Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

Dawei Wang; Ronghui Kou; Yang Ren; Cheng-Jun Sun; Hu Zhao; Ming-Jian Zhang; Yan Li; Ashifia Huq; J Y Peter Ko; Feng Pan; Yang-Kook Sun; Yong Yang; Khalil Amine; Jianming Bai; Zonghai Chen; Feng Wang

doi:10.1002/adma.201606715

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

Adv Mater. 2017 Oct;29(39). doi: 10.1002/adma.201606715. Epub 2017 Aug 25.

Authors

Dawei Wang^{1

2}, Ronghui Kou³, Yang Ren³, Cheng-Jun Sun³, Hu Zhao¹, Ming-Jian Zhang^{1

4}, Yan Li⁵, Ashifia Huq⁶, J Y Peter Ko⁷, Feng Pan⁴, Yang-Kook Sun⁸, Yong Yang², Khalil Amine⁵, Jianming Bai⁹, Zonghai Chen⁵, Feng Wang¹

Affiliations

¹ Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton, NY, 11973, USA.
² Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen, Fujian, 361005, China.
³ X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL, 60439, USA.
⁴ School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen, Guangdong, 518055, P. R. China.
⁵ Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, 60439, USA.
⁶ Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
⁷ The Cornell High Energy Synchrotron Source, Cornell University, Ithaca, NY, 14853, USA.
⁸ Department of Energy Engineering, Hanyang University, Seoul, 133-791, South Korea.
⁹ National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, 11973, USA.

PMID: 28841754
DOI: 10.1002/adma.201606715

Abstract

Nickel-rich layered transition metal oxides, LiNi_1-_x (MnCo)_x O₂ (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi_0.7 Mn_0.15 Co_0.15 O₂ (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs.

Keywords: X-ray absorption spectroscopy; cationic ordering; high-energy X-ray diffraction; layered oxide cathodes; lithium-ion batteries.