Electric double layers (EDLs) are ionic structures formed on charged surfaces and play an important role in various biological and industrial processes. An extensive study in the past decade has revealed the structure of the EDL in concentrated electrolyte solutions of both ordinary salts and ionic liquids. However, how the EDL structure affects their material properties remains a challenging topic due to technical difficulties of these measurements at nanoscale. In this work, we report the first detailed characterization of the viscoelasticity of the EDL formed over a wide range of ion concentrations, including concentrated electrolyte solutions. Specifically, we investigate the complex shear modulus of the EDL by measuring the resonant frequency and the energy dissipation of a quartz crystal microbalance (QCM), a surface-sensitive device, immersed in aqueous solutions containing three types of solutes: an ionic liquid, 1-butyl-3-methylimidazolium chloride (BmimCl); an ordinary salt, sodium chloride (NaCl); and a nonelectrolyte, ethylene glycol (EG). For the two electrolyte solutions, we observe a monotonic decrease in the resonant frequency and a monotonic increase in the energy dissipation with increasing ion concentrations due to the presence of the EDL. The complex shear modulus of the EDL is estimated through a wave propagation model in which the density and shear modulus of the EDL decay exponentially toward those of the bulk solution. Our results show that both the storage and the loss modulus of the EDL increase rapidly with increasing ion concentrations in the low ion concentration regime (<1 M) but reach saturation values with similar magnitude at a sufficiently high ion concentration. The shear viscosity of the EDL near the charged QCM surface is approximately 50 times for NaCl solutions and 500 times for BmimCl solutions of the bulk solution value at the saturation concentration. We also demonstrate that QCM can be utilized for analyzing the rheological properties of the EDL, thus providing a complementary, low-cost, and portable alternative to conventional laboratory instruments such as the surface force apparatus. Our results elucidate new perspectives on the viscoelastic properties of the EDL and can potentially guide device optimization for applications such as biosensing and fast charging of batteries.
Rheology of the Electric Double Layer in Electrolyte Solutions
Riccardo Funari
;
2020-01-01
Abstract
Electric double layers (EDLs) are ionic structures formed on charged surfaces and play an important role in various biological and industrial processes. An extensive study in the past decade has revealed the structure of the EDL in concentrated electrolyte solutions of both ordinary salts and ionic liquids. However, how the EDL structure affects their material properties remains a challenging topic due to technical difficulties of these measurements at nanoscale. In this work, we report the first detailed characterization of the viscoelasticity of the EDL formed over a wide range of ion concentrations, including concentrated electrolyte solutions. Specifically, we investigate the complex shear modulus of the EDL by measuring the resonant frequency and the energy dissipation of a quartz crystal microbalance (QCM), a surface-sensitive device, immersed in aqueous solutions containing three types of solutes: an ionic liquid, 1-butyl-3-methylimidazolium chloride (BmimCl); an ordinary salt, sodium chloride (NaCl); and a nonelectrolyte, ethylene glycol (EG). For the two electrolyte solutions, we observe a monotonic decrease in the resonant frequency and a monotonic increase in the energy dissipation with increasing ion concentrations due to the presence of the EDL. The complex shear modulus of the EDL is estimated through a wave propagation model in which the density and shear modulus of the EDL decay exponentially toward those of the bulk solution. Our results show that both the storage and the loss modulus of the EDL increase rapidly with increasing ion concentrations in the low ion concentration regime (<1 M) but reach saturation values with similar magnitude at a sufficiently high ion concentration. The shear viscosity of the EDL near the charged QCM surface is approximately 50 times for NaCl solutions and 500 times for BmimCl solutions of the bulk solution value at the saturation concentration. We also demonstrate that QCM can be utilized for analyzing the rheological properties of the EDL, thus providing a complementary, low-cost, and portable alternative to conventional laboratory instruments such as the surface force apparatus. Our results elucidate new perspectives on the viscoelastic properties of the EDL and can potentially guide device optimization for applications such as biosensing and fast charging of batteries.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
