Atomic Structural Features of Stacking Faults and Domain Connections in the Li- and Mn-Rich Cathode

Li- and Mn-rich layered oxides (LMRs), a class of earth-abundant materials for rechargeable Li-ion battery cathodes, crystallize into layered structures of two different symmetries: <i>C</i>2/<i>m</i> represented by Li₂MnO₃ and <i>R</i>3̅<i>m</i> represented by LiMn_0.5Ni_0.5O₂. Fundamental questions about how the <i>C</i>2/<i>m</i> and <i>R</i>3̅<i>m</i> domains spatially correlate within the same oxide grain and how the <i>C</i>2/<i>m</i> stacking faults arrange themselves when this happens still remain. Here, by using integrated differential phase contrast imaging in scanning transmission electron microscopy (STEM-iDPC), we probe the structural and compositional details of a prototypical, cobalt-free LMR material, 0.3Li₂MnO₃·0.7LiMn_0.5Ni_0.5O₂ (Li_1.13Mn_0.57Ni_0.3O₂). The connection between the <i>C</i>2/<i>m</i> and <i>R</i>3̅<i>m</i> domains is found to be abrupt, facilitated by the small lattice mismatch between the two structures. Stacking faults in the <i>C</i>2/<i>m</i> domains feature atomic plane shifting that accommodates stacking sequence changes, which explains why the stacking faults form in a random manner. Furthermore, a local disordering mechanism was identified to correlate with the <i>C</i>2/<i>m</i> stacking faults. Chemically, it is found that Ni coexists with Mn at the transition metal sites within the nominal Li₂MnO₃ domain. This study demonstrates that STEM-iDPC is a very useful tool for capturing all the elements in a single image, revealing atomic details on domain connections and stacking faults in the LMRs.