Molecular understanding of the Helmholtz capacitance difference between Cu(100) and graphene electrodes

Unraveling the origin of Helmholtz capacitance is of paramount importance for understanding the interfacial structure and electrostatic potential distribution of electric double layers (EDL). In this work, we combined the methods of ab initio molecular dynamics and classical molecular dynamics and modeled electrified Cu(100)/electrolyte and graphene/electrolyte interfaces for comparison. It was proposed that the Helmholtz capacitance is composed of three parts connected in series: the usual solvent capacitance, water chemisorption induced capacitance, and Pauling repulsion caused gap capacitance. We found the Helmholtz capacitance of graphene is significantly lower than that of Cu(100), which was attributed to two intrinsic factors. One is that graphene has a wider gap layer at interface, and the other is that graphene is less active for water chemisorption. Finally, based on our findings, we provide suggestions for how to increase the EDL capacitance of graphene-based materials in future work, and we also suggest that the new understanding of the potential distribution across the Helmholtz layer may help explain some experimental phenomena of electrocatalysis.

Automated summary

Unraveling the origin of Helmholtz capacitance is crucial for understanding the interfacial structure and electrostatic potential distribution of electric double layers. In this study, electrified Cu(100)/electrolyte and graphene/electrolyte interfaces were modeled using ab initio molecular dynamics and classical molecular dynamics methods. It was proposed that the Helmholtz capacitance is composed of three parts connected in series: usual solvent capacitance, water chemisorption induced capacitance, and Pauling repulsion caused gap capacitance. The Helmholtz capacitance of graphene was found to be significantly lower than that of Cu(100), due to the wider gap layer and lower water chemisorption activity of graphene. Based on these findings, suggestions for increasing the EDL capacitance of graphene-based materials were provided, and the new understanding of potential distribution across the Helmholtz layer was suggested to explain some experimental phenomena of electrocatalysis.