Anode-supported solid oxide fuel cell with yttria-stabilized zirconia/gadolinia-doped ceria bilalyer electrolyte prepared by wet ceramic co-sintering process

To protect the ceria electrolyte from reduction at the anode side, a thin film of yttria-stabilized zirconia (YSZ) is introduced as an electronic blocking layer to anode-supported gadolinia-doped ceria (GDC) electrolyte solid oxide fuel cells (SOFCs). Thin films of YSZ/GDC bilayer electrolyte are deposited onto anode substrates using a simple and cost-effective wet ceramic co-sintering process. A single cell, consisting of a YSZ (∼3 μm)/GDC (∼7 μm) bilayer electrolyte, a La_0.8Sr_0.2Co_0.2Fe_0.8O₃–GDC composite cathode and a Ni–YSZ cermet anode is tested in humidified hydrogen and air. The cell exhibited an open-circuit voltage (OCV) of 1.05 V at 800 °C, compared with 0.59 V for a single cell with a 10-μm GDC film but without a YSZ film. This indicates that the electronic conduction through the GDC electrolyte is successfully blocked by the deposited YSZ film. In spite of the desirable OCVs, the present YSZ/GDC bilayer electrolyte cell achieved a relatively low peak power density of 678 mW cm⁻² at 800 °C. This is attributed to severe mass transport limitations in the thick and low-porosity anode substrate at high current densities.     

High power-density single-chamber fuel cells operated on methane

Single-chamber solid oxide fuel cells (SC-SOFCs) incorporating thin-film Sm_0.15Ce_0.85O_1.925 (SDC) as the electrolyte, thick Ni + SDC as the (supporting) anode and SDC + BSCF (Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ) as the cathode were operated in a mixture of methane, oxygen and helium at furnace temperatures of 500–650 °C. Because of the exothermic nature of the oxidation reactions that occur at the anode, the cell temperature was as much as 150 °C greater than the furnace temperature. Overall, the open circuit voltage was only slightly sensitive to temperature and gas composition, varying from ∼0.70 to ∼0.78 V over the range of conditions explored. In contrast, the power density strongly increased with temperature and broadly peaked at a methane to oxygen ratio of ∼1:1. At a furnace temperature of 650 °C (cell temperature ∼790 °C), a peak power density of 760 mW cm⁻² was attained using a mixed gas with methane, oxygen and helium flow rates of 87, 80 and 320 mL min⁻¹ [STP], respectively. This level of power output is the highest reported in the literature for single chamber fuel cells and reflects the exceptionally high activity of the BSCF cathode for oxygen electro-reduction and its low activity for methane oxidation.     

Operation of PEM fuel cells at 120–150 °C to improve CO tolerance

Sulfonic acid modified perfluorocarbon polymer proton exchange membrane (PEM) fuel cells operated at elevated temperatures (120–150 °C) can greatly alleviate CO poisoning on anode catalysts. However, fuel cells with these PEMs operated at elevated temperature and atmospheric pressure typically experience low relative humidity (RH) and thus have increased membrane and electrode resistance. To operate PEM fuel cells at elevated temperature and high RH, work is needed to pressurize the anode and cathode reactant gases, thereby decreasing the efficiency of the PEM fuel cell system. A liquid-fed hydrocarbon-fuel processor can produce reformed gas at high pressure and high relative humidity without gas compression. If the anode is fed with this high-pressure, high-relative humidity stream, the water in the anode compartment will transport through the membrane and into the ambient pressure cathode structure, decreasing the cell resistance. This work studied the effect of anode pressurization on the cell resistance and performance using an ambient pressure cathode. The results show that high RH from anode pressurization at both 120 and 150 °C can decrease the membrane resistance and therefore increase the cell voltage. A cell running at 150 °C obtains a cell voltage of 0.43 V at 400 mA cm⁻² even with 1% CO in H₂. The results presented here provide a concept for the application of a coupled steam reformer and PEM fuel cell system that can operate at 150 °C with reformate and an atmospheric air cathode.     

Development and testing of anode-supported solid oxide fuel cells with slurry-coated electrolyte and cathode

A laboratory setup was designed and put into operation for the development of solid oxide fuel cells (SOFCs). The whole project consisted of the preparation of the component materials: anode, cathode and electrolyte, and the buildup of a hydrogen leaking-free sample chamber with platinum leads and current collectors for measuring the electrochemical properties of single SOFCs. Several anode-supported single SOFCs of the type (ZrO₂:Y₂O₃ + NiO) thick anode/(ZrO₂:Y₂O₃) thin electrolyte/(La_0.65Sr_0.35MnO₃ + ZrO₂:Y₂O₃) thin cathode have been prepared and tested at 700 and 800 °C after in situ H₂ anode reduction. The main results show that the slurry-coating method resulted in single-cells with good reproducibility and reasonable performance, suggesting that this method can be considered for fabrication of SOFCs.     

Anode-supported solid oxide fuel cell based on dense electrolyte membrane fabricated by filter-coating

A simple and cost-effective technique, filter-coating, has been developed to fabricate dense electrolyte membranes. Eight mole percent yttria-stabilized zirconia (YSZ) electrolyte membrane as thin as 7 μm was prepared by filter-coating on a porous substrate. The thickness of the YSZ film was uniform, and could be readily controlled by the concentration of the YSZ suspension and the rate of the suspension deposition. The YSZ electrolyte film was dense and was well bonded to the Ni-YSZ anode substrate. An anode-supported solid oxide fuel cell (SOFC) with a YSZ electrolyte film and a La_0.85Sr_0.15MnO₃ (LSM) + YSZ cathode was fabricated and its performance was evaluated between 700 and 850 °C with humidified hydrogen as the fuel and ambient air as the oxidant. An open circuit voltage (OCV) of 1.09 V was observed at 800 °C, which was close to the theoretical value, and the maximum power density measured was 1050 mW cm⁻². The results demonstrate that the dense YSZ film fabricated by filter-coating is suitable for application to SOFCs.     

Dual-phase electrolytes for advanced fuel cells

Double-phase electrolyte (DPE) consisting of doped CeO₂/NiAl solid phase and NaOH liquid phase was used for fuel cells utilizing LiNiO₂ anode and Ag cathode at working temperatures over 450 °C. It was shown that the cells can produce a maximum output power of 716.2 mW cm⁻² at 590 °C even though utilized with relatively large thickness of electrolyte, from 0.8 to 1.2 mm. Most measurements of open circuit voltage (OCV) range between 1 and 1.2 V; a significantly higher OCV value of 1.254 V was also obtained. Liquid channel conductive mechanism of NaOH in DPE is proposed; both O²⁻ and H⁺ concur to conduct the current; the doped CeO₂ transports O²⁻ ions, whereas the molten second phase transports H⁺ protons. Moreover, SEM observations and EDS analysis suggest that Na⁺ and OH⁻ also contribute to enhance both OCV and output power of our cells. The addition of NiAl to the doped CeO₂ increases the mechanical strength and the output power of DPE; however the reasons of this latter effect are still to be further investigated. The results show that DPE is a promising electrolyte to manufacture fuel cells with advanced performances.     

Elaboration of a new anode material for all-solid state Zn/MnO2 protonic cells

A new composite consisting of a mixture of zinc and hydrated ammonium zinc sulfate, Tutton salt, has been elaborated and studied as anode material for all-solid state protonic cells. The results obtained point out the ability of (NH₄)₂Zn(SO₄)₂·6H₂O double salt to concomitantly exchange protons with the solid proton conducting electrolyte and accommodate Zn²⁺ cations issued from oxidation. Such features have been evinced by thermal and crystallographic characterizations. The anode composition has been optimized through a kinetic study on a three-electrode type-cell, showing that a 35 wt.% salt-based composite displays the minimum polarization. Zn/MnO₂ cells prepared using such a composite anode achieve relatively high specific capacity and energy of, more than 30 Ah kg⁻¹ and 40 Wh kg⁻¹, respectively.     

A study of Ni + 8YSZ/8YSZ/La0.6Sr0.4CoO3−δ ITSOFC fabricated by atmospheric plasma spraying

An intermediate temperature solid oxide fuel cell (ITSOFC) based on 8YSZ electrolyte, La_0.6Sr_0.4CoO_3−δ (LSCo) cathode, and Ni − 8YSZ anode coatings were consecutively deposited onto a porous Ni-plate substrate by atmospheric plasma spraying (APS). The spray parameters including current, argon and hydrogen flow rate, and powder feed rate were investigated by an orthogonal experiment to fabricate a thin gas-tight 8YSZ electrolyte coating (80 μm). By proper selection of the spray parameters to decrease the particles velocity and temperature, the sprayed NiO + 8YSZ coating after reducing with hydrogen shows a good electrocatalytic activity for H₂ oxidation. With the same treatment, 100–170 μm dimensions LSCo particle could keep phase structure after spraying. And the deposited LSCo cathode shows a good cathode performance and chemical compatibility with 8YSZ electrolyte after operating at 800 °C for 50 h. Output power density of the sprayed cell achieved 410 mW cm⁻² at 850 °C and 260 mW cm⁻² at 800 °C. Electrochemical characterization indicated that IR drop of 8YSZ electrolyte, cathodic polarization, and the contact resistance at LSCo/8YSZ interface were the main factors restricting the cell performance. The results suggested that the use of APS cell allowed the reduction of the operating temperature of the SOFC to below 850 °C with lower production costs.     

Lithium batteries composed of aluminate polymer complexes as single-ion conductive solid electrolytes

Single-ionic conductors, which display lithium ion migration exclusively (without anion migration), have been realized as the polymeric solid electrolytes with lithium orthoaluminate repeating units carrying oligo(oxyethylene) main chain and two side chains of endomethoxy{oligo(oxyethylene)}. The ionic conductivity of the aluminate polymer complexes is about 10⁻⁶–10⁻⁷ S/cm at room temperature. Thin film lithium secondary batteries were fabricated into 5.5 cm×4.5 cm×0.02–0.03 cm (thick) cells from lithium foil (anode), aluminate polymer complex (electrolyte) and TiS₂ (cathode). These batteries show minimal decay of output voltage upon constant current discharging and their capacity of first cycle was about 146 mA h/g of active cathode material. By contrast typical bi-ionic conductor of (aluminate polymer complex+5% LiClO₄) hybrid system showed, on the contrary, rapid decay of output voltage, due to polarization.     

Adhesive copper films for an air-breathing polymer electrolyte fuel cell

A design for an air-breathing and passive polymer electrolyte fuel cell is presented. Such a type of fuel cell is in general promising for portable electronics. In the present design, the anode current collector is made of a thin copper foil. The foil is provided with an adhesive and conductive coating, which firstly tightens the hydrogen compartment without mask or clamping pressure, and secondly secures a good electronic contact between the anode backing and the current collector. The cathode comprises a backing, a gold-plated stainless steel mesh and a current collector cut out from a printed circuit board. Three geometries for the cathode current collector were evaluated. Single cells with an active area of 2 cm² yielded a peak power of 250–300 mW cm⁻² with air and pure H₂ in a complete passive mode except for the controlled flow of H₂. The cells’ response was investigated in steady state and transient modes.     

Polymeric rechargeable solid-state proton battery

Rechargeable proton conducting polymeric solid-state batteries have been fabricated with the configuration Zn + ZnSO₄·7H₂O || PEO:NH₄ClO₄ + PC || V₂O₅ + PbO₂ + C + E. The maximum cell voltage is ∼1.57 V at full charge. The discharge characteristics of the cell have been studied at different loads. The cell remains stable for more than 180 h for low current drain (∼μA) making it suitable for low current density application. The cell also showed a good rechargeability which was tested for nine cycles.     

Transient phenomenon of step switching for current or voltage in PEMFC

The transient phenomenon of fuel cell with 5 cm² active area is investigated in this study by current density step increase and switching voltage under different conditions. It is found that there is an undershoot when the current density step increase is at the loading of 60% RH anode cathode, 3 stoic., 70 °C, 15 psi for automobile applications. The voltage is almost zero under 0.2 step increase to 1.0 A/cm² due to the H⁺ transport in membrane or H₂/O₂ in catalyst layer is almost used up. The undershoot phenomenon is more serious under gases stoichiometries of 3.0/3.0 when H₂ is fully humidified due to low gas concentration or flooding on the electrode. This phenomenon would induce the degradation of fuel cell components.     

NiO–YSZ cermets supported low temperature solid oxide fuel cells

Solid oxide fuel cells with thin electrolyte of two types, Sm_0.2Ce_0.8O_1.9 (SDC) (15 μm) single-layer and 8 mol% Yttria stabilized zirconia (YSZ) (5 μm) + SDC (15 μm) bi-layer on NiO–YSZ cermet substrates were fabricated by screen printing and co-firing. A Sm_0.5Sr_0.5CoO₃ cathode was printed, and in situ sintered during a cell performance test. The SDC single-layer electrolyte cell showed high electrochemical performance at low temperature, with a 1180 mW cm⁻² peak power density at 650 °C. The YSZ + SDC bi-layer electrolyte cell generated 340 mW cm⁻² peak power density at 650 °C, and showed good performance at 700–800 °C, with an open circuit voltage close to theoretical value. Many high Zr-content micro-islands were found on the SDC electrolyte surface prior to the cathode preparation. The influence of co-firing temperature and thin film preparation methods on the Zr-islands’ appearance was investigated.     

Improved electrochemical properties of a coin cell using LiMn1.5Ni0.5O4 as cathode in the 5 V range

Phase pure LiMn_1.5Ni_0.5O₄ powders were synthesized by a chemical synthesis route and were subsequently characterized as cathode materials in a Li-ion coin cell comprising a Li anode and lithium hexafluorophosphate (LiPF₆), dissolved in dimethyl carbonate (DMC) + ethylene carbonate (EC) [1:1, v/v ratio] as electrolyte. The spinel structure and phase purity of the powders were characterized using X-ray diffraction and micro-Raman spectroscopy. The presence of both oxidation and reduction peaks in the cyclic voltammogram revealed Li⁺ extraction and insertion from the spinel structure. The charge–discharge characteristics of the coin cell were performed in the 3.0–4.8 V range. An initial discharge capacity of ∼140 mAh g⁻¹ was obtained with 94% initial discharge capacity retention after 50 repeated cycles. The microstructures and compositions of the cathode before and after electrochemistry were investigated using scanning electron microscopy and energy-dispersive analysis by X-ray analysis, respectively. Using X-ray diffraction, Raman spectroscopy and electrochemical analysis, we correlated the structural stability and the electrochemical performance of this cathode.     

Source of methane and methods to control its formation in single chamber microbial electrolysis cells

Methane production occurs during hydrogen gas generation in microbial electrolysis cells (MECs), particularly when single chamber systems are used which do not keep gases, generated at the cathode, separate from the anode. Few studies have examined the factors contributing to methane gas generation or the main pathway in MECs. It is shown here that methane generation is primarily associated with current generation and hydrogenotrophic methanogenesis and not substrate (acetate). Little methane gas was generated in the initial reaction time (<12 h) in a fed batch MEC when acetate concentrations were high. Most methane was produced at the end of a batch cycle when hydrogen and carbon dioxide gases were present at the greatest concentrations. Increasing the cycle time from 24 to 72 h resulted in complete consumption of hydrogen gas in the headspace (applied voltage of 0.7 V) with methane production. High applied voltages reduced methane production. Little methane (<4%) accumulated in the gas phase at an applied voltage of 0.6–0.9 V over a typical 24 h cycle. However, when the applied voltage was decreased to 0.4 V, there was a greater production of methane than hydrogen gas due to low current densities and long cycle times. The lack of significant hydrogen production from acetate was also supported by Coulombic efficiencies that were all around 90%, indicating electron flow was not altered by changes in methane production. These results demonstrate that methane production in single chamber MECs is primarily associated with current generation and hydrogen gas production, and not acetoclastic methanogenesis. Methane generation will therefore be difficult to control in mixed culture MECs that produce high concentrations of hydrogen gas. By keeping cycle times short, and using higher applied voltages (≥0.6 V), it is possible to reduce methane gas concentrations (<4%) but not eliminate methanogenesis in MECs.     

Solid-state Li/LiFePO4 polymer electrolyte batteries incorporating an ionic liquid cycled at 40 °C

The cycle behaviour and rate performance of solid-state Li/LiFePO₄ polymer electrolyte batteries incorporating the N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₃TFSI) room temperature ionic liquid (IL) into the P(EO)₂₀LiTFSI electrolyte and the cathode have been investigated at 40 °C. The ionic conductivity of the P(EO)₂₀LiTFSI + PYR₁₃TFSI polymer electrolyte was about 6 × 10⁻⁴ S cm⁻¹ at 40 °C for a PYR₁₃⁺/Li⁺ mole ratio of 1.73. Li/LiFePO₄ batteries retained about 86% of their initial discharge capacity (127 mAh g⁻¹) after 240 continuous cycles and showed excellent reversible cyclability with a capacity fade lower than 0.06% per cycle over about 500 cycles at various current densities. In addition, the Li/LiFePO₄ batteries exhibited some discharge capability at high currents up to 1.52 mA cm⁻² (2 C) at 40 °C which is very significant for a lithium metal-polymer electrolyte (solvent-free) battery systems. The addition of the IL to lithium metal-polymer electrolyte batteries has resulted in a very promising improvement in performance at moderate temperatures.     

Screen-printed thin YSZ films used as electrolytes for solid oxide fuel cells

A thin yttria-stabilized zirconia (8 mol% YSZ) film was successfully fabricated on a NiO-YSZ anode substrate by a screen-printing technique. The scanning electron microscope (SEM) results suggested that the YSZ film thickness was about 31 μm after sintering at 1400 °C for 4 h in air. A 60 wt% La_0.7Sr_0.3MnO₃ + 40 wt% YSZ was screen-printed onto the YSZ film surface as cathode. A single cell was tested from 650 to 850 °C using hydrogen as fuel and ambient air as oxidant, which showed an open circuit voltage (OCV) of 1.02 V and a maximum power density of 1.30 W cm⁻² at 850 °C. The OCV was higher than 1.0 V, which suggested that the YSZ film was quite dense and that the fuel gas leakage through the YSZ film was negligible. Screen-printing can be a promising method for manufacturing YSZ films for solid oxide fuel cells (SOFCs).     

Improvement in high temperature proton exchange membrane fuel cells cathode performance with ammonium carbonate

Proton exchange membrane (PEM) fuel cells with optimized cathode structures can provide high performance at higher temperature (120 °C). A “pore-forming” material, ammonium carbonate, applied in the unsupported Pt cathode catalyst layer of a high temperature membrane electrode assembly enhanced the catalyst activity and minimized the mass-transport limitations. The ammonium carbonate amount and Nafion^® loading in the cathode were optimized for performance at two conditions: 80 °C cell temperature with 100% anode/75% cathode R.H. and 120 °C cell temperature with 35% anode/35% cathode R.H., both under ambient pressure. A cell with 20 wt.% ammonium carbonate and 20 wt.% Nafion^® operating at 80 °C and 120 °C presented the maximum cell performance. Hydrogen/air cell voltages at a current density of 400 mA cm⁻² using the Ionomem/UConn membrane as the electrolyte with a cathode platinum loading of 0.5 mg cm⁻² were 0.70 V and 0.57 V at the two conditions, respectively. This was a 19% cell voltage increase over a cathode without the “pore-forming” ammonium carbonate at the 120 °C operating condition.     

Sulfonated poly(ether sulfone) for universal polymer electrolyte fuel cell operations

The performances of the proton exchange membrane fuel cell (PEMFC), direct formic acid fuel cell (DFAFC) and direct methanol fuel cell (DMFC) with sulfonated poly(ether sulfone) membrane are reported. Pt/C was coated on the membrane directly to fabricate a MEA for PEMFC operation. A single cell test was carried out using H₂/air as the fuel and oxidant. A current density of 730 mA cm⁻² at 0.60 V was obtained at 70 °C. Pt–Ru (anode) and Pt (cathode) were coated on the membrane for DMFC operations. It produced 83 mW cm⁻² maximum power density. The sulfonated poly(ether sulfone) membrane was also used for DFAFC operation under several different conditions. It showed good cell performances for several different kinds of polymer electrolyte fuel cell applications.     

Dynamic behaviour of SOFC short stacks

Electrical output behaviour obtained on solid oxide fuel cell stacks, based on planar anode supported cells (50 or 100 cm² active area) and metallic interconnects, is reported. Stacks (1–12 cells) have been operated with cathode air and anode hydrogen flows between 750 and 800 °C operating temperature. At first polarisation, an activation phase (increase in power density) is typically observed, ascribed to the cathode but not clarified. Activation may extend over days or weeks. The materials are fairly resistant to thermal cycling. A 1-cell stack cycled five times in 4 days at heating/cooling rates of 100–300 K h⁻¹, showed no accelerated degradation. In a 5-cell stack, open circuit voltage (OCV) of all cells remained constant after three full cycles (800–25 °C). Power output is little affected by air flow but markedly influenced by small fuel flow variation. Fuel utilisation reached 88% in one 5-cell stack test. Performance homogeneity between cells lay at ±4–8% for three different 5- or 6-cell stacks, but was poor for a 12-cell stack with respect to the border cells. Degradation of a 1-cell stack operated for 5500 h showed clear dependence on operating conditions (cell voltage, fuel conversion), believed to be related to anode reoxidation (Ni). A 6-cell stack (50 cm² cells) delivering 100 W_el at 790 °C (1 kW_el L⁻¹ or 0.34 W cm⁻²) went through a fuel supply interruption and a thermal cycle, with one out of the six cells slightly underperforming after these events. This cell was eventually responsible (hot spot) for stack failure.