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Title: Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale

Journal Article · · Journal of Materials Chemistry. A
DOI:https://doi.org/10.1039/C4TA06856D· OSTI ID:1214471
 [1];  [2];  [3];  [4];  [5];  [2];  [2]
  1. General Motors Global R&D Center, Warren, MI (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Washington, Seattle, WA (United States)
  4. Optimal, Inc., Plymouth, MI (United States)
  5. Optimal, Inc. Plymouth, MI (United States)
+ Show Author Affiliations

Li-rich layered oxides hold great promise for improving the energy density of present-day Li-ion batteries. However, their application is limited by the voltage decay upon cycling, and the origin of such a phenomenon is poorly understood. A major issue is determining the voltage range over which detrimental reactions originate. In the present study, a unique yet effective approach was employed to probe this issue. Instead of studying the materials during the first cycle, electrochemical behavior and evolution of the atomic structures were compared in extensively cycled specimens under varied charge/discharge voltages. With the upper cutoff voltage lowered from 4.8 to 4.4 V, the voltage decay ceased to occur even after 60 cycles. In the meantime, the material maintained its layered structure without any spinel phase emerging at the surface, which is unambiguously shown by the atomic-resolution Z-contrast imaging and electron energy loss spectroscopy. These results have conclusively demonstrated that structural/chemical changes responsible for the voltage decay began between 4.4 and 4.8 V, where the layered-to-spinel transition was the most dramatic structural change observed. Thus, this discovery lays important groundwork for the mechanistic understanding of the voltage decay in Li-rich layered cathode materials.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1214471
Journal Information:
Journal of Materials Chemistry. A, Vol. 3, Issue 10; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 76 works
Citation information provided by
Web of Science

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Cited By (18)

Layer‐Based Heterostructured Cathodes for Lithium‐Ion and Sodium‐Ion Batteries journal February 2019
A Novel Strategy to Suppress Capacity and Voltage Fading of Li‐ and Mn‐Rich Layered Oxide Cathode Material for Lithium‐Ion Batteries journal November 2016
Li‐ and Mn‐Rich Cathode Materials: Challenges to Commercialization journal December 2016
Unraveling the Voltage Decay Phenomenon in Li‐Rich Layered Oxide Cathode of No Oxygen Activity journal October 2019
Retarding Phase Transformation During Cycling in a Lithium‐ and Manganese‐Rich Cathode Material by Optimizing Synthesis Conditions journal January 2019
Phase Transformation of Lithium‐rich Oxide Cathode in Full Cell and its Suppression by Solid Electrolyte Interphase on Graphite Anode journal March 2020
A new lithium‐rich layer‐structured cathode material with improved electrochemical performance and voltage maintenance journal July 2019
Composite-Structure Material Design for High-Energy Lithium Storage journal July 2018
Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries journal January 2017
Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes journal December 2017
Understanding voltage decay in lithium-excess layered cathode materials through oxygen-centred structural arrangement journal August 2018
Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries journal April 2018
Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes journal January 2020
A novel strategy to significantly enhance the initial voltage and suppress voltage fading of a Li- and Mn-rich layered oxide cathode material for lithium-ion batteries journal January 2018
Li- and Mn-rich layered oxide cathode materials for lithium-ion batteries: a review from fundamentals to research progress and applications journal January 2018
A free-standing Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 /MWCNT framework for high-energy lithium-ion batteries journal January 2018
A LiPF 6 -electrolyte-solvothermal route for the synthesis of LiF/Li x PF y O z -coated Li-rich cathode materials with enhanced cycling stability journal January 2019
Si-doped high-energy Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 cathode with improved capacity for lithium-ion batteries journal December 2018

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