Nanocomposite Engineering of a High-Capacity Partially Ordered Cathode for Li-Ion Batteries

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., Li_1.2 Ni_0.13 Mn_0.54 Co_0.13 O₂ ) that are considered as nanocomposite layered materials with C2/m Li₂ MnO₃ -type medium-range order (MRO). Moreover, the Li-transport rate in high-capacity Mn-based disordered rock-salt (DRX) cathodes (e.g., Li_1.2 Mn_0.4 Ti_0.4 O₂ ) is found to be influenced by the short-range order of cations, underlining the importance of engineering the local cation order in designing high-energy materials. Herein, the nanocomposite is revealed, with a heterogeneous nature (like MRO found in LMR) of ultrahigh-capacity partially ordered cathodes (e.g., Li_1.68 Mn_1.6 O_3.7 F_0.3 ) 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). This work sheds light on the importance of nanocomposite engineering to develop ultrahigh-performance, low-cost Li-ion cathode materials.