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submitted by: M. Shirkhanzadeh Department of Mechanical and Materials Engineering, Queens University, Kingston, Ontario, K7L 3N6, Canada; shirkhan@queensu.ca checked by: James H. Maynard Department of Chemistry, University of WisconsinMadison, Madison, WI 53706
Many efforts are currently underway to develop and optimize novel forms of fuel cells. Among these, micro-fuel cells are believed to be particularly promising candidates for replacing solid-state batteries owing to their potential to offer greater energy densities (13). Because of the inherently low risk involved in handling small volume of fluids in micro-fuel cells, these devices can also be employed as safe teaching tools for demonstrating the operation of fuel cells. Hydrogen is the most common fuel for use with such systems because of its superior electrochemical reactivity and energy density, but its storage and safe handling are troublesome. For teaching and demonstrations in a classroom, it would be safer to use unitized regenerative fuel cells where hydrogen fuel is produced in situ by electrolysis. This would eliminate the need for an external source of hydrogen and the delivery system for supplying the fuel to electrodes. A simplified unitized regenerative fuel cell has been described for teaching and demonstration (4). The fuel cell is constructed by placing a pair of platinum wires in a beaker containing a dilute salt solution. The cell is charged by connecting the electrodes to a dc power source for a short time to generate hydrogen and chlorine gas bubbles at the cathode and anode, respectively. In the fuel cell mode, the cell utilizes the gas bubbles adhered to the electrodes to generate electricity. However, in practice, the cell voltage drops rapidly after the power source is disconnected owing to the departure of gas bubbles from the electrode surface and the onset of convective mixing associated with the gas evolution. As a result, sufficient power cannot be generated to drive a portable device for demonstration purposes. One way of increasing the output power of this cell is to use platinum electrodes with a large surface area to increase
the overall number of gas bubbles that can be adhered to the electrodes (4). This approach, however, can be prohibitively expensive due to the high cost of platinum metal. This article describes the design and construction of a thin-layer fuel cell that operates using ~40 L of electrolyte. The cell performs both as an electrolyzer and as a fuel cell. As an electrolyzer, an external power source such as a regulated dc power supply or a photovoltaic array is used to drive electrolysis to generate hydrogen and chlorine gas bubbles at the cathode and anode, respectively. As a fuel cell, the cell uses the stored hydrogen and chlorine to generate electricity. The cell design exploits the phenomenon of gas bubble coalescence to suppress the occurrence of bubble-induced turbulence mixing in the system. This minimizes the level of fuel crossover and cell depolarization and thus sufficient power can be generated to drive a small electronic calculator or a light-emitting diode (LED). The system is simple, safe, and easy to set up, and it is particularly useful for teaching and demonstration in a classroom setting. Materials and Methods A schematic illustration of the thin-layer fuel cell is shown in Figure 1 and a photograph of this cell is shown in Figure 4A. A list of materials for constructing and operating the fuel cell is available in the online material. The cell used in this work consisted of a pair of parallel platinum wire electrodes 28 mm apart and sandwiched between two closely spaced planar slides. The diameter of the platinum wires (127 m) defined the space between the planar slides. Electrical contact to the electrodes was provided using nickel-coated conductive terminals that
plastic base conductive terminal anchor post polystyrene cover Pt electrode glass or mirror Pt electrode glass or mirror
Figure 1. (left) Schematic design of the thin-layer regenerative fuel cell. (right) Schematic of the setup employed for measuring the anode and cathode potentials using an external Ag/AgCl reference electrode.
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were firmly secured to a rectangular plastic base as shown in Figure 1. In one configuration, the base was constructed with an optically transparent material such as plexiglass. A round glass cover slip (~25 mm diameter) together with an optically transparent polystyrene slide (2560 mm, 0.9mm thick) were used as the bottom and top slides, respectively. This standard configuration allowed the image of the cell to be displayed on a large screen using a conventional overhead projector. In another configuration of the cell, a round flat glass mirror (25 mm diameter) was used as the bottom slide instead of the round glass cover slip. This allowed the experimenter to clearly observe the growth and coalescence of gas bubbles during the course of electrolysis without visual aids. For demonstration in a large classroom, the cell can be used with a document camera. In the experiments, the cell was used with a round glass mirror as the bottom slide as shown in Figure 4A. In a typical run, ~40 L of the electrolyte (~1.9 g table salt dissolved in 100mL water) was first placed on the glass mirror between the pair of platinum electrodes using a micropipet. The polystyrene slide was then rested on the wire electrodes as shown in Figure 1. This resulted in the formation of a uniform thin layer of electrolyte (~127 m thick) sandwiched between the glass mirror and the polystyrene slide. The cell was then run as an electrolyzer to generate hydrogen and chlorine gas bubbles at the cathode and anode, respectively. A regulated dc power supply was used to consistently generate a constant voltage (9 V) to drive the cell as an electrolyzer for 35 s. Shortly after electrolysis was completed, the external power supply was disconnected and the performance of the cell in fuel cell mode was evaluated. The open circuit potential (OCP) generated by the fuel cell was recorded with time using a high impedance voltmeter. In addition, the individual anode and cathode potentials were measured against an external AgAgCl reference electrode. A schematic diagram of the setup employed for measuring the anode and cathode potentials using the external reference electrode is shown in Figure 1. For these measurements, contact between the external reference electrode and the electrolyte in the cell was established by cutting a small hole (~20 m diameter) in the center of the polystyrene slide. The hole can be cut using a needle with a sharp tip. A small drop (~25 L) of the salt solution was placed over the hole to facilitate ionic communication between the external reference electrode and the electrolyte inside the cell. The hydrophobic nature of the polystyrene surface together with the small size of the hole allowed the droplet to remain undisturbed on the surface of the polystyrene slide for more than 2 h. This permitted stable potential measurements to be made with the external AgAgCl reference electrode. A series of representative polarization curves were also recorded by taking the current and voltage readings of the system in fuel cell mode. The current densities were calculated with respect to the geometrical surface area of the electrode (0.096cm2) in contact with the electrolyte. Furthermore, the use of the external AgAgCl reference electrode during these tests allowed for separate analysis and evaluation of individual electrode performance characteristics. Characterization of the Cell as an Electrolyzer In unbuffered sodium chloride solutions, electrolysis favors the evolution of chlorine gas rather than oxygen (5). Chlorine evolution causes the solution adjacent to the anode to become
acidic through partial hydrolysis and conversion to ClO and H+ (6) as follows: Cl2 H2O HClO Cl H (1) (2) HClO ClO H Thermodynamically, oxidation of water molecules, which can lead to evolution of oxygen at the anode, is also possible since the equilibrium formation potential for oxygen is lower than that for chlorine (7). Oxidation of water molecules can cause solution close to the anode to become acidic through formation of hydrogen ions according to the following reaction: 2H2O O2 4H 4e (3) However, the kinetics of the oxygen evolution reaction is known to be slow owing to its well-known high overpotential (6). Thus, similar to the industrial production of chlorine by the electrolysis of chloride solutions (7), the chlorine formed at the anode is practically free from oxygen. Concomitant with the anodic reactions, the reduction of H+ is expected to lead to an increasing alkalinity in the vicinity of the cathode. To confirm the local pH changes during electrolysis, pH sensitive strips were attached to the upper surface of the glass mirror under the platinum electrodes. Visible and distinctive red and blue bands indicative of strong acidic and alkaline pH were clearly observed close to the anode and cathode, respectively. Visual observation of gas evolution during electrolysis revealed that the hydrogen and chlorine gas bubbles generated at the cathode and anode, respectively, tended to undergo rapid coalescence because of the surface tension forces in the narrow gap between the glass mirror and the polystyrene slide. Continual dynamic interactions between gas bubbles during electrolysis resulted in the formation of large and flat gas bubbles of hydrogen and chlorine that remained immobilized in close vicinity to the cathode and anode, respectively. This resulted in progressive increase in cell resistance and decline of the current from 10mA at the start of electrolysis to ~ 5 mA after 35 s. The overall process of bubble coalescence comprises three distinct phases: (i) establishment of close contact between two (or more) bubbles, (ii) the thinning of the interface film formed between bubbles and its subsequent rupture, and (iii) establishment of the interface for the newly formed bubble (8). The rapid coalescence and immobilization of gas bubbles resulted in the effective suppression of the bubble-induced turbulence and convective mixing that are normally observed in gas-evolving electrochemical systems (9). Because of the suppressed convective mixing, the pH gradients that were established close to electrodes persisted more than 1 h after electrolysis was terminated. The progression of the pH gradient toward the midpoint between the two electrodes was extremely slow. Without the polystyrene cover, pH gradients could not be stabilized close to electrodes owing to the vigorous convective mixing in the electrolyte caused by the gas bubbles. Some experiments were also performed using a clean glass slide as the cover slide instead of the polystyrene slide. Extensive coalescence close to the electrodes could be observed during electrolysis but gas bubbles could not be immobilized as effectively as when the polystyrene slide with a hydrophobic surface was used. This observation is attributed to the fact that the clean glass surface is hydrophilic and allows complete wetting and a zero contact angle and, therefore, surface tension forces
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do not effectively hinder bubble movement. Similar behavior of electrogenerated gas bubbles on hydrophilic surfaces has also been observed in the case of narrow gap cells used for chlorine production (10). Characterization of the Cell in Fuel Cell Mode The OCP values of the thin-layer cell operating in fuel cell mode shortly after electrolysis was stopped are shown in Figure 2A. The cell generates relatively high OCP values exceeding 1.5V during the entire period of the test. These results confirm that the cell can effectively suppress fuel crossover in the absence of an anodecathode separator. The cell design therefore eliminates the need for a physical barrier such as a proton exchange membrane that is commonly used for separating fuels in the anodic and cathodic compartments. It should be noted, however, that to effectively suppress the convective mixing in the cell, the cover slide should remain resting on the platinum wires. It is therefore important to place the cell on a stable platform during the tests and avoid excessive mechanical vibrations that might disturb the cover slide. Previous work on fuel cells that do not require a membrane has exploited the laminar flow that occurs in liquids flowing at a low Reynolds number to eliminate convective mixing in fuel cells (13). The individual OCPs for the cathode and anode of the cell operating in fuel cell mode are shown in Figure 2B. The electrode potentials were recorded using the external AgAgCl reference electrode shortly after electrolysis was stopped. The data show that during the test, the cathode potential remained stable and close to the standard electrode potential for the Cl2Cl (7) redox in acidic solutions. Cl2(aq) 2e 2Cl (aq) E = 1.39 V (vs SHE) (4)
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