Tailoring the Wadsley-Roth crystallographic shear structures for high-power lithium-ion batteries

• Published in: Energy & environmental science 2024-09, Vol.17 (18), p.6571-6581
• Main Authors: Jing, Panpan, Liu, Mengting, Ho, Hsin-Pei, Ma, Yifan, Hua, Weibo, Li, Haohui, Guo, Nan, Ding, Yong, Zhang, Weilin, Chen, Hailong, Zhao, Bote, Wang, Jenghan, Liu, Meilin
• Format: Article
• Language: English
• Subjects: Anisotropy; Anodes; Cations; Conductivity; Crystallography; Diffusion barriers; Diffusion coefficient; Diffusion rate; Ion currents; Ion storage; Lithium; Lithium-ion batteries; Niobium; Particulate composites; Phase transitions; Redox reactions; Shear; Storage capacity; Structural stability; Surface stability; Tetrahedra; Titanium; Tungsten; Tungsten oxide
• ISSN: 1754-5692; 1754-5706
• DOI: 10.1039/d4ee02293a

Exploring a universal strategy to increase Li-ion storage capacity and ionic conductivity while maintaining a robust crystal framework is a significant challenge for advancing Wadsley-Roth shear phases as promising anodes for high-power lithium-ion batteries. Here we report a potent cation-engineering driven crystallographic shear structure tailoring strategy, demonstrated through a novel titanium niobium tungsten oxide (TNWO). This is a significant model containing inspiring domains with tetrahedron, tetrahedron-free and large-size blocks in the lattice. Theoretical calculations reveal that the TNWO model, featuring the partial absence of a [WO 4 ] tetrahedron and intrinsic multiple cation features, not only exhibits enhanced electronic conductivity and alleviated Li + adsorbed structural distortion, but also facilitates both horizontal inter-block type and vertical-tunnel type Li + diffusions, accompanied by sufficient redox reactions. Accordingly, it offers 1.48 Li + per metal atom along with a high Li + diffusion coefficient of 10 −12 cm −2 s −1 and remarkable structural stability, featuring a reversible spatial phase transition. Additionally, through modification of surface anisotropy, dimensional uniformity and electronic conductivity of individual TNWO particles, a composite anode demonstrates ultrahigh rate capability (103.7 mA h g −1 at 15 A g −1 ) and excellent cycling stability (capacity retention of 80% at 5 A g −1 over 4900 cycles). This work is believed to have opened a new avenue for tailoring shear structures and creating unprecedented phases to transcend the existing Wadsley-Roth niobium-based oxide system for next-generation high-power lithium-ion batteries. A tailored Wadsley-Roth crystallographic shear structure containing inspiring domains with tetrahedron, tetrahedron-free and large-size blocks in the lattice of novel titanium niobium tungsten oxide for high-power lithium-ion batteries.