Speaker
Description
Controlling Li ion transport in glasses at atomic and molecular levels is key to realising all-solid-state batteries, a promising technology for electric vehicles. In this context, Li3PS4 glass, a promising solid electrolyte candidate, exhibits dynamic coupling between the Li+ cation mobility and the PS43− anion libration, which is commonly referred to as the paddlewheel effect1. In addition, it exhibits a concerted cation diffusion effect (i.e., a cation–cation interaction), which is regarded as the essence of high Li ion transport. However, the correlation between the Li+ ions within the glass structure can only be vaguely determined, due to the limited experimental information that can be obtained. We report that the Li ions present in glasses can be classified by evaluating their valence oscillations via Bader analysis to topologically analyse the chemical bonds. We found that three types of Li ions are present in Li3PS4 glass, and that the more mobile Li ions (i.e., the Li3-type ions, see Figure) exhibit a characteristic correlation at relatively long distances of 4.0–5.0 Å. Furthermore, reverse Monte Carlo simulations combined with deep learning potentials that reproduce X-ray, neutron, and electron diffraction pair distribution functions showed an increase in the number of Li3-type ions for partially crystallised glass structures with improved Li ion transport properties2. Our results show order within the disorder of the Li ion distribution in the glass by a topological analysis of their valences.
Keywords: sulfide glass, solid electrolyte, valence oscillation, pair distribution function
