Ce-doped cobalt-based hydroxide assisted with low-temperature molten salt for industrial oxygen evolution reaction
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摘要: 开发低成本、高性能的析氧电催化剂提升电化学水分解的效率，对于氢能的大规模利用具有重要的意义。钴基氢氧化物是一类极具潜力的析氧（OER）电催化剂，但是较差的导电性与催化活性严重制约了其应用推广。本研究采用一步低温熔盐法合成了铈掺杂的硝酸氢氧化钴电催化剂（Ce-CoNH/CF）。该催化剂在1 mol/L KOH电解液中具有最低的过电位（448 mV @ 1000 mA/cm2）。塔菲尔（Tafel）斜率、循环伏安（CV）和电化学阻抗谱（EIS）测试表明，快速的反应动力学、高效的电化学活性比表面积（ECSA）和极低的电荷转移电阻（Rct）共同作用使得催化剂具有优异的性能。并且在实验室条件下的模拟工业化测试也表明，Ce-CoNH/CF在工业级高温、高浓度的电解液（6 mol/L KOH，70 ℃）中同样展现出了出色的析氧性能。Abstract: Developing low cost and high-performance oxygen evolution electrocatalysts is significant to improve the efficiency of water electrolysis for large-scale hydrogen production. Cobalt hydroxide is a promising electrocatalyst for oxygen evolution reaction (OER), but its poor conductivity and activity seriously restrict the practical application. A simple one-step low temperature molten salt method was applied to successfully synthesize the Ce-doped cobalt hydroxide nitrate (Ce-CoNH/CF), which exhibits outstanding OER performance with a low overpotential of 448 mV at the current density of 1000 mA/cm2 in 1 mol/L KOH. The remarkable performance of Ce-CoNH/CF electrode in OER may be the comprehensive result of fast reaction kinetics, large electrochemical active specific surface area (ECSA) and small charge transfer resistance (Rct) as revealed by the Tafel, cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) analysis. Under the simulated industrial test conditions (6 mol/L KOH, 70 ℃), the Ce-CoNH/CF electrode still displays excellent OER performance.
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Key words:
- molten salt /
- oxygen evolution reaction /
- electrocatalytic /
- alkaline /
- doping
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图 2 （a） Ce-CoNH/CF和CoNH/CF的XRD谱图；（b） CoNH/CF和（c） Ce-CoNH/CF的SEM图像；（d） Ce-CoNH/CF的TEM和HRTEM图像；（e） Ce-CoNH/CF的EDS谱图和（f）元素映射图像
Figure 2 (a) XRD patterns of Ce-CoNH/CF and CoNH/CF; SEM images of (b) CoNH/CF and (c) Ce-CoNH/CF; (d) TEM and HRTEM images of Ce-CoNH/CF; EDS diagram (e) and corresponding SEM-Mapping (f) of Ce-CoNH/CF
图 3 （a） Ce-CoNH/CF和CoNH/CF的XPS全谱图；（b） Ce-CoNH/CF和CoNH/CF的XPS Co 2p谱图；（c） Ce-CoNH/CF和CoNH/CF的XPS O 1s谱图；（d） Ce-CoNH/CF的XPS Ce 3d谱图
Figure 3 (a) XPS spectra of Ce-CoNH/CF and CoNH/CF; (b) XPS spectra of Co 2p for Ce-CoNH/CF and CoNH/CF; (c) XPS spectra of O 1s for Ce-CoNH/CF and CoNH/CF; (d) XPS spectra of Ce 3d for Ce-CoNH/CF
图 4 在1 mol/L KOH电解液中不同样品的电化学性能： （a） LSV曲线；（b） 过电位柱状图； （c） 双电层电容曲线；（d） Tafel图；（e） EIS谱图；（f） Ce-CoNH/CF的稳定性测试
Figure 4 Electrocatalytic properties of different samples in 1 mol/L KOH: (a) LSV curves; (b) Histogram for overpotential; (c) Electric double layer capacitance curves; (d) Tafel diagram; (e) EIS spectra; (f) Stability test of Ce-CoNH/CF
图 5 在6和1 mol/L KOH电解液中Ce-CoNH/CF的电化学性能： （a） LSV曲线；（b） 过电位柱状图； （c） Tafel图；（d） 在不同电流密度下（200、400、600、800、1000 mA/cm2）阶梯型稳定性；（e） 模拟工业级测试条件下的恒电流稳定性测试
Figure 5 Electrocatalytic properties of different samples in 6 mol/L and 1 mol/L KOH: (a) LSV curves; (b) Histogram for overpotential; (c) Tafel diagram; (d) Multi-step chronopotentiometric curves at different current densities (200，400，600，800，1000 mA/cm2); (e) Stability test of Ce-CoNH/CF under simulating industrial condition
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