Construction of Bimetallic Selenides Encapsulated in Nitrogen/Sulfur Co‐Doped Hollow Carbon Nanospheres for High‐Performance Sodium/Potassium‐Ion Half/Full Batteries

Metallic selenides have been widely investigated as promising electrode materials for metal‐ion batteries based on their relatively high theoretical capacity. However, rapid capacity decay and structural collapse resulting from the larger‐sized Na⁺/K⁺ greatly hamper their application. Herein, a bimetallic selenide (MoSe₂/CoSe₂) encapsulated in nitrogen, sulfur‐codoped hollow carbon nanospheres interconnected reduced graphene oxide nanosheets (rGO@MCSe) are successfully designed as advanced anode materials for Na/K‐ion batteries. As expected, the significant pseudocapacitive charge storage behavior substantially contributes to superior rate capability. Specifically, it achieves a high reversible specific capacity of 311 mAh g^?1 at 10 A g^?1 in NIBs and 310 mAh g^?1 at 5 A g^?1 in KIBs. A combination of ex situ X‐ray diffraction, Raman spectroscopy, and transmission electron microscopy tests reveals the phase transition of rGO@MCSe in NIBs/KIBs. Unexpectedly, they show quite different Na⁺/K⁺ insertion/extraction reaction mechanisms for both cells, maybe due to more sluggish K⁺ diffusion kinetics than that of Na⁺. More significantly, it shows excellent energy storage properties in Na/K‐ion full cells when coupled with Na₃V₂(PO₄)₂O₂F and PTCDA@450 °C cathodes. This work offers an advanced electrode construction guidance for the development of high‐performance energy storage devices.