Synergetic Enhancement on Bulk and Grain Boundary Ionic Conduction of Mg Doped High-Entropy NASICON-Type Solid Electrolyte for Solid-State Na+ Batteries by Spray Flame Synthesis

TL;DR

This paper introduces a spray flame synthesis method to produce Mg-doped NASICON solid electrolytes with enhanced ionic conductivity for sodium batteries, achieving improvements in both bulk and grain boundary conduction.

Contribution

The study presents a scalable flame synthesis technique for Mg-doped NASICON nanoparticles that enhances ionic conductivity and reduces post-treatment costs compared to traditional methods.

Findings

Mg0.25NZSP exhibits 1.91 mS/cm ionic conductivity at room temperature.

Flame-synthesized nanoparticles show superior sinterability and uniform elemental distribution.

Enhanced grain boundary and bulk conduction due to secondary phase formation.

Abstract

All-solid-state sodium batteries represent a promising next-generation energy storage technology, owing to cost-effectiveness and enhanced safety. Among solid electrolytes for solid-state sodium batteries, NASICON-structured Na3Zr2Si2PO12 has emerged as a predominant candidate. However, its widespread implementation remains limited by suboptimal ionic conductivity in both bulk and grain boundary regions. In this study, we demonstrate a novel approach utilizing swirling spray flame synthesis to produce Mg-doped NASICON solid electrolyte nanoparticles. This method facilitates efficient doping and homogeneous mixing for scalable production, resulting in core-shell non-NASICON structures with nano-scale high-entropy mixing. Notably, the atomic migration distances achieved by flame synthesis are significantly reduced compared to conventional solid-state reactions, thereby enabling reactive sintering to preserve high sinterability of nanoparticles during post-treatment processes. High-temperature sintering yields dense NASICON-structured solid electrolytes. Among those, Mg0.25NZSP exhibits an optimal ionic conductivity of 1.91 mS/cm at room temperature and an activation energy of 0.200 eV. The enhancement mechanism can be attributed to incorporation into the NASICON phase and formation of a secondary phase. The low-melting-point secondary phase significantly improves grain boundary contact to enhance grain boundary conductivity. The process achieves simultaneous enhancement of both bulk and grain boundary conduction through a single-step procedure. Comparative analysis of sintering temperatures and ionic conductivities among NASICON solid electrolytes synthesized via different methods demonstrates flame-synthesized nanoparticles offer superior performance and reduced post-treatment costs, owing to their exceptional nano-scale sinterability and uniform elemental distribution.