Unraveling Mechanism for Microstructure Engineering toward High‐Capacity Nickel‐Rich Cathode Materials

Abstract Microstructural engineering on nickel‐rich layered oxide (NRLO) cathode materials is considered a promising approach to increase both the capacity and lifespan of lithium‐ion batteries by introducing high valence‐state elements. However, rational regulation on NRLO microstructures based on a deep understanding of its capacity enhancement mechanism remains challenging. Herein for the first time, it is demonstrated that an increase of 14 mAh g⁻¹ in reversible capacity at the first cycle can be achieved via tailoring the micro and nano structure of NRLO through introducing tungsten. Aberration‐corrected scanning transmission electron microscopy (STEM) characterization reveals that the formation of a modified microstructure featured as coherent spinel twin boundaries. Theoretical modeling and electrochemical investigations further demonstrate that the capacity increase mechanism is related to such coherent spinel twin boundaries, which can lower the Li⁺ diffusion barrier and thus allow more Li⁺ to participate in deeper phase transitions. Meanwhile, the surface and grain boundaries of NRLOs are found to be modified by generating a dense and uniform LiW_xO_y phase, which further extends its cycle life by reducing side reactions with electrolytes. This work enables a comprehensive understanding of the capacity‐increased mechanism and endows the remarkable potential of microstructural engineering for capacity‐ and lifespan‐increased NRLOs.