Solvent-mediated oxide hydrogenation in layered cathodes

Science, vol. 385, pp. 1230–1236

Abstract

Self-discharge and chemically induced mechanical effects degrade calendar and cycle life in intercalation-based electrochromic and electrochemical energy storage devices. In rechargeable lithium-ion batteries, self-discharge in cathodes causes voltage and capacity loss over time. The prevailing self-discharge model centers on the diffusion of lithium ions from the electrolyte into the cathode. We demonstrate an alternative pathway, where hydrogenation of layered transition metal oxide cathodes induces self-discharge through hydrogen transfer from carbonate solvents to delithiated oxides. In self-discharged cathodes, we further observe opposing proton and lithium ion concentration gradients, which contribute to chemical and structural heterogeneities within delithiated cathodes, accelerating degradation. Hydrogenation occurring in delithiated cathodes may affect the chemo-mechanical coupling of layered cathodes as well as the calendar life of lithium-ion batteries.

Authors 24

1. Gang Wan corresponding

   SLAC National Accelerator Laboratory · Stanford University

   Affiliation as printed

   Department of Mechanical Engineering, Stanford University, Stanford, CA 94305, USA

   SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA

2. Travis P. Pollard

   DEVCOM Army Research Laboratory · United States Army Combat Capabilities Development Command

   Affiliation as printed

   Battery Science Branch, Energy Science Division, Army Research Directorate, DEVCOM Army Research Laboratory, Adelphi, MD 20783, USA

3. Lin Ma

   University of North Carolina at Charlotte · DEVCOM Army Research Laboratory · United States Army Combat Capabilities Development Command

   Affiliation as printed

   Battery Science Branch, Energy Science Division, Army Research Directorate, DEVCOM Army Research Laboratory, Adelphi, MD 20783, USA

   Department of Mechanical Engineering and Engineering Science, The University of North Carolina at Charlotte, Charlotte, NC 28223, USA

4. Marshall A. Schroeder

   DEVCOM Army Research Laboratory · United States Army Combat Capabilities Development Command

   Affiliation as printed

   Battery Science Branch, Energy Science Division, Army Research Directorate, DEVCOM Army Research Laboratory, Adelphi, MD 20783, USA

5. Chia‐Chin Chen

   National Taiwan University

   Affiliation as printed

   Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan

6. Zihua Zhu

   Pacific Northwest National Laboratory · Environmental Molecular Sciences Laboratory

   Affiliation as printed

   Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99354, USA

7. Zhan Zhang

   Argonne National Laboratory · Advanced Photon Source

   Affiliation as printed

   Advanced Photon Source, Argonne National Laboratory, Lemont, IL 60439, USA

8. Cheng-Jun Sun

   Argonne National Laboratory · Advanced Photon Source

   Affiliation as printed

   Advanced Photon Source, Argonne National Laboratory, Lemont, IL 60439, USA

9. Jiyu Cai

   Argonne National Laboratory

   Affiliation as printed

   Chemical Science and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, USA

10. Harry L. Thaman

    Stanford University

    Affiliation as printed

    Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA

11. Artūras Vailionis

    Kaunas University of Technology · Stanford University

    Affiliation as printed

    Department of Physics, Kaunas University of Technology, LT-51368 Kaunas, Lithuania

    Stanford Nano Shared Facilities, Stanford University, Stanford, CA 94305, USA

12. Haoyuan Li

    Stanford University

    Affiliation as printed

    Department of Mechanical Engineering, Stanford University, Stanford, CA 94305, USA

13. Shelly D. Kelly

    Argonne National Laboratory · Advanced Photon Source

    Affiliation as printed

    Advanced Photon Source, Argonne National Laboratory, Lemont, IL 60439, USA

14. Zhenxing Feng

    Oregon State University

    Affiliation as printed

    School of Chemical, Biological, and Environmental Engineering, Oregon State University, Corvallis, OR 97331, USA

15. Joseph B. Franklin

    Lawrence Berkeley National Laboratory · University College London

    Affiliation as printed

    Department of Chemical Engineering, University College London, London WC1E 6BT, UK

    Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

16. Steven P. Harvey

    National Laboratory of the Rockies

    Affiliation as printed

    National Renewable Energy Laboratory, Golden, CO 80401, USA

17. Ye Zhang

    University of Houston

    Affiliation as printed

    Department of Electrical and Computer Engineering and Materials Science and Engineering Program, University of Houston, Houston, TX 77204, USA

18. Yingge Du

    Pacific Northwest National Laboratory

    Affiliation as printed

    Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA 99354, USA

19. Zonghai Chen

    Argonne National Laboratory

    Affiliation as printed

    Chemical Science and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, USA

20. Christopher J. Tassone

    SLAC National Accelerator Laboratory

    Affiliation as printed

    SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA

21. Hans‐Georg Steinrück Aachen Institute of Physical Chemistry

    Forschungszentrum Jülich · Paderborn University · SLAC National Accelerator Laboratory · RWTH Aachen University

    Affiliation as printed

    Department Chemie, Universität Paderborn, 33098 Paderborn, Germany

    Institute for a Sustainable Hydrogen Economy, Forschungszentrum Jülich GmbH, Marie-Curie-Straße 5, 52428 Jülich, Germany

    RWTH Aachen University, Institute of Physical Chemistry, Landoltweg 2, 52074 Aachen, Germany

    SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA

22. Kang Xu corresponding

    DEVCOM Army Research Laboratory · United States Army Combat Capabilities Development Command

    Affiliation as printed

    Battery Science Branch, Energy Science Division, Army Research Directorate, DEVCOM Army Research Laboratory, Adelphi, MD 20783, USA

    SES AI Corporation, Woburn, MA 01801, USA

23. Oleg A. Borodin corresponding

    DEVCOM Army Research Laboratory · United States Army Combat Capabilities Development Command

    Affiliation as printed

    Battery Science Branch, Energy Science Division, Army Research Directorate, DEVCOM Army Research Laboratory, Adelphi, MD 20783, USA

24. Michael F. Toney corresponding

    University of Colorado Boulder · SLAC National Accelerator Laboratory

    Affiliation as printed

    Department of Chemical and Biological Engineering, Materials Science and Engineering Program, Renewable and Sustainable Energy Institute, University of Colorado Boulder, Boulder, CO 80309, USA

    SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA