TY - JOUR
T1 - Effects of Sulfate Modification of Stoichiometric and Lithium-Rich LiNiO2 Cathode Materials
AU - Dong, Bo
AU - Poletayev, Andrey
AU - Cottom, Jonathon
AU - Castells-Gil, Javier
AU - Spencer, Ben F
AU - Li, Cheng
AU - Zhu, Pengcheng
AU - Chen, Yongxiu
AU - Price, Jaime-Marie
AU - Driscoll, Laura
AU - Allan, Phoebe
AU - Kendrick, Emma
AU - Islam, M. Saiful
AU - Slater, Peter
N1 - Acknowledgment: We would like to thank the Faraday Institution CATMAT (FIRG016, EP/S003053/1) and NEXTRODE (FIRG015) projects for funding. We would like to thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. The XPS/HAXPES work was supported by the Henry Royce Institute, funded through EPSRC grants EP/R00661X/1, EP/P025021/1 and EP/P025498/1. We are also grateful to the HEC Materials Chemistry Consortium (EP/R029431) for the use of Archer2 high-performance computing (HPC) facilities, and for the Faraday Institution’s Michael HPC resource. A portion of this research used resources at the Spallation Neutron Source, as appropriate, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.
PY - 2024/4/4
Y1 - 2024/4/4
N2 - Lithium nickel oxide, LiNiO2, has attracted considerable interest as a high energy cathode for next generation lithium ion batteries. Nevertheless, shortcomings such as significant cycling capacity decay and low stability in ambient atmosphere have hindered its practical application, and consequently most work has focused on the more stable Mn and Co doped analogues Li(Ni,Mn,Co)O2. Here, we report an investigation of an alternative strategy, sulfate modification, in the LiNiO2 (LNO) system. We show that improved performance can be achieved, attributed to the dual effect of a low level of bulk doping and the presence of a self-passivation Li2SO4 layer formed beyond the solid solution limit. Ab initio simulations suggest that the behavior is similar to that of other high valent dopants such as W and Mo. These dual effects contribute to the improved air stability and enhanced electrochemical performance for the sulfate modified lithium-rich LNO, leading to high initial capacities (~245 mAhg-1 at 25 mA/g, and ~205 mAhg-1 at 100 mA/g) and better capacity retention. Overall, the results show that polyanion modification represents an excellent alternative low cost strategy to improve the performance of lithium nickel oxide cathode materials.
AB - Lithium nickel oxide, LiNiO2, has attracted considerable interest as a high energy cathode for next generation lithium ion batteries. Nevertheless, shortcomings such as significant cycling capacity decay and low stability in ambient atmosphere have hindered its practical application, and consequently most work has focused on the more stable Mn and Co doped analogues Li(Ni,Mn,Co)O2. Here, we report an investigation of an alternative strategy, sulfate modification, in the LiNiO2 (LNO) system. We show that improved performance can be achieved, attributed to the dual effect of a low level of bulk doping and the presence of a self-passivation Li2SO4 layer formed beyond the solid solution limit. Ab initio simulations suggest that the behavior is similar to that of other high valent dopants such as W and Mo. These dual effects contribute to the improved air stability and enhanced electrochemical performance for the sulfate modified lithium-rich LNO, leading to high initial capacities (~245 mAhg-1 at 25 mA/g, and ~205 mAhg-1 at 100 mA/g) and better capacity retention. Overall, the results show that polyanion modification represents an excellent alternative low cost strategy to improve the performance of lithium nickel oxide cathode materials.
U2 - 10.1039/D4TA00284A
DO - 10.1039/D4TA00284A
M3 - Article
SN - 2050-7488
JO - Journal of Materials Chemistry A
JF - Journal of Materials Chemistry A
ER -