电催化分解液氨阳极材料的研究

doi:10.11949/0438-1157.20240144

摘要/Abstract

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

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

中图分类号:

TQ 151

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.

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.

图/表 11

图1 高压电化学反应系统

Fig.1 High voltage electrochemical reaction system

图2 不同材料通过LSV正向扫描得到的极化曲线

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

图3 不同材料的起始电位（电流密度0.05 mA/cm2时）与10 mA/cm2电流密度时的过电位

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

图4 不同材料的Tafel曲线比较

Fig.4 Comparison of Tafel curves for different materials

图5 铁、钼、钒、钛、304不锈钢和碳纸的双层电容

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

图6 几种材料的Nyquist图、等效电路拟合结果和DRT拟合结果

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

表1 EIS测试等效电路拟合结果

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

图7 304不锈钢、钼、钒、钛和碳纸在50 mA/cm2下的计时电位曲线

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

图8 单位时间下不同材料的腐蚀率

Fig.8 Corrosion rate of different materials per unit time

图9 扫描电镜下计时电位测试前后几种金属材料的微观形貌

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

图10 能谱测试得到的计时电位测试后几种金属材料表面元素分布情况

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

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