Effect of the structure and morphology of Ni-based porous deposits on their electrocatalytic activity towards hydrogen evolution reaction

T. S. Trofimova, A. B. Darintseva, T. N. Ostanina, V. M. Rudoi, I. E. Il’ina
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Abstract

Porous nickel and nickel-cobalt alloy deposits were obtained by electrodeposition on a dynamic hydrogen bubble template. Deposition was carried out from chloride electrolytes in a galvanostatic mode at a current density of 0.3 A/cm2. The porosity of the obtained deposits is associated with the macro- and micropores. It was found that the nickel and nickel-cobalt alloy deposits feature by different porous layer structures. In case of nickel, a typical foam structure is formed, while the Ni–Co alloy deposit morphology is more like loose (powder) metals. The total porosity of the obtained structures calculated based on experimental data decreased with the deposit thickness: from 0.4 to 0.1 for nickel foams, and from 0.9 to 0.8 for the Ni–Co deposit. It was shown that the dependences of the macropore number and the fraction of the surface occupied by them can be approximated by lognormal distribution. The agreement between the experimental values and values calculated by approximating equations indicates the stochastic nature of the macropore system formation. The catalytic properties of the obtained porous deposits toward the hydrogen evolution reaction in alkali were investigated. It was found that the decrease in the hydrogen evolution potential in comparison with a smooth electrode reaches 370 mV for nickel foams, and 440 mV for porous Ni–Co alloy deposits. However, the high porosity of the Ni–Co alloy caused poor adhesion of the deposit to the substrate; therefore, the porous Ni–Co deposit cannot be used without further strengthening. The dependences of the depolarization value during hydrogen evolution on the average diameter of pores, their number, and the macropore fraction were analyzed. Optimal properties of foams that reduce the potential of hydrogen evolution in alkali are as follows: pore diameters from 30 to 50 μm and their quantity from 50 to 100 pcs/mm2.
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镍基多孔镀层结构和形貌对析氢反应电催化活性的影响
在动态氢泡模板上电沉积多孔镍和镍钴合金镀层。氯化物电解质在电流密度为0.3 a /cm2的恒流模式下进行沉积。所得矿床的孔隙度与宏观和微观孔隙有关。发现镍和镍钴合金镀层具有不同的多孔层结构。以镍为例,形成典型的泡沫结构,而镍钴合金的沉积形态更像松散(粉末)金属。根据实验数据计算所得结构的总孔隙度随镀层厚度的增加而减小:泡沫镍镀层的孔隙度从0.4降至0.1,镍钴镀层的孔隙度从0.9降至0.8。结果表明,大孔数与大孔所占表面积的关系可以近似为对数正态分布。实验值与近似方程计算值吻合,表明大孔系统形成的随机性。研究了制备的多孔沉积材料对碱中析氢反应的催化性能。结果表明,与光滑电极相比,泡沫镍的析氢电位降低了370 mV,多孔镍钴合金的析氢电位降低了440 mV。然而,Ni-Co合金的高孔隙率导致镀层与基体的附着力较差;因此,多孔镍钴镀层必须进一步强化才能使用。分析了析氢过程中脱极化值与孔平均直径、孔数和大孔分数的关系。降低碱中析氢电位的泡沫的最佳性能为:孔径在30 ~ 50 μm之间,数量在50 ~ 100 pcs/mm2之间。
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