Nanocrystal Conversion Chemistry within Slit-like 2D Nanogap for High-Rate Cyclic Stability of Lithium-Ion Battery...

Nanoscale optimization of late transition-metal oxides for fixing the reversible lithiation/delithiation mechanism with an in-depth mechanistic understanding of nanocrystal (NC) conversion chemistry is important for furthering next-generation Li-ion battery (LIB) technologies. Herein, 1 nm-thin Ni₃CoO (1 nm-NCO) nanosheets synthesized through isomorphic transformation of NiCo layered double hydroxides within a two-dimensional (2D)-SiO₂ envelope are chosen. The interconversion of metal/metal-oxide NCs under redox-switching thermal treatment, while retaining reversibility, inspired the accomplishment of identical consequences under the harsh operational conditions of LIB redox cycles by application of the thin-NCO-defined 2D nanospace. During charge/discharge cycles, 1 nm-NCO covered with an in situ formed solid-electrolyte-interphase layer enables fully reversible interconversion between the reactive NC redox pairs, as evidenced by detailed morphological and electrochemical analyses, thus providing high-rate capability with a specific capacity of 61.2% at 5.0 C relative to 0.2 C, outstanding cycle stability delivering a reversible capacity of 1169 mAh g^-1, and 913 mAh g^-1 with high average Coulombic efficiency (>99.2%) at 3.0 and 5.0 C for 1000 cycles, respectively, which has not been achieved with other transition-metal oxides. Such a nanospace-confinement effect on sustainability of reactive NCs to follow-up a highly reversible conversion reaction at fast charging in LIBs is operative within a slit-like ultrathin 2D nanogap from 1 nm-NCO only, as a relatively thicker 7 nm-NCO anode, with accompanying larger space available, has evidenced poor reversibility of NCs and inadequate cyclic stability under potential high-power density LIB application.