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Title: Identifying the Distribution of Al 3+ in LiNi 0.8 Co 0.15 Al 0.05 O 2

The doping of Al into layered Li transition metal (TM) oxide cathode materials, LiTMO 2, is known to improve the structural and thermal stability, although the origin of the enhanced properties is not well understood. We have investigated the effect of aluminum doping on layer stabilization using a combination of techniques to measure the aluminum distribution in layered LiNi 0.8Co 0.15Al 0.05O 2 (NCA) over multiple length scales with 27Al and 7Li MAS NMR, local electron atom probe (LEAP) tomography, X-ray and neutron diffraction, DFT, and SQUID magnetic susceptibility measurements. LEAP tomographic maps show a homogenous distribution of Ni, Co, Al and O 2 throughout the structure at the particle level in agreement with the hightemperature phase diagram. 7Li and 27Al NMR indicates that the Ni 3+ ions undergo a dynamic Jahn-Teller (JT) distortion. 27Al NMR spectra indicate that the Al reduces the strain associated with the JT distortion, by preferential electronic ordering of the JT long bonds directed toward the Al 3+ ion. Our ability to understand the complex atomic and orbital ordering around Al 3+ demonstrated in the current method will be useful for studying the local environment of Al 3+ in a range of transition metal oxidemore » battery materials.« less
Authors:
 [1] ;  [1] ;  [2] ;  [3] ;  [4] ;  [3] ;  [5] ;  [3] ;  [6] ;  [4] ;  [4] ;  [4] ;  [5] ;  [3] ;  [2] ;  [1]
  1. Univ. of Cambridge (United Kingdom). Dept. of Chemistry
  2. Univ. of California, Santa Barbara, CA (United States). Materials Dept.
  3. Univ. of California, San Diego, CA (United States). Dept. of NanoEngineering
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source
  5. State Univ. of New York (SUNY), Binghamton, NY (United States). Inst. for Materials Research
  6. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357; SC0012583; AC05-76RL01830
Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 22; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 27 Al NMR; NCA; atom probe tomography; dynamic Jahn-Teller; paramagnetic NMR
OSTI Identifier:
1378325

Trease, Nicole M., Seymour, Ieuan D., Radin, Maxwell D., Liu, Haodong, Liu, Hao, Hy, Sunny, Chernova, Natalya, Parikh, Pritesh, Devaraj, Arun, Wiaderek, Kamila M., Chupas, Peter J., Chapman, Karena W., Whittingham, M. Stanley, Meng, Ying Shirley, Van der Van, Anton, and Grey, Clare P.. Identifying the Distribution of Al 3+ in LiNi 0.8 Co 0.15 Al 0.05 O 2. United States: N. p., Web. doi:10.1021/acs.chemmater.6b02797.
Trease, Nicole M., Seymour, Ieuan D., Radin, Maxwell D., Liu, Haodong, Liu, Hao, Hy, Sunny, Chernova, Natalya, Parikh, Pritesh, Devaraj, Arun, Wiaderek, Kamila M., Chupas, Peter J., Chapman, Karena W., Whittingham, M. Stanley, Meng, Ying Shirley, Van der Van, Anton, & Grey, Clare P.. Identifying the Distribution of Al 3+ in LiNi 0.8 Co 0.15 Al 0.05 O 2. United States. doi:10.1021/acs.chemmater.6b02797.
Trease, Nicole M., Seymour, Ieuan D., Radin, Maxwell D., Liu, Haodong, Liu, Hao, Hy, Sunny, Chernova, Natalya, Parikh, Pritesh, Devaraj, Arun, Wiaderek, Kamila M., Chupas, Peter J., Chapman, Karena W., Whittingham, M. Stanley, Meng, Ying Shirley, Van der Van, Anton, and Grey, Clare P.. 2016. "Identifying the Distribution of Al 3+ in LiNi 0.8 Co 0.15 Al 0.05 O 2". United States. doi:10.1021/acs.chemmater.6b02797. https://www.osti.gov/servlets/purl/1378325.
@article{osti_1378325,
title = {Identifying the Distribution of Al 3+ in LiNi 0.8 Co 0.15 Al 0.05 O 2},
author = {Trease, Nicole M. and Seymour, Ieuan D. and Radin, Maxwell D. and Liu, Haodong and Liu, Hao and Hy, Sunny and Chernova, Natalya and Parikh, Pritesh and Devaraj, Arun and Wiaderek, Kamila M. and Chupas, Peter J. and Chapman, Karena W. and Whittingham, M. Stanley and Meng, Ying Shirley and Van der Van, Anton and Grey, Clare P.},
abstractNote = {The doping of Al into layered Li transition metal (TM) oxide cathode materials, LiTMO2, is known to improve the structural and thermal stability, although the origin of the enhanced properties is not well understood. We have investigated the effect of aluminum doping on layer stabilization using a combination of techniques to measure the aluminum distribution in layered LiNi0.8Co0.15Al0.05O2 (NCA) over multiple length scales with 27Al and 7Li MAS NMR, local electron atom probe (LEAP) tomography, X-ray and neutron diffraction, DFT, and SQUID magnetic susceptibility measurements. LEAP tomographic maps show a homogenous distribution of Ni, Co, Al and O2 throughout the structure at the particle level in agreement with the hightemperature phase diagram. 7Li and 27Al NMR indicates that the Ni3+ ions undergo a dynamic Jahn-Teller (JT) distortion. 27Al NMR spectra indicate that the Al reduces the strain associated with the JT distortion, by preferential electronic ordering of the JT long bonds directed toward the Al3+ ion. Our ability to understand the complex atomic and orbital ordering around Al3+ demonstrated in the current method will be useful for studying the local environment of Al3+ in a range of transition metal oxide battery materials.},
doi = {10.1021/acs.chemmater.6b02797},
journal = {Chemistry of Materials},
number = 22,
volume = 28,
place = {United States},
year = {2016},
month = {10}
}