skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?

Abstract

The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitors containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltagemore » for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.« less

Authors:
 [1];  [1];  [2];  [3]
  1. East China Univ. of Science and Technology, Shanghai (China). State Key Lab. of Chemical Engineering
  2. Brigham Young Univ., Provo, UT (United States). Dept. of Chemistry and Biochemistry
  3. Univ. of California, Riverside, CA (United States). Dept. of Chemical and Environmental Engineering
Publication Date:
Research Org.:
Brigham Young Univ., Provo, UT (United States); Univ. of California, Riverside, CA (United States); East China Univ. of Science and Technology, Shanghai (China); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Chinese Scholarship Council; National Natural Science Foundation of China (NSFC)
OSTI Identifier:
1340472
Grant/Contract Number:  
AC05-00OR22725; 91334203; B08021
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physics. Condensed Matter
Additional Journal Information:
Journal Volume: 28; Journal Issue: 41; Journal ID: ISSN 0953-8984
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; energy storage; nonaqueous electrolytes; ionophobic nanopore; electrical double layer; classical density functional theory

Citation Formats

Lian, Cheng, Univ. of California, Riverside, CA, Liu, Honglai, Henderson, Douglas, and Wu, Jianzhong. Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?. United States: N. p., 2016. Web. doi:10.1088/0953-8984/28/41/414005.
Lian, Cheng, Univ. of California, Riverside, CA, Liu, Honglai, Henderson, Douglas, & Wu, Jianzhong. Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?. United States. https://doi.org/10.1088/0953-8984/28/41/414005
Lian, Cheng, Univ. of California, Riverside, CA, Liu, Honglai, Henderson, Douglas, and Wu, Jianzhong. 2016. "Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?". United States. https://doi.org/10.1088/0953-8984/28/41/414005. https://www.osti.gov/servlets/purl/1340472.
@article{osti_1340472,
title = {Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?},
author = {Lian, Cheng and Univ. of California, Riverside, CA and Liu, Honglai and Henderson, Douglas and Wu, Jianzhong},
abstractNote = {The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitors containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.},
doi = {10.1088/0953-8984/28/41/414005},
url = {https://www.osti.gov/biblio/1340472}, journal = {Journal of Physics. Condensed Matter},
issn = {0953-8984},
number = 41,
volume = 28,
place = {United States},
year = {Mon Aug 22 00:00:00 EDT 2016},
month = {Mon Aug 22 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: A slit pore model for a porous electrode containing: (a) an organic electrolyte; (b) an ionic liquid. In both cases, cations and anions are represented by hard spheres of equal diameter (σ = 0.5 nm). For the organic electrolyte, the solvent is modeled as a dielectric continuum (shadedmore » area).« less

Save / Share:

Works referenced in this record:

Ionic Liquids at Electrified Interfaces
journal, March 2014


A review of electrolyte materials and compositions for electrochemical supercapacitors
journal, January 2015


Structure and Nanostructure in Ionic Liquids
journal, June 2015


Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems
journal, June 2012


Capacitive Energy Storage: Current and Future Challenges
journal, August 2015


A review of molecular modelling of electric double layer capacitors
journal, January 2014


Formulation of Ionic-Liquid Electrolyte To Expand the Voltage Window of Supercapacitors
journal, March 2015


Curvature effects in carbon nanomaterials: Exohedral versus endohedral supercapacitors
journal, August 2010


High capacitance of coarse-grained carbide derived carbon electrodes
journal, February 2016


Graphene in Supercapacitor Applications
journal, October 2015


Molecular Insights into Carbon Supercapacitors Based on Room-Temperature Ionic Liquids
journal, September 2013


Graphene-based materials for flexible supercapacitors
journal, January 2015


Enhancing graphene capacitance by nitrogen: effects of doping configuration and concentration
journal, January 2016


Oscillation of Capacitance inside Nanopores
journal, December 2011


Relation between the Ion Size and Pore Size for an Electric Double-Layer Capacitor
journal, March 2008


Complex Capacitance Scaling in Ionic Liquids-Filled Nanopores
journal, October 2011


Nanoporous Carbon Supercapacitors in an Ionic Liquid: A Computer Simulation Study
journal, March 2010


The simplest model of charge storage in single file metallic nanopores
journal, January 2013


Single-File Charge Storage in Conducting Nanopores
journal, July 2014


Charging Dynamics and Optimization of Nanoporous Supercapacitors
journal, June 2013


Accelerating charging dynamics in subnanometre pores
journal, March 2014


Fundamental measure theory for the electric double layer: implications for blue-energy harvesting and water desalination
journal, April 2015


Modeling Swelling Behavior of Thermoresponsive Polymer Brush with Lattice Density Functional Theory
journal, April 2014


Fundamental measure theory for hard-sphere mixtures: a review
journal, January 2010


Fundamental measure theory for hard-sphere mixtures revisited: the White Bear version
journal, November 2002


Structures of hard-sphere fluids from a modified fundamental-measure theory
journal, December 2002


Density functional theory for differential capacitance of planar electric double layers in ionic liquids
journal, March 2011


Microscopic Insights into the Electrochemical Behavior of Nonaqueous Electrolytes in Electric Double-Layer Capacitors
journal, March 2013


Density functional theory study of the capacitance of single file ions in a narrow cylinder
journal, July 2015


A Generic Model for Electric Double Layers in Porous Electrodes
journal, April 2016


Phase behavior of the restricted primitive model and square-well fluids from Monte Carlo simulations in the grand canonical ensemble
journal, January 1999


On the components of the dielectric constants of ionic liquids: ionic polarization?
journal, January 2009


Works referencing / citing this record:

Time-dependent density functional theory for the charging kinetics of electric double layer containing room-temperature ionic liquids
journal, November 2016


The effect of finite pore length on ion structure and charging
journal, September 2017


The effect of finite pore length on ion structure and charging
text, January 2019


Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.