Non‐Carbon‐Dominated Catalyst Architecture Enables Double‐High‐Energy‐Density Lithium–Sulfur Batteries

Abstract The commonly used “catalyst on carbon” architecture as a sulfur host is difficult to jointly achieve high gravimetric and volumetric energy densities for lithium–sulfur (Li–S) batteries due to the contradiction between low tap density/poor catalytic activity of carbon and the easy agglomeration of metal‐based compounds without carbon. Here, a non‐carbon‐dominated catalytic architecture using macroporous nickel/cobalt phosphide (NiCoP) is reported as the sulfur host for Li–S batteries. The macroporous framework, which accommodates a large amount of sulfur, can accelerate the electrochemical reaction kinetics by accelerated e⁻ transport, Li⁺ diffusion, and superior adsorption and catalytic activity of inherent Ni₂P/CoP heterostructures. The high tap density (0.45 g cm⁻³) and mechanically hard features contribute to the excellent structural and physicochemical stability of the NiCoP@S electrode after the pressing and rolling process. These features enable the Li–S coin cell to exhibit excellent electrochemical performance under conditions of high sulfur loading (10.2 mg cm⁻²) and lean electrolyte (electrolyte/sulfur of 2 µL mg⁻¹). Inspiringly, the assembled pouch cell can simultaneously deliver a gravimetric energy density of 345.2 Wh kg⁻¹ and an impressive volumetric energy density of 952.7 Wh L⁻¹ based on the entire device configuration.