Measurement of hydroxide ion conductivity is paramount to understanding anion exchange membranes (AEM) operated under alkaline conditions, but the measurement is complicated by dissolved CO2 and the presence of bicarbonates and carbonates. A technique for accurate measurement has recently been reported that involves measuring the conductivity during water splitting, wherein hydroxide ions are assumed, but not proven, to be produced at the cathode and which purge out other anions. In this preliminary study, we visualize the formation of hydroxide ions and their diffusion from the cathode to anode. We do this by way of an anion exchange membrane cast with an acid/base pH indicator, such that visual confirmation of hydroxide production at the cathode is obtained during application of sustained current load. This proof of concept is demonstrated using the AEM, hexamethyl-p-terphenyl poly(methylbenzamidazolium), and pH indicator, thymolphthalein, included at 0.1 and 0.2 wt % concentration. An additional novelty of this work is that we perform conductivity measurements under potentiostatic load rather than galvanostatic load, which we find substantially increases (6x faster) the time required for the membrane to reach a steady state membrane conductivity.

The role of the ionomer in catalyst layers is critical to the performance of PEM fuel cells. Attention needs to be paid not only to the inherent properties of the ionomer but also to the choice of dispersing solvent and the catalyst support, as these also control the porosity and proton conductivity of the catalyst layer in conjunction with the ionomer. The ionomer also influences electrochemical FC kinetics through its influence on surface adsorption and gas permeability. Mass transport of oxygen in cathode catalyst layers (CCLs) is of particular importance in achieving high current densities in proton exchange membrane fuel cells. The technical push toward low platinum loading in CCLs has resulted in a disproportionate transport resistance attributed to oxygen transiting through thin ionomer films to reach active platinum sites. The replacement of PFSA ionomer in the catalyst layer with hydrocarbon ionomers is thus particularly challenging as this often decreases electrochemical fuel cell kinetics and mass transport. For these reasons, permeability phenomena of oxygen at the ionomer/platinum interface has gained renewed interest. Electrochemical techniques, such as potential step chronoamperometry at microelectrodes, will be shown to be a useful to probe oxygen diffusion and oxygen solubility at catalyst/membrane interface. Data obtained under different conditions and with different ionomers is useful for understanding oxygen transport resistance through ionomer films in the context of low platinum loaded cathode catalyst layers

Mass transport of oxygen through an ionomer contained within the cathode catalyst layer in an anion exchange membrane fuel cell is critical for a functioning fuel cell, yet is relatively unexplored. Moreover, because water is a reactant in the oxygen reduction reaction (ORR) in alkaline media, an adequate supply of water is required. In this work, ORR mass transport behavior is reported for methylated hexamethyl-p-terphenyl polymethylbenzimidazoles (HMT-PMBI), charge balanced by hydroxide ions (IEC from 2.1 to 2.5 mequiv/g), and commercial Fumatec FAA-3 membranes. Electrochemical mass transport parameters are determined by potential step chronoamperometry using a Pt microdisk solid-state electrochemical cell, in air at 60 °C, with relative humidity controlled between 70% and 98%. The oxygen diffusion coefficient (DbO2), oxygen concentration (cbO2), and oxygen permeability (DbO2·cbO2) were obtained by nonlinear curve fitting of the current transients using the Shoup-Szabo equation. Mass transport parameters are correlated to water content of the ionomer membrane. It is found that the oxygen diffusion coefficients decreased by 2 orders of magnitude upon reducing the water content of the ionomer membrane by lowering the relative humidity. The limitation of the Shoup-Szabo equation for extracting ORR mass transport parameters using thin ionomer films was evaluated by numerical modeling of the current transients, which revealed that a significant discrepancy (up to 29% under present conditions) was evident for highly hydrated membranes for which the oxygen diffusion coefficient was largest, and in which the oxygen depletion region reached the ionomer/gas interface during the chronoamperometric analysis.

Chronoamperometric analysis of the oxygen reduction reaction (ORR) at Pt microelectrode vertical bar perfluorosulfonic acid (PFSA) ionomer interfaces in a solid state electrochemical cell reveals an increase in both the oxygen diffusion coefficient (D-b) and oxygen permeability (D(b)c(b)) upon consecutive potential step measurements. From a vapor-equilibrated, electrochemically unperturbed state under conditions of 70% RH and 50 degrees C, D-b and D(b)c(b) increased by factors of 2 and 1.5, respectively. D-b and D(b)c(b) return to their initial values after resting the electrode at the open circuit potential. The electrochemical generation of water is believed responsible for the time-dependent mass transport parameters of ORR. (C) The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. All rights reserved.

Oxygen mass transport resistance through the ionomer component in the cathode catalyst layer is considered to contribute overpotential losses in polymer electrolyte membrane fuel cells. Whereas it is known that water uptake, water transport, and proton conductivity are reduced upon reducing relative humidity, the effect on oxygen mass transport remains unknown. We report a two-electrode approach to determine mass transport coefficients for the oxygen reduction reaction in air at the Pt/perfluorosulfonic acid ionomer membrane interface between 90 and 30% RH at 70 °C using a Pt microdisk in a solid state electrochemical cell. Potential-step chronoamperometry was performed at specific mass-transport limiting potentials to allow for the elucidation of the oxygen diffusion coefficient (D(bO2)) and oxygen concentration (c(bO2)). In our efforts, novel approaches in data acquisition, as well as analysis, were examined because of the dynamic nature of the membrane under lowered hydration conditions. Linear regression analysis reveals a decrease in oxygen permeability (D(bO2c(bO2)) by a factor of 1.7 and 3.4 from 90 to 30% RH for Nafion 211 membrane and membranes cast from Nafion DE2020 ionomer solutions, respectively. Additionally, nonlinear curve fitting by way of the Shoup-Szabo equation is employed to analyze the entire current transient during potential step controlled ORR. We also report on the presence of an RH dependence of our previously reported time-dependency measurements for O2 mass transport coefficients.

Solid state electrochemical techniques have provided insight into the effect of relative humidity on oxygen mass transport properties in Nafion® 117. Specifically, subsequent potential step coulometric measurements taken over a period of time have shown that the act of measurement affects the catalyst-membrane interface. It is postulated that the formation of product water at the interface leads to interactions with the Nafion® 117 surface and results in local domain changes. This effect has been shown to be reversible provided there is adequate rest time between measurements to allow for water diffusion from the interface.

Artificial muscles powered by a renewable energy source are desired for joint articulation in bio-inspired autonomous systems. In this study, a robotic underwater vehicle, inspired by jellyfish, was designed to be actuated by a chemical fuel source. The fuel-powered muscles presented in this work comprise nano-platinum catalyst-coated multi-wall carbon nanotube (MWCNT) sheets, wrapped on the surface of nickel–titanium (NiTi) shape memory alloy (SMA). As a mixture of oxygen and hydrogen gases makes contact with the platinum, the resulting exothermic reaction activates the nickel–titanium (NiTi)-based SMA. The MWCNT sheets serve as a support for the platinum particles and enhance the heat transfer due to the high thermal conductivity between the composite and the SMA. A hydrogen and oxygen fuel source could potentially provide higher power density than electrical sources. Several vehicle designs were considered and a peripheral SMA configuration under the robotic bell was chosen as the best arrangement. Constitutive equations combined with thermodynamic modeling were developed to understand the influence of system parameters that affect the overall actuation behavior of the fuel-powered SMA. The model is based on the changes in entropy of the hydrogen and oxygen fuel on the composite actuator within a channel. The specific heat capacity is the dominant factor controlling the width of the strain for various pulse widths of fuel delivery. Both theoretical and experimental strains for different diameter (100 and 150 µm) SMA/MWCNT/Pt fuel-powered muscles with dead weight attached at the end exhibited the highest magnitude under 450 ms of fuel delivery within 1.6 mm diameter conduit size. Fuel-powered bell deformation of 13.5% was found to be comparable to that of electrically powered (29%) and natural jellyfish (42%).

We report preparation and characterization of novel nanocomposite electrodes consisting of single-walled carbon nanotubes (SWNT) and polypyrrole (PPy) for electrochemical supercapacitors. The electrodes in the form of papers and fibers were prepared by i) vacuum filtration of SWNT/PPy methanol dispersion and ii) wet-spinning of SWNT/PPy aqueous dispersion, respectively. Electrochemical properties of prepared nanocomposites were investigated using cyclic voltammetry method in aqueous NaCl and NaPF6 electrolytes. The capacitance of the SWNT/PPy nanocomposite papers was about 5 times higher than that of pristine SWNT paper. The capacitance of SWNT/PPy fibers reached record 200 F/g values. Prospective applications of prepared materials range from supercapacitors to electrodes for batteries and electromechanical actuators.

Nanocomposite electrodes for supercapacitors in the form of sheets and fibers were prepared by i) vacuum filtration of SWNT-PPy methanol dispersion and ii) wet-spinning of SWNT-PPy aqueous dispersion, respectively. Electrochemical properties of prepared materials were investigated using cyclic voltammetry method in aqueous 1M NaCl and NaPF(6) electrolytes. The capacitance of the SWNT-PPy sheet was about 5 times higher than that of pristine SWNT paper. The capacitance of SWNT-PPy fibers reached record 200 F/g value. Prospective applications of prepared materials range from supercapacitors to electrodes for batteries and electromechanical actuators.

Electrical and magnetotransport properties of single walled carbon nanotube (SWCNT) fibers are reported. The dependencies of resistance on temperature can be approximated by the Mott law for three-dimensional variable range hopping (VRH) below 80 K and by typical law for fluctuation induced tunneling model within the range of 80–300 K. Both negative and positive magnetoresistances (MRs) were observed. At low fields, MR is negative. Positive upturn was observed on the MR curves, which shifted to the high field’s values with temperature increase. The upturn field of the MR effect was shifted from 1.5 T at 2 K to a value of about 20 T at 40 K. The value of positive MR varies as exp(B2), which changes to B1/3 at sufficiently high fields as expected for the VRH transport. The model of VRH transport is illustrated by the influence of strong microwave field and terahertz radiation induced photocurrent manifestation at low temperatures.