Phase-inversion constructed Mo₂C@NC microreactor with optimized pyridinic N p-band center for high-performance Li-S...

Nitrogen-doped carbon (NC) is widely employed as a conductive matrix in Li-S batteries, yet its intrinsic catalytic contribution is often overlooked when combined with metal compounds. Herein, we propose a hierarchical microreactor architecture that integrates conductive and catalytic functions through an intimately coupled Mo₂C@NC interface. Density functional theory calculations demonstrate that coupling NC with Mo₂C induces pronounced electron redistribution of N atoms, with pyridinic N exhibiting the strongest charge transfer from Mo₂C, making the p-band center closest to the Fermi level, thereby endowing superior LiPSs adsorption activity. Guided by this insight, a phase-inversion strategy is employed using pyridinic-N-rich polyacrylonitrile (PAN) and MoO₃ precursors to construct a cross-linked MoO₃@PAN network, which is subsequently transformed into Mo₂C@NC microreactors after carbonization. In this structure, Mo₂C nanowires are uniformly confined within pyridinic-N-rich carbon shells, forming a zero-distance conductive-catalytic interface that enables efficient electron transfer from Mo₂C to NC. This integrated microreactor provides continuous electron pathways, abundant catalytic sites, and unobstructed ion transport, effectively avoiding pore blockage commonly encountered in conventional composite cathodes. Consequently, the Mo₂C@NC cathode exhibits high cycling stability over 1000 cycles at 2.0 C with a low decay rate of 0.052% per cycle. Even at 4.0 C, it retains 790.6 mAh g^-1 for over 400 cycles with only 0.027% fading per cycle.