Anomalous Segregation in Lithium-Rich Layered Oxide Uncovers New Theoretical Design Rule for Stable Cathode in Lithium-Ion Battery

Abstract

Here we report the TEM, X-ray, and first-principle investigation of a promising high-capacity lithium-rich 3d-4d (Mn-Ru) transition-metal layered compound. The incorporation of 4d transition metals here offers an uncharted phase space for mechanistic exploration as compared to the well documented 3d transition metal (TM) oxides. Using state-of-the-art electron and X-ray based techniques, we find surprisingly, after cycling, ruthenium segregates out as metallic nanoclusters on the reconstructed surface. Our calculations show that the unexpected ruthenium metal segregation is due to its thermodynamic insolubility in the oxygen deprived surface. This insolubility can disrupt the reconstructed surface, which explains the formation of a porous structure in this material. The revealed mechanism allows us to provide predictive guidance for the future design of lithium-rich as well as stoichiometric layered cathode materials. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, and the Scientific Data and Computing Center, a component of the Computational Science Initiative, at Brookhaven National Laboratory under Contract No. DE-SC0012704. Dr. Enyuan Hu, Dr. Seongmin Bak, and Dr. Xiao-Qing Yang were supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program, including Battery500 Consortium under Contract DE-SC0012704. Work done by R.Z. is partially supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Award Number: DE-EE0008444. The work at IOP was supported by funding from Ministry of Science and Technology of China (Grants 2016YFA0202500) and the National Natural Science Foundation of China (51822211). H.C. and J-C.Z. were supported by the National Natural Science Foundation of China (51661135011). This research used resources 8-ID, 23-ID-2, and 28-ID-2 of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. This research used resources of beamline 8.0.1 of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. We acknowledge the technical support from beamline scientists Dr. Jianming Bai and Dr. Eric Dooryhee at the XPD beamline of NSLSII.