Intrinsic defects and dopants in LiNH2: a first-principles study
文献信息
E. Hazrati, G. Brocks, B. Buurman, G. A. de Wijs
The lithium amide (LiNH2) + lithium hydride (LiH) system is one of the most attractive light-weight materials options for hydrogen storage. Its dehydrogenation involves mass transport in the bulk (amide) crystal through lattice defects. We present a first-principles study of native point defects and dopants in LiNH2 using density functional theory. We find that both Li-related defects (the positive interstitial Li+i and the negative vacancy V−Li) and H-related defects (H+i and V−H) are charged. Li-related defects are most abundant. Having diffusion barriers of 0.3–0.5 eV, they diffuse rapidly at moderate temperatures. V−H corresponds to the [NH]2− ion. It is the dominant species available for proton transport with a diffusion barrier of ∼0.7 eV. The equilibrium concentration of H+i, which corresponds to the NH3 molecule, is negligible in bulk LiNH2. Dopants such as Ti and Sc do not affect the concentration of intrinsic defects, whereas Mg and Ca can alter it by a moderate amount. Ti and Mg are easily incorporated into the LiNH2 lattice, which may affect the crystal morphology on the nano-scale.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.












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