Ni-Fe/Ti和Ni-Fe-S/Ti的制备及其电催化水分解性能

doi:10.13208/j.electrochem.190114

摘要/Abstract

摘要：

以钛网为基底,采用电沉积法制备了Ni-Fe/Ti析氧电极,然后将得到的Ni-Fe/Ti电极通过固相硫化制备了Ni-Fe-S/Ti析氢电极. 分别考察了电沉积液中Ni ²⁺/Fe ³⁺离子摩尔浓度比和硫脲加入量对Ni-Fe/Ti和Ni-Fe-S/Ti结构和电化学性能的影响. 结果表明,随着电沉积液中Ni ²⁺含量的增加,Ni-Fe/Ti电极析氧性能先增强后减弱,Ni9Fe1/Ti电极具有最好的析氧性能;随着硫脲加入量的增加,Ni-Fe-S/Ti电极析氢性能呈现先增强后减弱的趋势,Ni9Fe1S0.25/Ti电极具有最好的析氢性能. 在50 mA·cm ^-2下,Ni9Fe1/Ti电极的析氧过电位为280 mV,Ni9Fe1S0.25/Ti电极的析氢过电位为269 mV,且均具有很好的稳定性. 将Ni9Fe1/Ti与Ni9Fe1S0.25/Ti分别作为阳极和阴极进行电催化全水分解,电流密度达到50 mA·cm ^-2所需电势仅1.69 V,表现出很好的全水解催化性能.

关键词: 镍铁氢氧化物, 镍铁硫化物, 氧气析出反应, 氢气析出反应, 电催化全水分解

Abstract:

The Ni-Fe/Ti oxygen evolution electrode was prepared by electrodeposition on a titanium mesh substrate. Then, the as prepared Ni-Fe/Ti electrode was used to derive the Ni-Fe-S/Ti hydrogen evolution electrode through solid phase sulfuration. The effects of the molar ratio of Ni ²⁺ to Fe ³⁺ in the electrolyte and the amount of thiourea on the structures and electrochemical performances of Ni-Fe/Ti and Ni-Fe-S/Ti electrodes were investigated. The results show that the oxygen evolution performance of Ni-Fe/Ti electrode was first increased and then decreased with the increase of nickel ion content in the electrolyte. The Ni9Fe1/Ti electrode exhibited the best oxygen evolution performance. With the increase of thiourea addition, the hydrogen evolution performance of Ni-Fe-S/Ti electrode was increased firstly and then decreased. The Ni9Fe1S0.25/Ti electrode showed the best hydrogen evolution performance. To achieve a current density of 50 mA·cm ^-2, an overpotential of 280 mV was required for oxygen evolution reaction (OER) with the Ni9Fe1/Ti electrode, while 269 mV for hydrogen evolution reaction (HER) with the Ni9Fe1S0.25/Ti electrode, both with good stabilities. Accordingly, the Ni9Fe1/Ti and Ni9Fe1S0.25/Ti electrode were used as anodes and cathodes, respectively, for overall water splitting tests. The current density of 50 mA·cm ^-2 was achieved at a voltage of 1.69 V, showing the good catalytic performance of overall water splitting.

Key words: nickel-iron hydroxide, nickel-iron sulfide, oxygen evolution reaction, hydrogen evolution reaction, overall water splitting

中图分类号:

O646

陆杭烁, 何小波, 银凤翔, 李国儒. Ni-Fe/Ti和Ni-Fe-S/Ti的制备及其电催化水分解性能[J]. 电化学（中英文）, 2020, 26(1): 136-147.

LU Hang-shuo, HE Xiao-bo, YIN Feng-xiang, LI Guo-ru. Preparations of Nickel-Iron Hydroxide/Sulfide and Their Electrocatalytic Performances for Overall Water Splitting[J]. Journal of Electrochemistry, 2020, 26(1): 136-147.

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Sample	Molar ratio of Ni²⁺/Fe³⁺	Deposition potential/ V(vs. Ag/AgCl)	Deposition time/min	Thiourea/g	Temperature of sulfuration/°C	Loading/ (mg·cm^-2)
Ni0Fe10/Ti	0:10	-1	20	—	—	0.2
Ni3Fe7/Ti	3:7	-1	20	—	—	2.3
Ni6Fe4/Ti	6:4	-1	20	—	—	3.0
Ni9Fe1/Ti	9:1	-1	20	—	—	7.4
Ni10Fe0/Ti	10:0	-1	20	—	—	7.0
Ni9Fe1S0.1/Ti	9:1	-1	20	0.10	200	8.2
Ni9Fe1S0.25/Ti	9:1	-1	20	0.25	200	7.9
Ni9Fe1S0.5/Ti	9:1	-1	20	0.50	200	8.1

Electrode	η₅₀/mV	Tafel slope/(mV·dec^-1)	C_dl/(mF·cm^-2)
Ti	—	—	0.25
Ni0Fe10/Ti	940	110	0.25
Ni3Fe7/Ti	503	80	0.17
Ni6Fe4/Ti	323	38	0.48
Ni9Fe1/Ti	280	30	5.16
Ni10Fe0/Ti	340	113	3.45

Electrode	η_-50/mV	Tafel slope/ (mV·dec^-1)	C_dl/ (mF·cm^-2)
Ni9Fe1/Ti	498	158	0.79
Ni9Fe1S0.1/Ti	379	145	17.68
Ni9Fe1S0.25/Ti	269	126	13.52
Ni9Fe1S0.5/Ti	347	131	4.31

Electrode	Ti	Ni0Fe10/Ti	Ni3Fe7/Ti	Ni6Fe4/Ti	Ni9Fe1/Ti	Ni10Fe0/Ti
R_s/(Ω·cm²)	4.95	2.75	4.01	3.58	2.45	4.02
R_ct/(Ω·cm²)	7.85	4.61	3.90	3.05	2.83	1.98

Electrode	Ni9Fe1/Ti	Ni9Fe1S0.1/Ti	Ni9Fe1S0.25/Ti	Ni9Fe1S0.5/Ti
R_s/(Ω·cm²)	2.69	1.90	1.34	2.50
R_ct/(Ω·cm²)	7.65	7.88	7.56	7.55