Effect of Cerium on Microstructure and Electrochemical Performance of Ti-V-Cr-Ni Electrode Alloy

Effect of cerium on the microstructure and electrochemical performance of the Ti0.25 V0.35 - x CexCr0.1Ni0.3(x = 0, 0.005) electrode alloy was investigated by X-ray diffraction (XRD), field emission scanning electron microscopy/energy dispersive X-ray spectrometry (FESEM-EDS), and electrochemical impedance spectroscopy (EIS) measurements. On the basis of XRD and FESEM-EDS analysis, the alloy was mainly composed of V-based solid solution with body-centered-cubic structure and TiNi-based secondary phase. Ce did not exist in two phases, instead, it existed as Ce-rich small white particles, with irregular edges, distributed near the grain boundaries of the V-based solid solution phase. Discharge capacity, cycle stability, and high-rate discharge ability of the alloy electrode were effectively improved with the addition of Ce at 293 K. It was very surprising that the charge retention was abnormal with larger discharge capacity after standing at the open circuit for 24 h. EIS indicated that addition of Ce improved the dynamic performance, which caused the charge transfer resistance (RT) to decrease and exchange current density (I0) to increase markedly. The exchange current density of the electrochemical reaction on the alloy surface with Ce addition was about 2.07 and 3.10 times larger than that of the alloy without Ce at 303 and 343 K, respectively. The diffusion coefficient of hydrogen (D) in the bulk alloy electrode decreased with addition of Ce, but it did not decrease so much, and the apparent activation energy (Δ,H) was far higher than that of the AB5 type alloy.