The LiNbV(PO) phosphate with the anti-NASICON structure ( = 12.126(1) Å, = 8.6158(4) Å, = 8.6959(6) Å, = 908.5(1) Å, S.G. ) has been synthesized using a Pechini sol-gel process. It exhibits reversible multielectron transitions Li and Na anodes. In a Li half-cell, it supports a 4e transfer due to the activation of the Nb/Nb and V/V redox couples, being the first example of 4d metal redox transitions within the anti-NASICON framework confirmed by XANES measurements. X-ray diffraction performed in and regimes disclosed a single-phase mechanism of lithium (de)intercalation. In a Na half-cell, the material demonstrates reversible uptake of 2.77 Na ions. Density functional theory calculations revealed percolation barriers of ∼0.5-0.7 eV for Na hopping, thus supporting the activation of Na ion diffusion in the NbV(PO) framework. This study introduces a new approach to improve anti-NASICON-structured electrode materials by utilizing redox transitions of 4d elements for energy storage.
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