Energy Storage Performance of Supercapacitors with Polyelectrolyte Surface Coatings: Effects of Dielectric Contrast

Yi-Yao Han; Ming-Yu Chen; Xiao-Fei Xu

doi:10.1007/s10118-026-3710-x

Your Location：

Home >

Browse articles >

Energy Storage Performance of Supercapacitors with Polyelectrolyte Surface Coatings: Effects of Dielectric Contrast

RESEARCH ARTICLE | Updated：2026-07-20

- Energy Storage Performance of Supercapacitors with Polyelectrolyte Surface Coatings: Effects of Dielectric Contrast
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-14(2026)
- Affiliations：
  
  State Key Laboratory of Chemical Engineering and School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
- Author bio：
  
  xuxf@ecust.edu.cn
- Funds：
- DOI：10.1007/s10118-026-3710-x
  CLC：
- Received：25 February 2026，
  
  Revised：2026-03-26，
  
  Accepted：08 April 2026，
  
  Online First：20 July 2026，
  
  Published：2026-05
- Accepted：
Scan QR Code
Han, Y. Y.; Chen, M. Y.; Xu, X. F. Energy storage performance of supercapacitors with polyelectrolyte surface coatings: effects of dielectric contrast. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3710-x

Yi-Yao Han, Ming-Yu Chen, Xiao-Fei Xu. Energy Storage Performance of Supercapacitors with Polyelectrolyte Surface Coatings: Effects of Dielectric Contrast[J/OL]. Chinese Journal of Polymer Science, 2026, 441-14.
Han, Y. Y.; Chen, M. Y.; Xu, X. F. Energy storage performance of supercapacitors with polyelectrolyte surface coatings: effects of dielectric contrast. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3710-x DOI：

Yi-Yao Han, Ming-Yu Chen, Xiao-Fei Xu. Energy Storage Performance of Supercapacitors with Polyelectrolyte Surface Coatings: Effects of Dielectric Contrast[J/OL]. Chinese Journal of Polymer Science, 2026, 441-14. DOI： 10.1007/s10118-026-3710-x.

摘要

Abstract

The interfacial structure at the electrode-electrolyte interface is a critical determinant of the performance of electrochemical supercapacitors. Although grafting polyelectrolyte (PE) brushes onto electrodes is a promising strategy to enhance charge storage

the role of dielectric contrast and its coupling with PE microstructure remains to be studied. In this work

a classical density functional theory (cDFT) is employed to elucidate the synergistic effects of dielectric contrast and PE microstructure on supercapacitor performance. The theory explicitly accounts for image-charge interaction induced by dielectric discontinuity

chain correlation of the PE

excluded volume effect

and electrostatic correlation. The results reveal that increasing the grafting density and chain length of the PE brushes significantly enhances the capacitance by providing more immobile charge sites and expanding the effective double-layer region

which facilitates stronger counterion adsorption. It is found that the dielectric contrast between the electrode substrate and solvent

which is often oversimplified in idealized models

plays a decisive role. A higher dielectric permittivity of the substrate weakens the shielding effect of the polarization field within the electrode. Consequently

the external electric field provides a stronger influence on the electrolyte

promoting a denser accumulation of counterions at the interface. Crucially

a high-dielectric substrate mitigates the repulsive image-charge interaction

effectively transforming it into an attractive force that further adsorbs charge near the electrode. This effect becomes particularly pronounced at high surface potentials. These results provide fundamental insights into the optimization of high-performance SCs using PE coatings.

关键词

Keywords

references

Patel, A.; Patel, S. K.; Singh, R. S.; Patel, R. P. Review on recent advancements in the role of electrolytes and electrode materials on supercapacitor performances. Discov. Nano 2024 , 19 , 188..

Zhai, Z.; Zhang, L.; Du, T.; Ren, B.; Xu, Y.; Wang, S.; Miao, J.; Liu, Z. A review of carbon materials for supercapacitors. Mater. Des. 2022 , 221 , 111017..

Kumar, N. A.; Choi, H.-J.; Shin, Y. R.; Chang, D. W.; Dai, L.; Baek, J. B. Polyaniline-grafted reduced graphene oxide for efficient electrochemical supercapacitors. ACS Nano 2012 , 6 , 1715−1723..

[Mazur, D.; Brandyshev, P.; Doronin, S.; Budkov, Y. A. Understanding the electric doublelayer at the electrode-electrolyte interface: part i - no ion specific adsorption. ChemPhysChem 2024 , e202400650..

Fumagalli, L.; Esfandiar, A.; Fabregas, R.; Hu, S.; Ares, P.; Janardanan, A.; Yang, Q.; Radha, B.; Taniguchi, T.; Watanabe, K.; Gomila, G.; Novoselov, K. S.; Geim, A. K. Anomalously low dielectric constant of confined water. Science 2018 , 360 , 1339−1342..

Goldsmith, Z. K.; Secor, M.; Hammes-Schiffer, S. Inhomogeneity of interfacial electric fields at vibrational probes on electrode surfaces. ACS Cent. Sci. 2020 , 6 , 304−311..

Jeanmairet, G.; Rotenberg, B.; Salanne, M. Microscopic simulations of electrochemical double-layer capacitors. Chem. Rev. 2022 , 122 , 10860−10898..

Zhou, T.; Bruch, D.; Wang, Z.-G. Image charge effects under metal and dielectric boundary conditions. Phys. Rev. E 2024 , 110 , 044129..

Wang, Z.; Zhang, W.; Tan, Y.; Liu, Y.; Kong, L.; Kang, L.; Ran, F. Electrolyte-philic electrode material with a functional polymer brush. ACS Appl. Mater. Interfaces 2019 , 11 , 16087−16095..

Ávila-Niño, J. A.; Olvera, L. I. Ionic self-assembled organogel polyelectrolytes for energy storage applications. RSC Adv. 2020 , 10 , 11743−11749..

He, X.; Zhang, K.; Li, T.; Jiang, Y.; Yu, P.; Mao, L. Micrometer-scale ion current rectification at polyelectrolyte brush-modified micropipets. J. Am. Chem. Soc. 2017 , 139 , 1396−1399..

Stehle, P.; Langer, F.; Vrankovic, D.; Anjass, M. Thickness variation of conductive polymer coatings on si anodes for the improved cycling stability in full pouch cells. ACS Appl. Mater. Interfaces 2024 , 16 , 27202−27208..

Ye, F.; Yang, W.; Liao, X.; Dong, C.; Xu, L.; Mai, L. A micro battery supercapacitor hybrid device with ultrahigh cycle lifespan and power density enabled by bi-functional coating design. Adv. Funct. Mater. 2025 , 35 , 2413379..

Qin, J. Charge polarization near dielectric interfaces and the multiple-scattering formalism. Soft Matter 2019 , 15 , 2125−2134..

Becker, M.; Loche, P.; Rezaei, M.; Wolde-Kidan, A.; Uematsu, Y.; Netz, R. R.; Bonthuis, D. J. Multiscale modeling of aqueous electric double layers. Chem. Rev. 2024 , 124 , 1−26..

Bonthuis, D. J.; Gekle, S.; Netz, R. R. Dielectric profile of interfacial water and its effect on double-layer capacitance. Phys. Rev. Lett. 2011 , 107 , 166102..

Groß, A.; Sakong, S. Ab initio simulations of water/metal interfaces. Chem. Rev. 2022 , 122 , 10746−10776..

Curtis, R. A.; Lue, L. Depletion forces due to image charges near dielectric discontinuities. Curr. Opin. Colloid Interface Sci. 2015 , 20 , 19−23..

Liang, J.; Yuan, J.; Luijten, E.; Xu, Z. Harmonic surface mapping algorithm for molecular dynamics simulations of particle systems with planar dielectric interfaces. J. Chem. Phys. 2020 , 152 , 134109..

Frydel, D. Polarizable poisson–boltzmann equation: the study of polarizability effects on the structure of a double layer. J. Chem. Phys. 2011 , 134 , 234704..

Lesniewska, N.; Beaussart, A.; Duval, J. F. L. Electrostatic interactions between soft nanoparticles beyond the derjaguin approximation: effects of finite size of ions and charges, dielectric decrement and ion correlations. J. Colloid Interface Sci. 2025 , 678 , 808−827..

Nap, R.; Gong, P.; Szleifer, I. Weak polyelectrolytes tethered to surfaces: effect of geometry, acid–base equilibrium and electrical permittivity. J. Polym. Sci., Part B: Polym. Phys. 2006 , 44 , 2638−2662..

Jiang, T.; Wu, J. Ionic effects in collapse of polyelectrolyte brushes. J. Phys. Chem. B 2008 , 112 , 7713−7720..

Balzer, C.; Wang, Z.-G. Electroresponse of weak polyelectrolyte brushes. Eur. Phys. J. E 2023 , 46 , 82..

Zhao, S.; Zhang, P.; Lian, Z. A fast stimuli-responsive brush with regulated exposed–adsorbed transition of minority polyelectrolyte chains. Macromolecules 2025 , 58 , 8498−8510..

Duan, C.; Agrawal, N. R.; Wang, R. Electrostatic correlation augmented self-consistent field theory and its application to polyelectrolyte brushes. Phys. Rev. Lett. 2025 , 134 , 048101..

Netz, R. R.; Andelman, D. Neutral and charged polymers at interfaces. Phys. Rep. 2003 , 380 , 1−95..

Qiu, G.; Qiu, Q.; Qing, L.; Zhou, J.; Xu, X.; Zhao, S. Effects of polyelectrolyte surface coating on the energy storage performance in supercapacitors. J. Phys. Chem. C 2022 , 126 , 8218−8226..

Qing, L.; Jiang, J. Enabling high-capacitance supercapacitors by polyelectrolyte brushes. ACS Nano 2023 , 17 , 17122−17130..

Li, Z.; Wu, J. Density functional theory for planar electric double layers: closing the gap between simple and polyelectrolytes. J. Phys. Chem. B 2006 , 110 , 7473−7484..

Jiang, D.; Meng, D.; Wu, J. Density functional theory for differential capacitance of planar electric double layers in ionic liquids. Chem. Phys. Lett. 2011 , 504 , 153−158..

Feng, J.; Wang, Y.; Xu, Y.; Sun, Y.; Tang, Y.; Yan, X. Ion regulation of ionic liquid electrolytes for supercapacitors. Energy Environ. Sci. 2021 , 14 , 2859−2882..

Park, J.; Lee, J.; Kim, W. Water-in-salt electrolyte enables ultrafast supercapacitors for ac line filtering. ACS Energy Lett. 2021 , 6 , 769−777..

Zheng, Q.; Goodwin, Z. A. H.; Gopalakrishnan, V.; Hoane, A. G.; Han, M.; Zhang, R.; Hawthorne, N.; Batteas, J. D.; Gewirth, A. A.; Espinosa-Marzal, R. M. Water in the electrical double layer of ionic liquids on graphene. ACS Nano 2023 , 17 , 9347−9360..

Shin, S. J.; Kim, D. H.; Bae, G.; Ringe, S.; Choi, H.; Lim, H.-K.; Choi, C. H.; Kim, H. On the importance of the electric double layer structure in aqueous electrocatalysis. Nat. Commun. 2022 , 13 , 174..

Xu, X. F. Surface polarization effects on collapse transition of polyelectrolyte brushes. Chinese J. Polym. Sci. 2024 , 42 , 1313−1320..

Chen, M.; Xu, X. Structure of a grafted polyelectrolyte layer at the dielectric interface: coupling effects of dielectric contrast, ionic strength, and excluded volume. J. Phys. Chem. B 2025 , 129 , 4595−4604..

Wu, Q.; Xu, Y.; Yao, Z.; Liu, A.; Shi, G. Supercapacitors based on flexible graphene/polyaniline nanofiber composite films. ACS Nano 2010 , 4 , 1963−1970..

Zhao, Y.; Liu, J.; Hu, Y.; Cheng, H.; Hu, C.; Jiang, C.; Jiang, L.; Cao, A.; Qu, L. Highly compression-tolerant supercapacitor based on polypyrrole-mediated graphene foam electrodes. Adv. Mater. 2013 , 25 , 591−595..

[Wu Jianzhong. Variational methods in molecular modeling. Springer Singap . 2017 , 10.1007/978-981-11-2502–0 ..

Te Vrugt, M.; Löwen, H.; Wittkowski, R. Classical dynamical density functional theory: from fundamentals to applications. Adv. Phys. 2020 , 69 , 121−247..

Xu, X.; Ting, C. L.; Kusaka, I.; Wang, Z.-G. Nucleation in polymers and soft matter. Annu. Rev. Phys. Chem. 2014 , 65 , 449−475..

Wu, J. Understanding the electric double-layer structure, capacitance, and charging dynamics. Chem. Rev. 2022 , 122 , 10821−10859..

Xu, X.; Cao, D.; Wu, J. Density functional theory for predicting polymeric forces against surface fouling. Soft Matter 2010 , 6 , 4631..

Xu, X.; Cao, D. Density functional theory for adsorption of colloids on the polymer-tethered surfaces: effect of polymer chain architecture. J. Chem. Phys. 2009 , 130 , 164901..

Yu, Y.-X.; Wu, J. Structures of hard-sphere fluids from a modified fundamental-measure theory. J. Chem. Phys. 2002 , 117 , 10156−10164..

Rosenfeld, Y. Free-energy model for the inhomogeneous hard-sphere fluid mixture and density-functional theory of freezing. Phys. Rev. Lett. 1989 , 63 , 980−983..

Roth, R.; Evans, R.; Lang, A.; Kahl, G. Fundamental measure theory for hard-sphere mixtures revisited: the white bear version. J. Phys. Condens. Matter 2002 , 14 , 12063−12078..

Jiang, J.; Liu, H.; Hu, Y.; Prausnitz, J. M. A molecular-thermodynamic model for polyelectrolyte solutions. J. Chem. Phys. 1998 , 108 , 780−784..

Jiang, J. W.; Blum, L.; Bernard, O.; Prausnitz, J. M. Thermodynamic properties and phase equilibria of charged hard sphere chain model for polyelectrolyte solutions. Mol. Phys. 2001 , 99 , 1121−1128..

Yu, Y.-X.; Wu, J. Density functional theory for inhomogeneous mixtures of polymeric fluids. J. Chem. Phys. 2002 , 117 , 2368−2376..

Wertheim, M. S. Fluids with highly directional attractive forces. iii. multiple attraction sites. J. Stat. Phys. 1986 , 42 , 459−476..

Wertheim, M. S. Fluids with highly directional attractive forces. IV. Equilibrium polymerization. J. Stat. Phys. 1986 , 42 , 477−492..

Waisman, E.; Lebowitz, J. L. Mean spherical model integral equation for charged hard spheres. ii. results. J. Chem. Phys. 1972 , 56 , 3093−3099..

Blum, L. Mean spherical model for asymmetric electrolytes: I. Method of solution. Mol. Phys. 1975 , 30 , 1529−1535..

Blum, L.; Hoeye, J. S. Mean spherical model for asymmetric electrolytes. 2. Thermodynamic properties and the pair correlation function. J. Phys. Chem. 1977 , 81 , 1311−1316..

Jiang, J.; Gillespie, D. Revisiting the charged shell model: a density functional theory for electrolytes. J. Chem. Theory Comput. 2021 , 17 , 2409−2416..

Wu,J.; Jiang, T.; Jiang, D.; Jin, Z.; Henderson, D. A classical density functional theory for interfacial layering of ionic liquids. Soft Matter 2011 , 7 , 11222..

Xu, X.; Qiu, Q.; Lu, C.; Zhao, S. Responsive properties of grafted polyanion chains: effects of dispersion interaction and salt. J. Chem. Eng. Data 2020 , 65 , 5708−5717..

Wang, Z. G. Fluctuation in electrolyte solutions: the self energy. Phys. Rev. E 2010 , 81 , 021501..

Wang, R.; Wang, Z. G. Effects of image charges on double layer structure and forces. J. Chem. Phys. 2013 , 139 , 124702..

[Wang, R. Effects of self energy of the ions on the double layer structure and properties at the dielectric interface. California Ins titute of Techology. 2015 , Ph.D Thesis.

Netz, R. R. Polyelectrolytes in electric fields. J. Phys. Chem. B 2003 , 107 , 8208−8217..

Xu, X.; Tang, W.; Gao, Q.; Qiao, C.; Peng, Y.; Zhao, S. Explaining thermodynamic potential to undergraduates. J. Chem. Educ. 2024 , 101 , 4714−4721..

Stierle, R.; Sauer, E.; Eller, J.; Theiss, M.; Rehner, P.; Ackermann, P.; Gross, J. Guide to efficient solution of pc-saft classical density functional theory in various coordinate systems using fast fourier and similar transforms. Fluid Phase Equilibria 2020 , 504 , 112306..

[Petsev, D. N.; van Swol, F.; Frink, L. J. D. Molecular theory of electric double layers ; IOP Publishing, 2021 , 2053−2563..

[Griffiths, D. J. Introduction to electrodynamics , 3 rd Ed.; New Jersey: Prentice Hall, Inc., 1999 ; p. 90..

Podgornik, R. Self-consistent-field theory for confined polyelectrolyte chains. J. Phys. Chem. 1992 , 96 , 884−896..

Zhao, B.; Zhu, L. Nanoscale phase separation in mixed poly( tert -butyl acrylate)/polystyrene brushes on silica nanoparticles under equilibrium melt conditions. J. Am. Chem. Soc. 2006 , 128 , 4574−4575..

Zhou, F.; Hu, H.; Yu, B.; Osborne, V. L.; Huck, W. T. S.; Liu, W. Probing the responsive behavior of polyelectrolyte brushes using electrochemical impedance spectroscopy. Anal. Chem. 2007 , 79 , 176−182..

Rud, O.; Chertopalov, S.; Borisov, O. Charge storage mechanisms in redox-active polymer brushes. Macromolecules 2026 , 59 , 2489−2499..

Willott, J. D.; Murdoch, T. J.; Webber, G. B.; Wanless, E. J. Nature of the specific anion response of a hydrophobic weak polyelectrolyte brush revealed byAFM force measurements. Macromolecules 2016 , 49 , 2327−2338..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Atif-V2.0: Extending Classical Density Functional Theory with Interfacial Statistical Associating Fluid Theory for Inhomogeneous Associating Fluids

An Overview of Stretchable Supercapacitors Based on Carbon Nanotube and Graphene

Response of Bi-disperse Polyelectrolyte Brushes to External Electric Fields-A Numerical Self-consistent Field Theory Study

Capacitance Performances of Supramolecular Hydrogels Based on Conducting Polymers

The Effect of Polymerization of Ionic Liquid [C4Vim]Br on Phase Behavior and Partitioning of L-tryptophan: Experimental and Molecular Dynamics Study

Related Author

Jian Jiang

Qiu-Hui Chang

Jian Zhang

Shi-Chao Li

Xiu-Jun Wang

Zhi-Hao Cai

Yi Huang

Guang-Hao Li

Related Institution

CNOOC Research Institute Co., Ltd.

State Key Laboratory of Offshore Oil and Gas Exploitation

Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences

University of Chinese Academy of Sciences

National Institute for Advanced Materials, Tianjin Key Laboratory of Metal and Molecule Based Material Chemistry, Key Laboratory of Functional Polymer Materials, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Materials Science and Engineering, Nankai University

⁰