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Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time-resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3̅m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3̅m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. This systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.

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The thermal instability of the cathode materials in lithium‐ion batteries is an important safety issue, requiring the incorporation of several approaches to prevent thermal runaway and combustion. Systematic studies, using combined well‐defined in situ techniques, are crucial to obtaining in‐depth understanding of the structural origin of this thermal instability in overcharged cathode materials. Here time‐resolved X‐ray diffraction, X‐ray absorption, mass spectroscopy, and high‐resolution transmission electron microscopy during heating are combined to detail the structural changes in overcharged LixNi0.8Co0.15Al0.05O2 and LixNi1/3Co1/3Mn1/3O2 cathode materials. By employing these several techniques in concert, various aspects of the structural changes are investigated in these two materials at an overcharged state; these include differences in phase‐distribution after overcharge, phase nucleation and propagation during heating, the preferred atomic sites and migration paths of Ni, Co, and Mn, and their individual contributions to thermal stability, together with measuring the oxygen release that accompanies these structural changes. These results provide valuable guidance for developing new cathode materials with improved safety characteristics.