The Na superionic conductor (aka Nasicon, NaZrSiPO, where 0 ≤ x ≤ 3) is one of the promising solid electrolyte materials used in advanced molten Na-based secondary batteries that typically operate at high temperature (over ∼270 °C). Nasicon provides a 3D diffusion network allowing the transport of the active Na-ion species (i.e., ionic conductor) while blocking the conduction of electrons (i.e., electronic insulator) between the anode and cathode compartments of cells. In this work, the standard Nasicon (NaZrSiPO, bare sample) and 10 at% Na-excess Nasicon (NaZrSiPO, Na-excess sample) solid electrolytes were synthesized using a solid-state sintering technique to elucidate the Na diffusion mechanism (i.e., grain diffusion or grain boundary diffusion) and the impacts of adding excess Na at relatively low and high temperatures. The structural, thermal, and ionic transport characterizations were conducted using various experimental tools including X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). In addition, an ab initio atomistic modeling study was carried out to computationally examine the detailed microstructures of Nasicon materials, as well as to support the experimental observations. Through this combination work comprising experimental and computational investigations, we show that the predominant mechanisms of Na-ion transport in the Nasicon structure are the grain boundary and the grain diffusion at low and high temperatures, respectively. Also, it was found that adding 10 at% excess Na could give rise to a substantial increase in the total conductivity (e.g., ∼1.2 × 10 S/cm at 300 °C) of Nasicon electrolytes resulting from the enlargement of the bottleneck areas in the Na diffusion channels of polycrystalline grains.

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All-Solid-State Batteries (ASSBs) that use oxide-based solid electrolytes (SEs) have been considered as a promising energy-storage platform to meet an increasing demand for Li-ion batteries (LIBs) with improved energy density and superior safety. However, high interfacial resistance between particles in the composite electrode and between electrodes and the use of Li metal in the ASBS hinder their practical utilization. Here, we review recent research progress on oxide-based SEs for the ASSBs with respect to the use of Li metal. We especially focus on research progress on garnet-type solid electrolytes (Li 7 La 3 Zr 2 O 12 ) because they have high ionic conductivity, good chemical stability with Li metal, and a wide electrochemical potential window. This review will also discuss Li dendritic behavior in the oxide-based SEs and its relationship with critical current density (CCD). We close with remarks on prospects of ASSB.

Asymmetric redox reaction pathways in LiVPO4F can be understood by a presence of oxygen defects in fluorine sites.