Possible Existence of a Monovalent Coordination for Nitrogen Atoms in LixPOyNz Solid Electrolyte: Modeling of X-ray Photoelectron Spectroscopy and Raman Spectra.

International audienceLixPOyNz is an amorphous solid electrolyte widely used in microbattery devices. The present study, based on a confrontation between expt. and theory, aims at providing new knowledge regarding the ionic cond. model of such systems in correlation with its structure. The computational strategy involved mol. dynamic simulations and first-principle calcns. on mol. and periodic models. The exptl. target data involve electronic and vibrational properties and were considered through the simulation of Raman and X-ray photoemission spectra in order to identify characteristic patterns of LixPOyNz. In particular, the presence of short phosphate chains is suggested by mol. dynamics calcns., and the simulation of Raman spectra clearly evidenced a new coordination for nitrogen atoms in the amorphous state, not considered until now in the exptl. structural model of the electrolyte and initially hypothesized based on core level binding energy computations. Monovalent nitrogen atoms together with short phosphate chains were used to build a structural model of the electrolyte and appeared to lead to a better reprodn. of the target exptl. results, while it implies a necessary refinement of the diffusion schemes commonly considered for lithium ions