Search Results (16)

The commercialization of proton-conducting fuel cells (PCFCs) is hindered by the limited electroactivity and durability of cathodes at intermediate temperatures ranging from 400 to 700 °C, a challenge exacerbated by an insufficient understanding of high-entropy perovskite (HEP) materials for oxygen reduction reaction (ORR) optimization. This study introduces an yttrium-doped HEP to address these limitations. A comparative analysis of Ce_0.2−xY_xBa_0.2Sr_0.2La_0.2Ca_0.2CoO_3−δ (x = 0, 0.2; designated as CBSLCC and YBSLCC) revealed that yttrium doping enhanced the ORR activity, reduced the thermal expansion coefficient (19.9 × 10⁻⁶ K⁻¹, 30–900 °C), and improved the thermomechanical compatibility with the BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ electrolytes. Electrochemical testing demonstrated a peak power density equal to 586 mW cm⁻² at 700 °C, with a polarization resistance equaling 0.3 Ω cm². Yttrium-induced lattice distortion promotes proton adsorption while suppressing detrimental Co spin-state transitions. These findings advance the development of durable, high-efficiency PCFC cathodes, offering immediate applications in clean energy systems, particularly for distributed power generation. Full article

Proton-conducting ceramics have gained significant attention in various applications. Yttrium-doped barium cerium zirconate (BaCe_xZr_1−x−yY_yO_3–δ) is the state-of-the-art proton-conducting electrolyte but poses a major challenge because of its high sintering temperature. Sintering aids have been found to substantially reduce the sintering temperature of BaCe_xZr_1−x−yY_yO_3–δ. This work evaluates, for the first time, the impact of NiO and ZnO addition in three different loadings (1, 3, 5 mol%), via wet mechanical mixing, on the sintering and electrical properties of a low cerium-containing composition, BaCe_0.2Zr_0.7Y_0.1O_3–δ (BCZY). The sintering temperature remarkably dropped from 1600 °C (for pure BCZY) to 1350 °C (for NiOBCZY and ZnOBCZY) while achieving > 95% densification. In general, ZnO gave higher densification than NiO, the highest being 99% for 5 mol% ZnOBCZY. Dilatometric studies revealed that ZnOBCZY attained complete shrinkage at temperatures lower than NiOBCZY. Up to 650 °C, ZnO showed higher conductivity compared to NiO for the same loading, mostly due to a higher extent of Zn incorporation inside the BCZY lattice as seen from the BCZY peak shift to a lower Bragg’s angle in X-ray diffractograms, and the bigger grain sizes of ZnO samples compared to NiO captured in scanning electron microscopy. At any temperature, the variation in conductivity as a function of sintering aid concentration followed the orders 1 mol% > 3 mol% > 5 mol% (for ZnO) and 1 mol% < 3 mol%~5 mol% (for NiO). This difference in conductivity trends has been attributed to the fact that Zn fully dissolves into the BCZY matrix, unlike NiO which mostly accumulates at the grain boundaries. At 600 °C, 1 mol% ZnOBCZY showed the highest conductivity of 5.02 mS/cm, which is, by far, higher than what has been reported in the literature for a Ce/Zr molar ratio <1. This makes ZnO a better sintering aid than NiO (in the range of 1 to 5 mol% addition) in terms of higher densification at a sintering temperature as low as 1350 °C, and higher conductivity. Full article

Ceramic proton conductors have the potential to lower the operating temperature of solid oxide cells (SOCs) to the intermediate temperature range of 400–600 °C. This is attributed to their superior ionic conductivity compared to oxide ion conductors under these conditions. However, prominent proton-conducting materials, such as yttrium-doped barium cerates and zirconates with specified compositions like BaCe_1−xY_xO_3−δ (BCY), BaZr_1−xY_xO_3−δ (BZY), and Ba(Ce,Zr)_1−yY_yO_3−δ (BCZY), face significant challenges in achieving dense electrolyte membranes. It is suggested that the incorporation of transition and alkali metal oxides as sintering additives can induce liquid phase sintering (LPS), offering an efficient method to facilitate the densification of these proton-conducting ceramics. However, current research underscores that incorporating these sintering additives may lead to adverse secondary effects on the ionic transport properties of these materials since the concentration and mobility of protonic defects in a perovskite are highly sensitive to symmetry change. Such a drop in ionic conductivity, specifically proton transference, can adversely affect the overall performance of cells. The extent of variation in the proton conductivity of the perovskite BCZY depends on the type and concentration of the sintering aid, the nature of the sintering aid precursors used, the incorporation technique, and the sintering profile. This review provides a synopsis of various potential sintering techniques, explores the influence of diverse sintering additives, and evaluates their effects on the densification, ionic transport, and electrochemical properties of BCZY. We also report the performance of most of these combinations in an actual test environment (fuel cell or electrolysis mode) and comparison with BCZY. Full article

Proton ceramic fuel cells offer numerous advantages compared with conventional fuel cells. However, the practical implementation of these cells is hindered by the poor sintering activity of the electrolyte. Despite extensive research efforts to improve the sintering activity of BCZY, the systematic exploration of the utilization of NiO as a sintering additive remains insufficient. In this study, we developed a novel BaCe_0.55Zr_0.35Y_0.1O_3-δ (BCZY) electrolyte and systematically investigated the impact of adding different amounts of NiO on the sintering activity and electrochemical performance of BCZY. XRD results demonstrate that pure-phase BCZY can be obtained by sintering the material synthesized via solid-state reaction at 1400 °C for 10 h. SEM analysis revealed that the addition of NiO has positive effects on the densification and grain growth of BCZY, while significantly reducing the sintering temperature required for densification. Nearly fully densified BCZY ceramics can be obtained by adding 0.5 wt.% NiO and annealing at 1350 °C for 5 h. The addition of NiO exhibits positive effects on the densification and grain growth of BCZY, significantly reducing the sintering temperature required for densification. An anode-supported full cell using BCZY with 0.5 wt.% NiO as the electrolyte reveals a maximum power density of 690 mW cm⁻² and an ohmic resistance of 0.189 Ω cm² at 650 °C. Within 100 h of long-term testing, the recorded current density remained relatively stable, demonstrating excellent electrochemical performance. Full article

Cermet films consisting of Ni, BaCe_0.4Zr_0.4Y_0.2O_3−δ (BCZY), and Gd_0.1Ce_0.9O_x (GDC), specifically, 60 wt%Ni–BCZY, 60 wt%Ni–BCZY–GDC, and 60 wt%Ni–GDC, were formed on BCZY electrolyte supports as anodes of proton ceramic fuel cells (PCFCs). The Ni grain size in these films after sintering at 1450 °C was around 2 μm. The GDC addition did not affect the Ni grain size in the case of the BCZY matrix. The anodic properties greatly depended on the oxide phase composition and worsened with increasing the GDC content. This probably occurred because of the addition of GDC, which has low proton conductivity and inhibited the proton conduction path of BCZY, reducing three-phase boundaries in the anode bulk. Since BCZY has a lower grain growth rate during sintering than BaCe_0.8Y_0.2O_3−δ, the Ni grain growth was likely suppressed by the surrounding Ni grains containing small BCZY grains. Full article

Strontium and cobalt-free LaNi_0.6Fe_0.4O_3–δ is considered one of the most promising electrodes for solid-state electrochemical devices. LaNi_0.6Fe_0.4O_3–δ has high electrical conductivity, a suitable thermal expansion coefficient, satisfactory tolerance to chromium poisoning, and chemical compatibility with zirconia-based electrolytes. The disadvantage of LaNi_0.6Fe_0.4O_3–δ is its low oxygen-ion conductivity. In order to increase the oxygen-ion conductivity, a complex oxide based on a doped ceria is added to the LaNi_0.6Fe_0.4O_3–δ. However, this leads to a decrease in the conductivity of the electrode. In this case, a two-layer electrode with a functional composite layer and a collector layer with the addition of sintering additives should be used. In this study, the effect of sintering additives (Bi_0.75Y_0.25O_2–δ and CuO) in the collector layer on the performance of LaNi_0.6Fe_0.4O_3–δ-based highly active electrodes in contact with the most common solid-state membranes (Zr_0.84Sc_0.16O_2–δ, Ce_0.8Sm_0.2O_2–δ, La_0.85Sr_0.15Ga_0.85Mg_0.15O_3–δ, La₁₀(SiO₄)₆O_3–δ, and BaCe_0.89Gd_0.1Cu_0.01O_3–δ) was investigated. It was shown that LaNi_0.6Fe_0.4O_3–δ has good chemical compatibility with the abovementioned membranes. The best electrochemical activity (polarization resistance about 0.02 Ohm cm² at 800 °C) was obtained for the electrode with 5 wt.% Bi_0.75Y_0.25O_1.5 and 2 wt.% CuO in the collector layer. Full article

The rare-earth-doped zirconia-based solid electrolytes have gained significant interest in protonic ceramic fuel cell (PCFC) applications due to their high ionic conductivity. However, these solid electrolytes are susceptible to low conductivity and chemical stability at low operating temperatures, which are of interest in commercializing ceramic fuel cells. Thus, tailoring the structural properties of these electrolytes towards gaining high ionic conductivity at low/intermediate temperatures is crucial. In this study, Ce (cerium) and Nd (neodymium) co-doped barium zirconate perovskites, BaZr_(0.80-x-y)Ce_xNd_yY_0.10Yb_0.10O_3-δ (BZCNYYO) of various doping fractions (x, y: 0, 0.5, 0.10, 0.15), were synthesized (by the Pechini method) to systematically analyze their structural and conductivity properties. The X-ray diffraction patterns showed a significant lattice strain, and the stress inferences for each co-doped BZCNYYO sample were compared with Nd-cation-free reference samples, BaZrO₃ and BaZr_(0.80-x-y-z)Ce_xY_yYb_zO_3-δ (x: 0, 0.70; y: 0.20, 0.10; z: 0, 0.10). The comparative impedance investigation at low-to-intermediate temperatures (300–700 °C) showed that BaZr_0.50Ce_0.15Nd_0.15Y_0.10Yb_0.10O_3-δ offers the highest lattice strain and stress characteristics with an ionic conductivity (σ) of 0.381 mScm⁻¹ at 500 °C and activation energy (E_a) of 0.47 eV. In addition, this σ value was comparable to the best reference sample BaZr_0.10Ce_0.70Y_0.10Yb_0.10O_3-δ (0.404 mScm⁻¹) at 500 °C, and it outperformed all the reference samples when the set temperature condition was ≥600 °C. The result of this study suggests that Ce- and Nd-doped BZCNYYO solid electrolytes will be a specific choice of interest for developing intermediate-temperature PCFC applications with high ionic conductivity. Full article

Fuel electrode-supported tubular protonic ceramic cells (FETPCCs) based on the BaZr_0.4Ce_0.4Y_0.15Zn_0.05O_3−δ (BZCYZ) membrane electrolyte was fabricated through a two-step method, in which the polyporous electrode-support tube was prepared with a traditional slip casting technique in a plaster mold, and the BZCYZ membrane was produced by a dip-coating process on the outside surface of the electrode-support tube. The dense thin-film electrolyte of BZCYZ with a thickness of ~25 μm was achieved by cofiring the fuel electrode support and electrolyte membrane at 1450 °C for 6 h. The electrochemical performances of the FETPCCs were tested under different solid oxide cell modes. In protonic ceramic fuel cell (PCFC) mode, the peak power densities of the cell reached 151–191 mW·cm⁻² at 550–700 °C and exhibited relatively stable performance during continuous operation over 100 h at 650 °C. It was found that the major influence on the performance of tubular PCFC was the resistance and cathode current collectors. Additionally, in protonic ceramic electrolysis cell (PCEC) mode, the current densities of 418–654 mA·cm⁻² were obtained at 600–700 °C with the applied voltage of 2.0 V when exposed to 20% CO₂–80% H₂ and 3% H₂O/air. Using distribution of relaxation time analysis, the electrolytic rate-limiting step of the PCEC model was determined as the adsorption and dissociation of the gas on the electrode surface. Full article

In recent years, tuning perovskite and fluorite-based materials and modifying them to ionic conductors has been an interesting but challenging topic for advanced low-temperature ceramic fuel cells (LT-CFCs). In this regard, we prepared a new composite heterostructure, BaCe_0.4Zr_0.4Y_0.1Yb_0.1O3-Sm_0.2Ce_0.8O₂ (BCZYYb-SDC), and evaluated it as an electrolyte to realize the fuel cell reaction. The developed electrolyte could be a hybrid ionic conductor, possess a very small ohmic area-specific resistance, and exhibit excellent fuel cell performance of over 1.0 W/cm² along with higher OCV of more than 1.1 V at a low operating temperature of 550 °C. The attained performance and ionic conductivity are specially accredited to constructing the heterostructure of BCZYYb-SDC. Moreover, various spectroscopy and microscopic analysis methods have been used to investigate the ions’ transportation, while on the other hand suppressing the electronic conduction. The developed composite heterostructure proposes and suggests new insight to design new electrolytes for LT-CFCs. Full article

BaCe_0.2Zr_0.6Y_0.2O_3−δ (BCZY) perovskite electrolytes were synthesized for intermediate-temperature solid oxide fuel cell with a cost-effective and versatile co-precipitation method. The synthesized BCZY electrolytes were sintered at 900, 1000, and 1100 °C to observe the effects of low sintering temperature on the structural, morphological, thermal, and electrical properties of BCZY. All BCZY electrolytes materials exhibited a crystalline perovskite structure and were found to be thermally stable. The crystallinity and conductivity of BCZY electrolyte enhanced with increased sintering temperature, due to the grain growth. At the same time, secondary phases of carbonates were also observed for samples sintered at a temperature lower than 1100 °C. The BCZY sintered at 1100 °C exhibited a density >95%, and a power density of 350 mWcm⁻² with open-circuit voltage 1.02 V at 650 °C was observed due its dense and airtight structure. Based on the current investigation, we suggest that the BaCe_0.2Zr_0.6Y_0.2O_3−δ perovskite electrolyte sintered at a temperature of 1100 °C is a suitable electrolyte for IT-SOFC. Full article

Proton-conducting solid–oxide fuel cell (H-SOFC) is an alternative promising low-temperature electrochemical cell for renewable energy, but the performance is insufficient because of the low activity of cathode materials at low temperatures. A layered perovskite oxide PrBaFe_1.9Zn_0.1O_5+δ (PBFZ) was synthesized and investigated as a promising cathode material for low-temperature H-SOFC. Here, the partial substitution of Fe by Zn further enhances the electrical conductivity and thermal compatibility of PrBaFe₂O_5+δ (PBF). The PBFZ exhibits improved conductivity in the air at intermediate temperatures and good chemical compatibility with electrolytes. The oxygen vacancy formed at the PBFZ lattice due to Zn doping enhances proton defects, resulting in an improved performance by extending the catalytic sites to the whole cathode area. A single cell with a Ni-BZCY anode, PBFZ cathode, and BaZr_0.7Ce_0.2Y_0.1O_3-δ (BZCY) electrolyte membrane was successfully fabricated and tested at 550–700 °C. The maximum power density and R_p were enhanced to 513 mW·cm⁻² and 0.3 Ω·cm² at 700 °C, respectively, due to Zn doping. Full article

In this study, Nd_1.6Ca_0.4Ni_1−yCu_yO_4+δ-based electrode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs) are investigated. Materials of the series (y = 0–0.4) are obtained by pyrolysis of glycerol-nitrate compositions. The study of crystal structure and high-temperature stability in air and under low oxygen partial pressure atmospheres are performed using high-resolution neutron and in situ X-ray powder diffraction. All the samples under the study assume a structure with Bmab sp.gr. below 350 °C and with I4/mmm sp.gr. above 500 °C. A transition in the volume thermal expansion coefficient values from 7.8–9.3 to 9.1–12.0 × 10⁻⁶, K⁻¹ is observed at approximately 400 °C in air and 500 °C in helium.The oxygen self-diffusion coefficient values, obtained using isotope exchange, monotonically decrease with the Cu content increasing, while concentration dependence of the charge carriers goes through the maximum at x = 0.2. The Nd_1.6Ca_0.4Ni_0.8Cu_0.2O_4+δ electrode materialdemonstrates chemical compatibility and superior electrochemical performance in the symmetrical cells with Ce_0.8Sm_0.2O_1.9, BaCe_0.8Sm_0.2O_3−δ, BaCe_0.8Gd_0.19Cu_0.1O_3−δ and BaCe_0.5Zr_0.3Y_0.1Yb_0.1O_3−δ solid electrolytes, potentially for application in IT-SOFCs. Full article

Perovskite materials have gained a lot of interest in solid oxide fuel cell (SOFC) applications owing to their exceptional properties; however, ideal perovskites exhibit proton conduction due to availability of low oxygen vacancies, which limit their application as SOFC electrolytes. In the current project, Sm was doped at the B-site of a BaCe_0.7-xSm_xZr_0.2Y_0.1O_3-δ perovskite electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs). BaCe_0.7-xSm_xZr_0.2Y_0.1O_3-δ electrolytes were synthesized through a cost-effective coprecipitation method and were sintered at a low sintering temperature. The effects of samarium (Sm) doping on the electrochemical performance of BaCe_0.7-xSm_xZr_0.2Y_0.1O_3-δ were investigated. X-ray diffraction (XRD) analysis confirmed that the BaCe_0.7-xSm_xZr_0.2Y_0.1O_3-δ electrolyte material retained the perovskite structure. The secondary phase of Sm₂O₃ was observed for BaCe_0.4Sm_0.3Zr_0.2Y_0.1O_3-δ. Scanning electron microscopic (SEM) imaging displayed the dense microstructure for all the compositions, while prominent crystal growth was observed for composition x = 0.3. The formation of the perovskite structure and the presence of the hydroxyl groups of metal oxides for all the compositions were confirmed by Fourier transform infrared spectroscopy (FTIR). An increased symmetrical disturbance was also observed for the increased doping ratio of the Sm. Thermogravimetric analysis (TGA) of all the compositions showed no major weight loss in the SOFC operating temperature range. It was also noted that the conductivity of BaCe_0.7-xSm_xZr_0.2Y_0.1O_3-δ gradually decreased with the increased contents of the Sm metal. The maximum power density of 390 mW cm⁻², and an open-circuit voltage (OCV) of 1.0 V at 600 °C, were obtained, showing that BaCe_0.7-xSm_xZr_0.2Y_0.1O_3-δ, synthesized by a cost-effective method and sintered at a low temperature, can be used as a proton-conducting electrolyte for IT-SOFCs. Full article

In this work, the challenges associated with the formation of single and bilayer coatings based on Ce_0.8Sm_0.2O_1.9 (SDC) and CuO modified BaCe_0.5Zr_0.3Y_0.1Yb_0.1O_3−δ (BCZYYbO-CuO) solid state electrolytes on porous non-conducting NiO-SDC anode substrates by the method of electrophoretic deposition (EPD) are considered. Various approaches that had been selected after analysis of the literature data in order to carry out the EPD, are tested: direct deposition on a porous non-conductive anode substrate and multiple options for creating the conductivity of the anode substrate under EPD conditions such as the reduction of the NiO-SDC substrate and the creation of a surface conducting sublayer via synthesizing a polypyrrole (PPy) film. New effective method was proposed based on the deposition of a platinum layer on the front side of the substrate. It was ascertained that, during the direct EPD on the porous NiO-SDC substrate, the formation of a continuous coating did not occur, which may be due to insufficient porosity of the substrate used. It was shown that the use of reduced substrates leads to cracking and, in some cases, to the destruction of the entire SDC/NiO-SDC structure. The dependence of the electrolyte film sinterability on the substrate shrinkage was studied. In contrast to the literature data, the use of the substrates with a reduced pre-sintering temperature had no pronounced effect on the densification of the SDC electrolyte film. It was revealed that complete sintering of the SDC electrolyte layer with the formation of a developed grain structure is possible at a temperature of 1550 °C. Full article

Steam electrolysis constitutes a prospective technology for industrial-scale hydrogen production. The use of ceramic proton-conducting electrolytes is a beneficial option for lowering the operating temperature. However, a significant challenge with this type of electrolyte has been upscaling robust planar type devices. The fabrication of such multi-layered devices, usually via a tape casting process, requires careful control of individual layers’ shrinkages to prevent warping and cracks during sintering. The present work highlights the successful processing of 50 × 50 mm² planar electrode-supported barium cerium yttrium zirconate BaZr_0.44Ce_0.36Y_0.2O_2.9 (BZCY(54)_8/92) half cells via a sequential tape casting approach. The sintering parameters of the half-cells were analyzed and adjusted to obtain defect-free half-cells with diminished warping. Suitably dense and gas-tight electrolyte layers are obtained after co-sintering at 1350 °C for 5 h. We then assembled an electrolysis cell using Ba_0.5La_0.5CoO_3−δ as the steam electrode, screen printed on the electrolyte layer, and fired at 800 °C. A typical Ba_0.5La_0.5CoO_3−δ|BaZr_0.44Ce_0.36Y_0.2O_3−δ(15 μm)|NiO-SrZr_0.5Ce_0.4Y_0.1O_3−δ cell at 600 °C with 80% steam in the anode compartment reached reproducible terminal voltages of 1.4 V @ 500 mA·cm⁻², achieving ~84% Faradaic efficiency. Besides electrochemical characterization, the morphology and microstructure of the layered half-cells were analyzed by a combination of high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray spectroscopy. Our results also provide a feasible approach for realizing the low-cost fabrication of large-sized protonic ceramic conducting electrolysis cells (PCECs). Full article