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Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR

Nature Materials volume 12, pages 351–358 (2013)Cite this article

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Abstract

Supercapacitors are electrochemical energy-storage devices that exploit the electrostatic interaction between high-surface-area nanoporous electrodes and electrolyte ions. Insight into the molecular mechanisms at work inside supercapacitor carbon electrodes is obtained with 13C and 11B ex situ magic-angle spinning nuclear magnetic resonance (MAS-NMR). In activated carbons soaked with an electrolyte solution, two distinct adsorption sites are detected by NMR, both undergoing chemical exchange with the free electrolyte molecules. On charging, anions are substituted by cations in the negative carbon electrode and cations by anions in the positive electrode, and their proportions in each electrode are quantified by NMR. Moreover, acetonitrile molecules are expelled from the adsorption sites at the negative electrode alone. Two nanoporous carbon materials were tested, with different nanotexture orders (using Raman and 13C MAS-NMR spectroscopies), and the more disordered carbon shows a better capacitance and a better tolerance to high voltages.

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Figure 1: Carbon-13 NMR spectra of soaked electrodes.
Figure 2: Boron-11 NMR spectra of soaked electrodes.
Figure 3: Chemical exchange between sites observed by NMR.
Figure 4: State of the electrolyte before and after one cycle.
Figure 5: Proportions of electrolyte species and chemical shift changes in carbon A.
Figure 6: Proportions of electrolyte species and chemical shift changes in carbon B.

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Acknowledgements

Authors from the CEMTHI and CRMD laboratories thank CNRS for its support, and the authors from CEMHTI acknowledge support from the Réseau sur le Stockage Electrochimique de l’Energie (RS2E FR3459 CNRS) and the STORE-EX Laboratory of Excellence (LabEx) for funding. The author from ICTE acknowledges the support of the Foundation for Polish Science within the WELCOME programme (ECOLCAP project).

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Authors and Affiliations

  1. CNRS, UPR3079 CEMHTI, 1D avenue de la Recherche Scientifique, 45071 Orléans cedex 2, France

    Michaël Deschamps, Mohammed Ramzi Ammar, Patrick Simon & Dominique Massiot

  2. Université d’Orléans, Faculté des Sciences, Avenue du Parc Floral, BP 6749, 45067 Orléans cedex 2, France

    Michaël Deschamps, Mohammed Ramzi Ammar, Patrick Simon & Dominique Massiot

  3. CRMD, CNRS-University, 1B rue de la Férollerie, 45071 Orléans, France

    Edouard Gilbert & Encarnación Raymundo-Piñero

  4. Batscap, Odet - 29500 Ergué-Gabéric, France

    Philippe Azais

  5. ICTE, Faculty of Chemical Technology, Poznan University of Technology, Piotrowo 3, 60-965 Poznan, Poland

    François Béguin

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  1. Michaël Deschamps
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Contributions

The NMR experiments and their analysis were performed by M.D. and D.M., the Raman experiments were performed by M.R.A. and P.S., and the supercapacitors were made by E.G. during his PhD (supervisors: E.R.P. and F.B.) in collaboration with P.A.

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Correspondence to Michaël Deschamps.

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Deschamps, M., Gilbert, E., Azais, P. et al. Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR. Nature Mater 12, 351–358 (2013). https://doi.org/10.1038/nmat3567

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