阳极功能层厚度对中温固体氧化物燃料电池电性能的影响

采用水系流延成型工艺,研究了阳极支撑型中温SOFC阳极功能层厚度对中温SOFC电性能的影响,运用电化学工作站对单电池的电性能进行了表征。结果表明,在相同的运行温度下,单电池的功率密度随着功能层厚度的增加而减小,而极化阻抗则相应增加;单电池的功率密度随着运行温度的提高而增大,对应的极化阻抗则减小。以H2＋3%水蒸气为燃料气,空气为氧化气,在750℃运行条件下,功能层厚度为25μm、30μm和35μm的单电池的功率密度分别为0.31 W/cm^2、0.10 W/cm^2和0.07 W/cm^2,相应的极化阻抗则分别为1.05Ωcm^2、2.41Ωcm^2和3.08Ωcm^2;阳极功能层厚度为25μm的单电池的测试温度在700℃、750℃和800℃,其功率密度分别为0.22 W/cm^2、0.31 W/cm^2和0.45 W/cm^2,对应极化阻抗分别为1.90Ωcm^2、1.05Ωcm^2和0.67Ω/cm^2。     

阳极功能层对SOFC单电池电性能的影响

采用水系流延(含双层水系流延)技术流延电解质/阳极(阳极功能层),叠压共烧技术制备大规格阳极支撑型半电池,利用丝网印刷技术印刷LSM-YSZ阴极,经烧成后获得单电池,对比研究了阳极功能层对SOFC单电池电性能的影响。采用SEM、电子负载及电化学工作站对单电池结构和电性能进行了表征。研究结果表明,阴极、电解质、阳极功能层和阳极支撑层之间结合紧密,阳极功能层的结构均匀,平均孔径为1.12μm。在单电池中增加阳极功能层,单电池以H_2+3%水蒸气为燃料气,空气为氧化气在750℃的最大功率密度由0.21W/cm~2变为0.31W/cm~2,极化阻抗由0.98Ω·cm~2降至0.69Ω·cm~2,单电池放电100h后衰减率由6.94%降至2.63%,衰减率降低了62.1%。     

PMMA含量对水系流延IT-SOFC性能的影响

通过向阳极添加单一分散性的球形造孔剂PMMA改善阳极的微观结构,研究不同含量的PMMA对阳极的孔隙率、显微结构、电性能的影响。文中分别制备了造孔剂(PMMA)含量分别为6wt.%、8wt.%、10wt.%和12wt.%四种阳极材料的单电池,通过测试阳极还原前的开口气孔率分别为17vol.%,22.4vol.%,30.6vol.%和42.1vol.%;单电池的最大功率密度分别为0.66W/cm2、0.78W/cm2、1.15W/cm2和1.01W/cm2;极化电阻分别为1.12Ω.cm2、1.03Ω.cm2、0.88Ω.cm2和1.02Ω.cm2。实验结果表明:以单一分散性的球形PMMA为SOFC阳极材料的造孔剂,其最佳添加量为10wt.%,所制备的单电池可以获得最佳的电化学性能,即以3%H2O+H2为燃料气,750℃下,单电池的开路电压(OCV)为1.01V,最大功率密度为1.15W/cm2,极化电阻为0.88Ω.cm2。     

阳极NiO/YSZ含量对SOFC电化学性能的影响

采用水系流延技术制备电解质,利用涂覆法分别在电解质面涂覆Ni O/YSZ阳极和LSM/YSZ阴极得到电解质支撑型单电池。采用SEM和电化学工作站等测试手段分别对半电池的结构和单电池的电性能进行表征。研究结果表明,经1500℃保温2h烧成电解质,经1250℃保温2 h烧成半电池,电解质表面致密,阳极与电解质结合性好。Ni O/YSZ=6∶4阳极的单电池以氢气+3%H2O为燃料气,空气为氧化气,在750℃运行的最大功率密度为0.20 W/cm2,极化阻抗为0.98Ω·cm2。     

YSZ修饰的花瓣状氧化镍粉体的制备及其电性能表征

采用均匀沉淀法制备了花瓣状NiO粉体,对该花瓣状NiO进行YSZ(Y2O3稳定的ZrO2)修饰,以提高花瓣状NiO粉体的耐高温性,进而构建纳微结构的阳极。采用离子浸渍法制备了YSZ修饰的花瓣状NiO粉体(NiO-YSZ粉体),通过热重--差热分析、X射线衍射、扫描电子显微镜、能谱仪、透射电子显微镜等分析手段对该粉体的热性能、物相、微观形貌、晶粒大小等进行了表征。分别采用商业NiO(颗粒状)粉体和自制花瓣状NiO-YSZ粉体制备了电解质支撑型单电池的阳极,该单电池的组成为NiO+8YSZ‖8YSZ‖LSM+8YSZ,并测试了其电化学性能。结果表明:采用花瓣状NiO-YSZ粉体制备的阳极单电池在操作温度为在750、800和850℃下最大功率密度分别为0.094、0.151和0.376W/cm2,且相对应的电极极化阻抗分别为2.496、1.589和0.814Ω·cm2;而采用商业NiO制备的阳极的单电池在操作温度为在750、800和850℃下的最大功率密度分别为0.024、0.072和0.149W/cm2,且相对应的电极极化阻抗分别为4.265、2.306和1.688Ω·cm2。     

阳极支撑三层一体化结构电池的制备及性能

采用流延工艺制备了NiO-8％Y2O3/ZrO2(YSZ)阳极支撑三层一体化结构单电池,在此基础上采用浸渍工艺在多孔YSZ基体上低温制备了高活性阴极La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF).研究发现:降低电极制备温度可以得到微观形貌可控、分布均匀的纳米电极,并且避免了电极与基体间的反应:通过控制浸渍次数,制备了不同LSCF含量的电池;随着浸渍量的增加,电极的极化电阻显著下降;在800℃时,LSCF质量分数为45％的电池的功率密度高达1090 mW/cm2,同时电池稳定运行90h,表现出了很好的稳定性.     

中低温固体氧化物燃料电池制备与性能

通过流延成型、丝网印刷等工艺制备了以La0.6Sr0.4Co3-δ钙钛矿材料为阴极的高性能阳极支撑型中低温固体氧化物燃料电池,研究了电池在650℃～750℃温度下的放电性能及热循环性能.测试结果表明,制备的单电池在中低温具有优异的输出性能,且一致性较好,在700℃最高功率密度为0.622 W/cm2,长时间恒流放电后没有出现衰减,但其抗热循环性能较差.     

以Ni-YSZ和Sm0.5Sr0.5Fe0.8Cu0.2O3-δ为电极的微管固体氧化物燃料电池的制备及电化学性能（英文）

分别以Ni-YSZ中空纤维为阳极和Sm0.5Sr0.5Fe0.8Cu0.2O3–δ–Sm0.2Ce0.8O1.9（SSFCu-SDC）为阴极制备了微管固体氧化物燃料电池（SOFC）。利用扫描电子显微镜（SEM）、电化学工作站表征了微管单电池的显微结构与电化学性能。SEM分析表明,采用相转化法制备的Ni-YSZ中空纤维阳极呈特殊的非对称结构,主要由中间海绵状结构和内外两侧的指孔状多孔结构构成。通过真空辅助浸渍涂覆法和与阳极共烧技术在阳极支撑体上制备了致密的YSZ电解质膜和SDC过渡层。分别采用湿氢为燃料和静态环境空气为氧化剂测定了制备的微管单电池在650～750℃时的电化学性能。结果表明,该微管单电池具有高的输出性能,在750、700℃和650℃时的最大功率密度分别可达到485.9、382.7mW/cm2和260.3mW/cm2。     

实心多孔支撑体全膜化微型固体氧化物燃料电池的制备及性能

提出一种实心多孔支撑体全膜化微型固体氧化物燃料电池(micro solid oxide fuel cell,μSOFC)设计模型.电池用氧化钇部分稳定的氧化锆[(ZrO2)0.97(Y2O3)0.03,partially stabilized zirconia,PSZ]多孔陶瓷作为支撑体,在其上制备NiO-YSZ阳极层,分别采用离心和浸渍两种成膜工艺制备YSZ电解质膜,以La0.8Sr0.2MnO3-YSZ复合材料为阴极,对组装好的单电池进行了电化学性能测试.在850℃和800℃时,离心沉积工艺制备的单电池最大输出功率密度分别为286 mW/cm2和254 mW/cm2,而浸渍涂布法制备单电池的最大输出功率密度则分别达到572 mW/cm2和388 mW/cm2.电化学阻抗谱显示;电极极化是影响电池性能的主要因素.     

固体氧化物燃料电池阴极材料LSCF纳米纤维的静电纺丝法制备

采用溶胶–凝胶–静电纺丝法制备了La0.6Sr0.4Co0.2Fe0.8O3–δ(LSCF)纳米纤维。分析了LSCF纳米纤维的结构和形貌。结果表明:所制备的LSCF纳米纤维为内部微晶排列有序、均匀的多晶纤维,纤维直径约为200nm,长度分布为10~30μm,经1100℃煅烧后仍然保持纤维状。以LSCF纤维作为阴极,制备了固体氧化物燃料电池(SOFC)纽扣电池(GDC+NiO║GDC║LSCF)及其阴极对称电池(LSCE║GDC║LSCF)。单电池的阴极阻抗和电化学性能测试表明,LSCF纳米纤维阴极具有较高的电化学活性和较低的极化阻抗,以氢气为燃料、空气为氧化剂,在650和700℃工作温度下,单电池的最大功率密度分别为0.82和1.07W/cm2;在工作温度分别为600、650、700和750℃下,其阻抗分别为1.09、0.78、0.32和0.11·cm2。     

沉淀法制备中温固体氧化物燃料电池电解质材料8YSZ

以Zr （NO3）4·5H2O与Y（NO3）3·6H2O为主要原料,以柠檬酸为缓冲溶液,采用沉淀法制备电解质用8YSZ粉体,利用涂覆法在水系流延技术制备的半电池上涂覆LSM阴极得到单电池.运用XRD、TEM、激光粒度仪、SEM和电化学工作站等测试手段对粉体的物相、结构和粒度分布及单电池的结构与电性能进行了表征.研究结果表明,分散均匀、颗粒尺寸为50～100 nm、立方相8YSZ电解质在1375℃烧成具有高致密度,单电池在750℃时,以氢气和3％水蒸汽为燃料气,空气为氧化气的条件下,获得了开路电压为1.13 V,最大功率为0.93 w/cm2,欧姆阻抗为0.19Ωcm2和极化阻抗为0.65 Ωcm2的电性能.     

Fabrication and Power Densities of Anode‐Supported Solid Oxide Fuel Cells with Different Ni‐YSZ Anode Functional Layer Thicknesses

We investigated an appropriate preparation condition for anode‐supported SOFCs: (La,Sr)MnO₃/cathode functional layer/YSZ/Ni‐YSZ were fabricated with and without a Ni‐YSZ anode functional layer (AFL) via the tape‐casting method, where the AFL thicknesses were controlled from approximately 20 to 80 μm. The warpage depended on the co‐sintering temperature of the electrolyte/AFL/anode‐support half‐cells, indicating that similar shrinkage of the electrolyte/AFL/anode support is significant for lower warpages. The electrical properties of SOFCs with AFLs were compared to those of SOFCs without AFLs. In this regard, the use of an AFL decreased the ohmic and activation polarization resistances due to both the decrease in contact resistance between the electrolyte and the AFL and the increase in three‐phase boundaries. However, the polarization diffusion increased when an AFL was employed, because AFL layers are denser than the anode support. The maximum power densities of samples with AFL were higher than those of SOFCs without AFLs, indicating that the decrease in both ohmic and activation‐polarization resistances is more significant for improving the power densities, as compared to the concentration polarization resistance.     

Fabrication and Characterization of Anode-Supported Tubular Solid-Oxide Fuel Cells by Slip Casting and Dip Coating Techniques

High-performance anode-supported tubular solid-oxide fuel cells (SOFCs) have been successfully developed and fabricated using slip casting, dip coating, and impregnation techniques. The effect of a dispersant and solid loading on the viscosity of the NiO/Y₂O₃–ZrO₂ (NiO/YSZ) slurry is investigated in detail. The viscosity of the slurry was found to be minimum when the dispersant content was 0.6 wt% of NiO/YSZ. The effect of sintering temperature on the shrinkage and porosity of the anode tubes, densification of the electrolyte, and performance of the cell at different solid loadings is also investigated. A Ni/YSZ anode-supported tubular cell fabricated from the NiO/YSZ slurry with 65 wt% solid loading and sintered at 1380°C produced a peak power output of ∼491 and ∼376 mW/cm² at 800°C in wet H₂ and CH₄, respectively. With the impregnation of Ce_0.8Gd_0.2O₂ (GDC) nanoparticles, the peak power density increased to ∼1104 and ∼770 mW/cm² at 800°C in wet H₂ and CH₄, respectively. GDC impregnation considerably enhances the electrochemical performance of the cell and significantly reduces the ohmic and polarization resistances of thin solid electrolyte cells.     

Tubular solid oxide fuel cells fabricated by a novel freeze casting method

Freeze casting is an established method for fabricating porous ceramic structures with controlled porosity and pore geometries. Herein, we developed a novel freeze casting and freeze drying process to fabricate tubular anode supports for solid oxide fuel cells (SOFCs). Freeze casting was performed by injecting aqueous anode slurry to a dual-purpose freeze casting and freeze drying mold wrapped with peripheral coils for flowing a coolant. With the use of an ice barrier layer, proper control of the experimental setup, and adjustments in the drying temperature profile, complete drying of the individual anode tubes was achieved in 4 hours. The freeze-cast anode tubes contained radially aligned columnar pore channels, thus significantly enhancing the gaseous diffusion. SOFC single cells with conventional Ni/yttria-stabilized zirconia/strontium-doped lanthanum manganite materials were prepared by dip coating the thin functional layers onto the anode support. Single cell tests showed that the concentration polarization was low owing to the highly porous anode support with directional pores. With H₂/N₂ (1:1) fuel, maximum power densities of 0.47, 0.36, and 0.27 W/cm² were recorded at 800°C, 750°C, and 700°C, respectively. Our results demonstrate the feasibility of using freeze casting to obtain tubular SOFCs with desired microstructures and fast turn-around times.     

Influences of feedstock and plasma spraying parameters on the fabrication of tubular solid oxide fuel cell anodes

This study developed a tubular solid oxide fuel cell (SOFC) anode support layer via atmospheric plasma spraying, which is considered one of the most promising methods for producing SOFCs because of its faster deposition rate and lower cost compared with other film formation processes. Plasma spraying can replace the traditional use of extrusion technology to manufacture the anode base tube, eliminating the need for high-temperature sintering steps. In this study, commercially available powders were used to make the anode of a tubular SOFC from NiO/yttria-stabilized zirconia (YSZ) powder, and Na₂CO₃ and polymethyl methacrylate were tested as pore-forming agents. The anode composite powder was sprayed on the graphite base pipe, and the final product was changed by altering the spraying parameters and anode powder ratio. The direct current (DC) resistance measurements showed that the conductivity of the Ni/YSZ tubular anode formed with higher power plasma spraying could reach 428.55?S/cm at 800?°C. The experimental results showed that the power and parameters of atmospheric plasma spraying could affect the porosity and electron conductivity of tubular SOFC anodes.     

Thin Yttrium-Stabilized Zirconia Electrolyte Solid Oxide Fuel Cells by Centrifugal Casting

A centrifugal casting technique was developed for depositing thin 8-mol%-yttrium-stabilized zirconia (YSZ) electrolyte layers on porous NiO-YSZ anode substrates. After the bilayers were cosintered at 1400°C, dense pinhole-free YSZ coatings with thicknesses of ∼25 μm were obtained, while the Ni-YSZ retained porosity. After La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF)-Ce_0.9Gd_0.1O_1.95 (GDC) or La_0.8Sr_0.2MnO₃ (LSM)-YSZ cathodes were deposited, single SOFCs produced near-theoretical open-circuit voltages and power densities of ∼1 W/cm² at 800°C. Impedance spectra measured during cell tests showed that polarization resistances accounted for ∼70%–80% of the total cell resistance.     

Slip casting combined with colloidal spray coating in fabrication of tubular anode-supported solid oxide fuel cells

A simple and cost-effective slip casting technique was successfully developed to fabricate NiO–YSZ anode substrates for tubular anode-supported single SOFCs. An YSZ electrolyte film was coated on the anode substrates by colloidal spray coating technique. A single cell, NiO–YSZ/YSZ (20 μm)/LSM–YSZ, using the tubular anode supports with YSZ coating, was assembled and tested to demonstrate the feasibility of the techniques applied. Using humidified hydrogen (75 ml/min) as fuel and ambient air as oxidant, the maximum power densities of the cell were 760 mW/cm² and 907 mW/cm² at 800 °C and 850 °C, respectively. The observed OCV was closed to the theoretical value and the SEM results revealed that the microstructure of the anode fabricated by slip casting is porous while the electrolyte film coated by colloidal spray coating is dense.     

Effect of Nickel Oxide/Yttria-Stabilized Zirconia Anode Precursor Sintering Temperature on the Properties of Solid Oxide Fuel Cells

An NiO/yttria-stabilized zirconia (YSZ) layer sintered at temperatures between 1100° and 1500°C onto dense YSZ electrolyte foils forms the precursor structure for a porous Ni/YSZ cermet anode for solid oxide fuel cells. Conflicting requirements for the electrochemical performance and mechanical strength of such cells are investigated. A minimum polarization resistance of 0.09 Ω^.cm²at 1000°C in moist hydrogen is obtained for sintering temperatures of 1300°–1400°C. The mechanical strength of the cells decreases with increased sintering temperature because of the formation of channel cracks in the electrode layers, originating in a thermal expansion coefficient mismatch between the layers.