University of Oulu

Sun, H., Hu, A., Spence, S., Kuai, C., Hou, D., Mu, L., Liu, J., Li, L., Sun, C., Sainio, S., Nordlund, D., Luo, W., Huang, Y., Lin, F., Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High-Voltage LiNi0.5Mn1.5O4 Spinel Cathode Materials. Adv. Funct. Mater. 2022, 32, 2112279.

Tailoring disordered/ordered phases to revisit the degradation mechanism of high-voltage LiNi0.5Mn1.5O4 spinel cathode materials

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Author: Sun, Huabin1,2; Hu, Anyang1; Spence, Stephanie1;
Organizations: 1Department of Chemistry, Virginia Tech, Blacksburg, VA, 24061 USA
2Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai, 201804 China
3Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831 USA
4Advanced Photon Source, Argonne National Laboratory, Argonne, IL, 60439 USA
5Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, 94025 USA
6Microelectronics Research Unit, Faculty of Information Technology and Electrical Engineering University of Oulu, P.O. Box. 4500, Oulu, 90570 Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 3.5 MB)
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Language: English
Published: , 2022
Publish Date: 2022-07-19


In the spinel oxide cathode family, LiNi0.5Mn1.5O4 (LNMO) shows a high operating voltage (≈4.7 V vs Li/Li⁺) and excellent Li-ion mobility with stable 3D conducting channels. Ni/Mn cation disordered and ordered phases usually coexist in LNMO materials, and they have distinct structural and electrochemical properties, resulting in different battery performances for LNMO materials with different phase compositions. Identifying the correlation between phase compositions and electrochemical properties is of significance to the improvement of battery performance and understanding of degradation mechanisms. Herein, the disordered/ordered phase compositions in LNMO materials are tailored by post-annealing strategies and their impacts on electrochemical performance and degradation mechanisms from the surface to the bulk are systematically investigated. The ordered phase increases rapidly as Mn³⁺ is oxidized to Mn⁴⁺ through a post-annealing process. LNMO with an intermediate fraction of disordered and ordered phases gives rise to improved cycling stability. This article further reports that a high ordered phase fraction can preferentially protect Ni from dissolution during cycling. However, these results suggest that the transition metal dissolution and surface structural change of LNMO do not exhibit a direct correlation with cycling stability. These results indicate the capacity fading mainly correlates with the bulk structural distortion, leading to decreased Li-ion kinetics.

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Volume: 32
Issue: 21
Article number: 2112279
DOI: 10.1002/adfm.202112279
Type of Publication: A1 Journal article – refereed
Field of Science: 216 Materials engineering
114 Physical sciences
Funding: The work at Virginia Tech was supported by Department of Chemistry startup funds. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The pristine LNMO powder was produced at the U.S. Department of Energy's (DOE) CAMP (Cell Analysis, Modeling and Prototyping) Facility, Argonne National Laboratory. The CAMP Facility is fully supported by the DOE Vehicle Technologies Program (VTP) within the core funding of the Applied Battery Research (ABR) for Transportation Program. This research used resources of the Advanced Photon Sources at Argonne National Laboratory, which is a U.S. DOE Office of Science User Facility under contract No. DE-AC02-06CH11357. The use of the Spallation Neutron Source at Oak Ridge National Laboratory was supported by the U.S. DOE Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC05-00OR22725. This research used resources of the Advanced Light Source at Lawrence Berkeley National Laboratory, which is a U.S. DOE Office of Science User Facility under contract No. DE-AC02-05CH11231. The authors thank Dr. Gi-Hyeok Lee and Dr. Wanli Yang for fruitful discussion and soft XAS experiments. S.S. acknowledges funding from the Walter Ahlström Foundation. S.S. received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 841621.
Copyright information: © 2022 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.