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Title: Identifying the chemical and structural irreversibility in LiNi 0.8 Co 0.15 Al 0.05 O 2 – a model compound for classical layered intercalation

Abstract

In this work, we extracted 95% of the electrochemically available Li from LiNi 0.8Co 0.15Al 0.05O 2 (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. Thus, our work clearly demonstrates that the NCA bulk retains a robust, single phase O3 structure throughout the wide delithiation range (up tomore » 0.9 Li per formula unit of NCA) and is suitable for higher energy density usage with proper modifications.« less

Authors:
 [1];  [2];  [3];  [4];  [2]; ORCiD logo [3];  [1];  [5];  [5];  [1];  [2];  [2]; ORCiD logo [6]; ORCiD logo [6]; ORCiD logo [6];  [2]; ORCiD logo [2];  [4];  [3]; ORCiD logo [1]
  1. Univ. of California, San Diego, CA (United States). Dept. of NanoEngineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS). X-ray Science Division
  3. Univ. of Cambridge (United Kingdom). Dept. of Chemistry
  4. State Univ. of New York (SUNY), Binghamton, NY (United States). Inst. for Materials Research
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  6. Chinese Academy of Sciences (CAS) Ningbo Inst. of Materials Technology and Engineering (NIMTE), Ningbo (China). Advanced Li-ion Battery Engineering Lab. and Key Lab. of Graphene Technologies and Applications
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1427639
Alternate Identifier(s):
OSTI ID: 1429894
Grant/Contract Number:  
AC05-00OR22725; SC0012583; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 9; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE; 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Haodong, Liu, Hao, Seymour, Ieuan D., Chernova, Natasha, Wiaderek, Kamila M., Trease, Nicole M., Hy, Sunny, Chen, Yan, An, Ke, Zhang, Minghao, Borkiewicz, Olaf J., Lapidus, Saul H., Qiu, Bao, Xia, Yonggao, Liu, Zhaoping, Chupas, Peter J., Chapman, Karena W., Whittingham, M. Stanley, Grey, Clare P., and Meng, Ying Shirley. Identifying the chemical and structural irreversibility in LiNi 0.8 Co 0.15 Al 0.05 O 2 – a model compound for classical layered intercalation. United States: N. p., 2018. Web. doi:10.1039/C7TA10829J.
Liu, Haodong, Liu, Hao, Seymour, Ieuan D., Chernova, Natasha, Wiaderek, Kamila M., Trease, Nicole M., Hy, Sunny, Chen, Yan, An, Ke, Zhang, Minghao, Borkiewicz, Olaf J., Lapidus, Saul H., Qiu, Bao, Xia, Yonggao, Liu, Zhaoping, Chupas, Peter J., Chapman, Karena W., Whittingham, M. Stanley, Grey, Clare P., & Meng, Ying Shirley. Identifying the chemical and structural irreversibility in LiNi 0.8 Co 0.15 Al 0.05 O 2 – a model compound for classical layered intercalation. United States. doi:10.1039/C7TA10829J.
Liu, Haodong, Liu, Hao, Seymour, Ieuan D., Chernova, Natasha, Wiaderek, Kamila M., Trease, Nicole M., Hy, Sunny, Chen, Yan, An, Ke, Zhang, Minghao, Borkiewicz, Olaf J., Lapidus, Saul H., Qiu, Bao, Xia, Yonggao, Liu, Zhaoping, Chupas, Peter J., Chapman, Karena W., Whittingham, M. Stanley, Grey, Clare P., and Meng, Ying Shirley. Wed . "Identifying the chemical and structural irreversibility in LiNi 0.8 Co 0.15 Al 0.05 O 2 – a model compound for classical layered intercalation". United States. doi:10.1039/C7TA10829J. https://www.osti.gov/servlets/purl/1427639.
@article{osti_1427639,
title = {Identifying the chemical and structural irreversibility in LiNi 0.8 Co 0.15 Al 0.05 O 2 – a model compound for classical layered intercalation},
author = {Liu, Haodong and Liu, Hao and Seymour, Ieuan D. and Chernova, Natasha and Wiaderek, Kamila M. and Trease, Nicole M. and Hy, Sunny and Chen, Yan and An, Ke and Zhang, Minghao and Borkiewicz, Olaf J. and Lapidus, Saul H. and Qiu, Bao and Xia, Yonggao and Liu, Zhaoping and Chupas, Peter J. and Chapman, Karena W. and Whittingham, M. Stanley and Grey, Clare P. and Meng, Ying Shirley},
abstractNote = {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. Thus, 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.},
doi = {10.1039/C7TA10829J},
journal = {Journal of Materials Chemistry. A},
number = 9,
volume = 6,
place = {United States},
year = {2018},
month = {2}
}

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Cited by: 7 works
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Figures / Tables:

Figure 1 Figure 1: X-ray and Neutron diffraction data joint refinement of NCA at 4.7V on first charge. a) Neutron and c) X-ray refinement from isotropic atomic displacement parameters model, b) Neutron and d) X-ray refinement from anisotropic atomic displacement parameters model.

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