Study on the processes of start-up and shutdown in proton exchange membrane fuel cells

Several different start-up and shutdown processes of a fuel cell were investigated in this paper by measuring cathode, anode and membrane potentials respectively versus reference hydrogen electrode (RHE). The membrane potential was measured by using thin copper wire sandwiched between two membranes. During the formation of hydrogen/air boundary at the anode caused by unprotected start-up and shutdown, the in-plane potential difference between membrane inlet and outlet was measured to be as high as 0.8 V, and the interfacial potential difference between cathode and membrane outlet increased to about 1.6 V, which in turn would cause carbon corrosion. Appropriate start-up and shutdown processes were suggested to avoid the formation of hydrogen/air boundary.     

Modeling hydrogen starvation conditions in proton-exchange membrane fuel cells

In this study, a steady state and isothermal 2D-PEM fuel cell model is presented. By simulation of a single cell along the channel and in through-plane direction, its behaviour under hydrogen starvation due to nitrogen dilution is analysed. Under these conditions, carbon corrosion and water electrolysis are observed on the cathode side. This phenomenon, causing severe cell degradation, is known as reverse current decay mechanism in literature. Butler-Volmer equations are used to model the electrochemical reactions. In addition, we account for permeation of gases through the membrane and for the local water content within the membrane. The results show that the membrane potential locally drops in areas starved from hydrogen. This leads to potential gradients >1.2 V between electrode and membrane on the cathode side resulting in significant carbon corrosion and electrolysis reaction rates. The model enables the analysis of sub-stoichiometric states occurring during anode gas recirculation or load transients.     

The effect of internal air bleed on CO poisoning in a proton exchange membrane fuel cell

It is found that carbon monoxide (CO) poisoning could be mitigated by increasing only cathode backpressure for a proton exchange membrane fuel cell (PEMFC) with ultra-thin membranes (≤25 μm). This mitigation can be explained by a heterogeneous oxidation of CO on a Pt-Ru/C anode by the permeated O₂ which is known as “internal air bleed” in his paper. A steady-state model which accounts for this internal air bleed has been developed to model the Pt-Ru/C anode polarization data when 50 ppm CO in H₂ is used as anode feed gas. The modeling results show that the mitigation of CO poisoning by the internal air bleed even exists at ambient conditions for a PEMFC with an ultra-thin membrane. Therefore, the effect of internal air bleed must be considered for modeling fuel cell performance or anode polarization data if an ultra-thin membrane and a low level of CO concentration are used for a Pt-Ru/C anode. An empirical relationship between the amount of internal air bleed used for the mitigation of CO poisoning and the fraction of free Pt sites is provided to facilitate the inclusion of an internal air bleed term in the modeling of anode polarization and the fuel cell performance.     

A novel proton exchange membrane fuel cell anode for enhancing CO tolerance

A novel proton exchange membrane fuel cell (PEMFC) anode which can facilitate the CO oxidation by air bleeding and reduce the direct combustion of hydrogen with oxygen within the electrode is described. This novel anode consists of placing Pt or Au particles in the diffusion layer which is called Pt- or Au-refined diffusion layer. Thus, the chemical oxidation of CO occurs at Pt or Au particles before it reaches the electrochemical catalyst layer when trace amount of oxygen is injected into the anode. All membrane electrode assemblies (MEAs) composed of Pt- or Au-refined diffusion layer do perform better than the traditionary MEA when 100 ppm CO/H₂ and 2% air are fed and have the performance as excellent as the traditionary MEA with neat hydrogen. Furthermore, CO tolerance of the MEAs composed of Au-refined diffusion layer was also assessed without oxygen injection. When 100 ppm CO/H₂ is fed, MEAs composed of Au-refined diffusion layer have the slightly better performance than traditionary MEA do because Au particles in the diffusion layer have activity in the water gas shift (WGS) reaction at low temperature.     

Polarization measurements on single-step co-fired solid oxide fuel cells (SOFCs)

Anode-supported planar solid oxide fuel cells (SOFC) were successfully fabricated by a single step co-firing process. The cells comprised of a Ni + yttria-stabilized zirconia (YSZ) anode, a YSZ or scandia-stabilized zirconia (ScSZ) electrolyte, a (La_0.85Ca_0.15)_0.97MnO₃ (LCM) + YSZ cathode active layer, and an LCM cathode current collector layer. The fabrication process involved tape casting of the anode, screen printing of the electrolyte and the cathode, and single step co-firing of the green-state cells in the temperature range of 1300–1330 °C for 2 h. Cells were tested in the temperature range of 700–800 °C with humidified hydrogen as fuel and air as oxidant. Cell test results and polarization modeling showed that the polarization losses were dominated by the ohmic loss associated with the electrodes and the activation polarization of the cathode, and that the ohmic loss due to the ionic resistance of the electrolyte and the activation polarization of the anode were relatively insignificant. Ohmic resistance associated with the electrode was lowered by improving the electrical contact between the electrode and the current collector. Activation polarization of the cathode was reduced by the improvement of the microstructure of the cathode active layer and lowering the cell sintering temperature. The cell performance was further improved by increasing the porosity in the anode. As a result, the maximum power density of 1.5 W cm⁻² was achieved at 800 °C with humidified hydrogen and air.     

Performance of a miniaturized silicon reformer-PrOx-fuel cell system

A fuel cell made with silicon is operated with hydrogen supplied by a reformer and a preferential oxidation (PrOx) reactor those are also made with silicon. The performance and durability of the fuel cell is analyzed and tested, then compared with the results obtained with pure hydrogen. Three components of the system are made using silicon technologies and micro electro-mechanical system (MEMS) technology. The commercial Cu-ZnO-Al₂O₃ catalyst for the reformer and the Pt-Al₂O₃ catalyst for the PrOx reactor are coated by means of a fill-and-dry method. A conventional membrane electrode assembly composed of a 0.375 mg cm⁻² PtRu/C catalyst for the anode, a 0.4 mg cm⁻² Pt/C catalyst for the cathode, and a Nafion™ 112 membrane is introduced to the fuel cell. The reformer gives a 27 cm³ min⁻¹ gas production rate with 3177 ppm CO concentration at a 1 cm³ h⁻¹ methanol feed rate and the PrOx reactor shows almost 100% CO conversion under the experimental conditions. Fuel cells operated with this fuel-processing system produce 230 mW cm⁻² at 0.6 V, which is similar to that obtained with pure hydrogen.     

Nanoporous H-sorbed carbon as anode of secondary cell

Nanoporous carbon is proposed as reversible hydrogen electrode for an electrochemical cell operating in aqueous KOH solution. Hydrogen is stored by water electroreduction on the carbon electrode during the charging step, while nickel gauze is used as auxiliary positive electrode. Then, electrical energy is harvested by using the charged electrode as anode associated to an air cathode. A specific capacity of 390–450 Ah kg⁻¹ of carbon material was measured. The system is technically more simple than a traditional fuel cell, since it does not require any hydrogen reservoir, membrane and noble metal for the hydrogen electrode.     

An air–metal hydride battery using MmNi3.6Mn0.4Al0.3Co0.7 in the anode and a perovskite in the cathode

Hydrogen storage alloy MmNi_3.6Mn_0.4Al_0.3Co_0.7 (MH) was tested as anode material in a metal hydride–air cell. The cathode was a non-noble metal air electrode based on a mixture of perovskite and pyrolyzed macrocycles on carbon. Polarization and discharge capacities of the electrodes were measured and compared at 22 °C and 40 °C using air or oxygen at the cathode. Discharge capacity reaching 330 mAh/g MH with pure oxygen at 40 °C and 305 mAh/g MH with air at 22 °C were obtained. Power densities and/or energy densities were found to significantly depend on the increase of the electrode kinetics on both the ORR (oxygen reduction reaction) and HOR (hydrogen oxidation reaction). However, for air electrode, an increase of oxygen concentration by using pure oxygen gas plays a more important role than an 18 °C temperature increase.     

A novel Rh–Ir electrocatalyst for the oxygen reduction reaction and the hydrogen and methanol oxidation reactions

A novel Rh–Ir based material was synthesized by pyrolysis of an Ir₄(CO)₁₂/Rh₆(CO)₁₆ mixture in a reductive (H₂) atmosphere. The material was characterized by FTIR spectroscopy, X-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy, and was evaluated as electrocatalyst for oxygen reduction and hydrogen and methanol oxidation by rotating disk electrode measurements. The bimetallic material shows a high catalytic activity for the oxygen reduction reaction and is also capable to carry out the hydrogen oxidation reaction even in the presence of carbon monoxide in different concentrations (100 ppm and 0.5%), in contrast with commercial platinum catalysts, which become easily deactivated by CO. The activity of the catalyst for methanol oxidation is acceptable but still low in comparison with Pt–Ru. The results show that the new bimetallic catalyst is a potential candidate to be evaluated as both cathode and anode in a reforming hydrogen PEMFC, and as an anode in a direct methanol fuel cell.     

Photoanodic and cathodic role of anodized tubular titania in light-sensitized enzymatic hydrogen production

An anodized tubular titania (TiO₂) electrode (ATTE) is prepared and utilized as both a photoanode and a cathode in a photoelectrochemical system designed to split water into hydrogen (for use in fuel cells) with the assistance of a hydrogenase enzyme and an external bias of 1.5 V. In particular, the cathodic ATTE acts as a substrate for the immobilization of the enzyme due to its large surface area that results from the tubular oxides. The optimum molar concentration of KOH in anode and cathode compartments is 1.0 M and the optimum amount of enzyme for the cathode is ca. 3.66 units per geometrical unit area (1 cm × 1 cm) of the cathodic ATTE. After exposure to air for three weeks, the enzyme shows a hydrogen evolution rate that is 85.8% of that of an argon-purged enzyme. The rate of hydrogen evolution is increased from ca. 65 (in a slurry system) to more than 140 μmol cm⁻² h⁻¹, even after eliminating the electron relay (methyl viologen) and costly platinum counter electrode.     

Investigations of a platinum-ruthenium/carbon nanotube catalyst formed by a two-step spontaneous deposition method

Platinum (Pt) is a popular catalyst for hydrogen oxidation on the anode side of solid polymer fuel cells (SPFC). It increases the electrode activity, which catalyzes the reaction of the fuel cell. There are two methods commonly used to produce hydrogen for SPFC: fuel reforming and methanol decomposition. Both of these methods produce carbon monoxide, which is considered to be a poison for SPFC because it deactivates Pt easily. Adding ruthenium (Ru) to a Pt catalyst is an efficient way to improve the inhibition of carbon monoxide (CO) formation and reduce the Pt loading requirement.This study introduces a method to synthesize a bimetal catalyst that is suitable for SPFC. To improve the electrocatalyst activity, a new process with two spontaneous deposition steps is adopted. In the first step, Ru is deposited on the wall of carbon nanotubes (CNTs) to obtain Ru/CNTs. Pt is then added in the second deposition step to form Pt-Ru/CNTs. The morphology and microstructure of catalysts are characterized with microscopes, and the performance of membrane electrode assembly is evaluated by cyclic voltammetry method. Experimental results have proved that even with a lower Pt loading, this home-brewed bimetal catalyst performs a compatible electrocatalytic activity, and is capable of resisting attack from CO when a syngas (H₂ + 20 ppm CO) is provided.     

XPS investigations of the proton exchange membrane fuel cell active layers aging: Characterization of the mitigating role of an anodic CO contamination on cathode degradation

This paper presents new results from XPS quantitative characterizations of cathode catalyst layers aged in a PEMFC with an anode operated under pure hydrogen and air and with 5 ppm CO contaminated hydrogen. Both oxygen rich and oxygen poor zones of the cathode catalyst layer were analyzed in order to show up heterogeneous degradation linked with gas distribution. The detailed chemical XPS analysis of the aged samples demonstrates in particular that in our operating conditions, the catalyst layer aging is mainly attributed to the oxidation of the carbon catalyst-support. A loss of the Nafion^® ionomer in the cathode is also highlighted by XPS. Furthermore, the characterization of the cathodic catalyst layer chemical composition when CO is introduced in the anode side shows that the catalyst layer degradation is lower. These results are in agreement with the experimental-modeling work by Franco et al. [1] demonstrating that anodic CO contamination decreases the reverse proton pumping effect between the cathode and the anode and enhances the PEMFC durability.     

Innovative microbial fuel cell for electricity production from anaerobic reactors

A submersible microbial fuel cell (SMFC) was developed by immersing an anode electrode and a cathode chamber in an anaerobic reactor. Domestic wastewater was used as the medium and the inoculum in the experiments. The SMFC could successfully generate a stable voltage of 0.428 ± 0.003 V with a fixed 470 Ω resistor from acetate. From the polarization test, the maximum power density of 204 mW m⁻² was obtained at current density of 595 mA m⁻² (external resistance = 180 Ω). The power generation showed a saturation-type relationship as a function of wastewater strength, with a maximum power density (P_max) of 218 mW m⁻² and a saturation constant (K_s) of 244 mg L⁻¹. The main limitations for achieving higher electricity production in the SMFC were identified as the high internal resistance at the electrolyte and the inefficient electron transfer at the cathode electrode. As the current increased, a large portion of voltage drop was caused by the ohmic (electrolyte) resistance of the medium present between two electrodes, although the two electrodes were closely positioned (about 3 cm distance; internal resistance = 35 ± 2 Ω). The open circuit potential (0.393 V vs. a standard hydrogen electrode) of the cathode was much smaller than the theoretical value (0.804 V). Besides, the short circuit potential of the cathode electrode decreased during the power generation in the SMFC. These results demonstrate that the SMFC could successfully generate electricity from wastewater, and has a great potential for electricity production from existing anaerobic reactors or other anaerobic environments such as sediments. The advantage of the SMFC is that no special anaerobic chamber (anode chamber) is needed, as existing anaerobic reactors can be used, where the cathode chamber and anode electrode are immersed.     

Characterization of energy losses in an upflow single-chamber microbial electrolysis cell

We characterized electrode energy losses and ohmic energy loss in an upflow, single-chamber microbial electrolysis cell (MEC) with no metal catalyst on the cathode. The MEC produced 0.57 m³-H₂/m³-d at an applied voltage of ∼1 V and achieved a cathodic conversion efficiency of 98% and a H₂ yield of 2.4 mol H₂/mol acetate. Eliminating the membrane lowered the ohmic energy loss to 0.005 V, and the pH energy loss became as small as 0.072 V. The lack of metal catalyst on the cathode led to a significant cathode energy loss of 0.56 V. The anode energy loss also was relatively large at 0.395 V, but this was artificial, due to the high positive anode potential, poised at +0.07 V (vs. the standard hydrogen electrode). The energy-conversion efficiency (ECE) was 75% in the single-chamber MEC when the energy input and outputs were compared directly as electrical energy. To achieve an energy benefit out of an MEC (i.e., an ECE >100%), the applied voltage must be less than 0.6 V with a cathodic conversion efficiency over 80%. An ECE of 180% could be achieved if the anode and cathode energy losses were reduced to 0.2 V each.     

A cobalt-free SrFe0.9Sb0.1O3−δ cathode material for proton-conducting solid oxide fuel cells with stable BaZr0.1Ce0.7Y0.1Yb0.1O3−δ electrolyte

A cobalt-free cubic perovskite oxide SrFe_0.9Sb_0.1O_3−δ (SFSb) is investigated as a novel cathode for proton-conducting solid oxide fuel cells (H-SOFCs). XRD results show that SFSb cathode is chemically compatible with the electrolyte BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb) for temperatures up to 1000 °C. Thin proton-conducting BZCYYb electrolyte and NiO-BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (NiO-BZCYYb) anode functional layer are prepared over porous anode substrates composed of NiO-BZCYYb by a one-step dry-pressing/co-firing process. Laboratory-sized quad-layer cells of NiO-BZCYYb/NiO-BZCYYb/BZCYYb/SFSb are operated from 550 to 700 °C with humidified hydrogen (∼3% H₂O) as fuel and the static air as oxidant. An open-circuit potential of 0.996 V, maximum power density of 428 mW cm⁻², and a low electrode polarization resistance of 0.154 Ω cm² are achieved at 700 °C. The experimental results indicate that the cobalt-free SFSb is a promising candidate for cathode material for H-SOFCs.     

Study of the cell reversal process of large area proton exchange membrane fuel cells under fuel starvation

In this research, the fuel starvation phenomena in a single proton exchange membrane fuel cell (PEMFC) are investigated experimentally. The response characteristics of a single cell under the different degrees of fuel starvation are explored. The key parameters (cell voltage, current distribution, cathode and anode potentials, and local interfacial potentials between anode and membrane, etc.) are measured in situ with a specially constructed segmented fuel cell. Experimental results show that during the cell reversal process due to the fuel starvation, the current distribution is extremely uneven, the local high interfacial potential is suffered near the anode outlet, hydrogen and water are oxidized simultaneously in the different regions at the anode, and the carbon corrosion is proved to occur at the anode by analyzing the anode exhaust gas. When the fuel starvation becomes severer, the water electrolysis current gets larger, the local interfacial potential turns higher, and the carbon corrosion near the anode outlet gets more significant. The local interfacial potential near the anode outlet increases from ca. 1.8 to 2.6 V when the hydrogen stoichiometry decreases from 0.91 to 0.55. The producing rate of the carbon dioxide also increases from 18 to 20 ml min⁻¹.     

Experimental evaluation of CO poisoning on the performance of a high temperature proton exchange membrane fuel cell

We experimentally studied a high temperature proton exchange membrane (PEM) fuel cell to investigate the effects of CO poisoning at different temperatures. The effects of temperature, for various percentages of CO mixed with anode hydrogen stream, on the current-voltage characteristics of the fuel cell are investigated. The results show that at low temperature, the fuel cell performance degraded significantly with higher CO percentage (i.e., 5% CO) in the anode hydrogen stream compared to the high temperature. A detailed electrochemical analysis regarding CO coverage on electrode surface is presented which indicates that electrochemical oxidation is favorable at high temperature. A cell diagnostic test shows that both 2% CO and 5% CO can be tolerated equally at low current density (<0.3 A cm⁻²) with high cell voltage (>0.5 V) at 180 °C without any cell performance loss. At high temperature, both 2% CO and 5% CO can be tolerated at higher current density (>0.5 A cm⁻²) with moderate cell voltage (0.2-0.5 V) when the cell voltage loss within 0.03-0.05 V would be acceptable. The surface coverage of platinum catalyst by CO at low temperature is very high compared to high temperature. Results suggest that the PEM fuel cell operating at 180 °C or above, the reformate gas with higher CO percentage (i.e., 2-5%) can be fed to the cell directly from the fuel processor.     

Initialization of a methane-fueled single-chamber solid-oxide fuel cell with NiO + SDC anode and BSCF + SDC cathode

The initialization of an anode-supported single-chamber solid-oxide fuel cell, with NiO + Sm_0.2Ce_0.8O_1.9 anode and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ + Sm_0.2Ce_0.8O_1.9 cathode, was investigated. The initialization process had significant impact on the observed performance of the fuel cell. The in situ reduction of the anode by a methane–air mixture failed. Although pure methane did reduce the nickel oxide, it also resulted in severe carbon coking over the anode and serious distortion of the fuel cell. In situ initialization by hydrogen led to simultaneous reduction of both the anode and cathode; however, the cell still delivered a maximum power density of ∼350 mW cm⁻², attributed to the re-formation of the BSCF phase under the methane–air atmosphere at high temperatures. The ex situ reduction method appeared to be the most promising. The activated fuel cell showed a peak power density of ∼570 mW cm⁻² at a furnace temperature of 600 °C, with the main polarization resistance contributed from the electrolyte.     

Biocatalyzed hydrogen production in a continuous flow microbial fuel cell with a gas phase cathode

A single liquid chamber microbial fuel cell (MFC) with a gas-collection compartment was continuously operated under electrically assisted conditions for hydrogen production. Graphite felt was used for anode construction, while the cathode was made of Pd/Pt coated Toray carbon fiber paper with a catalyst loading of 0.5 mg cm⁻². To achieve hydrogen production, the MFC was connected to a power supply and operated at voltages in a range of 0.5–1.3 V. Either acetate or glucose was used as a source of carbon. At an acetate load of 1.67 g (L_A d)⁻¹, the volumetric rate of hydrogen production reached 0.98 L_STP (L_A d)⁻¹ when a voltage of 1.16 V was applied. This corresponded to a hydrogen yield of 2 mol (mol-acetate)⁻¹ with a 50% conversion efficiency. Throughout the experiment, MFC efficiency was adversely affected by the metabolic activity of methanogenic microorganisms, which competed with exoelectrogenic microorganisms for the carbon source and consumed part of the hydrogen produced at the cathode.     

Electrochemically assisted methane production in a biofilm reactor

Microbial electrolysis is a new technology for the production of value-added products, such as gaseous biofuels, from waste organic substrates. This study describes the performance of a methane-producing microbial electrolysis cell (MEC) operated at ambient temperature with a Geobacter sulfurreducens microbial bioanode and a methanogenic microbial biocathode. The cell was initially operated at a controlled cathode potential of −850 mV (vs. standard hydrogen electrode, SHE) in order to develop a methanogenic biofilm capable of reducing carbon dioxide to methane gas using abiotically produced hydrogen gas or directly the polarized electrode as electron donors. Subsequently, G. sulfurreducens was inoculated at the anode and the MEC was operated at a controlled anode potential of +500 mV, with acetate serving as electron donor. The rate of methane production at the cathode was found to be primarily limited by the acetate oxidation kinetics and in turn by G. sulfurreducens concentration at the anode of the MEC. Temperature had also a main impact on acetate oxidation kinetics, with an apparent activation energy of 58.1 kJ mol⁻¹.