Reliable electrochemical
investigations of electrode materials
are indispensable for the development of next-generation energy storage
devices. In the case of multivalent cation-based electrochemistry,
intense attention should be paid to the cell configuration for obtaining
reliable data. In particular, the electrolyte and reference electrode
must be appropriately selected considering the potential window of
electrolyte and the validity of reference. Here, we demonstrate the
detailed electrochemical examination for the Mg2+-storage
capability of the NASICON-type framework derived from Na3V2(PO4)3 (NVP). A combination of
the Mg(BF4)2-based electrolyte with high anodic
stability and the reliable Ag pseudo-reference electrode offers decent
electrochemical test results. Despite suffering from the polarization
concerning magnesiation, the desodiated NVP electrode can deliver
a well-defined discharge plateau at ∼2.7 V (vs Mg2+/Mg) with the reversible capacity of >100 mAh g–1 at room temperature. The impedance analysis results indicate that
the increased charge transfer resistance on discharging due to the
high energy barrier for desolvation of divalent cations is responsible
for the large polarization but not extremely significant, allowing
for the room-temperature operation. The findings obtained herein also
highlight the importance of the structural robustness of host lattice,
which is required to withstand the strong amorphization during Na+ extraction and Mg2+ insertion/extraction.