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.