Li-CO₂ batteries are promising for integrating energy storage with CO₂ utilization, yet their practical application is limited by poor reversibility of discharge products formation/decomposition. Rational regulation of interfacial electronic environments is therefore crucial for improving reaction reversibility and enhancing electrochemical performance. Herein, a Co-based catalyst with localized Ru incorporation was constructed through a ZIF-67-derived structural confinement strategy. Localized Ru incorporation effectively reconstructs the local electronic environment of neighboring Co sites and induces interfacial electronic modulation. The Li-CO₂ battery with the Ru₁₅Co₈₅ nanoparticles (Ru₁₅Co₈₅-NPs) cathode delivers a low voltage gap of 1.11 V, a high coulombic efficiency of 99.7%, and stable cycling over 750 cycles (3100 h), significantly superior to those with Co-NPs and Ru₅₀Co₅₀-NPs counterparts. The optimized Ru₁₅Co₈₅ catalyst exhibits regulated interfacial reaction, enabling more efficient Li₂CO₃-related conversion and decomposition processes. Density functional theory calculations further reveal that moderate Ru incorporation lowers the free-energy barrier of the rate-determining Li₂CO₃ formation step and reduces the Li₂CO₃ dissociation barrier to 0.65 eV. This work provides an effective strategy for regulating interfacial electronic environments through moderate Ru incorporation and offers new insights into the design of highly reversible Li-CO₂ battery catalysts.

Sodium-ion batteries (SIBs) have been attracting considerable attention as a promising candidate for large-scale energy storage because of the abundance and low-cost of sodium resources. However, lack of appropriate anode materials impedes further applications. Herein, a novel self-template strategy is designed to synthesize uniform flowerlike N-doped hierarchical porous carbon networks (NHPCN) with high content of N (15.31 at.%) assembled by ultrathin nanosheets via a self-synthesized single precursor and subsequent thermal annealing. Relying on the synergetic coordination of benzimidazole and 2-methylimidazole with metal ions to produce a flowerlike network, a self-formed single precursor can be harvested. Due to the structural and compositional advantages, including the high N doping, the expanded interlayer spacing, the ultrathin two-dimensional nano-sized subunits, and the three-dimensional porous network structure, these unique NHPCN flowers deliver ultrahigh reversible capacities of 453.7 mAh·g^-1 at 0.1 A·g^-1 and 242.5 mAh·g^-1 at 1 A·g^-1 for 2,500 cycles with exceptional rate capability of 5 A·g^-1 with reversible capacities of 201.2 mAh·g^-1. The greatly improved sodium storage performance of NHPCN confirms the importance of reasonable engineering and synthesis of hierarchical carbon with unique structures.