An outstanding effect of graphite in nano-MgH2–TiH2 on hydrogen storage performance

Abstract

TiH₂-modified MgH₂ was prepared by high energy reactive ball milling (HRBM) of Mg and Ti in hydrogen and showed high weight H storage capacity and fast hydrogenation/dehydrogenation kinetics. However, a decrease in the reversible H storage capacity on cycling at high temperatures takes place and is a major obstacle for its use in hydrogen and heat storage applications. Reversible hydrogen absorption/desorption cycling of the materials requires use of the working temperature ≥330 °C and results in a partial step-by-step loss of the recoverable hydrogen storage capacity, with less significant changes in the rates of hydrogenation/dehydrogenation. After hydrogen desorption at 330–350 °C, hydrogen absorption can proceed at much lower temperatures, down to 24 °C. However, a significant decay in the reversible hydrogen capacity takes place with increasing number of cycles. The observed deterioration is caused by cycling-induced drastic morphological changes in the studied composite material leading to a segregation of TiH₂ particles in the cycled samples instead of their initial homogeneous distribution. However, the introduction of 5 wt% of graphite into the MgH₂–TiH₂ composite system prepared by HRBM leads to an outstanding improvement of the hydrogen storage performance. Indeed, hydrogen absorption and desorption characteristics remain stable through 100 hydrogen absorption/desorption cycles and are related to an effect of the added graphite. The TEM study showed that carbon is uniformly distributed between the MgH₂ grains covering segregated TiH₂, preventing the grain growth and thus keeping the reversible storage capacity and the rates of hydrogen charge and discharge unchanged. Modelling of the kinetics of hydrogen absorption and desorption in the Mg–Ti and Mg–Ti–C composites showed that the reaction mechanisms significantly change depending on the presence or absence of graphite, the number of absorption–desorption cycles and the operating temperature.