Boosting Energy Efficiency and Stability of Li–CO₂ Batteries via Synergy between Ru Atom Clusters and Single‐Atom Ru–N₄ sites in the Electrocatalyst Cathode

The Li-CO₂ battery is a novel strategy for CO₂ capture and energy-storage applications. However, the sluggish CO₂ reduction and evolution reactions cause large overpotential and poor cycling performance. Herein, a new catalyst containing well-defined ruthenium (Ru) atomic clusters (RuAC ) and single-atom Ru-N₄ (RuSA ) composite sites on carbon nanobox substrate (RuAC+SA @NCB) (NCB = nitrogen-doped carbon nanobox) is fabricated by utilizing the different complexation effects between the Ru cation and the amine group (NH₂ ) on carbon quantum dots or nitrogen moieties on NCB. Systematic experimental and theoretical investigations demonstrate the vital role of electronic synergy between RuAC and Ru-N₄ in improving the electrocatalytic activity toward the CO₂ evolution reaction (CO₂ ER) and CO₂ reduction reaction (CO₂ RR). The electronic properties of the Ru-N₄ sites are essentially modulated by the adjacent RuAC species, which optimizes the interactions with key reaction intermediates thereby reducing the energy barriers in the rate-determining steps of the CO₂ RR and CO₂ ER. Remarkably, the RuAC+SA @NCB-based cell displays unprecedented overpotentials as low as 1.65 and 1.86 V at ultrahigh rates of 1 and 2 A g⁻¹ , and twofold cycling lifespan than the baselines. The findings provide a novel strategy to construct catalysts with composite active sites comprising multiple atom assemblies for high-performance metal-CO₂ batteries.