Multiscale Investigation into Chemically Stable NASICON Solid Electrolyte in Acidic Solutions.

Natrium superionic conductor (NASICON) solid electrolyte has been attracting wide attention due to its high ionic conductivity, low cost, and environmental friendliness. In this work, the chemical stability of the NASICON solid electrolyte with the composition of Na3Zr2Si2PO12 was evaluated in acidic solutions with different pH values, and the corrosion mechanism of the NASICON solid electrolyte was revealed at the multiscale level. Variations in bulk impedance, grain boundary impedance, and surface crack impedance with immersion time were determined by an AC impedance method. Comprehensive studies upon scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) etching, X-ray diffraction (XRD), and Raman spectroscopy, the morphological transformation, degradation limit depth, Cl- penetration effect, and proton exchange between H3O+ and Na+ were examined ranging from macro- and meso- to microscales, respectively. With the decrease of the pH of the solution, the exchange rate between H3O+ and Na+ protons increases. The lack of Na+ within the crystallographic lattice leads to the shrinkage of phosphorus-oxygen tetrahedra, which is the main reason for the decrease of unit cell volume, grain refinement, and surface cracks gradually. This work features multiscale characterizations of crystal structure, grain boundaries, surface morphology changes, and Na+ transport, which deepens our physicochemical understanding of solid electrolytes with high chemical stability.