Improved Electrodes/Electrolyte Interfaces for Solid Oxide Fuel Cell by Using Dual‐Sized Powders in Electrolyte Slurry

The dense electrolyte film with the rough surfaces for solid oxide fuel cell (SOFC) was fabricated on NiO/yttria‐stabilized zirconia (YSZ) anode substrate by using dual‐sized YSZ powders without additional effort to roughen electrolyte film. The dual‐sized YSZ powders consisted of the fine YSZ powder and the coarse YSZ powder at different weight ratios. Incorporation of the coarse YSZ powder into the fine YSZ powder is in order to increase the surface roughness of electrolyte film, and the surface roughness obviously increased with the increase of coarse YSZ powder. The rough surfaces resulted in an enlargement of the electrochemical active area. It was found that electrode polarization was reduced evidently and cell electrochemical performance was enhanced, as the surface roughness increased. However, the excessive coarse YSZ powder was not beneficial for densification of electrolyte film and thus the open‐circuit voltage (OCV) was declined. The cell with 17 wt.% coarse YSZ powder in the electrolyte exhibited the best performance and the maximum power density was 1,930 mW cm^–2 at 800 °C.     

Electrophoretic Deposition of Zirconia Thin Film on Nonconducting Substrate for Solid Oxide Fuel Cell Application

Electrophoretic deposition (EPD) of 8 mol% yttria‐stabilized zirconia (YSZ) electrolyte thin film has been carried out onto nonconducting porous NiO‐YSZ cermet anode substrate using a fugitive and electrically conducting polymer interlayer for solid oxide fuel cell (SOFC) application. Such polymer interlayer burnt out during the high‐temperature sintering process (1400°C for 6 h) leaving behind a well adhered, dense, and uniform ceramic YSZ electrolyte film on the top of the porous anode substrate. The EPD kinetics have been studied in depth. It is found that homogeneous and uniform film could be obtained onto the polymer‐coated substrate at an applied voltage of 15 V for 1 min. After the half‐cell (anode + electrolyte) is co‐fired at 1400°C, a suitable cathode composition (La_0.65Sr_0.3MnO₃) thick film paste is screen printed on the top of the sintered YSZ electrolyte. A second stage of sintering of such cathode thick film at 1100°C for 2 h finally yield a single cell SOFC. Such single cell produced a power output of 0.91 W/cm² at 0.7 V when measured at 800°C using hydrogen and oxygen as fuel and oxidant, respectively.     

Preparation of Yttria-Stabilized Zirconia Thin Films on Strontium-Doped LaMnO3 Cathode Substrates via Electrophoretic Deposition for Solid Oxide Fuel Cells

A yttria-stabilized zirconia (YSZ) thin film on an La_0.8Sr_0.2MnO₃ porous cathode substrate was prepared, using electrophoretic deposition (EPD) to fabricate a solid oxide fuel cell (SOFC). The electrical conductivity of an La_0.8Sr_0.2MnO₃ substrate is satisfactorily high at room temperature; therefore, YSZ powder could be deposited electrophoretically onto an La_0.8Sr_0.2MnO₃ substrate without any extra surface treatment, such as a metal coating. Successive repetition of EPD and sintering was required to obtain a film without gas leakage, because of the thermal expansion coefficient mismatch between the YSZ and the La_0.8Sr_0.2MnO₃ substrate. On the other hand, the electromotive force of the oxygen concentration in the cell that used YSZ film prepared via EPD increased and attained the theoretical value when the number of deposition and calcination cycles was increased. Six or more successive repetitions were required to obtain a YSZ film without gas leakage. A planar-type SOFC was fabricated, using nickel as the anode and YSZ film (∼10 μm thick) that had been deposited onto the La_0.8Sr_0.2MnO₃ substrate as the electrolyte and cathode. The cell exhibited an open circuit voltage of 1.0 V and a maximum power density of 1.5 W/cm². Thus, the EPD method could be used as a colloidal process to prepare YSZ thin-film electrolytes for SOFCs.     

Thin film yttria-stabilized zirconia electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs) by chemical solution deposition

A 500 nm thick thin film YSZ (yttria-stabilized zirconia) electrolyte was successfully fabricated on a conventionally processed anode substrate by spin coating of chemical solution containing slow-sintering YSZ nanoparticles with the particle size of 20 nm and subsequent sintering at 1100 °C. Incorporation of YSZ nanoparticles was effective for suppressing the differential densification of ultrafine precursor powder by mitigating the prevailing bi-axial constraining stress of the rigid substrate with numerous local multi-axial stress fields around them. In particular, adding 5 vol% YSZ nanoparticles resulted in a dense and uniform thin film electrolyte with narrow grain size distribution, and fine residual pores in isolated state. The thin film YSZ electrolyte placed on a rigid anode substrate with the GDC (gadolinia-doped ceria) and LSC (La_0.6Sr_0.4CoO_3?δ) layers deposited by PLD (pulsed laser deposition) processes revealed that it had fairly good gas tightness relevant to a SOFC (solid oxide fuel cell) electrolyte and maintained its structural integrity during fabrication and operation processes. In fact, the open circuit voltage was 1.07 V and maximum power density was 425 mW/cm² at 600 °C, which demonstrates that the chemical solution route can be a viable means for reducing electrolyte thickness for low- to intermediate-temperature SOFCs.     

Preparation of Anode/Electrolyte Ceramic Composites by Coextrusion of Pastes

Anode/electrolyte two-layer ceramic composites for tubular solid oxide fuel cells were prepared through coextrusion of multiple pastes containing a water-based binder (an aqueous solution of hydroxypropyl methylcellulose). The multibillet extrusion (MBE) technique was found to be effective in achieving the anode/electrolyte composite pipes. Furthermore, it is possible to reduce the wall thickness of both anode and electrolyte layers by raising the extrusion ratio of each layer. The extrusion pressure and binder content required to obtain sound extrudates decreased with an increase in the fraction of nickel oxide in an anode layer. It is feasible to decrease the difference in the sintering shrinkage between the anode and electrolyte layers by incorporating calcined coarse yttria-stabilized zirconia (YSZ) powder in the electrolyte layer. The incorporation of coarse YSZ powder in an anode is effective in forming a continuous NiO network within the YSZ matrix.     

Low-temperature constrained sintering of YSZ electrolyte with Bi2O3 sintering sacrificial layer for anode-supported solid oxide fuel cells

Solid oxide fuel cells (SOFCs) have strong potential for next-generation energy conversion systems. However, their high processing temperature due to multi-layer ceramic components has been a major challenge for commercialization. In particular, the constrained sintering effect due to the rigid substrate in the fabrication process is a main reason to increase the sintering temperature of ceramic electrolyte. Herein, we develop a bi-layer sintering method composed of a Bi₂O₃ sintering sacrificial layer and YSZ main electrolyte layer to effectively lower the sintering temperature of the YSZ electrolyte even under the constrained sintering conditions. The Bi₂O₃ sintering functional layer applied on the YSZ electrolyte is designed to facilitate the densification of YSZ electrolyte at the significantly lowered sintering temperature and is removed after the sintering process to prevent the detrimental effects of residual sintering aids. Subsequent sublimation of Bi₂O₃ was confirmed after the sintering process and a dense YSZ monolayer was formed as a result of the sintering functional layer-assisted sintering process. The sintering behavior of the Bi₂O₃/YSZ bi-layer system was systematically analyzed, and material properties including the microstructure, crystallinity, and ionic conductivity were analyzed. The developed bi-layer sintered YSZ electrolyte was employed to fabricate anode-supported SOFCs, and a cell performance comparable to a conventional high temperature sintered (1400 °C) YSZ electrolyte was successfully demonstrated with significantly reduced sintering temperature (<1200 °C).     

Lowering the co-sintering temperature of cathode–electrolyte bilayers for micro-tubular solid oxide fuel cells

To prevent undesirable reactions between the cathode and electrolyte materials in cathode-supported solid oxide fuel cells (SOFCs), the co-sintering temperature of these two layers must be lowered. In the present work, we employed different strategies to lower the co-sintering temperature of cathode–electrolyte bilayers for micro-tubular SOFCs by increasing the cathode sintering shrinkage and adding sintering aids to the electrolyte. Strontium-doped lanthanum manganite (LSM) and yttria-stabilized zirconia (YSZ) were used as the cathode and electrolyte materials, respectively. To facilitate densification of the electrolyte layer by controlling the shrinkage of the cathode support, the particle size of the LSM powder was reduced by high-energy ball milling and different amounts of micro-crystalline cellulose pore former were used. Sintering aids, namely NiO and Fe₂O₃, were also added to the YSZ electrolyte to further improve its low-temperature sintering. Our results indicate that with the improvement in the cathode support shrinkage and use of the small amounts of sintering aids, the cathode–electrolyte co-sintering temperature can be reduced to 1250–1300 °C. It was also observed that the presence of the sintering aids helps to reduce the reactivity between the LSM cathode and YSZ electrolyte.     

Assembly of 8YSZ nanoparticles into gas-tight 1-2 μm thick 8YSZ electrolyte layers using wet coating methods

The application of a thin film electrolyte layer with a thickness in the micrometer range could greatly improve current solid oxide fuel cells (SOFCs) in terms of operating temperature and power output. Since the achievable minimal layer thickness with conventional powder coating methods is limited to ∼5 μm, a variety of thin film methods have been studied, but results on regular large-scale anode substrates are still lacking in the literature. In this paper, a wet coating process is presented for fabricating gas-tight 1-2 μm thick 8YSZ electrolyte layers on a regular NiO/8YSZ substrate, with a rough surface, a high porosity and a large pore size. These layers were deposited in a similar way as conventional suspension based layers, but the essential difference includes the use of coating liquids (nano-dispersion, sol) with a considerably smaller particle size (85 nm, 60 nm, 35 nm, 6 nm). Successful deposition of such layers was accomplished by means of an innovative coating process, which involves the preparation of a hybrid polyvinyl alcohol/8YSZ membrane by dip-coating or spin-coating and subsequently burning out the polymer part at 500 °C. Results from He leak tests confirmed that the sintered layers posses a very low number of defects and with values in the range 10⁻⁴-10⁻⁶ (hPa dm³)/(s cm²) the gas-tightness of the thin film layers is satisfactory for fuel cell operation. Moreover, preliminary results have also indicated a potential reduction of the sintering temperature from 1400 °C to the range 1200-1300 °C, using the presented coating process.     

浆料成分对NiO电极微观结构的影响

分别采用NiO浆料、Ni浆料和Ni/YSZ浆料制备NiO敏感电极.其中Ni/YSZ浆料是由在Ni浆料中添加15vol％ YSZ粉末制备的.结果表明,采用NiO浆料普通烧结得到的NiO电极致密且有裂纹;采用Ni浆料和Ni/YSZ浆料反应烧结分别制备的NiO电极和NiO/YSZ复合电极则疏松多孔且无裂纹.浆料中添加的YSZ不仅能够细化NiO电极晶粒,同时能增强电极和基底的界面附着,增加三相界面的数量和长度.     

Preparation of Dense Platinum-Yttria Stabilized Zirconia and Yttria Stabilized Zirconia Films on Porous La0.9Sr0.1MnO3 (LSM) Substrates

A sol–gel process has been developed to prepare fine powder of La_0.9Sr_0.1MnO₃ (LSM) with an average particle size ∼40 nm. The LSM powder is pressed to pellets, on which a uniform green yttria-stabilized zirconia (YSZ) film is deposited using an electrophoretic deposition process. A green composite film of platinum and YSZ (Pt-YSZ) is prepared on the top of the green YSZ film using a colloidal process, followed by filling the pores using a sol–gel process. The three-layered structure, a green Pt-YSZ film, and a green YSZ film on a green LSM substrate, is fired at 1250°C for 3 h, resulting in a dense Pt-YSZ and YSZ film supported by a porous LSM substrate. Electrical measurements show that the sensors with the three-layered structure display a well-defined diffusion-limited current in gases containing partial pressure of oxygen up to ∼9 vol%, implying that the quality of the Pt-YSZ and YSZ film is adequate for the sensor application.     

Processing of Composite Thin Film Solid Oxide Fuel Cell Structures

A solid oxide fuel cell (SOFC) structure is proposed in which a composite thin film cathode substrate supports a dense thin film electrolyte with a thickness of less than 1 μm. The cathode substrate has a graded porosity achieved through the partial sintering of a spin-coated CeO₂ colloidal suspension. The resulting surface has a pore size and surface roughness which allowed a fully dense ZrO₂:16%Y (YSZ) electrolyte to be spin-coated directly from a polymeric precursor without capillary forces removing the precursor from the surface of the porous substrate. Using this process, fuel cell structures were constructed with temperatures not exceeding 800°C. The porous CeO₂ interlayer should allow for decreased ohmic losses, as well as decreased reactions between the YSZ and the cathode substrate. In addition, the nanocrystalline grain sizes should allow for increased catalytic activity on the cathode. Calculated ohmic losses indicated the resistance of the CeO₂ interlayer limited the power of the structure, which was minimized by impregnating the porous layer with a mixed-conducting perovskite. The final structure shows significantly reduced ohmic losses as calculated at 400°C.     

ZnO对8YSZ电解质材料的烧结性与电化学性能的影响

用机械混合方法,在8%(摩尔分数,下同)Y2O3稳定的ZrO2(8%in mole yttria stabilized zirconia,8YSZ)中添加ZnO量分别为0,1%,2%,3%,4%,在不同温度下常压烧结制备了ZnO:8YSZ电解质。研究了烧结温度和ZnO含量对ZnO:8YSZ样品的烧结性、致密度、弯曲强度和电导率的影响。由ZnO:8YSZ电解质作为支撑组装了单电池,对电池的性能进行测试和评价。结果表明:在8YSZ中添加ZnO能改善8YSZ材料的烧结性,1400℃烧结2h的4%ZnO:8YSZ样品的致密度达99.9%,3%ZnO:8YSZ样品的弯曲强度超过200MPa,获得明显提高。4%ZnO:8YSZ样品在800℃下的电导率达1.68×10-2S/cm。在相同工作条件下,ZnO:8YSZ单电池比8YSZ单电池具有更好的工作性能和更高的效率,以3%ZnO:8YSZ单电池性能最好。     

添加Li_2O对YSZ电解质性能影响

8%（摩尔分数,下同）Y2O3稳定的ZrO2（8YSZ）是固体氧化物燃料电池（SOFC）中最常用的电解质材料,本文研究了在8YSZ基体中加入n%Li2O（n=0,0.25,0.50,1.00,1.50,1.70,2.00,2.50,3.00）后（记为n%Li2OYSZ）对其晶相结构、晶格常数、烧结性能、微观形貌、电导率及其作为SOFC电解质性能的影响。结果表明,Li2O中的Li＋可以固溶到YSZ的晶格内使其晶格常数减小;Li2O的加入量n〈1.70时,瓷体在烧结过程中不会发生相变。加入少量的Li2O（n=0.25,0.50）可以提高YSZ的致密度和电导率,0.25%Li2OYSZ和0.50%Li2OYSZ样品800℃的电导率分别高达0.030 2 S/cm和0.027 6 S/cm,分别是纯YSZ的1.35和1.24倍;当Li2O含量n≥1.00时,相同条件下烧结体致密度随Li2O加入量的增大而逐渐减小;当n≥1.70时,样品在烧结过程中虽然出现相变,但在高于1400℃可以烧结致密,并得到纯立方相YSZ。将1250℃烧结制得的0.25%Li2OYSZ和0.50%Li2OYSZ作为SOFC电解质的单电池,800℃时的开路电压高于1.0V,说明YSZ中没有出现电子电导,具有比纯YSZ为电解质的单电池更高的性能输出,表现出了良好的应用前景。     

热处理工艺对纳米氧化锆粉体微观结构与涂层性能的影响

研究了高温煅烧、等离子炬和等离子流场3种热处理工艺对ZrO2-8%(mol)Y2O3 (8YSZ)球形颗粒及其等离子喷涂涂层微观组织结构的影响. 结果表明,由等离子炬处理后的8YSZ颗粒制备的等离子喷涂涂层的结合强度最高,平均为25 MPa,抗热震性能最好,1200℃恒温5 min,水冷、热循环达41次;而采用等离子流场处理的颗粒所制涂层结合强度最差,平均为11 MPa,热震时涂层易开裂,热循环次数为17次;高温煅烧的颗粒所制涂层性能依赖于煅烧温度和时间,其中1200℃下煅烧2 h的颗粒所制涂层力学性能最优,平均结合强度为21 MPa,热循环次数为38次.     

Fabrication of YSZ electrolyte for intermediate temperature solid oxide fuel cell using electrostatic spray deposition: II – Cell performance

Electrostatic spray deposition (ESD) was applied to fabricate a thin-layer of yttria-stabilized zirconia (YSZ) electrolyte on a solid oxide fuel cell (SOFC) anode substrate consisting of nickel-YSZ cermet. A colloidal solution of 8 mol% YSZ in ethanol was sprayed onto the substrate anode surface at 250–300 °C by ESD. After sintering the deposited layer at 1250–1400 °C for 1–2 h depending on temperature, the cathode layer, consisting of lanthanum strontium manganate (LSM), was sprayed or brush coated onto the electrolyte layer. Performance tests and AC impedance measurements of the complete cell were carried out at 800 °C to evaluate the density and conductance of the electrolyte layer formed by ESD. With a 97% H₂/3% H₂O mixture and air as fuel and oxidant gas, respectively, the open-circuit voltage (OCV) was close to theoretical and electrolyte impedance was about 0.23Ω cm². A power density of 0.45 W cm⁻² at 0.62 V was obtained. No abnormal degradation was observed after 170 h operation. The electrolyte sintering temperature and time did not significantly affect the electrolyte impedance. on leave from     

Robust and reliable solid oxide fuel cells with modified thin film YSZ electrolyte

Reduce electrolyte thickness can improve solid oxide fuel cell (SOFC) performance. However, thinner electrolyte often contains prominent defects and flaws, which may decrease the yield and increase operation risk. This work proposes a method to modify the thin film YSZ electrolyte, to improve cell reliability and durability. The as-sintered anode supported half-cell with screen printed YSZ electrolyte was immersed in precursor solution of Y(NO₃)₃·6H₂O and Zr(NO₃)₄·5H₂O, and being treated under hydrothermal condition of 150°C for 12 h. As a result, the modified cells show slight increase in the OCV values. Furthermore, the hydrothermal modification effectively promotes interface sintering between YSZ electrolyte and GDC barrier layer, yielding a smaller ohmic resistance of .142 Ω·cm² (a decrease of ∼11%) and a higher peak power density of .964 W/cm² (an increase of ∼18%) at 750°C, than pristine cell. Moreover, the modified cell operates stably over 300 h, while the pristine cell presents large and irregular voltage fluctuations. This work suggests that the hydrothermal modification is an effective and promisingly industrial applicable method for thin film electrolyte recovery in SOFCs.     

Sintering behavior of a nanostructured thermal barrier coating deposited using electro-sprayed particles

During high temperature service, a series of microstructure and phase evolutions occur in thermal barrier coatings (TBCs), which result in degradation of thermal insulation and durability. In this study, the sintering behavior of an air plasma sprayed 8 wt% YSZ coating deposited using electro-sprayed nanostructured particles (ESP) as feedstock powder was investigated and compared with conventional YSZ coating deposited using hollow spherical powders (HOSP). Due to the distinct asymmetric porous structure formed by nanosized YSZ particles, the ESP powder was partially melted in the plasma jet during the deposition, which resulted in the formation of a nanostructured coating that consisted of porous nanozones and dense zones. The ESP coating not only shows a significantly lower initial thermal conductivity of 0.70 W/mK, but also exhibits a stronger sintering resistance in terms of phase stability and thermal insulation compared to the conventional coating. When subjected to prolonged sintering at 1400°C for 128 hours, the thermal conductivity of the ESP coating would gradually increase to about half that of the HOSP coating at 1.29 W/mK. These differences are ascribed to the interaction among different sintering behavior between nanozones and dense zones.     

Interaction of a ceria‐based anode functional layer with a stabilized zirconia electrolyte: Considerations from a materials perspective

We report on the materials interaction of gadolinium‐doped ceria (GDC) and yttria‐stabilized zirconia (YSZ) in the context of high‐temperature sintering during manufacturing of anode supported solid oxide fuel cells (AS–SOFC). While ceria‐based anodes are expected to show superior electrochemical performance and enhanced sulfur and coking tolerance in comparison to zirconia‐based anodes, we demonstrate that the incorporation of a Ni–GDC anode into an ASC with YSZ electrolyte decreases the performance of the ASC by approximately 50% compared to the standard Ni–YSZ cell. The performance loss is attributed to interdiffusion of ceria and zirconia during cell fabrication, which is investigated using powder mixtures and demonstrated to be more severe in the presence of NiO. We examine the physical properties of a GDC–YSZ mixed phase under reducing conditions in detail regarding ionic and electronic conductivity as well as reducibility, and discuss the expected impact of cation intermixing between anode and electrolyte.     

Digital light processing-stereolithography three-dimensional printing of yttria-stabilized zirconia

Digital light processing (DLP)-stereolithography three-dimensional (3D) printing is a well known technique for fabricating components with complex geometries. However, the application of DLP 3D printing to functional ceramics such as 8 mol% yttria-stabilized zirconia (8YSZ), which is one of the most extensively used electrolyte materials for solid oxide fuel cells, is still a great challenge. Therefore, the fabrication of fully 8YSZ monoliths via DLP 3D printing was attempted herein, including the preparation of UV-curable ceramic suspensions, shaping of green bodies, and debinding and sintering. The results show that intact green bodies printed using a 30 vol% 8YSZ-photosensitive resin suspension with 0.1 wt% oleic acid as the dispersant under the optimized printing conditions was sufficiently dense without connected pores after vacuum debinding and sintering in air. The successful fabrication of 8YSZ monoliths with design flexibility via 3D printing provides a simple method for preparing functional ceramic components and may expand the application of 3D printing technology to the energy field.     

Fabrication and Characterization of Anode‐Supported Low‐Temperature SOFC Based on Gd‐Doped Ceria Electrolyte

Large‐size, 9.5 cm × 9.5 cm, Ni‐Gd_0.1Ce_0.9O_1.95 (Ni‐GDC) anode‐supported solid oxide fuel cell (SOFC) has been successfully fabricated with NiO‐GDC anode substrate prepared by tape casting method and thin‐film GDC electrolyte fabricated by screen‐printing method. Influence of the sintering shrinkage behavior of NiO‐GDC anode substrate on the densification of thin GDC electrolyte film and on the flatness of the co‐sintered electrolyte/anode bi‐layer was studied. The increase in the pore‐former content in the anode substrate improved the densification of GDC electrolyte film. Pre‐sintering temperature of the anode substrate was optimized to obtain a homogeneous electrolyte film, significantly reducing the mismatch between the electrolyte and anode substrate and improving the electrolyte quality. Dense GDC electrolyte film and flat electrolyte/anode bi‐layer can be fabricated by adding 10 wt.% of pore‐former into the composite anode and pre‐sintering it at 1,100 °C for 2 h. Composite cathode, La_0.6Sr_0.4Fe_0.8Co_0.2O₃, and GDC (LSCF‐GDC), was screen‐printed on the as‐prepared electrolyte surface and sintered to form a complete single cell. The maximum power density of the single cell reached 497 mW cm^–2 at 600 °C and 953 mW cm^–2 at 650 °C with hydrogen as fuel and air as oxidant.