Effect of pressure for direct fuel cells using DME-based fuels

The performance of direct fuel cells using dimethyl ether(DME)-based fuels is presented at a relatively low temperature of 80 °C. DME is supplied to the fuel cells either by gas phase or aqueous phase for the operation of direct fuel cells. In order to keep DME in liquid phase during operation, fuel cells were operated at higher pressure up to 5 bar. For further increase of the power density from direct DME fuel cells, DME was mixed with methanol solution and fed into the fuel cells by the vapor pressure of DME itself without a liquid pump. In this study, we have obtained the highest power density of 210 mW cm⁻² at a temperature of 80 °C when the fuel cell is operated with the mixed fuel with 2 M methanol solution under 4 bar.     

Performance evaluation of tubular fuel cells fuelled by pulverized graphite

A fuel cell fuelled by carbonaceous graphite is proposed. The tubular fuel cell, with the carbon in a fixed-bed form on the anode side, is employed to convert directly the chemical energy of carbon into electricity. Surface platinum electrodes are coated on the cell electrolyte, which is a yttria-stabilized zirconia (YSZ) tube of 1.5 mm thickness. The effect of using different sizes of graphite powder (in the range 0-180 μm) as fuel is analyzed. Power density and actual open-circuit voltage (OCV) values are measured as the temperature is varied from 0 to 950 °C. The cell provides a maximum power density of 16.8 mW cm⁻² and an OCV of 1.115 V at the highest temperature condition (950 °C) tested in this study.     

Operational condition analysis for vapor-fed direct methanol fuel cells

This paper investigates the analysis and design of optimal operational conditions for vapor-fed direct methanol fuel cells (DMFCs). Methanol vapor at a temperature of 35 °C is carried with nitrogen gas together with water vapor at 75 °C. In this experimental condition, stoichiometry of 10 is maintained for each fuel gas. The results show that the optimal operational concentration was 25–30 wt.% under methanol vapor feeding at the anode. The peak power was 14 mW cm² in polarization curves. To analyze major losses, the activation losses of the anode and cathode were measured by an in situ reference electrode and a working electrode. The activation loss of the anode is proportional to the water content and the high methanol concentration caused the activation loss of the cathode to increase due to methanol crossover. In the vapor-fed DMFC, the activation loss of the anode is higher than that of the cathode. Also, depending on the variation of the methanol concentration, the IR loss and Faradaic impedance is measured via impedance analysis. The methanol concentration significantly affects the IR loss and kinetics. Although the IR loss was more than the desired value at the optimal condition (25–30 wt.%), it did not significantly affect the cell’s performance. The cell operated at room temperature and ambient pressure that is a typical operation environment of air-breathing fuel cells.     

Experimental investigation of 1 kW solid oxide fuel cell system with a natural gas reformer and an exhaust gas burner

An experimental investigation is performed to establish the optimal operating conditions of a porous media after-burner integrated with a 1 kW solid oxide fuel cell (SOFC) system fed by a natural gas reformer. The compositions of the anode off-gas and cathode off-gas emitted by the SOFC when operating with fuel utilizations in the range 0-0.6 are predicted using commercial GCTool software. The numerical results are then used to set the compositions of the anode off-gas and cathode off-gas in a series of experiments designed to clarify the effects of the fuel utilization, cathode off-gas temperature and excess air ratio on the temperature distribution within the after-burner. The experimental results show that the optimal after-burner operation is obtained when using an anode off-gas temperature of 650 °C, a cathode off-gas temperature of 390 °C, a flame barrier temperature of 700 °C, an excess air ratio of 2 and a fuel utilization of U_f = 0.6. It is shown that under these conditions, the after-burner can operate in a long-term, continuous fashion without the need for either cooling air or any additional fuel other than that provided by the anode off-gas.     

Testing and improving the redox stability of Ni-based solid oxide fuel cells

Despite active development, solid oxide fuel cells (SOFCs) based on Ni-YSZ anodes still suffer from thermomechanical instability under conditions where the anode side is exposed to oxidising conditions at high temperature. In the first part of the paper, structures and solutions, which could improve the redox stability of Ni-YSZ anode supported SOFC's in terms of dimensional and mechanical stability are reported. Porosity is identified as a major microstructural parameter linked to the dimensional and structural stability during redox cycling. The cumulative redox strain (CRS) after three isothermal redox cycles at 850 °C increases by a factor of more than 20 when the as-sintered porosity of the composites is reduced from 34 to 9%. The effect of reduction and redox cycling on the Ni-YSZ anode are discussed in light of electrochemical measurements using impedance spectroscopy on symmetric cells. When the symmetric cells are reduced and redox cycled isothermally at 850 °C, no major change in the serial or polarisation resistance of the cell and electrodes was measured. When the cells are, after the similar initial reduction treatment, redox cycled at 650 °C, the serial resistance remains almost unchanged but the polarisation resistance decreased by about 60%.     

Development of a PEM stack and performance analysis including the effects of water content in the membrane and cooling method

For the use of proton exchange membrane (PEM) fuel cell systems to become widespread, the components required to build one should be minimized. Because a PEM fuel cell has a limited operating temperature range, it requires some kind of cooling method. In this study, different cooling methods were investigated experimentally. A PEM fuel cell stack with an active area of 100 cm² and 8 cells in series was developed and used in this research. When 50% relative humidity inlet gases were supplied (at 15 A of current discharge and 70 °C), cell temperatures at the center increased from around 60 °C to 85 °C, and cell voltage dropped from 4.8 V to 3.2 V because of membrane drying (insufficient cooling). When fully hydrated inlet gases (100% relative humidity) were supplied to the PEM stack at the same test conditions, the cell temperature remained around 65 °C, and stack voltage remained around 5.7 V at 15 A of current discharge. Fully hydrated inlet gases play a positive role both for water transport (when the proton moves from the anode to the cathode) and to maintain the fuel cell stack temperature to prevent stack drying.     

An intermediate-temperature direct ammonia fuel cell with a molten alkaline hydroxide electrolyte

This paper describes the development and testing of a direct ammonia fuel cell utilizing a molten alkaline hydroxide electrolyte at temperatures between 200 and 450 °C. The advantages of a molten hydroxide fuel cell include the use of a highly conductive and very low-cost electrolyte, inexpensive base metal electrocatalysts, a wide operating temperature range, fuel flexibility, and fast electrode kinetics. The direct use of ammonia in such a fuel cell, even at temperatures as low as 200 °C, is made possible due to the very chemically aggressive nature of the melt. A test cell was constructed using a KOH–NaOH eutectic mixture and produced approximately 40 mW cm⁻² of power at 450 °C while operating on a stream of pure ammonia fed to the anode and compressed ambient air fed to the cathode.     

Fabrication and characterization of micro PEM fuel cells using pyrolyzed carbon current collector plates

A novel fabrication technique for micro proton exchange membrane fuel cells (μPEMFCs) based on carbon-MEMS (C-MEMS) was optimized to yield higher performance cells. Polymer manufacturing is relatively easy compared to directly patterning graphite as is typically done to make fuel cell bipolar plates. In a C-MEMS approach, fuel cell bipolar plates are fabricated by first patterning polymer Cirlex^® sheets. By subsequently pyrolyzing the machined polymer sheets at high temperature in an inert atmosphere, carbon bipolar plates with intricate groove structures to distribute the reactants are obtained. Using an improved assembly technique such as polishing the carbonized plates to minimize the contact resistance between gas diffusion layers (GDL) and bipolar plates, better pyrolysis temperature control and a better end plate design, a μPEMFC with a 0.64 cm² active surface was fabricated using the newly developed bipolar plates. At 1 atm and 25 °C a maximum power density of ∼76 mW cm⁻² was obtained, and at 2 atm and 25 °C ∼85 mW cm⁻² was achieved. These data are comparable with data reported in the literature for μPEMFCs and are a dramatic improvement over earlier results reported for the same C-MEMS based fuel cell. Electrochemical Impedance Spectroscopy (EIS) and cyclic voltammetry were carried out to characterize steady-state and transient characteristics of the novel C-MEMS fuel cell.     

Development of porous carbon foam polymer electrolyte membrane fuel cell

In order to prove the feasibility of using porous carbon foam material in a polymer electrolyte membrane fuel cell (PEMFC), a single PEMFC is constructed with a piece of 80PPI (pores per linear inch) Reticulated Vitreous Carbon (RVC) foam at a thickness of 3.5 mm employed in the cathode flow-field. The cell performance of such design is compared with that of a conventional fuel cell with serpentine channel design in the cathode and anode flow-fields. Experimental results show that the RVC foam fuel cell not only produces comparative power density to, but also offers interesting benefits over the conventional fuel cell. A 250 h long term test conducted on a RVC foam fuel cell shows that the durability and performance stability of the material is deemed to be acceptable. Furthermore, a parametric study is conducted on single RVC foam fuel cells. Effect of geometrical and material parameters of the RVC foam such as PPI and thickness and operating conditions such as pressure, temperature, and stoichiometric ratio of the reactant gases on the cell performance is experimentally investigated in detail. The single cell with the 80PPI RVC foam exhibits the best performance, especially if the thinnest foam (3.5 mm) is used. The cell performance improves with increasing the operating gauge pressure from 0 kPa to 80 kPa and the operating temperature from 40 °C to 60 °C, but deteriorates as it further increases to 80 °C. The cell performance improves as the stoichiometric ratio of air increases from 1.5 to 4.5; however, the improvement becomes marginal when it is raised above 3.0. On the other hand, changing the stoichiometric ratio of hydrogen does not have a significant impact on the cell performance.     

Evaluation of carbon deposition behavior on the nickel/yttrium-stabilized zirconia anode-supported fuel cell fueled with simulated syngas

The nickel/yttrium-stabilized zirconia (Ni/YSZ) anode-supported solid oxide fuel cells (SOFCs) have been operated under various simulated syngases at different temperatures to investigate the degradation behavior of the cells caused by carbon deposition. The results show that the carbon morphology and the cell performance degradation are influenced significantly by the operation temperature. The stability of the cell fueled with syngas can be improved by applying a constant current, but the cell degraded quickly after carbon deposition. The microstructure damage is close to the anode surface and leads to a conductivity decrease, which is an important reason for the cell degradation and failure at 750 °C. Conversely, the degradation behavior at 650 °C is mainly due to solid carbon deposits inside of the anode that impede fuel diffusion and electrochemical reactions on the anodic side. The effect of carbon deposition on the microstructure degradation is also investigated using transmission electron microscope.     

Fabrication of micro-tubular solid oxide fuel cells with a single-grain-thick yttria stabilized zirconia electrolyte

This study discusses the fabrication and electrochemical performance of micro-tubular solid oxide fuel cells (SOFCs) with an electrolyte consisting a single-grain-thick yttria stabilized zirconia (YSZ) layer. It is found that a uniform coating of an electrolyte slurry and controlled shrinkage of the supported tube leads to a dense, crack-free, single-grain-thick (less than 1 μm) electrolyte on a porous anode tube. The SOFC has a power density of 0.39 W cm⁻² at an operating temperature as low as 600 °C, with YSZ and nickel/YSZ for the electrolyte and anode, respectively. An examination is made of the effect of hydrogen fuel flow rate and shown that a higher flow rate leads to better cell performance. Hence a YSZ cell can be used for low-temperature SOFC systems below 600 °C, simply by optimizing the cell structure and operating conditions.     

High-temperature mechanical properties of a glass sealant for solid oxide fuel cell

The high-temperature mechanical properties of a newly developed silicate-based glass sealant, designated as GC-9, have been studied for use in planar solid oxide fuel cell (pSOFC). Four-point bending tests were conducted at room temperature, 550 °C, 600 °C, 650 °C, 700 °C and 750 °C to investigate the variation of flexural strength, elastic modulus, and stress relaxation with temperature for the given glass sealant. Weibull statistic analysis was applied to describe the fracture strength data. The results indicated that the flexural strength was increased with temperature when the testing temperature was below the glass transition temperature (T_g, 668 °C). This was presumably caused by a crack healing effect taking place at high temperatures for glasses. However, with a further increase of temperature to a level higher than T_g, significant stress relaxation was observed to cause extremely large deformation without breaking the specimen. When the controlled displacement rate was increased by an order of magnitude, the stress relaxation effect at 750 °C became less effective. However, the mechanical stiffness of the given glass was significantly reduced at a temperature higher than T_g.     

A high performance composite ionic conducting electrolyte for intermediate temperature fuel cell and evidence for ternary ionic conduction

The performance of a composite electrolyte composed of a samarium doped ceria (SDC) and a ternary eutectic carbonate melt phase was examined. The formation temperature of a continuous carbonate melt phase is crucial to the high conductivity of this material. The electrolyte contains 30 and 50 wt% carbonate exhibited a sharp increase of conductivity at a temperature close to the melting point of the eutectic carbonate, ca 400 °C, which is more than 100 °C lower than those electrolytes using binary carbonate. At around 650 °C, and with CO₂/O₂ used as the cathode gas, the fuel cell gave a power output 720 mW cm⁻² at a current density 1300 mA cm⁻². Water was measured in both the anode and cathode outlet gases and CO₂ was detected in the anode outlet gas. When discharged at 800 mA cm⁻², a stable discharge plateau was obtained. The CO₂ in the cathode gas enhances the power output and the stability of the single cell. Based on these experimental facts, a ternary ionic conducting scheme is proposed and discussed.     

Performance of metal-supported SOFCs with infiltrated electrodes

Metal-supported solid oxide fuel cells (SOFCs) with thin YSZ electrolyte films and infiltrated Ni and LSM catalysts are operated in the temperature range 650–750 °C. A five-layer structure consisting of porous metal-support/porous YSZ interlayer/dense YSZ electrolyte film/porous YSZ interlayer/porous metal current collector is prepared at 1300 °C in reducing atmosphere. This cell structure is then sealed and joined to a cell housing/gas manifold using a commercially available braze. Finally, the porous YSZ interlayers are infiltrated with Ni and LSM catalyst precursor solutions at low temperature prior to cell testing. Infiltrating the catalysts after the high temperature sintering and brazing steps avoids undesirable decomposition of LSM, Ni coarsening, and interdiffusion between Ni catalyst and FeCr in the support. Maximum power densities of 233 and 332 mW cm⁻² were achieved at 650 and 700 °C, respectively, with air as oxidant. With pure oxygen as oxidant, power densities of 726, 993, and >1300 mW cm⁻² were achieved at 0.7 V at 650, 700, and 750 °C, respectively.     

Basic properties of a liquid tin anode solid oxide fuel cell

An unconventional high temperature fuel cell system, the liquid tin anode solid oxide fuel cell (LTA-SOFC), is discussed. A thermodynamic analysis of a solid oxide fuel cell with a liquid metal anode is developed. Pertinent thermochemical and thermophysical properties of liquid tin in particular are detailed. An experimental setup for analysis of LTA-SOFC anode kinetics is described, and data for a planar cell under hydrogen indicated an effective oxygen diffusion coefficient of 5.3 × 10⁻⁵ cm² s⁻¹ at 800 °C and 8.9 × 10⁻⁵ cm² s⁻¹ at 900 °C. This value is similar to previously reported literature values for liquid tin. The oxygen conductivity through the tin, calculated from measured diffusion coefficients and theoretical oxygen solubility limits, is found to be on the same order of that of yttria-stabilized zirconia (YSZ), a traditional SOFC electrolyte material. As such, the ohmic loss due to oxygen transport through the tin layer must be considered in practical system cell design since the tin layer will usually be at least as thick as the electrolyte.     

Intermediate temperature solid oxide fuel cell based on lanthanum gallate electrolyte

The Kansai Electric Power Co. Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been developing intermediate temperature solid oxide fuel cells (IT-SOFCs) which are operable at a temperature range between 600 and 800 °C. There are some significant features in IT-SOFC of KEPCO–MMC: (1) highly conductive lanthanum gallate-based oxide is adopted as an electrolyte to realize high-performance disk-type electrolyte-supported cells; (2) the cell-stacks with seal-less structure using metallic separators allow residual fuel to burn around the stack and the combustion heat is utilized for thermally self-sustainable operation; (3) the separators have flexible arms by which separate compressive forces can be applied for manifold parts and interconnection parts. We are currently participating in the project by New Energy and Industrial Technology Development Organization (NEDO) to develop 10 kW-class combined heat and power (CHP) systems. In FY2006, a 10 kW-class module was developed, with which the electrical efficiency of 50%HHV was obtained based on DC 12.6 kW. In the first quarter of FY2007, the 10 kW-class CHP system using the module gave the electrical efficiency of 41%HHV on AC 10 kW and the overall efficiency of 82%HHV when exhaust heat was recovered as 60 °C hot water. Currently, the operation has been accumulated for about 2500 h to evaluate the long-term stability of the system.     

Solid oxide fuel cells with Sm0.2Ce0.8O2−δ electrolyte film deposited by novel aerosol deposition method

In this study, dense electrolyte ceramic Sm_0.2Ce_0.8O_2−δ (SDC) thin films are successfully deposited on NiO-SDC anode substrate by aerosol deposition (AD) with oxygen as the carrier gas at the substrate temperature ranging from room temperature to 300 °C. To remove the effect of humidity on the starting powders, this study found that, in depositing SDC films, having the starting powders preheat-treated at 200 °C helped generate a smooth and dense layer, though a lower deposition rate was achieved. At a deposition time of 22 min, SDC films with a uniform thickness of 1.5 μm and grain sizes of ≈67 nm are obtained. SOFC single cells are then built by screen printing a LSCF cathode on the anode-supported substrates with SDC electrolyte. The cross-sectional SEM micrographs exhibit highly dense, granular, and crack-free microstructures. The open circuit voltages (OCV) of the single cells decrease with the rise in temperature, dropping from 0.81 V at 500 °C to 0.59 V at 700 °C. Maximum power densities (MPD) decline with decreasing operating temperature from 0.34 to 0.01 W cm⁻² due to the increase of the R₀ and R_P of the single cells. The electrochemical results testify to the fine quality of SDC films as well as illustrate the electrolyte thickness effect and the effect of mixed ionic and electronic conduction of the SDC electrolyte in the reducing atmosphere.     

A basic model for analysis of molten carbonate fuel cell behavior

A simple mathematical model, based on the basic chemical reactions and mass transfer, was developed to predict some important characteristics of molten carbonate fuel cells (MCFC) with LiNaCO₃ and LiKCO₃ electrolytes for steady state operating conditions. The parallel and cross gas flow patterns were analyzed. Model simulates polarization characteristics, the effect of temperature, pressure and electrolyte type on the cell performance, various losses in the cell and gas flow rate changes through cell. The effect of fuel utilization on the cell potential and efficiency was also analyzed. Model predicts a better performance for the MCFC with LiNaCO₃ electrolyte and the cross flow pattern, in general. Results show a strong influence of the operating temperature on the cell potential at temperatures below 625 °C, where cell potential increases rapidly with increasing temperature. Above this temperature, however, the cell potential has almost a steady asymptotic profile. The model predicts cell efficiency steadily improving with increase in fuel utilization. The cell potential decreases almost linearly with increase in the fuel utilization percentage for both electrolytes. Models results show a stronger dependency of the cell potential on the operating pressure than that described by the Nerst equation which is in line with fact that the real variations in the cell potential can be higher due to decreased various losses.     

High-temperature mechanical properties of a solid oxide fuel cell glass sealant in sintered forms

High-temperature mechanical properties of a silicate-based glass sealant (GC-9) for planar solid oxide fuel cell have been studied in sintered forms. Ring-on-ring biaxial flexural tests are carried out at room temperature to 800 °C for the sintered GC-9 glass. The results are also compared with those in cast bulk forms. From the force-displacement curves, the glass transition temperature (T_g) of the non-aged, sintered GC-9 glass is estimated to be between 700 °C and 750 °C, while that of the aged one is between 750 °C and 800 °C. Due to a crack healing effect of the residual glass at high temperature, the flexural strength of the sintered GC-9 glass at temperature of 650 °C to T_g point is greater than that at room temperature. At temperature above T_g, the flexural strength and stiffness are considerably reduced to a level lower than the room-temperature one. The sintered GC-9 glass with pores and crystalline phases has a flexural strength lower than the cast bulk one at temperature of 650 °C and below. Due to a greater extent of crystallization, the flexural strength and stiffness of the sintered GC-9 glass are greater than those of the cast bulk one at 700-800 °C.     

Quaternized-chitosan membranes for possible applications in alkaline fuel cells

Novel crosslinked quaternized-chitosan membranes were fabricated and further investigated for possible applications in alkaline polyelectrolyte fuel cells. Impedance analysis indicated that some hydrated membranes could exhibit a conductivity close to 10⁻² S cm⁻¹. Several membranes were selected and integrated into unit fuel cells for the evaluations on their cell performance, using hydrogen as fuel, air as oxidant and platinum as the electrode catalyst, and a current density of 65 mA cm⁻² was already achieved with a flow rate of hydrogen at 50 mL min⁻¹ and air at 250 mL min⁻¹ at a relatively low running temperature of 50 °C.