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Electrolyte gating in graphene-based supercapacitors and its use for probing nanoconfined charging dynamics

Nature Nanotechnology volume 15, pages 683–689 (2020)Cite this article

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Abstract

Graphene-based nanoporous materials have been extensively explored as high-capacity ion electrosorption electrodes for supercapacitors. However, little attention has been paid to exploiting the interactions between electrons that reside in the graphene lattice and the ions adsorbed between the individual graphene sheets. Here we report that the electronic conductance of a multilayered reduced graphene oxide membrane, when used as a supercapacitor electrode, can be modulated by the ionic charging state of the membrane, which gives rise to a collective electrolyte gating effect. This gating effect provides an in-operando approach for probing the charging dynamics of supercapacitors electrically. Using this approach, we observed a pore-size-dependent ionic hysteresis or memory effect in reduced graphene oxide membranes when the interlayer distance is comparable to the ion diameter. Our results may stimulate the design of novel devices based on the ion–electron interactions under nanoconfinement.

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Fig. 1: Real-time monitoring of the conductance of a rGO MGM during capacitive charging.
Fig. 2: Comparison of the conventional back gating of a monolayered rGO with the electrolyte gating of a multilayered rGO membrane.
Fig. 3: Nanoconfined electrolyte gating of rGO membranes with different interlayer distances under negative polarization.
Fig. 4: Characterization of the interlayer distance-dependent hysteretic response of GMGM during galvanostatic charging/discharging cycles.
Fig. 5: Characterization of the memcapacitive effect (time-dependent GMGM) during the open-circuit process.

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The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

We acknowledge financial support from the Australia Research Council (DP140102624, DP180102890 and FL180100029) and the University of Melbourne. This work made use of the facilities at the Monash Centre for Electron Microscopy (MCEM) and Melbourne Centre for Nanofabrication (MCN).

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Author notes

  1. These authors contributed equally: Jing Xiao, Hualin Zhan.

Authors and Affiliations

  1. Department of Chemical Engineering, The University of Melbourne, Melbourne, Victoria, Australia

    Jing Xiao, Hualin Zhan, Xiao Wang, Zhiyuan Xiong & Dan Li

  2. Department of Materials Science and Engineering, Monash University, Melbourne, Victoria, Australia

    Jing Xiao, Zai-Quan Xu, Ke Zhang, George P. Simon & Dan Li

  3. School of Mathematical and Physical Sciences, University of Technology Sydney, Sydney, New South Wales, Australia

    Zai-Quan Xu

  4. Department of Mechanical Engineering, The University of Melbourne, Melbourne, Victoria, Australia

    Jefferson Zhe Liu

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Contributions

D.L. and J.X. formulated the concept of exploiting the electrolyte gating effect to probe the charging dynamics of supercapacitors with inputs from H.Z. and J.Z.L. J.X. designed and carried out most of the materials synthesis and electrochemical experiments under the guidance of D.L. and G.P.S. H.Z. carried out the analysis of the experiments with D.L. and J.Z.L. X.W. examined the effect of electrode thickness on the electrolyte gating. Z.-Q.X. carried out the back-gating experiments of single rGO sheets. Z.X. performed the in situ optical measurements of the thickness of the electrode under electrolyte gating. K.Z. characterized the interlayer distance of the MGMs. D.L., H.Z. and J.X. wrote the manuscript with contributions from all the other authors.

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Correspondence to Dan Li.

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Xiao, J., Zhan, H., Wang, X. et al. Electrolyte gating in graphene-based supercapacitors and its use for probing nanoconfined charging dynamics. Nat. Nanotechnol. 15, 683–689 (2020). https://doi.org/10.1038/s41565-020-0704-7

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