Structural Insights into Ni‐Stabilized Fe‐Rich High‐Voltage Spinels: LiNixFe0.5−xMn1.5O4

Small Structures, vol. 6

Abstract

Fe‐rich high‐voltage spinels are attractive positive electrode materials for next‐generation Li‐ion batteries that offer high resource efficiency and high operating voltages. However, Fe‐rich high‐voltage spinels do not provide stable cycling performance, especially when compared to the Ni‐ and Co‐rich members of the high‐voltage spinel family. To understand the failure mechanism of Fe‐rich high‐voltage spinels, the impact of Ni stabilization on the solid solutions LiNixFe0.5−xMn1.5O4 (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) is followed. Electrochemical analysis shows that stable cycling performance can be achieved at relatively low Ni substitution (x = 0.2). Rietveld and pair distribution function analysis show remarkable similarity in average and local structural features, supported by 4D scanning transmission electron microscopy. The cycling mechanism of LiFe0.5Mn1.5O4 and Ni‐stabilized LiNi0.2Fe0.3Mn1.5O4 is further compared via in situ powder X‐ray diffraction and in situ diffuse reflectance infrared Fourier transform spectroscopy. It is found that the presence of Ni in the electrodes leads to favorable electrolyte–electrode interactions that suppress oxidative reactions and the formation of large concentration polarizations, which is the predominant failure mechanism of LiFe0.5Mn1.5O4.

Authors 18

1. Anna Windmüller corresponding

   Forschungszentrum Jülich

   Affiliation as printed

   Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

2. Tingting Yang

   Forschungszentrum Jülich · Ernst Ruska Centre

   Affiliation as printed

   Ernst Ruska‐Centre for Microscopy and Spectroscopy with Electrons (ER‐C‐1) Forschungszentrum Jülich 52425 Jülich Germany

3. Kristian Schaps

   Forschungszentrum Jülich

   Affiliation as printed

   Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

4. Anna Domgans Aachen Institute of Physical Chemistry

   RWTH Aachen University · Forschungszentrum Jülich

   Affiliation as printed

   Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

   Institute of Physical Chemistry RWTH Aachen University D‐52074 Aachen Germany

5. Frederik Zantis Aachen Institute of Physical Chemistry

   RWTH Aachen University · Forschungszentrum Jülich

   Affiliation as printed

   Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

   Institute of Physical Chemistry RWTH Aachen University D‐52074 Aachen Germany

6. Baolin Wu Aachen Institute of Physical Chemistry

   RWTH Aachen University · Forschungszentrum Jülich

   Affiliation as printed

   Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

   Institute of Physical Chemistry RWTH Aachen University D‐52074 Aachen Germany

7. Leyela Hassen Adem

   National Taiwan University of Science and Technology

   Affiliation as printed

   Department of Chemical Engineering National Taiwan University of Science and Technology Taipei 10617 Taiwan

8. Bikila Nagasa Olana

   National Taiwan University of Science and Technology

   Affiliation as printed

   Department of Chemical Engineering National Taiwan University of Science and Technology Taipei 10617 Taiwan

9. Chih‐Long Tsai

   Forschungszentrum Jülich

   Affiliation as printed

   Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

10. Shicheng Yu

    Forschungszentrum Jülich

    Affiliation as printed

    Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

11. Luc H.J. Raijmakers

    Forschungszentrum Jülich

    Affiliation as printed

    Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

12. Hans Kungl

    Forschungszentrum Jülich

    Affiliation as printed

    Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

13. Hermann Tempel

    Forschungszentrum Jülich

    Affiliation as printed

    Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

14. Rafal E. Dunin‐Borkowski

    Forschungszentrum Jülich · Ernst Ruska Centre

    Affiliation as printed

    Ernst Ruska‐Centre for Microscopy and Spectroscopy with Electrons (ER‐C‐1) Forschungszentrum Jülich 52425 Jülich Germany

15. Shawn D. Lin

    National Taiwan University of Science and Technology

    Affiliation as printed

    Department of Chemical Engineering National Taiwan University of Science and Technology Taipei 10617 Taiwan

16. Mirijam Zobel Aachen Institute of Crystallography

    RWTH Aachen University · Forschungszentrum Jülich

    Affiliation as printed

    Institute of Crystallography RWTH Aachen University 52066 Aachen Germany

    Jülich Centre for Neutron Science ‐ Neutron Analytics for Energy Research (JCNS‐3) Forschungszentrum Jülich GmbH Wilhelm‐Johnen‐Straße 52428 Jülich Germany

17. Bing‐Joe Hwang

    National Taiwan University of Science and Technology

    Affiliation as printed

    Department of Chemical Engineering Nano‐electrochemistry Laboratory National Taiwan University of Science and Technology Taipei City 106 Taiwan

    Sustainable Electrochemical Energy Development Center National Taiwan University of Science and Technology Taipei City 106 Taiwan

18. Rüdiger‐A. Eichel Aachen Institute of Physical Chemistry

    RWTH Aachen University · Forschungszentrum Jülich

    Affiliation as printed

    Institute for Energy Technologies (IET–1: Fundamental Electrochemistry) Forschungszentrum Jülich D–52425 Jülich Germany

    Institute of Physical Chemistry RWTH Aachen University D‐52074 Aachen Germany