Nanocomposite Engineering of a High‐capacity Partially Ordered Cathode for Li‐ion Batteries

Abstract

Understanding the local cation order in the crystal structure and its correlation with electrochemical performances has advanced the development of high-energy Mn-rich cathode materials for Li-ion batteries, notably Li- and Mn-rich layered cathodes (LMR, e.g., Li1.2Ni0.13Mn0.54Co0.13O2) that are considered as nanocomposite layered materials with C2/m Li2MnO3-type medium-range order (MRO). Moreover, the Li-transport rate in high-capacity Mn-based disordered rock-salt (DRX) cathodes (e.g., Li1.2Mn0.4Ti0.4O2) was found to be influenced by the short-range order (SRO) of cations, underlining the importance of engineering the local cation order in designing high-energy materials. Herein, we reveal the nanocomposite, heterogeneous nature (like MRO found in LMR) of ultrahigh-capacity partially ordered cathodes (e.g., Li1.68Mn1.6O3.7F0.3) made of distinct domains of spinel-, DRX- and layered-like phases, contrary to conventional single-phase DRX cathodes. This multi-scale understanding of ordering informs engineering the nanocomposite material via Ti doping, altering the intra-particle characteristics to increase the content of the rock-salt phase and heterogeneity within a particle. This strategy markedly improves the reversibility of both Mn- and O-redox processes to enhance the cycling stability of the partially ordered DRX cathodes (nearly ∼30% improvement of capacity retention). Our work sheds light on the importance of nanocomposite engineering to develop ultrahigh-performance, low-cost Li-ion cathode materials.