SPEEK 燃料电池中使用聚 (1-乙烯基咪唑) 进行原位聚合介导的 MOF 交联,ACS Applied Polymer Materials

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SPEEK 燃料电池中使用聚 (1-乙烯基咪唑) 进行原位聚合介导的 MOF 交联
ACS Applied Polymer Materials ( IF 4.4 ) Pub Date : 2023-06-06 , DOI: 10.1021/acsapm.3c00287
Madhuparna Ray ₁ , Paresh Kumar Samantaray ₂ , Yuvraj Singh Negi ₁

Affiliation

_{本文合成的由 Zr 6}节点 (Zr ₆ O ₄ (OH) ₄ ) 和 BTC (苯-1,3,5-三羧酸) 构建的独特的锆基微孔 MOF-808已通过自由基原位聚合进一步定制1-乙烯基咪唑与N , N'-亚甲基双丙烯酰胺吸附在 MOF 孔道内后作为交联剂。将交联结构作为填料以 2 重量％和 4 重量％掺入磺化聚醚醚酮 (SPEEK) 溶液中，以配制混合基质复合质子交换膜 (PEM)。与原始 SPEEK 相比，复合膜具有更高的质子传导性、改进的燃料电池性能和热稳定性。MOF 通道中创建的高度有序的晶体控制 3D 聚合物交联网络解决了与在膜中添加低分子量唑类相关的不良浸出问题。此外，它还通过 MOF 孔生成高度有序的长程质子传导通道。咪唑和磺酸基官能团之间的酸碱相互作用导致含有 4 wt% 复合填料的 S4P3M 膜在 80 °C 和 70% RH 下质子电导率增加至 0.05 S/cm，是传统填料的 16.6 倍。纯SPEEK的。该膜在 100 °C 和 40% RH 下保持高达 0.04 S/cm 的质子电导率，表明其在低湿度条件下的质子传导能力。此外，S4P3M 的峰值功率密度达到 310 mW/cm²在 60 °C 和 347 mW/cm ²在 80 °C、70% 相对湿度下，这高于其他几篇报道的基于 SPEEK 的膜的文献研究。

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In Situ Polymerization-Mediated Cross-Linking of the MOF Using Poly(1-vinylimidazole) in SPEEK Fuel Cells

A unique zirconium-based microporous MOF-808 constructed from Zr₆ nodes (Zr₆O₄(OH)₄) and BTC (benzene-1,3,5-tricarboxylic acid) synthesized herein has been further tailored by radical in situ polymerization of 1-vinylimidazole alongside N,N′-methylene-bis(acrylamide) as the cross-linker after their adsorption inside MOF pore channels. The cross-linked architectures were incorporated as fillers at 2 and 4 wt % in sulfonated poly (ether ether ketone) (SPEEK) solution to formulate mixed-matrix composite Proton Exchange Membranes (PEMs). The composite membranes displayed considerably higher proton conductivity, improved fuel cell performance, and thermal stability than pristine SPEEK. The highly ordered crystal-controlled 3D polymeric cross-linked networks created in the MOF channels address the undesirable leaching associated with adding low-molecular-weight azoles in membranes. Additionally, it generates highly ordered long-range proton-conducting channels through the MOF pores. The acid–base interaction between the imidazole and sulfonic functional groups causes the conductivity of protons to increase to 0.05 S/cm at 80 °C and 70% RH for the S4P3M membrane containing 4 wt % complex filler, which is 16.6-fold higher than that of pure SPEEK. The membrane retains a proton conductivity of up to 0.04 S/cm at 100 °C and 40% RH, indicating its proton-conducting abilities at low humidity conditions. Furthermore, S4P3M achieves a peak power density of 310 mW/cm² at 60 °C and 347 mW/cm² at 80 °C under 70% relative humidity, which are higher than those in several other reported literature studies on SPEEK-based membranes.

更新日期：2023-06-06

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