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Nanofeather ruthenium nitride electrodes for electrochemical capacitors

Nature Materials (2024)Cite this article

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Abstract

Fast charging is a critical concern for the next generation of electrochemical energy storage devices, driving extensive research on new electrode materials for electrochemical capacitors and micro-supercapacitors. Here we introduce a significant advance in producing thick ruthenium nitride pseudocapacitive films fabricated using a sputter deposition method. These films deliver over 0.8 F cm–2 (~500 F cm–3) with a time constant below 6 s. By utilizing an original electrochemical oxidation process, the volumetric capacitance doubles (1,200 F cm–3) without sacrificing cycling stability. This enables an extended operating potential window up to 0.85 V versus Hg/HgO, resulting in a boost to 3.2 F cm–2 (3,200 F cm–3). Operando X-ray absorption spectroscopy and transmission electron microscopy analyses reveal novel insights into the electrochemical oxidation process. The charge storage mechanism takes advantage of the high electrical conductivity and the morphology of cubic ruthenium nitride and Ru phases in the feather-like core, leading to high electrical conductivity in combination with high capacity. Accordingly, we have developed an analysis that relates capacity to time constant as a means of identifying materials capable of retaining high capacity at high charge/discharge rates.

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Fig. 1: Schematic of the design and deposition of the nanofeather RuN electrode for an MSC.
Fig. 2: Structural and chemical analyses of thin RuN films.
Fig. 3: Structural and electrochemical analyses of thick RuN films.
Fig. 4: EOP on a RuN electrode.
Fig. 5: Investigation of EOP by operando XAS under synchrotron beam, TEM analyses and related electrochemical performance after oxidation.

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The data that support the findings of this study are available from the corresponding authors on reasonable request.

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Acknowledgements

This project received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 847568. We would like to thank the French National Research Agency (STORE-EX Labex Project ANR-10-LABX-76-01 and ARTEMIS ANR project). The French RENATECH network, the NANOFUTUR EquipEx+ program and the University of Lille are greatly acknowledged for supporting the Center of MicroNanoFabrication (CMNF) facility from IEMN. The Chevreul Institute (FR CNRS 2638) is thanked for providing access to X-ray and TEM facilities. It is funded by the ‘Ministère de l’Enseignement Supérieur de la Recherche et de l’Innovation’, Region ‘Hauts-de-France’, ERDF program of the European Union and ‘Métropole Européenne de Lille’. The XAS measurements were supported by a public grant overseen by the French National Research Agency (ANR) as part of the ‘Investissements d’Avenir’ program (reference: ANR-10-EQPX45). We acknowledge SOLEIL for the provision of the synchrotron radiation facilities (ROCK beamline, proposal no. 20220111). We also wish to thank the Department of Materials Science and Engineering (UCLA) for the use of their XPS facilities. This work received funding from the CPER Hauts-de-France projects, IMITECH and MEL.

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Authors and Affiliations

  1. Institut d’Electronique, de Microélectronique et de Nanotechnologies, Université de Lille, CNRS, Université Polytechnique des Hauts de France, Lille, France

    Huy Dinh Khac, Houssine Makhlouf, Isabelle Roch-Jeune & Christophe Lethien

  2. Unité de Catalyse et de Chimie du Solide (UCCS), Université de Lille, CNRS, Centrale Lille, Université d’Artois, Lille, France

    Huy Dinh Khac, Marielle Huvé & Pascal Roussel

  3. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), CNRS FR 3459, Amiens Cedex, France

    Huy Dinh Khac, Antonella Iadecola, Houssine Makhlouf, Camille Douard, Thierry Brousse & Christophe Lethien

  4. Department of Materials Science and Engineering, University of California, Los Angeles, CA, USA

    Grace Whang & Bruce Dunn

  5. Sorbonne Université, CNRS, Physicochimie des Electrolytes et Nanosystèmes Interfaciaux, UMR CNRS 8234, Paris, France

    Antonella Iadecola

  6. CIRIMAT, Université de Toulouse, CNRS, Université Toulouse III—Paul Sabatier, Toulouse Cedex 9, France

    Antoine Barnabé

  7. Université de Lille, CNRS, INRAE, Centrale Lille, Unité Matériaux et Transformations, Lille, France

    Adrien Teurtrie & Maya Marinova

  8. Université de Lille, CNRS, INRAE, Centrale Lille, Université d’Artois, FR 2638, IMEC—Institut Michel-Eugène Chevreul, Lille, France

    Maya Marinova

  9. Nantes Université, CNRS, Institut des Matériaux de Nantes Jean Rouxel, Nantes, France

    Camille Douard & Thierry Brousse

  10. Institut Universitaire de France (IUF), Paris, France

    Christophe Lethien

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  1. Huy Dinh Khac
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Contributions

H.D.K., I.R.-J., P.R. and C.L. were involved in the deposition of ruthenium films by sputtering techniques (methodology, investigation, formal analysis, visualization), their structural and morphological analyses and the writing of the original draft. H.D.K., H.M. and C.L. participated in the investigations of the electrochemical properties in aqueous electrolytes. A.B. investigated the chemical properties of the RuN films by GDOES. M.H., A.T. and M.M. were involved in the TEM analyses and the writing of the original draft. A.I., C.D., C.L. and T.B. were involved in the design of the XAS cells, data processing of the XAS spectra and the writing of the original draft. G.W. and B.D. were involved in the study of RuN films by XPS analyses and the writing of the original draft. P.R. and C.L. were involved in the resources, conceptualization, methodology, validation, writing of the original draft, editing, supervision, funding acquisition and project administration processes. G.W., B.D., T.B., P.R. and C.L. were involved in the revision process of the initial draft.

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Correspondence to Pascal Roussel or Christophe Lethien.

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Dinh Khac, H., Whang, G., Iadecola, A. et al. Nanofeather ruthenium nitride electrodes for electrochemical capacitors. Nat. Mater. (2024). https://doi.org/10.1038/s41563-024-01816-0

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