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Title: Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release

Abstract

Voltage fade is a major problem in battery applications for high-energy lithium- and manganese-rich (LMR) layered materials. As a result of the complexity of the LMR structure, the voltage fade mechanism is not well understood. For this, we conduct both in situ and ex situ studies on a typical LMR material (Li 1.2Ni 0.15Co 0.1Mn 0.55O 2) during charge-discharge cycling, using multi-lengthscale X-ray spectroscopic and three-dimensional electron microscopic imaging techniques. Through probing from the surface to the bulk, and from individual to whole ensembles of particles, we show that the average valence state of each type of transition metal cation is continuously reduced, which is attributed to oxygen release from the LMR material. Such reductions activate the lower-voltage Mn 3+/Mn 4+ and Co 2+/Co 3+ redox couples in addition to the original redox couples including Ni 2+/Ni 3+, Ni 3+/Ni 4+ and O 2-/O -, directly leading to the voltage fade. We also show that the oxygen release causes microstructural defects such as the formation of large pores within particles, which also contributes to the voltage fade. Surface coating and modification methods are suggested to be effective in suppressing the voltage fade through reducing the oxygen release.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [4];  [1]; ORCiD logo [5]; ORCiD logo [6];  [7];  [7];  [4];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division; Chinese Academy of Sciences (CAS), Beijing (China). Beijing National Lab. for Condensed Matter Physics and Inst. of Physics
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division and Center for Functional Nanomaterials (CFN)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  5. Dongguk Univ., Seoul (Korea, Republic of). Dept. of Energy and Materials Engineering
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  7. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Material Measurement Lab.
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Brookhaven National Lab. (BNL), Upton, NY (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) (SC-22); Chinese Academy of Sciences (CAS); National Key R&D Program of China; National Natural Science Foundation of China (NNSFC); National Research Foundation of Korea (NRF)
OSTI Identifier:
1467843
Alternate Identifier(s):
OSTI ID: 1460715
Report Number(s):
[BNL-207813-2018-JAAM]
[Journal ID: ISSN 2058-7546; 144252]
Grant/Contract Number:  
[AC02-06CH11357; SC0012704; 2016YFA0202500; 51421002; NRF-2017M1A2A2044502; AC02-98CH10886]
Resource Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
[ Journal Volume: 3; Journal Issue: 8]; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; batteries; electrochemistry

Citation Formats

Hu, Enyuan, Yu, Xiqian, Lin, Ruoqian, Bi, Xuanxuan, Lu, Jun, Bak, Seongmin, Nam, Kyung-Wan, Xin, Huolin L., Jaye, Cherno, Fischer, Daniel A., Amine, Kahlil, and Yang, Xiao-Qing. Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release. United States: N. p., 2018. Web. doi:10.1038/s41560-018-0207-z.
Hu, Enyuan, Yu, Xiqian, Lin, Ruoqian, Bi, Xuanxuan, Lu, Jun, Bak, Seongmin, Nam, Kyung-Wan, Xin, Huolin L., Jaye, Cherno, Fischer, Daniel A., Amine, Kahlil, & Yang, Xiao-Qing. Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release. United States. doi:10.1038/s41560-018-0207-z.
Hu, Enyuan, Yu, Xiqian, Lin, Ruoqian, Bi, Xuanxuan, Lu, Jun, Bak, Seongmin, Nam, Kyung-Wan, Xin, Huolin L., Jaye, Cherno, Fischer, Daniel A., Amine, Kahlil, and Yang, Xiao-Qing. Mon . "Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release". United States. doi:10.1038/s41560-018-0207-z. https://www.osti.gov/servlets/purl/1467843.
@article{osti_1467843,
title = {Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release},
author = {Hu, Enyuan and Yu, Xiqian and Lin, Ruoqian and Bi, Xuanxuan and Lu, Jun and Bak, Seongmin and Nam, Kyung-Wan and Xin, Huolin L. and Jaye, Cherno and Fischer, Daniel A. and Amine, Kahlil and Yang, Xiao-Qing},
abstractNote = {Voltage fade is a major problem in battery applications for high-energy lithium- and manganese-rich (LMR) layered materials. As a result of the complexity of the LMR structure, the voltage fade mechanism is not well understood. For this, we conduct both in situ and ex situ studies on a typical LMR material (Li1.2Ni0.15Co0.1Mn0.55O2) during charge-discharge cycling, using multi-lengthscale X-ray spectroscopic and three-dimensional electron microscopic imaging techniques. Through probing from the surface to the bulk, and from individual to whole ensembles of particles, we show that the average valence state of each type of transition metal cation is continuously reduced, which is attributed to oxygen release from the LMR material. Such reductions activate the lower-voltage Mn3+/Mn4+ and Co2+/Co3+ redox couples in addition to the original redox couples including Ni2+/Ni3+, Ni3+/Ni4+ and O2-/O-, directly leading to the voltage fade. We also show that the oxygen release causes microstructural defects such as the formation of large pores within particles, which also contributes to the voltage fade. Surface coating and modification methods are suggested to be effective in suppressing the voltage fade through reducing the oxygen release.},
doi = {10.1038/s41560-018-0207-z},
journal = {Nature Energy},
number = [8],
volume = [3],
place = {United States},
year = {2018},
month = {7}
}

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