Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2
Abstract
Nickel-rich layered materials are emerging as cathodes of choice for next-generation high energy density lithium ion batteries intended for electric vehicles. This is because of their higher practical capacities compared to compositions with lower Ni content, as well as the potential for lower raw materials cost. The higher practical capacity of these materials comes at the expense of shorter cycle life, however, due to undesirable structure and chemical transformations, especially at particle surfaces. To understand these changes more fully, the charge compensation mechanism and bulk and surface structural changes of LiNi0.6Mn0.2Co0.2O2 were probed using synchrotron techniques and electron energy loss spectroscopy in this study. In the bulk, both the crystal and electronic structure changes are reversible upon cycling to high voltages, whereas particle surfaces undergo significant reduction and structural reconstruction. While Ni is the major contributor to charge compensation, Co and O (through transition metal-oxygen hybridization) are also redox active. An important finding from depth-dependent transition metal L-edge and O K-edge X-ray spectroscopy is that oxygen redox activity exhibits depth-dependent characteristics. This likely drives the structural and chemical transformations observed at particle surfaces in Ni-rich materials.
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1425689
- Alternate Identifier(s):
- OSTI ID: 1458538; OSTI ID: 1466615; OSTI ID: 1466712
- Report Number(s):
- BNL-207961-2018-JAAM
Journal ID: ISSN 0013-4651; /jes/165/3/A696.atom
- Grant/Contract Number:
- AC02-05CH11231; SC0012704; AC02-76SF00515
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society Journal Volume: 165 Journal Issue: 3; Journal ID: ISSN 0013-4651
- Publisher:
- IOP Publishing - The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; cathode; Li-ion battery; NMC; 36 MATERIALS SCIENCE; Redox Behavior
Citation Formats
Tian, Chixia, Nordlund, Dennis, Xin, Huolin L., Xu, Yahong, Liu, Yijin, Sokaras, Dimosthenis, Lin, Feng, and Doeff, Marca M. Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2. United States: N. p., 2018.
Web. doi:10.1149/2.1021803jes.
Tian, Chixia, Nordlund, Dennis, Xin, Huolin L., Xu, Yahong, Liu, Yijin, Sokaras, Dimosthenis, Lin, Feng, & Doeff, Marca M. Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2. United States. https://doi.org/10.1149/2.1021803jes
Tian, Chixia, Nordlund, Dennis, Xin, Huolin L., Xu, Yahong, Liu, Yijin, Sokaras, Dimosthenis, Lin, Feng, and Doeff, Marca M. Thu .
"Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2". United States. https://doi.org/10.1149/2.1021803jes.
@article{osti_1425689,
title = {Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2},
author = {Tian, Chixia and Nordlund, Dennis and Xin, Huolin L. and Xu, Yahong and Liu, Yijin and Sokaras, Dimosthenis and Lin, Feng and Doeff, Marca M.},
abstractNote = {Nickel-rich layered materials are emerging as cathodes of choice for next-generation high energy density lithium ion batteries intended for electric vehicles. This is because of their higher practical capacities compared to compositions with lower Ni content, as well as the potential for lower raw materials cost. The higher practical capacity of these materials comes at the expense of shorter cycle life, however, due to undesirable structure and chemical transformations, especially at particle surfaces. To understand these changes more fully, the charge compensation mechanism and bulk and surface structural changes of LiNi0.6Mn0.2Co0.2O2 were probed using synchrotron techniques and electron energy loss spectroscopy in this study. In the bulk, both the crystal and electronic structure changes are reversible upon cycling to high voltages, whereas particle surfaces undergo significant reduction and structural reconstruction. While Ni is the major contributor to charge compensation, Co and O (through transition metal-oxygen hybridization) are also redox active. An important finding from depth-dependent transition metal L-edge and O K-edge X-ray spectroscopy is that oxygen redox activity exhibits depth-dependent characteristics. This likely drives the structural and chemical transformations observed at particle surfaces in Ni-rich materials.},
doi = {10.1149/2.1021803jes},
journal = {Journal of the Electrochemical Society},
number = 3,
volume = 165,
place = {United States},
year = {Thu Feb 08 00:00:00 EST 2018},
month = {Thu Feb 08 00:00:00 EST 2018}
}
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Cited by: 106 works
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Figures / Tables:
Figure 1: (a) SEM images of secondary particles and (inset) primary particles of NMC-622 prepared by spray pyrolysis. (b) XRD pattern with Rietveld refinement. (c) High-resolution Z-contrast ADF-STEM image of NMC-622 primary particle. (d) EELS survey image and (e) EELS spectra integrated from surface to bulk (red arrow direction) ofmore »
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