Protective NaSICON Interlayer between a Sodium-Tin Alloy Anode and Sulfide-Based Solid Electrolytes for All-Solid-State Sodium Batteries

Laura E Goodwin; Paul Till; Monika Bhardwaj; Nazia Nazer; Philipp Adelhelm; Frank Tietz; Wolfgang G Zeier; Felix H Richter; Jürgen Janek

doi:10.1021/acsami.3c09256

Protective NaSICON Interlayer between a Sodium-Tin Alloy Anode and Sulfide-Based Solid Electrolytes for All-Solid-State Sodium Batteries

ACS Appl Mater Interfaces. 2023 Nov 1;15(43):50457-50468. doi: 10.1021/acsami.3c09256. Epub 2023 Oct 19.

Authors

Laura E Goodwin^{1

2}, Paul Till³, Monika Bhardwaj⁴, Nazia Nazer⁵, Philipp Adelhelm⁵, Frank Tietz⁴, Wolfgang G Zeier^{3

6}, Felix H Richter^{1

2}, Jürgen Janek^{1

2}

Affiliations

¹ Institute for Physical Chemistry, Justus Liebig University Giessen, 35392 Giessen, Germany.
² Center for Materials Research (ZfM), Justus Liebig University Giessen, 35392 Giessen, Germany.
³ Institute for Inorganic and Analytical Chemistry, University of Münster, 48149 Münster, Germany.
⁴ Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany.
⁵ Institute of Chemistry, Humboldt University Berlin, 12489 Berlin, Germany.
⁶ Institut für Energie- und Klimaforschung (IEK), IEK-12: Helmholtz-Institut Münster, Forschungszentrum Jülich, 48149 Münster, Germany.

PMID: 37856165
DOI: 10.1021/acsami.3c09256

Abstract

This paper presents a suitable combination of different sodium solid electrolytes to surpass the challenge of highly reactive cell components in sodium batteries. The focus is laid on the introduction of ceramic Na_3.4Zr₂Si_2.4P_0.6O₁₂ serving as a protective layer for sulfide-based separator electrolytes to avoid the high reactivity with the sodium metal anode. The chemical instability of the anode|sulfide solid electrolyte interface is demonstrated by impedance spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. The Na_3.4Zr₂Si_2.4P_0.6O₁₂ disk shows chemical stability with the sodium metal anode as well as the sulfide solid electrolyte. Impedance analysis suggests an electrochemically stable interface. Electron microscopy points to a reaction at the Na_3.4Zr₂Si_2.4P_0.6O₁₂ surface toward the sulfide solid electrolyte, which does not seem to affect the performance negatively. The results presented prove the chemical stabilization of the anode-separator interface using a Na_3.4Zr₂Si_2.4P_0.6O₁₂ interlayer, which is an important step toward a sodium all-solid-state battery. Due to the applied pressure that is mandatory for battery cells with sulfide-based cathode composite, the use of a brittle ceramic in such cells remains challenging.

Keywords: NZSPO; NaSICON; all-solid-state battery; anode; protection layer; sodium battery; sodium tin; solid electrolyte.