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Compared to oxides, the nitrides are relatively unexplored, making them a promising chemical space for novel materials discovery. Of particular interest are nitrogen-rich nitrides, which often possess useful semiconducting properties for electronic and optoelectronic applications. However, such nitrogen-rich compounds are generally metastable, and the lack of a guiding theory for their synthesis has limited their exploration. Here, we review the remarkable metastability of observed nitrides, and examine the thermodynamics of how reactive nitrogen precursors can stabilize metastable nitrogen-rich compositions during materials synthesis. We map these thermodynamic strategies onto a predictive computational search, training a data-mined ionic substitution algorithm specifically for nitride discovery, which we combine with grand-canonical DFT-SCAN phase stability calculations to compute stabilizing nitrogen chemical potentials. We identify several new nitrogen-rich binary nitrides for experimental investigati...

Li–Fe antisite defects are commonly found in LiFePO4 particles and can impede or block Li diffusion in the single-file Li diffusion channels. However, due to their low concentration (∼1%), the effect of antisite defects on Li diffusion has only been systematically investigated by theoretical approaches. In this work, the exchange between Li in solid LiFePO4 (92.5% enriched with 6Li) and Li in the liquid Li electrolyte solution (containing natural abundance Li, 7.6% 6Li and 92.4% 7Li) was measured as a function of time by both ex situ and in situ solid-state nuclear magnetic resonance experiments. The experimental data reveal that the time dependence of the isotope exchange cannot be modeled by a simple single-file diffusion process and that defects must play a role in the mobility of ions in the LiFePO4 particles. By performing kinetic Monte Carlo simulations that explicitly consider antisite defects, which allow Li to cross over between adjacent channels, we show that the observed tracer exchange behavio...