Abstract
Porous carbons with ultrahigh specific surface area (> 3000 m2/g) prepared at low KOH/char ratio (e.g. less than 0.5) is of great importance for their future applications, yet this remains a significant challenge due to the uneven dispersion of the activating agent within carbon source. Herein, a universal combination strategy (solid-state reaction at room temperature followed by chemical activation) to prepare ultrahigh surface area porous carbons has been developed. The specific surface area can reach to 3775 m2/g even at a very low KOH/char ratio (0.19), and the morphologies, specific surface and pore size distributions of the products can be simply tuned by the KOH/char ratios. We found the solid-state reaction at room temperature prior to chemical activation is an efficient way to achieve the even dispersion of the activating agent and thus improve the utilization of KOH greatly. As a typical example, the as-obtained EDTA-3 K not only have an ultrahigh specific surface area up to 3614 m2/g, but also deliver a large total pore volume of 2.09 m3/g. Benefited from the ultrahigh specific surface area, hierarchically porous structure and unique morphology, the EDTA-3 K based supercapacitor exhibits excellent capacitive performance in both KOH and Li2SO4 electrolyte. Hence, this study not only exploits a new approach for the synthesis of hierarchically porous carbon materials with ultrahigh specific surface area for electrochemical energy storage applications, but also provides a universal combination strategy to improve the utilization ratio of activating reagent for the producing of porous carbons.
Similar content being viewed by others
References
P. Simon, Y. Gogotsi, B. Dunn, Where do batteries end and supercapacitors begin? Science 343, 1210–1211 (2014)
F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini, A.C. Ferrari, R.S. Ruoff, V. Pellegrini, Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage. Science 347, 1246501 (2015)
Z. Wu, L. Li, J.M. Yan, X.B. Zhang, Materials design and system construction for conventional and new-concept supercapacitors. Adv. Sci. 4(6), 1600382 (2017)
M. Areir, Y. Xu, D. Harrison, J. Fyson, A study of 3D printed flexible supercapacitors onto silicone rubber substrates. J. Mater. Sci. 28, 18254–18261 (2017)
J.X. Liang, Z.C. Xiao, Y. Gao, X.H. Xu, D.B. Kong, M. Wagner, L.J. Zhi, Ionothermal strategy towards template-free hierarchical porous carbons for supercapacitive energy storage. Carbon 143, 487–493 (2019)
L. Sun, Y.M. Zhou, L. Li, H. Zhou, X.Q. Liu, Q.Y. Zhang, B. Gao, Z.Z. Meng, D. Zhou, Y.L. Ma, Facile and green synthesis of 3D honeycomb-like N/S-codoped hierarchically porous carbon materials from bio-protic salt for flexible, temperature-resistant supercapacitors. Appl. Surf. Sci. 467, 382–390 (2019)
F. Béguin, V. Presser, A. Balducci, E. Frackowiak, Carbons and electrolytes for advanced supercapacitors. Adv. Mater. 26, 2219–2251 (2014)
F.X. Wang, X.W. Wu, X.H. Yuan, Z.C. Liu, Y. Zhang, L.J. Fu, Y.S. Zhu, Q.M. Zhou, Y.P. Wu, W. Huang, Latest advances in supercapacitors: from new electrode materials to novel device designs. Chem. Soc. Rev. 46, 6816–6854 (2017)
H. Yang, Y. Tang, X. Huang, L.X. Wang, Q.T. Zhang, Activated porous carbon derived from walnut shells with promising material properties for supercapacitors. J. Mater. Sci. 28, 18637–18645 (2017)
K.X. Zou, Y.F. Deng, J.P. Chen, Y.Q. Qian, Y.W. Yang, Y.W. Li, G.H. Chen, Hierarchically porous nitrogen-doped carbon derived from the activation of agriculture waste by potassium hydroxide and urea for high-performance supercapacitors. J. Power Sources 378, 579–588 (2018)
L. Jiao, X.X. Pan, Y.L. Xi, J.Z. Li, J.M. Cao, Q. Guo, W. Han, A facile synthesis of self-assembling reduced graphene oxide/cobalt carbonate hydroxide papers for high-performance supercapacitor applications. J. Mater. Sci. 30, 159–166 (2018)
F.Q. Guo, X.C. Jiang, X.L. Li, K.Y. Peng, C.L. Guo, Z.H. Rao, Carbon electrode material from peanut shell by one-step synthesis for high performance supercapacitor. J. Mater. Sci. 30, 159–166 (2018)
D. Wang, L. Xu, J. Nai, X. Bai, T. Sun, Morphology-controllable synthesis of nanocarbons and their application in advanced symmetric supercapacitor in ionic liquid electrolyte. Appl. Surf. Sci. 473, 1014–1023 (2019)
A.G. Pandolfo, A.F. Hollenkamp, Carbon properties and their role in supercapacitors. J. Power Sources 157, 11–27 (2006)
Q. Wang, J. Yan, Z. Fan, Carbon materials for high volumetric performance supercapacitors: design, progress, challenges and opportunities. Energy Environ. Sci. 9, 729–762 (2016)
Y. Wang, Y. Song, Y. Xia, Electrochemical capacitors: mechanism, materials, systems, characterization and applications. Chem. Soc. Rev. 4, 5925–5950 (2016)
C. Prehal, C. Koczwara, N. Jackel, A. Schreiber, M. Burian, H. Amenitsch, M.A. Hartmann, V. Presser, O. Paris, Quantification of ion confinement and desolvation in nanoporous carbon supercapacitors with modelling and in situ X-ray scattering. Nat. Energy 2, 16215 (2017)
D.W. Wang, Y.T. Wang, H.W. Liu, W. Xu, L. Xu, Unusual carbon nanomesh constructed by interconnected carbon nanocages for ionic liquid-based supercapacitor with superior rate capability. Chem. Eng. J. 342, 474–483 (2018)
G.S. Fu, Q. Li, J.L. Ye, J.L. Han, J.Q. Wang, L. Zhai, Y.W. Zhu, Hierarchical porous carbon with high nitrogen content derived from plant waste (pomelo peel) for supercapacitor. J. Mater. Sci. 29, 7707–7717 (2018)
D. Wang, L. Xu, J. Nai, T. Sun, A versatile Co-Activation strategy towards porous carbon nanosheets for high performance ionic liquid based supercapacitor applications. J. Alloys Compd. 786, 109–117 (2019)
J.C. Wang, S. Kaskel, KOH activation of carbon-based materials for energy storage. J. Mater. Chem. 22, 23710–23725 (2012)
V. Strauss, K. Marsh, M.D. Kowal, M. El-Kady, R.B. Kaner, A simple route to porous graphene from carbon nanodots for supercapacitor applications. Adv. Mater. 30, 1704449 (2018)
Z.P. Qiu, Y.S. Wang, X. Bi, T. Zhou, J. Zhou, J.P. Zhao, Z.C. Miao, W.M. Yi, P. Fu, S.P. Zhuo, Biochar-based carbons with hierarchical micro-meso-macro porosity for high rate and long cycle life supercapacitors. J. Power Sources 376, 82–90 (2018)
J. Pang, W. Zhang, H. Zhang, J. Zhang, H. Zhang, G. Cao, M. Han, Y. Yang, Sustainable nitrogen-containing hierarchical porous carbon spheres derived from sodium lignosulfonate for high-performance supercapacitors. Carbon 132, 280–293 (2018)
M. Sevilla, A.B. Fuertes, A general and facile synthesis strategy towards highly porous carbons: carbonization of organic salts. J. Mater. Chem. A 1, 13738–13741 (2013)
M. Sevilla, A.B. Fuertes, Direct synthesis of highly porous interconnected carbon nanosheets and their application as high-performance supercapacitors. ACS Nano 8, 5069–5078 (2014)
A.B. Fuertes, M. Sevilla, Hierarchical microporous/mesoporous carbon nanosheets for high-performance supercapacitors. ACS Appl. Mater. Interfaces 7, 4344–4353 (2015)
H. Luo, Y. Yang, Y. Sun, D. Chen, X. Zhao, D. Zhang, J. Zhang, Highly nanoporous carbons by single-step organic salt carbonization for high-performance supercapacitors. J. Appl. Electrochem. 45, 839–848 (2015)
X.Y. Chen, D.H. Xie, Z.J. Zhang, C. Cen, Tetraphenylborate-derived hierarchically porous carbons as efficient electrode materials for supercapacitors. J. Power Sources 246, 531–539 (2014)
J. Zhu, D. Xu, W. Qian, J. Zhang, F. Yan, Heteroatom-containing porous carbons derived from ionic liquid-doped alkali organic salts for supercapacitors. Small 12, 1935–1944 (2016)
H. Luo, Y. Yang, X. Zhao, J. Zhang, Y. Chen, 3D sponge-like nanoporous carbons via a facile synthesis for high-performance supercapacitors: direct carbonization of tartrate salt. Electrochim. Acta 169, 13–21 (2015)
W. Yang, W. Yang, F. Ding, L. Sang, Z. Ma, G. Shao, Template-free synthesis of ultrathin porous carbon shell with excellent conductivity for high-rate supercapacitors. Carbon 111, 419–427 (2017)
W.W. Kang, B.P. Lin, G.X. Huang, C.X. Zhang, Y.H. Yao, W.T. Hou, B. Xu, B. Xing, Peanut bran derived hierarchical porous carbon for supercapacitor. J. Mater. Sci. 29, 6361–6368 (2018)
R. Thangavel, A.G. Kannan, R. Ponraj, V. Thangavel, D.-W. Kim, Y.-S. Lee, High-energy green supercapacitor driven by ionic liquid electrolytes as an ultra-high stable next-generation energy storage device. J. Power Sources 383, 102–109 (2018)
C. Zhang, X. Zhu, M. Cao, M. Li, N. Li, L. Lai, J. Zhu, D. Wei, Hierarchical porous carbon materials derived from sheep manure for high-capacity supercapacitors. ChemSuschem 9, 932–937 (2016)
J. Wang, Y.L. Xu, B. Ding, Z. Chang, X.G. Zhang, Y. Yamauchi, K.C.W. Wu, Confined self-assembly in two-dimensional interlayer space: monolayered mesoporous carbon nanosheets with in-plane orderly arranged mesopores and a highly graphitized framework. Angew. Chem. Int. Ed. 57, 2894–2898 (2018)
B.B. Wang, D.H. Li, M.W. Tang, H.B. Ma, Y.G. Gui, X. Tian, F.Y. Quan, X.Q. Song, Y.Z. Xia, Alginate-based hierarchical porous carbon aerogel for high-performance supercapacitors. J. Alloys Compd 749, 517–522 (2018)
M.A. Pimenta, G. Dresselhaus, M.S. Dresselhaus, L.G. Cancado, A. Jorio, R. Saito, Studying disorder in graphite-based systems by Raman spectroscopy. Phys. Chem. Chem. Phys. 9, 1276–1291 (2007)
J.G. Wang, H. Liu, H. Sun, W. Hua, H. Wang, X. Liu, B. Wei, One-pot synthesis of nitrogen-doped ordered mesoporous carbon spheres for high-rate and long-cycle life supercapacitors. Carbon 127, 85–92 (2018)
A.C. Ferrari, J. Robertson, Raman spectroscopy of amorphous, nanostructured, diamond-like carbon, and nanodiamond. Philos. Trans. Roy. Soc. Series A 362, 2477–2512 (2004)
D.W. Wang, S.J. Liu, G.L. Fang, G.H. Geng, J.F. Ma, From trash to treasure: direct transformation of onion husks into three-dimensional interconnected porous carbon frameworks for high-performance supercapacitors in organic electrolyte. Electrochim. Acta 216, 405–411 (2016)
X.Y. Xie, X.J. He, H.F. Zhang, F. Wei, N. Xiao, J.S. Qiu, Interconnected sheet-like porous carbons from coal tar by a confined soft-template strategy for supercapacitors. Chem. Eng. J. 350, 49–56 (2018)
Z. Yang, J. Ren, Z. Zhang, X. Chen, G. Guan, L. Qiu, Y. Zhang, H. Peng, Recent advancement of nanostructured carbon for energy applications. Chem. Rev. 115, 5159–5223 (2015)
M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing, Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87, 1051–1069 (2015)
H. Xu, C.K. Wu, X.J. Wei, S.Y. Gao, Hierarchically porous carbon materials with controllable proportion of micropore area by dual-activator synthesis for high-performance supercapacitors. J. Mater. Chem. A 6, 15340–15347 (2018)
D.W. Wang, S.J. Liu, L. Jiao, G.L. Fang, G.H. Geng, J.F. Ma, Unconventional mesopore carbon nanomesh prepared through explosione-assisted activation approach: a robust electrode material for ultrafast organic electrolyte supercapacitors. Carbon 119, 30–39 (2017)
R.Y. Yan, M. Antonietti, M. Oschatz, Toward the experimental understanding of the energy storage mechanism and ion dynamics in ionic liquid based supercapacitors. Adv. Energy. Mater. 8, 1800026 (2018)
J. Chmiola, G. Yushin, Y. Gogotsi, C. Portet, P. Simon, P.L. Taberna, Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer. Science 313(5794), 1760–1763 (2006)
D.W. Wang, G.L. Fang, T. Xue, J.F. Ma, G.H. Geng, A melt route for the synthesis of activated carbon derived from carton box for high performance symmetric supercapacitor applications. J. Power Sources 307, 401–409 (2016)
D.W. Wang, J.W. Nai, H. Li, L. Xu, Y.T. Wang, A robust strategy for the general synthesis of hierarchical carbons constructed by nanosheets and their application in high performance supercapacitor in ionic liquid electrolyte. Carbon 141, 40–49 (2019)
J.E. Zuliani, S. Tong, C.Q. Jia, D.W. Kirk, Contribution of surface oxygen groups to the measured capacitance of porous carbon supercapacitors. J. Power Sources 395, 271–279 (2018)
C. Young, J.J. Lin, J. Wang, B. Ding, X.G. Zhang, S.M. Alshehri, T. Ahamad, R.R. Salunkhe, S.A. Hossain, J.H. Khan, Y. Ide, J. Kim, J. Henzie, K.C.W. Wu, N. Kobayashi, Y. Yamauchi, Significant effect of pore sizes on energy storage in nanoporous carbon supercapacitors. Chem. Eur. J. 24, 6127–6132 (2018)
J. Zhao, Y.F. Jiang, H. Fan, M. Liu, O. Zhuo, X.Z. Wang, Q. Wu, L.J. Yang, Y.W. Ma, Z. Hu, Porous 3D few-layer graphene-like carbon for ultrahigh-power supercapacitors with well-defined structure-performance relationship. Adv. Mater. 29, 1604569 (2017)
K. Fic, G. Lota, M. Meller, E. Frackowiak, Novel insight into neutral medium as electrolyte for high-voltage supercapacitors. Energy Environ. Sci. 5, 5842–5850 (2012)
Acknowledgements
The authors are grateful to the financial supports from the Scientific Research Foundation of the Higher Education Institutions of Ningxia (Grant No. NGY 2017148).
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Liang, H., Sun, T., Xu, L. et al. A universal strategy towards porous carbons with ultrahigh specific surface area for high-performance symmetric supercapacitor applications. J Mater Sci: Mater Electron 30, 13636–13646 (2019). https://doi.org/10.1007/s10854-019-01733-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10854-019-01733-y