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@ARTICLE{Nguyen:636702,
author = {Nguyen, Hung Quoc and Kanedal, Mikael Dahl and Todt, Juraj
and Jin, Feng and Do, Quyen and Zalka, Dora and Maximenko,
Alexey and Stoian, Dragos and Schell, Norbert and van Beek,
Wouter and Fitzek, Harald and Rattenberger, Johannes and
Siller, Valerie and Boles, Steven T. and El Kazzi, Mario and
Keckes, Jozef and Rettenwander, Daniel},
title = {{R}evealing the {H}idden {P}olysulfides in {S}olid-{S}tate
{N}a–{S} {B}atteries: {H}ow {P}ressure and {E}lectrical
{T}ransport {C}ontrol {K}inetic {P}athways},
journal = {Journal of the American Chemical Society},
volume = {147},
number = {27},
issn = {0002-7863},
address = {Washington, DC},
publisher = {ACS Publications},
reportid = {PUBDB-2025-03721},
pages = {23492 - 23503},
year = {2025},
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.},
cin = {DOOR ; HAS-User / Hereon},
ddc = {540},
cid = {I:(DE-H253)HAS-User-20120731 / I:(DE-H253)Hereon-20210428},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / PSI-FELLOW-III-3i -
International, Interdisciplinary $\&$ Intersectoral
Postdoctoral Fellowships at the Paul Scherrer Institut
(884104) / Sylinda - Synchrotron Light Industry Applications
(952148)},
pid = {G:(DE-HGF)POF4-6G3 / G:(EU-Grant)884104 /
G:(EU-Grant)952148},
experiment = {EXP:(DE-H253)P-P07-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:40550758},
doi = {10.1021/jacs.5c00465},
url = {https://bib-pubdb1.desy.de/record/636702},
}