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Influences from solvents on charge storage in titanium carbide MXenes

Nature Energy volume 4, pages 241–248 (2019)Cite this article

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Abstract

Pseudocapacitive energy storage in supercapacitor electrodes differs significantly from the electrical double-layer mechanism of porous carbon materials, which requires a change from conventional thinking when choosing appropriate electrolytes. Here we show how simply changing the solvent of an electrolyte system can drastically influence the pseudocapacitive charge storage of the two-dimensional titanium carbide, Ti3C2 (a representative member of the MXene family). Measurements of the charge stored by Ti3C2 in lithium-containing electrolytes with nitrile-, carbonate- and sulfoxide-based solvents show that the use of a carbonate solvent doubles the charge stored by Ti3C2 when compared with the other solvent systems. We find that the chemical nature of the electrolyte solvent has a profound effect on the arrangement of molecules/ions in Ti3C2, which correlates directly to the total charge being stored. Having nearly completely desolvated lithium ions in Ti3C2 for the carbonate-based electrolyte leads to high volumetric capacitance at high charge–discharge rates, demonstrating the importance of considering all aspects of an electrochemical system during development.

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Fig. 1: Macroporous Ti3C2 electrode with 1 M LiTFSI in DMSO, ACN and PC organic electrolytes.
Fig. 2: d-spacing evolution during cycling and molecular arrangements.
Fig. 3: Electrochemical performance of the macroporous Ti3C2 in LiTFSI with PC solvent.

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The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

References

  1. Simon, P. & Gogotsi, Y. Materials for electrochemical capacitors. Nat. Mater. 7, 845–854 (2008).

    Article  Google Scholar 

  2. Simon, P., Gogotsi, Y. & Dunn, B. Where do batteries end and supercapacitors begin? Science 343, 1210–1211 (2014).

    Article  Google Scholar 

  3. Salanne, M. et al. Efficient storage mechanisms for building better supercapacitors. Nat. Energy 1, 16070 (2016).

    Article  Google Scholar 

  4. Lukatskaya, M. R., Dunn, B. & Gogotsi, Y. Multidimensional materials and device architectures for future hybrid energy storage. Nat. Commun. 7, 12647 (2016).

    Article  Google Scholar 

  5. Nitta, N., Wu, F., Lee, J. T. & Yushin, G. Li-ion battery materials: present and future. Mater. Today 18, 252–264 (2015).

    Article  Google Scholar 

  6. Zhu, Y. et al. Carbon-based supercapacitors produced by activation of graphene. Science 332, 1537–1541 (2011).

    Article  Google Scholar 

  7. Zhong, C. et al. A review of electrolyte materials and compositions for electrochemical supercapacitors. Chem. Soc. Rev. 44, 7484–7539 (2015).

    Article  Google Scholar 

  8. Mourad, E. et al. Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors. Nat. Mater. 16, 446–453 (2017).

    Article  Google Scholar 

  9. Choi, D., Blomgren, G. E. & Kumta, P. N. Fast and reversible surface redox reaction in nanocrystalline vanadium nitride supercapacitors. Adv. Mater. 18, 1178–1182 (2006).

    Article  Google Scholar 

  10. Wang, G., Zhang, L. & Zhang, J. A review of electrode materials for electrochemical supercapacitors. Chem. Soc. Rev. 41, 797–828 (2012).

    Article  Google Scholar 

  11. Augustyn, V., Simon, P. & Dunn, B. Pseudocapacitive oxide materials for high-rate electrochemical energy storage. Energy Environ. Sci. 7, 1597–1614 (2014).

    Article  Google Scholar 

  12. Anasori, B., Lukatskaya, M. R. & Gogotsi, Y. 2D metal carbides and nitrides (MXenes) for energy storage. Nat. Rev. Mater. 2, 16098 (2017).

    Article  Google Scholar 

  13. Lukatskaya, M. R. et al. Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides. Nat. Energy 2, 17105 (2017).

    Article  Google Scholar 

  14. Lin, Z. et al. Capacitance of Ti3C2Tx MXene in ionic liquid electrolyte. J. Power Sources 326, 575–579 (2016).

    Article  Google Scholar 

  15. Dall’Agnese, Y., Rozier, P., Taberna, P.-L., Gogotsi, Y. & Simon, P. Capacitance of two-dimensional titanium carbide (MXene) and MXene/carbon nanotube composites in organic electrolytes. J. Power Sources 306, 510–515 (2016).

    Article  Google Scholar 

  16. Kajiyama, S. et al. Enhanced Li-ion accessibility in MXene titanium carbide by steric chloride termination. Adv. Energy Mater. 7, 1601873 (2017).

    Article  Google Scholar 

  17. Wang, X. et al. Geometrically confined favourable ion packing for high gravimetric capacitance in carbon–ionic liquid supercapacitors. Energy Environ. Sci. 9, 232–239 (2016).

    Article  Google Scholar 

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

    Article  Google Scholar 

  19. Brouillette, D., Perron, G. & Desnoyers, J. E. Effect of viscosity and volume on the specific conductivity of lithium salts in solvent mixtures. Electrochim. Acta 44, 4721–4742 (1999).

    Article  Google Scholar 

  20. Gogotsi, Y. & Penner, R. M. Energy storage in nanomaterials—capacitive, pseudocapacitive, or battery-like? ACS Nano 12, 2081–2083 (2018).

    Article  Google Scholar 

  21. Segalini, J., Daffos, B., Taberna, P.-L., Gogotsi, Y. & Simon, P. Qualitative electrochemical impedance spectroscopy study of ion transport into sub-nanometer carbon pores in electrochemical double layer capacitor electrodes. Electrochim. Acta 55, 7489–7494 (2010).

    Article  Google Scholar 

  22. Taberna, P., Simon, P. & Fauvarque, J.-F. Electrochemical characteristics and impedance spectroscopy studies of carbon–carbon supercapacitors. J. Electrochem. Soc. 150, A292–A300 (2003).

    Article  Google Scholar 

  23. Okubo, M., Sugahara, A., Kajiyama, S. & Yamada, A. MXene as a charge storage host. Acc. Chem. Res. 51, 591–599 (2018).

    Article  Google Scholar 

  24. Cabana, J., Monconduit, L., Larcher, D. & Palacin, M. R. Beyond intercalation-based Li-ion batteries: the state of the art and challenges of electrode materials reacting through conversion reactions. Adv. Mater. 22, E170–E192 (2010).

    Article  Google Scholar 

  25. Futamura, R. et al. Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores. Nat. Mater. 16, 1225 (2017).

    Article  Google Scholar 

  26. Come, J. et al. Controlling the actuation properties of MXene paper electrodes upon cation intercalation. Nano Energy 17, 27–35 (2015).

    Article  Google Scholar 

  27. Jäckel, N. et al. Electrochemical in situ tracking of volumetric changes in two-dimensional metal carbides (MXenes) in ionic liquids. ACS Appl. Mater. Interfaces 8, 32089–32093 (2016).

    Article  Google Scholar 

  28. Levi, M. D. et al. Solving the capacitive paradox of 2D MXene using electrochemical quartz-crystal admittance and in situ electronic conductance measurements. Adv. Energy Mater. 5, 1400815 (2015).

    Article  Google Scholar 

  29. Brousse, T., Bélanger, D. & Long, J. W. To be or not to be pseudocapacitive? J. Electrochem. Soc. 162, A5185–A5189 (2015).

    Article  Google Scholar 

  30. Ghidiu, M., Lukatskaya, M. R., Zhao, M.-Q., Gogotsi, Y. & Barsoum, M. W. Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance. Nature 516, 78–81 (2014).

    Google Scholar 

  31. Park, S. H., Kim, J., Lee, W.-E., Byun, D.-J. & Kim, M. H. One-step synthesis of hollow dimpled polystyrene microparticles by dispersion polymerization. Langmuir 33, 2275–2282 (2017).

    Article  Google Scholar 

  32. Alhabeb, M. et al. Guidelines for synthesis and processing of two-dimensional titanium carbide (Ti3C2Tx MXene). Chem. Mater. 29, 7633–7644 (2017).

    Article  Google Scholar 

  33. Li, K., Liu, J., Huang, Y., Bu, F. & Xu, Y. Integration of ultrathin graphene/polyaniline composite nanosheets with a robust 3D graphene framework for highly flexible all-solid-state supercapacitors with superior energy density and exceptional cycling stability. J. Mater. Chem. A 5, 5466–5474 (2017).

    Article  Google Scholar 

  34. Meyer, A., Dimeo, R., Gehring, P. & Neumann, D. The high-flux backscattering spectrometer at the NIST Center for Neutron Research. Rev. Sci. Instrum. 74, 2759–2777 (2003).

    Article  Google Scholar 

  35. Mitchell, J. B., Lo, W. C., Genc, A., LeBeau, J. & Augustyn, V. Transition from battery to pseudocapacitor behavior via structural water in tungsten oxide. Chem. Mater. 29, 3928–3937 (2017).

    Article  Google Scholar 

  36. Forse, A. C., Merlet, C., Griffin, J. M. & Grey, C. P. New perspectives on the charging mechanisms of supercapacitors. J. Am. Chem. Soc. 138, 5731–5744 (2016).

    Article  Google Scholar 

  37. Forse, A. C. et al. Direct observation of ion dynamics in supercapacitor electrodes using in situ diffusion NMR spectroscopy. Nat. Energy 2, 16216 (2017).

    Article  Google Scholar 

  38. Wang, H.-W., Naguib, M., Page, K., Wesolowski, D. J. & Gogotsi, Y. Resolving the structure of Ti3C2Tx MXenes through multilevel structural modeling of the atomic pair distribution function. Chem. Mater. 28, 349–359 (2015).

    Article  Google Scholar 

  39. Semino, R., Zaldívar, G., Calvo, E. J. & Laria, D. Lithium solvation in dimethyl sulfoxide–acetonitrile mixtures. J. Chem. Phys. 141, 214509 (2014).

    Article  Google Scholar 

Download references

Acknowledgements

The research was sponsored by the Fluid Interface Reactions, Structures, and Transport (FIRST) Center, an Energy Frontier Research Center (EFRC) funded by the US Department of Energy, Office of Science, and Office of Basic Energy Sciences. Access to the HFBS was provided by the Center for High Resolution Neutron Scattering, a partnership between the NIST and the NSF under agreement no. DMR-1508249. Certain commercial equipment, instruments or materials are identified in this paper in order to specify the experimental procedure adequately. Such identification is not intended to imply recommendation or endorsement by the National Institute of Standards and Technology, nor is it intended to imply that the materials or equipment identified are necessarily the best available for the purpose. J. Li and H. Wang from Drexel University are acknowledged for helping with material characterization. Y. Honda and Y. Soda from Murata Manufacturing Co. are acknowledged for helpful discussions and help with the characterization.

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Authors and Affiliations

  1. A. J. Drexel Nanomaterials Institute and Department of Materials Science and Engineering, Drexel University, Philadelphia, PA, USA

    Xuehang Wang, Tyler S. Mathis, Ke Li, Christine Hatter, Patrick Urbankowski, Asia Sarycheva & Yury Gogotsi

  2. Materials Science Department—CIRIMAT, Université Paul Sabatier, Toulouse, France

    Zifeng Lin & Patrice Simon

  3. Department of Materials Science and Engineering, Sichuan University, Chengdu, China

    Zifeng Lin

  4. Materials Science and Technology Division, Materials Theory Group, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Lukas Vlcek

  5. Joint Institute for Computational Sciences, University of Tennessee, Knoxville, Oak Ridge, TN, USA

    Lukas Vlcek

  6. Murata Manufacturing Co., Ltd, Nagaokakyo-shi, Kyoto, Japan

    Takeshi Torita

  7. Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Naresh C. Osti & Eugene Mamontov

  8. NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD, USA

    Madhusudan Tyagi

  9. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Madhusudan Tyagi

  10. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), CNRS FR3459, Amiens, France

    Patrice Simon

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  1. Xuehang Wang
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Contributions

X.W. and Y.G. planned the study. X.W., T.S.M, Z.L. and T.T. conducted electrochemical testing. K.L. synthesized all MXenes, Z.L. performed the in situ XRD measurement and L.V. performed the MD simulation. C.H., P.U. and A.S. performed TEM, XPS and Raman investigations, respectively. N.C.O., M.T. and E.M. performed the neutron scattering. All authors contributed to writing the manuscript under supervision from P.S. and Y.G.

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Correspondence to Yury Gogotsi.

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Supplementary Discussions 1–3, Supplementary Tables 1–3, Supplementary Figures 1–15, Supplementary references.

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Wang, X., Mathis, T.S., Li, K. et al. Influences from solvents on charge storage in titanium carbide MXenes. Nat Energy 4, 241–248 (2019). https://doi.org/10.1038/s41560-019-0339-9

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