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Title: Atomic-Resolution Visualization of Distinctive Chemical Mixing Behavior of Ni, Co and Mn with Li in Layered Lithium Transition-Metal Oxide Cathode Materials

Capacity and voltage fading of layer structured cathode based on lithium transition metal oxide is closely related to the lattice position and migration behavior of the transition metal ions. However, it is scarcely clear about the behavior of each of these transition metal ions. We report direct atomic resolution visualization of interatomic layer mixing of transition metal (Ni, Co, Mn) and lithium ions in layer structured oxide cathodes for lithium ion batteries. Using chemical imaging with aberration corrected scanning transmission electron microscope (STEM) and DFT calculations, we discovered that in the layered cathodes, Mn and Co tend to reside almost exclusively at the lattice site of transition metal (TM) layer in the structure or little interlayer mixing with Li. In contrast, Ni shows high degree of interlayer mixing with Li. The fraction of Ni ions reside in the Li layer followed a near linear dependence on total Ni concentration before reaching saturation. The observed distinctively different behavior of Ni with respect to Co and Mn provides new insights on both capacity and voltage fade in this class of cathode materials based on lithium and TM oxides, therefore providing scientific basis for selective tailoring of oxide cathode materials for enhanced performance.
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [3] ;  [4] ;  [5] ;  [1] ;  [1] ;  [1] ;  [6] ;  [1] ;  [1] ;  [2] ;  [4] ;  [1] ;  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Peking Univ., Beijing (China)
  3. Univ. of Electronic Science and Technology of China, Chengdu (China)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  6. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
OSTI Identifier:
1212242
Report Number(s):
PNNL-SA--110714
Journal ID: ISSN 0897-4756; 48379; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 27; Journal Issue: 15
Publisher:
American Chemical Society (ACS)
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
24 POWER TRANSMISSION AND DISTRIBUTION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Environmental Molecular Sciences Laboratory