Atomic-Level Changes during Electrochemical Cycling of Oriented LiMn₂O₄ Cathodic Thin Films

Spinel LiMn₂O₄ is an attractive lithium-ion battery cathode material that undergoes a complex series of structural changes during electrochemical cycling that lead to rapid capacity fading, compromising its long-term performance. To gain insights into this behavior, in this report we analyze changes in epitaxial LiMn₂O₄ thin films during the first few charge-discharge cycles with atomic resolution and correlate them with changes in the electrochemical properties. Impedance spectroscopy and scanning transmission electron microscopy are used to show that defect-rich LiMn₂O₄ surfaces contribute greatly to the increased resistivity of the battery after only a single charge. Sequences of {111} stacking faults within the films were also observed upon charging, increasing in number with further cycling. The atomic structures of these stacking faults are reported for the first time, showing that Li deintercalation is accompanied by local oxygen loss and relaxation of Mn atoms onto previously unoccupied sites. The stacking faults have a more compressed structure than the spinel matrix and impede Li-ion migration, which explains the observed increase in thin-film resistivity as the number of cycles increases. These results are used to identify key factors contributing to conductivity degradation and capacity fading in LiMn₂O₄ cathodes, highlighting the need to develop techniques that minimize defect formation in spinel cathodes to improve cycle performance.