Dense, thick, but fast-ion-conductive electrodes are critical yet challenging components of ultrafast electrochemical capacitors with high volumetric power/energy densities1,2,3,4. Here we report an exfoliation–fragmentation–restacking strategy towards thickness-adjustable (1.5‒24.0 μm) dense electrode films of restacked two-dimensional 1T-MoS2 quantum sheets. These films bear the unique architecture of an exceptionally high density of narrow (sub-1.2 nm) and ultrashort (~6.1 nm) hydrophobic nanochannels for confinement ion transport. Among them, 14-μm-thick films tested at 2,000 mV s−1 can deliver not only a high areal capacitance of 0.63 F cm−2 but also a volumetric capacitance of 437 F cm−3 that is one order of magnitude higher than that of other electrodes. Density functional theory and ab initio molecular dynamics simulations suggest that both hydration and nanoscale channels play crucial roles in enabling ultrafast ion transport and enhanced charge storage. This work provides a versatile strategy for generating rapid ion transport channels in thick but dense films for energy storage and filtration applications.
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4D printing of MXene hydrogels for high-efficiency pseudocapacitive energy storage
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Gogotsi, Y. & Simon, P. True performance metrics in electrochemical energy storage. Science 334, 917–918 (2011).
Zhu, Y. et al. Carbon-based supercapacitors produced by activation of graphene. Science 332, 1537–1541 (2011).
Lin, T. et al. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage. Science 350, 1508–1513 (2015).
Simon, P. & Gogotsi, Y. Perspectives for electrochemical capacitors and related devices. Nat. Mater. 19, 1151–1163 (2020).
Augustyn, V. & Gogotsi, Y. 2D materials with nanoconfined fluids for electrochemical energy storage. Joule 1, 443–452 (2017).
Choi, C. et al. Achieving high energy density and high power density with pseudocapacitive materials. Nat. Rev. Mater. 5, 5–19 (2019).
Gao, T. et al. 3D printing of tunable energy storage devices with both high areal and volumetric energy densities. Adv. Energy Mater. 9, 1802578 (2019).
Jiang, K. et al. Interfacial approach toward benzene‐bridged polypyrrole film–based micro‐supercapacitors with ultrahigh volumetric power density. Adv. Funct. Mater. 30, 1908243 (2020).
Feng, D. et al. Robust and conductive two-dimensional metal−organic frameworks with exceptionally high volumetric and areal capacitance. Nat. Energy 3, 30–36 (2018).
Sun, H. et al. Three-dimensional holey-graphene/niobia composite architectures for ultrahigh-rate energy storage. Science 356, 599–604 (2017).
Sheberla, D. et al. Conductive MOF electrodes for stable supercapacitors with high areal capacitance. Nat. Mater. 16, 220–224 (2017).
Koltonow, A. R. & Huang, J. Two-dimensional nanofluidics. Science 351, 1395–1396 (2016).
Sun, H. et al. Hierarchical 3D electrodes for electrochemical energy storage. Nat. Rev. Mater. 4, 45–60 (2019).
Li, Z. et al. Tuning the interlayer spacing of graphene laminate films for efficient pore utilization towards compact capacitive energy storage. Nat. Energy 5, 160–168 (2020).
Li, Y. et al. A general Lewis acidic etching route for preparing MXenes with enhanced electrochemical performance in non-aqueous electrolyte. Nat. Mater. 19, 894–899 (2020).
Yang, X., Cheng, C., Wang, Y., Qiu, L. & Li, D. Liquid-mediated dense integration of graphene materials for compact capacitive energy storage. Science 341, 534–537 (2013).
Lukatskaya, M. R. et al. Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides. Nat. Energy 2, 17105 (2017).
Xia, Y. et al. Thickness-independent capacitance of vertically aligned liquid-crystalline MXenes. Nature 557, 409–412 (2018).
Pomerantseva, E., Bonaccorso, F., Feng, X. L., Cui, Y. & Gogotsi, Y. Energy storage: the future enabled by nanomaterials. Science 366, eaan8285 (2019).
Wu, J. et al. Acid-assisted exfoliation toward metallic sub-nanopore TaS2 monolayer with high volumetric capacitance. J. Am. Chem. Soc. 140, 493–498 (2018).
Acerce, M., Voiry, D. & Chhowalla, M. Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials. Nat. Nanotechnol. 10, 313–318 (2015).
Yoo, J. et al. Ultrathin planar graphene supercapacitors. Nano Lett. 11, 1423–1427 (2011).
Yoon, Y. et al. Vertical alignments of graphene sheets spatially and densely piled for fast ion diffusion in compact supercapacitors. ACS Nano 8, 4580–4590 (2014).
de Grotthuss, C. J. T. Sur la décomposition de l’eau et des corps q’uelle tient en dissolution à l’aide de l’électricité galvanique. Ann. Chim. LVIII, 54–74 (1806).
Duan, C. H. & Majumdar, A. Anomalous ion transport in 2-nm hydrophilic nanochannels. Nat. Nanotechnol. 5, 848–852 (2010).
Tunuguntla, R. H., Allen, F. I., Kim, K., Belliveau, A. & Noy, A. Ultrafast proton transport in sub-1-nm diameter carbon nanotube porins. Nat. Nanotechnol. 11, 639–644 (2016).
Esfandiar, A. et al. Size effect in ion transport through angstrom-scale slits. Science 358, 511–513 (2017).
Chmiola, J. et al. Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer. Science 313, 1760–1763 (2006).
Chen, W. et al. Quantum dots of 1T phase transitional metal dichalcogenides generated via electrochemical Li intercalation. ACS Nano 12, 308–316 (2018).
Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013).
Lukatskaya, M. R. et al. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science 341, 1502–1505 (2013).
Lindström, H. et al. Li+ ion insertion in TiO2 (anatase). 2. Voltammetry on nanoporous films. J. Phys. Chem. B 101, 7717–7722 (1997).
Augustyn, V. et al. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat. Mater. 12, 518–522 (2013).
Bankura, A. & Chandra, A. Hydroxide ion can move faster than an excess proton through one-dimensional water chains in hydrophobic narrow pores. J. Phys. Chem. B 116, 9744–9757 (2012).
Zhan, C. et al. Specific ion effects at graphitic interfaces. Nat. Commun. 10, 4858 (2019).
Dellago, C., Naor, M. M. & Hummer, G. Proton transport through water-filled carbon nanotubes. Phys. Rev. Lett. 90, 105902 (2003).
Cheng, C. et al. Ion transport in complex layered graphene-based membranes with tuneable interlayer spacing. Sci. Adv. 2, e1501272 (2016).
Cheng, C., Jiang, G. P., Simon, G. P., Liu, J. Z. & Li, D. Low-voltage electrostatic modulation of ion diffusion through layered graphene-based nanoporous membranes. Nat. Nanotechnol. 13, 685–690 (2018).
Tao, Q. et al. Two-dimensional Mo1.33C MXene with divacancy ordering prepared from parent 3D laminate with in-plane chemical ordering. Nat. Commun. 8, 14949 (2017).
Sheng, L. et al. Multilayer‐folded graphene ribbon film with ultrahigh areal capacitance and high rate performance for compressible supercapacitors. Adv. Funct. Mater. 28, 1800597 (2018).
Tian, W. Q. et al. Multifunctional nanocomposites with high strength and capacitance using 2D Mxene and 1D nanocellulose. Adv. Mater. 31, 1902977 (2019).
Higgins, T. M. et al. Effect of percolation on the capacitance of supercapacitor electrodes prepared from composites of manganese dioxide nanoplatelets and carbon nanotubes. ACS Nano 8, 9567–9579 (2014).
Park, S. & Ruoff, R. S. Chemical methods for the production of graphenes. Nat. Nanotechnol. 4, 217–224 (2009).
Holt, J. et al. Fast mass transport through sub-2-nanometer carbon nanotubes. Science 312, 1034–1037 (2006).
Xu, Y. X. et al. Flexible solid-state supercapacitors based on three-dimensional graphene hydrogel films. ACS Nano 7, 4042–4049 (2013).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Giannozzi, P. et al. Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).
Hamann, D. R. Optimized norm-conserving Vanderbilt pseudopotentials. Phys. Rev. B 88, 085117 (2013).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 132, 154104 (2010).
Nishihara, S. & Otani, M. Hybrid solvation models for bulk, interface, and membrane: reference interaction site methods coupled with density functional theory. Phys. Rev. B 96, 115429 (2017).
Kovalenko, A. & Hirata, F. Self-consistent description of a metal–water interface by the Kohn–Sham density functional theory and the three-dimensional reference interaction site model. J. Chem. Phys. 110, 10095 (1999).
Matsugami, M., Yoshida, N. & Hirata, F. Theoretical characterization of the ‘ridge’ in the supercritical region in the fluid phase diagram of water. J. Chem. Phys. 140, 104511 (2014).
Heiranian, M., Wu, Y. B. & Aluru, N. R. Molybdenum disulfide and water interaction parameters. J. Chem. Phys. 147, 104706 (2017).
Jensen, K. P. & Jorgensen, W. L. Halide, ammonium, and alkali metal ion parameters for modeling aqueous solutions. J. Chem. Theory Comput. 2, 1499–1509 (2006).
Sugahara, A. et al. Negative dielectric constant of water confined in nanosheets. Nat. Commun. 10, 850 (2019).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Nosé, S. A unified formulation of the constant temperature molecular dynamics methods. J. Chem. Phys. 81, 511–519 (1984).
Shuichi, N. Constant temperature molecular dynamics methods. Prog. Theor. Phys. Suppl. 103, 1–46 (1991).
Bylander, D. & Kleinman, L. Energy fluctuations induced by the Nosé thermostat. Phys. Rev. B 46, 13756–13761 (1992).
Brehm, M. & Kirchner, B. TRAVIS—a free analyzer and visualizer for Monte Carlo and molecular dynamics trajectories. J. Chem. Inf. Model. 51, 2007–2023 (2011).
The work at SJTU was supported by the National Natural Science Foundation of China (grant numbers 52072241, 52071213 and 51772187); the Shanghai Science and Technology Committee (grant number 18JC1410500); and the Natural Science Funds for Colleges and Universities in Jiangsu Province, China (grant number 20KJB430048). The work at LLNL was performed under the auspices of the US Department of Energy under contract number DE-AC52-07NA27344. C.Z. and Y.M.W. acknowledge the support of UCOP Project number LFR-17-477237. T.A.P. was supported as part of the Center for Enhanced Nanofluidic Transport, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences (BES), under award number DESC0019112. B.D. was supported by the Office of Naval Research (grant number N00014-19-1-2113). We thank R. Luo for his help with TEM characterizations and analyses.
The authors declare no competing interests.
Peer review information Nature Nanotechnology thanks Xuebin Zhu and other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Supplementary Figs. 1–32, Tables 1–4 and references.
Supplementary Video 1
The animation of the diffusion of solvated H3O+ in a −1|e| charged 0.8 nm MoS2 channel from the AIMD trajectory in a top view along the z direction.
Supplementary Video 2
The animation of the diffusion of solvated K+ in a −1|e| charged 0.8 nm MoS2 channel from the AIMD trajectory in a top view along the z direction.
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Chen, W., Gu, J., Liu, Q. et al. Two-dimensional quantum-sheet films with sub-1.2 nm channels for ultrahigh-rate electrochemical capacitance. Nat. Nanotechnol. 17, 153–158 (2022). https://doi.org/10.1038/s41565-021-01020-0
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