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Title: Insight into the Atomic Structure of High-Voltage Spinel LiNi0.5Mn1.5O4 Cathode Material in the First Cycle

Application of high-voltage spinel LiNi0.5Mn1.5O4 cathode material is the closest and the most realistic approach to meeting the midterm goal of lithium-ion batteries for electric vehicles (EVs) and plug-in hybrid electric vehicles (HEVs). However, this application has been hampered by long-standing issues, such as capacity degradation and poor first-cycle Coulombic efficiency of LiNi0.5Mn1.5O4 cathode material. Although it is well-known that the structure of LiNi0.5Mn1.5O4 into which Li ions are reversibly intercalated plays a critical role in the above issues, performance degradation related to structural changes, particularly in the first cycle, are not fully understood. Here, we report detailed investigations of local atomic-level and average structure of LiNi0.5Mn1.5O4 during first cycle (3.5–4.9 V) at room temperature. We observed two types of local atomic-level migration of transition metals (TM) ions in the cathode of a well-prepared LiNi0.5Mn1.5O4//Li half-cell during first charge via an aberration-corrected scanning transmission electron microscopy (STEM). Surface regions (~2 nm) of the cycled LiNi0.5Mn1.5O4 particles show migration of TM ions into tetrahedral Li sites to form a Mn3O4-like structure. However, subsurface regions of the cycled particles exhibit migration of TM ions into empty octahedral sites to form a rocksalt-like structure. The migration of these TM ions are closely relatedmore » to dissolution of Ni/Mn ions and building-up of charge transfer impedance, which contribute significantly to the capacity degradation and the poor first-cycle Coulombic efficiency of spinel LiNi0.5Mn1.5O4 cathode material. Accordingly, we provide suggestions of effective stabilization of LiNi0.5Mn1.5O4 structure to obtain better electrochemical performance.« less
 [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [3]
  1. Chinese Academy of Sciences, Beijing (China)
  2. Brookhaven National Laboratory (BNL), Upton, NY (United States)
  3. CIC Energigune, Alava (Spain)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 0897-4756; R&D Project: MA453MAEA; VT1201000
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 1; Journal ID: ISSN 0897-4756
American Chemical Society (ACS)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States