Influence of Gas for Thermal Treatment on Hydrogen Permeation in V-Ni Alloy Membranes

Hydrogen separation is an important step for the utilization of hydrogen energy. Metallic alloys, such as vanadium-nickel, are potential hydrogen separation materials. Due to the strong propensity of vanadium to form oxides and hydrides, vanadium alloy has a lower hydrogen permeability, and it is difficult to maintain the permeability over time. Therefore, special preparation processes such as Pd coating have been suggested for hydrogen separation vanadium-based membranes. However, aside from the prohibitive price of palladium, the interdiffusion of palladium and vanadium makes the coated membrane inviable to be used at a high temperature. Thermal treatment with inert gas was investigated in this study to assess the applicability of the vanadium alloy without palladium coating for hydrogen separation and clarify the mechanism behind the thermal treatment. Argon is inert with vanadium and displayed permeability recovery after 43 h thermal treatment, but the permeability declined under certain conditions. In contrast, nitrogen is known to interact with vanadium and the hydrogen permeability was maintained at a level lower than the test with argon. Given that nitrogen can compete with hydrogen for the active sites on vanadium, nitrogen might hinder hydrogen adsorption and hydride formation, whereas argon reduced the partial pressure of hydrogen during the thermal treatment, enhancing the driving force of hydrogen desorption. In the X-ray diffraction spectrum, vanadium hydrides and oxides were confirmed after hydrogen permeation and thermal treatment. In the X-ray photoelectron spectroscopy data, oxygen was a dominant element due to vanadium oxides and adsorbed nitrogen was also observed. According to binding energy shifts of nitrogen, nitrogen used for thermal treatment might substitute or compete for active sites with adsorbed nitrogen and hydrogen, existing in vanadium lattice. Although thermal treatment can be used to recover hydrogen permeability, the alloy cannot be recovered as hydrogen-free. However, results demonstrate the potential of thermal treatment to complement an uncoated vanadium alloy for a hydrogen separation membrane.