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Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

Nature Energy volume 2, Article number: 17105 (2017) Cite this article

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Abstract

The use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improved ion accessibility to redox-active sites. A macroporous Ti3C2Tx MXene film delivered up to 210 F g−1 at scan rates of 10 V s−1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ∼1,500 F cm−3 reaching the previously unmatched volumetric performance of RuO2.

Typical commercial batteries require prolonged charging and therefore are limiting mobility of users. Systems that are capable of delivering high energy densities at relatively high charge/discharge rates are classified as pseudocapacitors and characterized by absence of phase transformations during operation1,2,3. Pseudocapacitors are a sub-class of supercapacitors that are differentiated from electrical double-layercapacitors (EDLCs) on the basis of charge storage mechanism. EDLCs store charge via formation of the electrical double layer at the electrode/electrolyte interface and, naturally, their capacitance is proportional to the electrode’s specific surface area available for electrosorption of ions. Pseudocapacitors, on the other hand, utilize fast redox reactions and therefore can potentially provide higher energy densities due to charge transfer.

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Figure 1: MXene electrodes.
Figure 2: Electrochemical performance of planar MXene electrodes.
Figure 3: Electrochemical performance of macroporous Ti3C2Tx electrodes.

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Acknowledgements

We thank C.(E.) Ren for help with material synthesis. XRD, SEM and TEM investigations were performed at the Core Research Facilities (CRF) at Drexel University. Y.G., M.R.L. and M.-Q.Z. were supported by the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, and Office of Basic Energy Sciences. S.K. was supported by the US National Science Foundation under grant number DMR-1310245. Z.-F. Lin was supported by China Scholarship Council (No. 201304490006). P.S. and P.-L.T. thank the ANR (LABEX STAEX) and RS2E for financial support. M.L. and N.S. acknowledge funding from the Binational Science Foundation (BSF) USA-Israel via Research Grant Agreement 2014083/2016.

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Author notes

  1. Maria R. Lukatskaya

    Present address: Department of Chemical Engineering, Stanford, California, 94305, USA

  2. Maria R. Lukatskaya, Sankalp Kota and Zifeng Lin: These authors contributed equally to this work.

Authors and Affiliations

  1. A. J. Drexel Nanomaterials Institute, Drexel University, Philadelphia, Pennsylvania 19104, USA

    Maria R. Lukatskaya, Meng-Qiang Zhao, Joseph Halim & Yury Gogotsi

  2. Department of Materials Science and Engineering, Drexel University, Philadelphia, Pennsylvania 19104, USA

    Maria R. Lukatskaya, Sankalp Kota, Meng-Qiang Zhao, Joseph Halim, Michel W. Barsoum & Yury Gogotsi

  3. CIRIMAT UMR CNRS 5085, Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse, France

    Zifeng Lin, Pierre-Louis Taberna & Patrice Simon

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

    Zifeng Lin, Pierre-Louis Taberna & Patrice Simon

  5. Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel

    Netanel Shpigel & Mikhael D. Levi

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  1. Maria R. Lukatskaya
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Contributions

M.R.L. and Y.G. planned the study. S.K., M.R.L., Z.L. and N.S. conducted electrochemical testing. Z.L. and S.K. performed XRD and SEM analysis. M.-Q.Z., Z.L. and J.H. synthesized MXenes and fabricated electrodes. M.-Q.Z. performed TEM analysis. Y.G., P.S., M.R.L., M.D.L., P.-L.T. and M.W.B. supervised the research and discussed the results.

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Correspondence to Patrice Simon or Yury Gogotsi.

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The authors declare no competing financial interests.

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Lukatskaya, M., Kota, S., Lin, Z. et al. Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides. Nat Energy 2, 17105 (2017). https://doi.org/10.1038/nenergy.2017.105

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