Constant chemical potential–quantum mechanical–molecular dynamics simulations of the graphene–electrolyte double layer

Author:

Di Pasquale Nicodemo1ORCID,Finney Aaron R.2ORCID,Elliott Joshua D.34ORCID,Carbone Paola3ORCID,Salvalaglio Matteo2ORCID

Affiliation:

1. Department of Chemical Engineering, Brunel University London 1 , Uxbridge UB8 3PH, United Kingdom

2. Department of Chemical Engineering, University College London 2 , London WC1E 7JE, United Kingdom

3. Department of Chemical Engineering, University of Manchester 3 , Manchester M13 9PL, United Kingdom

4. Diamond Light Source, Harwell Science and Innovation Park 4 , Didcot, Oxfordshire OX11 8UQ, United Kingdom

Abstract

We present the coupling of two frameworks—the pseudo-open boundary simulation method known as constant potential molecular dynamics simulations (CμMD), combined with quantum mechanics/molecular dynamics (QMMD) calculations—to describe the properties of graphene electrodes in contact with electrolytes. The resulting CμQMMD model was then applied to three ionic solutions (LiCl, NaCl, and KCl in water) at bulk solution concentrations ranging from 0.5 M to 6 M in contact with a charged graphene electrode. The new approach we are describing here provides a simulation protocol to control the concentration of electrolyte solutions while including the effects of a fully polarizable electrode surface. Thanks to this coupling, we are able to accurately model both the electrode and solution side of the double layer and provide a thorough analysis of the properties of electrolytes at charged interfaces, such as the screening ability of the electrolyte and the electrostatic potential profile. We also report the calculation of the integral electrochemical double layer capacitance in the whole range of concentrations analyzed for each ionic species, while the quantum mechanical simulations provide access to the differential and integral quantum capacitance. We highlight how subtle features, such as the adsorption of potassium graphene or the tendency of the ions to form clusters contribute to the ability of graphene to store charge, and suggest implications for desalination.

Funder

European Research Council

Engineering and Physical Sciences Research Council

Publisher

AIP Publishing

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

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