First-principles investigation of topological vanadium chalcogenide monolayers for synergistic sodium storage and sulfur conversion

Abstract

An atomic-level understanding of anion and cation intercalation is essential for advancing alkali-metal-ion electrodes and anchoring metal polysulfides. Sodium batteries present a more sustainable alternative to lithium-based systems. Developing electrode materials that support both sodium-ion storage and sodium-polysulfide conversion, each in its own cell configuration, is therefore of growing interest. In this study, two-dimensional quaternary vanadium-based chalcogenides (V₂WS₄, V₂WSe₄, V₂MoS₄, and V₂MoSe₄) are computationally investigated. They exhibit indistinguishable bonding environments, topological band gaps, and versatility across two distinct cell configurations: sodium-ion storage and polysulfide anchoring. The distinctive topological electronic properties of these monolayers enhance Na⁺/K⁺ adsorption and facilitate high charge flux, indicating strong chemisorption while maintaining conductivity. These materials exhibit rapid ion transport, as evidenced by low diffusion barriers of 0.22 eV and 0.16 eV for Na⁺ and K⁺ ions, respectively, and deliver higher capacities of up to 1,151 mAh g^-1 for Na⁺ and 821.9 mAh g^-1 for K⁺ compared to conventional graphitic electrodes, along with a low open-circuit voltage of approximately 0.21 V. Additionally, these materials suppress polysulfide shuttling via energetic anchoring and accelerate the reduction reactions, particularly for long-chain sodium polysulfides. Sulfur reduction reactions and kinetic calculations for sodium-sulfur clusters indicate that V₂MoSe₄ exhibits the lowest rate-limiting free-energy change, while V₂MoS₄, V₂WS₄, and V₂WSe₄ demonstrate moderate kinetics and redox stability. These vanadium-based topological chalcogenides are thus promising anode materials for sodium-ion storage and as anchoring platforms for sodium-sulfur battery cathodes.

Keywords

Density functional theory / alkali ions / diffusion barrier / sodium-sulfur battery / gibbs energy / charge density

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