Quasi-1D Chain-Based Zirconium Trisulfide as a Low-Potential High-Rate Anode: Structural and Reaction Mechanism Insights

Transition metal trichalcogenides (TMTCs) of Group IVB (e.g., ZrS₃) are promising lithium-ion battery (LIB) anodes owing to their tunable band gaps, anisotropic conductivity, and high specific capacities. Here, microsized ZrS₃ with a quasi-1D chain-based structure and van der Waals stacked layers were synthesized via a simple solid-state reaction. Subsequently, the ZrS₃ anode was evaluated across distinct voltage windows, the storage mechanism switched from intercalation (≥1.0 V) to conversion (down to 0.001 V). The ZrS₃ electrode delivers a high capacity of 844 mAh g⁻¹ at 50 mA g⁻¹ after 40 cycles, with excellent rate capability (281 mAh g⁻¹ at 3000 mA g⁻¹) and outstanding cycling stability, maintaining 408 mAh g⁻¹ over 2300 cycles at 3000 mA g⁻¹. Ex situ XRD/SEM-EDX/XPS track phase and surface evolution, while EIS resolves interfacial charge-transfer/ion-transport kinetics. DFT reveals low-barrier Li⁺ diffusion along interchain pathways in bulk (≈0.12 eV) and monolayer ZrS₃. A directional increase in the calculated Young's modulus under small strain suggests robust mechanics upon cycling. These experimental-theoretical insights establish ZrS₃ as a low-potential, high-rate anode for lithium-ion batteries and clarify the intercalation-conversion crossover in Group IVB TMTCs.