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Observation of Electron-Beam-Induced Phase Evolution Mimicking the Effect of the Charge–Discharge Cycle in Li-Rich Layered Cathode Materials Used for Li Ion Batteries

Journal Article · · Chemistry of Materials
DOI:https://doi.org/10.1021/cm5045573· OSTI ID:1185001
 [1];  [2];  [1];  [1];  [3];  [2]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environmental Directorate
+ Show Author Affiliations
Capacity loss, and voltage decrease upon electrochemical charge-discharge cycling observed in lithium-rich layered cathode oxides (Li[LixMnyTM1-x-y]O2, TM = Ni, Co or Fe) have recently been attributed to the formation of a surface reconstructed layer (SRL) that evolves from a thin (<2 nm), defect spinel layer upon the first charge, to a relatively thick (~5nm), spinel or rock-salt layer upon continuous charge-discharge cycling. Here we report observations of a SRL and structural evolution of the SRL on the Li[Li0.2Ni0.2Mn0.6]O2 (LNMO) particles, which are identical to those reported due to the charge-discharge cycle but are a result of electron-beam irradiation during scanning transmission electron microscopy (STEM) imaging. Sensitivity of the lithium-rich layered oxides to high-energy electrons leads to the formation of thin, defect spinel layer on surfaces of the particles when exposed to a 200kV electron beam for as little as 30 seconds under normal high-resolution STEM imaging conditions. Further electron irradiation produces a thicker layer of the spinel phase, ultimately producing a rock-salt layer at a higher electron exposure. Atomic-scale chemical mapping by electron dispersive X-ray spectroscopy in STEM indicates the electron-beam-induced SRL formation on LNMO is accomplished by migration of the transition metal ions to the Li sites without breaking down the lattice. The observation through this study provides an insight for understanding the mechanism of forming the SRL and also possibly a mean to study structural evolution in the Li-rich layered oxides without involving the electrochemistry.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1185001
Alternate ID(s):
OSTI ID: 1184938
Report Number(s):
SAND--2014-20362J; 547707
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 4 Vol. 27; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (6)

Narrowing the Gap between Theoretical and Practical Capacities in Li-Ion Layered Oxide Cathode Materials journal July 2017
Oxygen Release Degradation in Li‐Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches journal April 2019
Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries journal March 2018
Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries journal April 2017
Crystal structural design of exposed planes: express channels, high-rate capability cathodes for lithium-ion batteries journal January 2018
Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes journal January 2019

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