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。     

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.     

直通孔陶瓷在固体氧化物燃料电池中的应用EI北大核心CSCD

采用海藻酸钠自组装法制备了具有定向直通孔道的氧化钇稳定氧化锆(YSZ)支撑体,向多孔支撑体内部浸渍Ni纳米粒子得到固体氧化物燃料电池的阳极。结果表明:YSZ支撑体的孔径随固相含量的增大而减小,同时也随着CaCl2溶液浓度的增大而减小。使用氢气为燃料、空气为氧化剂,Ni–YSZ/YSZ/LSM–SDC电池在650℃的开路电压在1 V以上,800℃时的最大功率密度为225 m W/cm2。通过调节阳极的孔隙率及电解质厚度有望大幅度提高电池的输出性能,实现直通孔陶瓷在固体氧化物燃料电池上的应用。     

温度对微生物燃料电池电化学性能的影响

分别在20℃,37℃和45℃三个温度条件下以间歇方式运行大肠杆菌生物燃料电池(MFC),研究功率密度、电极电势、电化学阻抗等电化学性质随温度的变化规律.结果表明:温度从20℃提高到37℃,最大功率密度从53.35 mW/m2 (275 mA/m2)增加到610.5 mW/m2(2775 mA/m2),增长了10.5倍;同时阳极电极电势降低;且阳极电化学阻抗由741.9 Ω降低到42.4 Ω.在一定温度范围内,升高温度不仅能提高电池功率输出,而且能增强其电化学活性.但是,太高的温度反而不利于生物燃料电池的运行.45℃时的最大功率密度只有171 mW/m2(600 mA/m2),比37℃时最大功率610.5 mW/m2(2 775 mA/m2)减少72％;同时阳极电化学阻抗由42.4 Ω增加到416.1 Ω.大肠杆菌生物燃料电池在37℃时具有最佳的电化学性能.可见,温度在生物燃料电池运行中是一个非常重要的操作参数.     

乙烷质子交换膜燃料电池的研究

研究了以乙烷作为燃料、全氟磺酸高分子膜(Nafion膜)作为质子交换膜、Pt或Pt-Ru作为电极催化剂主要组分、并通过掺杂Nafion膜作为电极内的离子导体构成的燃料电池电化学性能.研究了两种电极催化剂:Pt与Pt-Ru复合催化剂的制备及构成的单电池在不同温度及运行时间下的电化学性能.温度增加,电池性能变好;运行时间增加,电池性能下降,在相同的温度与运行时间下,Pt-Ru复合催化剂构成的电池比Pt催化剂构成的电池极化小.通过分析电极反应产物,探讨了乙烷电极及电池的反应机理.结构为C2H6,( Pt-Ru+膜材料复合阳极)/Nafion膜/(Pt+膜材料复合阴极),O2 的质子交换膜燃料电池,在150℃时,电池的最大输出电流和功率密度分别高达70 mA·cm-2和22 mW·cm-2.     

直通孔陶瓷在固体氧化物燃料电池中的应用

采用海藻酸钠自组装法制备了具有定向直通孔道的氧化钇稳定氧化锆(YSZ)支撑体,向多孔支撑体内部浸渍Ni纳米粒子得到固体氧化物燃料电池的阳极。结果表明:YSZ支撑体的孔径随固相含量的增大而减小,同时也随着CaCl₂溶液浓度的增大而减小。使用氢气为燃料、空气为氧化剂,Ni–YSZ/YSZ/LSM–SDC电池在650℃的开路电压在1 V以上,800℃时的最大功率密度为225 m W/cm²。通过调节阳极的孔隙率及电解质厚度有望大幅度提高电池的输出性能,实现直通孔陶瓷在固体氧化物燃料电池上的应用。     

多层水系流延和共烧法制备具有阳极功能层固体氧化物燃料电池

采用多层水系流延和共烧方法制备具有阳极功能层的单电池。阳极基底、阳极功能层、电解质层和阴极层分别为Ni-YSZ、Ni-ScSZ、YSZ和LSM-ScSZ。在H2/空气气氛中,分别在700、750、800℃测试具有阳极功能层的单电池,其最大功率密度分别为：0.30、0.55W/cm2和0.8W/cm2;其对应的电池欧姆电阻（R0）分别为0.39、0.30cm2和0.19cm2。电池的极化电阻则分别为1.28、0.91cm2和0.62cm2。采用相同工艺制备无阳极功能层的单电池,其在700、750、800℃的最大功率密度分别为0.21、0.31W/cm2和0.56W/cm2,对应的R0为0.41、0.39cm2和0.28cm2。电池的极化电阻为1.40、1.27cm2和0.91cm2。这说明采用的多层水系流延和共烧法制备的固体氧化物燃料电池的阳极功能层能有效减小电池的活化极化,从而提高单电池的电化学性能。     

H2S燃料电池用质子传导膜及电池性能

研究了H2S燃料电池用的质子传导膜的制备及性能,考察了不同的Li2SO4与填充物Al2O3的匹配、微量元素B(H2BO3)的掺杂对膜及电池性能影响.研究了由H2S、(MoS2+NiS)/Li2SO4-Al2O3/pt、air构成的燃料电池在101.13kPa和600～700℃C时的电化学特性.在实验温度范围内,质子传导膜Li2SO4-Al2O3及整个电池系统在H2S气流下具有较好的化学稳定性.温度提高,质子传导膜的内阻减小,膜及电池性能变好.微量元素B的掺杂提高了膜的机械强度及膜的致密性,从而改善了电池的性能.在实验条件下,较适宜的B的掺杂量为2%～5%(质量百分数),较适宜的Li2SO4Al2O3(质量比)为(3～5)1,电池最大输出电流密度和功率密度在700℃时分别达到200mA.cm-2和55mW.cm-2.     

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。     

Co_3O_4浸渍La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_3-Sm_(0.2)Ce_(0.8)O_(1.9)复合阴极的制备及电化学性能

分别以固相反应法和甘氨酸法合成La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_3(LSCF)阴极粉体和Sm_(0.2)Ce_(0.8)O_(1.9)(SDC)电解质粉体。机械混合后,经压制烧结得到多孔LSCF-SDC复合阴极,通过水热法对多孔LSCF-SDC阴极浸渍Co_3O_4。研究Co_3O_4浸渍后的复合阴极的微观形貌和电化学性能。实验结果表明,对多孔LSCF-SDC阴极浸渍含Co盐溶液,经700℃焙烧后,在阴极表面形成针状Co_3O_4颗粒。浸渍处理使700℃下LSCF-SDC复合阴极的界面阻抗由0.49Ω·cm~2降低至0.19Ω·cm~2,阴极的氧还原反应活化能由1.52 eV降低至1.03 eV。此外,Co_3O_4浸渍阴极使700℃下单电池的功率密度由180 mW·cm~(-2)提高至260 mW·cm~(-2)。实验结果揭示,通过Co_3O_4浸渍,可有效提高LSCF-SDC复合阴极和燃料电池的电化学性能。     

Fabrication and Operation of Tubular Segmented‐In‐Series (SIS) Solid Oxide Fuel Cells (SOFC)

A tubular segmented‐in‐series (SIS) solid oxide fuel cell (SOFC) sub module for intermediate temperature (700–800 °C) operation was fabricated and operated in this study. For this purpose, we fabricated porous ceramic supports of 3 YSZ through an extrusion process and analyzed the basic properties of the ceramic support, such as visible microstructure, porosity, and mechanical strength, respectively. After that, we fabricated a tubular SIS SOFC single cell by using dip coating and vacuum slurry coating method in the case of electrode and electrolyte, and obtained at 800 °C a performance of about 400 mW cm^–2. To make a sub module for tubular SIS SOFC, ten tubular SIS SOFC single cells with an effective electrode area of 1.1 cm² were coated onto the surface of the prepared ceramic support and were connected in series by using Ag + glass interconnect between each single cell. The ten‐cell sub module of tubular SIS SOFC showed in 3% humidified H₂ and air at 800 °C a maximum power of ca. 390 mW cm^–2.     

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.     

Fabrication of a Flat Tubular Segmented‐in‐series Solid Oxide Fuel Cell Using Decalcomania Paper

A flat tubular segmented‐in‐series (SIS) solid oxide fuel cell (SOFC) was fabricated using decalcomania paper. The performance of a two‐cell stack with 4.5‐mm‐wide electrodes was investigated in a temperature range of 650–800 °C. The decalcomania paper allowed fabrication of the SIS‐SOFC on all sides of the flat tubular support and achieve an effective electrode area larger than that obtained using typical SOFC fabrication techniques such as screen printing or slurry coating. SEM observations revealed that each component layer was flat, uniformly thick, and well adherent to adjacent layers. Measured values of open circuit voltages were very close to the theoretical values; confirming that the processing technique utilizing decalcomania paper is suitable for SIS‐SOFC fabrication. The power densities of the two‐cell‐stack were 437.4, 375.6, 324.6, and 257.1 mW cm⁻² at 800, 750, 700 and 650 °C, respectively.     

Performances of micro-tubular solid oxide cell with novel asymmetric porous hydrogen electrode

Asymmetric-porous hollow-fiber has been fabricated by a phase-inversion process and employed as the hydrogen electrode for micro-tubular solid oxide cell (MT-SOC). The microstructure and electrochemical properties of MT-SOC were investigated in detail. The asymmetric-porous hydrogen electrode possesses unique two layer finger-like porous micro-structure with a thin functional layer and a thick fuel delivery layer. When the MT-SOC was operated in fuel cell mode, maximum power densities of 0.54, 0.71 and 1.25 W/cm² were obtained at 800, 850 and 900 °C, respectively. On the other hand, when the MT-SOC was operated in electrolysis mode at 900 °C with an applied voltage of 1.3 V, current densities of 0.68 A/cm² and 2.57 A/cm² were obtained at 30 vol.% and 80 vol.% absolute humidity (AH), respectively. These results indicate that novel-microstructured MT-SOC can be effectively fabricated towards high performance fuel cell and electrolysis cell.     

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.     

中温固体氧化物燃料电池SmBaCo_2O_（5＋δ）–Sm_（0.2）Ce_（0.8）O_（1.9）复合阴极材料的电化学性能

采用柠檬酸–硝酸盐自蔓延燃烧法分别合成了双钙钛矿结构的SmBaCo2O5＋δ（SBCO）阴极粉体和萤石型Sm0.2Ce0.8O1.9（SDC）电解质粉体,按3：2的质量比混合上述粉体研磨后得到复合阴极。利用X射线衍射仪研究化学相容性,直流四端子法测量电导率,热膨胀仪测量热膨胀系数;构建阳极支撑型单电池（Ni-SDC｜SDC｜SBCO-SDC）并进行了性能测试,用扫描电子显微镜观察电池的断面微结构,交流阻抗谱记录界面极化。结果表明：SBCO与SDC在1 000℃无相互作用;450～800℃,复合阴极的电导率在369～234 S/cm之间;SDC的加入降低了复合阴极的热膨胀系数;单电池具有理想的微观结构,阳极｜电解质｜阴极各界面彼此接触良好,650℃时极化电阻仅为0.031.cm2;以H2为燃料气（含体积分数3%水蒸气）,空气为氧化剂,650℃时电池的开路电压为0.77 V,输出功率最大值为640 mW/cm2。预示着SBCO-SDC是中温固体氧化物燃料电池有潜力的阴极材料。     

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.     

Effect of cathode fabrication method on characteristics of anode-supported tubular solid oxide fuel cells

We have adopted three different methods: dip-coating, brush pen painting, and ion-impregnating, to fabricate cathodes for anode-supported tubular solid oxide fuel cells; and studied the performances of the cells using cathodes fabricated by these three different methods. The cell with ion-impregnated cathode presented the best electrochemical performances in these three cells, and it generated a maximum power density of 446 mW cm⁻² at 850 °C, when operating with humidified hydrogen. The cells with dip-coated cathode and brush pen painted cathode produced acceptable electrochemical performances; they generated maximum power densities of 403 and 405 mW cm⁻² at 850 °C, respectively, when running on humidified hydrogen; also, they represented more stable, much easier processes and lower cost.     

Development and Fabrication of a New Concept Planar‐tubular Solid Oxide Fuel Cell (PT‐SOFC)

The paper reports a new concept of planar‐tubular solid oxide fuel cell (PT‐SOFC). Emphasis is on the fabrication of the required complex configuration of Ni‐yttria‐stabilised zirconia (YSZ) porous anode support by tert‐butyl alcohol (TBA) based gelcasting, particularly the effects of solid loading, amounts of monomers and dispersant on the rheological behaviour of suspension, the shrinkage of a wet gelcast green body upon drying, and the properties of final sample after sintering at 1350 °C and reduction from NiO‐YSZ to Ni‐YSZ. The results show that the gelcasting is a powerful method for preparation of the required complex configuration anode support. The anode support resulted from an optimised suspension with the solid loading of 25 vol% has uniform microstructure with 37% porosity, bending strength of 44 MPa and conductivity of 300 S cm^—1 at 700 °C, meeting the requirements for an anode support of SOFC. Based on the as‐prepared anode support, PT‐SOFC single cell of Ni‐YSZ/YSZ/LSCF has been fabricated by slurry coating and co‐sintering technique. The cell peak power density reaches 63, 106 and 141 mW cm^—2 at 700, 750 and 800 °C, respectively, using hydrogen as fuel and ambient air as oxidant.