Revisiting Primary Particles in Layered Lithium Transition‐Metal Oxides and Their Impact on Structural Degradation

Layered lithium transition‐metal oxide materials, e.g., Li(Ni1−x−yCoxMny)O2 (NCM) and Li(Ni1−x−yCoxAly)O2, are the most promising candidates for lithium‐ion battery cathodes. They generally consist of ≈10 µm spherical particles densely packed with smaller particles (0.1–1 µm), called secondary and primary particles, respectively. The micrometer‐ to nanometer‐sized particles are critical to the battery performance because they affect the reaction capability of the cathode. Herein, the crystal structure of the primary particles of NCM materials is revisited. Elaborate transmission electron microscopy investigations reveal that the so‐called primary particles, often considered as single crystals, are in fact polycrystalline secondary particles. They contain low‐angle and exceptionally stable special grain boundaries (GBs) presumably created during aggregation via an oriented attachment mechanism. Therefore, this so‐called primary particle is renamed as primary‐like particle. More importantly, the low‐angle GBs between the smaller true primary particles cause the development of nanocracks within the primary‐like particles of Ni‐rich NCM cathodes after repetitive electrochemical cycles. In addition to rectifying a prevalent misconception about primary particles, this study provides a previously unknown but important origin of structural degradation in Ni‐rich layered cathodes. The crystal structure of primary particles in layered lithium transition‐metal oxide materials is investigated by transmission electron microscopy. The micrometer‐ to nanometer‐sized particles, the so‐called primary particles, are in fact polycrystalline secondary particles containing low‐angle and special grain boundaries. The low‐angle grain boundaries in the so‐called primary particles can cause nanocrack development after repetitive electrochemical cycles in lithium‐ion batteries.