Probing the Mysterious Behavior of Tungsten as a Dopant Inside Pristine Cobalt‐Free Nickel‐Rich Cathode Materials

Nickel‐rich cathode materials with small amounts of tungsten (W) dopants have attracted extensive attention in recent years. However, the chemical state, crystalline form, compound chemistry, and location of W in these layered cathodes are still not well‐understood. In this study, these missing structural properties are determined through a combination of macro‐, to atomic‐sensitive characterization techniques and density functional theory (DFT). W‐doped LiNiO2 (LNO) particles, prepared with mechanofusion and coprecipitation methods, are used to probe changes in the structure and location of W‐species. The results indicate that W is mainly distributed on the surfaces and inside grain boundaries of the secondary particles, regardless of the doping method. Electron energy loss spectroscopy (EELS) mapping confirms the simultaneous presence of W, O, with and without Ni in the grain boundaries as well as W‐ and O‐rich regions on the very surface. The W‐rich areas inside the grain boundaries are found to be in two forms, crystalline and amorphous. This paper suggests the presence of kinetically stabilized‐Li4+xNi1‐xWO6 (x = 0, 0.1) with the possibility of LixWyOz phases in LNO which are consistent with the electron microscopy, X‐ray absorption and diffraction data. The multiple roles of W in this complex microstructure are discussed considering the W distribution. The location and form of tungsten (W) used as a dopant within Ni‐rich cathode materials is a debated topic in the field of engineered cathode structures. In this study, synchrotron X‐ray and electron‐based characterization techniques are used to reveal that W is preferably located on very thin layers on the surface and within the grain boundaries of the cathode secondary particles.