Role of the voltage window on the capacity retention of P2-Na2/3[Fe1/2Mn1/2]O2 cathode material for rechargeable sodium-ion batteries

Zarrabeitia Ipiña, Maider; Nobili, Francesco; Lakuntza Irigoien, Oier; Carrasco Rodríguez, Javier; Rojo Aparicio, Teófilo; Casas Cabanas, Montserrat; Muñoz Márquez, Miguel Angel

Ikusi/Ireki

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Data

2022-02

Egilea

Zarrabeitia Ipiña, Maider

Nobili, Francesco

Lakuntza Irigoien, Oier

Carrasco Rodríguez, Javier

Rojo Aparicio, Teófilo

Casas Cabanas, Montserrat

Muñoz Márquez, Miguel Angel

Metadata

Itemaren erregistro osoa erakusten du

Estadisticas en RECOLECTA
(LA Referencia)

Communications Chemistry 5 : (2022) // Article ID 11

URI

http://hdl.handle.net/10810/55488

Laburpena

[EN] P2-Na-2/3[Fe1/2Mn1/2]O-2 layered oxide is a promising high energy density cathode material for sodium-ion batteries. However, one of its drawbacks is the poor long-term stability in the operating voltage window of 1.5-4.25 V vs Na+/Na that prevents its commercialization. In this work, additional light is shed on the origin of capacity fading, which has been analyzed using a combination of experimental techniques and theoretical methods. Electrochemical impedance spectroscopy has been performed on P2-Na-2/3[Fe1/2Mn1/2]O-2 half-cells operating in two different working voltage windows, one allowing and one preventing the high voltage phase transition occurring in P2-Na-2/3[Fe1/2Mn1/2]O-2 above 4.0 V vs Na+/Na; so as to unveil the transport properties at different states of charge and correlate them with the existing phases in P2-Na-2/3[Fe1/2Mn1/2]O-2. Supporting X-ray photoelectron spectroscopy experiments to elucidate the surface properties along with theoretical calculations have concluded that the formed electrode-electrolyte interphase is very thin and stable, mainly composed by inorganic species, and reveal that the structural phase transition at high voltage from P2- to "Z"/OP4-oxygen stacking is associated with a drastic increased in the bulk electronic resistance of P2-Na-2/3[Fe1/2Mn1/2]O-2 electrodes which is one of the causes of the observed capacity fading. P2-Na-2/3[Fe1/2Mn1/2]O-2 is a promising high energy density cathode material for rechargeable sodium-ion batteries, but its poor long-term stability in the operating voltage window of 1.5-4.25 V vs Na+/Na hinders its commercial application. Here, the authors use a combination of electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and DFT calculations to investigate the origin of the capacity fading, which is attributed to an increase in bulk electronic resistance at high voltage that, among other factors, is nested in a structural phase transition.

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Bestelakorik adierazi ezean, itemaren baimena horrela deskribatzen da:This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.