高效镍基有序多孔电极气泡行为可视化观测及性能影响

doi:10.16085/j.issn.1000-6613.2023-1351

摘要/Abstract

摘要：

碱性电解水（AWE）制氢是目前应用最广、商业化规模最大的电解水制氢技术，在碱性电解水系统中，突破析氧反应（OER）的性能瓶颈对提升电解水性能有着巨大意义。析气反应中气泡的行为会造成电极电阻的增加、反应时运输阻力的增加及电极电化学活性表面积（ECSA）的减少等影响，特别是在高电流密度下气泡对于析气反应的传质传荷阻力增加十分巨大。在碱性电解水系统中对于电极内部气泡行为的观测研究目前暂有空白。本工作通过电火花放电技术（EDM）制作出了镍基有序多孔电极，实验观测到该结构电极对析气反应中的气泡合并、对通道表面的黏附及排除过程中的禁锢有所抑制。同时，该结构电极在碱性电解水析氧反应中表现出了优异的性能，其在相同高电位下的OER几何电流密度是普通工业用泡沫镍电极的三倍之多，ECSA归一化电流密度能达到11倍之多。本文阐释了在碱性电解水系统中电极内部气泡行为，以及镍基有序孔电极是如何影响电解水性能，为工业上电解水电极设计提供了一个高效可行的方案。

关键词: 电解, 多孔介质, 析气反应, 可视化实验, 两相流

Abstract:

Alkaline water electrolysis (AWE) is currently the most widely applied and commercially scaled technology for water electrolysis. In AWE systems, breaking through the performance limitations of oxygen evolution reaction (OER) holds great significance for enhancing electrolysis performance. The behavior of bubbles in the gas evolution reaction causes an increase in electrode resistance, transport resistance during the reaction, and a decrease in the electrochemical active surface area (ECSA) of the electrode. This effect is particularly significant at high current densities, where bubbles impose substantial mass and charge transport resistance on the gas evolution reaction. Currently, there is a lack of research on the observation of internal bubble behavior in AWE systems. This study employed the Electric Discharge Machining (EDM) technique to fabricate nickel-based electrodes with order square corn holes (OSCH-Ni). Experimental observations revealed that OSCH-Ni electrodes inhibit bubble coalescence during the gas evolution reaction and restrict bubble adhesion and expulsion processes on the channel surface.Furthermore, OSCH-Ni electrodes exhibited excellent performance in the oxygen evolution reaction in alkaline water electrolysis. At the same high potential, the geometric current density of OSCH-Ni for OER was more than three times that of a typical industrial foam nickel electrode, and the normalized current density of ECSA exceeded 11 times. This work elucidates the behavior of internal bubbles in alkaline water electrolysis systems and how nickel-based ordered porous electrodes affect water electrolysis performance. It also provides an efficient and feasible solution for the design of industrial water electrolysis electrodes.

Key words: electrolysis, porous media, gas evolution reaction, visualization experiments, two-phase flow

中图分类号:

胡志豪, 张皓景, 周叶, 吴睿. 高效镍基有序多孔电极气泡行为可视化观测及性能影响[J]. 化工进展, 2024, 43(2): 680-687.

HU Zhihao, ZHANG Haojing, ZHOU Ye, WU Rui. Visualization observation of bubble behavior and performance impact analysis in efficient nickel based ordered porous electrodes[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 680-687.

图/表 5

图1 可视化电解水实验系统1—光源控制器；2—光源；3—可视化石英电解槽；4—电化学工作站；5—计算机；6—高速摄像机

图2 OSCH-Ni-M电极及其SEM图像与NF电极及其SEM图像

图3 不同电极在IR补偿后的OER/HER电化学极化曲线和各电极jECSA相比于NF的jECSA比值

图4 OER过程中OSCH-Ni-L、OSCH-Ni-M和OSCH-Ni-H电极通道内部图像及NF电极内部气泡堵住过程图

图5 OER及HER过程中电极反应过程图像

参考文献 33

1	TRASATTI S. Water electrolysis: Who first?[J]. Journal of Electroanalytical Chemistry, 1999, 476(1): 90-91.
2	MATSUOKA Masaya, KITANO Masaaki, TAKEUCHI Masato, et al. Photocatalysis for new energy production[J]. Catalysis Today, 2007, 122(1/2): 51-61.
3	SOLIMAN Moustafa Aly, ZAKARIA Maryam. Kinetics of photolysis and photocatalytic oxidation of ammonium sulfite for hydrogen production[J]. Journal of King Saud University: Engineering Sciences. .
4	WERNER Håkan A F, BAUER Rupert. Hydrogen production by water photolysis using nitrilotriacetic acid as electron donor[J]. Journal of Photochemistry and Photobiology A: Chemistry, 1996, 97(3): 171-173.
5	COUTANCEAU Christophe, BARANTON Stève, AUDICHON Thomas. Hydrogen production from water electrolysis[M]//Hydrogen Electrochemical Production. Amsterdam: Elsevier, 2018: 17-62.
6	KRISHNAN Subramani, FAIRLIE Matthew, ANDRES Philipp, et al. Power to gas (H₂): Alkaline electrolysis[M]//Technological learning in the transition to a low-carbon energy system. Amsterdam: Elsevier, 2020: 165-187.
7	GRIGORIEV S A, FATEEV V N, BESSARABOV D G, et al. Current status, research trends, and challenges in water electrolysis science and technology[J]. International Journal of Hydrogen Energy, 2020, 45(49): 26036-26058.
8	LAKE Jack R, SOTO Álvaro Moreno, VARANASI Kripa K. Impact of bubbles on electrochemically active surface area of microtextured gas-evolving electrodes[J]. Langmuir, 2022, 38(10): 3276-3283.
9	KOU Tianyi, WANG Shanwen, SHI Rongpei, et al. Water splitting: Periodic porous 3D electrodes mitigate gas bubble traffic during alkaline water electrolysis at high current densities[J]. Advanced Energy Materials, 2020, 10(46): 2002955.
10	FUJIMURA Tatsuki, HIKIMA Wakana, FUKUNAKA Yasuhiro, et al. Analysis of the effect of surface wettability on hydrogen evolution reaction in water electrolysis using micro-patterned electrodes[J]. Electrochemistry Communications, 2019, 101: 43-46.
11	IWATA Ryuichi, ZHANG Lenan, WILKE Kyle L, et al. Bubble growth and departure modes on wettable/non-wettable porous foams in alkaline water splitting[J]. Joule, 2021, 5(4): 887-900.
12	Justin C BUI, DAVIS Jonathan T, ESPOSITO Daniel V. 3D-printed electrodes for membraneless water electrolysis[J]. Sustainable Energy & Fuels, 2020, 4(1): 213-225.
13	VANDER LINDE Peter, PABLO Peñas-López, ÁLVARO Moreno Soto, et al. Gas bubble evolution on microstructured silicon substrates[J]. Energy & Environmental Science, 2018, 11(12): 3452-3462.
14	ZHAO Xu, REN Hang, LUO Long. Gas bubbles in electrochemical gas evolution reactions[J]. Langmuir, 2019, 35(16): 5392-5408.
15	ANGULO Andrea, VAN DER LINDE Peter, GARDENIERS Han, et al. Influence of bubbles on the energy conversion efficiency of electrochemical reactors[J]. Joule, 2020, 4(3): 555-579.
16	JI Seong Min, KUMAR Anuj. Cellulose-derived nanostructures as sustainable biomass for supercapacitors: A review[J]. Polymers, 2022, 14(1): 169.
17	XU Ting, DU Haishun, LIU Huayu, et al. Advanced nanocellulose-based composites for flexible functional energy storage devices[J]. Advanced Materials, 2021, 33(48): 2101368.
18	WANG Lili, WANG Kang, LOU Zheng, et al. Plant-based modular building blocks for “green” electronic skins[J]. Advanced Functional Materials, 2018, 28(51): 1804510.
19	WAN Lei, XU Ziang, XU Qin, et al. Overall design of novel 3D-ordered MEA with drastically enhanced mass transport for alkaline electrolyzers[J]. Energy & Environmental Science, 2022, 15(5): 1882-1892.
20	DAVIS Jonathan T, QI Ji, FAN Xinran, et al. Floating membraneless PV-electrolyzer based on buoyancy-driven product separation[J]. International Journal of Hydrogen Energy, 2018, 43(3): 1224-1238.
21	HUANG Birou, WANG Xiaochen, LI Wenzheng, et al. Accelerating gas escape in anion exchange membrane water electrolysis by gas diffusion layers with hierarchical grid gradients[J]. Angewandte Chemie International Edition, 2023, 62(33): e202304230.
22	ZHANG Chunhui, XU Zhe, HAN Nana, et al. Superaerophilic/superaerophobic cooperative electrode for efficient hydrogen evolution reaction via enhanced mass transfer[J]. Science Advances, 2023, 9(3): eadd6978.
23	PENG Ci, ZHAO Luhaibo, TANG Zhiyong. Enhanced production of hydrogen from alkaline electrolysis by microbubbles removal on bionic electrode[J]. Physics of Fluids, 2023, 35(2): 022001.
24	ZOU Yajun, XIAO Bing, SHI Jianwen, et al. 3D hierarchical heterostructure assembled by NiFe LDH/(NiFe)S _x on biomass-derived hollow carbon microtubes as bifunctional electrocatalysts for overall water splitting[J]. Electrochimica Acta, 2020, 348: 136339.
25	VOGT H. The concentration overpotential of gas evolving electrodes as a multiple problem of mass transfer[J]. Journal of the Electrochemical Society, 1990, 137(4): 1179-1184.
26	KEMPLER Paul A, CORIDAN Robert H, LEWIS Nathan S. Effects of bubbles on the electrochemical behavior of hydrogen-evolving Si microwire arrays oriented against gravity[J]. Energy & Environmental Science, 2020, 13(6): 1808-1817.
27	LEISTRA James A, SIDES Paul J. Voltage components at gas evolving electrodes[J]. Journal of the Electrochemical Society, 1987, 134(10): 2442-2446.
28	DENG Xintao, YANG Fuyuan, LI Yangyang, et al. Quantitative study on gas evolution effects under large current density in zero-gap alkaline water electrolyzers[J]. Journal of Power Sources, 2023, 555: 232378.
29	QIAN K, CHEN Z D, Chen J J J. Bubble coverage and bubble resistance using cells with horizontal electrode[J]. Journal of Applied Electrochemistry, 1998, 28(10): 1141-1145.
30	KIUCHI Daisuke, MATSUSHIMA Hisayoshi, FUKUNAKA Yasuhiro, et al. Ohmic resistance measurement of bubble froth layer in water electrolysis under microgravity[J]. Journal of the Electrochemical Society, 2006, 153(8): E138.
31	VOGT H, H-D KLEINSCHRODT. Ohmic interelectrode voltage drop in alumina reduction cells[J]. Journal of Applied Electrochemistry, 2003, 33(7): 563-569.
32	HINE F, YASUDA M, NAKAMURA R, et al. Hydrodynamic studies of bubble effects on the IR-drops in a vertical rectangular cell[J]. Journal of the Electrochemical Society, 1975, 122(9): 1185-1190.
33	KREYSA G, KUHN M. Modelling of gas evolving electrolysis cells. ‍Ⅰ‍. The gas voidage problem[J]. Journal of Applied Electrochemistry, 1985, 15(4): 517-526.

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