Does capillary evaporation limit the accessibility of nonaqueous electrolytes to the ultrasmall pores of carbon electrodes?

Liu, Kun; Zhang, Pengfei; Wu, Jianzhong

doi:10.1063/1.5064360

Does capillary evaporation limit the accessibility of nonaqueous electrolytes to the ultrasmall pores of carbon electrodes?

Journal Article · Fri Dec 21 00:00:00 EST 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5064360· OSTI ID:1543899

^[1]; Zhang, Pengfei ^[2]; ^[1]

Univ. of California, Riverside, CA (United States)
California Inst. of Technology (CalTech), Pasadena, CA (United States)

Porous carbons have been widely utilized as electrode materials for capacitive energy storage. Whereas the significance of pore size and geometry on the device performance has been well recognized, little guidance is available for identification of carbon materials with ideal porous structures. Here, we study the phase behavior of ionic fluids in slit pores using the classical density functional theory. Within the framework of the restricted primitive model for nonaqueous electrolytes, we demonstrate that the accessibility of micropores depends not only on the ionic diameters (or desolvation) but also on their wetting behavior intrinsically related to the vapor-liquid or liquid-liquid phase separation of the bulk ionic systems. Narrowing the pore size from several tens of nanometers to subnanometers may lead to a drastic reduction in the capacitance due to capillary evaporation. The wettability of micropores deteriorates as the pore size is reduced but can be noticeably improved by raising the surface electrical potential. The theoretical findings provide fresh insights into the properties of confined ionic systems beyond electric double layer models commonly employed for rational design/selection of electrolytes and electrode materials.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1543899

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 149; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (68)

Toward Superior Capacitive Energy Storage: Recent Advances in Pore Engineering for Dense Electrodes Liu, Congcong; Yan, Xiaojun; Hu, Fei Advanced Materials, Vol. 30, Issue 17 https://doi.org/10.1002/adma.201705713	journal	March 2018
Computational Insights into Materials and Interfaces for Capacitive Energy Storage Zhan, Cheng; Lian, Cheng; Zhang, Yu Advanced Science, Vol. 4, Issue 7 https://doi.org/10.1002/advs.201700059	journal	April 2017
A comprehensive analysis of the BET area for nanoporous materials Tian, Yun; Wu, Jianzhong AIChE Journal, Vol. 64, Issue 1 https://doi.org/10.1002/aic.15880	journal	August 2017
Mean spherical approximation-mass action law theory of equilibrium and conductance in ionic solutions Ebeling, W.; Grigo, M. Journal of Solution Chemistry, Vol. 11, Issue 3 https://doi.org/10.1007/bf00667599	journal	March 1982
New microscopic approach to the statistical mechanics of chemical association Olaussen, K�re; Stell, George Journal of Statistical Physics, Vol. 62, Issue 1-2 https://doi.org/10.1007/bf01020867	journal	January 1991
Criticality and phase transitions in ionic fluids Stell, George Journal of Statistical Physics, Vol. 78, Issue 1-2 https://doi.org/10.1007/bf02183346	journal	January 1995
Density functional theory for differential capacitance of planar electric double layers in ionic liquids Jiang, De-en; Meng, Dong; Wu, Jianzhong Chemical Physics Letters, Vol. 504, Issue 4-6 https://doi.org/10.1016/j.cplett.2011.01.072	journal	March 2011
Measurements of differential capacitance in room temperature ionic liquid at mercury, glassy carbon and gold electrode interfaces Alam, Muhammad Tanzirul; Mominul Islam, Md.; Okajima, Takeyoshi Electrochemistry Communications, Vol. 9, Issue 9 https://doi.org/10.1016/j.elecom.2007.07.009	journal	September 2007
Templated mesoporous carbons for supercapacitor application Fuertes, A. B.; Lota, G.; Centeno, T. A. Electrochimica Acta, Vol. 50, Issue 14 https://doi.org/10.1016/j.electacta.2004.11.027	journal	May 2005
Effects of disordered porous media on the vapour-liquid phase equilibrium in ionic fluids: application of the association concept Holovko, Myroslav; Patsahan, Taras; Patsahan, Oksana Journal of Molecular Liquids, Vol. 228 https://doi.org/10.1016/j.molliq.2016.10.045	journal	February 2017
Application of the ionic association concept to the study of the phase behaviour of size-asymmetric ionic fluids in disordered porous media Holovko, M. F.; Patsahan, T. M.; Patsahan, O. V. Journal of Molecular Liquids, Vol. 235 https://doi.org/10.1016/j.molliq.2016.11.030	journal	June 2017
Ion–Image Interactions and Phase Transition at Electrolyte–Metal Interfaces Lee, Alpha A.; Perkin, Susan The Journal of Physical Chemistry Letters, Vol. 7, Issue 14 https://doi.org/10.1021/acs.jpclett.6b01324	journal	June 2016
Increase in Capacitance by Subnanometer Pores in Carbon Jäckel, Nicolas; Simon, Patrice; Gogotsi, Yury ACS Energy Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsenergylett.6b00516	journal	November 2016
Ionic Liquids at Electrified Interfaces Fedorov, Maxim V.; Kornyshev, Alexei A. Chemical Reviews, Vol. 114, Issue 5 https://doi.org/10.1021/cr400374x	journal	March 2014
Density Functional Theory for Planar Electric Double Layers: Closing the Gap between Simple and Polyelectrolytes Li, Zhidong; Wu, Jianzhong The Journal of Physical Chemistry B, Vol. 110, Issue 14 https://doi.org/10.1021/jp060127w	journal	April 2006
Double-Layer in Ionic Liquids: Paradigm Change? Kornyshev, Alexei A. The Journal of Physical Chemistry B, Vol. 111, Issue 20 https://doi.org/10.1021/jp067857o	journal	May 2007
Capillary Condensation of Ionic Liquid Solutions in Porous Electrodes Szparaga, Ryan; Woodward, Clifford E.; Forsman, Jan The Journal of Physical Chemistry C, Vol. 117, Issue 4 https://doi.org/10.1021/jp309794w	journal	January 2013
Static Dielectric Constant of Room Temperature Ionic Liquids: Internal Pressure and Cohesive Energy Density Approach Singh, Tejwant; Kumar, Arvind The Journal of Physical Chemistry B, Vol. 112, Issue 41 https://doi.org/10.1021/jp8059618	journal	October 2008
Supercapacitor Capacitance Exhibits Oscillatory Behavior as a Function of Nanopore Size Feng, Guang; Cummings, Peter T. The Journal of Physical Chemistry Letters, Vol. 2, Issue 22 https://doi.org/10.1021/jz201312e	journal	October 2011
Microscopic Insights into the Electrochemical Behavior of Nonaqueous Electrolytes in Electric Double-Layer Capacitors Jiang, De-en; Wu, Jianzhong The Journal of Physical Chemistry Letters, Vol. 4, Issue 8 https://doi.org/10.1021/jz4002967	journal	March 2013
Increasing Energy Storage in Electrochemical Capacitors with Ionic Liquid Electrolytes and Nanostructured Carbon Electrodes Vatamanu, Jenel; Hu, Zongzhi; Bedrov, Dmitry The Journal of Physical Chemistry Letters, Vol. 4, Issue 17 https://doi.org/10.1021/jz401472c	journal	August 2013
Oscillation of Capacitance inside Nanopores Jiang, De-en; Jin, Zhehui; Wu, Jianzhong Nano Letters, Vol. 11, Issue 12 https://doi.org/10.1021/nl202952d	journal	December 2011
Complex Capacitance Scaling in Ionic Liquids-Filled Nanopores Wu, Peng; Huang, Jingsong; Meunier, Vincent ACS Nano, Vol. 5, Issue 11 https://doi.org/10.1021/nn203260w	journal	October 2011
In Situ Small Angle Neutron Scattering Revealing Ion Sorption in Microporous Carbon Electrical Double Layer Capacitors Boukhalfa, Sofiane; Gordon, Daniel; He, Lilin ACS Nano, Vol. 8, Issue 3 https://doi.org/10.1021/nn406077n	journal	February 2014
Accelerating charging dynamics in subnanometre pores Kondrat, Svyatoslav; Wu, Peng; Qiao, Rui Nature Materials, Vol. 13, Issue 4 https://doi.org/10.1038/nmat3916	journal	March 2014
The liquid–liquid coexistence of binary mixtures of the room temperature ionic liquid 1-methyl-3-hexylimidazolium tetrafluoroborate with alcohols Wagner, Monika; Stanga, Olimpiu; Schröer, Wolffram Phys. Chem. Chem. Phys., Vol. 6, Issue 18 https://doi.org/10.1039/b404933k	journal	January 2004
Constant capacitance in nanopores of carbon monoliths García-Gómez, Alejandra; Moreno-Fernández, Gelines; Lobato, Belén Physical Chemistry Chemical Physics, Vol. 17, Issue 24 https://doi.org/10.1039/c5cp01904d	journal	January 2015
The ideal porous structure of EDLC carbon electrodes with extremely high capacitance Urita, K.; Urita, C.; Fujita, K. Nanoscale, Vol. 9, Issue 40 https://doi.org/10.1039/c7nr05307j	journal	January 2017
A fundamental-measure theory for inhomogeneous associating fluids Yu, Yang-Xin; Wu, Jianzhong The Journal of Chemical Physics, Vol. 116, Issue 16 https://doi.org/10.1063/1.1463435	journal	April 2002
Criticality and phase behavior in the restricted-primitive model electrolyte: Description of ion association Jiang, Jianwen; Blum, Lesser; Bernard, Oliver The Journal of Chemical Physics, Vol. 116, Issue 18 https://doi.org/10.1063/1.1468638	journal	May 2002
Structures of hard-sphere fluids from a modified fundamental-measure theory Yu, Yang-Xin; Wu, Jianzhong The Journal of Chemical Physics, Vol. 117, Issue 22 https://doi.org/10.1063/1.1520530	journal	December 2002
Equilibrium Thermodynamic Properties of the Mixture of Hard Spheres Mansoori, G. A.; Carnahan, N. F.; Starling, K. E. The Journal of Chemical Physics, Vol. 54, Issue 4 https://doi.org/10.1063/1.1675048	journal	February 1971
Phase behavior and critical properties of size-asymmetric, primitive-model electrolytes Qin, Yuan; Prausnitz, John M. The Journal of Chemical Physics, Vol. 121, Issue 7 https://doi.org/10.1063/1.1770651	journal	August 2004
Phase behavior of ionic fluids in slitlike pores: A density functional approach for the restricted primitive model Pizio, O.; Patrykiejew, A.; Sokołowski, S. The Journal of Chemical Physics, Vol. 121, Issue 23 https://doi.org/10.1063/1.1818677	journal	December 2004
Phase behavior of the restricted primitive model of ionic fluids with association in slitlike pores. Density-functional approach Pizio, O.; Sokołowski, S. The Journal of Chemical Physics, Vol. 122, Issue 14 https://doi.org/10.1063/1.1883165	journal	April 2005
Phase transition in porous electrodes Kiyohara, Kenji; Sugino, Takushi; Asaka, Kinji The Journal of Chemical Physics, Vol. 134, Issue 15 https://doi.org/10.1063/1.3578468	journal	April 2011
Phase transition in porous electrodes. II. Effect of asymmetry in the ion size Kiyohara, Kenji; Shioyama, Hiroshi; Sugino, Takushi The Journal of Chemical Physics, Vol. 136, Issue 9 https://doi.org/10.1063/1.3690084	journal	March 2012
Phase transition in porous electrodes. III. For the case of a two component electrolyte Kiyohara, Kenji; Shioyama, Hiroshi; Sugino, Takushi The Journal of Chemical Physics, Vol. 138, Issue 23 https://doi.org/10.1063/1.4809743	journal	June 2013
Direct measurements of forces between different charged colloidal particles and their prediction by the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO) Ruiz-Cabello, F. Javier Montes; Maroni, Plinio; Borkovec, Michal The Journal of Chemical Physics, Vol. 138, Issue 23 https://doi.org/10.1063/1.4810901	journal	June 2013
Effects of image charges on double layer structure and forces Wang, Rui; Wang, Zhen-Gang The Journal of Chemical Physics, Vol. 139, Issue 12 https://doi.org/10.1063/1.4821636	journal	September 2013
Revisiting density functionals for the primitive model of electric double layers Jiang, Jian; Cao, Dapeng; Henderson, Douglas The Journal of Chemical Physics, Vol. 140, Issue 4 https://doi.org/10.1063/1.4862990	journal	January 2014
On the theoretical description of weakly charged surfaces Wang, Rui; Wang, Zhen-Gang The Journal of Chemical Physics, Vol. 142, Issue 10 https://doi.org/10.1063/1.4914170	journal	March 2015
A variational approach to the liquid-vapor phase transition for hardcore ions in the bulk and in nanopores Loubet, Bastien; Manghi, Manoel; Palmeri, John The Journal of Chemical Physics, Vol. 145, Issue 4 https://doi.org/10.1063/1.4959034	journal	July 2016
Ion pairing and phase behaviour of an asymmetric restricted primitive model of ionic liquids Lu, Hongduo; Li, Bin; Nordholm, Sture The Journal of Chemical Physics, Vol. 145, Issue 23 https://doi.org/10.1063/1.4972214	journal	December 2016
Simulations of ionic liquids confined by metal electrodes using periodic Green functions Girotto, Matheus; dos Santos, Alexandre P.; Levin, Yan The Journal of Chemical Physics, Vol. 147, Issue 7 https://doi.org/10.1063/1.4989388	journal	August 2017
Capillary evaporation of the ionic liquid [EMIM][BF ₄ ] in nanoscale solvophobic confinement Shrivastav, Gourav; Remsing, Richard C.; Kashyap, Hemant K. The Journal of Chemical Physics, Vol. 148, Issue 19 https://doi.org/10.1063/1.5010259	journal	May 2018
The nature of the liquid-vapour interface and other topics in the statistical mechanics of non-uniform, classical fluids Evans, R. Advances in Physics, Vol. 28, Issue 2 https://doi.org/10.1080/00018737900101365	journal	April 1979
Thermodynamic properties and phase equilibria of charged hard sphere chain model for polyelectrolyte solutions Jiang, J. W.; Blum, L.; Bernard, O. Molecular Physics, Vol. 99, Issue 13 https://doi.org/10.1080/00268970110043414	journal	July 2001
Mean spherical model for asymmetric electrolytes: I. Method of solution Blum, L. Molecular Physics, Vol. 30, Issue 5 https://doi.org/10.1080/00268977500103051	journal	November 1975
Phase separation in confined systems Gelb, Lev D.; Gubbins, K. E.; Radhakrishnan, R. Reports on Progress in Physics, Vol. 62, Issue 12 https://doi.org/10.1088/0034-4885/62/12/201	journal	December 1999
Phase separation in confined systems Gelb, L. D.; Gubbins, K. E.; Radhakrishnan, R. Reports on Progress in Physics, Vol. 63, Issue 4 https://doi.org/10.1088/0034-4885/63/4/501	journal	March 2000
Wetting transitions Bonn, Daniel; Ross, David Reports on Progress in Physics, Vol. 64, Issue 9 https://doi.org/10.1088/0034-4885/64/9/202	journal	August 2001
Electrostatic correlations: from plasma to biology Levin, Yan Reports on Progress in Physics, Vol. 65, Issue 11 https://doi.org/10.1088/0034-4885/65/11/201	journal	September 2002
Fundamental measure theory for hard-sphere mixtures revisited: the White Bear version Roth, R.; Evans, R.; Lang, A. Journal of Physics: Condensed Matter, Vol. 14, Issue 46 https://doi.org/10.1088/0953-8984/14/46/313	journal	November 2002
Coupling Poisson Nernst Planck and density functional theory to calculate ion flux Gillespie, Dirk; Nonner, Wolfgang; Eisenberg, Robert S. Journal of Physics: Condensed Matter, Vol. 14, Issue 46 https://doi.org/10.1088/0953-8984/14/46/317	journal	November 2002
Density functional theory of the electrical double layer: the RFD functional Gillespie, Dirk; Valiskó, Mónika; Boda, Dezso Journal of Physics: Condensed Matter, Vol. 17, Issue 42 https://doi.org/10.1088/0953-8984/17/42/002	journal	October 2005
Liquid–liquid phase separation in solutions of ionic liquids: phase diagrams, corresponding state analysis and comparison with simulations of the primitive model Schröer, W.; Vale, V. R. Journal of Physics: Condensed Matter, Vol. 21, Issue 42 https://doi.org/10.1088/0953-8984/21/42/424119	journal	September 2009
Superionic state in double-layer capacitors with nanoporous electrodes Kondrat, S.; Kornyshev, A. Journal of Physics: Condensed Matter, Vol. 23, Issue 2 https://doi.org/10.1088/0953-8984/23/2/022201	journal	December 2010
Shells of charge: a density functional theory for charged hard spheres Roth, Roland; Gillespie, Dirk Journal of Physics: Condensed Matter, Vol. 28, Issue 24 https://doi.org/10.1088/0953-8984/28/24/244006	journal	April 2016
Vapour-liquid phase diagram for an ionic fluid in a random porous medium Holovko, M. F.; Patsahan, O.; Patsahan, T. Journal of Physics: Condensed Matter, Vol. 28, Issue 41 https://doi.org/10.1088/0953-8984/28/41/414003	journal	August 2016
Wedge wetting by electrolyte solutions Mußotter, Maximilian; Bier, Markus Physical Review E, Vol. 96, Issue 3 https://doi.org/10.1103/physreve.96.032605	journal	September 2017
Density-Functional Theory for Complex Fluids Wu, Jianzhong; Li, Zhidong Annual Review of Physical Chemistry, Vol. 58, Issue 1 https://doi.org/10.1146/annurev.physchem.58.032806.104650	journal	May 2007
Superionic state in double-layer capacitors with nanoporous electrodes Kondrat, S.; Kornyshev, A. arXiv https://doi.org/10.48550/arxiv.1010.0921	text	January 2010
Vapour-liquid phase diagram for an ionic fluid in a random porous medium Holovko, M. F.; Patsahan, O.; Patsahan, T. arXiv https://doi.org/10.48550/arxiv.1603.08352	text	January 2016
A variational approach to the liquid-vapor phase transition for hardcore ions in the bulk and in nanopores Loubet, Bastien; Manghi, Manoel; Palmeri, John arXiv https://doi.org/10.48550/arxiv.1604.05532	text	January 2016
Wedge wetting by electrolyte solutions Mußotter, Maximilian; Bier, Markus arXiv https://doi.org/10.48550/arxiv.1706.09678	text	January 2017
Simulations of ionic liquids confined by metal electrodes using periodic Green functions Girotto, Matheus; Santos, Alexandre P. dos; Levin, Yan arXiv https://doi.org/10.48550/arxiv.1712.04686	text	January 2017
Electrostatic correlations: from Plasma to Biology Levin, Yan arXiv https://doi.org/10.48550/arxiv.cond-mat/0207086	text	January 2002

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