Taohedul Islam, Sahar Bayat, Kathryn Pitton, Matthew A Wright, Muhammad Mominur Rahman, Misganaw Adigo Weret, Roland Yin, Subrata Chandra Roy, Renfei Feng, Roman Chernikov, Kamila M Wiaderek, Leighanne C Gallington, A M Milinda Abeykoon, Chad Risko, Ruhul Amin, Beth S Guiton, Saiful M Islam
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 MnxMo3S13-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 MnxMo3S13-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.