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Title: Using real-time electron microscopy to explore the effects of transition-metal composition on the local thermal stability in charged LixNiyMnzCo1-y-zO2 cathode materials

Journal Article · · Chemistry of Materials
 [1];  [2];  [3];  [4];  [4];  [4];  [5];  [3];  [4]
  1. Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of); Korea Inst. of Science and Technology, Seoul (Korea, Republic of)
  2. Korea Inst. of Science and Technology, Wanju-gun(Korea, Republic of)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Korea Inst. of Science and Technology, Seoul (Korea, Republic of)
  5. Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
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In this study, we use in-situ transmission electron microcopy (TEM) to investigate the thermal decomposition that occurs at the surface of charged LixNiyMnzCo1-y-zO2 (NMC) cathode materials of different composition (with y, z=0.8, 0.1 and 0.6, 0.2 and 0.4, 0.3), after they have been charged to their practical upper limit voltage (4.3V). By heating these materials inside the TEM, we are able to directly characterize near surface changes in both their electronic structure (using electron energy loss spectroscopy) and crystal structure and morphology (using electron diffraction and bright-field imaging). The most Ni-rich material (y, z = 0.8, 0.1) is found to be thermally unstable at significantly lower temperatures than the other compositions – this is manifested by changes in both the electronic structure and the onset of phase transitions at temperatures as low as 100°C. Electron energy loss spectroscopy indicates that the thermally induced reduction of Ni ions drives these changes, and that this is exacerbated by the presence of an additional redox reaction that occurs at 4.2V in the y, z = 0.8, 0.1 material. Exploration of individual particles shows that there are substantial variations in the onset temperatures and overall extent of these changes. Of the compositions studied, the composition of y, z = 0.6, 0.2 has the optimal combination of high energy density and reasonable thermal stability. The observations herein demonstrate that real time electron microscopy provide direct insight into the changes that occur in cathode materials with temperature, allowing optimization of different alloy concentrations to maximize overall performance.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC00112704
OSTI ID:
1214525
Report Number(s):
BNL-108321-2015-JA; R&D Project: EST431; KC0207010
Journal Information:
Chemistry of Materials, Vol. 27, Issue 11; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 87 works
Citation information provided by
Web of Science

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Cited By (14)

Towards deriving Ni-rich cathode and oxide-based anode materials from hydroxides by sharing a facile co-precipitation method journal January 2018
Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials journal July 2018
Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy journal August 2017
Revealing the role of NH 4 VO 3 treatment in Ni-rich cathode materials with improved electrochemical performance for rechargeable lithium-ion batteries journal January 2018
Microstructure‐Controlled Ni‐Rich Cathode Material by Microscale Compositional Partition for Next‐Generation Electric Vehicles journal February 2019
Ecofriendly Chemical Activation of Overlithiated Layered Oxides by DNA‐Wrapped Carbon Nanotubes journal January 2020
Editors' Choice—Coating-Dependent Electrode-Electrolyte Interface for Ni-Rich Positive Electrodes in Li-Ion Batteries journal January 2019
Kinetic Stability of Bulk LiNiO 2 and Surface Degradation by Oxygen Evolution in LiNiO 2 -Based Cathode Materials journal November 2018
Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies journal December 2019
Real-time monitoring of stress development during electrochemical cycling of electrode materials for Li-ion batteries: overview and perspectives journal January 2019
Using in situ and operando methods to characterize phase changes in charged lithium nickel cobalt aluminum oxide cathode materials journal January 2020
Anti‐Oxygen Leaking LiCoO 2 journal April 2019
Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy journal January 2020
Oxygen Release Degradation in Li‐Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches journal April 2019

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