This study presents a breakthrough in Li-CO₂ batteries by demonstrating high-performance catalysts that enable operation at high current densities. The research focuses on transition metal trichalcogenide (TMTC) alloys, specifically Sb₀.₆₇Bi₁.₃₃X₃ (X = S, Te), combined with an ionic liquid-based electrolyte. The Te-based catalyst, Sb₀.₆₇Bi₁.₃₃Te₃, shows exceptional activity and stability, allowing the battery to operate at 1 mA cm⁻² for up to 220 cycles. The study reveals that the type of chalcogenide (Te vs S) significantly affects the electronic and catalytic properties of the catalysts, with Te-based catalysts exhibiting higher activity for both CO₂ reduction and evolution reactions. Additionally, a coupled cation-electron charge transfer process facilitates the CO₂ reduction reaction during discharge, while the concentration of ionic liquid in the electrolyte controls the number of CO₂ molecules participating in the reactions. The optimal ionic liquid-to-DMSO ratio (4:6) enhances battery performance by improving CO₂ adsorption and reaction kinetics. The study also shows that the Te-based catalyst is more stable and efficient than the S-based counterpart, with a smaller bandgap contributing to its superior activity. Density functional theory (DFT) calculations support these findings, indicating that the Te-based catalyst's electronic structure enables faster electron transfer and better catalytic performance. The research introduces a new class of catalysts that could address the challenges of Li-CO₂ batteries, enabling high-current operation with long cycle life. The study highlights the importance of catalyst design and electrolyte composition in achieving efficient and stable Li-CO₂ battery performance.This study presents a breakthrough in Li-CO₂ batteries by demonstrating high-performance catalysts that enable operation at high current densities. The research focuses on transition metal trichalcogenide (TMTC) alloys, specifically Sb₀.₆₇Bi₁.₃₃X₃ (X = S, Te), combined with an ionic liquid-based electrolyte. The Te-based catalyst, Sb₀.₆₇Bi₁.₃₃Te₃, shows exceptional activity and stability, allowing the battery to operate at 1 mA cm⁻² for up to 220 cycles. The study reveals that the type of chalcogenide (Te vs S) significantly affects the electronic and catalytic properties of the catalysts, with Te-based catalysts exhibiting higher activity for both CO₂ reduction and evolution reactions. Additionally, a coupled cation-electron charge transfer process facilitates the CO₂ reduction reaction during discharge, while the concentration of ionic liquid in the electrolyte controls the number of CO₂ molecules participating in the reactions. The optimal ionic liquid-to-DMSO ratio (4:6) enhances battery performance by improving CO₂ adsorption and reaction kinetics. The study also shows that the Te-based catalyst is more stable and efficient than the S-based counterpart, with a smaller bandgap contributing to its superior activity. Density functional theory (DFT) calculations support these findings, indicating that the Te-based catalyst's electronic structure enables faster electron transfer and better catalytic performance. The research introduces a new class of catalysts that could address the challenges of Li-CO₂ batteries, enabling high-current operation with long cycle life. The study highlights the importance of catalyst design and electrolyte composition in achieving efficient and stable Li-CO₂ battery performance.