Probing the Mysterious Behavior of Tungsten as a Dopant Inside Pristine Cobalt-Free Nickel-Rich Cathode Materials |
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Authors: | Nafiseh Zaker Chenxi Geng Divya Rathore Ines Hamam Ning Chen Penghao Xiao Chongyin Yang J R Dahn Gianluigi A Botton |
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Affiliation: | 1. Department of Materials Science and Engineering, McMaster University, Hamilton, ON L8S 4M1 Canada;2. Department of Process Engineering and Applied Science, Dalhousie University, Halifax, NS B3H 4R2 Canada;3. Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS B3H 4R2 Canada;4. Department of Mechanical Engineering, Dalhousie University, Halifax, NS B3H 4R2 Canada;5. Canadian Light Source, 44 Innovation Boulevard, Saskatoon, SK S7N 2V3 Canada;6. Department of Process Engineering and Applied Science, Dalhousie University, Halifax, NS B3H 4R2 Canada
Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS B3H 4R2 Canada
Department of Mechanical Engineering, Dalhousie University, Halifax, NS B3H 4R2 Canada |
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Abstract: | 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. |
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Keywords: | coprecipitation engineered complex cathode structures Li-ion batteries mechanofusion Ni-rich cathodes tungsten dopants |
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