Crystal Chemistry of Argyrodites and A₃PS₄-Type Solid Electrolytes (A=Li, Na) for Batteries

Solid electrolytes are crucial for next-generation solid-state batteries and immense activity is going on worldwide on many structural families of interest, including the ionic conductors Na₃PS₄, Li₃PS_4,Li₄PS₄I and Argyrodite Li₆PS₅(Cl,Br,I). We will present our recent crystal chemistry findings on these materials. <br/> <br/>Li₃PS₄ is an attractive solid-electrolyte material that possesses high RT ionic conductivity (10^-4 S.cm⁻¹) but the effects of specific synthesis parameters on the material's local structure and transport properties still demand clarifications. In particular, mechano-chemistry induces the formation of a variety of P_xS_y^a− moieties that strongly influence the global transport properties of Li₃PS_4.<br/> <br/>Na₃PS₄ is another very interesting material with complex crystal chemistry that we will present. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium ion conductor Na₃PS₄ were not fully understood and we undertook comprehensive analysis based on diffraction (Bragg and pair distribution function), spectroscopy (impedance, Raman, NMR and INS), and ab initio simulations.<br/> <br/><b>References</b><br/>Ö. U. Kudu, T. Famprikis, S. Cretu, B. Porcheron, E. Salager, A. Demortiere, M. Courty, V. Viallet, T. Le Mercier, B. Fleutot, M.D. Braida & C. Masquelier, <i>Energy Storage Materials, </i><b>44</b>, 168-179 (2022)<br/>T. Famprikis, H. Bouyanfif, P. Canepa, M. Zbiri, J. Dawson, E. Suard, F. Fauth, H. Playford, D. Dambournet, O. Borkiewicz, M. Courty, O. Clemens, J.N. Chotard, M.S. Islam & C. Masquelier, <i>Chem. Mater.</i>, <b>33(14)</b>, 5652-5667 (2021)<br/>T. Famprikis, U. Kudu, J. Dawson, P. Canepa, F. Fauth, E. Suard, M. Zbiri, D. Dambournet, O. Borkiewicz, H. Bouyanfif, S. Emge, C. Grey, S. Cretu, J.N. Chotard, W. Zeier, M. S. Islam & C. Masquelier, <i>J. Amer. Chem. Soc.</i>, <b>142(43)</b>, 18422-18436 (2020)