Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High-Voltage LiNi0.5Mn1.5O4 Spinel Cathode Materials

Huabin Sun; Anyang Hu; Stephanie Spence; Chunguang Kuai; Dong Hou; Linqin Mu; Jue Liu; Luxi Li; Chengjun Sun; Sami Sainio; Dennis Nordlund; Wei Luo; Yunhui Huang; Feng Lin

doi:10.1002/adfm.202112279

Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High-Voltage LiNi_0.5Mn_1.5O₄ Spinel Cathode Materials

Huabin Sun, Anyang Hu, Stephanie Spence, Chunguang Kuai, Dong Hou, Linqin Mu, Jue Liu, Luxi Li, Chengjun Sun, Sami Sainio, Dennis Nordlund, Wei Luo, Yunhui Huang, Feng Lin

Powder Diffraction

Research output: Contribution to journal › Article › peer-review

44 Scopus citations

Abstract

In the spinel oxide cathode family, LiNi_0.5Mn_1.5O₄ (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.

Original language	English
Article number	2112279
Journal	Advanced Functional Materials
Volume	32
Issue number	21
DOIs	https://doi.org/10.1002/adfm.202112279
State	Published - May 19 2022

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. 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.

Funders	Funder number
Department of Chemistry startup funds
U.S. Department of Energy
Office of Science	DE‐AC02‐05CH11231, DE‐AC05‐00OR22725, DE‐AC02‐06CH11357
Basic Energy Sciences	DE‐AC02‐76SF00515
Argonne National Laboratory
Center for Advanced Materials Processing, Clarkson University
Horizon 2020 Framework Programme	841621
H2020 Marie Skłodowska-Curie Actions
Horizon 2020
Walter Ahlströmin Säätiö

Keywords

cycle life
disorder-to-order transition
fading mechanism
metal dissolution
spinel cathodes

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/adfm.202112279

Cite this

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. (2022). Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High-Voltage LiNi_0.5Mn_1.5O₄ Spinel Cathode Materials. Advanced Functional Materials, 32(21), Article 2112279. https://doi.org/10.1002/adfm.202112279

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abstract = "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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