Journal Article

PUBDB-2025-03721

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Revealing the Hidden Polysulfides in Solid-State Na–S Batteries: How Pressure and Electrical Transport Control Kinetic Pathways

Nguyen, H. Q.Extern* ; Kanedal, M. D.Extern* ; Todt, J.Extern* ; Jin, F.Extern* ; Do, Q. ; Zalka, D.Extern* ; Maximenko, A.Extern* ; Stoian, D. ; Schell, N.HZG*Hereon* ; van Beek, W. ; Fitzek, H. ; Rattenberger, J. ; Siller, V. ; Boles, S. T. ; El Kazzi, M. ; Keckes, J.Extern* ; Rettenwander, D. (Corresponding author)Extern*

2025
ACS Publications Washington, DC

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Please use a persistent id in citations: doi:10.1021/jacs.5c00465  doi:10.3204/PUBDB-2025-03721

Abstract: Room temperature operation of Na−S batterieswith liquid electrolytes is plagued by fundamental challengesstemming from polysulfide solubility and their shuttle effects.Inorganic solid electrolytes offer a promising solution by acting asbarriers to polysulfide migration, mitigating capacity loss. While thesequential formation of cycling products in molten-electrode andliquid electrolytes-based Na−S batteries generally aligns with theexpectations from the Na−S phase diagram, their presence,stability, and transitory behavior in systems with inorganic solidelectrolytes at room temperature, remain poorly understood. Toaddress this, we employed operando scanning microbeam X-raydiffraction, operando X-ray photoelectron spectroscopy and ex-situX-ray absorption spectroscopy to investigate the sulfur conversionmechanisms in Na−S cells with Na3PS4 and Na4(B10H10)(B12H12) electrolytes. Our findings reveal the formation of crystalline andamorphous polysulfides, including those predicted by the Na−S phase diagram (e.g., Na2S5, Na2S4, Na2S2, Na2S), high-orderpolysulfides observed in liquid-electrolyte systems (e.g., Na2Sx, where x = 6−8), and phases like Na2S3 typically stable only underhigh-temperature or high-pressure conditions. We demonstrate that these transitions are governed by diffusion-limited kinetics andlocalized stress concentrations, emphasizing the critical role of pressure, which serves as both a thermodynamic variable, as well as adesign parameter, for optimizing solid-state Na−S battery performance necessary for pushing these cells closer to the commercialfrontier.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)
2. Helmholtz-Zentrum Hereon (Hereon)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. PSI-FELLOW-III-3i - International, Interdisciplinary & Intersectoral Postdoctoral Fellowships at the Paul Scherrer Institut (884104) (884104)
3. Sylinda - Synchrotron Light Industry Applications (952148) (952148)

Experiment(s):

1. PETRA Beamline P07 (PETRA III)

Appears in the scientific report 2025

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Database coverage:
; ; ; BIOSIS Previews ; Biological Abstracts ; Chemical Reactions ; Clarivate Analytics Master Journal List ; Current Contents - Life Sciences ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 15 ; Index Chemicus ; JCR ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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