From structure to electrochemistry: the influence of transition metal ordering on Na+/vacancy orderings in P2-type NaxMO2 cathode materials for sodium-ion batteries†

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Date

2024-11-28

Authors

Pfeiffer, Lukas Fridolin
Dillenz, Manuel
Burgard, Nora
Beran, Premysl
Roscher, Daniel
Zarrabeitia, Maider
Drews, Paul
Hervoches, Charles
Mikhailova, Daria
Omar, Ahmad

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Wissenschaftlicher Artikel

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Journal of Materials Chemistry A, 2024

Abstract

P2-type layered oxides are attractive cathode active materials for sodium-ion batteries, however, these materials typically suffer from detrimental Na+/vacancy orderings. In this work, we investigate the origin as well as the influence of the transition metal ratio on Na+/vacancy orderings in P2-type cathode materials. A combination of X-ray diffraction (XRD), neutron diffraction, advanced electrochemical methods, operando XRD and DFT calculations is applied to study Na+/vacancy orderings in P2-NaxNi1/3Mn2/3O2 and P2-NaxMn3/4Ni1/4O2. In P2-NaxNi1/3Mn2/3O2, a honeycomb Ni/Mn superstructure leads to charge ordering within the transition metal slab and pronounced Na+/vacancy orderings, causing distinct voltage jumps at specific sodium contents (x = 2/3, 1/2 and 1/3). For P2-Na0.60Mn3/4Ni1/4O2, the Ni/Mn superstructure is disrupted, resulting in more complex charge orderings within the transition metal slab, partially suppressed Na+/vacancy orderings and an overall smoother potential profile. Based on our findings, guidelines to suppress Na+/vacancy orderings in P2-type cathode materials for sodium-ion batteries are postulated and discussed with respect to electrochemical measurements of various transition metal compositions. These guidelines can serve to predict the tendency towards Na+/vacancy orderings for a given cathode composition or to design new cathode compositions for enhanced cycle life based on the absence of Na+/vacancy orderings.

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Faculties

Fakultät für Naturwissenschaften

Institutions

Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg (ZSW)
Helmholtz-Institut Ulm (HIU)
Institut für Theoretische Chemie

Citation

DFG Project uulm

EXC 2154 / POLiS / POLiS - Post Lithium Storage Cluster of Excellence / DFG / 390874152
JUSTUS 2 / HPC Forschungscluster (bwForCluster) Computergestützte Chemie und Quantenwissenschaften / DFG / 405998092 [INST 40/575-1 FUGG]

EU Project THU

Other projects THU

ExcellBattUlm / ExcellBattUlm - Nachhaltige umweltfreundliche und sichere Materialien für Hochenergie-Lithium-Ionen-Batterien - Materialien Zellen Modellierung / BMBF / 03XP0257C
bwHPC / Land Baden-Württemberg

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DOI external

10.1039/d4ta04786a

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DFG Project THU

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Keywords

Natrium-Ionen-Akkumulator, Sodium ion batteries, DDC 540 / Chemistry & allied sciences