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

Title: Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

Abstract

Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. Here, we demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and rate performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3];  [1];  [1]; ORCiD logo [3];  [4];  [5]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
  5. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (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); National Science Foundation (NSF)
OSTI Identifier:
1419450
Grant/Contract Number:  
AC02-05CH11231; DGE-1106400
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Batteries

Citation Formats

Lee, Jinhyuk, Papp, Joseph K., Clément, Raphaële J., Sallis, Shawn, Kwon, Deok-Hwang, Shi, Tan, Yang, Wanli, McCloskey, Bryan D., and Ceder, Gerbrand. Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials. United States: N. p., 2017. Web. doi:10.1038/s41467-017-01115-0.
Lee, Jinhyuk, Papp, Joseph K., Clément, Raphaële J., Sallis, Shawn, Kwon, Deok-Hwang, Shi, Tan, Yang, Wanli, McCloskey, Bryan D., & Ceder, Gerbrand. Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials. United States. doi:10.1038/s41467-017-01115-0.
Lee, Jinhyuk, Papp, Joseph K., Clément, Raphaële J., Sallis, Shawn, Kwon, Deok-Hwang, Shi, Tan, Yang, Wanli, McCloskey, Bryan D., and Ceder, Gerbrand. Tue . "Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials". United States. doi:10.1038/s41467-017-01115-0. https://www.osti.gov/servlets/purl/1419450.
@article{osti_1419450,
title = {Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials},
author = {Lee, Jinhyuk and Papp, Joseph K. and Clément, Raphaële J. and Sallis, Shawn and Kwon, Deok-Hwang and Shi, Tan and Yang, Wanli and McCloskey, Bryan D. and Ceder, Gerbrand},
abstractNote = {Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. Here, we demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and rate performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.},
doi = {10.1038/s41467-017-01115-0},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {10}
}

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

Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Preparation of electrochemically active α-LiFeO2 at low temperature
journal, December 1998


Characterization of Disordered Li (1+ x ) Ti 2 x Fe (1–3 x ) O 2 as Positive Electrode Materials in Li-Ion Batteries Using Percolation Theory
journal, November 2015


Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016

  • Luo, Kun; Roberts, Matthew R.; Hao, Rong
  • Nature Chemistry, Vol. 8, Issue 7
  • DOI: 10.1038/nchem.2471

Isotropic High Field NMR Spectra of Li-Ion Battery Materials with Anisotropy >1 MHz
journal, January 2012

  • Hung, Ivan; Zhou, Lina; Pourpoint, Frédérique
  • Journal of the American Chemical Society, Vol. 134, Issue 4
  • DOI: 10.1021/ja209600m

First-Principles Prediction of Vacancy Order-Disorder and Intercalation Battery Voltages in Li x CoO 2
journal, July 1998


On the Efficacy of Electrocatalysis in Nonaqueous Li–O 2 Batteries
journal, November 2011

  • McCloskey, Bryan D.; Scheffler, Rouven; Speidel, Angela
  • Journal of the American Chemical Society, Vol. 133, Issue 45
  • DOI: 10.1021/ja207229n

The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials
journal, May 2016

  • Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander
  • Nature Chemistry, Vol. 8, Issue 7
  • DOI: 10.1038/nchem.2524

Synthesis and Electrochemical Properties of Li 4 MoO 5 –NiO Binary System as Positive Electrode Materials for Rechargeable Lithium Batteries
journal, January 2016


Synthesis and electrochemistry of cubic rocksalt Li–Ni–Ti–O compounds in the phase diagram of LiNiO2–LiTiO2–Li[Li1/3Ti2/3]O2
journal, October 2008


Oxidative Degradation of the Monolayer of 1-Palmitoyl-2-Oleoyl- sn -Glycero-3-Phosphocholine (POPC) in Low-Level Ozone
journal, October 2015

  • Qiao, Lin; Ge, Aimin; Liang, Yimin
  • The Journal of Physical Chemistry B, Vol. 119, Issue 44
  • DOI: 10.1021/acs.jpcb.5b08985

Determination of the Kinetic Parameters of Mixed-Conducting Electrodes and Application to the System Li[sub 3]Sb
journal, January 1977

  • Weppner, W.
  • Journal of The Electrochemical Society, Vol. 124, Issue 10
  • DOI: 10.1149/1.2133112

Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries
journal, January 2014


Battery materials for ultrafast charging and discharging
journal, March 2009

  • Kang, Byoungwoo; Ceder, Gerbrand
  • Nature, Vol. 458, Issue 7235, p. 190-193
  • DOI: 10.1038/nature07853

Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2
journal, August 2016

  • Luo, Kun; Roberts, Matthew R.; Guerrini, Niccoló
  • Journal of the American Chemical Society, Vol. 138, Issue 35
  • DOI: 10.1021/jacs.6b05111

Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li–O 2 Batteries
journal, March 2012

  • McCloskey, B. D.; Speidel, A.; Scheffler, R.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 8
  • DOI: 10.1021/jz300243r

Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides
journal, July 1997


Identification of cathode materials for lithium batteries guided by first-principles calculations
journal, April 1998

  • Ceder, G.; Chiang, Y. -M.; Sadoway, D. R.
  • Nature, Vol. 392, Issue 6677
  • DOI: 10.1038/33647

Electronic structure of Li-doped NiO
journal, January 1992


Synthesis and electrochemical properties of Li 1.3 Nb 0.3 V 0.4 O 2 as a positive electrode material for rechargeable lithium batteries
journal, January 2016

  • Yabuuchi, Naoaki; Takeuchi, Mitsue; Komaba, Shinichi
  • Chemical Communications, Vol. 52, Issue 10
  • DOI: 10.1039/C5CC08034G

Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li 2 MnO 3 −LiCo 1/3 Ni 1/3 Mn 1/3 O 2
journal, March 2011

  • Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek
  • Journal of the American Chemical Society, Vol. 133, Issue 12
  • DOI: 10.1021/ja108588y

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

NMR evidence of LiF coating rather than fluorine substitution in Li(Ni0.425Mn0.425Co0.15)O2
journal, December 2008


Why LiFePO 4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation
journal, January 2015

  • Liu, Xiaosong; Wang, Yung Jui; Barbiellini, Bernardo
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 39
  • DOI: 10.1039/C5CP04739K

The Configurational Space of Rocksalt-Type Oxides for High-Capacity Lithium Battery Electrodes
journal, May 2014

  • Urban, Alexander; Lee, Jinhyuk; Ceder, Gerbrand
  • Advanced Energy Materials, Vol. 4, Issue 13
  • DOI: 10.1002/aenm.201400478

Synthesis of “Li[sub 1.1](Ni[sub 0.425]Mn[sub 0.425]Co[sub 0.15])[sub 0.9]O[sub 1.8]F[sub 0.2]” Materials by Different Routes: Is There Fluorine Substitution for Oxygen?
journal, January 2009

  • Croguennec, L.; Bains, J.; Ménétrier, M.
  • Journal of The Electrochemical Society, Vol. 156, Issue 5
  • DOI: 10.1149/1.3080659

Direct In situ Observation of Li 2 O Evolution on Li-Rich High-Capacity Cathode Material, Li[Ni x Li (1–2 x )/3 Mn (2– x )/3 ]O 2 (0 ≤ x ≤0.5)
journal, January 2014

  • Hy, Sunny; Felix, Felix; Rick, John
  • Journal of the American Chemical Society, Vol. 136, Issue 3
  • DOI: 10.1021/ja410137s

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries
journal, December 2016

  • Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13814

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

High-capacity electrode materials for rechargeable lithium batteries: Li 3 NbO 4 -based system with cation-disordered rocksalt structure
journal, June 2015

  • Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 25
  • DOI: 10.1073/pnas.1504901112

A new class of high capacity cation-disordered oxides for rechargeable lithium batteries: Li–Ni–Ti–Mo oxides
journal, January 2015

  • Lee, Jinhyuk; Seo, Dong-Hwa; Balasubramanian, Mahalingam
  • Energy & Environmental Science, Vol. 8, Issue 11
  • DOI: 10.1039/C5EE02329G

Solvents’ Critical Role in Nonaqueous Lithium–Oxygen Battery Electrochemistry
journal, May 2011

  • McCloskey, B. D.; Bethune, D. S.; Shelby, R. M.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 10, p. 1161-1166
  • DOI: 10.1021/jz200352v

    Works referencing / citing this record:

    Three-dimensional SWCNT and MWCNT hybrid networks for extremely high-loading and high rate cathode materials
    journal, January 2019

    • Kim, Dae-wook; Zettsu, Nobuyuki; Teshima, Katsuya
    • Journal of Materials Chemistry A, Vol. 7, Issue 29
    • DOI: 10.1039/c9ta03870a

    Three-dimensional SWCNT and MWCNT hybrid networks for extremely high-loading and high rate cathode materials
    journal, January 2019

    • Kim, Dae-wook; Zettsu, Nobuyuki; Teshima, Katsuya
    • Journal of Materials Chemistry A, Vol. 7, Issue 29
    • DOI: 10.1039/c9ta03870a