2022/07/11 by Zachary A. H. Goodwin, Goodwin, Zachary A. H., Alexei A. Kornyshev +1
Chemical Engineering · Chemistry · Physics and Astronomy · #Electrochemical Analysis and Applications #FOS: Physical sciences #Ionic liquids properties and applications #Soft Condensed Matter (cond-mat.soft) #Spectroscopy and Quantum Chemical Studies #Statistical Mechanics (cond-mat.stat-mech)
paper · pdf · doi:10.48550/arxiv.2207.04753
openalex publication_date 2022/07/11 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01
Here we investigate a limiting case of the theory for aggregation and gelation in the electrical double layer (EDL) of ionic liquids (ILs). The limiting case investigated only accounts for ion pairs, ignoring the possibility of larger clusters and a percolating ionic network. This simplification, however, permits analytical solutions for the properties of the EDL. The resulting equations demonstrate the competition between the free energy of an association and the electrostatic potential in the EDL. For small electrostatic potentials and large negative free energies of associations, the ion pairs dominate in the EDL. Whereas, for electrostatic potential energies larger than the free energy of an association, electric-field-induced cracking of ion pairs occurs. The differential capacitance for this consistent ion pairing theory has a propensity to have a ``double hump camel'' shape. We compare this theory against previous free ion approaches, which do not consistently treat the reversible associations in the EDL.