Chlorine Oxidation Catalyzed Collaboratively by Metal‐Ligand Enables Large‐Current Tolerance in Rechargeable Li/SOCl ₂ Batteries

ABSTRACT Lithium/thionyl chloride (Li/SOCl 2 ) batteries are considered a promising alternative for next‐generation energy storage, offering high energy density and a broad operating temperature range. However, current rechargeable Li/SOCl 2 batteries exhibit poor large‐current tolerance due to sluggish chloride ion (Cl − ) oxidation kinetics. Reported strategies for Cl − oxidation catalysis remain confined to the single catalytic sites, posing a significant challenge to achieve ultra‐high current Li/SOCl 2 batteries. Herein, the collaborative catalysis of metal‐ligand was proposed to accelerate Cl − oxidation kinetics, which was realized by the cobalt phthalocyanine containing pyridyl‐nitrogen (CoTAP). The central Co 2+ facilitates Cl − capture, while the peripheral pyridine ligand synergistically accepts electrons. This collaboration mediates electron exchange between the electrode and Cl − , enabling a kinetically optimized Cl − oxidation in a rechargeable Li/SOCl 2 battery. Consequently, rechargeable Li/SOCl 2 batteries catalyzed by CoTAP can durably operate at ultra‐high current densities (up to 20 mA cm −2 ) while maintaining a constant coulombic efficiency (almost 100%) during long‐term cycling. Meanwhile, it shows excellent cycling capability under a wide temperature range from −40°C to 50°C. This work proposes a synergistic catalysis mechanism of metal‐ligand on Cl − oxidation, which provides a new design concept for rechargeable Li/SOCl 2 batteries.