Abstract Lithium-rich oxide cathodes lose energy density during cycling due to atomic disordering and nanoscale structural rearrangements, which are both challenging to characterize. Here we resolve the kinetics and thermodynamics of these processes in an exemplar layered Li-rich (Li 1.2– x Mn 0.8 O 2 ) cathode using a combined approach of ab initio molecular dynamics and cluster expansion-based Monte Carlo simulations. We identify a kinetically accessible and thermodynamically favourable mechanism to form O 2 molecules in the bulk, involving Mn migration and driven by interlayer oxygen dimerization. At the top of charge, the bulk structure locally phase segregates into MnO 2 -rich regions and Mn-deficient nanovoids, which contain O 2 molecules as a nanoconfined fluid. These nanovoids are connected in a percolating network, potentially allowing long-range oxygen transport and linking bulk O 2 formation to surface O 2 loss. These insights highlight the importance of developing strategies to kinetically stabilize the bulk structure of Li-rich O-redox cathodes to maintain their high energy densities.
McColl et al. (2024) studied this question.