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

Mortemard de Boisse, Benoit; Carlier, Dany; Guignard, Marie; Guerin, Elodie; Duttine, Mathieu; Wattiaux, Alain; Delmas, Claude

doi:10.1021/acs.chemmater.8b02953

Title: Influence of Mn/Fe Ratio on Electrochemical and Structural Properties of P2-Na_xMn _1–yFe_yO₂ Phases as Positive Electrode Material for Na-Ion Batteries

Journal Article · Wed Oct 03 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b02953· OSTI ID:1484781

Mortemard de Boisse, Benoit ^[1];

^[1];

^[1]; Guerin, Elodie ^[1]; Duttine, Mathieu ^[1]; Wattiaux, Alain ^[1];

^[1]

CNRS, Univ. de Bordeaux, Cedex (France). Centre national de la recherche scientifique (CNRS)

The comparative structural, Mössbauer, and electrochemical studies of the Na_xMn_2/3Fe_1/3O₂ and Na_xMn_1/2Fe_1/2O₂ systems show that the change in the Mn/Fe ratio has a significant influence on the overlap between the Mn^3+/4+ and Fe^3+/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⁺.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: Agence Nationale de la Recherché (ANR); Region Aquitaine; The French National Centre for Scientific Research (CNRS); USDOE Office of Science (SC)

Grant/Contract Number:: 2011-IS08-01; AC02-06CH11357

OSTI ID:: 1484781

Journal Information:: Chemistry of Materials, Vol. 30, Issue 21; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 22 works

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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

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Title: Influence of Mn/Fe Ratio on Electrochemical and Structural Properties of P2-Na_xMn _1–yFe_yO₂ Phases as Positive Electrode Material for Na-Ion Batteries