1%)。该合成路线的原料来源广泛,价格低廉,不涉及危险的磺化反应,易于工业放大。制得的SPFEK-x均具有良好的机械性能和氧化稳定性。
文摘Proton conductive membrane plays a decisive role in polymer electrolyte membrane fuel cell systems. To prepare polymer electrolyte membranes for direct methanol fuel cell(DMFC), a series of novel sulfonated polyimides(SPI) were synthesized from sulfonated diamine,2,5-bis(4-aminophenoxy)benzene sulfonic acid (S-TBDA) with 3,3′,4,4′- benzophenone tetracarboxylic dianhydride (BTDA) and non-sulfonated diamine(ODA) via direct polymerization in this study.The sulfonation degree of the polymers was controlled by changing the molar ratio of the monomers. The obtained SPI membrane was then characterized with FTIR and the influence of sulfonation degree on proton conductivity, methanol permeability and other properties were investigated.With the increase of sulfonation degree,the proton conductivity and methanol permeability increased gradually.The proton conductivity of the SPI membranes ranged from 3.9×10 -3 to 3.4×10 -2 S·cm -1 and the methanol permeability was less than 1×10 -7 cm2 ·s -1.The experiment result indicated the potential of such proton conductive membrane for fuel cell applications.
基金supported by the National Science Fund for Distinguished Young Scholars(21125627)the Program for New Century Excellent Talents in University(NCET-10-0623)the Programme of Introducing Talents of Discipline to Universities(B06006)~~
