高温质子交换膜燃料电池的复合催化层电极

doi:10.11944/j.issn.1000-0518.2019.09.190034

摘要/Abstract

摘要：

高温质子交换膜燃料电池具有耐毒化,稳定性好的优势,是具有较强应用前景的一种能源转换装置。本文制备了具有复合催化层结构的气体扩散电极,用于增强燃料电池阳极的催化性能。在气体扩散电极中,将偏氟乙烯-六氟丙烯共聚物和聚苯基咪唑聚合物作为催化剂的粘结材料,调节了电极界面的浸润结构。通过对电极表面形貌和润湿性的表征,发现该种结构的催化层孔隙率和粗糙度更高,双层结构的润湿性差别明显(接触角分别为149°和19°),这有利于形成稳定的三相反应界面。测试结果表明,该种结构的催化层能够有效提高催化材料的利用效率,燃料电池对氢气燃料的峰值功率密度提高约22%。与此同时,使用含一氧化碳质量浓度为10000和30000 mg/m³的氢气燃料,电池峰值功率密度能够分别保持82.1%和71.4%,证明该燃料电池对一氧化碳杂质保持了良好的耐毒性。

关键词: 氢气催化氧化, 磷酸燃料电池, 气体扩散电极, 耐毒性, 聚苯基咪唑膜

Abstract:

High temperature proton exchange membrane fuel cell is a promising energy conversion device with the advantages of toxicity resistance and good stability. In this report, the multilayered catalytic structure was designed to improve anode electrode catalytic activity of fuel cell. Poly vinylidene fluoride co-hexafluoropropylene(PVDF-HFP) and polybenzimidazoles(PBI) are used as electrode binders to adjust the wettability of the diffusion electrode interface. The surface morphology and wettability of the electrode catalyst have been characterized. It was found that the porosity and roughness of the electrode layer were improved. The wettability distinction between layers(contact angles:149° for PVDF-HFP and 19° for PBI) was conducive to produce more stable three-phase reaction interfaces. The catalytic performance of fuel cells shows that the peak power density is enhanced by about 22%, and it has retained 82.1% and 71.4% in H₂ fuel containing CO at the concentrations of 10000 mg/m³ and 30000 mg/m³, respectively. It is concluded that the catalytic layer with such structure could increase the catalyst utilization and still maintain good toxic resistance to CO impurity inside fuel gas.

Key words: hydrogen electro-oxidation, phosphoric acid fuel cell, gas diffusion electrode, anti-poison, polybenzimidazoles membrane

刘世伟, 梁亮, 李晨阳, 刘长鹏, 邢巍, 董献堆. 高温质子交换膜燃料电池的复合催化层电极[J]. 应用化学, 2019, 36(9): 1085-1090.

LIU Shiwei, LIANG Liang, LI Chenyang, LIU Changpeng, XING Wei, DONG Xiandui. Multilayered Anode Catalytic Electrode in High-Temperature Proton Exchange Membrane Fuel Cell[J]. Chinese Journal of Applied Chemistry, 2019, 36(9): 1085-1090.

参考文献

[1]	Wang S Y,Jiang S P.Prospects of Fuel Cell Technologies[J]. Nat Sci Rev,2017,4(2):163-166.
[2]	Krishnana N N,Lee S,Ghorpade R V,et al. Polybenzimidazole(PBI-OO) Based Composite Membranes Using Sulfophenylated TiO2 as Both Filler and Crosslinker, and Their Use in the HT-PEM Fuel Cell[J]. J Membr Sci,2018,560:11-20.
[3]	Rosli R E,Sulong A B,Daud W R W,et al. A Review of High-Temperature Proton Exchange Membrane Fuel Cell(HT-PEMFC) System[J]. Int J Hydrogen Energy,2017,42(14):9293-9314.
[4]	Araya S S,Zhou F,Liso V,et al. A Comprehensive Review of PBI-Based High Temperature PEM Fuel Cells[J]. Int J Hydrogen Energy,2016,41(46):21310-21344.
[5]	Asensio J A,Sanchez E M, Gomez-Romero P.Proton-Conducting Membranes Based on Benzimidazole Polymers for High-Temperature PEM Fuel Cells. A Chemical Quest[J]. Chem Soc Rev,2010,39(8):3210-3239.
[6]	Melchior J P,Majer G,Kreuer K D.Why do Proton Conducting Polybenzimidazole Phosphoric Acid Membranes Perform well in High-Temperature PEM Fuel Cells?[J]. Phys Chem Chem Phys,2016,19(1):601-612.
[7]	Xu W,Lu Z,Sun X,et al., Superwetting Electrodes for Gas-Involving Electrocatalysis[J]. Acc Chem Res,2018,51(7):1590-1598.
[8]	Ma Y L,Wainright J S,Litt M H,et al. Conductivity of PBI Membranes for High-Temperature Polymer Electrolyte Fuel Cells[J]. J Electrochem Soc,2004,151(1):A8-A16.
[9]	Orogbemi O M,Ingham D B,Ismail M S,et al. The Effects of the Composition of Microporous Layers on the Permeability of Gas Diffusion Layers Used in Polymer Electrolyte Fuel Cells[J]. Int J Hydrogen Energy,2016,41(46):21345-21351.
[10]	Yuk S,Lee D H,Choi S,et al. An Electrode-Supported Fabrication of Thin Polybenzimidazole Membrane-Based Polymer Electrolyte Membrane Fuel Cell[J]. Electrochim Acta,2018,270:402-408.
[11]	Su H N,Xu Q,Chong J J,et al. Eliminating Micro-Porous Layer from Gas Diffusion Electrode for Use in High Temperature Polymer Electrolyte Membrane Fuel Cell[J]. Power Sources,2017,341:302-308.
[12]	Majlan E H,Rohendi D,Daud W R W,et al. Electrode for Proton Exchange Membrane Fuel Cells:A review[J]. Renew Sust Energ Rev,2018,89:117-134.
[13]	Lv Q,Li K,Liu C,et al. TiO2 Inserted Carbon Materials with Fine-Tuned Pore Structure as Effective Model Supports for Electrocatalysts of fuel Cells[J]. Carbon,2016,98:126-137.
[14]	YANG Juan,YUAN Ting,ZHANG Haifeng,et al. Effect of Hydrophobicity of Anodic Backing Layer on Mass Transfer Characteristics of Passive DMFCs[J]. Chinese J Appl Chem,2010,27(7):754-758(in Chinese). 杨娟,袁婷,张海峰,等. 阳极支撑层憎水性对被动式直接甲醇燃料电池传质性能的影响[J]. 应用化学,2013,30(11):1348-1353.