Doped Ceria Research Articles

Antimony-doped cerium ferrite: a robust photocatalyst for the mitigation of diclofenac potassium, an emerging contaminant

The present work reports an improvement in the photocatalytic performance of cerium ferrite (CeFeO3) via doping of antimony (Sb) towards the photodegradation of toxic pharmaceutical pollutant i.e. diclofenac potassium. The variable concentrations of Ce1-xSbxFeO3 (x = 0.00, 0.01, 0.03, 0.05, 0.06, 0.07, 0.09) were prepared using facile co-precipitation route and subsequently characterized for their optical, structural, morphological, and dielectric properties using various analytical techniques. It was established that an increase in Sb concentration as dopant (up to x = 0.07) reduced the optical band gap from 2.74 eV to 2.42 eV making it suitable candidate for photodegradation. The X-ray diffraction (XRD) pattern revealed orthorhombic phase of synthesized materials with small crystallite sizes in the range of 15.28 to 2.42 nm. The high value of dielectric constant (3.5841 × 106) for Ce0.93Sb0.07FeO3 with small loss tan (3.1208) compared with the CeFeO3 indicated its ability as photocatalyst to effectively store charges to make them utilize for photocatalytic activity. The degradation efficiency of Ce0.93Sb0.07FeO3 reached 86.7% in 120 min of light irradiation under optimized conditions (pH = 4, catalyst dosage = 15 mg, primary drug concentration = 5 mg/L). Ce0.93Sb0.07FeO3 was also found to be stable over its multiple catalytic runs as only 6.5% decline in degradation efficiency was observed in recyclability test. The remarkable performance of antimony doped cerium ferrite against the removal of persistent pharmaceutical pollutant indicated its strong potential to be used in wastewater treatment in future works.

Multifunctional Ce+3 doped nickel-cobalt mixed ferrites via co-precipitation method for photocatalytic and antibacterial activity

The overuse of industrial dyes and anti-bacterial drugs are destroying fresh water reservoirs and making bacteria more resistant, respectively. To sort out these problems, we have synthesized Cerium doped Nickel-Cobalt mixed ferrites (Ce-@NCMF) with chemical composition [Ni0.4Co0.6CexFe2-xO4 (where x = 0.00, 0.10, 0.15, 0.20 and 0.25)] via co-precipitation method. Influence of cerium doping on the structural, optical, electrical, magnetic, photocatalytic and anti-bacterial properties of Ce-@NCMF studied. Powder x-ray diffraction analysis (PXRD) confirmed the synthesis of Ce-@NCMF. Decrease of crystallite size from 29.71 to 24.95 nm was observed with increase in dopant concentration. Tauc’s plot indicated the decrease of energy bandgap from 2.10 to 1.89 eV with increase in dopant concentration, which revealed the absorption of light in visible region to generate electron–hole pairs for photocatalytic applications. FTIR spectra indicated the presence of M-O bonds as major functional group present in Ce-@NCMF. Electrical properties demonstrated the prominent increase of electrical conductivity with increase of Ce-doping. VSM analysis was performed to analyse the magnetic properties of materials and showed prominent decrease in saturation magnetization value from 84.66 to 19.85 emu g−1. Owing to optical bandgap in the visible region, all the synthesized samples were evaluated for their photocatalytic potential for the degradation of methylene blue. Ce-@NCMF at x = 25% dopant value showed maximum degradation efficiency (95%) under sunlight irradiation of 90 min. Kinetic studies of dye degradation followed pseudo-1st order kinetics with maximum rate constant (k) value of 2.78×10−2 min−1. Antibacterial activity results showed the bioactive nature of Ce-@NCMF against all strains of bacteria in consistent with the crystallite size of samples. Smallest crystallite size Ce-@NCMF were found most active against gram-negative bacterial strains.

Doxorubicin loaded cerium substituted hydroxyapatite nanoparticles: A promising new therapeutic approach for bone regeneration, doxorubicin delivery, and cancer treatment

The current study used the precipitation method to prepare pure calcium hydroxyapatite (HA) and cerium-substituted hydroxyapatite (Ce-HA) nanoparticles, where cerium ions were exchanged into the HA structure at different concentrations ranging from 3 to 7 wt%. X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), Fourier transform infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) surface area measurements, and zeta potential were used to examine the structural characteristics of the nanoparticles. Additionally, the antibacterial and antifungal effects of the produced materials on Gram-positive, Gram-negative, and fungal bacterial species were studied. Nanoparticles with cerium doping showed effective antibacterial and antifungal properties. All samples were tested for bioactivity in simulated body fluid (SBF), and the formation of an apatite layer on their surfaces was highlighted using SEM in conjunction with energy-dispersive X-rays (EDX).Doxorubicin (DOX) release from Ce-HA nanoparticles and pure HA was tested in phosphate-buffered saline (PBS) for up to 28 days. Both nanoparticles were able to release the drug while still being semi-fully loaded. Similarly, the cytotoxic effect of all produced samples on the MG-63 cell line was evaluated, and all samples showed good cytocompatibility. The cytotoxic effect of doxorubicin-loaded nanoparticles showed promising anticancer activity against bone cancer cells, especially samples with high cerium content. The resulting nanoparticles show excellent promising ability for the delivery of doxorubicin to bone cancer with the capacity for bone regeneration.

Enhanced Mechanical and Electromechanical Properties of Compositionally Complex Zirconia Zr1-x(Gd1/5Pr1/5Nd1/5Sm1/5Y1/5)xO2-δ Ceramics.

Compositionally complex oxides (CCOs) or high-entropy oxides (HEOs) are new multielement oxides with unexplored physical and functional properties. In this work, we report fluorite structure-derived compositionally complex zirconia with composition Zr1-x(Gd1/5Pr1/5Nd1/5Sm1/5Y1/5)xO2-δ (x = 0.1 and 0.2) synthesized in solid-state reaction route and sintered via hot pressing at 1350 °C. We explore the evolution of these oxides' structural, microstructural, mechanical, electrical, and electromechanical properties regarding phase separation and sintering mechanisms. Highly dense ceramics are achieved by bimodal mass diffusion, composing nanometric tetragonal and micrometric cubic grains microstructure. The material exhibits an anomalously large electrostriction response exceeding the M33 value of 10-17 m2/V2 at room temperature and viscoelastic properties of primary creep in nanoindentation measurement under fast loading. These findings are strikingly similar to those reported for doped ceria and bismuth oxide derivates, highlighting the presence of a large concentration of point defects linked to structural distortion and anelastic behavior, which are characteristics of nonclassical ionic electrostrictors.

Gadolinium Doped Ceria as Nickel–Free Fuel Electrode in High Temperature CO2‐Electrolysis

AbstractIn this work, the performance, electrochemical processes, and stability of GDC (Ce0.8Gd0.2O1.9) fuel electrode containing single cells (GDC/8YSZ/GDC/LSCF) were examined in CO2 electrolysis conditions. The current density and area specific resistance is determined for different operation conditions. The examined cells showed a higher performance compared to state‐of‐the‐art Ni−YSZ fuel electrode (Ni‐YSZ/8YSZ/GDC/LSCF) based single cells with a similar production route. Furthermore, the cells were examined by means of electrochemical impedance spectroscopy (EIS) and the recorded data were evaluated by the distribution of relaxation times (DRT) analysis. An equivalent circuit model (ECM) consisting of four time constants and a Gerischer impedance (LR−RQ1−RQ2−G−RQ4−RQ5) was established to gain further insight into the individual processes in the cells. For instance, the low–frequency process P5 referring to RQ5 is the rate‐determining step in CO2 electrolysis and is assigned to a surface reaction including the charge transfer and possibly the gas diffusion in the GDC fuel electrode. A long–term stability test was performed in CO2 electrolysis conditions at 900 °C with a constant current load of −0.5 A ⋅ cm−2 for up to 1200 h. A degradation rate of 62 mV ⋅ kh−1 was observed. By EIS analysis, a similar contribution of the ohmic and polarization resistances to the degradation was determined. The low–frequency process P5 and thus the surface reaction including the charge transfer in the GDC fuel electrode is contributing most to the increase in polarization resistance. After the long–term stability test, scanning electron microscopy (SEM) analysis was carried out and a coarsening of GDC particles in the fuel electrode was observed.

A highly stable and conductive cerium‐doped Li7P3S11 glass‐ceramic electrolyte for solid‐state lithium–sulfur batteries

AbstractIn this report, a facile wet chemical method using acetonitrile combined with thermal annealing was used to prepare Li2S‐P2S5 (LPS) based glass‐ceramic electrolytes with (1 wt%, 3 wt%, and 5 wt% Ce2S3) and without Ce2S3 doping. The crystal structure, ionic conductivity, and chemical stability of Li7P3S11 glass‐ceramic electrolytes were examined at varying temperatures (250–350°C). The results indicated that the highest ionic conductivity of 3.15 × 10−4 S cm−1 for pure Li7P3S11 was observed at a temperature of 325°C. By incorporating 1 wt% Ce2S3 and subjecting it to a heat treatment at 250°C, the glass ceramic electrolyte attained a remarkable ionic conductivity of 7.7 × 10−4 (S cm−1) at 25°C. Furthermore, it exhibited a stable and extensive electrochemical potential range, reaching up to 5 volts when compared to the Li/Li+ reference electrode. By tuning the glass transition and crystallization temperature, cerium doping seems to make Li7P3S11 more chemically stable, compared to its original 70Li2S‐30P2S5 counterpart. According to Raman and X‐ray photoelectron spectroscopy analyses, cerium doping inhibits the decomposition of highly conductive P2S74‐ (pyro‐thiophosphate) to PS43− and P2S64−. Doped LPS has a greater crystallinity and more uniform microstructure than pure LPS, according to XRD, Raman spectroscopy, and scanning electron microscopy analysis. Consequently, Li7P2.9Ce0.1S11 electrolyte shows great potential as a solid‐state electrolyte for constructing high‐performance sulfide‐based all‐solid‐state batteries.

Optical and microstructural characterization of Er3+ doped epitaxial cerium oxide on silicon

Rare-earth ion dopants in solid-state hosts are ideal candidates for quantum communication technologies, such as quantum memories, due to the intrinsic spin–photon interface of the rare-earth ion combined with the integration methods available in the solid state. Erbium-doped cerium oxide (Er:CeO2) is a particularly promising host material platform for such a quantum memory, as it combines the telecom-wavelength (∼1.5μm) 4f–4f transition of erbium, a predicted long electron spin coherence time when embedded in CeO2, and a small lattice mismatch with silicon. In this work, we report on the epitaxial growth of Er:CeO2 thin films on silicon using molecular beam epitaxy, with controlled erbium concentration between 2 and 130 parts per million (ppm). We carry out a detailed microstructural study to verify the CeO2 host structure and characterize the spin and optical properties of the embedded Er3+ ions as a function of doping density. In as-grown Er:CeO2 in the 2–3 ppm regime, we identify an EPR linewidth of 245(1) MHz, an optical inhomogeneous linewidth of 9.5(2) GHz, an optical excited state lifetime of 3.5(1) ms, and a spectral diffusion-limited homogeneous linewidth as narrow as 4.8(3) MHz. We test the annealing of Er:CeO2 films up to 900 °C, which yields narrowing of the inhomogeneous linewidth by 20% and extension of the excited state lifetime by 40%.

The effect of cerium, neodymium, and ytterbium doping on UO2 dissolution

The dissolution rate of spent nuclear fuel under environmental conditions has been studied heavily to understand the impacts of a failed waste package on potential radionuclide release from a geologic repository. Multiple countries have evaluated these scenarios in oxidizing and reducing environments respective to their relevant repository conditions. The repository environment (e.g., water chemistry, temperature, oxygen content) and the fuel itself (i.e., chemical composition of the fuel) both heavily impact the dissolution rate of the spent fuel. This work examined the impact that rare earth element dopants (Ce, Nd, Yb) have on the fuel dissolution under repository relevant conditions with decreasing oxidizing conditions using a single pass flowthrough system. UO2 samples were doped with Ce, Nd, or Yb with concentrations between 1 and 5 at%. The addition of dopants to the samples reduced the dissolution rates on most samples relative to pure UO2 samples. Preliminary experiments that occurred in a less oxidizing environment showed a reduction in dissolution rate compared to fully oxidizing conditions. The results within highlight the importance of dopant behavior in used fuel dissolution modeling.

Chemical expansion of La3+ and Yb3+ incorporated Zr-doped ceria ceramics for concentrated solar energy-driven thermochemical production of fuels

Redox studies on Zr, La, Yb doped ceria (Ce0.9M3+/4+0.1O2-x, M3+/4+ = Zr4+, La3+, Yb3+ and CeZr0.05 M3+0.05O1.95, M3+ = La3+, Yb3+) ceramics were performed using dilatometry and mass change measurements to analyze the chemical and thermal volume changes depending on reduction state which can have dramatic effects on the long-term stability of these ceramics in Concentrated Solar Energy (CSE)–driven applications relevant to the synthesis of fuels. The reduction extents determined by both methods under vacuum (p = 2×10−5 mbar) are similar up to 1673 K. At higher temperatures, CeO2, which has a higher vapor pressure than the oxides of the dopant ions, evaporates. As a result, there is an accumulation of doping ions, which leads to a porous surface zone. Surface enrichment of dopants, especially that of Zr4+, is crucial for re-oxidation kinetics. Co-doping with trivalent doping ions such as La3+ and Yb3+ reduces the extent of selective evaporation materializing it into a thinner porous surface layer. Trivalent dopants and their additional oxygen vacancies also influence the chemical expansion/contraction of the Zr4+ doped ceria crystal lattice during the redox reaction and thus lead to a reduction of mechanical stresses. We assume that additional oxygen vacancies from trivalent dopant ions promote the disordering of intrinsic oxygen vacancies, while smaller tetravalent ions such as Zr4+ compensates this effect. This explains that doped ceria with trivalent and tetravalent ions show almost the same chemical expansion as pure ceria. The new results on alteration, thermal and chemical expansions/contractions at high temperature are particularly important for the development of metal oxide ceramic components exposed to cyclic reducing and oxidizing atmospheres at elevated temperatures achieved via CSE.

Synthesis and characterization of Nd-doped CeO2 thin films grown by spray pyrolysis method: Structural, optical and electrochemical properties

In the present research, we successfully synthesized thin films of Cerium Oxide (CeO2) and Neodymium (Nd) doped CeO2 on both glass and ITO substrates using the chemical spray pyrolysis method. Their structural, morphological, optical and electrochemical properties were experimentally studied. X-ray diffraction analyses showed that all the layers exhibited the cubic fluorite phase characteristic of CeO2. Raman spectroscopy reveals a downward F2g band shift in all Nd3+-doped CeO2 films due to oxygen vacancies. The asymmetry and broadening of the Raman modes arise from the injection of Nd3+ ions in CeO2 thin films, which leads to variations in the presence of Ce3+ and oxygen vacancies. Additionally, the morphology of the films changes with different levels of Nd-doping. The UV–Vis-NIR spectra obtained in the wavelength scale between 300 nm and 1800 nm showed a noticeable reduction in the band gap from 3.46 eV to 3.30 eV. The cyclic voltammetry (CV) results indicate that the addition of Nd improves the ion storage capacities (ISC) of the cerium oxide thin film. Even after the intercalation/deintercalation of lithium ions, the doped cerium oxide thin films remain fully transparent. These significant findings broaden the potential applications of this oxide, particularly for electrochromic devices.

Impact of magnetic, thermal, structural, morphological and optical characteristics on room temperature ferromagnetism of pristine and cerium doped ZnO nanocomposites

An excellent fit between the theoretical and experimental studies of the related to structure, optics, and magnetism features of pristine and cerium-modified Zn-O NPs prepared through the wet chemical technique. Refining the XR-D pattern using the Rietveld-method reveals that the samples have a hexagonal Wurtzite structure. Absorption spectra reveal a shrinking bandwidth gap as cerium doping increases, substantiating ce2+ ion's essential function in ZnO's spectral qualities. The narrowing of the bandwidth gap due to the presence of impurity states was also verified by first-principles calculations. The residual magnetization increases with Cerium doping, and magnetic tests show roomtemperature weak-ferromagnetism (RTFM). In addition, ferromagnetism for cerium doping is confirmed by both first-principles calculations and experiments. Theoretical calculations imply that the cerium atoms may agglomerate to generate metallicantiferromagnetic chromium oxide when cerium doping reaches 8%. At ambient temperature, however, ferromagnetic behaviour is feasible since both ferromagnetic and antiferromagnetic behaviour are degraded when cerium is widely disseminated throughout the lattice as revealed by XRD studies

Synergistic sensitization effects of single-atom gold and cerium dopants on mesoporous SnO2 nanospheres for enhanced volatile sulfur compound sensing

A concept of synergistic sensitization effects involving single-atom Au and Ce dopants on mesoporous SnO2 nanospheres is proposed for ultrasensitive and real-time monitoring of ppb-level volatile sulfur compounds.

Modulation of the electronic structure of metallic bismuth catalysts by cerium doping to facilitate electrocatalytic CO2 reduction to formate

Bi(0) metal was utilized as a CO2RR catalyst to achieve enhanced durability in cathodic applications. Besides, the CO2RR activity was effectively improved by a promising strategy of electronic structure modulation through Ce doping.

Cerium Doping Effect in 3DOM Perovskite-Type La2−xCexCoNiO6 Catalysts for Boosting Soot Oxidation

Herein, we present an in-depth investigation into the enhancement of catalytic soot oxidation through cerium-doped three-dimensional ordered macroporous (3DOM) La-Co-Ni-based perovskites synthesized with the colloidal crystal template (CCT) method. The 3DOM structure significantly contributes to the accessibility and interaction efficiency between soot and catalyst. Based on the results of powder X-ray diffraction (XRD), N2 adsorption-desorption measurements, scanning electron microscopy (SEM), temperature-programmed oxidation of NO (NO-TPO), temperature-programmed reduction of H2 (H2-TPR), in situ infrared Fourier transform spectroscopy (In-situ DRIFTS), and temperature-programmed oxidation (TPO) reactions, the role of cerium doping in modifying the structural and catalytic properties of 3DOM perovskite-type La2−xCexCoNiO6 catalysts was investigated systematically. The optimized cerium doping ratio in La2−xCexCoNiO6 catalysts can improve the microenvironment for efficient soot-catalyst contact, enhancing the catalytic activity of soot oxidation. Among the catalysts, the 3DOM La0.8Ce1.2CoNiO6 catalyst shows the highest catalytic activity for soot oxidation, whose T10, T50, and T90 values are 306 °C, 356 °C, and 402 °C, respectively. The mechanism of the cerium doping effect for boosting soot oxidation is proposed: The doping of Ce ions can increase the surface oxygen species, which is the main active species for promoting the key step of NO oxidation to NO2 in catalyzing soot oxidation. This research provides a new strategy to develop high-efficient non-noble metal catalysts for soot oxidation in pollution control and sustainable environmental practices.

Core-Shell Nanofiber Composites As Highly Active and Robust Anodes for Direct-Hydrocarbon Fueled Solid Oxide Fuel Cells

Direct use of methane in solid oxide fuel cells (SOFCs) can be a key to realize the high-efficiency advantage of fuel cell technologies before mature hydrogen economy. One of the most critical issues for direct-methane SOFCs is to prevent anode, particularly Ni-based, from carbon deposition (coking) that drastically degrades performance. A number of ceramic anodes have been developed to exhibit excellent coking resistance but their application is still limited by relatively low electrochemical activity. Impregnating catalytically active and high oxygen ion-conducting materials such as doped ceria to form nanoscale composites, some ceramic anodes demonstrated enhanced activity comparable to Ni-based anodes. However, fabrication methods employed so far require repetitive series of a coating and high-temperature calcination step to optimize the performance, which detrimentally affects nanoarchitectures. To address this issue, we demonstrate electrospinning as efficient route to prepare nanocomposite ceramic anodes. We successfully achieve highly active and robust anodes based on core-shell-like La0.75Sr0.25Cr0.5Mn0.5O3@Sm0.2Ce0.8O1.9 nanofibers through co-electrospinning method. Such nanoscale morphologies are maintained by the durable ceria shells at elevated temperature. Compared to the traditionally mixed counterpart, it shows nearly a half polarization resistance due to the increased active reaction sites and high stability in a wet methane at 700℃ for about 100 h.

Boosting the Stability and Performance of SOFCs: A New Approach to Oxygen Storage Capacity Using Lanthanum-Doped Ceria Interlayer Technology

Being carbon neutral is one of the world's most important objectives. More than 65 percent of the countries that emit harmful greenhouse gases have committed to achieving net-zero emissions by the middle of the century.[1] There are numerous essential ways to gather energy for worldwide missions, including fuel cells, solar power, wind power, etc. The growing marketplace of fuel cells is following the trend of green-energy demand. Solid oxide fuel cells (SOFCs) are gaining popularity in the next-generation energy industry due to their high energy conversion efficiency, fuel flexibility, and low emissions.[2]The main challenges for the commercialization of SOCs that need to address are high performance, long-term durability, and effective cost. Stabilized zirconia such as Yttria-stabilized zirconia (YSZ) and Scandia-stabilized zirconia (ScSZ) is commonly used as a self-standing electrolyte support. The inability of zirconia-based electrolytes to react with Sr-rich cathode materials like LSC, LSCF, BSCF, etc. Therefore, the electrodes and the zirconia-based electrolyte must have the best-interlayered buffer structure. Optimizing interlayer microstructures to make them more effective at high-performance ESCs is of great interest. Several Rare-earth doped ceria (RDC) materials, including (Gd, Ce)O2, (Sm, Ce)O2, and (La, Ce)O2, have been used as efficient interlayers to lessen reactivity and preserve ionic conductivity in the interface. However, the difference in the thermal expansion coefficient (TEC) between the GDC and the YSZ poses a significant problem for starting and halting SOCs. In the present work, we focus on the commercial lanthanum-doped ceria (Ce0.6La0.4O1.8 - LDC) as a buffer layer between the YSZ electrolyte and the LSCF cathode because of its higher oxygen storage capacitance. The reactivity of the YSZ/GDC composite was higher than that of the YSZ/LDC composite. And the total conductivity of the LDC/YSZ composite is higher than GDC/YSZ composite even though LDC has lower conductivity than GDC. Moreover, the mismatching of TEC was reduced by replacing the GDC with the LDC bilayer.Consequently, the maximum power density for the electrolyte-supported cell SOFC with LDC interlayer was ~0.55 W.cm−2 at 1073 K. A variety of additives (Co, Mn, and Cu) was added to the LDC buffer layer to examine the sintering properties. The addition of copper not only obtained the highest microstructural density but also improve mechanical stability under cost-effective processes.

(Invited) Ruddlesden-Popper Oxides As Bi-Functional Oxygen Electrodes

Incorporating more renewables into our energy mix is a major challenge that confronts our transition to a carbon free economy. Solid oxide electrochemical cells when operated alternately in fuel cell and electrolysis modes, enable the incorporation and integration of far greater amounts of solar and wind energy into our power grid. As islanded systems, they can also function as distributed generation systems thereby decreasing our reliance on the power grid. In this talk, we present a recent survey of results on rSOCs based on rare earth nickelate – rare-earth doped ceria composite oxygen electrodes that exhibit excellent cycling behavior when operated alternately in solid oxide fuel cell (SOFC) and solid oxide electrochemical cell (SOEC) modes of operation. The degradation in such cells is significantly mitigated by mode-switching operation when compared to operating in single mode operation in electrolysis mode. By comparing distributed relaxation times (DRT) analysis of impedance spectra obtained from single-mode (electrolysis) operated cells, and cells operated in switched-modes, we obtain clues into cell degradation mechanisms.

(Invited) Challenges with Ceria Diffusion Barrier Layer

Sr-doped perovskite has been the most commonly used oxygen electrode material for solid oxide cells due to their high conductivity and catalytic activity for oxygen reduction and oxygen evolution reactions. Direct contact of the electrode material with the doped zirconia electrolyte leads to formation of resistive Sr- and La-zirconate phases during cell fabrication and long-term operation leads to performance loss. A doped ceria barrier layer is applied between the electrolyte and the oxygen electrode to avoid the reactions that form the resistive phase. The ceria layer is applied using a variety of processes and screen printing is the preferred method as the oxygen electrode also uses the same fabrication option. The barrier layer is sintered at high temperature to target a thin, dense layer. The barrier layer sintering temperature needs to balance good resulting density without any reaction with the electrolyte. The ceria-zirconia solid solution is more resistive than the end members. Thus, it is accepted to limit the sintering temperature which results in a porous barrier layer.OxEon stacks tested for several thousand hours were post-test analyzed at the Pacific Northwest National Laboratory using an array of electron microscopes, and Sr migration to the zirconia interface through pores and discontinuity in the barrier layer was confirmed. The use of Sr-free electrode composition between the barrier layer and the Sr-containing electrode layer did not prevent Sr migration to the electrolyte interface when discontinuities are present in the barrier layer.In addition, the dopant in ceria, samaria in this case, also migrates into zirconia during long-term operation while as fabricated cells do not show migration of samaria.Investigations are ongoing to improve the density of the barrier layer without deleterious interdiffusion during fabrication.

Process Intensification and Performance Assessment of Sputtered Gadolinium Doped Ceria (GDC) Barrier Layer in Large-Area Solid Oxide Fuel Cell Short Stack

In recent years, Gadolinium Doped Ceria (GDC) barrier layers have been reported to enhance the performance of Solid Oxide Fuel Cells (SOFCs)by reducing cathode/electrolyte interface diffusion and improving ionic conductivity. Prior investigations have demonstrated that GDC thin film sputtered at room-temperature yields substantial enhancements in Solid Oxide Fuel Cells (SOFCs).This enhancement is evidenced by a noteworthy increase in output current (+78%) and a considerable reduction in ohmic resistance (up to -42%), compared to conventionally screen-printed industrial SOFCs. To probe the intricate interplay between morphology and stoichiometry, which fundamentally determines the Ce3+/Ce4+ ratio governing both ionic and electronic conductivity, this study utilized quantitative X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS) techniques. Results revealed that annealing parameters played a role in the number of available oxygen vacancies in the oxygen-reduction reaction (ORR), inducing different changes in the investigated samples. Non-destructive investigations utilizing Distribution of Relaxation Time (DRT) analysis were conducted on two short stacks with varying thickness, employing different sputtering Modalities. These studies revealed that thickness significantly influences the ultimate performance.

Gadolinia Doped Ceria with Engineered Grain Boundaries as Potential Electrolyte Material for Thin-Film Solid Oxide Fuel Cells

Thin-film solid oxide fuel cells are receiving increasing attention within the scientific community thanks to their high energy density and high efficiency in different temperature ranges. To be utilized as power supply systems for portable electronic devices, thin-film solid oxide fuel cells must demonstrate high power supply and low-temperature operation capabilities. Both capabilities are highly dependent on the function of the electrolyte layer, commonly comprised of ceramic mixed-ionic-electronic conductors [1]. The state-of-the-art thin-film solid oxide fuel cells utilize yttrium stabilized zirconia as an electrolyte material, despite its relatively low ionic conductivity within the typical working-temperature range of solid oxide fuel cells (up to 1000 °C). Moreover, the ionic conductivity of yttrium stabilized zirconia dramatically reduces with decreased temperature, limiting its performance as an electrolyte material for low-temperature (below 600 °C) solid oxide fuel cells [2].Gadolinia doped ceria is an alternative promising electrolyte material for low temperature solid oxide fuel cells. Its relatively high ionic conductivity below 600 °C makes it attractive as an electrolyte material although its partial electronic conductivity is a significant drawback [3]. This drawback is more pronounced in ultra-thin layers (sub-micron scale) solid oxide fuel cells devices. As a result, gadolinia doped ceria have been utilized only to a limited extent for thin-film solid oxide fuel cells.The issue of partial electronic conductivity might be resolved thanks to a non-conventional deposition technique of polycrystalline gadolinia doped ceria thin films. The proposed sputtering technique includes metallic alloy target and results in a granular morphology, as opposed to the columnar morphology obtained using the conventional sputtering method. As electrical conductivity of polycrystalline thin films is higher along the grain boundaries [4], gadolinia doped ceria layers with random crystallographic orientation are expected to be less electronically conductive. Here, we investigated the integration and the performance of granular gadolinia doped ceria as an electrolyte material for thin-film solid oxide fuel cells. The electronic-conduction properties along the grain boundaries of gadolinia doped ceria were studied, and a thin-film solid oxide fuel cell prototype was fabricated. Such devices with engineered grain boundaries hold the potential for low-temperature operation, high power output, and silicone-compatibility for novel integration opportunities and bulk-fabrication.