Hydrogen formation from a real biogas using electrochemical cell with gadolinium-doped ceria porous electrolyte

The electrochemical cell consisting of a gadolinium-doped ceria (GDC, Ce_0.9Gd_0.1O_1.95) porous electrolyte, Ni–GDC cathode and Ru–GDC anode was applied for the dry-reforming (CH₄+CO₂→2H₂+2CO) of a real biogas (CH₄ 60.0%, CO₂ 37.5%, N₂ 2.5%) produced from waste sweet potato. The composition of the supplied gas was adjusted to CH₄/CO₂=1/1 volume ratio. The supplied gas changed continuously into a H₂–CO mixed fuel with H₂/CO=1/0.949–1/1.312 vol ratios at 800 °C for 24 h under the applied voltage of 1–2 V. The yield of the mixed fuel was higher than 80%. This dry-reforming reaction was thermodynamically controlled at 800 °C. The application of external voltage assisted the reduction of NiO and the elimination of solid carbon deposited slightly in the cathode. The decrease of heating temperature to 700 °C reduced gradually the fraction of the H₂–CO fuel (61.3–18.6%) within 24 h. Because the Gibbs free energy change was calculated to be negative values at 700–600 °C, the above result at 700–600 °C originated from the gradual deposition of carbon over Ni catalyst through the competitive parallel reactions (CH₄→C+2H₂, 2CO→C+CO₂). The application of external voltage decreased the formation temperature of carbon by the disproportionation of CO gas. At 600 °C, the H₂–CO fuel based on the Faraday's law was produced continuously by the electrochemical reforming of the biogas.     

Electrochemical reforming of CH4−CO2 mixed gas using porous Gd-doped ceria electrolyte with Cu electrode

This paper reports on the composition and flow rate of outlet gas and current density during the reforming of CH₄ with CO₂ using three different electrochemical cells: cell A, with Ni−GDC (Gd-doped ceria: Ce_0.8Gd_0.2O_1.9) cathode/porous GDC electrolyte/Cu−GDC anode, cell B, with Cu−GDC cathode/ porous GDC electrolyte/Cu−GDC anode and cell C, with Ru−GDC cathode/ porous GDC electrolyte/ Cu−GDC anode. In the cathode, CO₂ reacts with supplied electrons to form CO fuel and O²⁻ ions (CO₂+2e⁻→CO+O²⁻). Too low affinity of Cu cathode to CO₂ in cell B reduced the reactivity of the CO₂ with electrons. The CO fuel, O²⁻ ions and CH₄ gas were transported to the anode through the porous GDC mixed conductor of O²⁻ ions and electrons. In the anode, CH₄ reacts with O²⁻ ions to produce CO and H₂ fuels (CH₄+O²⁻→2 H₂+CO+2e⁻). The reforming efficiency at 700−800 °C was lowest in cell B and highest in cell A. The Cu anode in cells A and C worked well to oxidize CH₄ with O²⁻ ions (2Cu+O²⁻→Cu₂O+2e⁻, Cu₂O+CH₄→2Cu+CO+2H₂). However, a blockage of the outlet gas occurred in all the cells at 700−800 °C. The gas flow is inhibited due to a reduction in pore size in the cermet cathode, as well as sintering and grain growth of Cu metal in the anode during the reforming.     

Characterization of IT-SOFC non-symmetrical anode sintered through conventional furnace and microwave

This work investigated the mechanical and electrical properties of NiO–SDC/SDC anode sintered by two different methods: in a microwave at about 1200 °C for 1 h and in a conventional furnace at 1200 °C with a holding time of 1 h (total sintering time of 21 h). Nano-powders Sm_0.2Ce_0.8O_1.9 (SDC) and NiO were mixed using a high-energy ball mill, followed by the co-pressing technique at a compaction pressure of 400 MPa. No binder was used between the layers. The electrical behaviors of all sintered samples were studied using electrochemical impedance spectra in the frequency range of 0.01–10⁵ Hz under 97% H₂–3% H₂O, an amplitude of 10 mV, and at high temperature range of 600–800 °C. Results indicate that the non-symmetrical NiO–SDC/SDC anode achieved through microwave sintering has finer grain size and higher electrochemical performance. However, hardness and Young׳s modulus increased in the samples sintered through a conventional furnace.     

Proton conducting solid oxide fuel cells with chemically stable BaZr0.75Y0.2Pr0.05O3-δ electrolyte

A BaZrO₃-based electrolyte with low Pr-doping concentration is proposed as electrolyte for proton-conducting solid oxide fuel cells (SOFCs). The new material BaZr_0.75Y_0.2Pr_0.05O_3-δ (BZYP5) shows a good chemical stability against CO₂. In addition, the low doping concentration of Pr in BaZrO₃ improves the sinterability of BaZrO₃ and also allows its structure to remain stable even in the reducing atmosphere, which is critical for fuel cell applications. The cell with BZYP5 as electrolyte shows maximum power densities of 124, 70, and 43 mW cm⁻² at 600, 550, and 500 °C, respectively, which are larger than that for the cell with conventional high Pr-doping BaZrO₃ electrolyte reported previously. Electrochemical analysis indicates that the BZYP5 electrolyte shows a good ionic conductivity. These results suggest that the low Pr-doping strategy presented in this study promotes the densification for BaZrO₃ and the good electrolyte conductivity of BaZrO₃ is maintained which could be the reason for the improved cell performance, suggesting BZYP5 is a promising electrolyte for proton-conducting SOFCs.     

Phase change and electrical resistivity of Zn–Mn–Ni–O-based NTC thermistors produced using IZC powder recycled from used dry batteries

Zn–Mn–Ni–Oxide-based NTC thermistors with variable Ni/Mn ratios were fabricated from powder mixtures of recycled IZC, and commercial MnCO₃ and NiCO₃. Solid phases and electrical resistivity of each sintered sample were studied as a function of Ni/Mn ratio, sintering temperature and sintering time. At 1200 °C for 2 h, samples with the Ni/Mn ratios of 0.38 and higher were found to consist of cubic spinel as a major phase. After sintering at 1250 °C for 10 h, densification proceeded with a phase change from cubic spinel to tetragonal one. The electrical resistivity of the samples obtained at 1200 °C for 2 h progressively decreased with an increasing Ni/Mn ratio up to 0.38, at which the value became the lowest (4.2 × 10³ Ω cm at room temperature) of all the samples fabricated.     

Liquid-phase synthesis of SrCo0.9Nb0.1O3-δ cathode material for proton-conducting solid oxide fuel cells

A novel liquid-phase synthesis strategy is demonstrated for the preparation of the Nb-containing ceramic oxide SrCo_0.9Nb_0.1O_3-δ (SCN). In comparison with the traditional solid-state reaction (SSR) method, the liquid-phase synthesis route offers a couple of advantages, including a lower phase formation temperature and a smaller particle size of the SCN materials that are beneficial for applications as proton-conducting fuel cell cathode. With BaCe_0.4Zr_0.4Y_0.2O_3-δ (BCZY442) as the electrolyte and the SCN synthesized in this work as the cathode, a proton-conducting solid oxide fuel cell (SOFC) shows a peak power density of 348 mW cm^?2 at 700 °C, significantly higher than that of a SOFC fabricated with SCN cathode prepared using the SSR method, which can only deliver 204 mW cm^?2 at the same temperature. Additionally, this new synthesis strategy allows impregnation of Sr²⁺, Co³⁺and Nb⁵⁺ on the solid backbone in aqueous solution, further improving cell performance to reach a peak power density of 488 mW cm^?2 at 700 °C.     

Preparation and characterization of graded SSC-SDC MIEC cathode for low-temperature solid oxide fuel cells

Mixed ionic/electronic conductor (MIEC) cathodes with graded composition and microstructures have been fabricated using improved spin-coating technique. Two components, Sm_0.2Ce_0.8O_1.9 (SDC) and Sm_0.5Sr_0.5CoO₃ (SSC), were utilized to prepare the graded MIEC cathode. Graded microstructures, i.e., a SSC-rich outer layer with large interconnected pores and a SDC-rich inner layer with small interconnected pores, were observed. The corresponding single cell had an increase of 13.3% in maximum power density at operating temperature of 600 °C. The present work suggests that the graded MIEC cathode has great potential in improving performance of solid oxide fuel cells operated at lower temperature.     

Synthesis of nanocrystalline gadolinium doped ceria via sol–gel combustion and sol–gel synthesis routes

Gadolinium doped ceria (GDC) has been investigated as a promising material for application as an electrolyte in intermediate temperature solid oxide fuel cells (IT-SOFC). In this work, 10GDC powders (Gd_0.1Ce_0.9O_1.95) were synthesized by sol–gel combustion and sol–gel synthesis routes using the same complexing agents in both procedures. The thermal behavior of Gd–Ce–O precursor gels was investigated by TG–DSC measurements. X-ray diffraction (XRD) analysis was used for the characterization of phase purity and crystallinity of synthesized samples. Scanning electron microscopy (SEM) was employed for the estimation of surface morphological features. Nitrogen adsorption–desorption (BET model) was used for evaluation of specific surface area. The surface composition was determined by X-ray photoelectron spectroscopy (XPS). Electrical properties of synthesized ceramic samples were studied by means of impedance spectroscopy.     

Microstructure and electrical conductivity of fast fired Sr- and Mg-doped lanthanum gallate

La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ solid electrolytes were consolidated by fast firing aiming to investigate the effects of the sintering method on densification, microstructure and ionic conductivity. Powder mixtures were prepared by solid state reaction at 1250 and 1350 °C for 12 h, and fast fired at 1450 and 1500 °C temperatures for 5 and 10 min. The content of impurity phases was found to be quite low with this sintering method. Relatively high density (>90% of the theoretical value) and low porosity (<1.5%) were readily obtained for powder mixtures calcined at 1250 °C. The activation energy for conduction was approximately 1 eV. Specimens fast fired at 1450 °C for 10 min with a mean grain size of 2.26 µm reached the highest value of total ionic conductivity, 22 mS cm⁻¹, at 600 °C.     

Enhanced ionic conductivity of scandia-ceria-stabilized-zirconia (10Sc1CeSZ) electrolyte synthesized by the microwave-assisted glycine nitrate process

Scandia-stabilized-zirconia is a potential zirconia-based electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs). In this study, the properties of zirconia co-doped with 10 mol% Sc and 1 mol% Ce (scandia-ceria-stabilized-zirconia, 10Sc1CeSZ) electrolyte synthesized by the microwave-assisted glycine nitrate process (MW-GNP) were determined. The effects of microwave heating on the sintering temperature, microstructure, densification and ionic conductivity of the 10Sc1CeSZ electrolyte were evaluated. The phase identification, microstructure and specific surface area of the prepared powder were investigated using X-ray diffraction, transmission electron microscopy and the Brunauer-Emmett-Teller technique, respectively. Using microwave heating, a single cubic-phase powder was produced with nanosized crystallites (19.2 nm) and a high specific surface area (16 m²/g). It was found that the relative density, porosity and total ionic conductivity of the 10Sc1CeSZ electrolyte are remarkably influenced by the powder processing method and the sintering temperature. The pellet sintered at 1400 °C exhibited a maximum ionic conductivity of 0.184 S/cm at 800 °C. This is the highest conductivity value of a scandia-stabilized-zirconia based electrolyte reported in the literature for this electrolyte type. The corresponding value of the activation energy of electrical conductivity was found to be 0.94 eV in the temperature range of 500–800 °C. Overall, the use of microwave heating has successfully improved the properties of the 10Sc1CeSZ electrolyte for application in an IT-SOFC.     

Synthesis of porous iron oxide ceramics using Greek wooden templates and mill scale waste for EMI applications

The scope of this study is the synthesis of low cost iron oxide ceramics with porous structure for lightweight Electromagnetic Interference (EMI) shielding applications, using mill scale waste as the initial material, utilizing Greek wood templates. These wood-templated iron oxide (Fe₂O₃) ceramics were prepared by impregnation of inorganic precursor solution, derivated from mill scale waste, into four different kinds of Greek native wood templates; pine, fir, poplar and beech, followed by thermal treatment.Scanning Electron Microscopy (SEM) was used to investigate the microstructure of the prepared wood-templated iron oxide specimens. Their iron and oxygen contents were validated by Scanning Electron Microscopy-Energy-Dispersive X-ray Spectroscopy (SEM-EDX) and their mineralogical composition by X-ray Powder Diffractometry (XRD). The wooden substances were found to be completely removed and the synthesized Fe₂O₃ (hematite) was confirmed by XRD, as a single phase. It is also demonstrated that the structures of the iron oxide were hierarchically porous developed according to the wood templates. Moreover, the pore shape and size distribution showed a dependence on the calcination temperature and wood template. Specifically, the temperature increase from 1000 °C to 1200 °C created larger but less pores in μm scale. Finally these low cost iron oxide ceramics exhibited electrical (mainly) and magnetic properties suitable for electromagnetic shielding applications.     

Dielectric relaxation and electrical conductivity in Ca5Nb4TiO17 ceramics

The temperature dependence of dielectric properties and electrical conduction of Ca₅Nb₄TiO₁₇ ceramics were characterized in a broad temperature range. A dielectric anomaly with strong frequency dispersion was detected in the temperature range 700–1010 °C. This dielectric relaxation could be almost removed completely by annealing in an oxidizing atmosphere. Complex impedance analysis confirmed the electrical inhomogeneity of the ceramics with different contributions from the bulk and grain boundaries. This suggests that the main mechanism for the observed relaxation is the Maxwell–Wagner polarization. ac conductivity results revealed the variation of conduction mechanism with increasing temperatures from localized hopping to long-range motion of the doubly ionized oxygen vacancies.     

Fabrication and properties of Mn1.56Co0.96Ni0.48O4 free-standing ultrathin chips

Mn_1.56Co_0.96Ni_0.48O₄ (MCN) free-standing ultrathin chips are successfully fabricated by using screen printing. The structure, electrical and IR absorption properties have been investigated as a function of the sintering temperature. The X-ray diffraction, X-ray photoelectron spectroscopy and field emission scanning electron microscope analyses show remarkable improvements in crystallinity, stoichiometry and relative density for MCN chips. From the electrical experimental results, it is found that the resistivity of the chip samples sharply decreases from 2660 to 21.9 Ω cm. Such feature is attributed to the decrease in the grain boundary resistance and the increase in Mn³⁺/Mn⁴⁺ ratio with increasing sintering temperature. Furthermore, Fourier transform infrared spectra show that the absorption bands ν1 (around 1160 cm⁻¹) at 1100 °C almost disappears while the others still remain. It is ascribed to the increase in the density of samples. The intensities of symmetry bands ν2 (850 cm⁻¹) are also found to be consistent with an increase in ratio of Mn³⁺ to Mn⁴⁺ ions with increasing sintering temperature.     

Effect of temperature on the porosity, microstructure, and properties of porous La0.8Sr0.2MnO3 cathode materials

Porous La_0.8Sr_0.2MnO₃ cathode materials were prepared by the gelcasting technology. Carbon was employed to produce pores. It is shown that the open porosity decreases with increasing temperature. The proper sintering temperature is 1100 °C and the median pore size of the sample obtained at this temperature is about 460 nm. The microstructure indicates that the grain grows as the sintering temperature increases, which leads to the decrease of the number of open pores. Generally, the pores are located at multi-grain boundaries. Some closed pores appear in the sample prepared at 1100 °C and more. Both the conductivity and the interface bonding between La_0.8Sr_0.2MnO₃ and YSZ get better as the temperature increases. When the sintering temperature is more than 1250 °C, La and Mn ions begin to diffuse into YSZ, and therefore interface reactions happen. According to ln(σT)  1/T curves, E_a was calculated to be 10.18 kJ/mol.     

Influence of cobalt and sintering temperature on structure and electrical properties of BaZr0.05Ti0.95O3 ceramics

Pure and Co-modified BaZr_0.05Ti_0.95O₃ ceramics were fabricated by the traditional solid state reaction technique. The influence of cobalt and sintering temperature on structure, dielectric, ferroelectric properties and diffuse phase transition of BZT ceramics were investigated systematically. 1300 °C was the optimal sintering temperature for BZT ceramics. The solid solubility limit of Co ions in BZT matrix was determined to be 0.4 mol%. The introduction of a moderate amount of Co ions was believed to benefit the microstructure development and make the grain size more uniform. Compared with undoped counterparts, 0.4 mol% Co-modified ceramics showed equivalent ferroelectric properties with a high remnant polarization (P_r=9.6 μC/cm²) and a low coercive field (E_c=0.21 kV/mm). Besides these, a relative high dielectric coefficient (ε_r=2030) and a low dielectric loss (tan δ=1.85%) were also obtained on this composition. The degree of diffuse phase transition was enhanced by the addition of Co ions. The related mechanism of the diffused phase transition behavior was discussed.     

Enhancement of the interfacial polarization resistance of La0.6Sr0.4Co0.2Fe0.8O3-δ cathode by microwave-assisted combustion method

Thermogravimetry, phase formation, microstructural evolution, specific surface area, and electrical properties of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) cathode were studied as functions of its preparation technique. The pure perovskite LSCF cathode powder was synthesized through glycine–nitrate process (GNP) using microwave heating technique. Compared with conventional heating technique, microwave heating allows the rapid combustion to occur simultaneously between the nitrates and glycine in a controllable manner. The resulting powder is a single-phase nanocrystallite with a mean particle size of 113 nm and a high specific surface area of 12.2 m²/g, after calcination at 800 °C. Impedance analysis indicates that microwave heating has significantly reduced the polarization resistance of LSCF cathode. The area specific resistance (ASR) value of 0.059 and 0.097 Ω cm² at 800 °C and 750 °C, respectively, were observed. These values were twofold lower than the corresponding ASR of the cathode (0.133 and 0.259 Ω cm² at 800 °C and 750 °C, respectively) prepared through conventional heating. Results suggest that the microwave heating GNP strongly contributes to the enhancement of the LSCF cathode performance for intermediate temperature solid oxide fuel cells.     

Utilization of granodiorite in the production of porcelain stoneware tiles

In the present study, the use of granodiorite, as fluxing agent in a body mix for stoneware ceramic tiles production, was assessed. Four batches were formulated using clay from Khaboba, and natural granodiorite from Saint Katherine, Sinai, Egypt. The batches were tailored to completely replace both feldspatic and inert components of stoneware ceramic tiles. Densification was studied according to ISO rules, while sinterability was estimated by optical dilatometry. The dependence of microstructure and mechanical properties of stoneware ceramic tiles on granodiorite content was discussed. Strength measurements showed that increasing granodiorite content the bending strength of the bodies increased. In particular the studied batches can be used for the production of industrial fast firing tiles. The obtained ceramic tiles possess properties similar to commercial ceramic floor and/or wall tiles.     

Processing and performance of solid oxide fuel cell with Gd-doped ceria electrolyte

Fuel Cell performance was measured at 792-1095 K for Ni-GDC (Gd-doped ceria) anode-supported GDC film (60 μm thickness) with a (La_0.8Sr_0.2)(Co_0.8Fe_0.2)O₃ cathode using H₂ fuel containing 3 vol% H₂O. A maximum power density, 436 mW/cm², was obtained at 1095 K. The electrical conductivity of GDC electrolyte in N₂ atmosphere of 10⁻¹⁵-10⁰ Pa oxygen partial pressures (Po₂) at 773-1073 K was independent of Po₂, which indicated the diffusion of oxide ions. The conductivity of GDC in H₂O/H₂ atmosphere increased because of the further formation of electrons due to the dissociation of hydrogen in GDC (H₂ → 2H⁺ + 2e⁻). The hole conductivity was observed at 873 K in Po₂ = 10⁰-10⁴ Pa. The key factors in increasing power density are the increase of open circuit voltage and the suppression of H₂ fuel dissolution in GDC electrolyte. These are controlled by the cathode material and Gd-dopant composition.     

Microstructure and electromagnetic properties of LiFe5O8 ferrite ceramics prepared from wet- and dry-milled powders

The effect of dry and wet ball milling of LiFe₅O₈ ferrite powder on the microstructure and electromagnetic properties of ferrite ceramics was studied using XRD analysis, scanning electron microscopy, dilatometry, thermogravimetry, calorimetry, and measurement of specific magnetization and electrical resistance. The sintering temperature was 1050 °C; the sintering time was 2 h. It was found that ferrite fabricated from dry-milled powder exhibits an ordered α-LiFe₅O₈ phase with bulk density of 91%. Its saturation magnetization and Curie temperature are 55 emu/g and 628°С, respectively. Specific electrical resistance is 4?10⁶ Ω cm. Wet milling in isopropyl alcohol causes formation of a disordered β-LiFe₅O₈ phase. Ceramics produced by this method shows higher bulk density (97%) and low porosity, and an order of magnitude lower resistivity. Its saturation magnetization and Curie temperature are 51 emu/g and 607°С, respectively.     

Electrochemical decomposition of CO2 and CO gases using porous yttria-stabilized zirconia cell

Electrochemical decomposition of CO₂ and CO gases using a porous cell of Ru-8 mol% yttria-stabilized zirconia (YSZ) anode/porous YSZ electrolyte/Ni–YSZ cathode system at 400–800 °C was studied by analyzing the flow rate and composition of outlet gas, current density, and phases and elementary distribution of the electrodes and electrolyte. A part of CO₂ gas supplied at 50 ml/min was decomposed to solid carbon and O₂ gas through the cell at the electric field strengths of 0.9–1.0 V/cm. The outlet gas at a flow rate of 3 ml/min included 61–63% CO₂ and 37–39% O₂ at 700–800 °C and the outlet gas at a flow rate of 50 ml/min included 73–96% (average 85%) CO₂ and 4–27% (average 15%) O₂ at 800 °C. On the other hand, the supplied CO gas was also decomposed to solid carbon, O₂ and CO₂ gases at 800 °C. The fraction of outlet gas at a flow rate of 50 ml/min during the CO decomposition at 800 °C for 5 h was 11–36% CO, 59–81% O₂ and 2–9% CO₂. The detailed decomposition mechanisms of CO₂ and CO gases are discussed. Both Ni metal in the cathode and porous YSZ grains under the DC electric field have the ability to decompose CO gas into solid carbon and O²⁻ ions or O₂ gas.