Inorganic Chemistry, Vol.58, No.21, 14600-14607, 2019
Destabilizing the Dehydrogenation Thermodynamics of Magnesium Hydride by Utilizing the Immiscibility of Mn with Mg
Hydrogen storage is a key technology for the advancement of hydrogen and fuel cell power technologies in stationary and portable applications. MgH2, an example of a high-capacity hydrogen storage material, has two major material challenges for practical applications: slow hydrogen desorption kinetics and high hydrogen desorption temperature. Numerous studies have reported enhancements in kinetics but only a few in thermodynamics. Here, we present a simple but effective way to improve upon both the kinetic and thermodynamic aspects of desorption by utilizing the immiscibility of Mn, a non-hydrogen absorbing metal, with Mg. Mg0.25Mn0.75, prepared through ball milling MgH2 and Mn powders, is a nanocomposite where the nanometer-sized MgH2 domains are randomly embedded in a Mn matrix. This sample readily and reversibly absorbs and desorbs deuterium even at a temperature of 200 degrees C without the addition of any catalysts. This is nearly 180 degrees C lower than the typical operating temperature of conventional bulk Mg. Furthermore, at a given temperature, its deuterium desorption pressure is clearly elevated compared to that of pure Mg, indicating the destabilization of MgD2. The average crystallite size of MgD2 in deuterated Mg0.25Mn0.75 determined from X-ray diffraction data is around 9 nm. Nuclear magnetic resonance spectroscopy studies show that MgD2 domains are heavily strained and some of the D atoms are coordinated by a few Mn atoms, suggesting that a large number of lattice defects, including the partial substitution of Mg with Mn, are introduced during ball milling. Furthermore, the Mn matrix firmly locks nanosized MgD2, preventing the agglomeration of MgD2 below 250 degrees C. Our study suggests that a synergistic effect created by nanosizing, large lattice distortions, and robust interfaces between MgD2 and the Mn matrix can effectively and concurrently improve the kinetics and thermodynamics of MgD2 in Mg0.25Mn0.75. Our work demonstrates the possibility of utilizing the immiscibility of metals with Mg to synthesize a robust nanostructure that can alter the kinetics and stability of MgH2.