基于电极修饰质子交换膜燃料电池自增湿研究进展

doi:10.16085/j.issn.1000-6613.2019-1028

摘要/Abstract

摘要：

自增湿对于质子交换膜燃料电池的实际应用具有重要意义。本文从电极组分和结构修饰这一角度出发，介绍了近年来质子交换膜燃料电池自增湿研究的一些重要进展和发展趋势。首先介绍了基于催化层修饰实现质子交换膜燃料电池自增湿的发展状况，指出吸湿性催化剂开发是实现高效自增湿催化层的关键；其次介绍了基于气体扩散层修饰和电极结构改进实现质子交换膜燃料电池自增湿的研究进展，分析了两种方式各自的优缺点，讨论了其后续的发展方向；最后针对现有自增湿工艺存在的问题，提出了未来的研究方向和重点，对这类自增湿研究的发展趋势及应用前景进行了展望，指出吸湿性催化剂研发以及多种工艺协同互补将是今后自增湿质子交换膜燃料电池发展的重要方向。

关键词: 燃料电池, 自增湿, 催化层, 气体扩散电极, 电极修饰

Abstract:

Self-humidifying is of great significance for the practical application of proton exchange membrane fuel cells (PEMFC). From the perspectives of electrode component and structure modification, this paper introduces some important progress and development trends of PEMFC self-humidifying studies in recent years. Firstly, the development of PEMFC self-humidifying based on the modification of the catalytic layer is introduced, and the importance of developing a hygroscopic catalyst to achieve an efficient self-humidifying catalytic layer is pointed out. Secondly, the research progress of PEMFC self-humidifying based on gas diffusion layer modification and electrode structure improvement is introduced. The advantages and disadvantages of the two methods are analyzed, and the future development direction is discussed. Finally, in view of the problems in the existing self-humidifying process, we provide some suggestions on its future research directions and priorities, i.e. the research and development of hygroscopic catalyst and the combinations of various methods.

Key words: fuel cell, self-humidifying, catalyst layer, gas diffusion electrode, electrode modification

中图分类号:

TM911.4

解政, 张玮琦, 马强, 徐谦, 苏华能. 基于电极修饰质子交换膜燃料电池自增湿研究进展[J]. 化工进展, 2020, 39(6): 2363-2369.

Zheng XIE, Weiqi ZHANG, Qiang MA, Qian XU, Huaneng SU. Progress in self-humidifying of proton exchange membrane fuel cell based on electrode modification[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2363-2369.

参考文献

1	RAHNAVARD A, ROWSHANZAMIR S, PARNIAN M J, et al. The effect of sulfonated poly (ether ether ketone) as the electrode ionomer for self-humidifying nanocomposite proton exchange membrane fuel cells[J]. Energy, 2015, 82: 746-757.
2	KO D, DOH S, PARK H S, et al. The effect of through plane pore gradient GDL on the water distribution of PEMFC[J]. International Journal of Hydrogen Energy, 2018, 43(4): 2369-2380.
3	SHIN S H, KODIR A, SHIN D, et al. Perfluorinated composite membranes with organic antioxidants for chemically durable fuel cells[J]. Electrochimica Acta, 2019, 298: 901-909.
4	CASTANHEIRA L, BEDOUET M, KUCERNAK A, et al. Influence of microporous layer on corrosion of metallic bipolar plates in fuel cells[J]. Journal of Power Sources, 2019, 418: 147-151.
5	GUO X, ZENG Y, WANG Z, et al. Improvement of PEMFC performance and endurance by employing continuous silica film incorporated water transport plate[J]. Electrochimica Acta, 2016, 191: 116-123.
6	BAKANGURA E, GE L, MUHAMMAD M, et al. Sandwich structure SPPO/BPPO proton exchange membranes for fuel cells: morphology-electrochemical properties relationship[J]. Journal of Membrane Science, 2015, 475: 30-38.
7	LEE H K, KIM J I, PARK J H, et al. A study on self-humidifying PEMFC using Pt-ZrP-Nafion composite membrane[J]. Electrochimica Acta, 2004, 50(2): 761-768.
8	YANG B, FU Y Z. MANTHIRAM A. Operation of thin Nafion-based self-humidifying membranes in proton exchange membrane fuel cells with dry H₂ and O₂[J]. Journal of Power Sources, 2005, 139(1): 170-175.
9	HAGIHARA H, UCHIDA H. WATANABE M. Preparation of highly dispersed SiO₂ and Pt particles in Nafionn^?112 for self-humidifying electrolyte membranes in fuel cells[J]. Electrochimica Acta, 2006, 51(19): 3979-3985.
10	WANG L, XING D M, LIU Y H, et al. Pt/SiO₂ catalyst as an addition to Nafion/PTFE self-humidifying composite membrane[J]. Journal of Power Sources, 2006, 161(1): 61-67.
11	ZHU X, ZHANG H, ZHANG Y, et al. An ultrathin self-humidifying membrane for PEM fuel cell application: fabrication, characterization, and experimental analysis[J]. Journal of Physical Chemistry B, 2006, 110(29): 14240-14248.
12	ZHANG W, LI M K S, POLOCK YUE A, et al. Exfoliated Pt-clay/Nafion nanocomposite membrane for self-humidifying polymer electrolyte fuel cells[J]. Langmuir, 2008, 24(6): 2663-2670.
13	ZHANG Y, ZHANG H, CHENG B, et al. An inorganic/organic self-humidifying composite membranes for proton exchange membrane fuel cell application[J]. Electrochimica Acta, 2008, 53(12): 4096-4103.
14	YANG H N, LEE D C, PARK S H, et al. Preparation of Nafion/various Pt-containing SiO₂ composite membranes sulfonated via different sources of sulfonic group and their application in self-humidifying PEMFC[J]. Journal of Membrane Science, 2013, 443(37): 210-218.
15	LEE S H, CHOI S H, GOPALAN S A, et al. Preparation of new self-humidifying composite membrane by incorporating graphene and phosphotungstic acid into sulfonated poly(ether ether ketone) film[J]. International Journal of Hydrogen Energy, 2014, 39(30): 17162-17177.
16	WANG R, ZHANG W, HE G, et al. Controlling fuel crossover and hydration in ultra-thin proton exchange membrane-based fuel cells using Pt-nanosheet catalysts[J]. Journal of Materials Chemistry A, 2014, 2(39): 16416-16423.
17	ROWSHANZAMIR S, PEIGHAMBARDOUST S J, PARNIAN M J, et al. Effect of Pt-C_2.5H_0.5PW₁₂O₄₀ catalyst addition on durability of self-humidifying nanocomposite membranes based on sulfonated poly(ether ether ketone) for proton exchange membrane fuel cell applications[J]. International Journal of Hydrogen Energy, 2015, 40(1): 549-560.
18	PARK C H, LEE S Y, HWANG D S, et al. Nanocrack-regulated self-humidifying membranes[J]. Nature, 2016, 532: 480-495.
19	BAE I, OH K H, YUN M, et al. Nanostructured composite membrane with cross-linked sulfonated poly(arylene ether ketone)/silica for high-performance polymer electrolyte membrane fuel cells under low relative humidity[J]. Journal of Membrane Science, 2018, 549: 567-574.
20	OH K H, BAE I, LEE H, et al. Silica-embedded hydrogel nanofiller for enhancing low humidity proton conduction of a hydrocarbon-based polymer electrolyte membrane[J]. Journal of Membrane Science, 2017, 543: 106-113.
21	邹浩斌,侯三英,熊子昂, 等. 免增湿型空气自呼吸燃料电池的研究进展[J]. 化工进展, 2016, 35(1): 91-97.
21	ZOU Haobin, HOU Sanying, XIONG Zi’ang, et al. Progress in the R&D of self-humidifying and air-breathing proton exchange membrane fuel cell[J]. Chemical Industry and Engineering Progress, 2016, 35(1): 91-97.
22	JUNG U H, PARK K T, PARK E H, et al. Improvement of low-humidity performance of PEMFC by addition of hydrophilic SiO₂ particles to catalyst layer[J]. Journal of Power Sources, 2006, 159(1): 529-532.
23	JUNG U H, JEONG S U, PARK K T, et al. Improvement of water management in air-breathing and air-blowing PEMFC at low temperature using hydrophilic silica nano-particles[J]. International Journal of Hydrogen Energy, 2007, 32(17): 4459-4465.
24	LIN C L, HSU S C, HO W Y. Addition of sulfonated silicon dioxide on an anode catalyst layer to improve the performance of a self-humidifying proton exchange membrane fuel cell[J]. Functional Materials Letters, 2016, 9(2):160025.
25	CHAO W K, LEE C M, TSAI D C, et al. Improvement of the proton exchange membrane fuel cell(PEMFC) performance at low-humidity conditions by adding hygroscopic γ-Al₂O₃ particles into the catalyst layer[J]. Journal of Power Sources, 2008, 185(1): 136-142.
26	HUANG R H, CHIU T W, LIN T J, et al. Improvement of proton exchange membrane fuel cells performance by coating hygroscopic zinc oxide on the anodic catalyst layer[J]. Journal of Power Sources, 2013, 227: 229-236.
27	LIN C L, LIU C W, HUANG C H, et al. Embedding TiO₂ nanopowder in anode catalyst layers to fabricate self-humidifying proton exchange membrane fuel cells[J]. Advanced Materials Research, 2014, 953/954: 957-960.
28	LIANG H, ZHENG L, LIAO S. Self-humidifying membrane electrode assembly prepared by adding PVA as hygroscopic agent in anode catalyst layer[J]. International Journal of Hydrogen Energy, 2012, 37(17): 12860-12867.
29	LIANG H, DANG D, XIONG W, et al. High-performance self-humidifying membrane electrode assembly prepared bysimultaneously adding inorganic and organic hygroscopic materials to the anode catalyst layer[J]. Journal of Power Sources, 2013, 241(6): 367-372.
30	KIM E Y, YIM S D, BAE B, et al. Study of a highly durable low-humidification membrane electrode assembly using crosslinked polyvinyl alcohol for polymer electrolyte membrane fuel cells[J]. Journal of Solid State Electrochemistry, 2016, 20(6): 1723-1730.
31	HOU S, LIAO S, DAI D, et al. Self-humidifying membrane electrode assembly prepared by adding microcrystalline cellulose in anode catalyst layer as preserve moisture[J]. International Journal of Hydrogen Energy, 2014, 39(24): 12842-12848.
32	HOU S, LIAO S, XIONG Z, et al. Improvement of proton exchange membrane fuel cell performance in low-humidity conditions by adding hygroscopic agarose powder to the catalyst layer[J]. Journal of Power Sources, 2015, 273: 168-173.
33	侯三英, 熊子昂, 廖世军. 燃料电池自增湿膜电极的研究进展[J]. 化工进展, 2015, 34(1): 80-85.
33	HOU Sanying, XIONG Zi’ang, LIAO Shijun. Progress of R&D of self-humidifying membrane electrode assembly for fuel cell application[J]. Chemical Industry and Engineering Progress, 2015, 34(1): 80-85.
34	SU H N, XU L M, ZHU H P, et al. Self-humidification of a PEM fuel cell using a novel Pt/SiO₂/C anode catalyst[J]. International Journal of Hydrogen Energy, 2010, 35(15): 7874-7880.
35	SU H N, YANG L J, LIAO S J, et al. Membrane electrode assembly with Pt/SiO₂/C anode catalyst for proton exchange membrane fuel cell operation under low humidity conditions[J]. Electrochimica Acta, 2010, 55(28): 8894-8900.
36	ZHENG L P, ZENG Q, LIAO S J, et al. Highly performed non-humidification membrane electrode assembly prepared with binary RuO₂-SiO₂ oxide supported Pt catalysts as anode[J]. International Journal of Hydrogen Energy, 2012, 37(17): 13103-13109.
37	LO A Y, HUANG C Y, SUNG L Y, et al. Electrophoretic deposited Pt/C/SiO₂ anode for self-humidifying and improved catalytic activity in PEMFC[J]. Electrochimica Acta, 2015, 180: 610-615.
38	GANESAN A, NARAYANASAMY M, SHUNMUGAVEL K. Self-humidifying manganese oxide-supported Pt electrocatalysts for highly-durable PEM fuel cells[J]. Electrochimica Acta, 2018, 285: 47-59.
39	LUO F, LIU M, CHI B, et al. Enhanced durability and self-humidification of platinum catalyst through decoration with SnSi binary oxide[J]. Journal of Applied Electrochemistry, 2018, 48(10): 1163-1173.
40	KANNAN A M, CINDRELLA L. MUNUKUTLA L. Functionally graded nano-porous gas diffusion layer for proton exchange membrane fuel cells under low relative humidity conditions[J]. Electrochimica Acta, 2008, 53(5): 2416-2422.
41	CINDRELLA L, KANNAN A M. Membrane electrode assembly with doped polyaniline interlayer for proton exchange membrane fuel cells under low relative humidity conditions[J]. Journal of Power Sources, 2009, 193(2): 447-453.
42	CINDRELLA L, KANNAN A M, AHMAD R, et al. Surface modification of gas diffusion layers by inorganic nanomaterials for performance enhancement of proton exchange membrane fuel cells at low RH conditions[J]. International Journal of Hydrogen Energy, 2009, 34(15): 6377-6383.
43	HOU S Y, SU H N, ZOU H B, et al. Enhanced low-humidity performance in a proton exchange membrane fuel cell by the insertion of microcrystalline cellulose between the gas diffusion layer and the anode catalyst layer[J]. International Journal of Hydrogen Energy, 2015, 40(45): 15613-15621.
44	覃群,罗志平,桂丹, 等. 微孔层对PEMFC自增湿性能的影响[J]. 电池, 2008, 38(2): 79-81.
44	QIN Qun, LUO Zhiping, GUI Dan, et al. Effects of micro-porous layer on the self-humidifying performance of PEMFC[J]. Battery Bimonthly, 2008, 38(2): 79-81.
45	KITAHARA T, NAKAJIMA H, MORI K. Hydrophilic and hydrophobic double microporous layer coated gas diffusion layer for enhancing performance of polymer electrolyte fuel cells under no-humidification at the cathode[J]. Journal of Power Sources, 2012, 199(1): 29-36.
46	KITAHARA T, NAKAJIMA H, INAMOTO M, et al. Novel hydrophilic and hydrophobic double microporous layer coated gas diffusion layer to enhance performance of polymer electrolyte fuel cells under both low and high humidity[J]. Journal of Power Sources, 2013, 234: 129-138.
47	池滨,侯三英,刘广智, 等. 高性能高功率密度质子交换膜燃料电池膜电极[J]. 化学进展, 2018,30(2/3): 243-251.
47	CHI Bin, HOU Sanying, LIU Guangzhi, et al. High performance and high power density membrane electrode assembly for proton exchange membrane fuel cells[J]. Progress in Chemistry, 2018, 30(2/3): 243-251.
48	GE S, LI X, HSING I M. Internally humidified polymer electrolyte fuel cells using water absorbing sponge[J]. Electrochimica Acta, 2005, 50(9): 1909-1916.
49	WANG E D, SHI P F, DU C Y. A novel self-humidifying membrane electrode assembly with water transfer region for proton exchange membrane fuel cells[J]. Journal of Power Sources, 2008, 175(1): 183-188.
50	KOH B S, YOO J H, JANG E K, et al. Fabrication of highly effective self-humidifying membrane electrode assembly for proton exchange membrane fuel cells via electrostatic spray deposition[J]. Electrochemistry Communications, 2018, 93: 76-80.
51	LIANG H G, XU R Y, CHEN K C, et al. Self-humidifying membrane electrode assembly with dual cathode catalyst layer structure prepared by introducing polyvinyl alcohol into the inner layer[J]. RSC Advances, 2016, 6: 1333-1338.
52	ROH C W, CHOI J, LEE H, et al. Hydrophilic-hydrophobic dual catalyst layers for proton exchange membrane fuel cells under low humidity[J]. Electrochemistry Communications, 2018, 97: 105-109.
53	YAN Y, JING L, CHANG Y F, et al. Design of Pt-C/Fe-N-S-C cathode dual catalyst layers for proton exchange membrane fuel cells under low humidity[J]. Electrochimica Acta, 2019, 296: 450-457.

[1]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[2]	陈匡胤, 李蕊兰, 童杨, 沈建华. 质子交换膜燃料电池气体扩散层结构与设计研究进展[J]. 化工进展, 2023, 42(S1): 246-259.
[3]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[4]	蒋博龙, 崔艳艳, 史顺杰, 常嘉城, 姜楠, 谭伟强. 过渡金属Co₃O₄/ZnO-ZIF氧还原催化剂Co/Zn-ZIF模板法制备及其产电性能[J]. 化工进展, 2023, 42(6): 3066-3076.
[5]	马哲杰, 张文励, 赵炫凯, 李平. PEMFC阴极催化层氧传质阻力影响的研究进展[J]. 化工进展, 2023, 42(6): 2860-2873.
[6]	于海强, 郭泉忠, 杜克勤, 汪川. 脉冲电沉积PbO₂涂层在PEMFC不锈钢双极板上的应用[J]. 化工进展, 2023, 42(2): 917-924.
[7]	高帷韬, 殷屺男, 涂自强, 龚繁, 李阳, 徐宏, 王诚, 毛宗强. 金属有机框架材料中的质子传导及其在质子交换膜中的应用[J]. 化工进展, 2022, 41(S1): 260-268.
[8]	陈哲坤, 潘伟童, 姚顶松, 丁路, 王辅臣. 质子交换膜燃料电池微孔层浆液微观结构与流变性[J]. 化工进展, 2022, 41(7): 3808-3815.
[9]	潘文政, 纪志永, 汪婧, 李淑明, 黄智辉, 郭小甫, 刘杰, 赵颖颖, 袁俊生. 微生物燃料电池处理偶氮含盐废水的产电性能和降解过程[J]. 化工进展, 2022, 41(6): 3306-3313.
[10]	高帷韬, 雷一杰, 张勋, 胡晓波, 宋平平, 赵卿, 王诚, 毛宗强. 质子交换膜燃料电池研究进展[J]. 化工进展, 2022, 41(3): 1539-1555.
[11]	张东, 张瑞, 张彬, 安周建, 雷彻. 基于质子交换膜燃料电池的冷热电联产系统研究进展[J]. 化工进展, 2022, 41(3): 1608-1621.
[12]	陈诗雨, 许志成, 杨婧, 徐浩, 延卫. 微生物燃料电池在废水处理中的研究进展[J]. 化工进展, 2022, 41(2): 951-963.
[13]	冯占雄, 汪云, 马强, 张创, 王诚. 连续管道微波技术制备Pt/C催化剂及其氧还原性能[J]. 化工进展, 2022, 41(12): 6377-6384.
[14]	万年坊. 质子交换膜水电解制氢膜电极研究进展[J]. 化工进展, 2022, 41(12): 6385-6394.
[15]	杜新, 范进伟, 郭丽君, 王金龙. 用非均匀团聚体模型模拟燃料电池老化过程[J]. 化工进展, 2022, 41(11): 5755-5760.