Article | Published:

Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR

Nature Materials volume 12, pages 351358 (2013) | Download Citation

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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    , , , & Desolvation of ions in subnanometer pores and its effect on capacitance and double-layer theory. Angew. Chem. Int. Ed. 47, 3392–3395 (2008).

  2. 2.

    , & Theoretical model for nanoporous carbon supercapacitors. Angew. Chem. Int. Ed. 47, 520–524 (2008).

  3. 3.

    , & Electrolytes in porous electrodes: Effects of the pore size and the dielectric constant of the medium. J. Chem. Phys. 132, 144705 (2010).

  4. 4.

    , , , & Relationship between the nanoporous texture of activated carbons and their capacitance properties in different electrolytes. Carbon 43, 1293–1302 (2005).

  5. 5.

    et al. Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer. Science 313, 1760–1763 (2006).

  6. 6.

    , & Pore size distribution analysis of microporous carbons: A density functional theory approach. J. Phys. Chem. 97, 4786–4796 (1993).

  7. 7.

    , , , & Application of a quartz-crystal microbalance to measure ionic fluxes in microporous carbons for energy storage. Nature Mater. 8, 872–875 (2009).

  8. 8.

    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).

  9. 9.

    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).

  10. 10.

    et al. On the molecular origin of supercapacitance in nanoporous carbon electrodes. Nature Mater. 11, 306–310 (2012).

  11. 11.

    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).

  12. 12.

    et al. Causes of supercapacitors ageing in organic electrolyte. J. Power Sources 171, 1046–1053 (2007).

  13. 13.

    , , & Adsorption competition onto activated carbon, studied by magic-angle spinning NMR. J. Chem. Soc. Faraday Trans. 92, 2615–2618 (1996).

  14. 14.

    et al. A magic-angle spinning NMR study into the adsorption of deuterated water by activated carbon. Carbon 34, 1275–1279 (1996).

  15. 15.

    , , , & High-resolution 2H solid-state NMR of 2H2O adsorbed onto activated carbon. J. Chem. Soc. Faraday Trans. 91, 1795–1799 (1995).

  16. 16.

    , & Magic angle spinning NMR study of adsorbate reactions on activated charcoal. Langmuir 11, 1439–1442 (1995).

  17. 17.

    , , & Phosphorus-31 NMR studies of adsorption onto activated carbon. Carbon 37, 1425–1430 (1999).

  18. 18.

    , , , & Oxygen-17 and deuterium NMR investigation into the adsorption of water on activated carbon. Magn. Reson. Chem. 38, 918–924 (2000).

  19. 19.

    , , & Evolution of carbon structure in chemically activated wood. Carbon 33, 1247–1254 (1995).

  20. 20.

    et al. A two-dimensional 13C-NMR study of powdered and oriented mesophase pitches. Carbon 34, 729–739 (1996).

  21. 21.

    et al. A solid-state NMR study of C70: A model molecule for amorphous carbons. Solid State NMR 42, 81–86 (2012).

  22. 22.

    & Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 61, 14095–14107 (2000).

  23. 23.

    et al. Real-time NMR studies of electrochemical double layer capacitors. J. Am. Chem. Soc. 133, 19270–19273 (2011).

  24. 24.

    New perspectives on the structure of graphitic carbons. Critical Rev. Solid State Mater. Sci. 30, 235–253 (2005).

  25. 25.

    et al. Simulations of nanoporous carbons: A chemically constrained structure. Phil. Mag. B79, 1499–1518 (1999).

  26. 26.

    , , , & Local structure of nanoporous carbons. Phil. Mag. B79, 1519–1530 (1999).

  27. 27.

    , & Porous amorphous carbon models from periodic Gaussian chains of amorphous polymers. Carbon 43, 3099–3111 (2005).

  28. 28.

    , & Active Carbon (Marcel Dekker, 1988).

  29. 29.

    , , & Investigation of exchange processes by two-dimensional NMR spectroscopy. J. Chem. Phys. 71, 4546–4553 (1979).

  30. 30.

    , & Aromaticity and Antiaromaticity (Wiley, 1994).

  31. 31.

    & 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).

  32. 32.

    & Electrochemical stability of organic electrolytes in supercapacitors: Spectroscopy and gas analysis of decomposition products. J. Power Sources 176, 555–567 (2008).

  33. 33.

    , , , & Partially reduced graphite oxide for supercapacitor electrodes: Effect of graphene layer spacing and huge specific capacitance. Electrochem. Commun. 13, 90–92 (2011).

  34. 34.

    Chemistry of the fullerenes: The manifestation of strain in a class of continuous aromatic molecules. Science 261, 1545–1550 (1993).

  35. 35.

    et al. Probing the interior of fullerenes by 3He NMR spectroscopy of endohedral 3He@C60 and 3He@C70. Nature 367, 256–258 (1994).

  36. 36.

    , , & Fullerene anions: Unusual charge distribution in C706−. Angew. Chem. Int. Ed. 40, 455–457 (2001).

  37. 37.

    , , , & Reduction of fulleroids C71H2: Probing the magnetic properties of C706−. J. Am. Chem. Soc. 122, 9038–9039 (2000).

  38. 38.

    et al. Metallic properties of Li-intercalated carbon nanotubes investigated by NMR. Phys. Rev. B 74, 073416 (2006).

  39. 39.

    & Electrochemical activation of expanded graphite electrode for electrochemical capacitor. J. Electrochem. Soc. 155, A685–A692 (2008).

  40. 40.

    , , , & Genesis of porosity in polyfurfuryl alcohol derived nanoporous carbon. Carbon 44, 2957–2963 (2006).

  41. 41.

    , , & Probing phase structure and location of reverse units in poly(vinylidene fluoride) by solid-state NMR. Macromolecules 38, 1789–1796 (2005).

  42. 42.

    , , , & Heteronuclear decoupling in rotating solids. J. Chem. Phys. 103, 6951–6958 (1995).

  43. 43.

    et al. Modelling one and two-dimensional solid-state NMR spectra. Magn. Reson. Chem. 40, 70–76 (2002).

  44. 44.

    et al. 91Zr nuclear magnetic resonance spectroscopy of solid zirconium halides at high magnetic field. Inorg. Chem. 48, 8709–8717 (2009).

Download references

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

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

Authors

  1. Search for Michaël Deschamps in:

  2. Search for Edouard Gilbert in:

  3. Search for Philippe Azais in:

  4. Search for Encarnación Raymundo-Piñero in:

  5. Search for Mohammed Ramzi Ammar in:

  6. Search for Patrick Simon in:

  7. Search for Dominique Massiot in:

  8. Search for François Béguin in:

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.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Michaël Deschamps.

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    Supplementary Information

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nmat3567

Further reading