Al2O3-Induced Phase Conversion Regulation of WS2 Anode Enhances the Lithium Storage Reversibility

WS₂ is an attractive anode in alkali metal ion batteries (AMIBs) due to its 2D-layered structure and high theoretical capacity. However, the shuttle effect of sulfur and the spontaneous growth of W nanoparticles are key issues that limit the alkali-ion accommodation ability. Now, it is still a great challenge to achieve in situ control of the microstructure evolution paths in enclosed batteries for extending the cycling reversibility/lifespan. Herein, the phase conversion paths of both film- and powder-type WS₂ anodes are investigated in lithium-ion batteries. It is found that the reversible conversion mechanism is beneficial for alleviating the shuttle effect through strong W–Li_xS_y bonding. Also, once the size of the phase-converted W/WS₂ redox pair exceeds ∼10 nm inside the anode layer, the Li⁺ storage ability will severely decay due to uncontrollable W precipitation. To maintain high reversibility, amorphous Al₂O₃ is introduced upon pristine WS₂. After initializing the battery test, the particle size of the W/WS₂ redox pair is in situ modulated within the range of ∼3–5 nm because of the refinement effect of gradually pulverized Al₂O₃. Thus, the decay suppression effect lasting over 750–1400 cycles is obtained with enhanced W ↔ WS₂ conversion efficiency and good capacity retention. This is expected to promote the optimization of Mo-group sulfides/selenides/tellurides toward AMIBs.