Enhancing the electrochemical performance of Li-rich layered oxide Li1.13Ni0.3Mn0.57O2 via WO3 doping and accompanying spontaneous surface phase formation

• Published in: Journal of power sources 2018-01, Vol.375 (C), p.21-28
• Main Authors: Huang, Jiajia, Liu, Haodong, Hu, Tao, Meng, Ying Shirley, Luo, Jian
• Format: Article
• Language: English
• Subjects: Complexion; High energy density cathode; Li-excess layered oxide; Lithium ion batteries; Surface phase
• ISSN: 0378-7753; 1873-2755
• DOI: 10.1016/j.jpowsour.2017.11.048

WO3 doping and accompanying spontaneous formation of a surface phase can substantially improve the discharge capacity, rate capability, and cycling stability of Co-free Li-rich layered oxide Li1.13Ni0.3Mn0.57O2 cathode material. X-ray photoelectron spectroscopy, in conjunction with ion sputtering, shows that W segregates to the particle surfaces, decreases the surface Ni/Mn ratio, and changes the surface valence state. High-resolution transmission electron microscopy further suggests that W segregation increases surface structural disorder. The spontaneous and simultaneous changes in the surface structure, composition, and valence state represent the formation of a surface phase (complexion) as the preferred surface thermodynamic state. Consequently, the averaged discharge capacity is increased by ∼13% from 251 to 284 mAh g−1 at a low rate of C/20 and by ∼200% from 30 to 90 mAh g−1 at a high rate of 40C, in comparison with an undoped specimen processed under identical conditions. Moreover, after 100 cycles at a charge/discharge rate of 1C, the WO3 doped specimen retained a discharge capacity of 188 mAh g−1, being 27% higher than that of the undoped specimen. In a broader context, this work exemplifies an opportunity of utilizing spontaneously-formed surface phases as a scalable and cost-effective method to improve materials properties. •WO3 doping improves the Li1.13Ni0.3Mn0.57O2 performance via forming a surface phase.•The surface phase forms spontaneously via a facile mixing and annealing route.•The surface phase has distinct structure, composition, and valence state.•The discharge capacity is increased by ∼13% at C/20 and by ∼200% at 40C.•The spontaneously-formed surface phase also improves the cycling stability.