Electron-Extraction Engineering Induced 1T''-1T' Phase Transition of Re_0.75 V_0.25 Se₂ for Ultrafast Sodium Ion...

Inducing new phases of transition metal dichalcogenides by controlling the d-electron-count has attracted much interest due to their novel structures and physicochemical properties. 1T'' ReSe₂ is a promising candidate for sodium storage, but the low electronic conductivity and limited active sites hinder its electrochemical capacity. Herein, new-phase 1T' Re_0.75 V_0.25 Se₂ crystals (P2/m) with zig-zag chains are successfully synthesized. The 1T''-1T' phase transition results from the electronic reorganization of 5d orbitals via electron extraction after V-atom doping. The electrical conductivity of 1T' Re_0.75 V_0.25 Se₂ is 2.7 × 10⁵ times higher than that of 1T'' ReSe₂ . Moreover, density functional theory (DFT) calculations reveal that 1T' Re_0.75 V_0.25 Se₂ has a larger interlayer spacing, lower bonding energy, and migration energy barrier for Na⁺ ions than 1T'' ReSe₂ . As a result, 1T' Re_0.75 V_0.25 Se₂ electrode shows an excellent rate capability of 203 mAh g^-1 at 50 C with no capacity fading over 5000 cycles for sodium storage, which is superior to most reported sodium-ion anode materials. This 1T' Re_0.75 V_0.25 Se₂ provides a new platform for various applications such as electronics, catalysis, and energy storage.