Multilevel spatial confinement of transition metal selenides porous microcubes for efficient and stable potassium storage.

Recently, potassium-ion batteries (PIBs) have been considered as one of the most promising energy storage systems; however, the slow kinetics and large volume variation induced by the large radius of potassium ions (K) during chemical reactions lead to inferior structural stability and weak electrochemical activity for most potassium storage anodes. Herein, a multilevel space confinement strategy is proposed for developing zinc-cobalt bimetallic selenide (ZnSe/CoSe@NC@C@rGO) as high-efficient anodes for PIBs by in-situ carbonizing and subsequently selenizing the resorcinol-formaldehyde (RF)-coated zeolitic imidazolate framework-8/zeolitic imidazolate framework-67 (ZIF-8/ZIF-67) encapsulated into 2D graphene. The highly porous carbon microcubes derived from ZIF-8/ZIF-67 and carbon shell arising from RF provide rich channels for ion/electron transfer, present a rigid skeleton to ensure the structural stability, offer space for accommodating the volume change, and minimize the agglomeration of active material during the insertion/extraction of large-radius K. In addition, the three-dimensional (3D) carbon network composed of graphene and RF-derived carbon-coated microcubes accelerates the electron/ion transfer rate and improves the electrochemical reaction kinetics of the material. As a result, the as-synthesized ZnSe/CoSe@NC@C@rGO as the anode of PIBs possesses the excellent rate capability of 203.9 mA h g at 5 A g and brilliant long-term cycling performance of 234 mA h g after 2,000 cycles at 2 A g. Ex-situ X-ray diffraction (Ex-situ XRD) diffraction reveals that the intercalation/de-intercalation of K proceeds through the conversion-alloying reaction. The proposed strategy based on the spatial confinement engineering is highly effective to construct high-performance anodes for PIBs.