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Title: Investigating the reversibility of structural modifications of LixNiyMnzCo1-y-zO₂ cathode materials during initial charge/discharge, at multiple length scales

Journal Article · · Chemistry of Materials
 [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)
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In this work, we investigate the structural modifications occurring at the bulk, subsurface, and surface scales of LixNiyMnzCo1-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 few 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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
SC00112704
OSTI ID:
1214530
Report Number(s):
BNL-108340-2015-JA; VT1201000
Journal Information:
Chemistry of Materials, Vol. 27, Issue 17; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 69 works
Citation information provided by
Web of Science

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Cited By (10)

Surface and Subsurface Reactions of Lithium Transition Metal Oxide Cathode Materials: An Overview of the Fundamental Origins and Remedying Approaches journal September 2018
In‐Depth TEM Investigation on Structural Inhomogeneity within a Primary Li x Ni 0.835 Co 0.15 Al 0.015 O 2 Particle: Origin of Capacity Decay during High‐Rate Discharge journal February 2020
Synthesis and Characterization of Core-Shell Nanocrystals of Co-Rich Cathodes journal October 2019
Kinetic Stability of Bulk LiNiO 2 and Surface Degradation by Oxygen Evolution in LiNiO 2 -Based Cathode Materials journal November 2018
Role of double interfaces in inspiring energy storage devices in CC@Ni(OH)Cl@NiO flexible electrodes journal January 2020
Using in situ and operando methods to characterize phase changes in charged lithium nickel cobalt aluminum oxide cathode materials journal January 2020
Degradation Mechanisms and Mitigation Strategies of Nickel-Rich NMC-Based Lithium-Ion Batteries journal October 2019
Probing the Nature of Li + /Ni 2+ Disorder on the Structure and Electrochemical Performance in Ni-Based Layered Oxide Cathodes journal January 2019
In‐Depth TEM Investigation on Structural Inhomogeneity within a Primary Li x Ni 0.835 Co 0.15 Al 0.015 O 2 Particle: Origin of Capacity Decay during High‐Rate Discharge journal November 2019
Overall structural modification of a layered Ni-rich cathode for enhanced cycling stability and rate capability at high voltage journal January 2019

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