<p>Molybdenum disulfide (MoS₂), as a representative transition-metal sulfide, exhibits high capacity for Li⁺ storage processes. However, its large volume expansion and low conductivity during Li⁺ storage result in poor cycling stability and insufficient fast-charging performance, severely limiting its practical applications. Here, an atomic-level stacked structure consisting of Ni-doped MoS₂ and carbon layers is fabricated. The stacked structure maximizes the intimate atomic-scale interfacial contact between MoS₂ and carbon layers, improves the structural stability of MoS₂ during Li⁺ storage, and enhances its electronic conductivity. Ni doping transforms the semiconductor properties of MoS₂ into metallic properties and simultaneously reduces its Li⁺ transport energy barrier, thus enhancing its charge transport capability. More interestingly, <i>ex situ</i> transmission electron microscopy and <i>in situ</i> magnetometry reveal that the doped Ni atoms can convert into superparamagnetic Ni nanoparticles during discharge, which serve as carriers to store electrons and facilitate the storage of Li⁺ in Li₂S. The process induces a spin-polarized surface capacitance effect at the interfaces between Ni and Li₂S, enhancing the storage and transport of Li⁺. As a result, the composite material delivers high Li⁺ storage capacity, superior stability, and excellent fast-charging capability in both coin-type half-cells and Ah-level pouch full cells. This work first confirms the enhancement mechanism of spin-polarized surface capacitance effect in the Li⁺ storage performance of MoS₂, providing insights for advancing high-performance MoS₂-based lithium battery anodes.</p> Graphical abstract <p></p>