Ponomarev Igor I, Razorenov Dmitry Y, Skupov Kirill M, Ponomarev Ivan I, Volkova Yulia A, Lyssenko Konstantin A, Lysova Anna A, Vtyurina Elizaveta S, Buzin Mikhail I, Klemenkova Zinaida S
A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Vavilova St., 28, Bld. 1, 119334 Moscow, Russia.
Faculty of Chemistry, Lomonosov Moscow State University, GSP-1, Leninskie Gory, 1-3, 119991 Moscow, Russia.
Membranes (Basel). 2023 May 25;13(6):552. doi: 10.3390/membranes13060552.
The development of phosphorylated polybenzimidazoles (PBI) for high-temperature polymer-electrolyte membrane (HT-PEM) fuel cells is a challenge and can lead to a significant increase in the efficiency and long-term operability of fuel cells of this type. In this work, high molecular weight film-forming pre-polymers based on ,-bis(3-methoxyphenyl)-1,2,4,5-benzenetetramine and [1,1'-biphenyl]-4,4'-dicarbonyl dichloride were obtained by polyamidation at room temperature for the first time. During thermal cyclization at 330-370 °C, such polyamides form -methoxyphenyl substituted polybenzimidazoles for use as a proton-conducting membrane after doping by phosphoric acid for H/air HT-PEM fuel cells. During operation in a membrane electrode assembly at 160-180 °C, PBI self-phosphorylation occurs due to the substitution of methoxy-groups. As a result, proton conductivity increases sharply, reaching 100 mS/cm. At the same time, the current-voltage characteristics of the fuel cell significantly exceed the power indicators of the commercial BASF Celtec P1000 MEA. The achieved peak power is 680 mW/cm at 180 °C. The developed approach to the creation of effective self-phosphorylating PBI membranes can significantly reduce their cost and ensure the environmental friendliness of their production.
用于高温聚合物电解质膜(HT-PEM)燃料电池的磷酸化聚苯并咪唑(PBI)的开发是一项挑战,但可显著提高此类燃料电池的效率和长期可操作性。在本工作中,首次通过室温下的聚酰胺化反应,制得了基于α,β-双(3-甲氧基苯基)-1,2,4,5-苯四胺和[1,1'-联苯]-4,4'-二羰基二氯的高分子量成膜预聚物。在330-370℃的热环化过程中,此类聚酰胺形成α-甲氧基苯基取代的聚苯并咪唑,经磷酸掺杂后用作H/空气HT-PEM燃料电池的质子传导膜。在膜电极组件中于160-180℃运行时,由于甲氧基的取代,PBI发生自磷酸化。结果,质子电导率急剧增加,达到100 mS/cm。同时,燃料电池的电流-电压特性显著超过了商业巴斯夫Celtec P1000 MEA的功率指标。在180℃时实现的峰值功率为680 mW/cm²。所开发的制备有效自磷酸化PBI膜的方法可显著降低其成本,并确保其生产的环境友好性。