Study of anode materials for electrocatalytic decomposition of liquid ammonia

doi:10.11949/0438-1157.20240144

Abstract

Abstract:

Ammonia is a chemical storage material with high hydrogen storage density. Efficient use of energy can be achieved through ammonia-hydrogen conversion. The decomposition of ammonia into hydrogen plays a pivotal role in this conversion process, and electrocatalytic direct decomposition of liquid ammonia is theoretically the most energy-efficient pathway. A key challenge lies in reducing the overpotential at the anode during liquid ammonia direct electrolysis to unlock the full potential of electrocatalytic ammonia decomposition in the hydrogen economy. This study employs linear scanning voltammetry (LSV), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronopotential (CP) tests to investigate the electrochemical properties and corrosion resistance of various materials, including copper, cobalt, iron, molybdenum, vanadium, titanium, carbon paper and 304 stainless steel, as anode materials in the electrolysis of liquid ammonia. The tests were conducted in a 2.0 mol/L NH₄Cl liquid ammonia solution. The findings indicate that titanium exhibits subpar electrocatalytic activity as an anode for the liquid ammonia electrolysis process. While copper, cobalt, and iron display excellent electrocatalytic activity, they also experience pronounced corrosion at forward potentials. 304 stainless steel showcases impressive electrocatalytic activity but exhibits average stability at high current densities. Carbon paper, despite its modest electrocatalytic activity, demonstrates commendable stability at elevated current densities, coupled with a large active surface area, rendering it suitable as a substrate material for the anode in liquid ammonia electrolysis. Moreover, molybdenum and vanadium exhibit superior electrocatalytic activity compared to carbon paper, with slower corrosion rates at high current density, positioning them as viable materials for the anode in liquid ammonia electrolysis.

Key words: electrocatalysis, ammonia oxidation, electrolysis, liquid ammonia, electrochemistry, corrosion, chemical hydrogen storage

摘要：

氨是一种具有高储氢密度的化学储氢材料，通过氨氢转换可以实现能源的高效利用。氨分解产氢是氨氢转换过程的重要一环，在氨分解的途径中电催化直接分解液氨理论上具有最低能耗，若能有效降低液氨直接电解阳极的过电位，电催化分解液氨在氢经济中将具有广阔的前景。依次使用铜、钴、铁、钼、钒、钛、碳纸和304不锈钢作为液氨电解过程阳极材料进行线性扫描伏安测试、循环伏安测试、电化学阻抗谱测试和计时电位测试，以研究这些材料在2.0 mol/L NH₄Cl的液氨溶液中的电催化活性和在高电流密度下的耐腐蚀性能。结果表明：钛作为液氨电解过程的阳极电催化活性很差；铜、钴和铁虽具有优异的电催化活性，但在正向电位下会发生严重腐蚀；304不锈钢虽具有优异的电催化活性，但在高电流密度下稳定性一般；碳纸电催化活性较差，但高电流密度下具有良好的稳定性，且活性表面积较大，适合作为液氨电解阳极催化剂基底材料；钼和钒电催化活性优于碳纸，在高电流密度下腐蚀率较低，可以作为液氨电解阳极材料。

关键词: 电催化, 氨氧化, 电解, 液氨, 电化学, 腐蚀, 化学储氢

CLC Number:

TQ 151

Xinzhe PEI, Zhuxing SUN, Yuxiang LIN, Chaoyang ZHANG, Yong QIAN, Xingcai LYU. Study of anode materials for electrocatalytic decomposition of liquid ammonia[J]. CIESC Journal, 2024, 75(5): 1843-1854.

裴欣哲, 孙朱行, 林钰翔, 张朝阳, 钱勇, 吕兴才. 电催化分解液氨阳极材料的研究[J]. 化工学报, 2024, 75(5): 1843-1854.

Figures/Tables 11

Fig.1 High voltage electrochemical reaction system

Fig.2 Polarization curves of different materials obtained by LSV forward scanning

Fig.3 Initiation potential (at current density 0.05 mA/cm2) and overpotential at 10 mA/cm2 current density for different materials

Fig.4 Comparison of Tafel curves for different materials

Fig.5 Double layer capacitor with iron, molybdenum, vanadium, titanium, 304 stainless steel and carbon paper

Fig.6 Nyquist plots, equivalent circuit fitting results, and DRT fitting results for several materials

Table 1 EIS test equivalent circuit fitting results

等效电路拟合元件	Fe	304不锈钢	Mo	V	碳纸	Ti
R_s/Ω	1.407	1.094	1.42	1.54	2.33	1.24
R_p1/Ω	33710	2750	13285	37633	48838	11.57
CPE1-T	3.87×10^-4	1.11×10^-3	1.21×10^-3	6.9×10^-4	5.43×10^-4	1.9×10^-4
CPE1-P	0.917	1.027	1.033	0.847	0.959	0.915
R_p2/Ω	126680	45000	72772			147550
CPE2-T	3.06×10^-4	3.02×10^-4	4.2×10^-4			1.5×10^-4
CPE2-P	0.816	0.761	0.812			0.893

Fig.7 Chronopotential curves of 304 stainless steel, molybdenum, vanadium, titanium and carbon paper at 50 mA/cm2

Fig.8 Corrosion rate of different materials per unit time

Fig.9 Microscopic morphology of several metallic materials before and after chronopotential testing under SEM

Fig.10 Distribution of elements on the surface of several metallic materials after the chronopotential test obtained from the EDS

References 40

1	Zhao Y, Setzler B P, Wang J H, et al. An efficient direct ammonia fuel cell for affordable carbon-neutral transportation[J]. Joule, 2019, 3(10): 2472-2484.
2	Cai Z H, Huang M M, Wei G F, et al. Numerical study of the effect of pressure on the combustion characteristics of ammonia/coal-derived syngas mixture under gas turbine operating conditions[J]. Fuel, 2023, 347: 128463.
3	Mi S J, Wu H Q, Pei X Z, et al. Potential of ammonia energy fraction and diesel pilot-injection strategy on improving combustion and emission performance in an ammonia-diesel dual fuel engine[J]. Fuel, 2023, 343: 127889.
4	Lhuillier C, Brequigny P, Contino F, et al. Experimental study on ammonia/hydrogen/air combustion in spark ignition engine conditions[J]. Fuel, 2020, 269: 117448.
5	Oh S, Park C, Kim S, et al. Natural gas-ammonia dual-fuel combustion in spark-ignited engine with various air-fuel ratios and split ratios of ammonia under part load condition[J]. Fuel, 2021, 290: 120095.
6	Mercier A, Mounaïm-Rousselle C, Brequigny P, et al. Improvement of SI engine combustion with ammonia as fuel: effect of ammonia dissociation prior to combustion[J]. Fuel Communications, 2022, 11: 100058.
7	Giddey S, Badwal S P S, Munnings C, et al. Ammonia as a renewable energy transportation media[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(11): 10231-10239.
8	Mukherjee S, Devaguptapu S V, Sviripa A, et al. Low-temperature ammonia decomposition catalysts for hydrogen generation[J]. Applied Catalysis B: Environmental, 2018, 226: 162-181.
9	Galloway J N, Townsend A R, Erisman J W, et al. Transformation of the nitrogen cycle: recent trends, questions, and potential solutions[J]. Science, 2008, 320(5878): 889-892.
10	Valera-Medina A, Xiao H, Owen-Jones M, et al. Ammonia for power[J]. Progress in Energy and Combustion Science, 2018, 69: 63-102.
11	Ouyang L, Liang J, Luo Y S, et al. Recent advances in electrocatalytic ammonia synthesis[J]. Chinese Journal of Catalysis, 2023, 50: 6-44.
12	Najafian A, Cundari T R. Computational mechanistic study of electro-oxidation of ammonia to N₂ by homogenous ruthenium and iron complexes[J]. The Journal of Physical Chemistry A, 2019, 123(37): 7973-7982.
13	Lucentini I, Garcia X, Vendrell X, et al. Review of the decomposition of ammonia to generate hydrogen[J]. Industrial & Engineering Chemistry Research, 2021, 60(51): 18560-18611.
14	Liu H Y, Lant H M C, Cody C C, et al. Electrochemical ammonia oxidation with molecular catalysts[J]. ACS Catalysis, 2023, 13(7): 4675-4682.
15	Katsounaros I, Figueiredo M C, Calle-Vallejo F, et al. On the mechanism of the electrochemical conversion of ammonia to dinitrogen on Pt(1 0 0) in alkaline environment[J]. Journal of Catalysis, 2018, 359: 82-91.
16	Xu W, Du D W, Lan R, et al. Electrodeposited NiCu bimetal on carbon paper as stable non-noble anode for efficient electrooxidation of ammonia[J]. Applied Catalysis B: Environmental, 2018, 237: 1101-1109.
17	Sacré N, Duca M, Garbarino S, et al. Tuning Pt-Ir interactions for NH₃ electrocatalysis[J]. ACS Catalysis, 2018, 8(3): 2508-2518.
18	Keener M, Peterson M, Hernández Sánchez D R, et al. Towards catalytic ammonia oxidation to dinitrogen: a synthetic cycle by using a simple manganese complex[J]. Chemistry-A European Journal, 2017, 23(48): 11479-11484.
19	Habibzadeh F, Miller S L, Hamann T W, et al. Homogeneous electrocatalytic oxidation of ammonia to N₂ under mild conditions[J]. Proceedings of the National Academy of Sciences of the United States of America, 2019, 116(8): 2849-2853.
20	Nakajima K, Toda H, Sakata K, et al. Ruthenium-catalysed oxidative conversion of ammonia into dinitrogen[J]. Nature Chemistry, 2019, 11: 702-709.
21	Bhattacharya P, Heiden Z M, Chambers G M, et al. Catalytic ammonia oxidation to dinitrogen by hydrogen atom abstraction[J]. Angewandte Chemie (International Ed. in English), 2019, 58(34): 11618-11624.
22	Ahmed M E, Raghibi Boroujeni M, Ghosh P, et al. Electrocatalytic ammonia oxidation by a low-coordinate copper complex[J]. Journal of the American Chemical Society, 2022, 144(46): 21136-21145.
23	de Vooys A C A, Koper M T M, van Santen R A, et al. The role of adsorbates in the electrochemical oxidation of ammonia on noble and transition metal electrodes[J]. Journal of Electroanalytical Chemistry, 2001, 506(2): 127-137.
24	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.
	Zhang Q, Zhao H, Rong J F. Research progress of anti-toxicity electrocatalysts for oxygen reduction reaction in PEMFC[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4677-4691.
25	Gutmann V. Reactions in some non-aqueous ionising solvents[J]. Quarterly Reviews, Chemical Society, 1956, 10(4): 451-462.
26	Dong B X, Tian H, Wu Y C, et al. Improved electrolysis of liquid ammonia for hydrogen generation via ammonium salt electrolyte and Pt/Rh/Ir electrocatalysts[J]. International Journal of Hydrogen Energy, 2016, 41(33): 14507-14518.
27	Goshome K, Yamada T, Miyaoka H, et al. High compressed hydrogen production via direct electrolysis of liquid ammonia[J]. International Journal of Hydrogen Energy, 2016, 41(33): 14529-14534.
28	Little D J, Edwards D O, Smith M R, et al. As precious as platinum: iron nitride for electrocatalytic oxidation of liquid ammonia[J]. ACS Applied Materials & Interfaces, 2017, 9(19): 16228-16235.
29	Little D J, Smith I, Hamann T W. Electrolysis of liquid ammonia for hydrogen generation[J]. Energy & Environmental Science, 2015, 8(9): 2775-2781.
30	Akagi N, Hori K, Sugime H, et al. Systematic investigation of anode catalysts for liquid ammonia electrolysis[J]. Journal of Catalysis, 2022, 406: 222-230.
31	Wan T H, Saccoccio M, Chen C, et al. Influence of the discretization methods on the distribution of relaxation times deconvolution: implementing radial basis functions with DRTtools[J]. Electrochimica Acta, 2015, 184: 483-499.
32	Ciucci F, Chen C. Analysis of electrochemical impedance spectroscopy data using the distribution of relaxation times: a Bayesian and hierarchical Bayesian approach[J]. Electrochimica Acta, 2015, 167: 439-454.
33	Effat M B, Ciucci F. Bayesian and hierarchical Bayesian based regularization for deconvolving the distribution of relaxation times from electrochemical impedance spectroscopy data[J]. Electrochimica Acta, 2017, 247: 1117-1129.
34	Liu J P, Wan T H, Ciucci F. A Bayesian view on the Hilbert transform and the Kramers-Kronig transform of electrochemical impedance data: probabilistic estimates and quality scores[J]. Electrochimica Acta, 2020, 357: 136864.
35	Vijh A K. The anodic behavior of some materials in liquid ammonia in presence and absence of methane or ethylene[J]. Journal of the Electrochemical Society, 1972, 119(7): 861.
36	Brown O R, Thornton S A. Kinetics of electrode reactions in liquid ammonia(part 2): Fe^Ⅲ/Fe^Ⅱ and Co^Ⅲ/Co^Ⅱ redox couples[J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1974, 70: 14.
37	Heusler K E, Kutzmutz S. The nickel electrode in liquid ammonia[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1990, 285(1/2): 93-101.
38	王成. 不锈钢表面电化学处理及耐腐蚀机理研究[D]. 厦门: 厦门大学, 2018.
	Wang C. Study on the electrochemical surface modification of stainless steel and its mechanism of corrosion resistance[D].Xiamen: Xiamen University, 2018.
39	焦照临, 徐流杰, 徐照宁, 等. Al₂O₃掺杂钼合金的显微组织及电化学腐蚀行为研究[J]. 稀有金属与硬质合金, 2022, 50(5): 59-65, 69.
	Jiao Z L, Xu L J, Xu Z N, et al. Study on microstructure and electrochemical corrosion behavior of Al₂O₃ doped molybdenum alloys[J]. Rare Metals and Cemented Carbides, 2022, 50(5): 59-65, 69.
40	袁天孝. TA9合金与0Cr18Ni9钢氨环境下腐蚀过程研究[D]. 银川: 宁夏大学, 2022.
	Yuan T X. Study on corrosion process of TA9 alloy and 0Cr18Ni9 steel in ammonia environment[D].Yinchuan: Ningxia University, 2022.

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