Unlocking Li‐CO ₂ Battery Catalytic Potential via High‐Entropy Alloy‐Driven Synergistic Coupling for Amorphous Pathway Stabilization

ABSTRACT Li‐CO 2 batteries utilizing greenhouse gas CO 2 as feedstock offer high energy density and environmental benefits. However, the sluggish CO 2 redox kinetics at cathodes lead to high overpotentials and low Coulombic efficiency, severely limiting practical applications. Here, the potential of Li‐CO 2 batteries is unlocked through a high‐entropy alloy (HEA)‐driven synergistic coupling strategy using a PtPdFeCoCuZn (PPFCCZ) catalyst (∼2.2 nm). The unique multi‐element composition of the PPFCCZ catalyst creates an interfacial environment that enables ternary synergistic coupling among the interface metal, Li 2 CO 3 , and Li 2 C 2 O 4 , collectively stabilizing the amorphous Li 2 C 2 O 4 formation pathway. This design achieves a record discharge voltage of 3.1 V with an ultralow overpotential (0.48 V) in Li‐CO 2 batteries. Additionally, it achieves a cycling lifespan exceeding 1000 h at a current density of 20 µA cm −2 , overcoming the conventional trade‐off between voltage and reversibility. This work provides a paradigm for designing multi‐functional HEA catalysts to manipulate reaction pathways in Li‐CO 2 batteries.