质子交换膜电解水技术关键材料的研究进展与展望

doi:10.19799/j.cnki.2095-4239.2022.0319

摘要/Abstract

摘要：

氢是碳中和能源系统的重要组成部分，为重工业和长途运输等难以脱碳的行业提供了一种可替代路径。可再生能源电解制氢是最可持续的制氢技术，为整合间歇性可再生能源提供了额外的灵活性，并可以作为季节性储能。质子交换膜(PEM)电解水技术具有电流密度高、运行压力高、电解槽体积小、整体性和灵活性好等优势，与波动性较大的风电和光伏有很好的适配性，但目前的主要挑战之一是其成本较高。本文对PEM电解水技术的成本组成及应用现状进行了总结，并详细分析了PEM电解槽中的关键材料、制备工艺及组件制造的研究进展。研究认为，通过新型的结构设计、制备策略和制造技术，可以提升贵金属催化剂的活性和利用率，减少膜厚度以降低欧姆极化，降低双极板的原料和加工成本，改善电解槽的结构设计和组装。最后提出了未来PEM电解水技术的研发方向和目标，通过材料性能的技术创新、组件制造工艺的优化、电解槽生产规模的扩大，能显著降低PEM电解水设备的成本，加速PEM制氢的规模化发展。

关键词: 质子交换膜(PEM), 电解水, 材料, 组件, 电解槽

Abstract:

Hydrogen is an essential element for a net carbon energy system that provides an alternative to difficult sectors for deep decarbonization, including heavy industry and long-haul transport. Electrolytic hydrogen synthesized through renewables is the most sustainable technology. It offers additional flexibility to integrate intermittent renewable energy and also can be used as seasonal energy storage. High current density, high operating pressure, small electrolyzer size, good integrity, and flexibility are all benefits of proton exchange membrane (PEM) water electrolysis technology. It also has good adaptability to the high volatility of wind and PV power. However, one of the main challenges is its high cost. The cost composition and application status of PEM water electrolysis are summarized in this study, and the research progress in critical materials, preparation technology, and component manufacturing are addressed in depth. According to research, novel structure-design preparation strategies and manufacturing technology are expected to improve electrolyzer design and construction, decrease the cost of raw materials and manufacturing for bipolar plates, decrease ohmic polarization by reducing membrane thickness, and increase the activity and utilization of noble-metal catalysts. Finally, the future R&D direction and target of PEM water electrolysis are proposed. With technology innovation in material performance, optimization of component manufacturing, and an increase in electrolyzer plant scale, significantly reducing the cost of PEM water electrolysis equipment and accelerating the large-scale development of PEM hydrogen production.

Key words: proton exchange membrane, water electrolysis, materials, component, electrolyzer

中图分类号:

TK 91

徐滨, 王锐, 苏伟, 何广利, 缪平. 质子交换膜电解水技术关键材料的研究进展与展望[J]. 储能科学与技术, 2022, 11(11): 3510-3520.

Bin XU, Rui WANG, Wei SU, Guangli HE, Ping MIAO. Research progress and prospect of key materials of proton exchange membrane water electrolysis[J]. Energy Storage Science and Technology, 2022, 11(11): 3510-3520.

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参考文献 50

1	CHI J, YU H M. Water electrolysis based on renewable energy for hydrogen production[J]. Chinese Journal of Catalysis, 2018, 39(3): 390-394.
2	RASHID M D, MESFER M K, NASSEM H, et al. Hydrogen production by water electrolysis: A review of alkaline water electrolysis, PEM water electrolysis and high temperature water electrolysis[J/OL]. International Journal of Engineering and Advanced Technology, 2015, 4(3). https://www.ijeat.org/portfolio-item/C3749024315/
3	KUMAR S S, HIMABINDU V. Hydrogen production by PEM water electrolysis-A review[J]. Materials Science for Energy Technologies, 2019, 2(3): 442-454.
4	BABIC U, SUERMANN M, BÜCHI F N, et al. Critical review-Identifying critical gaps for polymer electrolyte water electrolysis development[J]. Journal of the Electrochemical Society, 2017, 164(4): F387-F399.
5	俞红梅, 邵志刚, 侯明, 等. 电解水制氢技术研究进展与发展建议[J]. 中国工程科学, 2021, 23(2): 146-152.
	YU H M, SHAO Z G, HOU M, et al. Hydrogen production by water electrolysis: Progress and suggestions[J]. Strategic Study of CAE, 2021, 23(2): 146-152.
6	FENG Q, YUAN X Z, LIU G Y, et al. A review of proton exchange membrane water electrolysis on degradation mechanisms and mitigation strategies[J]. Journal of Power Sources, 2017, 366: 33-55.
7	TAIBI E, MIRANDA R, CARMO M. Green hydrogen cost reduction[R/OL]. International Renewable Energy Agency (IRENA), 2020[2021-12-01]. https://www.irena.org/publications/2020/Dec/Green-hydrogen-cost-reduction.
8	CHENG J B, ZHANG H M, CHEN G B, et al. Study of IrxRu_1- xO₂ oxides as anodic electrocatalysts for solid polymer electrolyte water electrolysis[J]. Electrochimica Acta, 2009, 54(26): 6250-6256.
9	SIRACUSANO S, DIJK N V, PAYNE-JOHNSON E, et al. Nanosized IrOx and IrRuOx electrocatalysts for the O₂ evolution reaction in PEM water electrolysers[J]. Applied Catalysis B: Environmental, 2015, 164: 488-495.
10	XU C B, MA L R, LI J L, et al. Synthesis and characterization of novel high-performance composite electrocatalysts for the oxygen evolution in solid polymer electrolyte (SPE) water electrolysis[J]. International Journal of Hydrogen Energy, 2012, 37(4): 2985-2992.
11	JIANG G, YU H M, HAO J K, et al. An effective oxygen electrode based on Ir_0.6Sn_0.4O₂ for PEM water electrolyzers[J]. Journal of Energy Chemistry, 2019, 39: 23-28.
12	PUTHIYAPURA V K, MAMLOUK M, PASUPATHI S, et al. Physical and electrochemical evaluation of ATO supported IrO₂ catalyst for proton exchange membrane water electrolyser[J]. Journal of Power Sources, 2014, 269: 451-460.
13	ZHAO S, STOCK A, RASIMICK B, et al. Highly active, durable dispersed iridium nanocatalysts for PEM water electrolyzers[J]. Journal of the Electrochemical Society, 2018, 165(2): F82.
14	李佳坤. 质子交换膜(PEM)水电解制氢用新型析氧电极研究[D]. 长沙: 湖南大学, 2019.
	LI J K. Research on novel oxygen evolution electrode for proton exchange membrane water electrolysis[D]. Changsha: Hunan University, 2019.
15	SUI S, MA L R, ZHAI Y C. Investigation on the proton exchange membrane water electrolyzer using supported anode catalyst[J]. Asia-Pacific Journal of Chemical Engineering, 2009, 4(1): 8-11.
16	PHAM C V, BÜHLER M, KNÖPPEL J, et al. IrO₂ coated TiO₂ core-shell microparticles advance performance of low loading proton exchange membrane water electrolyzers[J]. Applied Catalysis B: Environmental, 2020, 269: doi: 10.1016/j.apcatb.2020.118762.
17	ZHU J H, WEI M, MENG Q H, et al. Ultrathin-shell IrCo hollow nanospheres as highly efficient electrocatalysts towards the oxygen evolution reaction in acidic media[J]. Nanoscale, 2020, 12(47): 24070-24078.
18	PARK J, SA Y J, BAIK H, et al. Iridium-based multimetallic Nanoframe@Nanoframe structure: An efficient and robust electrocatalyst toward oxygen evolution reaction[J]. ACS Nano, 2017, 11(6): 5500-5509.
19	LEWINSKI K, VLIET D V D, LUOPA S M. NSTF advances for PEM electrolysis-The effect of alloying on activity of NSTF electrolyzer catalysts and performance of NSTF based PEM electrolyzers[J]. ECS transactions, 2015, 69(17):893-917.
20	JIANG G, YU H M, LI Y H, et al. Low-loading and highly stable membrane electrode based on an Ir@WOxNR ordered array for PEM water electrolysis[J]. ACS Applied Materials & Interfaces, 2021, 13(13): 15073-15082.
21	SHI Y X, PAN H L, XIA J Y, et al. Designing of highly efficient oxygen evolution reaction electrocatalysts utilizing A correlation factor: Theory and experiment[J]. ACS Applied Materials & Interfaces, 2021, 13(26): 30533-30541.
22	CHONG L N, WANG H, LIU D J. PGM-Free Oer Catalysts for PEM Electrolyzer Application[C]//ECS Meeting Abstracts. IOP Publishing, 2019 (29): 1443.
23	KIRSHENBAUM M J, RICHTER M, DASOG M. Electrochemical water oxidation in acidic solution using titanium diboride (TiB₂) catalyst[J]. ChemCatChem, 2019, 11(16): 3877-3881.
24	SIRACUSANO S, BAGLIO V, STASSI A, et al. Performance analysis of short-side-chain Aquivion® perfluorosulfonic acid polymer for proton exchange membrane water electrolysis[J]. Journal of Membrane Science, 2014, 466: 1-7.
25	SUN S C, SHAO Z G, YU H M, et al. Investigations on degradation of the long-term proton exchange membrane water electrolysis stack[J]. Journal of Power Sources, 2014, 267: 515-520.
26	JANG I Y, KWEON O H, KIM K E, et al. Application of polysulfone (PSf)-and polyether ether ketone (PEEK)-tungstophosphoric acid (TPA) composite membranes for water electrolysis[J]. Journal of Membrane Science, 2008, 322(1): 154-161.
27	唐金库, 巴俊洲, 蒋亚雄, 等. 等离子体刻蚀对Nafion膜性能的影响[J]. 舰船科学技术, 2007, 29(6): 135-138.
	TANG J K, BA J Z, JIANG Y X, et al. Effects of plasma etching on Nafion membrane performances[J]. Ship Science and Technology, 2007, 29(6): 135-138.
28	史言, 杨芬, 胡晓宏, 等. Nafion膜的处理对PEM水电解器中氧气纯度的影响[J]. 航天医学与医学工程, 2013, 26(5): 391-393.
	SHI Y, YANG F, HU X H, et al. Effects of nafion membrane modification on oxygen purity in PEM water electrolyze[J]. Space Medicine ＆ Medical Engineering, 2013, 26(5): 391-393.
29	BUKOLA S, CREAGER S. Graphene-based proton transmission and hydrogen crossover mitigation in electrochemical hydrogen pump cells[J]. ECS Transactions, 2019, 92(8): 439.
30	PARK J, KANG Z Y, BENDER G, et al. Roll-to-roll production of catalyst coated membranes for low-temperature electrolyzers[J]. Journal of Power Sources, 2020, 479: doi:10.1016/j.jpowsour.2020.228819
31	KIM T H, YI J Y, JUNG C Y, et al. Solvent effect on the Nafion agglomerate morphology in the catalyst layer of the proton exchange membrane fuel cells[J]. International Journal of Hydrogen Energy, 2017, 42(1): 478-485.
32	XIE Z Q, YU S L, YANG G Q, et al. Optimization of catalyst-coated membranes for enhancing performance in proton exchange membrane electrolyzer cells[J]. International Journal of Hydrogen Energy, 2021, 46(1): 1155-1162.
33	MAUGER S A, NEYERLIN K C, YANG-NEYERLIN A C, et al. Gravure coating for roll-to-roll manufacturing of proton-exchange-membrane fuel cell catalyst layers[J]. Journal of the Electrochemical Society, 2018, 165(11): F1012-F1018.
34	MAYYAS A, MANN M. Emerging manufacturing technologies for fuel cells and electrolyzers[J]. Procedia Manufacturing, 2019, 33: 508-515.
35	ITO H, MAEDA T, NAKANO A, et al. Influence of pore structural properties of current collectors on the performance of proton exchange membrane electrolyzer[J]. Electrochimica Acta, 2013, 100: 242-248.
36	张萍俊, 孙树成, 俞红梅, 等. 不同材料作为阳极扩散层对质子交换膜水电解池性能的影响[J]. 可再生能源, 2019, 37(10): 1429-1433.
	ZHANG P J, SUN S C, YU H M, et al. Influence of different materials as anode diffusion layer on performance of PEMWE[J]. Renewable Energy Resources, 2019, 37(10): 1429-1433.
37	KANG Z Y, MO J K, YANG G Q, et al. Investigation of thin/well-tunable liquid/gas diffusion layers exhibiting superior multifunctional performance in low-temperature electrolytic water splitting[J]. Energy & Environmental Science, 2017, 10(1): 166-175.
38	KANG Z Y, YANG G Q, MO J K, et al. Developing titanium micro/nano porous layers on planar thin/tunable LGDLs for high-efficiency hydrogen production[J]. International Journal of Hydrogen Energy, 2018, 43(31): 14618-14628.
39	MO J K, DEHOFF R R, PETER W H, et al. Additive manufacturing of liquid/gas diffusion layers for low-cost and high-efficiency hydrogen production[J]. International Journal of Hydrogen Energy, 2016, 41(4): 3128-3135.
40	TOOPS T J, BRADY M P, ZHANG F Y, et al. Evaluation of nitrided titanium separator plates for proton exchange membrane electrolyzer cells[J]. Journal of Power Sources, 2014, 272: 954-960.
41	LETTENMEIER P, WANG R, ABOUATALLAH R, et al. Durable membrane electrode assemblies for proton exchange membrane electrolyzer systems operating at high current densities[J]. Electrochimica Acta, 2016, 210: 502-511.
42	YANG G Q, MO J K, KANG Z Y, et al. Fully printed and integrated electrolyzer cells with additive manufacturing for high-efficiency water splitting[J]. Applied Energy, 2018, 215: 202-210.
43	BAREIß K, DE LA RUA C, MÖCKL M, et al. Life cycle assessment of hydrogen from proton exchange membrane water electrolysis in future energy systems[J]. Applied Energy, 2019, 237: 862-872.
44	刘晓天, 尹永利, 李明宇, 等. 新型低成本PEM水电解槽的研制与测试[J]. 航天医学与医学工程, 2020, 33(4): 350-355.
	LIU X T, YIN Y L, LI M Y, et al. Development and test of a low cost new PEM water electrolyzer[J]. Space Medicine & Medical Engineering, 2020, 33(4): 350-355.
45	邓庆. 一种纯水制氢PEM电解槽: CN214937843U[P], 2021-11-30
	DENG Q. A pure water to hydrogen PEM electrolyzer: CN214937843U[P], 2021-11-30
46	黄天旗, 黄立. 顶丝反压式PEM电解槽机构: CN216427426U[P]. 2022-05-03.
	HUANG T Q, HUANG L. Jackscrew back pressure type PEM electrolytic bath mechanism: CN216427426U[P]. 2022-05-03.
47	KIM H, PARK M, LEE K S. One-dimensional dynamic modeling of a high-pressure water electrolysis system for hydrogen production[J]. International Journal of Hydrogen Energy, 2013, 38(6): 2596-2609.
48	ESPINOSA-LÓPEZ M, DARRAS C, POGGI P, et al. Modelling and experimental validation of a 46 kW PEM high pressure water electrolyzer[J]. Renewable Energy, 2018, 119: 160-173.
49	BUTTLER A, SPLIETHOFF H. Current status of water electrolysis for energy storage, grid balancing and sector coupling via power-to-gas and power-to-liquids: A review[J]. Renewable and Sustainable Energy Reviews, 2018, 82: 2440-2454.
50	AßMANN P, GAGO A S, GAZDZICKI P, et al. Toward developing accelerated stress tests for proton exchange membrane electrolyzers[J]. Current Opinion in Electrochemistry, 2020, 21: 225-233.

项目名称	规模	时间地点	开发商	PEM设备供应商
氢能创新产业园	1.25 MW	2020北京延庆	国家电投	西门子
兆瓦级可再生电力电解水制氢示范项目	2.5 MW	2021河南濮阳	中石化中原油田	康明斯
“源网荷储一体化”示范项目	2.5 MW	2021内蒙古乌兰察布	中国三峡集团	康明斯
兆瓦级质子交换膜PEM电解制氢项目	1 MW	2021安徽六安	国网安徽公司	中科院大化所
MW级PEM膜电解水制氢技术研发项目	1 MW	2022北京	北京燕山石化	中石化

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