Dynamic Ni–O Bonding Induced by Orbital Degeneracy Breaking for Efficient Li ₂ CO ₃ Decomposition

Lithium carbonate, the primary discharge product in Li–CO 2 batteries with high thermodynamic stability and a wide band gap, leads to significant electrochemical inertness, limiting efficiency and cycle life. The strongly delocalized p z orbital at a lower‐energy HOMO level in Li 2 CO 3 causes weak coupling with the O‐p z orbitals, increasing decomposition resistance owing to d‐orbital degeneracy in high‐local‐symmetry catalysts. This study introduces metastable tetragonal‐pyramidal nickel sulfide (tp‐NiS) with low‐symmetry NiS 5 coordination, breaking d‐orbital degeneracy and bringing d z 2 , d xz , and d yz orbitals closer to the Fermi level. Enhanced orbital overlap with Li 2 CO 3 O‐p z orbitals facilitates robust Ni–O bond formation. In situ spectroscopy confirms reversible Ni–O bond formation during cycling, ensuring electron transfer and complete Li 2 CO 3 decomposition. Conversely, weak interfacial interactions in octahedral NiS with highly symmetric local coordination only allow decomposition‐resistant Li 2 CO 3 and interface passivation. Consequently, tp‐NiS exhibits superior electrochemical performance, with the best reported reversibility and stability, a charge potential below 4.0 V, and 92.03% capacity retention after 1800 h. This metal redox‐driven mechanism establishes a reversible geometric conversion pathway, emphasizing the critical role of symmetry‐engineered Ni–O interactions in bifunctional catalysts.