Electrochemistry, ion adsorption and dynamics in the double layer: a study of NaCl(aq) on graphite

@article{Finney2021ElectrochemistryIA,
  title={Electrochemistry, ion adsorption and dynamics in the double layer: a study of NaCl(aq) on graphite},
  author={Aaron R. Finney and Ian James McPherson and Patrick R. Unwin and Matteo Salvalaglio},
  journal={Chemical Science},
  year={2021},
  volume={12},
  pages={11166 - 11180}
}
Graphite and related sp2 carbons are ubiquitous electrode materials with particular promise for use in e.g., energy storage and desalination devices, but very little is known about the properties of the carbon–electrolyte double layer at technologically relevant concentrations. Here, the (electrified) graphite–NaCl(aq) interface was examined using constant chemical potential molecular dynamics (CμMD) simulations; this approach avoids ion depletion (due to surface adsorption) and maintains a… 
7 Citations

Figures from this paper

Do specific ion effects influence the physical chemistry of aqueous graphene-based supercapacitors? Perspectives from multiscale QMMD simulations
Whether or not specific ion effects determine the charge storage properties of aqueous graphene and graphite based supercapcitors remains a highly debated topic. In this work we present a multiscale
Do specific ion effects determine performance of aqueous graphene-based supercapacitors? Perspectives from multiscale QMMD simulations
Whether or not specific ion effects determine the charge storage properties of aqueous graphene and graphite based supercapcitors remains a highly debated topic. In this work we present a multiscale
Electrolyte-Gated Organic Field-Effect Transistors for Quantitative Monitoring of the Molecular Dynamics of Crystallization at the Solid–Liquid Interface
Quantitative measurements of molecular dynamics at the solid–liquid interface are of crucial importance in a wide range of fields, such as heterogeneous catalysis, energy storage, nanofluidics,
Multiple pathways in NaCl homogeneous crystal nucleation.
NaCl crystal nucleation from metastable solutions has long been considered to occur according to a single-step mechanism where the growth in the size and crystalline order of the emerging nuclei is

References

SHOWING 1-10 OF 115 REFERENCES
Demystifying the Stern layer at a metal-electrolyte interface: Local dielectric constant, specific ion adsorption, and partial charge transfer.
TLDR
This work investigates the charging behavior of an Ag (111) electrode in NaF aqueous solutions leveraging experimental results and theoretical calculations based on the classical density functional theory for ion distributions in the diffuse layer and on the jointdensity functional theory (JDFT) for the electronic structure.
Molecular dynamics simulations of the electric double layer capacitance of graphene electrodes in mono-valent aqueous electrolytes
Electrical double layer (EDL) capacitors based on recently emergent graphene materials have shown several folds performance improvement compared to conventional porous carbon materials, driving a
Specific ion effects at graphitic interfaces
TLDR
This work combines hybrid first-principles/continuum simulations with electrochemical measurements to investigate adsorption of several alkali-metal cations at the interface with graphene and within graphene slit-pores, and concludes that the measured interfacial capacitance trends result from a complex interplay between voltage, confinement, and specific ion effects-including ion hydration and charge transfer.
Ion Adsorption at the Graphene/Electrolyte Interface
The segregation of ions (Na+, OH–, H3O+, and Cl–) at the graphene/water interface, as well as at the graphene oxide/water interface, is investigated by classical molecular dynamics simulations
Charge storage at the nanoscale: understanding the trends from the molecular scale perspective
Supercapacitors or electrical double layer (EDL) capacitors store charge via rearrangement of ions in electrolytes and their adsorption on electrode surfaces. They are actively researched for
Double layer theory
  • W. Schmickler
  • Chemistry
    Journal of Solid State Electrochemistry
  • 2020
The double layer is the heart of electrochemistry: All electrochemical reactions occur in this region, and it determines one of the basic macroscopic relations of electrochemistry, that between the
Electronic Effects in the Electric Double Layer.
All electrochemical reactions take place at the interface between an electronic conductor, the electrode, and an ionic conductor, the electrolyte. Since the course of these reactions and their
Effective Polarization in Pairwise Potentials at the Graphene-Electrolyte Interface.
TLDR
A simple method to parametrize the ion-carbon interaction from density functional theory, implicitly modeling the solution using the conductor-like polarizable continuum model and can predict the ion adsorption trend so far only achievable using first-principles simulations.
Understanding the electrochemistry of “water-in-salt” electrolytes: basal plane highly ordered pyrolytic graphite as a model system†
TLDR
This work describes the electrochemical behavior of a simple 1 : 1 electrolyte based on highly concentrated aqueous solutions of potassium fluoride (KF), which was applied to symmetrical supercapacitors (using graphene and activated carbon as active materials) in order to quantify its performance in energy storage applications.
...
...