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Highlighting the reversible manganese electroactivity in Na‐rich manganese hexacyanoferrate material for Li‐ and Na‐ion storage

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peer-reviewed

Erstveröffentlichung
2019-09-25
Authors
Mullaliu, Angelo
Asenbauer, Jakob
Aquilanti, Giuliana
Passerini, Stefano
Giorgetti, Marco
Wissenschaftlicher Artikel


Published in
Small Methods ; 4 (2019), 1. - Art.-Nr. 1900529. - eISSN 2366-9608
Link to original publication
https://dx.doi.org/10.1002/smtd.201900529
Institutions
Helmholtz-Institut Ulm
Document version
published version (publisher's PDF)
Abstract
The electroactivity of sodium-rich manganese hexacyanoferrate (MnHCF) material constituted of only abundant elements, as insertion host for Li- and Na-ions is herein comprehensively discussed. This material features high specific capacities (>130 mAh g−1) at high potentials when compared to other materials of the same class, i.e., Prussian blue analogs. The reversible electronic and structural modifications occurring during ion release/uptake, which are responsible for such high specific capacity, are revealed herein. The in-depth electronic and structural analysis carried out combining X-ray diffraction and X-ray absorption spectroscopy (XAS), demonstrates that both Fe and Mn sites are involved in the electrochemical process, being the high delivered capacity the result of a reversible evolution in oxidation states of the metallic centers (Fe3+/Fe2+ and Mn2+/Mn3+). Along with the Mn2+/Mn3+ oxidation, the Mn local environment experiences a substantial yet reversible Jahn–Teller effect, being the equatorial Mn-N distances shrunk by 10% (2.18 Å → 1.96 Å). Na-rich MnHCF material offers slightly higher performance upon uptake and release of Na-ions (469 Wh kg−1) than Li-ions (457 Wh kg−1), being, however, the electronic and structural transformation independent of the adopted medium, as observed by XAS spectroscopy.
Project uulm
POST-LI BATTERIES / Helmholtz Institut Ulm / ExNet-0035 / pLB
Is supplemented by
https://onlinelibrary.wiley.com/action/downloadSupplement?doi=10.1002%2Fsmtd.201900529&file=smtd201900529-sup-0001-S1.pdf
Subject headings
[GND]: EXAFS | Jahn-Teller-Effekt | Röntgenabsorptionsspektroskopie | Röntgenstreuung
[LCSH]: Jahn-Teller effect | X-ray diffraction imaging
[Free subject headings]: manganese hexacyanoferrate | X‐ray absorption | X‐ray diffraction
[DDC subject group]: DDC 540 / Chemistry & allied sciences
License
CC BY-NC-ND 4.0 International
https://creativecommons.org/licenses/by-nc-nd/4.0/

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DOI & citation

Please use this identifier to cite or link to this item: http://dx.doi.org/10.18725/OPARU-43904

Mullaliu, Angelo et al. (2022): Highlighting the reversible manganese electroactivity in Na‐rich manganese hexacyanoferrate material for Li‐ and Na‐ion storage. Open Access Repositorium der Universität Ulm und Technischen Hochschule Ulm. http://dx.doi.org/10.18725/OPARU-43904
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