Synergistic Defect Engineering and Interface Stability of Activated Carbon Nanotubes Enabling Ultralong Lifespan All-Solid-State Lithium–Sulfur Batteries

Due to the high energy density, high safety, and low cost of sulfur, all-solid-state lithium-sulfur batteries (ASSLSBs) are considered one of the most promising next-generation energy storage devices. Nevertheless, the insufficient interfacial contact between solid electrolytes (SEs) and the active material of sulfur leads to inadequate electronic and ionic conduction, which increases interfacial resistance and capacity decay. In this paper, commercial carbon nanotubes (CNTs) are activated to form porous-CNTs (P-CNTs), which are used as sulfur-bearing matrix, forming S@P-CNTs-based composite cathodes for ASSLSBs. Compared with CNTs, P-CNTs possess a larger specific surface area and more oxygen-containing groups, providing enhanced interfacial contact and stability between S@P-CNTs and Li₆PS₅Cl SE, which are confirmed by scanning electron microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. Moreover, P-CNTs can form a 3D conductive network in the composite cathodes, facilitating the migration of electrons and the diffusion of ions, as well as improving the utilization of sulfur. As a result, the S@P-CNTs-based ASSLSBs display excellent electrochemical performances, especially rarely reported ultralong lifespan, which deliver a capacity of 1099.2 mA h g^-1 at a current density of 1.34 mA cm^-2, and remarkably maintain 70.4% of the initial capacity over 1400 cycles.