Engineering metal-sulfides with cations-tunable metal-oxides electrocatalysts with promoted catalytic conversion for robust ions-storage capability

Abstract

Metal rich-sulfides, with remarkable theoretical capacity, still suffer from the disolving of polysulfides and sluggish kinetics. Electrocatalysts, as the vital meditors, have been applied in Li-S systems with notable improvements, but scarcely explored for ions-storage battery. Herein, for introducting cation-tunable MOx (M=Mn/Fe/Co/Ni) as electrocatalysts, various MoS2@MOx are designed through chemical-precipitation and thermal-treatment manners. Benefitting from the high affinity of MoS2 and MOx, the interfacial chemical bonds Mo-S-M are established, boosting the improvement of ions/electrons transferring and structural integrality. Owing to the evolution of outer orbitals and ionic radius, the capturing and conversion of Li2S8 are tailored in order of Fe2O3>MnO>CoO>NiO. Supported by unique 3d-orbital/ion-radiu and Mo-S-Fe bonds, the ultra-fast ability of MoS2@Fe2O3 remains ∼612 mAh g−1 after 3,000 loops even at 5.0 A g−1, meanwhile delivering ∼800 mAh g−1 at 0.5 A g−1 in full-cell. Assisted by detailed kinetic behaviors and theoretical calculations, the redox reaction mechisms are clearly proposed, whilst the reduced Gibbs free energy (-1.25 of Fe2O3) serves crucial roles in the reaction (Li2S8 → Li2S6). This work is expected to shed light on the in-depth understanding of fourth-periods MOx electrocatalysts, and offers more possibilities for designing advanced metal-sulfides electrodes.MoS2 nanosheets uniformly anchored with MOx (M=Mn, Fe, Co, Ni) were rationally engineered, accompanied by the establishment of Mo-S-M interfacial chemical bonds. The electrocatalytic abilities of introduced MOx were successfully tailored by the evolution of cationic outer orbitals and ionic radius, inducing the fascinated catalytic conversion behaviors.