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@ARTICLE{Yaqoob:1050081,
author = {Yaqoob, Najma and Huijben, Mark and Kaghazchi, Payam},
title = {{O}n the origin of phase transition suppression of
{P}2–{N}a 0.67 {M}n{O} 2 by substitution of {M}n with
{L}i},
journal = {Physical chemistry, chemical physics},
volume = {27},
number = {48},
issn = {1463-9076},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2025-05789},
pages = {26131 - 26138},
year = {2025},
abstract = {Mn-based layered oxides are promising cathode materials for
Na-ion batteries, but their low cyclability due to phase
transition during charge/discharge remains a challenge.
P2–Na0.67MnO2 compound undergoes a severe phase transition
of P2 → O2 during charging. It has been proposed that this
behavior results from the desodiation-induced change in the
Jahn–Teller (J–T) activity of Mn after its oxidation
from 3+ to 4+. In this work, we show that the driving force
of the phase transition is indeed the oxidation of Mn3+ to
Mn4+ but not the suppression of J–T activity with
desodiation. Combining density functional theory
calculations and electrostatic analyses indicates that the
main factor stabilizing the P2 phase is the Na–Mn
interaction, which strongly favors this phase over the O2
phase. Desodiation induced-weakening of this interaction
leads to the formation of O2–Na0.11MnO2, which is driven
by O–O interaction. Substituting Mn with Li stabilizes
P2–NaxLi0.22Mn0.78O2 even at low Na content (x = 0.11).
This is because the Na–Mn interaction is more favorable
for the P2 phase, and this energy preference remains almost
unchanged after desodiation. The absorption energy of Na at
Na sites close to LiTM is much stronger than at sites near
MnMn, and favors P2 phase. As the overall Na absorption
energy (dictated by Na–Mn repulsion) is mainly determined
by the nearest Na–Mn neighbor interaction, which does not
change much with desodiation, no phase transition to O2
occurs for NaxLi0.22Mn0.78O2 at x = 0.11. Overall, the phase
stability of Na-based layered oxide materials is driven by
electrostatic forces, which can be tuned by substitution of
Mn by a metal ion of appropriate charge and concentration.},
cin = {IMD-2},
ddc = {540},
cid = {I:(DE-Juel1)IMD-2-20101013},
pnm = {1221 - Fundamentals and Materials (POF4-122)},
pid = {G:(DE-HGF)POF4-1221},
typ = {PUB:(DE-HGF)16},
doi = {10.1039/D5CP02620B},
url = {https://juser.fz-juelich.de/record/1050081},
}