金属醇盐水解法制备纳米氧化物LiAlO2

向100mL乙醇和1mL乙酰丙酮混合溶液中加入0.18g锂片,采用金属阳极溶解法控制电流为0.2A电解铝片6h,制得纳米LiAlO2前驱体.将电解液控制pH为9.0直接水解形成凝胶,经洗涤、干燥后在550℃煅烧2h,制得纳米LiAlO2粉体.产物通过傅立叶变换红外光谱(FT-IR)、电子透射显微镜(TEM)、差热-热重分析(TG-DTA)、X射线衍射(XRD)进行表征.结果表明,所得前驱体结构为LiAl(OEt)(4-n)(acac)n(acac为乙酰丙酮基);干凝胶粒径20～30nm,适宜煅烧温度为550℃;煅烧后所得纳米LiAlO2粉体粒径为30nm.     

金属阳极溶解法制备纳米氧化物NiAl2O4

在乙醇和乙酰丙酮混合溶液中,50～55℃,导电盐Bu4NBr浓度为0 040mol/L,控制阳极电流0 2A电解铝片6h,再电解镍片2h,制得前驱体NiAl2(OCH2CH3)(8 y)(acac)y[acac为乙酰丙酮基]。将电解液控制pH=8 5直接水解形成凝胶,凝胶经洗涤、干燥后在350℃煅烧2h,制得纳米NiAl2O4粉体,粒径20～30nm。用红外(IR)、差热-热重分析(TG-DTA)、X射线衍射(XRD)、电子透射技术(TEM)等手段对前驱体和纳米NiAl2O4进行了表征。     

电化学溶解镁阳极制备纳米MgO粉体

该文以"牺牲"阳极溶解法在0.04mol／L(Bu4N)Br的乙醇和乙酰丙酮混合溶液中,电流强度控制在0.2A,电解镁片6h,制得纳米氧化物粉体MgO的前驱体Mg(OEt)2-x(acac)xo控制pH=8.0左右,将含有前驱体的电解液直接水解。水解产物经洗涤、干燥后于500℃煅烧2h,制得纳米MgOg粉体。采用红外(IR)、差热-热重分析(TG-DTA)、X-射线衍射(XRD)、电子透射技术(TEM)等手段对前驱体和纳米MgO进行了表征。结果表明:制备得到的纳米粉体呈单分散结构,平均粒径在12nm左右。用此种方法比较容易制得所需产物,是一种合成纳米氧化物的很有前途的方法。     

静电纺丝法制备中温固体氧化物燃料电池阴极用纳米La_(0.6)Sr_(0.4)Co_(0.4)Fe_(0.6)O_3纤维

采用静电纺丝技术和溶胶–凝胶法制备了聚乙烯吡咯烷酮(polyvinylpyrrolidone,PVP)/La0.6Sr0.4Co0.4Fe0.6O3(LSCF)复合纳米纤维,经过不同温度煅烧处理,获得了具有单晶结构的LSCF纳米纤维,并对纤维样品的煅烧过程、形貌、物相、结构以及电性能进行了表征。结果表明:PVP/LSCF复合纳米纤维中的水分和有机物在达到560℃前已经完全挥发和分解。经煅烧处理,可获得具有斜方六面体结构LSCF。经800℃煅烧后的LSCF纳米纤维的直径主要分布在130～240nm;以LSCF纳米纤维为阴极制备的单电池在750℃工作温度下,其最大功率密度为1.18W/cm2。与用传统溶胶–凝胶法在相同条件下制得的LSCF粉体相比,其单电池的电流–电压–功率性能有显著提高。     

两步沉淀法制备纳米Cr_2O_3粉体的研究

为制备分散均匀且超细的纳米Cr2O3粉体,以Cr(NO3)3·9H2O为主原料,以聚乙烯吡咯烷酮(即PVP)为分散剂,采用两步沉淀法制备了纳米Cr2O3粉体。在Cr(NO3)3浓度为0.031 6 mol·L-1的条件下,研究了沉淀剂种类(氨水、碳酸钾和水合肼)、p H(4.8、5.2、6.5、7和7.9)及煅烧温度(300、400、450和500℃)等对合成纳米Cr2O3粉体晶粒尺寸的影响,并采用差热分析、FE-SEM及XRD等对所合成粉体进行了表征。结果表明:随煅烧温度及p H的升高,纳米Cr2O3粉体的晶粒尺寸先减小后增加。在Cr(NO3)3浓度为0.031 6 mol·L-1、以氨水为沉淀剂、p H=7、煅烧温度为450℃及保温时间为2 h的条件下可以制得晶粒尺寸在20 nm左右、分散良好的纳米Cr2O3粉体。     

花状NiO纳米片自组装体的制备与表征

以硝酸镍、尿素为原料,在醇-水介质中,85℃恒温条件下,用均匀沉淀法制备出花状纳米片自组装结构Ni(OH)_2沉淀,该沉淀经400℃煅烧制得具有花状形貌的NiO纳米片自组装体.采用X射线衍射、扫描电镜、透射电镜、Fourier变换红外光谱、Brunauer-Ennett-Teller(BET)比表面积方法对粉体进行表征.研究表明:该NiO粉体为六方结构,其纳米片尺寸约为2μm × 3μm,厚度约为100nm,曲面间隙约为0.8μm,具有微孔结构.BET法测得粉体的比表面积为108.66m~2/g,制得的粉体具有明显的纳米效应,Ni-O键振动峰值(403.6cm~(-1))较非纳米颗粒(487.1 cm~(-1))蓝移了84.5cm~(-1),乙醇对花状结构NiO纳米片自组装体的形成具有重要作用.分析了花状NiO纳米片自组装体的形成机理.     

纳米Dy/TiO_2粉体的制备及光催化性能研究

以钛酸正丁酯和硝酸镝为主要原料,主要采用了微波-溶胶胶法制备出了一系列稀土Dy掺杂的纳米TiO_2粉体(Dy/TiO_2)。并且以甲基橙溶液为目标降解物,系统地研究了煅烧温度、稀土Dy掺量、煅烧时间等因素对纳米Dy/TiO_2粉体光催化性能的具体影响。通过SEM、XRD、UV-vis-DRS等表征手段对样品进行了分析。结果表明:在550℃下将稀土Dy掺量为1.3%的纳米TiO_2粉体煅烧4 h,降解效率就达到90%以上。稀土掺杂后不仅仅使得纳米TiO_2颗粒尺寸减小,带隙减小,吸收波长红移约30 nm,还能有效的抑制光生电子-空穴的复合。     

50t/a纳米TiO2工业化生产工艺条件的研究

以钛液(TiOSO4)为原料,尿素为沉淀剂,生成偏钛酸沉淀;再加入0.01MH2SO4和去离子水、溶胶剂、表面活性剂,然后絮凝分离、喷雾干燥、回转窑煅烧,获得纳米TiO2粒子;其中550℃煅烧产物为锐钛矿晶型,大于750℃煅烧为金红石型;50t/a纳米TiO2粉体工业化生产的最佳工艺条件为:反应温度98±2℃,反应时间2—3.5h,反应物摩尔比TiOSO4:CO(NH2)2=2:1,溶胶剂与偏钛酸浓度之比4:1,絮凝剂用量9.5mgL;得到的纳米TiO2粒径为20—50nm,收率达92％。     

Sol-Gel-SPD制备超细Al2O3-SiO2二元粉体材料

以硝酸铝(Al(NO3)3·9H2O)和正硅酸乙酯(TEOS)为原料,采用溶胶-凝胶(Sol-Gel)技术并结合喷雾干燥(SPD)技术制得超细Al2O3-SiO2二元复合粉体材料,并分别于400℃、800℃、1000℃、1150℃和1200℃煅烧2 h;采用全自动比表面积与孔隙率分析仪、TEM、TG-DSC及XRD等仪器研究了热处理温度、pH值(分别为5.5、7和8)以及干燥方法对粉体材料的表面性能、显微形貌、物相组成及Al2O3-SiO2二元系晶体转变过程的影响.结果表明由Sol-Gel-SPD制备的超细Al2O3-SiO2二元粉体材料的比表面积＞448 m2·g-1,而经1200℃煅烧2 h后所得的超细莫来石的比表面积34.05m2·g-1;TG-DSC分析表明采用Sol-Gel-SPD制得的Al2O3-SiO2二元粉体材料的质量损失主要发生在500℃之前;XRD分析表明粉体试样的开始莫来石化温度为1000℃,铝硅尖晶石(6Al2O3·SiO2)与非晶态SiO2在1150～1200℃完全转化为莫来石;比较不同pH值试样经1200℃煅烧后的TEM照片发现,当pH=7时,得到的超细莫来石粉体粒径最小,为50 nm.     

溶胶-凝胶-喷雾干燥法制备超细Al_2O_3-SiO_2二元粉体材料

以硝酸铝(Al(NO3)3.9H2O)和正硅酸乙酯(TEOS)为原料,采用溶胶-凝胶(Sol-Gel)技术并结合喷雾干燥(SPD)技术制得超细Al2O3-SiO2二元复合粉体材料,并分别于400℃、800℃、1000℃、1150℃和1200℃煅烧2h;采用全自动比表面积与孔隙率分析仪、TEM、TG-DSC及XRD等仪器研究了热处理温度、pH值(分别为5.5、7和8)以及干燥方法对粉体材料的表面性能、显微形貌、物相组成及Al2O3-SiO2二元系晶体转变过程的影响。结果表明:由Sol-Gel-SPD制备的超细Al2O3-SiO2二元粉体材料的比表面积>448m2.g-1,而经1200℃煅烧2h后所得的超细莫来石的比表面积为34.05m2.g-1;TG-DSC分析表明:采用Sol-Gel-SPD制得的Al2O3-SiO2二元粉体材料的质量损失主要发生在500℃之前;XRD分析表明:粉体试样的开始莫来石化温度为1000℃,铝硅尖晶石(6Al2O3.SiO2)与非晶态SiO2在1150~1200℃完全转化为莫来石;比较不同pH值试样经1200℃煅烧后的TEM照片发现,当pH=7时,得到的超细莫来石粉体粒径最小,为50nm。     

In suit Investigation of Anode Support on Cell Performance Reduced under Various Temperatures for Planar Solid Oxide Fuel Cells

The performance of anode support of Ni‐YSZ reduced from room temperature (T_R) to working temperature (T_w) and at T_w in anode‐supported planar solid oxide fuel cell was investigated quantitatively in situ. A 2 μm thick Pt voltage probe was embedded at the interface between the anode support and the function anode in the cell. Results showed that the power densities of the stack that was reduced from T_R to T_w (stack 1) and stack reduced at T_w (stack 2) were 0.343 W cm⁻² and 0.583 W cm⁻² with the corresponding fuel utilization of 36.28% and 63.87%, respectively, under the operating voltage of 0.8 V. The degradation rate of stack 1 was 7.76 times more than that of stack 2 when the stack was discharged under a constant current of 0.476 Acm⁻² for 100 h. Ni particles agglomerated in the anode support of the cell inside stack 1, whereas Ni particles in the anode support of the cell inside stack 2 were evenly distributed. The performance of stack 1 was poor mainly because of the increasing ohmic and polarization resistances caused by Ni agglomeration and decreasing porosity of the anode support.     

Achieving 360 NL h−1 Hydrogen Production Rate Through 30‐Cell Solid Oxide Electrolysis Stack with LSCF–GDC Composite Oxygen Electrode

A 30‐cell solid oxide electrolysis (SOE) stack consisting of 30‐cell planar Ni–YSZ hydrogen electrode‐supported single cell with La_0.6Sr_0.4Co_0.2Fe_0.8O_3–δ–Ce_0.9Gd_0.1O_1.95 (LSCF–GDC) composite oxygen electrodes, interconnects, and sealing materials was tested at 750 °C in steam electrolysis mode for hydrogen production. The direction of gas flow in the stack was a cross‐flow configuration, and the stack configuration was designed to open gas flow channels at the air outlet. The electrolysis efficiency of the stack was higher than 100% at 90/10H₂O/H₂ ratio under <0.5 A cm⁻² current density. During hydrogen production, the stack was operated at 750 °C under 0.5 A cm⁻² constant current density for more than 500 h with 4.06% k h⁻¹ degradation rate. Up to 73% steam conversion rate and 91.6% current efficiency were obtained; the net hydrogen production rate reached as high as 361.4 NL h⁻¹. Our results suggested that the SOE stack that was designed with LSCF–GDC composite oxygen electrode could be used to conduct large‐scale hydrogen production.     

Effect of Contact between Electrode and Interconnect on Performance of SOFC Stacks

This work investigates the effect of contact between electrodes and alloy interconnects on output performance of solid oxide fuel cell (SOFC) stacks. The measured maximum output power density (p_max) of the unit cell increases from 0.07 to 0.1 W cm^–2 by increasing the tip area of the interconnect from 40 to 60 cm². The p_max increases from 0.07 to 0.15 W cm^–2 upon the addition of nickel foam and Ag mesh on the anode and cathode side, respectively. An additional (La_0.75Sr_0.25)_0.95MO_3–σ cathode current collecting layer is re‐printed on the original cathode current collecting layer, which aims to further improve the performance of the stack and individual cell. The performance of a 3‐cell short stack assembled by the cells with a new cathode current collecting layer is evaluated by measuring the current–voltage curve. The results indicate that the p_max values of the stack and individual cells are enhanced from 0.07 to 0.37 W cm^–2 and 0.15 to 0.5 W cm^–2 at 850 °C, respectively. The performance of the whole stack and individual cells is greatly improved due to the interconnect embedded in the re‐printed new cathode current collecting layer.     

Cell/stack electrochemical performance and stability of cone-shaped tubular SOFCs for direct operation with methane

Cone-shaped tubular anode-supported solid oxide fuel cells (SOFCs) and two-cell-stack based on NiO-YSZ traditional anodes direct utilization methane as fuel were successfully developed in this study. The single cell exhibited maximum power densities of 1.255 W cm⁻² for hydrogen and 1.099 W cm⁻² for methane at 800 °C, respectively. A stability test of the single cell was performed with different constant current densities at 700 °C in methane. The results indicated that the single cell can be operated stable at high current density in methane. And EDX results showed that there is no measurable coking effect of operation in methane at relatively high current density.A two-cell-stack based on the above-mentioned SOFCs was fabricated and tested by direct utilization of methane. Its typical electrochemical performance was investigated. The two-cell-stack provided a maximum power output of about 3.5 W (350 mW cm⁻² calculated using effective cathode area) by directly using methane at 800 °C. The stack experienced 20 h durability testing. The results demonstrated that the stack was kept at around 1 V (J = 0.05 A cm⁻²) at 700 °C. The stack presented basically stably during the whole test, and the performance of the stack is acceptable for application.     

Investigation of 30-cell solid oxide electrolyzer stack modules for hydrogen production

The 30-cell nickel-yttria stabilized zirconia (Ni-YSZ) hydrogen electrode-supported planar solid oxide electrolyzer (SOE) stack modules were manufactured and tested at 800 °C in steam electrolysis mode for hydrogen production. The electrolysis efficiency of the stack modules was higher than 100% at a total steam and hydrogen flow of 2.1 sccm cm⁻², a H₂O/H₂ ratio of 80/20, and a current density of <0.2 A cm⁻². The electrolysis efficiency, current efficiency, and actual hydrogen production rate of the stack modules increased with increasing H₂O/H₂ ratio at a constant current density. However, the electrolysis and current efficiencies decreased steadily at high current densities. During hydrogen production, the stack modules were operated at 800 °C and a constant current density of 0.15 A cm⁻² for up to 1100 h. A steam conversion rate of 62% and current efficiency of 87.4% were obtained; the actual hydrogen production rate reached as high as 103.6 N L h⁻¹. Post-mortem analysis showed that delamination of the LSM–YSZ oxygen electrode mainly occurred in the steam and air inlet area of the 10×10 cm² cells.     

Experimental results on the direct electrochemical oxidation of methanol in PEM fuel cells

The cell performance of direct methanol fuel cells (DMFC) is 0.5 V at 0.5 A cm^–2 under high pressure oxygen operation (3 bar abs.) at 110 °C. However, high oxygen pressure operation at high temperatures is only useful in special market niches. Therefore, our work has now focused on air operation of a DMFC under low pressure (up to 1.5 bar abs.). At present, a power density of more than 100 mW cm^–2 can be achieved at 0.5 V on air operation at 110 °C. These measurements were carried out in single cells with an electrode area of 3 cm² and the air stoichiometry only amounted to 10. The effects of methanol concentration and temperature on the anode performance were studied by pseudo half cell measurements and the results are presented together with their impact on the cell voltage. A cell design with an electrode area of 550 cm², which is appropriate for assembling a DMFC stack, was tested. A three-celled stack based on this design revealed nearly the same power densities as in the small experimental cells at low air excess pressure and the voltage–current curves for the three cells were almost identical. At 110 °C a power output of 165 W at a stack voltage of 1.5 V can be obtained in the air mode.     

Fabrication and characterizations of Cr3+-doped ZnGa2O4 transparent ceramics with persistent luminescence

0.5 at.% Cr:ZnGa₂O₄ precursor was synthesized by the co-precipitation method with nitrates as raw materials, using ammonium carbonate as the precipitant. Low-agglomerated Cr:ZnGa₂O₄ powders with an average particle size of 43 nm were obtained by calcining the precursor at 900℃ for 4 h. Using the powders as starting materials, 0.5 at.% Cr:ZnGa₂O₄ ceramics with an average grain size of about 515 nm were prepared by presintering at 1150℃ for 5 h in air and HIP post-treatment at 1100℃ for 3 h under 200 MPa Ar. The in-line transmittance of 0.5 at.% Cr:ZnGa₂O₄ ceramics with a thickness of 1.3 mm reaches 59.5% at the wavelength of 700 nm. The Cr:ZnGa₂O₄ ceramics can be effectively excited by visible light and produce persistent luminescence at 700 nm. For Cr:ZnGa₂O₄ transparent ceramics, the brightness of afterglow was larger than 0.32 mcd/m² after 30 min, which is far superior to that of Cr:ZnGa₂O₄ persistent luminescence powders.     

Fabrication and properties of transparent Tb2Ti2O7 magneto-optical ceramics

Transparent Tb₂Ti₂O₇ magneto-optical ceramics were fabricated from co-precipitated nano-powders by vacuum pre-sintering with hot isostatic pressing (HIP) post-treatment. The formation of pyrochlore phase, decomposition of the precursor, and the morphology of powders calcined at different temperatures were investigated. The in-line transmittance of Tb₂Ti₂O₇ ceramics, which were pre-sintered at 1350 ℃ for 2 h with HIP post-treatment at 1450 ℃ for 3 h and subsequently annealed at 800 ℃ for 20 h in NH₃ atmosphere, reaches 65.5 % at 1064 nm. The Verdet constant of Tb₂Ti₂O₇ ceramics is −229.0 ± 0.6 rad·T⁻¹ m⁻¹ at the wavelength of 633 nm, which is 71 % higher than that of the commercial Tb₃Ga₅O₁₂ crystals. Tb₂Ti₂O₇ magneto-optical ceramics show a promising application for Faraday rotators.     

Photocatalytic degradation of ammonia by light expanded clay aggregate (LECA)-coating of TiO2 nanoparticles

Photocatalytic degradation of ammonia on supported TiO₂ nanoparticles was investigated. The TiO₂ nanoparticles used as photocatalyst were coated on light expanded clay aggregate granules (LECA), which is a porous and light weight support. Photocatalytic reaction activity of prepared catalyst was determined by ammonia degradation from water synthetically polluted with ammonia. Experiment results showed significantly high photocatalytic activity for the immobilized catalysts. The ammonia was removed more than 85% within 300 min of the process with optimum calcinations temperature 550 °C and pH 11. Kinetics of the photocatalytic reaction followed a pseudo-first order model. XRF, XRD and SEM analyses revealed a rather uniform coating of TiO₂ on the support. By using floated TiO₂/LECA as a photocatalyst in aqueous solution of NH ₃ ^? , the ammonia was photodegraded into N₂ and H₂ gases, while NO ₂ ^? and NO ₃ ^? were formed at very low concentrations.     

Monitoring the degradation of a solid oxide fuel cell stack during 10,000 h via electrochemical impedance spectroscopy

A 5-cell solid oxide fuel cell stack was tested during 10,000 h of continuous operation with simulated reformate gas as fuel (71 vol.% H₂, 20.7 vol.% CO₂ and 8.3 vol.% steam) under high fuel utilization (73%) and constant current load (0.5 A cm^?2 or 25 A) at 750 °C. In situ electrochemical impedance spectroscopy was used to monitor the evolution of ohmic and polarisation resistances of individual cells in the stack without interrupting the current load. Impedance spectra were recorded on each cell periodically (every 1000 h) or after uncontrolled incidents happened with the test setup. It has been found that the stack degradation is mainly attributed to the increased ohmic resistance, pointing to possible causes such as interconnect corrosion and reduced effective contact areas between cells and interconnects. The degradation rate during the first 5000 h was about 1% kh^?1, but increased afterwards up to 1.5% kh^?1 due to the impact of incidents. Both types of incidents (fuel supply fluctuations and overloading failure of the electronic load) were complicated by inhomogeneous fuel distribution among cells, leading to most probably partial re-oxidation of the anode, accelerating the stack degradation.