This study investigates the performance of Li-CO₂ batteries, which have a high theoretical energy density of 1876 Wh kg⁻¹, by exploring the use of transition metal trichalcogenide alloy catalysts. The researchers found that using an ionic liquid-based electrolyte, the Sb₀.₆₇Bi₁.₃₃X₃ (X = S, Te) catalysts enable the battery to operate at a high current density of 1 mA cm⁻² for up to 220 cycles. Key findings include: 1. **Catalyst Type**: The type of chalcogenide (Te vs S) significantly affects the electronic and catalytic properties of the catalysts, with Te-based catalysts showing higher CO₂ reduction reaction (CO₂RR) and carbon dioxide evolution reaction (CO₂ER) activity. 2. **Coupled Cation-Electron Transfer**: A coupled cation-electron transfer process facilitates the CO₂RR during discharge, enhancing the reaction rate. 3. **Ionic Liquid Concentration**: The concentration of the ionic liquid in the electrolyte controls the number of participating CO₂ molecules in the reactions, with an optimal ratio of 4:6 (DMSO:IL) providing the best performance. 4. **DFT Calculations**: Density Functional Theory (DFT) calculations support the experimental results, indicating that the Te-based catalyst has a smaller bandgap, contributing to its superior activity for CO₂RR and CO₂ER. 5. **Electrolyte Structure**: The structure of the electrolyte/catalyst interface, as analyzed using Atomistic Model-Informed Dynamics (AIMD), shows that the presence of ionic liquid near the catalyst surface helps attract more CO₂ molecules, enhancing the reaction. These findings introduce a new class of catalysts that could fundamentally solve the challenges of high current rates in Li-CO₂ batteries, making them more practical for energy storage applications.This study investigates the performance of Li-CO₂ batteries, which have a high theoretical energy density of 1876 Wh kg⁻¹, by exploring the use of transition metal trichalcogenide alloy catalysts. The researchers found that using an ionic liquid-based electrolyte, the Sb₀.₆₇Bi₁.₃₃X₃ (X = S, Te) catalysts enable the battery to operate at a high current density of 1 mA cm⁻² for up to 220 cycles. Key findings include: 1. **Catalyst Type**: The type of chalcogenide (Te vs S) significantly affects the electronic and catalytic properties of the catalysts, with Te-based catalysts showing higher CO₂ reduction reaction (CO₂RR) and carbon dioxide evolution reaction (CO₂ER) activity. 2. **Coupled Cation-Electron Transfer**: A coupled cation-electron transfer process facilitates the CO₂RR during discharge, enhancing the reaction rate. 3. **Ionic Liquid Concentration**: The concentration of the ionic liquid in the electrolyte controls the number of participating CO₂ molecules in the reactions, with an optimal ratio of 4:6 (DMSO:IL) providing the best performance. 4. **DFT Calculations**: Density Functional Theory (DFT) calculations support the experimental results, indicating that the Te-based catalyst has a smaller bandgap, contributing to its superior activity for CO₂RR and CO₂ER. 5. **Electrolyte Structure**: The structure of the electrolyte/catalyst interface, as analyzed using Atomistic Model-Informed Dynamics (AIMD), shows that the presence of ionic liquid near the catalyst surface helps attract more CO₂ molecules, enhancing the reaction. These findings introduce a new class of catalysts that could fundamentally solve the challenges of high current rates in Li-CO₂ batteries, making them more practical for energy storage applications.