Hierarchical porous Co0.85Se@reduced graphene oxide ultrathin nanosheets with vacancy-enhanced kinetics as superior anodes for sodium-ion batteries

Highlights: • The hierarchical porous Co_0.85Se nanosheets are prepared by the solvent-controlled hydrothermal method. • These voids not only accelerate the ion transfer in electrode but also reserve space for relieving the volume expansion. • The robust Se-C bonds construct fast electron transfer paths between the isolated Co_0.85Se nanosheets. • The vertically orientated Co_0.85Se nanosheets enhance the volume energy density and structural stability. • The superior sodium storage kinetics and reversible redox reactions were verified via the GITT, ex-situ measurements and DFT calculations. Metal selenides have received much attention from the rechargeable battery community owing to their considerable capacity. However, attainment of a long cycle life and fast Na⁺ storage kinetics are still needed to enable their practical application. Co_0.85Se nanosheets prepared using a simple hydrothermal method exhibit a hierarchical porous structure, which is conducive to fast electrolyte transport and rapid adsorption of Na⁺ ions. Herein, to improve the electronic conductivity of Co_0.85Se, reduced graphene oxide (rGO) is introduced to construct a three-dimensional network and achieve fast electronic transport. This defect-controlled Co_0.85Se@rGO anode exhibits a highly reversible capacity of 460 mA h g⁻¹ at a current density of 0.5 A g⁻¹. Outstanding durability and remarkable rate stability are also achieved via the synergistic effects of vacancy transport and the heterostructure between Co_0.85Se and rGO. Furthermore, the Na⁺ insertion/extraction mechanism is systematically investigated using ex situ X-ray diffraction, Raman spectroscopy, high-resolution transmission electron microscopy, and a series of electrochemical analyses. These analyses enable detailed characterization of the ionic diffusion kinetics and corresponding components and structural changes. Finally, a first-principles approach is employed to determine the diffusion energy barrier of Na⁺ ions in perfect CoSe and defective Co_0.85Se.