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Title: High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions

Abstract

The reversibility and cyclability of anionic redox in battery electrodes hold the key to its practical employments. Here, through mapping of resonant inelastic X-ray scattering (mRIXS), we have independently quantified the evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. Here, the bulk Mn redox emerges from initial discharge and is quantified by inverse partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn activities likely lead to the voltage fade. O-K super-partial fluorescence yield (sPFY) analysis of mRIXS shows 79% lattice oxygen redox reversibility during the initial cycle, with 87% capacity sustained after 100 cycles. In Li1.17Ni0.21Co0.08Mn0.54O2, lattice oxygen redox is 76% initial-cycle reversible but with only 44% capacity retention after 500 cycles. These results unambiguously show the high reversibility of lattice oxygen redox in both Li-ion and Na-ion systems. The contrast between Na2/3Mg1/3Mn2/3O2 and Li1.17Ni0.21Co0.08Mn0.54O2 systems suggests the importance of distinguishing lattice oxygen redox from other oxygen activities for clarifying its intrinsic properties.

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1600603
Alternate Identifier(s):
OSTI ID: 1564006
Grant/Contract Number:  
N150204017; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Joule
Additional Journal Information:
Journal Name: Joule Journal Volume: 3 Journal Issue: 2; Journal ID: ISSN 2542-4351
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; anionic redox reaction; quantification; Na-ion battery; Li-ion battery; soft X-ray spectroscopy; cathode material layered oxide; Li-rich material; mapping of resonant inelastic X-ray scattering (mRIXS); reversibility of oxygen redox

Citation Formats

Dai, Kehua, Wu, Jinpeng, Zhuo, Zengqing, Li, Qinghao, Sallis, Shawn, Mao, Jing, Ai, Guo, Sun, Chihang, Li, Zaiyuan, Gent, William E., Chueh, William C., Chuang, Yi-de, Zeng, Rong, Shen, Zhi-xun, Pan, Feng, Yan, Shishen, Piper, Louis F. J., Hussain, Zahid, Liu, Gao, and Yang, Wanli. High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions. United States: N. p., 2019. Web. doi:10.1016/j.joule.2018.11.014.
Dai, Kehua, Wu, Jinpeng, Zhuo, Zengqing, Li, Qinghao, Sallis, Shawn, Mao, Jing, Ai, Guo, Sun, Chihang, Li, Zaiyuan, Gent, William E., Chueh, William C., Chuang, Yi-de, Zeng, Rong, Shen, Zhi-xun, Pan, Feng, Yan, Shishen, Piper, Louis F. J., Hussain, Zahid, Liu, Gao, & Yang, Wanli. High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions. United States. https://doi.org/10.1016/j.joule.2018.11.014
Dai, Kehua, Wu, Jinpeng, Zhuo, Zengqing, Li, Qinghao, Sallis, Shawn, Mao, Jing, Ai, Guo, Sun, Chihang, Li, Zaiyuan, Gent, William E., Chueh, William C., Chuang, Yi-de, Zeng, Rong, Shen, Zhi-xun, Pan, Feng, Yan, Shishen, Piper, Louis F. J., Hussain, Zahid, Liu, Gao, and Yang, Wanli. Fri . "High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions". United States. https://doi.org/10.1016/j.joule.2018.11.014.
@article{osti_1600603,
title = {High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions},
author = {Dai, Kehua and Wu, Jinpeng and Zhuo, Zengqing and Li, Qinghao and Sallis, Shawn and Mao, Jing and Ai, Guo and Sun, Chihang and Li, Zaiyuan and Gent, William E. and Chueh, William C. and Chuang, Yi-de and Zeng, Rong and Shen, Zhi-xun and Pan, Feng and Yan, Shishen and Piper, Louis F. J. and Hussain, Zahid and Liu, Gao and Yang, Wanli},
abstractNote = {The reversibility and cyclability of anionic redox in battery electrodes hold the key to its practical employments. Here, through mapping of resonant inelastic X-ray scattering (mRIXS), we have independently quantified the evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. Here, the bulk Mn redox emerges from initial discharge and is quantified by inverse partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn activities likely lead to the voltage fade. O-K super-partial fluorescence yield (sPFY) analysis of mRIXS shows 79% lattice oxygen redox reversibility during the initial cycle, with 87% capacity sustained after 100 cycles. In Li1.17Ni0.21Co0.08Mn0.54O2, lattice oxygen redox is 76% initial-cycle reversible but with only 44% capacity retention after 500 cycles. These results unambiguously show the high reversibility of lattice oxygen redox in both Li-ion and Na-ion systems. The contrast between Na2/3Mg1/3Mn2/3O2 and Li1.17Ni0.21Co0.08Mn0.54O2 systems suggests the importance of distinguishing lattice oxygen redox from other oxygen activities for clarifying its intrinsic properties.},
doi = {10.1016/j.joule.2018.11.014},
journal = {Joule},
number = 2,
volume = 3,
place = {United States},
year = {Fri Feb 01 00:00:00 EST 2019},
month = {Fri Feb 01 00:00:00 EST 2019}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1016/j.joule.2018.11.014

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Works referencing / citing this record:

Reversible Anionic Redox Activities in Conventional LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathodes
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Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes
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Anionic defect engineering of transition metal oxides for oxygen reduction and evolution reactions
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  • DOI: 10.1039/c8ta12477a

Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes
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P2-type Na 2/3 Ni 1/3 Mn 2/3 O 2 Cathode Material with Excellent Rate and Cycling Performance for Sodium-Ion Batteries
journal, January 2019

  • Mao, Jing; Liu, Xin; Liu, Jianwen
  • Journal of The Electrochemical Society, Vol. 166, Issue 16
  • DOI: 10.1149/2.0211916jes

Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering
journal, January 2019