首页|全钒液流电池用磺化聚芴醚酮质子交换膜的制备及性能

全钒液流电池用磺化聚芴醚酮质子交换膜的制备及性能

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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 1HNMR、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 mA/cm2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.
Preparation and properties of sulfonated poly(fluorenyl ether ketone)proton exchange membranes for vanadium redox flow battery
Poly(fluorenyl ether ketone)s(PFEK-x)were firstly synthesized from high-temperature polycondensation of 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)fluorene(DMBHF),9,9-bis(4-hydroxyphenyl)fluorene(BHF)and 4,4'-difluorophenone(DFB),herein,x=30,40,50,and refers to the content of DMBHF(based on the amount of substance of DFB,the same below).The PFEK-x obtained were then brominated by bromination of the methyl groups and then reacted with sodium 4-hydroxybenzenesulfonate to yield sulfonated poly(fluorenyl ether ketone)s(SPFEK-x)with different ion exchange capacities.Finally,novel and low-cost proton exchange membranes(PEMs)were prepared by solution-casting SPFEK-x into membranes and acidification.The samples were characterized by 1HNMR,FTIR and TGA,followed by analysis on their properties.The results showed that SPFEK-40 membrane exhibited excellent comprehensive performances,such as high proton conductivity and icon selectivity,low VO2+ permeability,and low surface resistance.The energy efficiency of vanadium redox flow battery(VRFB)assembled with SPFEK-40 membrane reached 88.2%at a current density of 80 mA/cm2,higher than that of the VRFB assembled with Nafion 212(84.8%).In addition,the discharge capacity retention ratio of the VRFB assembled with SPFEK-40 membrane after 30 cycles was 84.3%,which was much higher than that of the VRFB assembled with Nafion 212(66.1%).Moreover,the synthetic route could be scaled-up easily since it was based on inexpensive raw materials without dangerous sulfonation reactions.The SPFEK-x membranes also displayed good mechanical properties and oxidation stability.

vanadium redox flow batteriesproton exchange membranespoly(fluorenyl ether ketones)proton conductivityenergy efficiencyfunctional materials

叶洲麟、熊雷、林起浪、陈栋阳

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福州大学 材料科学与工程学院,福建 福州 350116

全钒液流电池 质子交换膜 聚芴醚酮 质子传导率 能量效率 功能材料

国家自然科学基金项目福建省自然科学基金项目

518730372020J01475

2024

精细化工
大连化工研究院设计院 中国化工学会精细化工专业委员会 辽宁省化工研究院

精细化工

CSTPCD北大核心
影响因子:0.557
ISSN:1003-5214
年,卷(期):2024.41(2)
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