Effects of Li doping on H-diffusion in MgH$_2$: a first-principles study

Abstract: The effects of Li doping in MgH$2$ on H-diffusion process are investigated, using first-principles calculations. We have identified two key effects: (1) The concentration of H vacancy in the $+1$ charge state (V$_H^{+1}$) can increase by several orders of magnitude upon Li doping, which significantly increases the vacancy mediated H diffusion rate. It is caused by the preferred charge states of substitutional Li in the $-1$ state (Li${Mg}^{-1}$) and of interstitial Li in the $+1$ state (Li$i^{+1}$), which indirectly reduce the formation energy of V$_H^{+1}$ by up to 0.39 eV depending on the position of Fermi energy. (2) The interaction between V$_H^{+1}$ and Li${Mg}^{-1}$ is found to be attractive with a binding energy of 0.55 eV, which immobilizes the V$H^{+1}$ next to Li${Mg}^{-1}$ at high Li doping concentration. As a result, the competition between these two effects leads to large enhancement of H diffusion at low Li doping concentration due to the increased H-vacancy concentration, but only limited enhancement at high Li concentration due to the immobilization of H vacancies by too many Li.