Identifying the chemical and structural irreversibility in LiNi0.8Co0.15Al0.05O2-a model compound for classical layered intercalation

Haodong Liu; Hao Liu; Ieuan D. Seymour; Natasha Chernova; Kamila M. Wiaderek; Nicole M. Trease; Sunny Hy; Yan Chen; Ke An; Minghao Zhang; Olaf J. Borkiewicz; Saul H. Lapidus; Bao Qiu; Yonggao Xia; Zhaoping Liu; Peter J. Chupas; Karena W. Chapman; M. Stanley Whittingham; Clare P. Grey; Ying Shirley Meng

doi:10.1039/c7ta10829j

Identifying the chemical and structural irreversibility in LiNi_0.8Co_0.15Al_0.05O₂-a model compound for classical layered intercalation

Haodong Liu, Hao Liu, Ieuan D. Seymour, Natasha Chernova, Kamila M. Wiaderek, Nicole M. Trease, Sunny Hy, Yan Chen, Ke An, Minghao Zhang, Olaf J. Borkiewicz, Saul H. Lapidus, Bao Qiu, Yonggao Xia, Zhaoping Liu, Peter J. Chupas, Karena W. Chapman, M. Stanley Whittingham, Clare P. Grey, Ying Shirley Meng^* (Corresponding Author)

^*Corresponding author for this work

Chemistry

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

48 Citations (Scopus)

Abstract

In this work, we extracted 95% of the electrochemically available Li from LiNi_0.8Co_0.15Al_0.05O₂ (NCA) by galvanostatically charging the NCA/MCMB full cell to 4.7 V. Joint powder X-ray and neutron diffraction (XRD & ND) studies were undertaken for NCA at highly charged states at the first cycle, and discharged states at different cycles. The results indicate that the bulk structure of NCA maintains the O3 structure up to the extraction of 0.90 Li per formula unit. In addition, we found that the transition metal layer becomes more disordered along the c-axis than along the a- and b-axes upon charging. This anisotropic disorder starts to develop no later than 4.3 V on charge and continues to grow until the end of charge. As Li is re-inserted during discharge, the structure that resembles the pristine NCA is recovered. The irreversible loss of Li and the migration of Ni to the Li layer have been quantified by the joint XRD and ND refinement and the results were further verified by solid state ⁷Li NMR and magnetic measurements. Our work clearly demonstrates that the NCA bulk retains a robust, single phase O3 structure throughout the wide delithiation range (up to 0.9 Li per formula unit of NCA) and is suitable for higher energy density usage with proper modifications.

Original language	English
Pages (from-to)	4189-4198
Number of pages	10
Journal	Journal of Materials Chemistry A
Volume	6
Issue number	9
DOIs	https://doi.org/10.1039/c7ta10829j
Publication status	Published - 7 Feb 2018

Bibliographical note

Funding Information:
This work was supported by the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award no. DE-SC0012583. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 and the resources of the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The neutron experiments benefited from the SNS user facility, sponsored by the office of Basic Energy Sciences (BES), the Office of Science of the DOE.

Funding Information:
This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).

Publisher Copyright:
© 2018 The Royal Society of Chemistry.

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Cite this

Liu, H., Liu, H., Seymour, I. D., Chernova, N., Wiaderek, K. M., Trease, N. M., Hy, S., Chen, Y., An, K., Zhang, M., Borkiewicz, O. J., Lapidus, S. H., Qiu, B., Xia, Y., Liu, Z., Chupas, P. J., Chapman, K. W., Whittingham, M. S., Grey, C. P., & Meng, Y. S. (2018). Identifying the chemical and structural irreversibility in LiNi_0.8Co_0.15Al_0.05O₂-a model compound for classical layered intercalation. Journal of Materials Chemistry A, 6(9), 4189-4198. https://doi.org/10.1039/c7ta10829j

Liu, H, Liu, H, Seymour, ID, Chernova, N, Wiaderek, KM, Trease, NM, Hy, S, Chen, Y, An, K, Zhang, M, Borkiewicz, OJ, Lapidus, SH, Qiu, B, Xia, Y, Liu, Z, Chupas, PJ, Chapman, KW, Whittingham, MS, Grey, CP & Meng, YS 2018, 'Identifying the chemical and structural irreversibility in LiNi_0.8Co_0.15Al_0.05O₂-a model compound for classical layered intercalation', Journal of Materials Chemistry A, vol. 6, no. 9, pp. 4189-4198. https://doi.org/10.1039/c7ta10829j

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title = "Identifying the chemical and structural irreversibility in LiNi0.8Co0.15Al0.05O2-a model compound for classical layered intercalation",

abstract = "In this work, we extracted 95% of the electrochemically available Li from LiNi0.8Co0.15Al0.05O2 (NCA) by galvanostatically charging the NCA/MCMB full cell to 4.7 V. Joint powder X-ray and neutron diffraction (XRD & ND) studies were undertaken for NCA at highly charged states at the first cycle, and discharged states at different cycles. The results indicate that the bulk structure of NCA maintains the O3 structure up to the extraction of 0.90 Li per formula unit. In addition, we found that the transition metal layer becomes more disordered along the c-axis than along the a- and b-axes upon charging. This anisotropic disorder starts to develop no later than 4.3 V on charge and continues to grow until the end of charge. As Li is re-inserted during discharge, the structure that resembles the pristine NCA is recovered. The irreversible loss of Li and the migration of Ni to the Li layer have been quantified by the joint XRD and ND refinement and the results were further verified by solid state 7Li NMR and magnetic measurements. Our work clearly demonstrates that the NCA bulk retains a robust, single phase O3 structure throughout the wide delithiation range (up to 0.9 Li per formula unit of NCA) and is suitable for higher energy density usage with proper modifications.",

author = "Haodong Liu and Hao Liu and Seymour, {Ieuan D.} and Natasha Chernova and Wiaderek, {Kamila M.} and Trease, {Nicole M.} and Sunny Hy and Yan Chen and Ke An and Minghao Zhang and Borkiewicz, {Olaf J.} and Lapidus, {Saul H.} and Bao Qiu and Yonggao Xia and Zhaoping Liu and Chupas, {Peter J.} and Chapman, {Karena W.} and Whittingham, {M. Stanley} and Grey, {Clare P.} and Meng, {Ying Shirley}",

note = "Funding Information: This work was supported by the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award no. DE-SC0012583. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 and the resources of the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The neutron experiments benefited from the SNS user facility, sponsored by the office of Basic Energy Sciences (BES), the Office of Science of the DOE. Funding Information: This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). Publisher Copyright: {\textcopyright} 2018 The Royal Society of Chemistry.",

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T1 - Identifying the chemical and structural irreversibility in LiNi0.8Co0.15Al0.05O2-a model compound for classical layered intercalation

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AU - Liu, Hao

AU - Seymour, Ieuan D.

AU - Chernova, Natasha

AU - Wiaderek, Kamila M.

AU - Trease, Nicole M.

AU - Hy, Sunny

AU - Chen, Yan

AU - An, Ke

AU - Zhang, Minghao

AU - Borkiewicz, Olaf J.

AU - Lapidus, Saul H.

AU - Qiu, Bao

AU - Xia, Yonggao

AU - Liu, Zhaoping

AU - Chupas, Peter J.

AU - Chapman, Karena W.

AU - Whittingham, M. Stanley

AU - Grey, Clare P.

AU - Meng, Ying Shirley

N1 - Funding Information: This work was supported by the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award no. DE-SC0012583. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 and the resources of the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The neutron experiments benefited from the SNS user facility, sponsored by the office of Basic Energy Sciences (BES), the Office of Science of the DOE. Funding Information: This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). Publisher Copyright: © 2018 The Royal Society of Chemistry.

PY - 2018/2/7

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N2 - In this work, we extracted 95% of the electrochemically available Li from LiNi0.8Co0.15Al0.05O2 (NCA) by galvanostatically charging the NCA/MCMB full cell to 4.7 V. Joint powder X-ray and neutron diffraction (XRD & ND) studies were undertaken for NCA at highly charged states at the first cycle, and discharged states at different cycles. The results indicate that the bulk structure of NCA maintains the O3 structure up to the extraction of 0.90 Li per formula unit. In addition, we found that the transition metal layer becomes more disordered along the c-axis than along the a- and b-axes upon charging. This anisotropic disorder starts to develop no later than 4.3 V on charge and continues to grow until the end of charge. As Li is re-inserted during discharge, the structure that resembles the pristine NCA is recovered. The irreversible loss of Li and the migration of Ni to the Li layer have been quantified by the joint XRD and ND refinement and the results were further verified by solid state 7Li NMR and magnetic measurements. Our work clearly demonstrates that the NCA bulk retains a robust, single phase O3 structure throughout the wide delithiation range (up to 0.9 Li per formula unit of NCA) and is suitable for higher energy density usage with proper modifications.

AB - In this work, we extracted 95% of the electrochemically available Li from LiNi0.8Co0.15Al0.05O2 (NCA) by galvanostatically charging the NCA/MCMB full cell to 4.7 V. Joint powder X-ray and neutron diffraction (XRD & ND) studies were undertaken for NCA at highly charged states at the first cycle, and discharged states at different cycles. The results indicate that the bulk structure of NCA maintains the O3 structure up to the extraction of 0.90 Li per formula unit. In addition, we found that the transition metal layer becomes more disordered along the c-axis than along the a- and b-axes upon charging. This anisotropic disorder starts to develop no later than 4.3 V on charge and continues to grow until the end of charge. As Li is re-inserted during discharge, the structure that resembles the pristine NCA is recovered. The irreversible loss of Li and the migration of Ni to the Li layer have been quantified by the joint XRD and ND refinement and the results were further verified by solid state 7Li NMR and magnetic measurements. Our work clearly demonstrates that the NCA bulk retains a robust, single phase O3 structure throughout the wide delithiation range (up to 0.9 Li per formula unit of NCA) and is suitable for higher energy density usage with proper modifications.

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