Abstract
With the increasingly prominent energy and environmental issues, the supercapacitors, as a highly efficient and clean energy conversion and storage devices, meet the requirements well. However, it is still a challenge to enhance the capacitance and energy density of supercapacitors. A novel and highly conductive dodecaborate/MXene composites have been designed for high performance supercapacitors. The surface charge property of MXene was modified by a simple ultrasonic treatment with ammonium ion, and the dodecaborate ion can be inserted into the inner surface of MXene by electrostatic adsorption. Due to the unique icosahedral cage conjugate structure formed by the B-B bond and the highly delocalized three-dimensional π bond structure of the electrons, the negative charge is delocalied on the whole dodecaborate ion, which reduces the ability to bind to cations. Therefore, the cations can move easily, and the dodecaborate can act as a “lubricant” for ion diffusion between the MXene layers, which significantly improves the ion transfer rate of supercapacitors. The dodecaborate/MXene composites can achieve an extremely high specific capacitance of 366 F.g-1 at a scan rate of 2 mV.s-1, which is more than eight times higher than that of MXene (43 F1-) at the same scan rate. Our finding provides a novel route on the fabrication of the high performance supercapacitors.
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Dubai, D. P.; Ayyad, O.; Ruiz, V.; Gomez-Romero, P. Hybrid energy storage: The merging of battery and supercapacitor chemistries. Chem. Soc. Rev.2015, 44, 1777–1790.
Li, P. X.; Shi, E. Z.; Yang, Y. B.; Shang, Y. Y.; Peng, Q. Y.; Wu, S. T.; Wei, J. Q.; Wang, K. L.; Zhu, H. W.; Yuan, Q. et al. Carbon nanotube-polypyrrole core-shell sponge and its application as highly compressible supercapacitor electrode. Nano Res.2014, 7, 209–218.
Yang, Y. B.; Li, P. X.; Wu, S. T.; Li, X. Y.; Shi, E. Z.; Shen, Q. C.; Wu, D. H.; Xu, W. J.; Cao, A. Y.; Yuan, Q. Hierarchically designed three-dimensional macro/mesoporous carbon frameworks for advanced electrochemical capacitance storage. Chem.- Eur. J.2015, 21, 6157–6164.
Anasori, B.; Lukatskaya, M. R.; Gogotsi Y. 2D metal carbides and nitrides (MXenes) for energy storage. Nat. Rev. Mater.2017, 2, 16098.
Zhang, X.; Zhang, Z. H.; Zhou, Z. MXene-based materials for electrochemical energy storage. J. Energy Chem.2018, 27, 73–85.
Naguib, M.; Kurtoglu, M.; Presser, V.; Lu, J.; Niu, J. J.; Heon, M.; Hultman, L.; Gogotsi, Y.; Barsoum, M. W. Two-dimensional nano- crystals produced by exfoliation of Ti3AlC2. Adv. Mater.2011, 23, 4248–4253.
Alhabeb, M.; Maleski, K.; Anasori, B.; Lelyukh, P.; Clark, L.; Sin, S.; Gogotsi, Y. Guidelines for synthesis and processing of two-dimensional titanium carbide (Ti3C2T, MXene). Chem. Mater.2017, 29, 7633–7644.
Naguib, M.; Mochalin, V. N.; Barsoum, M. W.; Gogotsi, Y. 25th anniversary article: MXenes: A new family of two-dimensional materials. Adv. Mater.2014, 26, 992–1005.
Naguib, M.; Mashtalir, O.; Carle, J.; Presser, V.; Lu, J.; Hultman, L.; Gogotsi, Y.; Barsoum, M. W. Two-dimensional transition metal carbides. ACS Nano2012, 6, 1322–1331.
Ghidiu, M.; Lukatskaya, M. R.; Zhao, M. Q.; Gogotsi, Y.; Barsoum, M. W. Conductive two-dimensional titanium carbide “clay” with high volumetric capacitance. Nature2014, 516, 78–81.
Lukatskaya, M. R.; Mashtalir, O.; Ren, C. E.; Dall’Agnese, Y.; Rozier, P.; Taberna, P. L.; Naguib, M.; Simon, P.; Barsoum, M. W.; Gogotsi, Y. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science2013, 341, 1502–1505.
Dall’Agnese, Y.; Lukatskaya, M. R.; Cook, K. M.; Taberna, P. L.; Gogotsi, Y.; Simon, P. High capacitance of surface-modified 2D titanium carbide in acidic electrolyte. Electrochem. Commun.2014, 48, 118–122.
Hu, M. M.; Li, Z. J.; Zhang, H.; Hu, T.; Zhang, C.; Wu, Z.; Wang, X. H. Self-assembled Ti3C2Tx MXene film with high gravimetric capacitance. Chem. Commun.2015, 57, 13531–13533.
Scholes, D. T.; Yee, P. Y.; Lindemuth, J. R.; Kang, H.; Onorato, J.; Ghosh, R.; Luscombe, C. K.; Spano, F. C.; Tolbert, S. H.; Schwartz, B. J. The effects of crystallinity on charge transport and the structure of sequentially processed F4TCNQ-doped conjugated polymer films. Adv. Fund. Mater.2017, 27, 1702654.
Zhao, C. J.; Wang, Q.; Zhang, H.; Passerini, S.; Qian, X. Z. Two-dimensional titanium carbide/RGO composite for high-performance supercapacitors. ACS Appl. Mater. Interfaces2016, 8, 15661–15667.
Zhao, M. Q.; Ren, C. K.; Ling, Z.; Lukatskaya, M. R.; Zhang, C. E.; van Aken, K. L.; Barsoum, M. W.; Gogotsi, Y. Flexible MXene/carbon nanotube composite paper with high volumetric capacitance. Adv. Mater.2015, 27, 339–345.
Pitochelli, A. R.; Hawthorne, F. M. The isolation of the icosahedral Bi2H122- ion. Am. Chem. Soc.1960, 82, 3228–3229.
Spokoyny, A. M. New ligand platforms featuring boron-rich clusters as organomimetic substituents. Pure Appl. Chem.2013, 85, 903–919.
Sivaev, I. B.; Sjoberg, S.; Bregadze, V. I.; Gabel, D. Synthesis of alkoxy derivatives of dodecahydro-closo-dodecaborate anion [B12H12]2-. Tetrahedron Lett.1999, 40, 3451–3454.
Hawthorne, M. F.; Pushechnikov, A. Polyhedral borane derivatives: Unique and versatile structural motifs. Pure Appl. Chem.2012, 84, 2279–2288.
Miller, H. C.; Miller, N. E.; Muetterties, E. L. Chemistry of boranes. XX. syntheses of polyhedral boranes. Inorg. Chem.1964, 3, 1456–1463.
Geis, V.; Guttsche, K.; Knapp, C.; Scherer, H.; Uzun, R. Synthesis and characterization of synthetically useful salts of the weakly-coordinating dianion [Bi2Cl12]2-. Dalton Trans.2009, 2687–2694.
Wen, Y. Y.; Rufford, T. E.; Chen, X. Z.; Li, N.; Lyu, M. Q.; Dai, L. M.; Wang, L. Z. Nitrogen-doped Ti3C2Tx MXene electrodes for high-performance supercapacitors. Nano Energy2017, 38, 368–376.
Melanova, K.; Holub, J.; Hynek, J.; Fanfrlik, J.; Benes, L.; Kutalek, P.; Krejcova, A.; Hnyk, D.; Zima, V. Outerly functionalized and non-functionalized boron clusters intercalated into layered hydroxides with different modes of binding: Materials for superacid storage. Dalton Trans.2018, 47, 11669–11679.
Rude, L. H.; Filsø, U.; D’Anna, V.; Spyratou, A.; Richter, B.; Hino, S.; Zavorotynska, O.; Baricco, M.; Serby, M. H.; Hauback, B. C. et al. Hydrogen-fluorine exchange in NaBFL-NaBF4. Phys. Chem. Chem. Phys.2013, 75, 18185–18194.
Li, Z. Y.; Wang, L. B.; Sun, D. D.; Zhang, Y. D.; Liu, B. Z.; Hu, Q. K.; Zhou, A. G. Synthesis and thermal stability of two-dimensional carbide MXene Ti3C2. Mater. Sci. Eng. B2015, 797, 33–40.
Udovic, T. J.; Matsuo, M.; Tang, W. S.; Wu, H.; Stavila, V.; Soloninin, A. V.; Skoryunov, R. V.; Babanova, O. A.; Skripov, A. V.; Rush, J. J. et al. Exceptional superionic conductivity in disordered sodium decahydro-closo-decaborate. Adv. Mater.2014, 26, 7622–7626.
Yuan, W. Y.; Cheng, L. F.; An, Y. R.; Wu, H.; Yao, N.; Fan, X. L.; Guo, X. H. MXene nanofibers as highly active catalysts for hydrogen evolution reaction. ACS Sustainable Chem. Eng.2018, 6, 8976–8982.
Mashtalir, O.; Naguib, M.; Mochalin, V. N; Dall’Agnese, Y.; Heon, M.; Barsoum, M. W.; Gogotsi, Y. Intercalation and delamination of layered carbides and carbonitrides. Nat. Commun.2013, 4, 1716.
Hu, M. M.; Hu, T.; Li, Z. J.; Yang, Y.; Cheng, R. R.; Yang, J. X.; Cui, C.; Wang, X. H. Surface functional groups and interlayer water determine the electrochemical capacitance of Ti3C2T, MXene. ACS Nano2018, 12, 3578–3586.
Rakhi, R. B.; Ahmed, B.; Hedhili, M. N.; Anjum, D. H.; Alshareef, H. N. Effect of postetch annealing gas composition on the structural and electrochemical properties of Ti2CTX MXene electrodes for supercapacitor applications. Chem. Mater.2015, 27, 5314–5323.
Oñate, J. I.; Garcia, A.; Bellido, V.; Viviente, J. L. Deposition of hydrogenated B-C thin films and their mechanical and chemical characterization. Surf. Coat. Technol.1991, 49, 548–553.
Kerber, S. J.; Bruckner, J. J.; Wozniak, K.; Seal, S.; Hardcastle, S.; Barr, T. L. The nature of hydrogen in X-ray photoelectron spectroscopy: General patterns from hydroxides to hydrogen bonding. J. Vac. Sci. Technol. A1996, 14, 1314–1320.
Halim, J.; Lukatskaya, M. R.; Cook, K. M.; Lu, J.; Smith, C. R.; Naslund, L.; May, S. J.; Hultman, L.; Gogotsi, Y.; Eklund, P. et al. Transparent conductive two-dimensional titanium carbide epitaxial thin films. Chem. Mater.2014, 26, 2374–2381.
Hu, M. M.; Li, Z. J.; Hu, T; Zhu, S. H.; Zhang, C.; Wang, X. H. High-capacitance mechanism for Ti3C2Tx MXene by in situ electrochemical Raman spectroscopy investigation. ACSNano2016, 10, 11344–11350.
Kumar, R.; Singh, R. K.; Vaz, A. R.; Savu, R.; Moshkalev, S. A. Self-assembled and one-step synthesis of interconnected 3D network of Fe304/reduced graphene oxide nanosheets hybrid for high-performance supercapacitor electrode. ACS Appl. Mater. Interfaces2017, 9, 8880–8890.
Augustyn, V.; Simon, P.; Dunn, B. Pseudocapacitive oxide materials for high-rate electrochemical energy storage. Energy Environ. Sci.2014, 7, 1597–1614.
Augustyn, V.; Come, J.; Lowe, M. A.; Kim, J. W.; Taberna, P. L.; Tolbert, S. H; Abruña, H. D.; Simon, P.; Dunn, B. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat. Mater.2013, 12, 518–522.
Acknowledgements
The authors acknowledge financial support from the National Natural Science Foundation of China (No. 61674109), the National Key R&D Program of China (No. 2016YFA0202400), the Natural Science Foundation of Jiangsu Province (No. BK20170059), the Beijing Natural Science Foundation (No. 2182061) and Science Foundation of China University of Petroleum, Beijing (No. 2462019BJRC001). This project is also funded by the Collaborative Innovation Center of Suzhou Nano Science and Technology, the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).
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Li, Z., Ma, C., Wen, Y. et al. Highly conductive dodecaborate/MXene composites for high performance supercapacitors. Nano Res. 13, 196–202 (2020). https://doi.org/10.1007/s12274-019-2597-z
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DOI: https://doi.org/10.1007/s12274-019-2597-z