Scandia-stabilized zirconia-impregnated (La,Sr)MnO3 cathode for tubular solid oxide fuel cells

We have studied the properties of a LSM-ScSZ composite cathode fabricated by a two-step process including dip-coating LSM framework and ion-impregnating ScSZ, for using with anode-supported tubular solid oxide fuel cells. A preliminary examination of the single tubular cell, consisting of a Ni-YSZ anode support tube, a Ni-ScSZ anode functional layer, a ScSZ electrolyte film, and a LSM-ScSZ cathode fabricated by ion-impregnating, has been carried out, and an improved performance was obtained. The polarization resistance of the cathode side clearly decreased for impregnating the electronic conducting phase (LSM) with the ionic conducting phase (ScSZ). And the single cell with the impregnated cathode generated a maximum power density of 433 mW cm⁻² at 850 °C, when operating with humidified hydrogen.     

A direct-methane solid oxide fuel cell with a double-layer anode

A tubular anode-supported solid oxide fuel cell with a double-layer anode for the direct conversion of CH₄ has been prepared and operated at 800 °C successfully. The double-layer anode was composed of NiO–YSZ and CoO–NiO–SDC acting as supporting layer and active reforming layer, respectively. At 800 °C, a maximum power density of 350 mW cm⁻² was obtained with CH₄ as fuel and air as oxidant. The time-dependent impedance spectra of the tubular cell were examined and discussed. No carbon deposition was observed on the surface of the anode when the cell was operated at a constant current density of 250 mA cm⁻².     

Improvement in performance of a direct ethanol fuel cell: Effect of sulfuric acid and Ni-mesh

A direct ethanol fuel cell (DEFC) is developed with low catalyst loading at anode and cathode compared to that reported in the literature. Pt/Ru (40%:20% by wt.)/C and Pt-black were used as anode and cathode catalyst with loadings in the range of 0.5–1.2 mg/cm². The temperatures of anode and cathode were varied from 34 °C to 110 °C, and the pressure was maintained at 1 bar. Although low catalyst loading was used, the cell performance is enhanced by 40–50% with the use of low concentration of sulfuric acid in ethanol and Ni-mesh as current collector at the anode. The power density 15 mW/cm² at 32 mA/cm² of current density is obtained from the single cell with 0.5 mg/cm² loading of Pt–Ru/C at anode (90 °C) and Pt-black at cathode (110 °C). The performance of DEFC increases with the increase in ethanol and sulfuric acid concentrations, electrocatalyst loadings up to 1 mg cm⁻² at anode and cathode. However, the performance of DEFC decreases with further increase in electrocatalyst loading.     

A novel single phase cathode material for a proton-conducting SOFC

A novel single phase BaCe_0.5Bi_0.5O_3 ? δ (BCB) was employed as a cathode material for a proton-conducting solid oxide fuel cell (SOFC). The single cell, consisting of a BaZr_0.1Ce_0.7Y_0.2O_3 ? δ (BZCY7)-NiO anode substrate, a BZCY7 anode functional layer, a BZCY7 electrolyte membrane and a BCB cathode layer, was assembled and tested from 600 to 700 °C with humidified hydrogen (～3% H₂O) as the fuel and the static air as the oxidant. An open-circuit potential of 0.96 V and a maximum power density of 321 mW cm^?2 were obtained for the single cell. A relatively low interfacial polarization resistance of 0.28Ω cm² at 700 °C indicated that the BCB was a promising cathode material for proton-conducting SOFCs.     

A novel single electrode supported direct methanol fuel cell

In this paper a single electrode supported direct methanol fuel cell (DMFC) is fabricated and tested. The novel architecture combines the elimination of the polymer electrolyte membrane (PEM) and the integration of the anode and cathode into one component. The thin film fabrication involves a sequential deposition of an anode catalyst layer, a cellulose acetate electronic insulating layer and a cathode catalyst layer onto a single carbon fibre paper substrate. The single electrode supported DMFC has a total thickness of 3.88 × 10^?2 cm and showed a 104% improvement in volumetric specific power density over a two electrode DMFC configuration under passive conditions at ambient temperature and pressure (1 atm, 25 °C).     

Optimization on fabrication and performance of A-site-deficient La0.58Sr0.4Co0.2Fe0.8O3-δ cathode for SOFC

A-site-deficient perovskite cathode material La_0.58Sr_0.4Co_0.2Fe_0.8O_3 − δ (L58SCF) is coated on the yttria-stabilized zirconia electrolyte by screen-printing technique. Several key fabrication parameters including selection of additives (binder and pore former), effect of coating thickness, sintering temperature and time on the microstructure, and electrochemical performance of cathode are investigated by scanning electron microscopy and electrochemical impedance spectroscopy. We study the microstructure and the electrochemical property of the cathode with different kinds of additives. Results show that the cathode possesses fine microstructure, enough porosity, and ideal electrochemical property when polyvinyl butyral serves as both binder and pore former in the cathode. The cathode with three screen-printing coats (thickness 28 ± 7 μm, weight 6.07 ± 0.72 mg cm⁻²) sintering at 1,000 °C for 2 h shows lower polarization resistance of 0.183 Ω cm² at 800 °C. Based on the optimized parameters, the polarization resistances of the L58SCF–Ce_0.8Gd_0.2O_{1.9 – δ} composite cathode display the R _p values of 0.067 Ω cm² at 800 °C, 0.106 Ω cm² at 750 °C, 0.225 Ω cm² at 700 °C, and 0.550 Ω cm² at 650 °C.     

Cost-effective solid oxide fuel cell prepared by single step co-press-firing process with lithiated NiO cathode

A cost-effective cell fabrication process was developed for intermediate temperature solid oxide fuel cells (IT-SOFCs). Co-doped ceria Ce_0.8Gd_0.05Y_0.15O_1.9 (GYDC) was synthesized by carbonate co-precipitation method. Lithiated NiO was prepared by glycine-nitrate combustion method and adopted as cathode material for IT-SOFCs. Single cell was fabricated by one-step dry-pressing and co-firing anode, anode functional layer (AFL), electrolyte and cathode together at 1200 °C for 4 h. The cell presented decent performance and an overall electrode polarization resistance of 0.54 Ω cm² has been achieved at 600 °C. These results demonstrate the possibility of using lithiated NiO as cathode material for ceria-based IT-SOFCs and the development of affordable fuel cell devices is encouraged.     

Kinetics for the Oxygen Evolution Reaction and Application of the Ti/SnO<Subscript>2</Subscript> + RuO<Subscript>2</Subscript> + MnO<Subscript>2</Subscript> Electrode

A Ti/SnO₂ + RuO₂ + MnO₂ electrode was prepared by thermal decomposition of their salts. Results from SEM and XPS analyses, respectively, indicate that the coating layer exhibits a compact structure and the oxidation state of Mn in the coating layer is +IV. The experimental activation energy for the oxygen evolution reaction, which increased linearly with increasing overpotential, is about 8 kJ⋅mol⁻¹ at the equilibrium potential (η=0). The electrocatalytic characteristics of the anode are discussed in terms of ligand substitution reaction mechanisms (Sn1 and Sn2). It was found that the transition state for oxygen evolution at the anode in acidic solution follows a dissociative mechanism (Sn1 reaction). The Ti/SnO₂ + RuO₂ + MnO₂ anode in conjunction with UV illumination was used to degrade phenol solutions, where the concentration of phenol remaining was determined by high-performance liquid chromatography (HPLC). The results indicate that the degradation efficiency of phenol on the anode can reach 96.3% after photoelectrocatalytic oxidation for 3 h.     

Study of transition metal oxide doped LaGaO3 as electrode materials for LSGM-based solid oxide fuel cells

Transition metal oxide doped lanthanum gallates, La_0.9Sr_0.1Ga_0.8M_0.2O₃ (where M=Co, Mn, Cr, Fe, or V), are studied as mixed ionic-electronic conductors (MIECs) for electrode applications. The electrochemical properties of these materials in air and in H₂ are characterized using impedance spectroscopy, open cell voltage measurement, and gas permeation measurement. Three single cells based on La_0.9Sr_0.1Ga_0.8 Mg_0.2O₃ (LSGM) electrolyte (1.13 to 1.65 mm thick) but with different electrode materials are studied under identical conditions to characterize the effectiveness of the lanthanum gallate-based MIECs for electrode applications. At 800 °C, a single cell using La_0.9Sr_0.1- Ga_0.8Co_0.2O₃ as the cathode and La_0.9Sr_0.1Ga_0.8Mn_0.2O₃ as the anode shows a maximum power density of 88 mW/cm², which is better than that of a cell using Pt as both electrodes (20 mW/cm²) and that of a cell using La_0.6Sr_0.4CoO₃ (LSC) as the cathode and CeO₂-Ni as the anode (61 mW/cm²) under identical conditions. The performance of LSGM-based fuel cells with MIEC electrodes may be further improved by reducing the electrolyte thickness and by optimizing the microstructures of the electrodes through processing. Received: 9 January 1998 / Accepted: 1 May 1998     

Effect of the cathode structure on the electrochemical performance of anode-supported solid oxide fuel cells

The study elementarily investigated the effect of the cathode structure on the electrochemical performance of anode-supported solid oxide fuel cells. Four single cells were fabricated with different cathode structures, and the total cathode thickness was 15, 55, 85, and 85 μm for cell-A, cell-B, cell-C, and cell-D, respectively. The cell-A, cell-B, and cell-D included only one cathode layer, which was fabricated by ( \textLa_0.74 \textBi_0.10 \textSr_0.16 )\textMnO_{3 - d} \left( {{\text{La}}_{0.74} {\text{Bi}}_{0.10} {\text{Sr}}_{0.16} } \right){\text{MnO}}_{{3 - \delta }} (LBSM) electrode material. The cathode of the cell-C was composed of a ( \textLa_0.74 \textBi_0.10 \textSr_0.16 )\textMnO_{3 - d} - ( \textBi_0.7 \textEr_0.3 \textO_1.5 ) \left( {{\text{La}}_{0.74} {\text{Bi}}_{0.10} {\text{Sr}}_{0.16} } \right){\text{MnO}}_{{3 - \delta }} - \left( {{\text{Bi}}_{0.7} {\text{Er}}_{0.3} {\text{O}}_{1.5} } \right) (LBSM–ESB) cathode functional layer and a LBSM cathode layer. Different cathode structures leaded to dissimilar polarization character for the four cells. At 750°C, the total polarization resistance (R _p) of the cell-A was 1.11, 0.41 and 0.53 Ω cm² at the current of 0, 400, and 800 mA, respectively, and that of the cell-B was 1.10, 0.39, and 0.23 Ω cm² at the current of 0, 400, and 800 mA, respectively. For cell-C and cell-D, their polarization character was similar to that of the cell-B and R _p also decreased with the increase of the current. The maximum power density was 0.81, 1.01, 0.79, and 0.43 W cm⁻² at 750°C for cell-D, cell-C, cell-B, and cell-A, respectively. The results demonstrated that cathode structures evidently influenced the electrochemical performance of anode-supported solid oxide fuel cells.     

A completely spray-coated membrane electrode assembly

We present a proton exchange membrane fuel cell (PEMFC) manufacturing route, in which a thin layer of polymer electrolyte solution is spray-coated on top of gas diffusion electrodes (GDEs) to work as a proton exchange membrane. Without the need for a pre-made membrane foil, this allows inexpensive, fast, large-scale fabrication of membrane-electrode assemblies (MEAs), with a spray-coater comprising the sole manufacturing device. In this work, a catalyst layer and a membrane layer are consecutively sprayed onto a fibrous gas diffusion layer with applied microporous layer as substrate. A fuel cell is then assembled by stacking anode and cathode half-cells with the membrane layers facing each other. The resultant fuel cell with a low catalyst loading of 0.1 mg Pt/cm² on each anode and cathode side is tested with pure H₂ and O₂ supply at 80 °C cell temperature and 92% relative humidity at atmospheric pressure. The obtained peak power density is 1.29 W/cm² at a current density of 3.25 A/cm². By comparison, a lower peak power density of 0.93 W/cm² at 2.2 A/cm² is found for a Nafion NR211 catalyst coated membrane (CCM) reference, although equally thick membrane layers (approx. 25 μm), and identical catalyst layers and gas diffusion media were used. The superior performance of the fuel cell with spray-coated membrane can be explained by a decreased low frequency (mass transport) resistance, especially at high current densities, as determined by electrochemical impedance spectroscopy.     

Development of micro-tubular SOFCs with an improved performance via nano-Ag impregnation for intermediate temperature operation

Micro-tubular solid-oxide fuel cell consisting of a 10-μm thick (ZrO₂)_0.89(Sc₂O₃)_0.1(CeO₂)_0.01 (ScSZ) electrolyte on a support NiO/(ScSZ) anode (1.8 mm diameter, 200 μm wall thickness) with a Ce_0.8Gd_0.2O_1.9 (GDC) buffer-layer and a La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)/GDC functional cathode has been developed for intermediate temperature operation. The functional cathode was in situ formed by impregnating the well-dispersed nano-Ag particles into the porous LSCF/GDC layer using a citrate method. The cells yielded maximum power densities of 1.06 W cm⁻² (1.43 A cm⁻², 0.74 V), 0.98 W cm⁻² (1.78 A cm⁻², 0.55 V) and 0.49 W cm⁻² (1.44 A cm⁻², 0.34 V), at 650, 600 and 550 °C, respectively.     

Improved sintering and electrical properties of La-doped CeO<Subscript>2</Subscript> buffer layer for intermediate temperature solid oxide fuel cells using doped LaGaO<Subscript>3</Subscript> film prepared by screen printing process

Effects of a sintering agent for La-doped ceria (LDC) as a buffer layer to prevent a chemical reaction between Ni in anode and Sr- and Mg-doped lanthanum gallate (LSGM) electrolyte during sintering were studied for improving sintering and electrical properties. Electrochemical performance of anode-supported solid oxide fuel cells (SOFCs) using LDC and LSGM films prepared by screen printing and co-sintering (1,350 °C) was also investigated. The prepared cell with dense LDC (ca. 17 μm) and LSGM electrolyte (ca. 60 μm) films showed an open circuit voltage close to the theoretical value of 1.10 V and a high maximum power density (0.831 W cm^–2) at 700 °C. The addition of 1 wt.% LSGM to porous LDC buffer layer was effective for improving the sintering density and electrical conductivity, resulting in the high power density due to the decreased internal resistance loss.     

Effect of nanoscale CeO<Subscript>2</Subscript> on PVDF-HFP-based nanocomposite porous polymer electrolytes for Li-ion batteries

New poly (vinylidenefluoride-co-hexafluoro propylene) (PVDF-HFP)/CeO₂-based microcomposite porous polymer membranes (MCPPM) and nanocomposite porous polymer membranes (NCPPM) were prepared by phase inversion technique using N-methyl 2-pyrrolidone (NMP) as a solvent and deionized water as a nonsolvent. Phase inversion occurred on the MCPPM/NCPPM when it is treated by deionized water (nonsolvent). Microcomposite porous polymer electrolytes (MCPPE) and nanocomposite porous polymer electrolytes (NCPPE) were obtained from their composite porous polymer membranes when immersed in 1.0 M LiClO₄ in a mixture of ethylene carbonate/dimethyl carbonate (EC/DMC) (v/v = 1:1) electrolyte solution. The structure and porous morphology of both composite porous polymer membranes was examined by scanning electron microscope (SEM) analysis. Thermal behavior of both MCPPM/NCPPM was investigated from DSC analysis. Optimized filler (8 wt% CeO₂) added to the NCPPM increases the porosity (72%) than MCPPM (59%). The results showed that the NCPPE has high electrolyte solution uptake (150%) and maximum ionic conductivity value of 2.47 × 10⁻³ S cm⁻¹ at room temperature. The NCPPE (8 wt% CeO₂) between the lithium metal electrodes were found to have low interfacial resistance (760 Ω cm²) and wide electrochemical stability up to 4.7 V (vs Li/Li⁺) investigated by impedance spectra and linear sweep voltammetry (LSV), respectively. A prototype battery, which consists of NCPPE between the graphite anode and LiCoO₂ cathode, proves good cycling performance at a discharge rate of C/2 for Li-ion polymer batteries.     

Anode performance of Mn-doped ceria–ScSZ for solid oxide fuel cell

The 70 wt.% Mn-doped CeO₂ (MDC)-30 wt.% Scandia-stabilized zirconia (ScSZ) composites are evaluated as anode materials for solid oxide fuel cells (SOFCs) in terms of chemical compatibility, thermal expansion coefficient, electrical conductivity, and fuel cell performance in H₂ and CH₄. The conductivity of MDC10 (10 mol.% Mn-doping), MDC20, and CeO₂ are 4.12, 2.70, and 1.94 S cm⁻¹ in H₂ at 900 °C. With 10 mol.% Mn-doping, the fuel cells performances improve from 166 to 318 mW cm⁻² in H₂ at 900 °C. The cell with MDC10–ScSZ anode exhibits a better performance than the one with MDC20–ScSZ in CH₄, the maximum power density increases from 179 to 262 mW cm⁻². Electrochemical impedance spectra indicate that the Mn doping into CeO₂ can reduce the ohmic and polarization resistance, thus leading to a higher performance. The results demonstrate the potential ability of MDC10–ScSZ composite to be used as SOFCs anode.     

Voltammetric investigation and amperometric detection of the bisphosphonate drug sodium alendronate using a copper nanoparticles-modified electrode

The electrochemical behavior of sodium alendronate on copper microparticle- and copper nanoparticle-modified carbon paste electrodes was investigated. In the voltammograms recorded using microparticles, a single anodic oxidation peak appeared, while using nanoparticles, two anodic peaks appeared. The anodic currents were related to the electrocatalytic oxidation of alendronate via the active species of Cu(III). The catalytic rate constant for the electrocatalytic oxidation process and the diffusion coefficient of alendronate were obtained to be 1.57 × 10³ cm³ mol⁻¹ s⁻¹ and 2.44 × 10⁻⁶ cm² s⁻¹, respectively. A sensitive and time-saving detection procedure was developed for the analysis of alendronate, and the corresponding analytical parameters were reported. Alendronate was determined with a limit of detection of 11.26 μmol L⁻¹ with a linear range of 50–6,330 μmol L⁻¹. The proposed amperometric method was applied to the analysis of commercial pharmaceutical tablets, and the results were in good agreement with the declared values.     

An ion mobility spectrometer sensor system for subsurface use

An ion mobility spectrometer (IMS) probe system for real-time, subsurface soil-gas sampling applications is presented. The system includes an IMS and supporting electronics encased in a 51 mm diameter stainless steel probe housing. The IMS was challenged in the laboratory with 2,6-di-tert-butylpyridine (DtBP) and tetrachloroethylene (PCE) in zero air yielding reduced ion mobility constants (K_o) values of 1.42 cm²/Vs (n = 3) and 1.79 ± 0.01 cm²/Vs (n = 3), respectively. A resolving power of 38 and 31 was obtained for DtBP and PCE, respectively. The system was deployed at a PCE-contaminated site to demonstrate its performance under field conditions. PCE was detected in the vapor samples as evidenced by peaks with a K_o value of 1.80 ± 0.01 cm²/Vs for two measurements that were taken 6 min apart. The presence of PCE at the contaminated site was confirmed by GC-MS analysis of a gas sample at an EPA-certified laboratory, suggesting that this IMS system can be used to detect PCE under field conditions.     

Concentric glucose/O2 biofuel cell

A concentric glucose/O₂ biofuel cell has been developed. The device is constituted of two carbon tubular electrodes, one in the other, and combines glucose electrooxidation at the anode and oxygen electroreduction at the cathode. The anodic catalyst is glucose oxidase co-immobilized with the mediator 8-hydroxyquinoline-5-sulfonic acid hydrate, and the cathodic catalyst is bilirubin oxidase co-immobilized with the mediator 2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt. Both enzymes and mediators are entrapped at the surface of the tubular electrodes by an electrogenerated polypyrrole polymer. The originality of the concentric configuration is to compartmentalize the anode and cathode electrodes and to supply dissolved oxygen separate from the electrolyte in order to avoid secondary reactions. The dissolved oxygen circulates through the inside of the cathode tube and diffuses from the inner to the external surface of the tube to react directly with the immobilized bilirubin oxidase. The assembled biofuel cell is studied at 37 °C in phosphate buffer pH 7.4. We show the influence of the thickness of the polypyrrole polymer on the electrochemical activity of the biocathodes. We also demonstrate the effect of the chemical reticulation of the enzymes by glutaraldehyde within the polymer on the performances of the bioelectrodes. The maximum power density delivered by the assembled glucose/O₂ biofuel cell reaches 42 μW cm⁻², evaluated from the geometric area of the electrodes, at a cell voltage of 0.30 V with 10 mM glucose. The results demonstrate that the concentric design of the BFC based on compartmented electrodes is a promising architecture for further development of micro electronic devices.     

MEA with double-layered catalyst cathode to mitigate methanol crossover in DMFC

Methanol permeation is one of the key problems for direct methanol fuel cell (DMFC) applications. It is necessary to change the structure of the cathode of membrane electrode assembly (MEA). Therefore, a novel MEA with double-layered catalyst cathode was prepared in this paper. The double-layered catalyst consists of PtRu black as inner catalyst layer and Pt black as outer catalyst layer. The inner catalyst layer is prepared for oxidation of the methanol permeated from anode. The results indicate that this double-layered catalyst reduced the effects of methanol crossover and assimilated mixed potential losses. The performance of MEA with double-layered catalyst cathode was 52.2 mW cm⁻², which was a remarkable improvement compared with the performance of MEA with traditional cathode. The key factor responsible for the improved performance is the optimization of the electrode structure.     

Electrocatalytic activity and stability of Ti/IrO2 + MnO2 anode in 0.5 M NaCl solution

Ti/IrO₂(x) + MnO₂(1-x) anodes have been fabricated by thermal decomposition of a mixed H₂IrCl₆ and Mn(NO₃)₂ hydrosolvent. Cyclic voltammetry (CV) and polarization curve have been utilized to investigate the electrochemical behavior and electrocatalytic activity of Ti/IrO₂(x) + MnO₂(1-x) anodes in 0.5 M NaCl solution (pH = 2). Ti/IrO₂+MnO₂ anode with 70 mol% IrO₂ content has the maximum value of q*, indicating that Ti/IrO₂(0.7) + MnO₂(0.3) anode has the most excellent electrocatalytic activity for the synchronal evolution of Cl₂ and O₂ in dilute NaCl solution. Tafel lines displayed two distinct linear regions with one of the slope close to 62 mV dec⁻¹ in the low potential region and the other close to 295 mV dec⁻¹ in the high potential region. Electrochemical impedance spectroscopic is employed to investigate the impedance behavior of Ti/IrO₂(x) + MnO₂(1-x) anodes in 0.5 M NaCl solution. It is observed that as the R _ct, R _s and R _f values for Ti/IrO₂(0.7) + MnO₂(0.3) anode become smaller, electrocatalytic activity of Ti/IrO₂(0.7) + MnO₂(0.3) anode becomes better than that of other Ti/IrO₂ + MnO₂ anodes with different compositions. Ti/IrO₂(0.7) + MnO₂(0.3) anode fabricated at 400 °C has been observed to possess the highest service life of 225 h, whereas the accelerated life test is carried out under the anodic current of 2 A cm⁻² at the temperature of 50 °C in 0.5 M NaCl solution (pH = 2).