Unveiling Poisoning Mechanism Toward the Rational Design of Durable Amine‐Containing Catalysts for Na/Cl ₂ Batteries

Rechargeable Na/Cl 2 batteries are promising for next‐generation energy storage owing to sodium abundance and high theoretical energy density. However, achieving fast and stable NaCl/Cl 2 conversion is extremely challenging because of the high lattice energy of NaCl. While amine‐containing organic catalysts can accelerate NaCl/Cl 2 redox kinetics, a sharp rise in polarization voltage under sustained operation causes severe energy output loss, hindering their practical application. Herein, for the first time, we identify a previously unrecognized poisoning process of nucleophilic amine‐based organocatalysts in the AlCl 3 /SOCl 2 electrolyte using in situ Fourier‐transform infrared spectroscopy, producing N‐sulfinylated species. Based on these insights, a resonance‐assisted hydrogen‐bonding strategy is proposed to construct a “resonance quasi‐ring” structure, which simultaneously suppresses SOCl 2 /AlCl 3 ‐induced poisoning and further enhances the reaction kinetics. As a result, the anti‐poisoning is improved by an order of magnitude (10‐fold). The assembled Na/Cl 2 cells delivered a greatly enhanced cycle life (from 200 to 1500 cycles) with only a 90 mV increase in polarization voltage. The effect was further validated in Ah‐level pouch cell models. This work opens a new perspective for constructing efficient and robust organic catalytic systems in harsh electrochemical environments.