Focus on the catalysts to resist the phosphate poisoning in high-temperature proton exchange membrane fuel cells  

高温质子交换膜燃料电池阴极抗磷酸中毒催化剂的研究进展

作　　者：Liyuan Gong Li Tao Lei Wang Xian-Zhu Fu Shuangyin Wang 贡立圆;陶李;王雷;符显珠;王双印(深圳大学材料科学与工程学院,广东深圳518055;深圳大学物理与光电工程学院,广东深圳518060;湖南大学化学生物传感与计量学国家重点实验室,化学化工学院,长沙国家超算中心,先进催化教育部工程研究中心,湖南长沙410082;湖大粤港澳大湾区创新研究院(广州增城),广东广州511300)

机构地区：[1]College of Materials Science and Engineering,Shenzhen University,Shenzhen 518055,Guangdong,China [2]College of Physics and Optoelectronic Engineering,Shenzhen University,Shenzhen 518060,Guangdong,China [3]State Key Laboratory of Chemo/Bio-Sensing and Chemometrics,College of Chemistry and Chemical Engineering,the National Supercomputer Centers in Changsha,Advanced Catalytic Engineering Research Center of the Ministry of Education,Hunan University,Changsha 410082,Hunan,China [4]Greater Bay Area Institute for Innovation,Hunan University,Guangzhou 511300,Guangdong,China

出　　处：《Chinese Journal of Catalysis》2025年第1期155-176,共22页催化学报(英文)

基　　金：国家重点研发计划(2021YFA1500900);国家自然科学基金(22425021,22102053);湖南省自然科学基金(2024JJ2012);湖南省科技创新项目(2022RC1036);广东基础和应用基础研究基金(2024A1515012889);深圳科技项目(JCYJ20210324122209025);湖南省自然科学基金重大项目(2021JC0006).

摘　　要：Investigating highly effective electrocatalysts for high-temperature proton exchange membrane fuel cells(HT-PEMFC)requires the resistance to phosphate acid(PA)poisoning at cathodic oxygen reduction reaction(ORR).Recent advancements in catalysts have focused on alleviating phosphoric anion adsorption on Pt-based catalysts with modified electronic structure or catalytic interface and developing Fe-N-C based catalysts with immunity of PA poisoning.Fe-N-C-based catalysts have emerged as promising alternatives to Pt-based catalysts,offering significant potential to overcome the characteristic adsorption of phosphate anion on Pt.An overview of these developments provides insights into catalytic mechanisms and facilitates the design of more efficient catalysts.This review begins with an exploration of basic poisoning principles,followed by a critical summary of characterization techniques employed to identified the underlying mechanism of poisoning effect.Attention is then directed to endeavors aimed at enhancing the HT-PEMFC performance by well-designed catalysts.Finally,the opportunities and challenges in developing the anti-PA poisoning strategy and practical HT-PEMFC is discussed.Through these discussions,a comprehensive understanding of PA-poisoning bottlenecks and inspire future research directions is aim to provided.燃料电池作为一种清洁、高效的电化学能源转换器件,能量转换效率高,是未来氢能应用的主要途径之一.高温聚合物电解质膜燃料电池(HT-PEMFC)工作温度为120-300℃,具有水、热管理系统简单,反应动力学速率快,抗CO等杂质中毒等优点.HT-PEMFC更加简化的系统和对高纯氢的低依赖度等诸多优势将有望突破传统PEMFC应用瓶颈,推动燃料电池和氢能的发展.目前,HT-PEMFC主要以磷酸掺杂的聚合物膜作为电解质,磷酸在催化剂表面的强吸附会堵塞催化剂活性位点,导致铂用量是目前低温PEMFC的10倍,增加了燃料电池的实际应用成本.目前,对HT-PEMFC抗磷酸毒化催化剂的研究较少,缺乏对毒化机制的科学认识.因此,对抗磷酸毒化催化材料研究的最新进展进行系统地梳理和总结对进一步推动HT-PEMFC的发展具有重要意义.本文综述了磷酸掺杂聚苯并咪唑(PBI)电解质膜应用的HT-PEMFC中磷酸阴离子严重吸附和毒害阴极催化剂的瓶颈问题.首先介绍了催化剂磷酸中毒的基本原理,为针对性地解决抗中毒问题提供深入的理论根据.此外,由于催化剂表界面发生的磷酸阴离子吸附/脱附行为至关重要,因此对相关的表征技术进行了系统地归纳总结.其次,重点介绍了铂基电催化剂的研究进展,详细地阐述了目前的抗磷酸中毒策略包括晶面调控策略、合金策略、有机物小分子隔离策略、碳/氧化物包覆策略以及磷酸分布迁移调控策略,并且介绍了一些成功的典型实例,对目前优越的电池性能进行了总结另外强调了具有磷酸中毒免疫能力的铁基材料的重要性,用以取代易中毒且昂贵的铂基材料,是目前最具有应用潜力的非贵金属催化剂.介绍了铁基催化剂近年在HT-PEMFC抗毒化研究的成功研究案例:包括(1)对抗磷酸阴离子吸附的位点构型探究,通过对几何/电子结构进行构建实现更高的抗磷酸毒化能力和本征活性;

关 键 词：Fuel cell High-temperature Phosphate acid poisoning Activitydegradation Electrocatalystdesign 

分 类 号：O64[理学—物理化学]