Investigation of Binary Metal (Ni, Co) Selenite as Li‐Ion Battery Anode Materials and Their Conversion Reaction Mechanism with Li Ions

Abstract Highly efficient anode materials with novel compositions for Li‐ion batteries are actively being researched. Multicomponent metal selenite is a promising candidate, capable of improving their electrochemical performance through the formation of metal oxide and selenide heterostructure nanocrystals during the first cycle. Here, the binary nickel–cobalt selenite derived from Ni–Co Prussian blue analogs (PBA) is chosen as the first target material: the Ni–Co PBA are selenized and partially oxidized in sequence, yielding (NiCo)SeO 3 phase with a small amount of metal selenate. The conversion mechanism of (NiCo)SeO 3 for Li‐ion storage is studied by cyclic voltammetry, in situ X‐ray diffraction, ex situ X‐ray photoelectron spectroscopy, in situ electrochemical impedance spectroscopy, and ex situ transmission electron microscopy. The reversible reaction mechanism of (NiCo)SeO 3 with the Li ions is described by the reaction: NiO + CoO + x SeO 2 + (1 ‐ x )Se + (4 x + 6)Li + + (4 x + 6)e − ↔ Ni + Co + (2 x + 2)Li 2 O + Li 2 Se. To enhance electrochemical properties, polydopamine‐derived carbon is uniformly coated on (NiCo)SeO 3 , resulting in excellent cycling and rate performances for Li‐ion storage. The discharge capacity of C‐coated (NiCo)SeO 3 is 680 mAh g −1 for the 1500th cycle when cycled at a current density of 5 A g −1 .