%0 Journal Article
%A Nguyen, Hung Quoc
%A Kanedal, Mikael Dahl
%A Todt, Juraj
%A Jin, Feng
%A Do, Quyen
%A Zalka, Dora
%A Maximenko, Alexey
%A Stoian, Dragos
%A Schell, Norbert
%A van Beek, Wouter
%A Fitzek, Harald
%A Rattenberger, Johannes
%A Siller, Valerie
%A Boles, Steven T.
%A El Kazzi, Mario
%A Keckes, Jozef
%A Rettenwander, Daniel
%T Revealing the Hidden Polysulfides in Solid-State Na–S Batteries: How Pressure and Electrical Transport Control Kinetic Pathways
%J Journal of the American Chemical Society
%V 147
%N 27
%@ 0002-7863
%C Washington, DC
%I ACS Publications
%M PUBDB-2025-03721
%P 23492 - 23503
%D 2025
%X 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.
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:40550758
%R 10.1021/jacs.5c00465
%U https://bib-pubdb1.desy.de/record/636702