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)SeO3 phase with a small amount of metal selenate. The conversion mechanism of (NiCo)SeO3 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)SeO3 with the Li ions is described by the reaction: NiO + CoO + xSeO(2) + (1 - x)Se + (4x + 6)Li+ + (4x + 6)e(-) <-> Ni + Co + (2x + 2)Li2O + Li2Se. To enhance electrochemical properties, polydopamine-derived carbon is uniformly coated on (NiCo)SeO3, resulting in excellent cycling and rate performances for Li-ion storage. The discharge capacity of C-coated (NiCo)SeO3 is 680 mAh g(-1) for the 1500th cycle when cycled at a current density of 5 A g(-1).