Non-equilibrium Structural Evolution of the Lithium-Rich Li1+yMn₂O₄ Cathode within a Battery

Lithium-ion batteries are undergoing rapid development to meet the energy demands of the transportation and renewable energy-generation sectors. The capacity of a lithium-ion battery is dependent on the amount of lithium that can be reversibly incorporated into the cathode. This work directly quantifies the time- and current-dependent lithium transfer within a cathode functioning under conventional charge–discharge cycling. We examine Li1+yMn2O4 under real working conditions using in situ neutron powder diffraction and link the atomic-scale structure to the battery performance. The lithium location and content, oxygen positional parameter, and lattice parameter of the cathode are measured and linked to the battery’s charge/discharge characteristics. Lithium insertion (discharge) differs from extraction (charge), a feature that may explain the relative ease of discharge (compared with charge) of this material. An atomic-scale understanding of cathode functionality, such as revealed here, will direct improvements in battery performance at both the practical and the fundamental level.