Uncovering the Potential of M1‐Site‐Activated NASICON Cathodes for Zn‐Ion Batteries

There is a long-standing consciousness that the rhombohedral NASICON-type compounds as promising cathodes for Li⁺ /Na⁺ batteries should have inactive M1(6b) sites with ion (de)intercalation occurring only in the M2 (18e) sites. Of particular significance is that M1 sites active for charge/discharge are commonly considered undesirable because the ion diffusion tends to be disrupted by the irregular occupation of channels, which accelerates the deterioration of battery. However, it is found that the structural stability can be substantially improved by the mixed occupation of Na⁺ /Zn²⁺ at both M1 and M2 when using NaV₂ (PO₄ )₃ (NVP) as a cathode for Zn-ion batteries. The results of atomic-scale scanning transmission electron microscopy, analysis of ab initio molecular dynamics simulations, and an accurate bond-valence-based structural model reveal that the improvement is due to the facile migration of Zn²⁺ in NVP, which is enabled by a concerted Na⁺ /Zn²⁺ transfer mechanism. In addition, significant improvement of the electronic conductivity and mechanical properties is achieved in Zn²⁺ -intercalated ZnNaV₂ (PO₄ )₃ in comparison with those of Na₃ V₂ (PO₄ )₃ . This work not only provides in-depth insight into Zn²⁺ intercalation and dynamics in NVP unlocked by activating the M1 sites, but also opens a new route toward design of improved NASICON cathodes.