Polyanionic (Phosphates, Silicates, Sulfates) Frameworks as Electrode Materials for Rechargeable Li (or Na) Batteries

The concept of investigating three-dimensional frameworks based on the NASICON structure as hosts for reversible insertion/extraction of alkali cations (electrodes) arose in the mid 1980s mostly from concerns about possible stability or reactivity versus metallic Na (or Li) when used as solid electrolytes. The NASICON framework was used by Goodenough in the late 1980s as a very demonstrative example of the possibility for the chemist to elaborate electrode materials functioning at controlled operating voltages. Noticeably, these structures have been recently investigated by three independent groups as model compounds for the understanding of complex Li NMR signals in paramagnetic compounds, and useful insights into the activation energies for hopping between the lithium sites were provided.