Understanding the effects of electrode meso-macropore structure and solvent polarity on electric double layer capacitors based on a continuum model

doi:10.1016/j.cjche.2022.06.011

中国化学工程学报 ›› 2022, Vol. 50 ›› Issue (10): 423-434.DOI: 10.1016/j.cjche.2022.06.011

• Energy Science and Technology • 上一篇下一篇

Understanding the effects of electrode meso-macropore structure and solvent polarity on electric double layer capacitors based on a continuum model

Haotian Lu^1,2, Jinghong Zhou¹, Yueqiang Cao¹, Tongxin Shang³, Guanghua Ye¹, Quan-Hong Yang^2,3, Xinggui Zhou¹

1 State-Key Laboratory of Chemical Engineering, East China University of Science of Technology, Shanghai 200237, China;
2 Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China;
3 Nanoyang Group, State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China

收稿日期:2022-03-09 修回日期:2022-06-09 出版日期:2022-10-28 发布日期:2023-01-04
通讯作者: Jinghong Zhou,E-mail:jhzhou@ecust.edu.cn
基金资助:
This work was financially supported by the National Basic Research Program of China (2014CB239702), the National Natural Science Foundation of China (21676082and 22008067), and the China Postdoctoral Science Foundation (2020M681202 and 2021T140204).

Understanding the effects of electrode meso-macropore structure and solvent polarity on electric double layer capacitors based on a continuum model

Haotian Lu^1,2, Jinghong Zhou¹, Yueqiang Cao¹, Tongxin Shang³, Guanghua Ye¹, Quan-Hong Yang^2,3, Xinggui Zhou¹

1 State-Key Laboratory of Chemical Engineering, East China University of Science of Technology, Shanghai 200237, China;
2 Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China;
3 Nanoyang Group, State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China

Received:2022-03-09 Revised:2022-06-09 Online:2022-10-28 Published:2023-01-04
Contact: Jinghong Zhou,E-mail:jhzhou@ecust.edu.cn
Supported by:
This work was financially supported by the National Basic Research Program of China (2014CB239702), the National Natural Science Foundation of China (21676082and 22008067), and the China Postdoctoral Science Foundation (2020M681202 and 2021T140204).

摘要/Abstract

摘要： The structures of electrode meso-macropore and the solvent polarity are the crucial factors dominating the performance of the electric double layer capacitors (EDLCs), but their impacts are usually tangled and difficult to decouple and quantitate. Here the effects of electrode meso-macropore structure and solvent polarity on the specific capacitance of an EDLC are quantitatively investigated using a steady-state continuum model. The simulation results indicate the specific capacitances are significantly affected by the meso-macropore surface structure. The specific capacitances significantly decrease for both convex surface structures but obviously increase for both concave surface structures, with the increase of curvature radius from 1 to 20 nm. As for solvents, the polar solvent with high saturated dielectric permittivity improves the capacitance performance. Moreover, the electrode meso-macropore structure is of more concern compared with solvent polarity when aiming at enhancing the specific capacitance. These results provide fundamentals for the rational design of porous electrodes and polar electrolytes for EDLCs.

关键词: Electric double layer capacitors, Numerical simulation, Meso-macropore, Electrolytes, Saturated dielectric permittivity

Abstract: The structures of electrode meso-macropore and the solvent polarity are the crucial factors dominating the performance of the electric double layer capacitors (EDLCs), but their impacts are usually tangled and difficult to decouple and quantitate. Here the effects of electrode meso-macropore structure and solvent polarity on the specific capacitance of an EDLC are quantitatively investigated using a steady-state continuum model. The simulation results indicate the specific capacitances are significantly affected by the meso-macropore surface structure. The specific capacitances significantly decrease for both convex surface structures but obviously increase for both concave surface structures, with the increase of curvature radius from 1 to 20 nm. As for solvents, the polar solvent with high saturated dielectric permittivity improves the capacitance performance. Moreover, the electrode meso-macropore structure is of more concern compared with solvent polarity when aiming at enhancing the specific capacitance. These results provide fundamentals for the rational design of porous electrodes and polar electrolytes for EDLCs.

Key words: Electric double layer capacitors, Numerical simulation, Meso-macropore, Electrolytes, Saturated dielectric permittivity

Haotian Lu, Jinghong Zhou, Yueqiang Cao, Tongxin Shang, Guanghua Ye, Quan-Hong Yang, Xinggui Zhou. Understanding the effects of electrode meso-macropore structure and solvent polarity on electric double layer capacitors based on a continuum model[J]. 中国化学工程学报, 2022, 50(10): 423-434.

参考文献

[1] J.R. Miller, P. Simon, Materials science. Electrochemical capacitors for energy management, Science 321 (5889) (2008) 651-652.pubmed.ncbi.nlm.nih.gov/18669852/
[2] P. Simon, Y. Gogotsi, B. Dunn, Materials science. Where do batteries end and supercapacitors begin? Science 343 (6176) (2014) 1210-1211.pubmed.ncbi.nlm.nih.gov/24626920/
[3] S. Bose, T. Kuila, A.K. Mishra, R. Rajasekar, N.H. Kim, J.H. Lee, Carbon-based nanostructured materials and their composites as supercapacitor electrodes, J. Mater. Chem. 22 (3) (2012) 767-784.Doi:10.1039/c1jm14468e
[4] L.L. Zhang, R. Zhou, X.S. Zhao, Graphene-based materials as supercapacitor electrodes, J. Mater. Chem. 20 (29) (2010) 5983.Doi:10.1039/c000417k
[5] P. Simon, Y. Gogotsi, Capacitive energy storage in nanostructured carbon-electrolyte systems, Acc. Chem. Res. 46 (5) (2013) 1094-1103.pubmed.ncbi.nlm.nih.gov/22670843/
[6] C. Portet, G. Yushin, Y. Gogotsi, Electrochemical performance of carbon Onions, nanodiamonds, carbon black and multiwalled nanotubes in electrical double layer capacitors, Carbon 45 (13) (2007) 2511-2518.Doi:10.1016/j.carbon.2007.08.024
[7] G. Lota, K. Fic, E. Frackowiak, Carbon nanotubes and their composites in electrochemical applications, Energy Environ. Sci. 4 (5) (2011) 1592.Doi:10.1039/c0ee00470g
[8] J.J. Yoo, K. Balakrishnan, J.S. Huang, V. Meunier, B.G. Sumpter, A. Srivastava, M. Conway, A.L. Mohana Reddy, J. Yu, R. Vajtai, P.M. Ajayan, Ultrathin planar graphene supercapacitors, Nano Lett. 11 (4) (2011) 1423-1427.Doi:10.1021/nl200225j
[9] L. Wei, M. Sevilla, A.B. Fuertes, R. Mokaya, G. Yushin, Hydrothermal carbonization of abundant renewable natural organic chemicals for high-performance supercapacitor electrodes, Adv. Energy Mater. 1 (3) (2011) 356-361.Doi:10.1002/aenm.201100019
[10] Y. Tao, X.Y. Xie, W. Lv, D.M. Tang, D.B. Kong, Z.H. Huang, H. Nishihara, T. Ishii, B.H. Li, D. Golberg, F.Y. Kang, T. Kyotani, Q.H. Yang, Towards ultrahigh volumetric capacitance:Graphene derived highly dense but porous carbons for supercapacitors, Sci. Rep. 3 (2013) 2975.Doi:10.1038/srep02975
[11] H. Li, Y. Tao, X.Y. Zheng, J.Y. Luo, F.Y. Kang, H.M. Cheng, Q.H. Yang, Ultra-thick graphene bulk supercapacitor electrodes for compact energy storage, Energy Environ. Sci. 9 (10) (2016) 3135-3142.Doi:10.1039/c6ee00941g
[12] J. Vatamanu, Z.Z. Hu, D. Bedrov, C. Perez, Y. Gogotsi, Increasing energy storage in electrochemical capacitors with ionic liquid electrolytes and nanostructured carbon electrodes, J. Phys. Chem. Lett. 4 (17) (2013) 2829-2837.Doi:10.1021/jz401472c
[13] C. Merlet, B. Rotenberg, P.A. Madden, P.L. Taberna, P. Simon, Y. Gogotsi, M. Salanne, On the molecular origin of supercapacitance in nanoporous carbon electrodes, Nat. Mater. 11 (4) (2012) 306-310.Doi:10.1038/nmat3260
[14] M. Salanne, B. Rotenberg, K. Naoi, K. Kaneko, P.L. Taberna, C.P. Grey, B. Dunn, P. Simon, Efficient storage mechanisms for building better supercapacitors, Nat. Energy 1 (6) (2016) 16070.Doi:10.1038/nenergy.2016.70
[15] J.S. Huang, B.G. Sumpter, V. Meunier, Theoretical model for nanoporous carbon supercapacitors, Angew. Chem. Int. Ed Engl. 47 (3) (2008) 520-524.pubmed.ncbi.nlm.nih.gov/18058966/
[16] P. Simon, Y. Gogotsi, Materials for electrochemical capacitors, Nat. Mater. 7 (11) (2008) 845-854.pubmed.ncbi.nlm.nih.gov/18956000/
[17] Y. Shim, H.J. Kim, Solvation of carbon nanotubes in a room-temperature ionic liquid, ACS Nano 3 (7) (2009) 1693-1702.ubmed.ncbi.nlm.nih.gov/19583191/
[18] G. Feng, R. Qiao, J.S. Huang, B.G. Sumpter, V. Meunier, Ion distribution in electrified micropores and its role in the anomalous enhancement of capacitance, ACS Nano 4 (4) (2010) 2382-2390.pubmed.ncbi.nlm.nih.gov/20364850/
[19] M. Sevilla, A.B. Fuertes, Direct synthesis of highly porous interconnected carbon nanosheets and their application as high-performance supercapacitors, ACS Nano 8 (5) (2014) 5069-5078.pubmed.ncbi.nlm.nih.gov/24731137/
[20] N. Jung, S. Kwon, D. Lee, D.M. Yoon, Y.M. Park, A. Benayad, J.Y. Choi, J.S. Park, Synthesis of chemically bonded graphene/carbon nanotube composites and their application in large volumetric capacitance supercapacitors, Adv. Mater. 25 (47) (2013) 6854-6858.Doi:10.1002/adma.201302788
[21] C. Zhong, Y.D. Deng, W.B. Hu, J.L. Qiao, L. Zhang, J.J. Zhang, A review of electrolyte materials and compositions for electrochemical supercapacitors, Chem. Soc. Rev. 44 (21) (2015) 7484-7539.pubmed.ncbi.nlm.nih.gov/26050756/
[22] A. Burke, M. Miller, The power capability of ultracapacitors and lithium batteries for electric and hybrid vehicle applications, J. Power Sources 196 (1) (2011) 514-522.Doi:10.1016/j.jpowsour.2010.06.092
[23] D.S. Hall, J. Self, J.R. Dahn, Dielectric constants for quantum chemistry and Li-ion batteries:Solvent blends of ethylene carbonate and ethyl methyl carbonate, J. Phys. Chem. C 119 (39) (2015) 22322-22330.Doi:10.1021/acs.jpcc.5b06022
[24] A. Jänes, E. Lust, Use of organic esters as co-solvents for electrical double layer capacitors with low temperature performance, J. Electroanal. Chem. 588 (2) (2006) 285-295.Doi:10.1016/j.jelechem.2006.01.003
[25] K. Xu, Electrolytes and interphases in Li-ion batteries and beyond, Chem. Rev. 114 (23) (2014) 11503-11618.pubmed.ncbi.nlm.nih.gov/25351820/
[26] B.E. Conway, W.G. Pell, Power limitations of supercapacitor operation associated with resistance and capacitance distribution in porous electrode devices, J. Power Sources 105 (2) (2002) 169-81.Doi:10.1016/S0378-7753(01)00936-3
[27] M. Kaus, J. Kowal, D.U. Sauer, Modelling the effects of charge redistribution during self-discharge of supercapacitors, Electrochimica Acta 55 (25) (2010) 7516-7523.Doi:10.1016/j.electacta.2010.01.002
[28] L. Yang, B.H. Fishbine, A. Migliori, L.R. Pratt, Molecular simulation of electric double-layer capacitors based on carbon nanotube forests, J. Am. Chem. Soc. 131 (34) (2009) 12373-12376.pubmed.ncbi.nlm.nih.gov/19655756/
[29] H.N. Wang, L. Pilon, Physical interpretation of cyclic voltammetry for measuring electric double layer capacitances, Electrochimica Acta 64 (2012) 130-139.Doi:10.1016/j.electacta.2011.12.118
[30] H. Lu, J. Zhou, G. Ye, X. Zhou, Recent advances in continuous models of electrochemical supercapacitors, J. Electrochem. 24 (2018) 517-528
[31] H.N. Wang, J. Fang, L. Pilon, Scaling laws for carbon-based electric double layer capacitors, Electrochimica Acta 109 (2013) 316-321.Doi:10.1016/j.electacta.2013.07.044
[32] H.N. Wang, L. Pilon, Accurate simulations of electric double layer capacitance of ultramicroelectrodes, J. Phys. Chem. C 115 (33) (2011) 16711-16719.Doi:10.1021/jp204498e
[33] J.S. Huang, R. Qiao, B.G. Sumpter, V. Meunier, Effect of diffuse layer and pore shapes in mesoporous carbon supercapacitors, J. Mater. Res. 25 (8) (2010) 1469-1475.Doi:10.1557/jmr.2010.0188
[34] H.N. Wang, J. Varghese, L. Pilon, Simulation of electric double layer capacitors with mesoporous electrodes:Effects of morphology and electrolyte permittivity, Electrochimica Acta 56 (17) (2011) 6189-6197.http://dx.Doi:10.1016/j.electacta.2011.03.140
[35] I.N. Daniels, Z.X. Wang, B.B. Laird, Dielectric properties of organic solvents in an electric field, J. Phys. Chem. C 121 (2) (2017) 1025-1031.Doi:10.1021/acs.jpcc.6b10896
[36] H. Lu, Y. Chen, J. Zhou, Z. Sui, X. Zhou, Simulation and optimization of electrochemical double layer capacitors:Effects of ion size and diffusion coefficient, CIESC J. 70 (2019) 4021-4031.(in Chinese)
[37] M.Z. Bazant, M.S. Kilic, B.D. Storey, A. Ajdari, Towards an understanding of induced-charge electrokinetics at large applied voltages in concentrated solutions, Adv. Colloid Interface Sci. 152 (1-2) (2009) 48-88.pubmed.ncbi.nlm.nih.gov/19879552/
[38] J. Dzubiella, J.P. Hansen, Electric-field-controlled water and ion permeation of a hydrophobic nanopore, J. Chem. Phys. 122 (23) (2005) 234706.Doi:10.1063/1.1927514
[39] S. Senapati, A. Chandra, Dielectric constant of water confined in a nanocavity, J. Phys. Chem. B 105 (22) (2001) 5106-5109.Doi:10.1021/jp011058i
[40] J.J. Bikerman, XXXIX. Structure and capacity of electrical double layer, Lond. Edinb. Dublin Philos. Mag. J. Sci. 33 (220) (1942) 384-397.Doi:10.1080/14786444208520813
[41] M.S. Kilic, M.Z. Bazant, A. Ajdari, Steric effects in the dynamics of electrolytes at large applied voltages. II. Modified Poisson-Nernst-Planck equations, Phys. Rev. E Stat. Nonlin. Soft Matter Phys. 75 (2 Pt 1) (2007) 021503.pubmed.ncbi.nlm.nih.gov/17358344/
[42] H.N. Wang, L. Pilon, Mesoscale modeling of electric double layer capacitors with three-dimensional ordered structures, J. Power Sources 221 (2013) 252-260.Doi:10.1016/j.jpowsour.2012.08.002
[43] 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) (2006) 1760-1763.Doi:10.1126/science.1132195
[44] E. Stura, C. Nicolini, New nanomaterials for light weight lithium batteries, Anal. Chimica Acta 568 (1-2) (2006) 57-64.Doi:10.1016/j.aca.2005.11.025
[45] D. J. Griffiths, Introduction to Electrodynamics, Cambridge University Press, Cambridge, 2017
[46] P. Ratajczak, M.E. Suss, F. Kaasik, F. Béguin, Carbon electrodes for capacitive technologies, Energy Storage Mater. 16 (2019) 126-145.Doi:10.1016/j.ensm.2018.04.031
[47] E. Frackowiak, F. Béguin, Carbon materials for the electrochemical storage of energy in capacitors, Carbon 39 (6) (2001) 937-950.Doi:10.1016/S0008-6223(00)00183-4
[48] C. Vix-Guterl, E. Frackowiak, K. Jurewicz, M. Friebe, J. Parmentier, F. Béguin, Electrochemical energy storage in ordered porous carbon materials, Carbon 43 (6) (2005) 1293-1302.Doi:10.1016/j.carbon.2004.12.028
[49] M. Arulepp, L. Permann, J. Leis, A. Perkson, K. Rumma, A. Jänes, E. Lust, Influence of the solvent properties on the characteristics of a double layer capacitor, J. Power Sources 133 (2) (2004) 320-328.Doi:10.1016/j.jpowsour.2004.03.026
[50] D.E. Jiang, J.Z. Wu, Unusual effects of solvent polarity on capacitance for organic electrolytes in a nanoporous electrode, Nanoscale 6 (10) (2014) 5545-5550.Doi:10.1039/c4nr00046c
[51] S. Zhang, Z. Bo, H.C. Yang, J.Y. Yang, L.P. Duan, J.H. Yan, K.F. Cen, Insights into the effects of solvent properties in graphene based electric double-layer capacitors with organic electrolytes, J. Power Sources 334 (2016) 162-169.Doi:10.1016/j.jpowsour.2016.10.021
[52] H.C. Yang, J.Y. Yang, Z. Bo, X. Chen, X.R. Shuai, J. Kong, J.H. Yan, K.F. Cen, Kinetic-dominated charging mechanism within representative aqueous electrolyte-based electric double-layer capacitors, J. Phys. Chem. Lett. 8 (15) (2017) 3703-3710.Doi:10.1021/acs.jpclett.7b01525
[53] Y.B. Band, Y. Ben-Shimol, Molecules with an induced dipole moment in a stochastic electric field, Phys. Rev. E Stat. Nonlin. Soft Matter Phys. 88 (4) (2013) 042149.pubmed.ncbi.nlm.nih.gov/24229157/
[54] L. Onsager, Electric moments of molecules in liquids, J. Am. Chem. Soc. 58 (8) (1936) 1486-1493.Doi:10.1021/ja01299a050
[55] I. Yang, S.G. Kim, S.H. Kwon, M.S. Kim, J.C. Jung, Relationships between pore size and charge transfer resistance of carbon aerogels for organic electric double-layer capacitor electrodes, Electrochimica Acta 223 (2017) 21-30.Doi:10.1016/j.electacta.2016.11.177
[56] I. Yang, S.G. Kim, S.H. Kwon, J.H. Lee, M.S. Kim, J.C. Jung, Pore size-controlled carbon aerogels for EDLC electrodes in organic electrolytes, Curr. Appl. Phys. 16 (6) (2016) 665-672.Doi:10.1016/j.cap.2016.03.019

Understanding the effects of electrode meso-macropore structure and solvent polarity on electric double layer capacitors based on a continuum model

Understanding the effects of electrode meso-macropore structure and solvent polarity on electric double layer capacitors based on a continuum model

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