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Title: Influence of Mn/Fe Ratio on Electrochemical and Structural Properties of P2-NaxMn 1–yFeyO2 Phases as Positive Electrode Material for Na-Ion Batteries

Abstract

The comparative structural, Mössbauer, and electrochemical studies of the NaxMn2/3Fe1/3O2 and NaxMn1/2Fe1/2O2 systems show that the change in the Mn/Fe ratio has a significant influence on the overlap between the Mn3+/4+ and Fe3+/4+ redox couples. The P2-type structure is maintained in the 0.3 < x < 0.8 domain. For the highest intercalation amount, structural distortions occur due to the Jahn–Teller effect of the Mn3+ ions. The macroscopic distortion results from a competition between the opposite effects of Mn3+ and Fe3+: the isotropic character of Fe3+ tends to prevent the macroscopic distortion. For the lower sodium amounts, the instability of the interstitial trigonal prismatic space leads to the formation, by slab gliding, of a very disordered structure. Even if this structural transition is reversible, we note a strong capacity fading is observed if the cell is charged above 4 V verus Na/Na+.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]
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  1. CNRS, Univ. de Bordeaux, Cedex (France). Centre national de la recherche scientifique (CNRS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
Agence Nationale de la Recherché (ANR); Region Aquitaine; The French National Centre for Scientific Research (CNRS); USDOE Office of Science (SC)
OSTI Identifier:
1484781
Grant/Contract Number:  
2011-IS08-01; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 21; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
25 ENERGY STORAGE; Iron; Redox reactions; Transition metals; Materials; Ions

Citation Formats

Mortemard de Boisse, Benoit, Carlier, Dany, Guignard, Marie, Guerin, Elodie, Duttine, Mathieu, Wattiaux, Alain, and Delmas, Claude. Influence of Mn/Fe Ratio on Electrochemical and Structural Properties of P2-NaxMn 1–yFeyO2 Phases as Positive Electrode Material for Na-Ion Batteries. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b02953.
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Mortemard de Boisse, Benoit, Carlier, Dany, Guignard, Marie, Guerin, Elodie, Duttine, Mathieu, Wattiaux, Alain, & Delmas, Claude. Influence of Mn/Fe Ratio on Electrochemical and Structural Properties of P2-NaxMn 1–yFeyO2 Phases as Positive Electrode Material for Na-Ion Batteries. United States. https://doi.org/10.1021/acs.chemmater.8b02953
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Mortemard de Boisse, Benoit, Carlier, Dany, Guignard, Marie, Guerin, Elodie, Duttine, Mathieu, Wattiaux, Alain, and Delmas, Claude. Wed . "Influence of Mn/Fe Ratio on Electrochemical and Structural Properties of P2-NaxMn 1–yFeyO2 Phases as Positive Electrode Material for Na-Ion Batteries". United States. https://doi.org/10.1021/acs.chemmater.8b02953. https://www.osti.gov/servlets/purl/1484781.
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@article{osti_1484781,
title = {Influence of Mn/Fe Ratio on Electrochemical and Structural Properties of P2-NaxMn 1–yFeyO2 Phases as Positive Electrode Material for Na-Ion Batteries},
author = {Mortemard de Boisse, Benoit and Carlier, Dany and Guignard, Marie and Guerin, Elodie and Duttine, Mathieu and Wattiaux, Alain and Delmas, Claude},
abstractNote = {The comparative structural, Mössbauer, and electrochemical studies of the NaxMn2/3Fe1/3O2 and NaxMn1/2Fe1/2O2 systems show that the change in the Mn/Fe ratio has a significant influence on the overlap between the Mn3+/4+ and Fe3+/4+ redox couples. The P2-type structure is maintained in the 0.3 < x < 0.8 domain. For the highest intercalation amount, structural distortions occur due to the Jahn–Teller effect of the Mn3+ ions. The macroscopic distortion results from a competition between the opposite effects of Mn3+ and Fe3+: the isotropic character of Fe3+ tends to prevent the macroscopic distortion. For the lower sodium amounts, the instability of the interstitial trigonal prismatic space leads to the formation, by slab gliding, of a very disordered structure. Even if this structural transition is reversible, we note a strong capacity fading is observed if the cell is charged above 4 V verus Na/Na+.},
doi = {10.1021/acs.chemmater.8b02953},
journal = {Chemistry of Materials},
number = 21,
volume = 30,
place = {United States},
year = {Wed Oct 03 00:00:00 EDT 2018},
month = {Wed Oct 03 00:00:00 EDT 2018}
}
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https://doi.org/10.1021/acs.chemmater.8b02953
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