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Title: Depth-Dependent Redox Behavior of LiNi 0.6Mn 0.2Co 0.2O 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 LiNi 0.6Mn 0.2Co 0.2O 2 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. In conclusion, this likely drives the structural and chemical transformations observed at particle surfaces in Ni-rich materials.

Authors:
 [1];  [2];  [3];  [4];  [2];  [2]; ORCiD logo [5]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States); Donghua Univ., Shanghai (People's Republic of China)
  5. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
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; TRN: US1901474
Grant/Contract Number:  
AC02-05CH11231; SC0012704; AC02-76SF00515
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 3; Journal ID: ISSN 0013-4651
Publisher:
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 LiNi0.6Mn0.2Co0.2O2. 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 LiNi0.6Mn0.2Co0.2O2. United States. doi:10.1149/2.1021803jes.
Tian, Chixia, Nordlund, Dennis, Xin, Huolin L., Xu, Yahong, Liu, Yijin, Sokaras, Dimosthenis, Lin, Feng, and Doeff, Marca M. Mon . "Depth-Dependent Redox Behavior of LiNi0.6Mn0.2Co0.2O2". United States. doi:10.1149/2.1021803jes.
@article{osti_1425689,
title = {Depth-Dependent Redox Behavior of LiNi0.6Mn0.2Co0.2O2},
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. In conclusion, 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 = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1149/2.1021803jes

Citation Metrics:
Cited by: 7 works
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Figures / Tables:

Figure 1 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 » the area in the green box in Figure 1(d).« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.