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@ARTICLE{Ghoshal:639476,
author = {Ghoshal, Amit and Thakur, Vikas Singh and Pramanik, Susmita
and Mehta, Vanshika and Meena, Sher Singh and Hirsbrunner,
Moritz and Kaushik, S. D. and Dan, Tinku and Törnblom,
Pontus and Duda, Laurent and Ghosh, Anirudha and Såthe,
Conny and Tokushima, Takashi and Ghosh, Subham and Banerjee,
Swastika and Maitra, Urmimala},
title = {{U}nlocking high performance in a {N}a–{F}e–{M}n–{O}
cathode through phase-transition-free cycling},
journal = {EES batteries},
volume = {1},
number = {5},
issn = {3033-4071},
address = {Washington DC},
publisher = {Royal Society of Chemistry},
reportid = {PUBDB-2025-04562},
pages = {1255 - 1266},
year = {2025},
abstract = {Fe–Mn-based Na-layered oxide cathodes suffer from severe
phase transitions at high states of charge, accompanied by
transition metal migration and large-volume collapse. We
propose the incorporation of a small amount of Li+ into the
transition metal layer to enable phase-transition-free
cycling across a wide state-of-charge (SOC) range. In
contrast to the previously studied undoped or Li/Mg/Ni doped
P2-type Na–Fe–Mn–O cathodes, our
P2-Na0.7Li0.127Fe0.127Mn0.746O2 (NLFM) cathode, which has
optimized Li, Fe and Mn contents and a disordered
transition-metal layer, exhibits the remarkable property of
complete suppression of O-type layer formation up to the
highest charge voltage of 4.5 V. The cathode demonstrates
reversible high-voltage Fe and O redox reactions without any
phase transition. The P to O phase transition, accompanied
by transition-metal-migration and □–O–□ (□ =
vacancy) formation, is essential for the activation of
O-redox in undoped Fe–Mn cathodes. The highly ionic
character of Li–O bonds in NLFM increases the electron
density over the O orbitals, making O-redox feasible in the
P2-phase even in the absence of □–O–□. By retaining
its P2 phase at the highest state of charge, the cathode
shows a negligible volume change of less than $1.8\%,$
thereby yielding high energy density along with excellent
retention. The improved electrochemical performance of the
Li-doped cathode arises from dopant-induced static and
dynamic disorder, ensuring structural stability across a
wide SOC range.},
cin = {DOOR ; HAS-User / FS-NL},
ddc = {620},
cid = {I:(DE-H253)HAS-User-20120731 / I:(DE-H253)FS-NL-20120731},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / 6G3 - PETRA III (DESY) (POF4-6G3) /
INDIA-DESY - INDIA-DESY Collaboration
$(2020_Join2-INDIA-DESY)$ / FS-Proposal: I-20240481 EC
(I-20240481-EC)},
pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G3 /
$G:(DE-HGF)2020_Join2-INDIA-DESY$ /
G:(DE-H253)I-20240481-EC},
experiment = {EXP:(DE-H253)P-P65-20150101},
typ = {PUB:(DE-HGF)16},
doi = {10.1039/D5EB00106D},
url = {https://bib-pubdb1.desy.de/record/639476},
}