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Title: Investigating the reversibility of structural modifications of Li xNi yMn zCo 1-y-zO₂ cathode materials during initial charge/discharge, at multiple length scales

In this work, we investigate the structural modifications occurring at the bulk, subsurface, and surface scales of Li xNi yMn zCo 1-y-zO₂ (NMC; y, z = 0.8, 0.1 and 0.4, 0.3, respectively) cathode materials during the initial charge/discharge. Various analytical tools, such as X-ray diffraction, selected-area electron diffraction, electron energy-loss spectroscopy, and high-resolution electron microscopy, are used to examine the structural properties of the NMC cathode materials at the three different scales. Cut-off voltages of 4.3 and 4.8 V are applied during the electrochemical tests as the normal and extreme conditions, respectively. The high-Ni-content NMC cathode materials exhibit unusual behaviors, which is deviate from the general redox reactions during the charge or discharge. The transition metal (TM) ions in the high-Ni-content NMC cathode materials, which are mostly Ni ions, are reduced at 4.8 V, even though TMs are usually oxidized to maintain charge neutrality upon the removal of Li. It was found that any changes in the crystallographic and electronic structures are mostly reversible down to the sub-surface scale, despite the unexpected reduction of Ni ions. However, after the discharge, traces of the phase transitions remain at the edges of the NMC cathode materials at the scale of a fewmore » nanometers (i.e., surface scale). This study demonstrates that the structural modifications in NMC cathode materials are induced by charge as well as discharge at multiple length scales. These changes are nearly reversible after the first cycle, except at the edges of the samples, which should be avoided because these highly localized changes can initiate battery degradation.« less
 [1] ;  [2] ;  [3] ;  [1] ;  [1]
  1. Korea Institute of Science and Technology (KIST), Seoul (Republic of Korea)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Institute of Advanced Composite Materials, KIST, Wanju-gun (Republic of Korea)
Publication Date:
Report Number(s):
Journal ID: ISSN 0897-4756; VT1201000
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 17; Journal ID: ISSN 0897-4756
American Chemical Society (ACS)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
25 ENERGY STORAGE; cathode materials
OSTI Identifier: