TY  - JOUR
AU  - Nguyen, Hung Quoc
AU  - Kanedal, Mikael Dahl
AU  - Todt, Juraj
AU  - Jin, Feng
AU  - Do, Quyen
AU  - Zalka, Dora
AU  - Maximenko, Alexey
AU  - Stoian, Dragos
AU  - Schell, Norbert
AU  - van Beek, Wouter
AU  - Fitzek, Harald
AU  - Rattenberger, Johannes
AU  - Siller, Valerie
AU  - Boles, Steven T.
AU  - El Kazzi, Mario
AU  - Keckes, Jozef
AU  - Rettenwander, Daniel
TI  - Revealing the Hidden Polysulfides in Solid-State Na–S Batteries: How Pressure and Electrical Transport Control Kinetic Pathways
JO  - Journal of the American Chemical Society
VL  - 147
IS  - 27
SN  - 0002-7863
CY  - Washington, DC
PB  - ACS Publications
M1  - PUBDB-2025-03721
SP  - 23492 - 23503
PY  - 2025
AB  - 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.
LB  - PUB:(DE-HGF)16
C6  - pmid:40550758
DO  - DOI:10.1021/jacs.5c00465
UR  - https://bib-pubdb1.desy.de/record/636702
ER  -