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Na 3 V(PO 4 ) 2 was reported recently as a novel cathode material with high theoretical energy density for Sodium-ion batteries (SIBs). However, whether V 3+ /V 4+ /V 5+ multielectron reactions can be realized during the charging process is still an open question. In this work, Na 3 V(PO 4 ) 2 is synthesized by using a solid-state method. Its atomic composition and crystal structure are verified by X-ray diffraction (XRD) and neutron diffraction (ND) joint refinement. The electrochemical performance of Na 3 V(PO 4 ) 2 is evaluated in two different voltage windows, namely 2.5-3.8 and 2.5-4.3 V. 51 V solid-state NMR (ssNMR) results disclose the presence of V 5+ in Na 2- x  V(PO 4 ) 2 when charging Na 3 V(PO 4 ) 2 to 4.3 V, confirming Na 3 V(PO 4 ) 2 is a potential high energy density cathode through realization of V 3+ /V 4+ /V 5+ multielectron reactions.

Recognition of V3+/V4+/V5+ Multielectron Reactions in Na3V(PO4)2: A Potential High Energy Density Cathode for Sodium-Ion Batteries