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

Journal Article · · Chemistry of Materials
 [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)
+ Show Author Affiliations

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC02-06CH11357; SC0012583; AC05-76RL01830; SC0001294
OSTI ID:
1378325
Journal Information:
Chemistry of Materials, Vol. 28, Issue 22; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 73 works
Citation information provided by
Web of Science

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Cited By (5)

Narrowing the Gap between Theoretical and Practical Capacities in Li-Ion Layered Oxide Cathode Materials journal July 2017
Review of Modified Nickel-Cobalt Lithium Aluminate Cathode Materials for Lithium-Ion Batteries journal December 2019
Understanding the role of aluminium in determining the surface structure and electrochemical performance of layered cathodes journal January 2019
Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes. journalarticle January 2019
High‐Voltage Performance of Ni‐Rich NCA Cathodes: Linking Operating Voltage with Cathode Degradation journal August 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
27 Al NMR
NCA
atom probe tomography
dynamic Jahn-Teller
paramagnetic NMR