Journal Article

IMPULSE-2024-00199

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png From structure to electrochemistry: the influence of transition metal ordering on Na$^{+}$ /vacancy orderings in P2-type Na$_{x}$MO$_{2}$ cathode materials for sodium-ion batteries

Pfeiffer, L. F. (Corresponding author) ; Dillenz, M. ; Burgard, N. ; Beran, P. ; Roscher, D. ; Zarrabeitia, M. ; Drews, P. ; Hervoches, C. ; Mikhailova, D. ; Omar, A. ; Baran, V. ; Paul, N.MLZ* ; Sotoudeh, M. ; Busch, M. ; Wohlfahrt-Mehrens, M. ; Groß, A. ; Passerini, S. ; Axmann, P. (Corresponding author)

2025
RSC London ˜[u.a.]œ

Please use a persistent id in citations: doi:10.1039/D4TA04786A

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.

Keyword(s): Energy (1st) ; Crystallography (2nd) ; Materials Science (2nd)

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Contributing Institute(s):

1. DEVA (DEVA)

Experiment(s):

1. Measurement at external facility

Appears in the scientific report 2025

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Clarivate Analytics Master Journal List ; Current Contents - Engineering, Computing and Technology ; Current Contents - Engineering, Computing and Technology ; Current Contents - Physical, Chemical and Earth Sciences ; Current Contents - Physical, Chemical and Earth Sciences ; Essential Science Indicators ; Essential Science Indicators ; IF >= 10 ; IF >= 10 ; JCR ; JCR ; National-Konsortium ; National-Konsortium ; SCOPUS ; SCOPUS ; Science Citation Index Expanded ; Science Citation Index Expanded ; Web of Science Core Collection ; Web of Science Core Collection

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