Long‐lasting, reinforced electrical networking in a high‐loading Li₂S cathode for high‐performance lithium–sulfur batteries

Abstract Realizing a lithium sulfide (Li₂S) cathode with both high energy density and a long lifespan requires an innovative cathode design that maximizes electrochemical performance and resists electrode deterioration. Herein, a high‐loading Li₂S‐based cathode with micrometric Li₂S particles composed of two‐dimensional graphene (Gr) and one‐dimensional carbon nanotubes (CNTs) in a compact geometry is developed, and the role of CNTs in stable cycling of high‐capacity Li–S batteries is emphasized. In a dimensionally combined carbon matrix, CNTs embedded within the Gr sheets create robust and sustainable electron diffusion pathways while suppressing the passivation of the active carbon surface. As a unique point, during the first charging process, the proposed cathode is fully activated through the direct conversion of Li₂S into S₈ without inducing lithium polysulfide formation. The direct conversion of Li₂S into S₈ in the composite cathode is ubiquitously investigated using the combined study of in situ Raman spectroscopy, in situ optical microscopy, and cryogenic transmission electron microscopy. The composite cathode demonstrates unprecedented electrochemical properties even with a high Li₂S loading of 10 mg cm^–2; in particular, the practical and safe Li–S full cell coupled with a graphite anode shows ultra‐long‐term cycling stability over 800 cycles.