Spatially Coupled Cl₂ Confinement and Activation at Curved Ni Single-Atom Sites for Highly Reversible Li-Cl₂...

Leveraging the high-potential Cl₂/LiCl redox couple (∼3.6 V), rechargeable Li-Cl₂ batteries hold compelling promise for next-generation energy storage. However, their practical viability is severely impeded by poor Cl₂ retention and sluggish conversion kinetics, particularly under deep-cycling and high-rate regimes. Here, we present a spatially coupled Cl₂-management cathode that integrates Cl₂ confinement and short-range transport within a micropore-rich matrix with spontaneous activation at dense pore wall-anchored, curved Ni single-atom sites. Via this closed-loop pathway from Cl₂ storage to LiCl deposition, the Li-Cl₂ battery achieves a remarkable 1.21 V polarization reduction at 1500 mAh g^-1 cut-off capacity at 2000 mA g^-1. Consequently, an ultrahigh cumulative capacity exceeding 1.0 million mAh g^-1, which doubles the lifespan of state-of-the-art Li-Cl₂ systems, is achieved through the integrated approach incorporating this pathway, the robust, partially graphitized support, and an optimized discharge-cutoff protocol. Furthermore, the exceptional all-climate robustness (-40°C to +70°C), coupled with a high reversible areal capacity of 7.65 mAh cm^-2 in pouch cells, establishes a new paradigm for practical, high-energy storage systems.