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Nanoporous carbons play an important role in different electrochemical applications such as being utilized as electrodes in supercapacitors. Application of electric potential to a porous electrode in electrolyte solution stimulates adsorption or desorption of ions on the electrode surface. Electrosorption causes appearance of solvation pressure in the pores and results in electrode deformation. In this work, using molecular dynamics simulations and the continuum theory based on the modified Poisson-Boltzmann equation, we studied the structure of the electrical double layer in slit graphitic micropores filled with a NaCl aqueous solution, and solvation pressure in these pores. We focused on the behavior of the solvation pressure as a function of pore width and surface charge density. Within molecular dynamics simulations, two different water models were used -- an explicit model based on SPC/E water molecules and an implicit model, i.e., structureless background with fixed dielectric permittivity. The latter allows us to relate molecular dynamics simulations to the continuum theory. Simulations with explicit water show a qualitatively different behavior of the solvation pressure in the 1 and 2 nm pores as a function of the surface charge density. We demonstrated that the value of the solvation pressure is defined by a delicate balance between Van der Waals and electrostatic contributions. We demonstrated that the theory predicts the dependence of the solvation pressure on the pore width, which matches the results of simulations using the implicit water model. Finally, we adapted the continuum theory, developed for adsorption-induced deformation to estimate the deformation of a carbon electrode due to electrosorption. Our results can be used in the further development of nanoporous actuators working based on electrosorption-induced deformation.
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A network model to predict ionic transport in porous materials
Understanding the dynamics of electric-double-layer (EDL) charging in porous media is essential for advancements in next-generation energy storage devices. Due to the high computational demands of direct numerical simulations and a lack of interfacial boundary conditions for reduced-order models, the current understanding of EDL charging is limited to simple geometries. Here, we present a network model to predict EDL charging in arbitrary networks of long pores in the Debye–Hückel limit without restrictions on EDL thickness and pore radii. We demonstrate that electrolyte transport is described by Kirchhoff’s laws in terms of the electrochemical potential of charge (the valence-weighted average of the ion electrochemical potentials) instead of the electric potential. By employing the equivalent circuit representation suggested by these modified Kirchhoff’s laws, our methodology accurately captures the spatial and temporal dependencies of charge density and electric potential, matching results obtained from computationally intensive direct numerical simulations. Our network model provides results up to six orders of magnitude faster, enabling the efficient simulation of a triangular lattice of five thousand pores in 6 min. We employ the framework to study the impact of pore connectivity and polydispersity on electrode charging dynamics for pore networks and discuss how these factors affect the time scale, energy density, and power density of capacitive charging. The scalability and versatility of our methodology make it a rational tool for designing 3D-printed electrodes and for interpreting geometric effects on electrode impedance spectroscopy measurements.
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- Award ID(s):
- 2238412
- PAR ID:
- 10566438
- Publisher / Repository:
- United States National Academy of Sciences
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 121
- Issue:
- 22
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.2401656121
