Surface Chemical CoordinationStabilizes Ni-Rich Cathodesfor High-Energy Li-Metal Batteries

The stability of the electrode–electrolyte interface is a critical factor influencing the electrochemical performance of Li-metal batteries. However, on the delithiated Ni-rich cathode surface, the strong catalytic effects of transition metals with coordination deficiency significantly aggravate the parasitic reactions with Li-metal-compatible ether-based electrolytes, thereby reducing the cycling stability of high-voltage Ni-rich batteries. Here, we propose an <i>sp</i>²-induction mechanism to address coordination deficiency through the coupling of interfacial orbitals between molecules and the cathode surface. <i>Sp</i>²-hybrid high-fluorinated olefins, characterized by unsaturated bonds, exhibit highly delocalized electronic properties (electron delocalization index >0.95 au) and elevated anodic stability (ionization potential >10 eV). These characters ensure robust and stable interactions with the Ni-rich cathode, facilitating the formation of induced orbitals. These low-energy orbitals accommodate Ni 3<i>d</i> electrons, effectively mitigating the interfacial coordination deficiency and inhibiting surface side reactions. Among the <i>sp</i>²-hybrid high-fluorinated olefins, (perfluorobutyl)ethylene (PFBE) is identified as an optimal inducing molecule due to its strongest interaction and excellent coordination complementarity on the cathode surface. The PFBE-based electrolyte significantly alleviates the degradation of cathode surface structure and demonstrates remarkable cyclic stability, achieving 80% capacity retention over 320 cycles for a 4.4 V Li||LiNi_0.8Mn_0.1Co_0.1O₂ (30 μm Li, high load 3.7 mAh cm^–2 NMC811) full cell, compared to 175 cycles with a PFBE-absent electrolyte. This work elucidates the <i>sp</i>²-induction mechanism for passivating the high-catalytic cathode interface, paving the way for durable, high-energy aggressive Li-metal batteries.