Electrical double layer formation on glassy carbon in aqueous solution

Davey, Sofia B.; Cameron, Amanda P.; Latham, Kenneth G.; Donne, Scott W.

doi:10.1016/j.electacta.2021.138416

Cited by 12 publications

(12 citation statements)

References 29 publications

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“…As we have reported previously, [22][23][24][28][29][30][31] each individual i-t transient can be deconvoluted into contributions from various charge storage processes based on their response to the imposition of a potential step. Specifically, we have identified capacitive, diffusional, and residual processes as contributing to the overall i-t transient.…”

Section: Resultsmentioning

confidence: 81%

“…Recent outcomes from our own laboratory [22][23][24] have focused on a planar non-porous glassy carbon electrode (GCE) in an aqueous electrolyte to examine charge storage at the electrified interface. The GCE was chosen because complications associated with porosity have been removed, while aqueous electrolytes were chosen because of the known polarity of solvent water, and its solvation towards inorganic salts.…”

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confidence: 99%

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Capacitive Charge Storage at the Glassy Carbon Electrode: Comparison Between Aqueous and Non-Aqueous Electrolytes

Cameron

Davey

Latham

et al. 2021

J. Electrochem. Soc.

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Herein the charge storage capabilities of a planar non-porous glassy carbon electrode (GCE) in electrolytes of aqueous 0.5 M Na2SO4 and 1 M tetraethylammonium tetrafluoroborate (TEABF4) in acetonitrile are compared using a combination of cyclic voltammetry (CV), step potential electrochemical spectroscopy (SPECS) and electrochemical impedance spectroscopy (EIS). In all techniques the resultant capacitance was substantially higher for the GCE in 1 M TEABF4 compared to 0.5 M Na2SO4, with the differences due to solvation of the adsorbing electrolyte ions. Adsorbing Na+ cations in the aqueous system have a substantial solvation sheath that increases the resistance associated with capacitive charge storage, decreases the capacitance, as well as inhibits the packing of similar electrolyte ions in the vicinity of the GCE. Conversely, the adsorbing BF4− ions in the acetonitrile-based electrolyte exhibit a low resistance to charge storage, a greatly enhanced capacitance, as well as exhibit an improved ability to pack at the electrode-electrolyte interface. The impact of this behaviour on electrode performance has also been discussed.

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Section: Resultsmentioning

confidence: 81%

mentioning

confidence: 99%

Capacitive Charge Storage at the Glassy Carbon Electrode: Comparison Between Aqueous and Non-Aqueous Electrolytes

Cameron

Davey

Latham

et al. 2021

J. Electrochem. Soc.

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“…These results support previous work indicating a thick electrolyte charge storage layer (∼500 μm). [35][36][37][38] The cathodic capacitance is shown in Fig. 1c, together with the anodic-to-cathodic capacitance ratio (efficiency).…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we have used advanced techniques to probe the electrified interface between planar non-porous glassy carbon and common aqueous and non-aqueous electrolytes [35][36][37][38] to show that mass transport of ions to the interface boosted charge storage, and that the diffuse layer was quite thick (∼500 μm). To provide additional supporting data, we report here on the use of a glassy carbon rotating disk electrode (RDE) to examine interfacial capacitance.…”

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confidence: 99%

Communication—Demonstrating the Role of Mass Transport in Double Layer Formation

Cameron¹,

Davey²,

Callahan³

et al. 2022

J. Electrochem. Soc.

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Herein we present insight into the structure and behaviour of the electrified interface formed between a planar non-porous glassy carbon electrode and an aqueous solution of 0.5 M Na2SO4. Specifically, a glassy carbon rotating disk electrode was used to show correspondence between a decreasing rotation rates, and hence a decreasing boundary layer thickness, with a decreasing interfacial capacitance. The implication is that electrolyte counter charge is being dissipated by convective flow outside of the boundary layer. With the boundary layer thickness being macroscopic, it is clear that electrolyte counter-charge extends a substantial distance into the electrolyte.

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“…In fact, the limitation of the narrow electrochemical window can be overcome in highly concentrated aqueous electrolytes, also known as water-in-salt (WiS) electrolytes [ 8 , 9 , 10 , 11 , 12 , 13 ], which have been shown to significantly widen the electrochemical stability window to over 3.0 V, via interface modification [ 14 , 15 ], or the development of chemically stable, high surface area carbon structures [ 16 , 17 , 18 ]. As a result, aqueous electrolytes are still popular in the study of EDLCs [ 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 ].…”

Section: Introductionmentioning

confidence: 99%

Capacitive Behavior of Aqueous Electrical Double Layer Based on Dipole Dimer Water Model

2022

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The aim of the present paper is to investigate the possibility of using the dipole dimer as water model in describing the electrical double layer capacitor capacitance behaviors. Several points are confirmed. First, the use of the dipole dimer water model enables several experimental phenomena of aqueous electrical double layer capacitance to be achievable: suppress the differential capacitance values gravely overestimated by the hard sphere water model and continuum medium water model, respectively; reproduce the negative correlation effect between the differential capacitance and temperature, insensitivity of the differential capacitance to bulk electrolyte concentration, and camel–shaped capacitance–voltage curves; and more quantitatively describe the camel peak position of the capacitance–voltage curve and its dependence on the counter-ion size. Second, we fully illustrate that the electric dipole plays an irreplaceable role in reproducing the above experimentally confirmed capacitance behaviors and the previous hard sphere water model without considering the electric dipole is simply not competent. The novelty of the paper is that it shows the potential of the dipole dimer water model in helping reproduce experimentally verified aqueous electric double layer capacitance behaviors. One can expect to realize this potential by properly selecting parameters such as the dimer site size, neutral interaction, residual dielectric constant, etc.

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Electrical double layer formation on glassy carbon in aqueous solution

Cited by 12 publications

References 29 publications

Capacitive Charge Storage at the Glassy Carbon Electrode: Comparison Between Aqueous and Non-Aqueous Electrolytes

Capacitive Charge Storage at the Glassy Carbon Electrode: Comparison Between Aqueous and Non-Aqueous Electrolytes

Communication—Demonstrating the Role of Mass Transport in Double Layer Formation

Capacitive Behavior of Aqueous Electrical Double Layer Based on Dipole Dimer Water Model

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