Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery

Ruoqian Lin; Enyuan Hu; Mingjie Liu; Yi Wang; Hao Cheng; Jinpeng Wu; Jin Cheng Zheng; Qin Wu; Seongmin Bak; Xiao Tong; Rui Zhang; Wanli Yang; Kristin A. Persson; Xiqian Yu; Xiao Qing Yang; Huolin L. Xin

doi:10.1038/s41467-019-09248-0

Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery

Ruoqian Lin, Enyuan Hu, Mingjie Liu, Yi Wang, Hao Cheng, Jinpeng Wu, Jin Cheng Zheng, Qin Wu, Seongmin Bak, Xiao Tong, Rui Zhang, Wanli Yang, Kristin A. Persson, Xiqian Yu, Xiao Qing Yang, Huolin L. Xin

Department of Materials Science and Engineering

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

Abstract

Despite the importance of studying the instability of delithiated cathode materials, it remains difficult to underpin the degradation mechanism of lithium-rich cathode materials due to the complication of combined chemical and structural evolutions. Herein, we use state-of-the-art electron microscopy tools, in conjunction with synchrotron X-ray techniques and first-principle calculations to study a 4d-element-containing compound, Li₂Ru_0.5Mn_0.5O₃. 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. This work reveals the importance of studying the thermodynamic stability of the reconstructed film on the cathode materials and offers a theoretical guidance for choosing manganese substituting elements in lithium-rich as well as stoichiometric layer-layer compounds for stabilizing the cathode surface.

Original language	English
Article number	1650
Journal	Nature communications
Volume	10
Issue number	1
DOIs	https://doi.org/10.1038/s41467-019-09248-0
Publication status	Published - 2019 Dec 1

Bibliographical note

Funding Information:
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.

Publisher Copyright:
© 2019, The Author(s).

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Chemistry(all)
Biochemistry, Genetics and Molecular Biology(all)
Physics and Astronomy(all)

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Cite this

Lin, R., Hu, E., Liu, M., Wang, Y., Cheng, H., Wu, J., Zheng, J. C., Wu, Q., Bak, S., Tong, X., Zhang, R., Yang, W., Persson, K. A., Yu, X., Yang, X. Q., & Xin, H. L. (2019). Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery. Nature communications, 10(1), [1650]. https://doi.org/10.1038/s41467-019-09248-0

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abstract = "Despite the importance of studying the instability of delithiated cathode materials, it remains difficult to underpin the degradation mechanism of lithium-rich cathode materials due to the complication of combined chemical and structural evolutions. Herein, we use state-of-the-art electron microscopy tools, in conjunction with synchrotron X-ray techniques and first-principle calculations to study a 4d-element-containing compound, Li2Ru0.5Mn0.5O3. 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. This work reveals the importance of studying the thermodynamic stability of the reconstructed film on the cathode materials and offers a theoretical guidance for choosing manganese substituting elements in lithium-rich as well as stoichiometric layer-layer compounds for stabilizing the cathode surface.",

author = "Ruoqian Lin and Enyuan Hu and Mingjie Liu and Yi Wang and Hao Cheng and Jinpeng Wu and Zheng, {Jin Cheng} and Qin Wu and Seongmin Bak and Xiao Tong and Rui Zhang and Wanli Yang and Persson, {Kristin A.} and Xiqian Yu and Yang, {Xiao Qing} and Xin, {Huolin L.}",

note = "Funding Information: 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{\textquoteright}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. Publisher Copyright: {\textcopyright} 2019, The Author(s).",

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AU - Hu, Enyuan

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AU - Wang, Yi

AU - Cheng, Hao

AU - Wu, Jinpeng

AU - Zheng, Jin Cheng

AU - Wu, Qin

AU - Bak, Seongmin

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AU - Zhang, Rui

AU - Yang, Wanli

AU - Persson, Kristin A.

AU - Yu, Xiqian

AU - Yang, Xiao Qing

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N2 - Despite the importance of studying the instability of delithiated cathode materials, it remains difficult to underpin the degradation mechanism of lithium-rich cathode materials due to the complication of combined chemical and structural evolutions. Herein, we use state-of-the-art electron microscopy tools, in conjunction with synchrotron X-ray techniques and first-principle calculations to study a 4d-element-containing compound, Li2Ru0.5Mn0.5O3. 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. This work reveals the importance of studying the thermodynamic stability of the reconstructed film on the cathode materials and offers a theoretical guidance for choosing manganese substituting elements in lithium-rich as well as stoichiometric layer-layer compounds for stabilizing the cathode surface.

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Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery

Abstract

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