Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na<sub>2</sub>  IrO<sub>3</sub>

Arnaud J. Perez; Dmitry Batuk; Matthieu Saubanère; Gwenaelle Rousse; Dominique Foix; Eric Mccalla; Erik J. Berg; Romain Dugas; Karel H. W. van den Bos; Marie-Liesse Doublet; Danielle Gonbeau; Artem M. Abakumov; Gustaaf van Tendeloo; Jean‐marie Tarascon

doi:10.1021/acs.chemmater.6b03338

Journal articles

Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na₂ IrO₃

Arnaud J. Perez ¹ Dmitry Batuk ^{2, 1} Matthieu Saubanère ^{3, 4, 1} Gwenaelle Rousse ^{1, 3} Dominique Foix ^{5, 3} Eric Mccalla ^{6, 1, 3} Erik J. Berg ⁷ Romain Dugas ^{1, 3} Karel H. W. van den Bos ² Marie-Liesse Doublet ^{3, 4} Danielle Gonbeau ^{3, 5} Artem M. Abakumov ^{8, 2} Gustaaf van Tendeloo ² Jean‐marie Tarascon ^{1, 3, *}

* Corresponding author

1 Chaire Chimie du solide et énergie

CSE - Chimie du solide et de l'énergie

2 UA - University of Antwerp

3 RS2E - Réseau sur le stockage électrochimique de l'énergie

4 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

5 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux

6 UMN - University of Minnesota [Twin Cities]

7 PSI - Paul Scherrer Institute

8 Skoltech - Skolkovo Institute of Science and Technology [Moscow]

Abstract : The recent revival of the Na-ion battery concept has prompted intense activities in the search for new Na-based layered oxide positive electrodes. The largest capacity to date was obtained for a Na-deficient layered oxide that relies on cationic redox processes only. To go beyond this limit, we decided to chemically manipulate these Na-based layered compounds in a way to trigger the participation of the anionic network. We herein report the electrochemical properties of a Na-rich phase Na2IrO3, which can reversibly cycle 1.5 Na+ per formula unit while not suffering from oxygen release nor cationic migrations. Such large capacities, as deduced by complementary XPS, X-ray/neutron diffraction and transmission electron microscopy measurements, arise from cumulative cationic and anionic redox processes occurring simultaneously at potentials as low as 2.7 V vs Na+/Na. The inability to remove more than 1.5 Na+ is rooted in the formation of an O1-type phase having highly stabilized Na sites as confirmed by DFT calculations, which could rationalize as well the competing metal/oxygen redox processes in Na2IrO3. This work will help to define the most fertile directions in the search for novel high energy Na-rich materials based on more sustainable elements than Ir.

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Chemical Sciences / Material chemistry

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Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na₂ IrO₃

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Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na2 IrO3

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Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na₂ IrO₃