State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics Chinese Academy of Sciences, Shanghai, 200050, P. R. China.
Laboratory of Advanced Materials, Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200438, P. R. China.
Adv Sci (Weinh). 2022 Dec;9(36):e2205680. doi: 10.1002/advs.202205680. Epub 2022 Nov 13.
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'' ReSe 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 V Se 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 V Se is 2.7 × 10 times higher than that of 1T'' ReSe . Moreover, density functional theory (DFT) calculations reveal that 1T' Re V Se has a larger interlayer spacing, lower bonding energy, and migration energy barrier for Na ions than 1T'' ReSe . As a result, 1T' Re V Se electrode shows an excellent rate capability of 203 mAh g 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 V Se provides a new platform for various applications such as electronics, catalysis, and energy storage.
通过控制 d 电子数来诱导过渡金属二卤化物的新相转变引起了人们的极大兴趣，因为它们具有新颖的结构和物理化学性质。1T'' ReSe 是一种很有前途的钠离子存储材料，但电子电导率低和活性位点有限限制了其电化学容量。在此，我们成功合成了具有之字形链的新型 1T' Re V Se 晶体（P2/m）。1T''-1T' 相转变是通过 V 原子掺杂后电子提取导致 5d 轨道的电子重新排布引起的。1T' Re V Se 的电导率比 1T'' ReSe 高 2.7×10 倍。此外，密度泛函理论（DFT）计算表明，与 1T'' ReSe 相比，1T' Re V Se 具有更大的层间距、更低的成键能和 Na 离子迁移能垒。因此，1T' Re V Se 电极在 50 C 下具有 203 mAh g 的出色倍率性能，并且在 5000 次循环内没有容量衰减，优于大多数报道的钠离子阳极材料。这种 1T' Re V Se 为电子、催化和储能等各种应用提供了新的平台。
