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In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors

Nature Materials volume 14, pages 812–819 (2015)Cite this article

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Abstract

Supercapacitors store charge through the electrosorption of ions on microporous electrodes. Despite major efforts to understand this phenomenon, a molecular-level picture of the electrical double layer in working devices is still lacking as few techniques can selectively observe the ionic species at the electrode/electrolyte interface. Here, we use in situ NMR to directly quantify the populations of anionic and cationic species within a working microporous carbon supercapacitor electrode. Our results show that charge storage mechanisms are different for positively and negatively polarized electrodes for the electrolyte tetraethylphosphonium tetrafluoroborate in acetonitrile; for positive polarization charging proceeds by exchange of the cations for anions, whereas for negative polarization, cation adsorption dominates. In situ electrochemical quartz crystal microbalance measurements support the NMR results and indicate that adsorbed ions are only partially solvated. These results provide new molecular-level insight, with the methodology offering exciting possibilities for the study of pore/ion size, desolvation and other effects on charge storage in supercapacitors.

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Figure 1: NMR spectra of individual supercapacitor electrodes showing in- and ex-pore cation and anion environments.
Figure 2: In-pore ion populations per gram of YP-50F at 0 V plotted as a function of concentration for the PEt4-BF4/ACN electrolyte.
Figure 3: In situ 31P and 19F NMR spectra of individual supercapacitor electrodes at different states of charge.
Figure 4: In-pore ion populations for supercapacitor electrodes at different states of charge in the range −1.5 V to +1.5 V.
Figure 5: Comparisons of the magnitudes of ionic and electronic charge stored on supercapacitor electrodes in the range −1.5 V to +1.5 V.
Figure 6: EQCM data for a YP-50F electrode in 0.75 M PEt4–BF4/ACN electrolyte.

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References

  1. Salitra, G., Soffer, A., Eliad, L., Cohen, Y. & Aurbach, D. Carbon electrodes for double layer capacitors. I. Relations between ion and pore dimensions. J. Electrochem. Soc. 147, 2486–2493 (2000).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  3. Largeot, C. et al. Relation between the ion size and pore size for an electric double-layer capacitor. J. Am. Chem. Soc. 130, 2730–2731 (2008).

    Article  CAS  Google Scholar 

  4. Vix-Guterl, C. et al. Electrochemical energy storage in ordered porous carbon materials. Carbon 43, 1293–1302 (2005).

    Article  CAS  Google Scholar 

  5. 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).

    Article  CAS  Google Scholar 

  6. Fedorov, M. V. & Kornyshev, A. A. Ionic liquids at electrified interfaces. Chem. Rev. 114, 2978–3036 (2014).

    Article  CAS  Google Scholar 

  7. Burt, R., Birkett, G. & Zhao, X. S. A review of molecular modeling of electric double layer capacitors. Phys. Chem. Chem. Phys. 16, 6519–6538 (2014).

    Article  CAS  Google Scholar 

  8. Feng, G. & Cummings, P. T. Supercapacitor capacitance exhibits oscillatory behaviour as a function of nanopore size. J. Phys. Chem. Lett. 2, 2859–2864 (2011).

    Article  CAS  Google Scholar 

  9. Wu, P., Huang, J., Meunier, V., Sumpter, B. G. & Qiao, R. Complex capacitance scaling in ionic liquids-filled nanopores. ACS Nano 5, 9044–9051 (2011).

    Article  CAS  Google Scholar 

  10. Kondrat, S. & Kornyshev, A. Superionic state in double-layer capacitors with nanoporous electrodes. J. Phys. Condens. Matter 23, 022201 (2011).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  12. Merlet, C. et al. Highly confined ions store charge more efficiently in supercapacitors. Nature Commun. 4, 2701 (2013).

    Article  CAS  Google Scholar 

  13. Kondrat, S., Wu, P., Qiao, R. & Kornyshev, A. A. Accelerating charging dynamics in subnanometre pores. Nature Mater. 13, 387–393 (2014).

    Article  CAS  Google Scholar 

  14. 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).

    Article  CAS  Google Scholar 

  15. Tsai, W.-Y., Taberna, P.-L. & Simon, P. Electrochemical quartz crystal microbalance (EQCM) study of ion dynamics in nanoporous carbons. J. Am. Chem. Soc. 136, 8722–8728 (2014).

    Article  CAS  Google Scholar 

  16. Richey, F. W., Dyatkin, B., Gogotsi, Y. & Elabd, Y. A. Ion dynamics in porous carbon electrodes in supercapacitors using in situ infrared spectroelectrochemistry. J. Am. Chem. Soc. 135, 12818–12826 (2013).

    Article  CAS  Google Scholar 

  17. Richey, F. W., Tran, C., Kalra, V. & Elabd, Y. A. Ionic liquid dynamics in nanoporous carbon nanofibers in supercapacitors measured with in operando infrared spectroelectrochemistry. J. Phys. Chem. C 118, 21846–21855 (2014).

    Article  CAS  Google Scholar 

  18. Forse, A. C. et al. Nuclear magnetic resonance study of ion adsorption on microporous carbide-derived carbon. Phys. Chem. Chem. Phys. 15, 7722–7730 (2013).

    Article  CAS  Google Scholar 

  19. Borchardt, L., Oschatz, M., Paasch, S., Kaskel, S. & Brunner, E. Interaction of electrolyte molecules with carbon materials of well-defined porosity: Characterization by solid-state NMR spectroscopy. Phys. Chem. Chem. Phys. 15, 15177–15184 (2013).

    Article  CAS  Google Scholar 

  20. Deschamps, M. et al. Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR. Nature Mater. 12, 351–358 (2013).

    Article  CAS  Google Scholar 

  21. Wang, H. et al. Real-time NMR studies of electrochemical double-layer capacitors. J. Am. Chem. Soc. 133, 19720–19273 (2011).

    Google Scholar 

  22. Wang, H. et al. In situ NMR spectroscopy of supercapacitors: Insight into the charge storage mechanism. J. Am. Chem. Soc. 135, 18968–18980 (2013).

    Article  CAS  Google Scholar 

  23. Griffin, J. M. et al. Ion counting in supercapacitor electrodes using NMR spectroscopy. Faraday Discuss. 176, 49–68 (2014).

    Article  CAS  Google Scholar 

  24. Ilott, A. J., Trease, N. M., Grey, C. P. & Jerschow, A. Multinuclear in situ magnetic resonance imaging of electrochemical double-layer capacitors. Nature Commun. 5, 4536 (2014).

    Article  CAS  Google Scholar 

  25. Forse, A. C., Griffin, J. M., Presser, V., Gogotsi, Y. & Grey, C. P. Ring current effects: Factors affecting the NMR chemical shift of molecules adsorbed on porous carbons. J. Phys. Chem. C 118, 7508–7514 (2014).

    Article  CAS  Google Scholar 

  26. Kim, Y.-J., Masutzawa, Y., Ozaki, S., Endo, M. & Dresselhaus, M. S. PVDC-based carbon material by chemical activation and its application to nonaqueous EDLC. J. Electrochem. Soc. 151, E199–E205 (2004).

    Article  CAS  Google Scholar 

  27. Sauerbrey, G. Verwendung von Schwingquarzen zur Wägung dünner Schichten und zur Mikrowägung [The use of resonance quartz crystals for weighing thin layers and as a microbalance]. Z. Phys. 155, 206–222 (1959).

    Article  CAS  Google Scholar 

  28. 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).

    Article  CAS  Google Scholar 

  29. Levi, M. D., Sigalov, S., Aurbach, D. & Daikhin, L. In situ electrochemical quartz crystal admittance methodology for tracking compositional and mechanical changes in porous carbon electrodes. J. Phys. Chem. C 117, 14876–14889 (2013).

    Article  CAS  Google Scholar 

  30. Fukano, M. et al. Vertically oriented propylene carbonate molecules and tetraethyl ammonium ions in carbon slit pores. J. Phys. Chem. C 117, 5752–5757 (2013).

    Article  CAS  Google Scholar 

  31. Hantel, M. M., Presser, V., Kötz, R. & Gogotsi, Y. In situ electrochemical dilatometry of carbide-derived carbons. Electrochem. Commun. 13, 1221–1224 (2011).

    Article  CAS  Google Scholar 

  32. Kondrat, S., Georgi, N., Fedorov, M. V. & Kornyshev, A. A. A superionic state in nano-porous double-layer capacitors: Insights from Monte Carlo simulations. Phys. Chem. Chem. Phys. 13, 11359–11366 (2011).

    Article  CAS  Google Scholar 

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Acknowledgements

A.C.F., J.M.G. and C.P.G. acknowledge the Sims Scholarship (A.C.F.), EPSRC (through the Supergen consortium for J.M.G.) and the EU ERC (through an Advanced Fellowship to C.P.G.) for financial support. P.S. and W.-Y.T. acknowledge support from the European Research Council (ERC, Advanced Grant, ERC-2011-AdG, Project 291543–IONACES). P.S. also acknowledges financial support from the Chair ‘Embedded Multi-Functional Nanomaterials’ from the Airbus Group Foundation. A.C.F. and J.M.G. thank the NanoDTC Cambridge for travel funding. We also thank A. Kornyshev, S. Kondrat and C. Merlet for useful discussions.

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Authors and Affiliations

  1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK,

    John M. Griffin, Alexander C. Forse & Clare P. Grey

  2. Université Paul Sabatier Toulouse III, CIRIMAT, UMR-CNRS 5085, F-31062 Toulouse, France

    Wan-Yu Tsai, Pierre-Louis Taberna & Patrice Simon

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

    Wan-Yu Tsai, Pierre-Louis Taberna & Patrice Simon

  4. Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400, USA

    Clare P. Grey

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Contributions

J.M.G., A.C.F. and C.P.G. designed the research. J.M.G. made supercapacitor cells and electrolytes, performed NMR experiments and analysed the NMR data. W.-Y.T., P.-L.T. and P.S. designed the EQCM work. W.-Y.T. carried out the EQCM experiments and W.-Y.T., P.-L.T. and P.S. analysed the data. All authors contributed to discussion of the data and writing the paper.

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Correspondence to Clare P. Grey.

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Griffin, J., Forse, A., Tsai, WY. et al. In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors. Nature Mater 14, 812–819 (2015). https://doi.org/10.1038/nmat4318

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