YSZ films fabricated by a spin smoothing technique and its application in solid oxide fuel cell

A dense single-layer YSZ film has been successfully fabricated by a spin smoothing method. Followed by a simplified slurry coating, an additional spin smoothing process was conducted to obtain a thinner and smoother film. By employment of high-viscosity slurry including high YSZ content, the film has a suitable thickness by a single coating cycle. With Sm_0.2Ce_0.8O_1.9 (SDC)-impregnated La_0.7Sr_0.3MnO₃ (LSM) cathode and porous NiO–YSZ anode, single solid oxide fuel cell (SOFC) based on an 8-μm-thick YSZ film was obtained. Open-circuit voltage (OCV) of the cell was 1.04 V at 800 °C, and maximum power densities were 676, 965 and 1420 mW cm⁻² at 700, 750 and 800 °C, respectively, using H₂ at a flow rate of 40 mL min⁻¹ as fuel and ambient air as oxidant. The power density could be increased to 1648 mW cm⁻² at 800 °C when the flow rate of H₂ was enhanced to 200 mL min⁻¹.     

Effect of carbon fiber cloth with different structure on the performance of low temperature proton exchange membrane fuel cells

This study uses fuel cell gas diffusion layers (GDLs) fabricated in the laboratory from carbon fiber cloth with different structure in proton exchange membrane fuel cells (PEMFCs), and investigates the relationship between the structure of the carbon fiber cloth and fuel cell performance.The paper discusses the relationship between fuel cell performance and structure of the carbon fiber cloth, and also examines the effect of the carbon fiber cloth’s thickness, air permeability, surface resistivity, XRD and elemental analysis. Carbon fiber cloth is carbonized at rates of 190, 220, 250, 280, and 310 °C min⁻¹ respectively, and the resulting carbon fiber cloth is tested in cells. When the test piece area is 25 cm², the test temperature 40 °C, the gasket thickness 0.36 mm, and the carbonization rate 280 °C min⁻¹, a fuel cell using the carbon fiber cloth achieves a current density of 1968 mA cm⁻² and a maximum power density of 633 mW cm⁻² at 0.3 V.     

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.     

Characterization of bubble formation in microfluidic fuel cells employing hydrogen peroxide

In order to examine bubble evolution and discuss the effects of bubbles effect on the performance of microfluidic fuel cells, two 1.2-mm-depth microfluidic fuel cells employing 0.1-M H₂O₂ dissolved in 0.1-M NaOH solution and 0.05-M H₂SO₄ solution as fuel and oxidant, respectively, with transparent lids having width of 1.0 mm and 0.5 mm, are fabricated in the present study for both cell performance measurement and flow visualization. The results show that the present cells operating at either a higher volumetric flow or a smaller microchannel width yield both better performance and more violent bubble growth. The bubble growth rate, Q_g, in a given microfluidic fuel cell is almost the same at different regions of that cell at a given volumetric flow rate, i.e. 10⁻⁵ cm³ s⁻¹ and 5 × 10⁻⁵ cm³ s⁻¹, respectively, for cells having widths of 0.5 mm and 1.0 mm at Q_l = 0.05 mL min⁻¹, and slightly increases at higher volumetric flow rates. Furthermore, the present study reports approximately constant values of Q_g/C_dA at various volumetric flow rates, which are 2 × 10⁻² and 5 × 10⁻² cm³ s⁻¹ A⁻¹, respectively, for cells having channel widths of 0.5 mm and 1.0 mm. In addition, the 0.5-mm-wide cell has higher cell output and performs more tortuous polarization curve.     

Effect of gas flow rates and Boudouard reactions on the performance of Ni/YSZ anode supported solid oxide fuel cells with solid carbon fuels

The effects of carrier gas flow rates and Boudouard reaction on the performance of Ni/YSZ anode-supported solid oxide fuel cells (SOFCs) have been studied with coconut coke fuels at 800 °C. Decreasing flow rates of carrier gas from 1000 to 50 ml min⁻¹ increased open circuit voltages and current densities from 0.71 to 0.87 V and from 0.12 to 0.34 A cm⁻², respectively. The increased cell performance was attributed to the increasing extent of electrochemical oxidation of CO, a product of Boudouard reaction. The contribution of CO oxidation to current generation was estimated to 66% in flowing inert carrier gas at 50 ml min⁻¹. The pulse transient studies confirmed the effect of flow rates on cell performance and also revealed that CO and CO₂ can displace adsorbed hydrogen on carbon fuels. Flowing CO₂ over coconut coke fuel produced CO via Boudouard reaction. The presence of CO led to a highest power density of 95 mW cm⁻², followed by a concurrent decline of power density and CO concentration. The declined power density along with decreasing CO concentration further verified contribution of gaseous CO to the power generation of C-SOFC; the decreasing CO concentration showed a typical kinetics behavior of Boudouard reaction, suggesting the loss of active sites on carbon surface for the reaction.     

Improved fuel use efficiency in microchannel direct methanol fuel cells using a hydrophilic macroporous layer

We demonstrate state-of-the-art room temperature operation of silicon microchannel-based micro-direct methanol fuel cells (μDMFC) having a very high fuel use efficiency of 75.4% operating at an output power density of 9.25 mW cm⁻² for an input fuel (3 M aqueous methanol solution) flow rate as low as 0.55 μL min⁻¹. In addition, an output power density of 12.7 mW cm⁻² has been observed for a fuel flow rate of 2.76 μL min⁻¹. These results were obtained via the insertion of novel hydrophilic macroporous layer between the standard hydrophobic carbon gas diffusion layer (GDL) and the anode catalyst layer of a μDMFC; the hydrophilic macroporous layer acts to improve mass transport, as a wicking layer for the fuel, enhancing fuel supply to the anode at low flow rates. The results were obtained with the fuel being supplied to the anode catalyst layer via a network of microscopic microchannels etched in a silicon wafer.     

Performance of a direct methanol alkaline membrane fuel cell

A study of a direct methanol fuel cell (DMFC) operating with hydroxide ion conducting membranes is reported. Evaluation of the fuel cell was performed using membrane electrode assemblies incorporating carbon-supported platinum/ruthenium anode and platinum cathode catalysts and ADP alkaline membranes. Catalyst loadings used were 1 mg cm⁻² Pt for both anode and cathode. The effect of temperature, oxidant (air or oxygen) and methanol concentration on cell performance is reported. The cell achieved a power density of 16 mW cm⁻², at 60 °C using oxygen. The performance under near ambient conditions with air gave a peak power density of approximately 6 mW cm⁻².     

Characterisation of electrical performance of anode supported micro-tubular solid oxide fuel cell with methane fuel

The reduction and operation of Ni–YSZ anode-supported tubular cells on methane fuel is described. Cells were reduced on pure methane from 650 °C to 850 °C, varying reduction time and methane flow rate. The effect on electrochemical performance with methane fuel was then investigated at 850 °C after which temperature-programmed oxidation (TPO) was employed to measure carbon deposition. Results showed that carbon deposition was minimized after certain reduction conditions. The conclusion was that 30 min reduction at 650 °C with 10 ml min⁻¹ methane reduction flow rate led to the highest current output over 1.2 A cm⁻² at 0.5 V when the cell operated at 850 °C between 10 ml min⁻¹ and 12.5 ml min⁻¹ methane running flow rate. From these results, it is evident that solid oxide fuel cell (SOFC) performance can be substantially improved by optimising preparation, reduction and operating conditions without the need for hydrogen.     

BaCe0.85Tb0.05Co0.1O3−δ perovskite hollow fibre membranes for hydrogen/oxygen permeation

Co-doped BaCe_0.85Tb_0.05Co_0.1O_3−δ (BCTCo) nanopowder was synthesized via a sol–gel method using ethylenediaminetetraacetic acid (EDTA) and citric acid as the chelating agents. Using the resultant powder, BCTCo perovskite hollow fibre membranes were then fabricated by the combined phase inversion and sintering technique. Properties of the BCTCo powder and the hollow fibre membranes in terms of crystalline phase, morphology, electrical conductivity, porosity, mechanical strength and hydrogen/oxygen permeation were investigated by a variety of characterization methods. The results indicated that doping of cobalt in the BCTb oxide led to a higher electrical conductivity and lower calcination temperature for the powder precursor to a perovskite structure as well as sintering temperature for the hollow fibre precursors to gastight membranes. In order to obtain gastight and robust hollow fibre membranes, the sintering temperature should be controlled between 1300 and 1450 °C. The maximum hydrogen flux through the BCTCo hollow fibre membranes reached up to 0.385 mL cm⁻² min⁻¹ at 1000 °C under 50% H₂–He/N₂ gradient, which is higher than that of the un-doped BCTb hollow fibre membranes with the same effective thickness, and especially much higher than that obtained from other proton conductors due to the asymmetric structure of the membrane designed. Moreover, the BCTCo hollow fibre membrane also exhibited noticeable oxygen permeation fluxes, i.e. 0.122 mL cm⁻² min⁻¹ at 1000 °C under the air/He gradient. However, doping of cobalt might damage the mechanical stability of the perovskite membranes in the hydrogen-containing atmosphere.     

Performance of micro-PEM fuel cells with different flow fields

Four designs of flow fields were applied to micro-proton exchange membrane fuel cells (μ-PEMFCs) using microelectromechanical system (MEMS) technology. The flow fields and membrane electrolyte assembly (MEA) of 2.25 cm² active area were assembled to μ-PEMFCs. Electrochemical behaviors of these μ-PEMFCs were investigated by polarization method at reactants flow rates of 15 ml min⁻¹, 30 ml min⁻¹ and 50 ml min⁻¹, respectively. This study emphasized the effects of different topologies of flow fields on performance of μ-PEMFCs. Results demonstrated that μ-PEMFCs with different flow fields have similar behavior at reactants flow rates of 50 ml min⁻¹. However, at reactants flow rates of 15 ml min⁻¹ and 30 ml min⁻¹, performance of the μ-PEMFC with long and narrow micro-channels rapidly deteriorated due to the flooding in micro-channels. The mixed serpentine design had a good ability to resist the flooding, but it displayed a low maximum power density because of its short effective length of micro-channels. The results in this study suggested that the μ-PEMFC with a mixed multichannel design flow field and long micro-channels yielded the best performance.     

Water and air management systems for a passive direct methanol fuel cell

In this paper water and air management systems were developed for a miniature, passive direct methanol fuel cell (DMFC). The membrane thickness, water management system, air management system and gas diffusion electrodes (GDE) were examined to find their effects on the water balance coefficient, fuel utilization efficiency, energy efficiency and power density. Two membranes were used, Nafion^® 112 and Nafion^® 117. Nafion^® 117 cells had greater water balance coefficients, higher fuel utilization efficiency and greater energy efficiency. A passive water management system which utilizes additional cathode gas diffusion layers (GDL) and a passive air management system which makes use of air filters was developed and tested. Water management was improved with the addition of two additional cathode GDLs. The water balance coefficients were increased from −1.930 to 1.021 for a cell using a 3.0 mol kg⁻¹ solution at a current density of 33 mA cm⁻². The addition of an air filter further increased the water balance coefficient to 1.131. Maximum power density was improved from 20 mW cm⁻² to 25 mW cm⁻² for 3.0 mol kg⁻¹ solutions by upgrading from second to third generation GDEs, obtained from E-TEK. There was no significant difference in water management found between second and third generation GDEs. A fuel utilization efficiency of 63% and energy efficiency of 16% was achieved for a 3.0 mol kg⁻¹ solution with a current density of 66 mA cm⁻² for third generation GDEs.     

Electrochemical and fuel cell evaluation of Co based catalyst for oxygen reduction in anion exchange polymer membrane fuel cells

Co based catalyst were evaluated for oxygen reduction (ORR) in liquid KOH and alkaline anion exchange membrane fuel cells (AAEMFCs). In liquid KOH solution the catalyst exhibited good performance with an onset potential 120 mV more negative than platinum and a Tafel slope of ca. 120 mV dec⁻¹. The hydrogen peroxide generated, increased from 5 to 50% as the electrode potential decreased from 175 to −300 mV vs. SHE.In an AAEMFC environment, one catalyst (GP2) showed promising performance for ORR, i.e. at 50 mA cm⁻² the differences in cell potential between the stable performance for platinum (more positive) and cobalt cathodes with air and oxygen, were only 45 and 67 mV respectively. The second catalyst (GP4) achieved the same stable power density as with platinum, of 200 and 145 mW cm⁻², with air at 1 bar (gauge) pressure and air (atm) cathode feed (60 °C), respectively. However the efficiency was lower (i.e. cell voltage was lower) i.e. 40% in comparison to platinum 47.5%.     

Performance of anode-supported solid oxide fuel cell using novel ceria electrolyte

The potential of a novel co-doped ceria material Sm_0.075Nd_0.075Ce_0.85O_2−δ as an electrolyte was investigated under fuel cell operating conditions. Conventional colloidal processing was used to deposit a dense layer of Sm_0.075Nd_0.075Ce_0.85O_2−δ (thickness 10 μm) over a porous Ni-gadolinia doped ceria anode. The current-voltage performance of the cell was measured at intermediate temperatures with 90 cm³ min⁻¹ of air and wet hydrogen flowing on cathode and anode sides, respectively. At 650 °C, the maximum power density of the cell reached an exceptionally high value of 1.43 W cm⁻², with an area specific resistance of 0.105 Ω cm². Impedance measurements show that the power density decrease with decrease in temperature is mainly due to the increase in electrode resistance. The results confirm that Sm_0.075Nd_0.075Ce_0.85O_2−δ is a promising alternative electrolyte for intermediate temperature solid oxide fuel cells.     

Polyelectrolyte complexes of chitosan and phosphotungstic acid as proton-conducting membranes for direct methanol fuel cells

Polyelectrolyte complexes (PECs) of chitosan and phosphotungstic acid have been prepared and evaluated as novel proton-conducting membranes for direct methanol fuel cells. Phosphotungstic acid can be fixed within PECs membranes through strong electrostatic interactions, which avoids the decrease of conductivity caused by the dissolving of phosphotungstic acid as previously reported. Scanning electron microscopy (SEM) shows that the PECs membranes are homogeneous and dense. Fourier transform infrared spectroscopy (FTIR) demonstrates that hydrogen bonding is formed between chitosan and phosphotungstic acid. Thermogravimetric analysis (TGA) shows that the PECs membranes have good thermal stability up to 210 °C. The PECs membranes exhibit good swelling properties and low methanol permeability (P, 3.3 × 10⁻⁷ cm² s⁻¹). Proton conductivity (σ) of the PECs membranes increases at elevated temperature, reaching the value of 0.024 S cm⁻¹ at 80 °C.     

Microstructure tailoring of YSZ/Ni-YSZ dual-layer hollow fibers for micro-tubular solid oxide fuel cell application

YSZ/NiO-YSZ dual-layer hollow fibers with a thin YSZ top layer integrated on a porous NiO-YSZ (60:40 in weight) support, have been developed by one step method via a co-spinning-sintering process. Hydrogen reduction was performed to form YSZ/Ni-YSZ micro tube as the half solid oxide fuel cells (SOFCs). The microstructure of the dual-layer hollow fibers was tailored by adding ethanol as non-solvent in the initial mixture dopes for NiO-YSZ anode spinning. LSM cathode containing 20 wt%-YSZ was deposited on the electrolyte surface by dip-coating method to fabricate micro-tubular SOFCs. Experimental results indicate that the dual-layer hollow fibers from the anode dopes containing 15–20 wt% of ethanol possess the desired microstructure with optimized properties, such as the bending strength of 180 MPa, the porosity of 38–35% and the conductivity of 3000 S cm⁻¹ at room temperature. The micro-tubular SOFCs fabricated from such hollow fibers show a maximum power density up to 485 mW cm⁻² at 850 °C with 20 mL min⁻¹ of H₂ as fuel and 30 mL min⁻¹ air as oxidant, respectively.     

Hydrogen generation utilizing alkaline sodium borohydride solution and supported cobalt catalyst

Supported Co catalysts with different supports were prepared for hydrogen generation (HG) from catalytic hydrolysis of alkaline sodium borohydride solution. As a result, we found that a γ-Al₂O₃ supported Co catalyst was very effective because of its special structure. A maximum HG rate of 220 mL min⁻¹ g⁻¹ catalyst and approximately 100% efficiency at 303 K were achieved using a Co/γ-Al₂O₃ catalyst containing 9 wt.% Co. The catalyst has quick response and good durability to the hydrolysis of alkaline NaBH₄ solution. It is feasible to use this catalyst in hydrogen generators with stabilized NaBH₄ solutions to provide on-site hydrogen with desired rate for mobile applications, such as proton exchange membrane fuel cell (PEMFC) systems.     

Passive cathodic water/air management device for micro-direct methanol fuel cells

A high efficient passive water/air management device (WAMD) is proposed and successfully demonstrated in this paper. The apparatus consists of cornered micro-channels and air-breathing windows with hydrophobicity arrangement to regulate liquids and gases to flow on their predetermined pathways. A high performance water/air separation with water removal rate of about 5.1 μl s⁻¹ cm⁻² is demonstrated. The performance of the proposed WAMD is sufficient to manage a cathode-generated water flux of 0.26 μl s⁻¹ cm⁻² in the micro-direct methanol fuel cells (μDMFCs) which are operated at 100 mW cm⁻² or 400 mA cm⁻². Furthermore, the condensed vapors can also be collected and recirculated with the existing micro-channels which act as a passive water recycling system for μDMFCs. The durability testing shows that the fuel cells equipped with WAMD exhibit improved stability and higher current density.     

A novel design of solid-state NaBH4 composite as a hydrogen source for 2 W PEMFC applications

Hydrolysis of sodium borohydride (NaBH₄) is a promising method for on-board hydrogen supply to polymer electrolyte membrane fuel cells (PEMFC). This article presents an attempt to design a novel solid-state NaBH₄ composite, which is made up of NaBH₄ powder, Co²⁺/IR-120 catalyst and silicone rubber, for hydrogen generator. The silicone rubber can act as a stabilizer in the solid-state NaBH₄ composite because of its surface hydrophobicity leading to reduced diffusion rate of water into the composite. The solid-state NaBH₄ composite can produce hydrogen stably near 25 mL min⁻¹ for at least 2 h without employment of any mechanical control system. Using the hydrogen generated from the solid-state NaBH₄ composite, a 2 W PEMFC stack is successfully operated to power a cellular phone.     

Characterization of direct methanol fuel cell (DMFC) applications with H2SO4 modified chitosan membrane

Chitosan (Chs) flakes were prepared from chitin materials that were extracted from the exoskeleton of Cape rock lobsters in South Africa. The Chs flakes were prepared into membranes and the Chs membranes were modified by cross-linking with H₂SO₄. The cross-linked Chs membranes were characterized for the application in direct methanol fuel cells. The Chs membrane characteristics such as water uptake, thermal stability, proton resistance and methanol permeability were compared to that of high performance conventional Nafion 117 membranes. Under the temperature range studied 20-60 °C, the membrane water uptake for Chs was found to be higher than that of Nafion. Thermal analysis revealed that Chs membranes could withstand temperature as high as 230 °C whereas Nafion 117 membranes were stable to 320 °C under nitrogen. Nafion 117 membranes were found to exhibit high proton resistance of 284 s cm⁻¹ than Chs membranes of 204 s cm⁻¹. The proton fluxes across the membranes were 2.73 mol cm⁻² s⁻¹ for Chs- and 1.12 mol cm⁻² s⁻¹ Nafion membranes. Methanol (MeOH) permeability through Chs membrane was less, 1.4 × 10⁻⁶ cm² s⁻¹ for Chs membranes and 3.9 × 10⁻⁶ cm² s⁻¹ for Nafion 117 membranes at 20 °C. Chs and Nafion membranes were fabricated into membrane electrode assemblies (MAE) and their performances measure in a free-breathing commercial single cell DMFC. The Nafion membranes showed a better performance as the power density determined for Nafion membranes of 0.0075 W cm⁻² was 2.7 times higher than in the case of Chs MEA.     

Direct borohydride fuel cell using Ni-based composite anodes

In this study, nickel-based composite anode catalysts consisting of Ni with either Pd on carbon or Pt on carbon (the ratio of Ni:Pd or Ni:Pt being 25:1) were prepared for use in direct borohydride fuel cells (DBFCs). Cathode catalysts used were 1 mg cm⁻² Pt/C or Pd electrodeposited on activated carbon cloth. The oxidants were oxygen, oxygen in air, or acidified hydrogen peroxide. Alkaline solution of sodium borohydride was used as fuel in the cell. High power performance has been achieved by DBFC using non-precious metal, Ni-based composite anodes with relatively low anodic loading (e.g., 270 mW cm⁻² for NaBH₄/O₂ fuel cell at 60 °C, 665 mW cm⁻² for NaBH₄/H₂O₂ fuel cell at 60 °C). Effects of temperature, oxidant, and anode catalyst loading on the DBFC performance were investigated. The cell was operated for about 100 h and its performance stability was recorded.