Impact of Microstructural Properties on Ionic and Heat Transport in NaSICON Glass Ceramics

Batteries & Supercaps, vol. 8

Abstract

Two composition series of Zr‐deficient NaSICON materials are investigated with respect to their ionic and thermal transport properties. The bulk conductivity varies between 1.4 and 6.6 mS cm−1. The total conductivity showdecreasing values with increasing Zr deficiency due to the impact of the increasing fraction of glass phase. The calculated grain boundary conductivity is about two orders of magnitude lower than the total conductivity but does not correspond to the conductivity of any known glass composition of sodium silicates/phosphates. Nuclear magnetic resonance reveals three 23Na relaxation rates, the fastest of which is attributed to the NaSICON phase and the two slower relaxation rates to sodium orthophosphates and the glass phase. Thermal conductivity varies between 0.9 and 1.0 W m−1 K−1 at 25 °C. At elevated temperatures, a clear trend is observed toward lower thermal conductivity with a higher glass fraction. In addition, atom probe tomography is applied to precisely quantify the composition of specific microstructural regions found within the glassy phase. A scanning electron microscopy study of the surfaces of sintered pellets shows an increasing amount of glass phase between the NaSICON particles with increasing Zr deficiency. Furthermore, a time‐dependent phase separation is observed in relation to the dynamic formation and dissolution of Na3PO4 domains.

Authors 11

1. Frank Tietz corresponding

   Forschungszentrum Jülich · Helmholtz-Institute Münster

   Affiliation as printed

   Institute of Energy Materials and Devices IMD‐2: Materials Synthesis and Processing Forschungszentrum Jülich GmbH 52425 Jülich Germany

   Institute of Energy Materials and Devices IMD‐4: Helmholtz Institute Münster – Ionics in Energy Storage Forschungszentrum Jülich GmbH 52425 Jülich Germany

2. Philipp Odenwald

   Forschungszentrum Jülich

   Affiliation as printed

   Institute of Energy Materials and Devices IMD‐2: Materials Synthesis and Processing Forschungszentrum Jülich GmbH 52425 Jülich Germany

   Keysight Technologies Deutschland GmbH Herrenberger Straße 130 71034 Böblingen Germany

3. Doris Sebold

   Forschungszentrum Jülich

   Affiliation as printed

   Institute of Energy Materials and Devices IMD‐2: Materials Synthesis and Processing Forschungszentrum Jülich GmbH 52425 Jülich Germany

4. Mareen Schaller

   Karlsruhe Institute of Technology

   Affiliation as printed

   Institute for Applied Materials – Energy Storage Systems Karlsruhe Institute of Technology Hermann‐von‐Helmholtz‐Platz 1 76344 Eggenstein‐Leopoldshafen Germany

5. Thorben Böger

   University of Münster

   Affiliation as printed

   Institute of Inorganic and Analytical Chemistry University of Münster Corrensstraße 28/30 48149 Münster Germany

   International Graduate School for Battery Chemistry, Characterization, Analysis, Recycling and Application (BACCARA) University of Münster 48149 Münster Germany

6. Jan Köttgen Aachen I. Physical Institute (IA)

   RWTH Aachen University

   Affiliation as printed

   I. Physical Institute (IA) RWTH Aachen University 52056 Aachen Germany

7. Qianli Ma

   Forschungszentrum Jülich

   Affiliation as printed

   Institute of Energy Materials and Devices IMD‐2: Materials Synthesis and Processing Forschungszentrum Jülich GmbH 52425 Jülich Germany

8. Sylvio Indris

   Karlsruhe Institute of Technology

   Affiliation as printed

   Institute for Applied Materials – Energy Storage Systems Karlsruhe Institute of Technology Hermann‐von‐Helmholtz‐Platz 1 76344 Eggenstein‐Leopoldshafen Germany

9. Wolfgang G. Zeier

   Forschungszentrum Jülich · University of Münster · Helmholtz-Institute Münster

   Affiliation as printed

   Institute of Energy Materials and Devices IMD‐4: Helmholtz Institute Münster – Ionics in Energy Storage Forschungszentrum Jülich GmbH 48149 Münster Germany

   Institute of Inorganic and Analytical Chemistry University of Münster Corrensstraße 28/30 48149 Münster Germany

10. Oana Cojocaru‐Mirédin

    University of Freiburg

    Affiliation as printed

    Department of Sustainable Systems Engineering (INATECH) University of Freiburg Georges‐Köhler‐Allee 102 79110 Freiburg Germany

11. Dina Fattakhova‐Rohlfing

    Forschungszentrum Jülich · Helmholtz-Institute Münster · University of Duisburg-Essen

    Affiliation as printed

    Faculty of Engineering and Center for Nanointegration Duisburg‐Essen (CENIDE) University of Duisburg‐Essen Lotharstraße 1 47057 Duisburg Germany

    Institute of Energy Materials and Devices IMD‐2: Materials Synthesis and Processing Forschungszentrum Jülich GmbH 52425 Jülich Germany

    Institute of Energy Materials and Devices IMD‐4: Helmholtz Institute Münster – Ionics in Energy Storage Forschungszentrum Jülich GmbH 52425 Jülich Germany