Crystal Structure of Na2V2(PO4)3, an Intriguing Phase Spotted in the Na3V2(PO4)3-Na1V2(PO4)3 System

The Na superionic conductor (NASICON) Na3V2(PO4)(3) is an important positive electrode material for Na-ion batteries. Here, we investigate the mechanisms of phase transition in NaxV2(PO4)(3) (1 <= x <= 4) upon nonequilibrium battery cycling. Unlike the widely believed two-phase reaction in a Na3V2(PO4)(3)-Na1V2(PO4)(3) system, we determine, for the first time, the structure of a recently reported intermediate Na2V2(PO4)(3) phase using operando synchrotron X-ray diffraction. Density functional theory calculations further support the existence of the Na2V2(PO4)(3) phase. We propose two possible crystal structures of Na2V2(PO4)(3) analyzed by Rietveld refinement. The two structure models with the space groups P2(1)/c or P2/c for the new intermediate Na2V2(PO4)(3) phase show similar unit cell parameters but different atomic arrangements, including vanadium charge ordering. As the appearance of the intermediate Na2V2(PO4)(3) phase is accompanied by symmetry reduction, Na(1) and Na(2) sites split into several positions in Na2V2(PO4)(3), in which one of the splitting Na(2) position is found to be a vacancy, whereas the Na(1) positions are almost fully filled. The intermediate Na2V2(PO4)(3) phase reduces the lattice mismatch between Na3V2(PO4)(3) and Na1V2(PO4)(3) phases, facilitating a fast phase transition. This work paves the way for a better understanding of great rate capabilities of Na3V2(PO4)(3).

Automated summary

This study investigates the mechanisms of phase transition in Na3V2(PO4)(3) upon nonequilibrium battery cycling and determines the structure of the intermediate Na2V2(PO4)(3) phase for the first time. The splitting of Na sites and symmetry reduction in Na2V2(PO4)(3) contribute to a fast phase transition, reducing lattice mismatch between different phases. This work lays the foundation for a better understanding of the high rate capabilities of Na3V2(PO4)(3).