Electrochemical performance of a new structured low temperature SOFC with BZY electrolyte

A symmetrical solid oxide fuel cell (SOFC) with a novel microstructure of BaZr_0.9Y_0.1O_3–δ (BZY) as the electrolyte is investigated in this study. The cell with the Ni_0.8Co_0.15Al_0.05LiO₂ (NCAL)-foam Ni/BZY/foam Ni-NCAL structure is prepared by a co-pressing method. The maximum obtained power density is 735.6 mW cm^?2 in H₂ at 550 °C, which is comparable to the results obtained using Ni cermet anode-supported SOFCs with an extremely thin electrolyte. The ionic conductivity of the BZY electrolyte prepared in this study is much higher than that of the conventional BZY electrolyte. The activation energy of ionic conduction is much lower than that of traditional oxygen ion or proton conduction. Electrochemical impedance spectra (EIS) results of the cell with the BZY electrolyte measured in different atmospheric conditions and the results of oxygen ion filtration experiments for the cell using the BZY/Ce_0.9Gd_0.1O₂ (GDC) bilayer electrolyte indicate that oxygen ion is one of the carriers in the BZY electrolyte prepared in this study. According to the results of X-ray photoelectron spectroscopy (XPS) and Fourier Transform infrared spectroscopy (FTIR), an interfacial O^2? conduction mechanism at the interface of BZY particles in the electrolyte is discussed.     

Superprotonic KH(PO3H)–SiO2 composite electrolyte for intermediate temperature fuel cells

Novel thin film composite electrolyte membranes, prepared by dispersion of nano-sized SiO₂ particles in the solid acid compound KH(PO₃H), can be operated under both oxidizing and reducing conditions. Long-term stable proton conductivity is observed at 140 °C, i.e., slightly above the superprotonic phase transition temperature of KH(PO₃H), under conditions of relatively low humidification (pH₂O ≈ 0.02 atm).     

CeO2 coated NaFeO2 proton-conducting electrolyte for solid oxide fuel cell

Nowadays, the low-temperature operation has become an inevitable trend for the development of SOFCs. Transition metal layered oxides are considered as promising electrolyte materials for low-temperature solid oxide fuel cells (LT-SOFCs). In this work, we report the CeO₂ coated NaFeO₂ as an electrolyte material for LT-SOFC. The study results revealed that the piling of CeO₂ significantly influenced the open-circuit voltage (OCV) as well as the power output of the fuel cells. In comparison with pure NaFeO₂, the denser structure of CeO₂ coated NaFeO₂ leads to higher OCV (1.06 V, 550 °C). The electrochemical impedance spectrum (EIS) fitted results showed that NaFeO₂–CeO₂ composites possessed higher ionic boundary conductivity. This is because that the hetero-interfaces between NaFeO₂ and CeO₂ provide fast ion conducting path. The high ionic conductivity of CeO₂ coated NaFeO₂ lead to admirable fuel cell power output of 727 mW cm^?2 at 550 °C.     

Samarium doped ceria-(Li/Na)2CO3 composite electrolyte and its electrochemical properties in low temperature solid oxide fuel cell

A composite of samarium doped ceria (SDC) and a binary carbonate eutectic (52 mol% Li₂CO₃/48 mol% Na₂CO₃) is investigated with respect to its morphology, conductivity and fuel cell performances. The morphology study shows the composition could prevent SDC particles from agglomeration. The conductivity is measured under air, argon and hydrogen, respectively. A sharp increase in conductivity occurs under all the atmospheres, which relates to the superionic phase transition in the interface phases between SDC and carbonates. Single cells with the composite electrolyte are fabricated by a uniaxial die-press method using NiO/electrolyte as anode and lithiated NiO/electrolyte as cathode. The cell shows a maximum power density of 590 mW cm⁻² at 600 °C, using hydrogen as the fuel and air as the oxidant. Unlike that of cells based on pure oxygen ionic conductor or pure protonic conductor, the open circuit voltage of the SDC-carbonate based fuel cell decreases with an increase in water content of either anodic or cathodic inlet gas, indicating the electrolyte is a co-ionic (H⁺/O²⁻) conductor. The results also exhibit that oxygen ionic conductivity contributes to the major part of the whole conductivity under fuel cell circumstances.     

Electrical properties of nanocube CeO2 in advanced solid oxide fuel cells

Search for electrolyte materials with a high ionic conductivity at low temperatures has always been a key challenge for the development of solid oxide fuel cells (SOFCs). In present work, we found un-doped CeO₂ nanocubes used as an electrolyte for advanced fuel cell showed remarkable performances. The CeO₂ nanocubes were synthesized by a simple hydrothermal approach. The synthesized CeO₂ nanocubes were used as an electrolyte sandwiched between two layers of semiconducting Ni_0.8Co_0.15Al_0.05LiO_2-δ to fabricate the fuel cell. Such device has achieved an excellent maximum power density of 406 mW cm^?2 at 600 °C. These results demonstrate CeO₂/CeO_2-δ heterogeneous interfaces could provide a high ionic conductive path conductor for the electrolyte in SOFCs, which widen the selecting range of the electrolyte candidates for advanced SOFCs.     

Electrical properties of ceria Co-doped with Sm and Nd

Ceria co-doped with Sm³⁺ and Nd³⁺ powders are successfully synthesized by citric acid–nitrate low-temperature combustion process. In order to optimize the electrical properties of the series of ceria co-doped with Sm³⁺ and Nd³⁺, the effects of co-doping, doping content and sintering conditions on grain and grain boundary conductivity are investigated in detail. For the series of Ce_0.9(Sm_xNd_1−x)_0.1O_1.95 (x = 0, 0.5, 1) and Ce_1−x(Sm_0.5Nd_0.5)_xO_δ (x = 0.05, 0.10, 0.15, 0.20) sintered under the same condition, Ce_0.9(Sm_0.5Nd_0.5)_0.1O_1.95 exhibits both higher grain and grain boundary conductivity. Compared with Ce_0.9Gd_0.1O_1.95 and Ce_0.8Sm_0.2O_1.9, Ce_0.9(Sm_0.5Nd_0.5)_0.1O_1.95 sintered at 1350–1400 °C shows higher total conductivity with the value of 1.0 × 10⁻² S cm⁻¹ at 550 °C. In addition, it can be found the trends of grain and grain boundary activation energies of Ce_1−x(Sm_0.5Nd_0.5)_xO_δ are both consistent with those of Ce_1−xNd_xO_δ, but different from those of Ce_1−xSm_xO_δ, which can be explained as: the local ordering of oxygen vacancies maybe occurs more easily in Nd-doped ceria than in Sm-doped ceria; the segregation amount of Sm³⁺ is more than that of Nd³⁺ to the grain boundaries in ceria co-doped with Sm³⁺ and Nd³⁺, which is confirmed by X-ray photoelectron spectroscopy (XPS).     

Natural CuFe2O4 mineral for solid oxide fuel cells

Natural mineral, cuprospinel (CuFe₂O₄) originated from natural chalcopyrite ore (CuFeS₂), has been used for the first time in low temperature solid oxide fuel cells. Three different types of devices are fabricated to explore the optimum application of CuFe₂O₄ in fuel cells. Device with CuFe₂O₄ as a cathode catalyst exhibits a maximum power density of 180 mW/cm² with an open circuit voltage 1.07 V at 550 °C. And a power output of 587 mW/cm² is achieved from the device using a homogeneous mixture membrane of CuFe₂O₄, Li₂O-ZnO-Sm_0.2Ce_0.8O₂ and LiNi_0.8Co_0.15Al_0.05O₂. Electrochemical impedance spectrum analysis reveals different mechanisms for the devices. The results demonstrate that natural mineral, chalcopyrite, can provide a new implementation to utilize the natural resources for next-generation fuel cells being cost-effective and make great contributions to the environmentally friendly sustainable energy.     

High-performance low-temperature solid oxide fuel cells using thin proton-conducting electrolyte with novel cathode

We have fabricated BaCe_0.8Gd_0.2O_3−δ (BCGO) thin films with thickness in the range of 5–10 μm over substrates composed of Ce_0.8Gd_0.2O_1.9 (CGO)-NiO using a colloidal spray deposition method. A perovskite-type BaZr_0.2Co_0.4Fe_0.4O_3−δ (BZCFO) was employed as a novel cathode material. The performances of solid oxide fuel cells were investigated from 450 °C to 600 °C. The fuel cell with the BCGO film of 9 μm in thickness showed maximum power outputs of 237, 192, 136 and 89 mW cm⁻² at 600, 550, 500 and 450 °C, respectively. The impedance measurements at open circuit conditions showed the polarization resistances of the electrode were about 0.25 and 1.00 Ω cm² at 600 and 500 °C, respectively. The low interfacial resistances indicated that the BZCFO was a promising cathode material for low-temperature proton-conducing solid oxide fuel cells.     

Micro-tubular solid oxide fuel cells with graded anodes fabricated with a phase inversion method

Micro-tubular proton-conducting solid oxide fuel cells (SOFCs) are developed with thin film BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb) electrolytes supported on Ni-BZCYYb anodes. The substrates, NiO-BZCYYb hollow fibers, are prepared by an immersion induced phase inversion technique. The resulted fibers have a special asymmetrical structure consisting of a sponge-like layer and a finger-like porous layer, which is propitious to serving as the anode supports for micro-tubular SOFCs. The fibers are characterized in terms of porosity, mechanical strength, and electrical conductivity regarding their sintering temperatures. To make a single cell, a dense BZCYYb electrolyte membrane about 20 μm thick is deposited on the hollow fiber by a suspension-coating process and a porous Sm_0.5Sr_0.5CoO₃ (SSC)-BZCYYb cathode is subsequently fabricated by a slurry coating technique. The micro-tubular proton-conducting SOFC generates a peak power density of 254 mW cm⁻² at 650 °C when humidified hydrogen is used as the fuel and ambient air as the oxidant.     

A new perspective of co-doping and Nd segregation effect on proton stability and transportation in Y and Nd co-doped BaCeO3

Bulk and surface properties of proton stability and transportation in Y and Nd co-doped BaCeO₃ (BCYN), especially the effect of Nd segregation, were investigated by first-principles calculations. Since the structure of doped BaCeO₃ at the operating temperature of proton-conducting has been unclear for a long time, we have summarized the latest experimental results and calculated the structure of the asymmetric BCYN for the first time. The results show that compared with Y, Nd doping promotes oxygen vacancy formation, however reduces proton stability. Our calculation can also provide a possible explanation for the formation of space charge layer at the grain boundary of doped BaCeO₃ in experiment. Unlike the stable Y in BCYN, Nd is calculated to be easily segregated, which can facilitate both proton hydration and proton transportation near the surface. Moreover, Nd segregation at the grain boundary is predicted to be beneficial for proton transportation between grains.     

Effect of MgO addition and grain size on the electrical properties of Ce0.9Gd0.1O1.95 electrolyte for IT-SOFCs

The aim of this study is to investigate the effect of grain size on the electrical properties of Ce_0.9Gd_0.1O_1.95-x mol% MgO (GDC-xMgO) and to evaluate them as electrolytes for use in intermediate-temperature solid oxide fuel cells (IT-SOFCs). For this purpose, GDC-xMgO (x = 0–15) electrolytes were synthesized by the glycine-nitrate process and sintered at different temperatures. Impedance spectroscopy measurements revealed that for each composition, the grain-boundary resistivity decreased with decreasing grain size for the samples with grain size of >0.4 μm. Much too small grain sizes (0.2 < d_g < 0.3 μm) produced an increase in grain-boundary resistivity. The addition of MgO could weaken the influence of grain sizes on the grain-boundary resistivity. The interfacial polarization resistances could be decreased by adding MgO to GDC. The GDC-1MgO sample sintered at 1200 °C exhibited the highest total conductivity of 8.11 × 10^?2 S cm^?1 at 800 °C. The maximum power density of the GDC-1MgO-based cell was 0.73 W cm^?2 at 800 °C, which was much higher than that of the GDC-based cell. The results indicated that the GDC-1MgO was a potential electrolyte for IT-SOFCs.     

The heterogeneous electrolyte of CuFeO2 nano-flakes composited with flower-shaped ZnO for advanced solid oxide fuel cells

The flower-shaped ZnO was synthesized to form composite with the delafossite structure CuFeO₂. The composite heterojunction formed for the ZnO-CuFeO₂ composite material demonstrates a profound significance for exploring novel materials in solid oxide fuel cell (SOFC) field. At 550 °C, power outputs of 300 mW cm^?2 and 468 mW cm^?2 were achieved for SOFC devices using pure ZnO and composite with CuFeO₂ as the electrolytes, respectively. The composite showed a good performance at low temperatures, for instance, it showed a power output of 148 mW cm^?2 at 430 °C. The studies on photocurrent-time curves with visible light on/off irradiation provided an evidence for electron-hole separation. The heterojunctions separate holes and electrons, preventing short-circuiting while used in the SOFC device. These results demonstrate that introducing the heterojunctions in the electrolyte is an innovative approach for advanced SOFCs.     

Developing cuprospinel CuFe2O4–ZnO semiconductor heterostructure as a proton conducting electrolyte for advanced fuel cells

The interfacial properties of electrolyte materials have a crucial impact on the ionic conductivity of solid batteries and solid oxide fuel cells. Here we construct cuprospinel CuFe₂O₄ (CFO)–ZnO composite as a functional electrolyte for fuel cell device. In an optimal composition of 0.3CFO-0.7ZnO electrolyte fuel cell, the maximum power output of 675 mW cm^?2 is obtained at 550 °C. The electrical properties and electrochemical performance are strongly dependent on the ratios between CFO and ZnO in CFO-ZnO composite. Notably, surprising fuel cell performance with high ionic conductivity is attained by constructing this p-type CFO composited with n-type ZnO. Proton conduction was further verified experimentally. The interfacial ionic conduction pathway between the two constituent phases plays a vital role to enhance the proton conductivity, and the bulk p-n heterojunction can block internal electronic pass. An excellent current and power densities of CFO-ZnO composite are observed along with a high conductivity of 0.35 S·cm-1 at 550 °C. This work opens a new perspective for the semiconductor materials that can widely be developed for electrolytes, based on their tunable band structure.     

Enhanced ionic conductivity of yttria-stabilized ZrO2 with natural CuFe-oxide mineral heterogeneous composite for low temperature solid oxide fuel cells

We report for the first time that the commercial yttrium stabilized zirconia (YSZ) nanocomposite with a natural CuFe-oxide mineral (CF) exhibits a greatly enhanced ionic conductivity in the low temperature range (500–600 °C), e.g. 0.48 S/cm at 550 °C. The CF–YSZ composite was prepared via a nanocomposite approach. Fuel cells were fabricated by using a CF–YSZ electrolyte layer between the symmetric electrodes of the Ni_0.8Co_0.2Al_0.5Li (NCAL) coated Ni foam. The maximum power output of 562 mW/cm² has been achieved at 550 °C. Even the CF alone to replace the electrolyte the device reached the maximum power of 281 mW/cm² at the same temperature. Different ion-conduction mechanisms for YSZ and CF–YSZ are proposed. This work provides a new approach to develop natural mineral composites for advanced low temperature solid oxide fuel cells with a great marketability.     

Chemical stability and electrical and mechanical properties of BaZrxCe0.8-xY0.2O3 with CeO2 protection method

This study investigated the decline in the conductivity and mechanical strength after CO₂ poisoning and found a new protective method for BaZr_xCe_0.8-xY_0.2O₃ proton-conducting electrolyte. The high temperature solid state reaction (SSR) was used in synthesizing electrolyte to naturally generate CeO₂ on the surface. A comparison of the oxides in the conductivity decline test revealed that the sample with CeO₂ on the surface substantially improved the stability of conductivity, reducing the decline ratio from 56% to 7% for BCY electrolyte and 50% to 7% for BCZY sample. Raman mapping results indicate the naturally generated CeO₂ on electrolyte surface can considerably reduce impurity formation and maintain the microstructure of electrolyte. This work demonstrates that samples with CeO₂ on the surface effectively protect the BaCeO₃-based proton-conducting electrolyte from CO₂ poisoning. This method may be applied to similar BaCeO₃-based perovskite materials as a new protective method.     

Electrical conductivity and related properties of molten carbonates coexisting with ceria-based oxide powder for hybrid electrolyte

The electrical, thermal and structural properties of composite electrolyte containing Ce_0.9Gd_0.1O_1.95 (GDC) powder and (Li_0.52Na_0.48)₂CO₃ eutectics are investigated by AC impedance, differential thermal analysis and polarized Raman scattering spectroscopy. The system shows a dependence of the electrical conductivity upon the temperature. The transition point varies with the apparent average thickness of the liquid phase, while the activation energy, ΔE_a, remains constant at any distance from the solid phase. Higher electrical conductivity was obtained for the GDC/(Li_0.52Na_0.48)₂CO₃ composite than that for α-Al₂O₃/(Li_0.52Na_0.48)₂CO₃. Even in the N₂ or Air gas flow, the weight loss caused by decomposition of CO₃²⁻ ion based on Lux–Flood equilibrium was rarely observed. The symmetric stretching mode of the polarized Raman spectra shows that carbonate ion maintains its D_3h symmetry in the presence of ceria. A constant value of the depolarization ratio of the ν₁(A′₁) mode with regard to the apparent average thickness confirms that the symmetry of carbonate ions in the molten state is not altered by the presence of ceria powder. It was more stable than that for the system containing α-Al₂O₃ as a reference sample. These findings contribute to the understanding of the properties of ceria-based carbonate electrolyte for intermediate temperature solid oxide fuel cells.     

Porous YFe0.5Co0.5O3 thin sheets as cathode for intermediate-temperature solid oxide fuel cells

In this work, porous YFe_0.5Co_0.5O₃ (YFC) thin sheets were synthesized by citric acid method. The crystal structure, morphology, thermal expansion, electrical conductivity, and electrochemical properties of YFC were investigated to evaluate it as a possible cathode on BaZr_0.1Ce_0.7Y_0.2O₃ (BZCY) electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs). An orthorhombic perovskite structure was observed in YFC. The conductivity of YFC is 183 S cm ^?1 at 750 °C in air. The coefficient of thermal expansion of composite cathode YFC-BZCY is closer to BZCY electrolyte than YFC. The composite cathode represents a relatively low polarization resistance (R_p) of 0.07 Ω cm² at 750 °C in air due to the porous thin sheet-like cathode. The oxygen reduction reaction process and the reaction activation energy of cathode were also analyzed. An anode-supported cell of NiO-BZCY∣BZCY∣YFC-BZCY is fabricated by a simple method of co-pressing. The power density of the cell is 303 mW cm^?2 at 750 °C as the thickness of electrolyte is 400 μm. The results suggest that YFC is a promising cathode candidate for IT-SOFC.     

Fabrication and performance of a carbon dioxide-tolerant proton-conducting solid oxide fuel cells with a dual-layer electrolyte

A proton-conducting solid oxide fuel cells with a dual-layer electrolyte, constructed of a highly protonic conductive BaCe_0.8Y_0.2O_3−δ (BCY) electrolyte and chemically stable BaZr_0.4Ce_0.4Y_0.2O_3−δ (BZCY4) electrolyte, was easily fabricated by dry pressing the electrolyte powders onto an NiO + BZCY4 anode substrate, followed by co-sintering at a high temperature. The performance of the as-fabricated cell with the BCY and BZCY4 dual-layer electrolyte was studied. Peak power densities of 249 and 101 mW cm⁻² were achieved at 700 and 500 °C, respectively. Zinc was applied as a sintering promoter to increase the relative density of the BZCY4 electrolyte. Cross-sectional micrographs of the as-fabricated, dual-layer electrolyte cells were obtained by scanning electron microscopy. The results showed that the sintering ability of BZCY4 was improved by using zinc as sintering aid. A cell with BCY and zinc-modified BZCY4 dual-layer electrolyte delivered peak power densities of 276 and 247 mW cm⁻² and OCVs of 1.03 and 1.02 V at 700 °C under humidified hydrogen and 15% CO₂-containing hydrogen atmospheres, respectively. The operation stability of the dual-layer electrolyte cell under a 15% CO₂-containing hydrogen atmosphere was also investigated.     

Industrial grade rare-earth triple-doped ceria applied for advanced low-temperature electrolyte layer-free fuel cells

In this study, the mixed electron-ion conductive nanocomposite of the industrial-grade rare-earth material (La³⁺, Pr³⁺ and Nd³⁺ triple-doped ceria oxide, noted as LCPN) and commercial p-type semiconductor Ni_0.8Co_0.15Al_0.05Li-oxide (hereafter referred to as NCAL) were studied and evaluated as a functional semiconductor-ionic conductor layer for the advanced low temperature solid oxide fuel cells (LT-SOFCs) in an electrolyte layer-free fuel cells (EFFCs) configuration. The enhanced electrochemical performance of the EFFCs were analyzed based on the different semiconductor-ionic compositions with various weight ratios of LCPN and NCAL. The morphology and microstructure of the raw material, as-prepared LCPN as well the commercial NCAL were investigated and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and energy-dispersive X-ray spectrometer (EDS), respectively. The EFFC performances and electrochemical properties using the LCPN-NCAL layer with different weight ratios were systematically investigated. The optimal composition for the EFFC performance with 70 wt% LCPN and 30 wt% NCAL displayed a maximum power density of 1187 mW cm^?2 at 550 °C with an open circuit voltage (OCV) of 1.07 V. It has been found that the well-balanced electron and ion conductive phases contributed to the good fuel cell performances. This work further promotes the development of the industrial-grade rare-earth materials applying for the LT-SOFC technology. It also provides an approach to utilize the natural source into the energy field.