Orientation‐Engineered Anderson‐Type Polyoxometalate Sub‐1 nm Nanosheets for High‐Performance Lithium‐Ion Battery Anodes

The unique atomic‐scale active site exposure of two‐dimensional sub‐1 nm nanosheets (2D SNSs) effectively shorten the electron/ion diffusion distance, significantly enhancing the rapid charge–discharge performance of lithium‐ion batteries (LIBs). However, it is still challenging to precisely regulate the exposed sites of the building blocks. Herein, Zn‐ZnMo 6 sub‐1 nm nanosheets (Zn‐ZnMo 6 SNSs) were successfully synthesized through the cluster self‐assembly strategy. Molecular dynamics (MD) simulations confirmed two stable configurations (Zn‐ZnMo 6 ‐1 and Zn‐ZnMo 6 ‐0.05) with distinct active sites exposure. Notably, Zn‐ZnMo 6 ‐1 exhibited excellent performance as lithium‐ion battery (LIB) anodes, with a reversible capacity of 1361.9 mAh g −1 for 1500 cycles at 1 A g −1 , significantly outperforming Zn‐ZnMo 6 ‐0.05 (258.5 mAh g −1 ). Electrochemical mechanism and density functional theory (DFT) calculations revealed that the terminal‐oxygen (O t ) sites exposed in Zn‐ZnMo 6 ‐1 enabled optimal lithium‐ions adsorption ( E ads = −6.54 eV), which facilitated rapid lithium storage behavior and exhibited exceptional redox reversibility. This study would provide a promising novel approach for the design and synthesis of 2D SNSs at molecule level.