skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes

Abstract

The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na 0.6[Li 0.2Mn 0.8]O 2and compare it with Na 2/3[Mg 1/3Mn 2/3]O 2. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na 0.6[Li 0.2Mn 0.8]O 2stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na 2/3[Mg 1/3Mn 2/3]O 2. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes.

Authors:
ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [5]; ORCiD logo [6];  [7]; ORCiD logo [8]; ORCiD logo [9]; ORCiD logo [6];  [6]; ORCiD logo [3];  [10]; ORCiD logo [11]; ORCiD logo [6]
  1. Stanford Univ., CA (United States). Geballe Lab. for Advanced Materials; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
  2. Peking Univ. Shenzhen Graduate School, Shenzhen (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics; Univ. of Chinese Academy of Sciences, Beijing (China)
  4. Northeastern Univ., Shenyang (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. Binghamton Univ., NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  7. Peking Univ. Shenzhen Graduate School, Shenzhen (China)
  8. Binghamton Univ., NY (United States)
  9. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  10. Tsinghua Univ., Beijing (China)
  11. Stanford Univ., CA (United States). Geballe Lab. for Advanced Materials; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES); Stanford Univ., CA (United States)
Publication Date:
Research Org.:
Binghamton Univ., NY (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; China’s National Key R&D Programmes; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1598793
Alternate Identifier(s):
OSTI ID: 1573374; OSTI ID: 1601224
Grant/Contract Number:  
[SC0012583; AC02-05CH11231; AC02-76SF00515]
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
[ Journal Volume: 6; Journal Issue: 6]; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Wu, Jinpeng, Zhuo, Zengqing, Rong, Xiaohui, Dai, Kehua, Lebens-Higgins, Zachary, Sallis, Shawn, Pan, Feng, Piper, Louis F. J., Liu, Gao, Chuang, Yi-de, Hussain, Zahid, Li, Qinghao, Zeng, Rong, Shen, Zhi-xun, and Yang, Wanli. Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes. United States: N. p., 2020. Web. doi:10.1126/sciadv.aaw3871.
Wu, Jinpeng, Zhuo, Zengqing, Rong, Xiaohui, Dai, Kehua, Lebens-Higgins, Zachary, Sallis, Shawn, Pan, Feng, Piper, Louis F. J., Liu, Gao, Chuang, Yi-de, Hussain, Zahid, Li, Qinghao, Zeng, Rong, Shen, Zhi-xun, & Yang, Wanli. Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes. United States. doi:10.1126/sciadv.aaw3871.
Wu, Jinpeng, Zhuo, Zengqing, Rong, Xiaohui, Dai, Kehua, Lebens-Higgins, Zachary, Sallis, Shawn, Pan, Feng, Piper, Louis F. J., Liu, Gao, Chuang, Yi-de, Hussain, Zahid, Li, Qinghao, Zeng, Rong, Shen, Zhi-xun, and Yang, Wanli. Sat . "Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes". United States. doi:10.1126/sciadv.aaw3871. https://www.osti.gov/servlets/purl/1598793.
@article{osti_1598793,
title = {Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes},
author = {Wu, Jinpeng and Zhuo, Zengqing and Rong, Xiaohui and Dai, Kehua and Lebens-Higgins, Zachary and Sallis, Shawn and Pan, Feng and Piper, Louis F. J. and Liu, Gao and Chuang, Yi-de and Hussain, Zahid and Li, Qinghao and Zeng, Rong and Shen, Zhi-xun and Yang, Wanli},
abstractNote = {The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na0.6[Li0.2Mn0.8]O2and compare it with Na2/3[Mg1/3Mn2/3]O2. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na0.6[Li0.2Mn0.8]O2stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na2/3[Mg1/3Mn2/3]O2. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes.},
doi = {10.1126/sciadv.aaw3871},
journal = {Science Advances},
number = [6],
volume = [6],
place = {United States},
year = {2020},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries
journal, September 2017


Challenges for Rechargeable Li Batteries
journal, February 2010

  • Goodenough, John B.; Kim, Youngsik
  • Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
  • DOI: 10.1021/cm901452z

Spectroscopic Signature of Oxidized Oxygen States in Peroxides
journal, October 2018

  • Zhuo, Zengqing; Pemmaraju, Chaitanya Das; Vinson, John
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 21
  • DOI: 10.1021/acs.jpclett.8b02757

A new electrode material for rechargeable sodium batteries: P2-type Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 with anomalously high reversible capacity
journal, January 2014

  • Yabuuchi, Naoaki; Hara, Ryo; Kubota, Kei
  • J. Mater. Chem. A, Vol. 2, Issue 40
  • DOI: 10.1039/C4TA04351K

Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides
journal, May 2013


Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries
journal, October 2018


Origin of Carbon Dioxide Evolved during Cycling of Nickel-Rich Layered NCM Cathodes
journal, October 2018

  • Hatsukade, Toru; Schiele, Alexander; Hartmann, Pascal
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 45
  • DOI: 10.1021/acsami.8b13158

Anionic Redox Reaction-Induced High-Capacity and Low-Strain Cathode with Suppressed Phase Transition
journal, February 2019


Direct evidence of gradient Mn(II) evolution at charged states in LiNi0.5Mn1.5O4 electrodes with capacity fading
journal, January 2015


Decoupling Cationic–Anionic Redox Processes in a Model Li-Rich Cathode via Operando X-ray Absorption Spectroscopy
journal, November 2017


Anionic redox processes for electrochemical devices
journal, January 2016

  • Grimaud, A.; Hong, W. T.; Shao-Horn, Y.
  • Nature Materials, Vol. 15, Issue 2
  • DOI: 10.1038/nmat4551

Oxygen release and oxygen redox
journal, July 2018


Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2
journal, January 2018

  • Maitra, Urmimala; House, Robert A.; Somerville, James W.
  • Nature Chemistry, Vol. 10, Issue 3
  • DOI: 10.1038/nchem.2923

Revealing and suppressing surface Mn(II) formation of Na0.44MnO2 electrodes for Na-ion batteries
journal, September 2015


Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries
journal, April 2018


Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes
journal, December 2017


Modular soft x-ray spectrometer for applications in energy sciences and quantum materials
journal, January 2017

  • Chuang, Yi-De; Shao, Yu-Cheng; Cruz, Alejandro
  • Review of Scientific Instruments, Vol. 88, Issue 1
  • DOI: 10.1063/1.4974356

Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

New O2/P2-type Li-Excess Layered Manganese Oxides as Promising Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries
journal, May 2014

  • Yabuuchi, Naoaki; Hara, Ryo; Kajiyama, Masataka
  • Advanced Energy Materials, Vol. 4, Issue 13
  • DOI: 10.1002/aenm.201301453

Critical Role of Oxygen Evolved from Layered Li–Excess Metal Oxides in Lithium Rechargeable Batteries
journal, July 2012

  • Hong, Jihyun; Lim, Hee-Dae; Lee, Minah
  • Chemistry of Materials, Vol. 24, Issue 14
  • DOI: 10.1021/cm3005634

Distinction between Intrinsic and X-ray-Induced Oxidized Oxygen States in Li-Rich 3d Layered Oxides and LiAlO 2
journal, May 2019

  • Lebens-Higgins, Zachary W.; Vinckeviciute, Julija; Wu, Jinpeng
  • The Journal of Physical Chemistry C, Vol. 123, Issue 21
  • DOI: 10.1021/acs.jpcc.9b01298

Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode
journal, January 2018


Elucidating anionic oxygen activity in lithium-rich layered oxides
journal, March 2018


A novel P3-type Na 2/3 Mg 1/3 Mn 2/3 O 2 as high capacity sodium-ion cathode using reversible oxygen redox
journal, January 2019

  • Song, Bohang; Hu, Enyuan; Liu, Jue
  • Journal of Materials Chemistry A, Vol. 7, Issue 4
  • DOI: 10.1039/C8TA09422E

Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging
journal, July 2018


Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides
journal, December 2017


Residual Lithium Carbonate Predominantly Accounts for First Cycle CO 2 and CO Outgassing of Li-Stoichiometric and Li-Rich Layered Transition-Metal Oxides
journal, November 2017

  • Renfrew, Sara E.; McCloskey, Bryan D.
  • Journal of the American Chemical Society, Vol. 139, Issue 49
  • DOI: 10.1021/jacs.7b08461

What Triggers Oxygen Loss in Oxygen Redox Cathode Materials?
journal, April 2019


High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source
journal, March 2017

  • Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing
  • Review of Scientific Instruments, Vol. 88, Issue 3
  • DOI: 10.1063/1.4977592

Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li 2 MnO 3 Content
journal, January 2018

  • Teufl, Tobias; Strehle, Benjamin; Müller, Philipp
  • Journal of The Electrochemical Society, Vol. 165, Issue 11
  • DOI: 10.1149/2.0691811jes

The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

  • Goodenough, John B.; Park, Kyu-Sung
  • Journal of the American Chemical Society, Vol. 135, Issue 4
  • DOI: 10.1021/ja3091438

Direct Quantification of Anionic Redox over Long Cycling of Li-Rich NMC via Hard X-ray Photoemission Spectroscopy
journal, October 2018


Oxygen Release and Its Effect on the Cycling Stability of LiNi x Mn y Co z O 2 (NMC) Cathode Materials for Li-Ion Batteries
journal, January 2017

  • Jung, Roland; Metzger, Michael; Maglia, Filippo
  • Journal of The Electrochemical Society, Vol. 164, Issue 7
  • DOI: 10.1149/2.0021707jes

Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy
journal, September 2016


Key electronic states in lithium battery materials probed by soft X-ray spectroscopy
journal, October 2013

  • Yang, Wanli; Liu, Xiaosong; Qiao, Ruimin
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 190
  • DOI: 10.1016/j.elspec.2013.03.008

Exploring reversible oxidation of oxygen in a manganese oxide
journal, January 2016

  • Du, Ke; Zhu, Jinyou; Hu, Guorong
  • Energy & Environmental Science, Vol. 9, Issue 8
  • DOI: 10.1039/C6EE01367H

Tunable-excitation soft X-ray fluorescence spectroscopy of high-Tc superconductors: an inequivalent-site seeing story
journal, October 2000

  • Butorin, Sergei M.; Guo, Jinghua; Wassdahl, Nial
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 110-111
  • DOI: 10.1016/S0368-2048(00)00167-5

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries
journal, April 2017