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@ARTICLE{Mitchell:639375,
author = {Mitchell, Nicole C. and Thomas, Oliver O. and Meyer,
Benjamin G. and Garcia-Fernandez, Mirian and Zhou, Ke-Jin
and Grant, Patrick S. and Bruce, Peter G. and Heap, Richard
and Sayers, Ruth and House, Robert},
title = {{I}nfluence of {I}on {S}ize on {S}tructure and {R}edox
{C}hemistry in {N}a‐{R}ich and {L}i‐{R}ich {D}isordered
{R}ocksalt {B}attery {C}athodes},
journal = {Advanced materials},
volume = {37},
number = {32},
issn = {0935-9648},
address = {Weinheim},
publisher = {Wiley-VCH},
reportid = {PUBDB-2025-04469},
pages = {2419878},
year = {2025},
abstract = {Li-rich disordered rocksalts are promising next-generation
cathode materials for Li-ion batteries. Recent reports have
shown it is also possible to obtain Na-rich disordered
rocksalts, however, it is currently poorly understood how
the knowledge of the structural and redox chemistry
translates from the Li-rich to the Na-rich analogs. Here,
the properties of Li2MnO2F and Na2MnO2F are compared, which
have different ion sizes (Li+ = 0.76 vs Na+ = 1.02 Å) but
the same disordered rocksalt structure and stoichiometry. It
is found that Na2MnO2F exhibits lower voltage Mn- and
O-redox couples, opening access to a wider compositional
range within the same voltage limits. Furthermore, the
intercalation mechanism switches from predominantly
single-phase solid solution behavior in Li2MnO2F to a
two-phase transition in Na2MnO2F, accompanied by a greater
decrease in the average Mn─O/F bond length. Li2MnO2F
retains its long-range disordered rocksalt structure
throughout the first cycle. In contrast, Na2MnO2F becomes
completely amorphous during charge and develops a local
structure characteristic of a post-spinel. This
amorphization is partially reversible on discharge. The
results show how the ion intercalation behavior of
disordered rocksalts differs dramatically when changing from
Li- to Na-ions and offers routes to control the
electrochemical properties of these high-energy-density
cathodes.},
cin = {DOOR ; HAS-User},
ddc = {660},
cid = {I:(DE-H253)HAS-User-20120731},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3)},
pid = {G:(DE-HGF)POF4-6G3},
experiment = {EXP:(DE-H253)P-P02.1-20150101},
typ = {PUB:(DE-HGF)16},
doi = {10.1002/adma.202419878},
url = {https://bib-pubdb1.desy.de/record/639375},
}