Covalently Integrated Amorphous Mn_xMo₃S₁₃–GO Chalcocarbogel for High Capacity and Long-Life Sulfur Equivalent Conversion Electrodes

Developing long-life, high-capacity sulfur-based electrodes from earth-abundant elements remains a major challenge because of structural degradation and polysulfide dissolution during multielectron conversion reactions. Here, we report a hybrid amorphous Mn_xMo₃S₁₃–GO (x = 0.5) chalcocarbogel synthesized by a room-temperature, acid-free sol–gel process. The resulting framework comprises chemically integrated M─S/O, (M = Mn, Mo), and C─S bonding motifs that form a mechanically and chemically robust electroactive network. Synchrotron X-ray PDF, XANES/EXAFS, XPS, Raman spectroscopy, magnetic susceptibility, and density functional theory (DFT)-based ab initio molecular dynamics reveal short-range Mo₃S₁₃-like clusters and MnS₂-like coordination environments within the amorphous framework. Mn incorporation shortens polysulfide chains and strengthens Lewis acid–base interactions with redox-active sulfur species, while graphene oxide enhances electronic connectivity and structural integrity through chemically coupled interfaces. As a lithium-ion battery cathode, the Mn_xMo₃S₁₃–GO chalcocarbogel delivers a reversible capacity of ∼525 mAh g⁻¹ after 1000 cycles at C/3, corresponding to 83% capacity retention with >99.99% Coulombic efficiency. These findings establish Mo₃S₁₃ cluster-engineered chalcocarbogels as a versatile platform for durable amorphous sulfur-redox electrodes, where synergistic metal–sulfur and graphene oxide interactions at the atomic level enable long-term electrochemical stability and high-performance energy storage.