Unlocking Li-CO₂ Battery Catalytic Potential via High-Entropy Alloy-Driven Synergistic Coupling for Amorphous Pathway Stabilization

Li-CO₂ batteries utilizing greenhouse gas CO₂ as feedstock offer high energy density and environmental benefits. However, the sluggish CO₂ redox kinetics at cathodes lead to high overpotentials and low Coulombic efficiency, severely limiting practical applications. Here, the potential of Li-CO₂ 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, Li₂CO₃, and Li₂C₂O₄, collectively stabilizing the amorphous Li₂C₂O₄ formation pathway. This design achieves a record discharge voltage of 3.1 V with an ultralow overpotential (0.48 V) in Li-CO₂ 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-CO₂ batteries.