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Title: Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction

Abstract

Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Lix/3Ni(3/8-3x/8)Co(1/4-x/4)Mn(3/8+7x/24)O2 (x = 0.6, HLR) and low Li-rich Li(Lix/3Ni(1/3-x/3)Co(1/3-x/3)Mn(1/3+x/3)O2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. The lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate once the high voltagemore » plateau is reached.« less

Authors:
 [1];  [2];  [3];  [1];  [1];  [1]
  1. Univ. of California, San Diego, CA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Envia Systems, Newark, CA (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1261356
Alternate Identifier(s):
OSTI ID: 1785873
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Liu, Haodong, An, Ke, Venkatachalam, Subramanian, Qian, Danna, Zhang, Minghao, and Meng, Ying Shirley. Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction. United States: N. p., 2016. Web. https://doi.org/10.1002/aenm.201502143.
Liu, Haodong, An, Ke, Venkatachalam, Subramanian, Qian, Danna, Zhang, Minghao, & Meng, Ying Shirley. Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction. United States. https://doi.org/10.1002/aenm.201502143
Liu, Haodong, An, Ke, Venkatachalam, Subramanian, Qian, Danna, Zhang, Minghao, and Meng, Ying Shirley. Wed . "Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction". United States. https://doi.org/10.1002/aenm.201502143. https://www.osti.gov/servlets/purl/1261356.
@article{osti_1261356,
title = {Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction},
author = {Liu, Haodong and An, Ke and Venkatachalam, Subramanian and Qian, Danna and Zhang, Minghao and Meng, Ying Shirley},
abstractNote = {Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Lix/3Ni(3/8-3x/8)Co(1/4-x/4)Mn(3/8+7x/24)O2 (x = 0.6, HLR) and low Li-rich Li(Lix/3Ni(1/3-x/3)Co(1/3-x/3)Mn(1/3+x/3)O2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. The lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate once the high voltage plateau is reached.},
doi = {10.1002/aenm.201502143},
journal = {Advanced Energy Materials},
number = 7,
volume = 6,
place = {United States},
year = {2016},
month = {4}
}

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