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.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Chmiola, J., Largeot, C., Taberna, P. L., Simon, P. & Gogotsi, Y. Desolvation of ions in subnanometer pores and its effect on capacitance and double-layer theory. Angew. Chem. Int. Ed. 47, 3392–3395 (2008).
Huang, J., Sumpter, B. G. & Meunier, V. Theoretical model for nanoporous carbon supercapacitors. Angew. Chem. Int. Ed. 47, 520–524 (2008).
Kiyohara, K., Sugino, T. & Asaka, K. Electrolytes in porous electrodes: Effects of the pore size and the dielectric constant of the medium. J. Chem. Phys. 132, 144705 (2010).
Vix-Guterl, C., Frackowiak, E., Jurewicz, K., Friebe, M. & Béguin, F. Relationship between the nanoporous texture of activated carbons and their capacitance properties in different electrolytes. Carbon 43, 1293–1302 (2005).
Chmiola, J. et al. Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer. Science 313, 1760–1763 (2006).
Lastoskie, C., Gubbins, K. E. & Quirke, N. Pore size distribution analysis of microporous carbons: A density functional theory approach. J. Phys. Chem. 97, 4786–4796 (1993).
Levi, M. D., Salitra, G., Levy, N., Aurbach, D. & Maier, J. Application of a quartz-crystal microbalance to measure ionic fluxes in microporous carbons for energy storage. Nature Mater. 8, 872–875 (2009).
Levi, M. D. et al. Electrochemical quartz crystal microbalance (EQCM) studies of ions and solvents insertion into highly porous activated carbons. J. Am. Chem. Soc. 132, 13220–13222 (2010).
Tanaka, A. et al. Effect of a quaternary ammonium salt on propylene carbonate structure in slit-shape carbon nanopores. J. Am. Chem. Soc. 132, 2112–2113 (2010).
Merlet, C. et al. On the molecular origin of supercapacitance in nanoporous carbon electrodes. Nature Mater. 11, 306–310 (2012).
Lee, S. I. et al. 11B NMR study of the BF4− anion in activated carbons at various stages of charge of EDLCs in organic electrolyte. Carbon 44, 2578–2586 (2006).
Azaïs, P. et al. Causes of supercapacitors ageing in organic electrolyte. J. Power Sources 171, 1046–1053 (2007).
Harris, R. K., Thompson, T. V., Norman, P. R. & Pottage, C. Adsorption competition onto activated carbon, studied by magic-angle spinning NMR. J. Chem. Soc. Faraday Trans. 92, 2615–2618 (1996).
Harris, R. K. et al. A magic-angle spinning NMR study into the adsorption of deuterated water by activated carbon. Carbon 34, 1275–1279 (1996).
Harris, R. K., Thompson, T. V., Norman, P. R., Pottage, C. & Trethewey, A. N. High-resolution 2H solid-state NMR of 2H2O adsorbed onto activated carbon. J. Chem. Soc. Faraday Trans. 91, 1795–1799 (1995).
Wagner, G. W., MacIver, B. K. & Yang, Y-C. Magic angle spinning NMR study of adsorbate reactions on activated charcoal. Langmuir 11, 1439–1442 (1995).
Harris, R. K., Thompson, T. V., Norman, P. R. & Pottage, C. Phosphorus-31 NMR studies of adsorption onto activated carbon. Carbon 37, 1425–1430 (1999).
Dickinson, L. M., Harris, R. K., Shaw, J. A., Chinn, M. & Norman, P. R. Oxygen-17 and deuterium NMR investigation into the adsorption of water on activated carbon. Magn. Reson. Chem. 38, 918–924 (2000).
Solum, M. S., Pugmire, R. J., Jagtoyen, M. & Derbyshire, F. Evolution of carbon structure in chemically activated wood. Carbon 33, 1247–1254 (1995).
Hsu, M-L. et al. A two-dimensional 13C-NMR study of powdered and oriented mesophase pitches. Carbon 34, 729–739 (1996).
Deschamps, M. et al. A solid-state NMR study of C70: A model molecule for amorphous carbons. Solid State NMR 42, 81–86 (2012).
Ferrari, A. C. & Robertson, J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 61, 14095–14107 (2000).
Wang, H. et al. Real-time NMR studies of electrochemical double layer capacitors. J. Am. Chem. Soc. 133, 19270–19273 (2011).
Harris, P. J. F. New perspectives on the structure of graphitic carbons. Critical Rev. Solid State Mater. Sci. 30, 235–253 (2005).
Acharya, M. et al. Simulations of nanoporous carbons: A chemically constrained structure. Phil. Mag. B79, 1499–1518 (1999).
Petkov, V., Difrancesco, R. G., Billinge, S. J. L., Acharya, M. & Foley, H. C. Local structure of nanoporous carbons. Phil. Mag. B79, 1519–1530 (1999).
Kumar, A., Lobo, R. F. & Wagner, N. J. Porous amorphous carbon models from periodic Gaussian chains of amorphous polymers. Carbon 43, 3099–3111 (2005).
Bansal, R. C., Donnet, J. B. & Stoeckli, F. Active Carbon (Marcel Dekker, 1988).
Jeener, J., Meier, B. H., Bachmann, P. & Ernst, R. R. Investigation of exchange processes by two-dimensional NMR spectroscopy. J. Chem. Phys. 71, 4546–4553 (1979).
Minkin, V. I., Glukhovtsev, M. N. & Simkin, B. Y. Aromaticity and Antiaromaticity (Wiley, 1994).
Lazzeretti, P. & Taddei, F. An interpretation of 1H and 13C chemical shifts in substituted benzenes on the basis of M.O. charge densities. Org. Magn. Reson. 3, 283–291 (1971).
Kurzweil, P. & Chwistek, M. Electrochemical stability of organic electrolytes in supercapacitors: Spectroscopy and gas analysis of decomposition products. J. Power Sources 176, 555–567 (2008).
Hantel, M. M., Kaspar, T., Nesper, R., Wokaun, A. & Kötz, R. Partially reduced graphite oxide for supercapacitor electrodes: Effect of graphene layer spacing and huge specific capacitance. Electrochem. Commun. 13, 90–92 (2011).
Haddon, R. C. Chemistry of the fullerenes: The manifestation of strain in a class of continuous aromatic molecules. Science 261, 1545–1550 (1993).
Saunders, M. et al. Probing the interior of fullerenes by 3He NMR spectroscopy of endohedral 3He@C60 and 3He@C70 . Nature 367, 256–258 (1994).
Sternfeld, T., Hoffman, R. E., Aprahamian, I. & Rabinovitz, M. Fullerene anions: Unusual charge distribution in C706−. Angew. Chem. Int. Ed. 40, 455–457 (2001).
Sternfeld, T., Hoffman, R. E., Thilgen, C., Diederich, F. & Rabinovitz, M. Reduction of fulleroids C71H2: Probing the magnetic properties of C706−. J. Am. Chem. Soc. 122, 9038–9039 (2000).
Schmid, M. et al. Metallic properties of Li-intercalated carbon nanotubes investigated by NMR. Phys. Rev. B 74, 073416 (2006).
Ka, B. H. & Oh, S. M. Electrochemical activation of expanded graphite electrode for electrochemical capacitor. J. Electrochem. Soc. 155, A685–A692 (2008).
Burket, C. L., Rajagopalan, R., Marencic, A. P., Dronvajjala, K. & Foley, H. C. Genesis of porosity in polyfurfuryl alcohol derived nanoporous carbon. Carbon 44, 2957–2963 (2006).
Hucher, C., Beaume, F., Eustache, R-P. & Tekely, P. Probing phase structure and location of reverse units in poly(vinylidene fluoride) by solid-state NMR. Macromolecules 38, 1789–1796 (2005).
Bennett, A. E., Rienstra, C. M., Auger, M., Lakshmi, K. V. & Griffin, R. G. Heteronuclear decoupling in rotating solids. J. Chem. Phys. 103, 6951–6958 (1995).
Massiot, D. et al. Modelling one and two-dimensional solid-state NMR spectra. Magn. Reson. Chem. 40, 70–76 (2002).
Pauvert, O. et al. 91Zr nuclear magnetic resonance spectroscopy of solid zirconium halides at high magnetic field. Inorg. Chem. 48, 8709–8717 (2009).
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).
Author information
Authors and Affiliations
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.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary Information
Supplementary Information (PDF 1168 kb)
Rights and permissions
About this article
Cite this article
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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nmat3567
This article is cited by
-
Advances in Supercapacitor Development: Materials, Processes, and Applications
Journal of Electronic Materials (2023)
-
Controllable preparation of green biochar based high-performance supercapacitors
Ionics (2022)
-
Perspectives for electrochemical capacitors and related devices
Nature Materials (2020)
-
Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy
Nature Communications (2019)
-
Salt concentration and charging velocity determine ion charge storage mechanism in nanoporous supercapacitors
Nature Communications (2018)