电沉积法制备碱性电解水镍基析氧电极的研究进展

doi:10.16085/j.issn.1000-6613.2023-0067

摘要/Abstract

摘要：

在“碳达峰、碳中和”的目标下，绿氢成为极具前景的清洁能源。碱性电解水制取绿氢技术商业化程度最高，但由于析氧反应（OER）动力学过程缓慢且需要较高的过电位，成为制约电解水电极效率的主要瓶颈。商业电解槽中广泛使用的镍网或泡沫镍电极的OER性能仍有很大提升空间，在其上复合镍基催化功能层，开发新型高活性的析氧电极有利于提高电极效率，降低制氢成本。电沉积技术具有工艺简单、条件温和、利于放大生产自支撑电极的优势，成为工业化生产OER电极的理想工艺之一。本文综述了近年来利用电沉积技术制备的镍基析氧电极并用于碱性电解水的研究进展。采用电沉积技术在镍网或泡沫镍基底上制备镍（氢）氧化物、双金属及多元金属以及非金属掺杂的镍基催化剂作为催化功能层，通过增强催化功能层的电导率及金属间的协同作用、增加活性位点数量、减小扩散路径以及改变表面原子构型等方式提高镍基自支撑电极的OER性能。最后，展望了镍基自支撑电极在电解水领域的应用，同时指出了电沉积法制备电极材料存在的挑战。

关键词: 电解, 制氢, 催化剂, 镍基自支撑电极, 析氧反应, 电沉积法

Abstract:

Under the goal of "peak carbon dioxide emissions, carbon neutral", green hydrogen has become a promising clean energy source. The technology of producing green hydrogen by alkaline electrolysis of water has the highest degree of commercialization, but because of the slow kinetic process of oxygen evolution reaction (OER) and the high overpotential, it has become the main bottleneck restricting the efficiency of electrolytic water electrode. There is still much room to improve the OER performance of nickel mesh or nickel foam electrode widely used in commercial electrolytic cells. It is beneficial to improve the electrode efficiency and reduce the cost of hydrogen production by compounding nickel-based catalytic functional layer on it and developing new high-activity oxygen evolution electrode. Electrodeposition technology has the advantages of simple process and mild conditions, which is beneficial to scale up the production of self-supporting electrodes, and has become one of the ideal processes for industrial production of OER electrodes. In this paper, the research progress of nickel-based oxygen evolution electrode prepared by electrodeposition technology and used in alkaline electrolysis of water in recent years is reviewed. Nickel-based (hydrogen) oxides, bimetals, multi-metals and nonmetal-doped nickel-based catalysts are prepared on nickel mesh or nickel foam substrate by electrodeposition technology as catalytic functional layers. The OER performance of nickel-based self-supporting electrodes is improved by enhancing the conductivity of catalytic functional layers and the synergistic effect between metals, increasing the number of active sites, reducing the diffusion path and changing the surface atomic configuration. In addition, the application of nickel-based self-supporting electrode in water electrolysis field is clarified, and the challenges of electrodeposition method are pointed out.

Key words: electrolysis, hydrogen production, catalyst, nickel-based self-supporting electrode, oxygen evolution reaction, electrodeposition method

中图分类号:

TQ151.1

张静, 贺业亨, 王晶晶, 夏博文, 赵秦峰, 王延飞, 余颖龙, 邵晨熠, 龙川. 电沉积法制备碱性电解水镍基析氧电极的研究进展[J]. 化工进展, 2023, 42(12): 6239-6250.

ZHANG Jing, HE Yeheng, WANG Jingjing, XIA Bowen, ZHAO Qinfeng, WANG Yanfei, YU Yinglong, SHAO Chenyi, LONG Chuan. Research progress on nickel-based oxygen evolution electrode prepared by electrodeposition for alkaline water electrolysis[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6239-6250.

图/表 11

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催化剂名称	基底	电流密度 /mA·cm^-2	过电位 /mV	塔菲尔斜率 /mV·dec^-1	电解液	沉积液	参考文献
α-Ni(OH)₂·0.75H₂O/NF	NF	100	357^①	128.7	1.0mol/L KOH	NiCl₂	[40]
Ni(OH)₂/NF/N-CNTs	NF/N-CNTs	10	254	84	1.0mol/L KOH	Ni(NO₃)₂·6H₂O	[27]
α-Ni(OH)₂/NF	NF	10	192^①	108	1.0mol/L KOH	Ni(NO₃)₂·6H₂O	[39]
NiO/NiNDs@NF	NF	50	360^①	90	1.0mol/L KOH	Ni(NO₃)₂乙腈溶液	[37]
NiFe(OH)x-500/Ni	镍网	10	204^①	39	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+ FeSO₄·7H₂O	[48]
NiFe/NF	NF	10	191^①	44.1	1.0mol/L KOH	NiCl₂·6H₂O+FeCl₂·4H₂O	[43]
NiFe-LDHs/NF	NF	10	283^①	47.76	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+ Fe(NO₃)₂·9H₂O	[47]
Ni(Co_0.5Fe_0.5)/NF	NF	10	209^①	54	1.0mol/L KOH	Ni(NO₃)₂+Co(NO₃)₂+FeSO₄	[28]
Ag@NiCo LDH/NF	NF	100	304^①	64.6	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+Co(NO₃)₂·6H₂O	[51]
NiFeCr/NF	NF	—	—^①	36	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+Fe(NO₃)₂·9H₂O+ Cr(NO₃)₂·9H₂O	[20]
NiFeMo/NF	NF	10	306^①	77.1	30% KOH	NiSO₄·6H₂O+NaCl+H₃BO₃+ FeSO₄·6H₂O+Na₃C₆H₅O₇·2H₂O+ Na₂MoO₄·2H₂O	[50]
Ni_0.65Ga_0.30Fe_0.05/NF	NF	10	200	42	1.0mol/L KOH	Ga(NO₃)₃∙xH₂O+Ni(NO₃)₂∙6H₂O+ Fe(NO₃)₂∙9H₂O	[19]
NiFeSn/NF	NF	10	253^①	61.5	30% KOH	NiSO₄·6H₂O+NaCl+H₃BO₃+ FeSO₄·6H₂O+C₆H₅Na₃O₇·2H₂O+ SnCl₂·6H₂O	[44]
Ni-Fe-W-Mo/Ni	镍网	10	152^①	—	5.35mol/L KOH	NiSO₄·6H₂O+FeSO₄·7H₂O+ Na₂WO₄·2H₂O+C₆H₈O₇·7H₂O+ Na₂MoO₄·2H₂O+抗坏血酸	[41]
Ni(OH)₂/Ni₃S₂/NF	NF	10	210^①	72	1.0mol/L KOH	NiCl₂·6H₂O+CS(NH₂)₂+NaCl+H₂SO₄	[52]
NiFeS/NF	NF	10	287^①	64.74	1.0mol/L KOH	NiSO₄·6H₂O+CoCl₂·6H₂O+CH₄N₂S+H₃BO₃+ C₆H₅Na₃O₇·2H₂O+NaCl	[57]
NiFe-Pi/P-12/NF	NF	20	255^①	50	1.0mol/L KOH	NiCl₂·6H₂O+FeCl₃·6H₂O+NaOH+柠檬酸溶液	[54]
NiFeCuP@Ni₃S₂/NF	NF	10	230	42	1.0mol/L KOH	NaH₂PO₄+NH₄Cl+Ni(NO₃)₂·6H₂O+ FeSO₄·7H₂O+CuSO₄·5H₂O	[58]
Ni-S-P/NF	NF	10	219^①	82	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+CH₄N₂S Ni(NO₃)₂·6H₂O+NaH₂PO₂+CH₃COONa	[59]
NiSP/NF	NF	10	281^①	68.51	1.0mol/L KOH	NiSO₄·6H₂O+CH₄N₂S+Na₂HPO₄·2H₂O+ C₆H₅Na₃O₇·2H₂O+NaCl	[60]

催化剂名称	基底	电流密度 /mA·cm^-2	过电位 /mV	塔菲尔斜率 /mV·dec^-1	电解液	沉积液	参考文献
α-Ni(OH)₂·0.75H₂O/NF	NF	100	357^①	128.7	1.0mol/L KOH	NiCl₂	[40]
Ni(OH)₂/NF/N-CNTs	NF/N-CNTs	10	254	84	1.0mol/L KOH	Ni(NO₃)₂·6H₂O	[27]
α-Ni(OH)₂/NF	NF	10	192^①	108	1.0mol/L KOH	Ni(NO₃)₂·6H₂O	[39]
NiO/NiNDs@NF	NF	50	360^①	90	1.0mol/L KOH	Ni(NO₃)₂乙腈溶液	[37]
NiFe(OH)x-500/Ni	镍网	10	204^①	39	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+ FeSO₄·7H₂O	[48]
NiFe/NF	NF	10	191^①	44.1	1.0mol/L KOH	NiCl₂·6H₂O+FeCl₂·4H₂O	[43]
NiFe-LDHs/NF	NF	10	283^①	47.76	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+ Fe(NO₃)₂·9H₂O	[47]
Ni(Co_0.5Fe_0.5)/NF	NF	10	209^①	54	1.0mol/L KOH	Ni(NO₃)₂+Co(NO₃)₂+FeSO₄	[28]
Ag@NiCo LDH/NF	NF	100	304^①	64.6	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+Co(NO₃)₂·6H₂O	[51]
NiFeCr/NF	NF	—	—^①	36	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+Fe(NO₃)₂·9H₂O+ Cr(NO₃)₂·9H₂O	[20]
NiFeMo/NF	NF	10	306^①	77.1	30% KOH	NiSO₄·6H₂O+NaCl+H₃BO₃+ FeSO₄·6H₂O+Na₃C₆H₅O₇·2H₂O+ Na₂MoO₄·2H₂O	[50]
Ni_0.65Ga_0.30Fe_0.05/NF	NF	10	200	42	1.0mol/L KOH	Ga(NO₃)₃∙xH₂O+Ni(NO₃)₂∙6H₂O+ Fe(NO₃)₂∙9H₂O	[19]
NiFeSn/NF	NF	10	253^①	61.5	30% KOH	NiSO₄·6H₂O+NaCl+H₃BO₃+ FeSO₄·6H₂O+C₆H₅Na₃O₇·2H₂O+ SnCl₂·6H₂O	[44]
Ni-Fe-W-Mo/Ni	镍网	10	152^①	—	5.35mol/L KOH	NiSO₄·6H₂O+FeSO₄·7H₂O+ Na₂WO₄·2H₂O+C₆H₈O₇·7H₂O+ Na₂MoO₄·2H₂O+抗坏血酸	[41]
Ni(OH)₂/Ni₃S₂/NF	NF	10	210^①	72	1.0mol/L KOH	NiCl₂·6H₂O+CS(NH₂)₂+NaCl+H₂SO₄	[52]
NiFeS/NF	NF	10	287^①	64.74	1.0mol/L KOH	NiSO₄·6H₂O+CoCl₂·6H₂O+CH₄N₂S+H₃BO₃+ C₆H₅Na₃O₇·2H₂O+NaCl	[57]
NiFe-Pi/P-12/NF	NF	20	255^①	50	1.0mol/L KOH	NiCl₂·6H₂O+FeCl₃·6H₂O+NaOH+柠檬酸溶液	[54]
NiFeCuP@Ni₃S₂/NF	NF	10	230	42	1.0mol/L KOH	NaH₂PO₄+NH₄Cl+Ni(NO₃)₂·6H₂O+ FeSO₄·7H₂O+CuSO₄·5H₂O	[58]
Ni-S-P/NF	NF	10	219^①	82	1.0mol/L KOH	Ni(NO₃)₂·6H₂O+CH₄N₂S Ni(NO₃)₂·6H₂O+NaH₂PO₂+CH₃COONa	[59]
NiSP/NF	NF	10	281^①	68.51	1.0mol/L KOH	NiSO₄·6H₂O+CH₄N₂S+Na₂HPO₄·2H₂O+ C₆H₅Na₃O₇·2H₂O+NaCl	[60]

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