Substantial oxygen loss and chemical expansion in lithium-rich layered oxides at moderate delithiation

Delithiation of layered oxide electrodes triggers irreversible oxygen loss, one of the primary degradation modes in lithium-ion batteries. However, the delithiation-dependent mechanisms of oxygen loss remain poorly understood. Here we investigate the oxygen non-stoichiometry in Li_1.18–xNi_0.21Mn_0.53Co_0.08O_2–δ electrodes as a function of Li content by using cycling protocols with long open-circuit voltage steps at varying states of charge. Surprisingly, we observe substantial oxygen loss even at moderate delithiation, corresponding to 2.5, 4.0 and 7.6 ml O₂ per gram of Li_1.18–xNi_0.21Mn_0.53Co_0.08O_2–δ after resting at upper capacity cut-offs of 135, 200 and 265 mAh g⁻¹ for 100 h. Our observations suggest an intrinsic oxygen instability consistent with predictions of high oxygen activity at intermediate potentials versus Li/Li⁺. In addition, we observe a large chemical expansion coefficient with respect to oxygen non-stoichiometry, which is about three times greater than those of classical oxygen-deficient materials such as fluorite and perovskite oxides. Our work challenges the conventional wisdom that deep delithiation is a necessary condition for oxygen loss in layered oxide electrodes and highlights the importance of calendar ageing for investigating oxygen stability.