Noncovalent Functionalization of Graphene Nanoplatelets and Their Applications in Supercapacitors.

We demonstrate a simple noncovalent functionalization technique, which involves graphite exfoliation and subsequent coating of the resulting graphene nanoplatelets (GNPs) with trimellitic anhydride (TMA), using a thermomechanical exfoliation process. TMA adsorbs on the surface of the GNPs, resulting in a reduction of the specific surface area to 312 ± 9 m2/g compared to 410 ± 12 m2/g for the unmodified GNPs. Detailed imaging, thermogravimetric, and X-ray diffraction analysis showed that the modified GNPs (TMA-GNPs) maintain similar structure to the unmodified GNPs. The presence of functional groups, confirmed by X-ray photoelectron spectroscopy analysis, caused an increase in the surface energy from 45.6 mJ/m2 for the GNPs to 57.9 mJ/m2 for TMA-GNPs. The resulting coated TMA-GNPs form stable dispersions in water while maintaining their inherent conductive properties, thus enabling applications, such as the manufacture of conductive films and supercapacitors. As a proof-of-concept, electrodes for supercapacitors are prepared from concentrated aqueous dispersions of the functionalized GNPs. Electrochemical characterization of the supercapacitors using electrochemical impedance spectroscopy, cyclic voltammetry and galvanostatic charge/discharge tests showed a specific capacitance of 22.2 F/cm3 at a scan rate of 1 mV/s from cyclic voltammetry and 17.3 F/cm3 at a current density of 1 A/g from galvanostatic charge/discharge tests, with a 90% capacitance retention after 10,000 cycles.

Charge and Electrical Double Layer Formation in a Nonpolar Solvent Using a Nonionic Surfactant.

In this work, we study the charge formation and the characteristics of the electrical double layer in a nonpolar medium using electrical impedance spectroscopy. To stabilize the free ionic species, a nonionic surfactant is added to the system. The conductivity and permittivity of the medium are obtained from high- to medium-frequency impedance data. Based on the correlation between (viscosity-adjusted) conductivity and surfactant concentration, we conclude that charge formation occurs due to a disproportionation mechanism. We accordingly estimate the concentration of the charge carriers in the sample and the Debye length of the diffuse double layer. The capacitance of the electrical double layer can be extracted from the low-frequency impedance data. We use this data to calculate the electrode distance of an equivalent parallel-plate capacitor. It is found that this distance is on the order of magnitude of Angstroms, indicating that the measured electrical double-layer capacitance is in fact the Stern layer capacitance.

Structure of the Electrical Double Layer Revisited: Electrode Capacitance in Aqueous Solutions.

The structure of the electrical double layer at the interface of planar electrodes and aqueous solutions is investigated. Electrical impedance spectroscopy is used to measure the impedance of aqueous solutions of sodium chloride and two different surfactants over a wide range of concentrations. The electrode capacitance is directly inferred from the admittance spectra as well as by regression of the impedance spectra to an equivalent circuit. It is found that the electrode capacitance remains on the same order of magnitude over the entire range of investigated concentrations. This is contradictive to the predictions of the Gouy-Chapman-Stern theory which predicts that, at low concentrations, the electrode capacitance should be determined by the diffuse layer. It is concluded that the Stern layer capacitance always dominates the electrode capacitance, even at very low concentrations, and the establishment of a diffuse layer capacitance requires an ionic strength of around 1 mM.

Dielectric relaxation spectroscopy of aqueous micellar electrolyte solutions: A novel application to infer Dukhin number and zeta potential of a micelle.

The complex permittivities of aqueous SDS solutions, with and without the addition of sodium chloride (NaCl), are measured in the frequency range from 200 MHz to 14 GHz. The SDS concentrations are chosen such that the SDS molecules aggregate to micelles. In this frequency range, the measured spectra allow for the identification of two different relaxation processes. That is, the relaxation of the water molecules at frequencies above 1 GHz and the micellar relaxation at frequencies lower than 1 GHz. It is found that the addition of NaCl to the system mostly affects the micellar relaxation process. In detail, the time constant as well as the amplitude of the relaxation decrease by adding NaCl. These effects are attributed to the change in the solution conductivity that changes the properties of the micelle's electrical double layer. We also extract the Dukhin number of the micelles as a function of surfactant and electrolyte content from the measurements. The Dukhin number is a dimensionless group that describes the influence of the surface conductivity on a phenomena. A regression between Dukhin numbers and free sodium ions is found so that all data collapses on a single curve independent of the surfactant concentration. The surface conductivity is a manifestation of the electrical double layer and we use the Bikerman equation to infer the zeta potential of the micelles. Comparison to literature data shows very good agreement and proves that dielectric relaxation spectroscopy can be engaged to infer the zeta potential of micelles. Abbreviations: CMC critical micelle concentration, DRS dielectric relaxation spectroscopy, EDL electrical double layer.

Optimized inkjet-printed silver nanoparticle films: theoretical and experimental investigations.

We study the influence of inkjet printing scheme and sintering parameter on the electrical resistivity of multi-layer silver nanoparticle films. A central composite Design Of Experiments (DOE) is employed to maximize experimental efficiency and improve the statistical significance of parameter estimates. The resulting mathematical correlations allow to interpret the influence of the print and sintering parameters. Detailed inspection of the correlations reveals the existence of local extrema and indicates that a structured approach such as the DOE would be significantly more effective for fabricating films with a minimum of resistivity. Furthermore, we modify the well-known Fuchs-Sondheimer Mayadas-Shatzkes model to correlate the resistivity of a multi-layer nanoparticle film with the sintering temperature and time. The modified model uses literature data but one constant inferred from two experiments. After model adjustment, the resistivities of films fabricated with different parameters can be predicted with good accuracy. This validation tremendously increases applicability and relevance of the model.

Zeta Potential of Poly(methyl methacrylate) (PMMA) in Contact with Aqueous Electrolyte-Surfactant Solutions.

The addition of surfactants can considerably impact the electrical characteristics of an interface, and the zeta potential measurement is the standard method for its characterization. In this article, a comprehensive study of the zeta potential of poly(methyl methacrylate) (PMMA) in contact with aqueous solutions containing an anionic, a cationic, or a zwitterionic surfactant at different pH and ionic strength values is conducted. Electrophoretic mobilities are inferred from electrophoretic light scattering measurements of the particulate PMMA. These values can be converted into zeta potentials using permittivity and viscosity measurements of the continuous phase. Different behaviors are observed for each surfactant type, which can be explained with the various adsorption mechanisms on PMMA. For the anionic surfactant, the absolute zeta potential value below the critical micelle concentration (CMC) increases with the concentration, while it becomes rather constant around the CMC. At concentrations above the CMC, the absolute zeta potential increases again. We propose that hydrophobic-based adsorption and, at higher concentrations, the competing micellization process drive this behavior. The addition of cationic surfactant results in an isoelectric point below the CMC where the negative surface charge is neutralized by a layer of adsorbed cationic surfactant. At concentrations near the CMC, the positive zeta potential is rather constant. In this case, we propose that electrostatic interactions combined with hydrophobic adsorption are responsible for the observed behavior. The zeta potential in the presence of zwitterionic surfactant is influenced by the adsorption, because of hydrophobic interactions between the surfactant tail and the PMMA surface. However, there is less influence, compared to the ionic surfactants. For all three surfactant types, the zeta potential changes to more-negative or less-positive values for alkaline pH values, because of hydroxide adsorption. An increase of the ionic strength decreases the absolute value of the zeta potential, because of the shielding effects.

Fabrication and Characterization of Thin Film Nickel Hydroxide Electrodes for Micropower Applications.

The utilization of micropower sources is attractive in portable microfluidic devices where only low-power densities and energy contents are required. In this work, we report on the microfabrication of patterned α-Ni(OH)2 films on glass substrates which can be used for rechargeable microbatteries as well as for microcapacitors. A multilayer deposition technique is developed based on e-beam evaporation, ultraviolet lithography, and electroplating/electrodeposition which creates thin-film electrodes that are patterned with arrays of micropillars. The morphology and the structure of the patterned electrode films are characterized by employing field emission scanning electron microscopy. The chemical (elemental) composition is investigated by using X-ray diffraction and X-ray photoelectron spectroscopy. Finally, cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge measurements are used to evaluate the electrochemical performance of the patterned thin film electrodes compared to patternless electrodes. We observe that patterning of the electrodes results in significantly improved stability and, thus, longer endurance while good electrochemical performance is maintained.

Streaming potential revisited: the influence of convection on the surface conductivity.

Electrokinetic phenomena play an important role in the electrical characterization of surfaces. In terms of planar or porous substrates, streaming potential and/or streaming current measurements can be used to determine the zeta potential of the substrates in contact with aqueous electrolytes. In this work, we perform electrical impedance spectroscopy measurements to infer the electrical resistance in a microchannel with the same conditions as for a streaming potential experiment. Novel correlations are derived to relate the streaming current and streaming potential to the Reynolds number of the channel flow. Our results not only quantify the influence of surface conductivity, and here especially the contribution of the stagnant layer, but also reveal that channel resistance and therefore zeta potential are influenced by the flow in the case of low ionic strengths. We conclude that convection can have a significant impact on the electrical double layer configuration which is reflected by changes in the surfaces conductivity.

The zeta potential of PMMA in contact with electrolytes of various conditions: theoretical and experimental investigation.

Many unit operations required in microfluidics can be realised by electrokinetic phenomena. Electrokinetic phenomena are related to the presence of electrical surface charges of microfluidic substrates in contact with a liquid. As surface charges cannot be directly measured, the zeta potential is considered as the relevant parameter instead. PMMA is an attractive microfluidic substrate since micron-sized features can be manufactured at low costs. However, the existence of PMMA surface charges is not well understood and the zeta potential data found in the literature show significant disagreement. In this article, we present a thorough investigation on the zeta potential of PMMA. We use computations of the potential distribution in the electrical double layer to predict the influence of various electrolyte parameters. The generated knowledge is compared to extensive experiments where we investigate the influence of ionic strength, pH, temperature and the nature of the electrolyte. Our findings imply that two different mechanisms influence the zeta potential depending on the pH value. We propose pure shielding in the acidic and neutral milieus while adsorption of co-ions occurs along with shielding in the alkaline milieu.

Optimization of an electrokinetic mixer for microfluidic applications.

This work is concerned with the investigation of the concentration fields in an electrokinetic micromixer and its optimization in order to achieve high mixing rates. The mixing concept is based on the combination of an alternating electrical excitation applied to a pressure-driven base flow in a meandering microchannel geometry. The electrical excitation induces a secondary electrokinetic velocity component, which results in a complex flow field within the meander bends. A mathematical model describing the physicochemical phenomena present within the micromixer is implemented in an in-house finite-element-method code. We first perform simulations comparable to experiments concerned with the investigation of the flow field in the bends. The comparison of the complex flow topology found in simulation and experiment reveals excellent agreement. Hence, the validated model and numerical schemes are employed for a numerical optimization of the micromixer performance. In detail, we optimize the secondary electrokinetic flow by finding the best electrical excitation parameters, i.e., frequency and amplitude, for a given waveform. Two optimized electrical excitations featuring a discrete and a continuous waveform are discussed with respect to characteristic time scales of our mixing problem. The results demonstrate that the micromixer is able to achieve high mixing degrees very rapidly.

Determination of the zeta potential of porous substrates by droplet deflection: II. Generation of electrokinetic flow in a nonpolar liquid.

Here we study the nature and extent of free electrical charges in nonpolar liquids, using a recently introduced technique of observing droplet deflection generated by electrokinetic flow in a porous substrate. In the presence of dispersed water, surfactant molecules agglomerate and inverted micelles are generated which may act as charge carriers. In the present work, the conductivities of solutions of a nonpolar liquid with several concentrations of a dissolved surfactant are measured by electrical transients. The induced current densities are proportional to the applied voltage, indicating that the solutions represent an ohmic system. The conductivity does not scale simply with the surfactant concentration, though. It is inferred that different micellization mechanisms exist depending on the surfactant concentration, and a model is sketched. Further experiments reveal that flows of such solutions can be generated within saturated porous substrates when they are subjected to moderate electric fields. An investigation of the phenomena leads to the conclusion that these flows exist due to the presence of an electrical double layer; that is, they are of electrokinetic (electroosmotic) origin. Hence, the measured electrokinetic flow rates can be related to the zeta potential of the porous substrate saturated with the solution. Plotting the zeta potential against the logarithm of the ionic strength reveals a linear relationship.

Determination of the zeta potential of porous substrates by droplet deflection. I. The influence of ionic strength and pH value of an aqueous electrolyte in contact with a borosilicate surface.

This paper presents a new method to determine the zeta potential of porous substrates in contact with a liquid. Electroosmosis, arising near the solid/liquid boundaries within a fully saturated porous substrate, pumps against the capillary pressure arising from the surface tension of a droplet placed in series with the pump. The method is based on measuring the liquid/gas interface deflection due to the imposed electric potential difference. The distinguishing features of our technique are accuracy, speed, and reliability, accomplished with a straightforward and cost-effective setup. In this particular setup, a bistable configuration of two opposing droplets is used. The energy barrier between the stable states defines the range of capillary resistance and can be tuned by the total droplet volume. The electroosmotic pump is placed between the droplets. The large surface area-to-volume ratio of the porous substrate enables the pumping strength to exceed the capillary resistance even for droplets small enough that their shapes are negligibly influenced by gravity. Using a relatively simple model for the flow within the porous substrate, the zeta potential resulting from the substrate-liquid combination is determined. Extensive measurements of a borosilicate substrate in contact with different aqueous electrolytes are made. The results of the measurements clarify the influence of the ionic strength and pH value on the zeta potential and yield an empirical relationship important to engineering approaches.

Model and verification of electrokinetic flow and transport in a micro-electrophoresis device.

We investigate the electrokinetic flow and transport within a micro-electrophoresis device. A mathematical model is set up, which allows to perform two-dimensional, time-dependent finite-element simulations. The model reflects the dominant features of the system, namely electroosmosis, electrophoresis, externally-applied electrical potentials, and equilibrium chemistry. For the solution of the model equations we rely on numerical simulations of the core region, while the immediate wall region is treated analytically at leading order. This avoids extreme refinements of the numerical grid within the EDL. An asymptotic matching of both solutions and subsequent superposition, nevertheless, provides an approximation for the solution in the entire domain. The results of the simulations are verified against experimental observation and show good agreement.