循环伏安沉积纳米氧化钌基超级电容器电极材料

在三氯化钌(RuCl3)水溶液中,采用循环伏安法在钽电极表面电化学沉积无定形水合氧化钌(RuO2.xH2O)作为超级电容器电极材料。能谱分析表明,在循环伏安负向扫描时Ru3+在钽电极表面还原为钌金属(Ru),沉积的Ru在随后的正向扫描时被氧化为RuO2.xH2O。扫描电镜观测显示出负向扫描沉积的Ru为纳米尺度,因而获得了纳米结构的RuO2.xH2O。由于纳米结构可以提高电极比表面积和显著缩短离子和电子的传输路径,因而获得了具有高电化学活性的RuO2基超级电容器电极材料。循环伏安、恒电流充放电和电化学阻抗谱测试证实,该电极材料在38%(质量分数,下同)的H2SO4溶液中具有接近理想电容器的容量行为,比容量高达730F.g-1(扫描速率为50mV.s-1)。在质量负载为1.2mg.cm-2时,比容量仍高达700F.g-1。另外,其容量在10万次循环后仍保持不变,充放电效率接近100%。并且该方法可以直接在钽金属基底上电化学沉积RuO2.xH2O,避免了在常规电化学沉积法中需要的预涂层。     

均匀沉淀法制备LiFePO4/C及其电化学性能

以FeSO4·7H2O、H3PO4、H2O2和尿素为原料,采用均匀沉淀法制备LiFePO4的前驱体FePO4·xH2O,研究表面活性剂PEG对前驱体FePO4·xH2O形貌的影响。并将获得的FePO4·xH2O与Li2CO3及葡萄糖混合后合成LiFePO4/C。利用XRD、SEM、循环伏安测试、电化学性能测试、交流阻抗测试等手段对LiFePO4/C进行表征。结果表明:当不添加表面活性剂PEG时,FePO4·xH2O颗粒呈球形,但团聚现象严重;添加PEG后,颗粒较分散,形貌为多面体,合成的LiFePO4/C在0.1C时的首次放电比容量为151.0 mA·h/g,倍率性能好,振实密度达1.44 g/cm3。     

金属合金化X（X=Sr、Zr、Sn、Ce）对RuAl抗氧化性能影响的计算研究

目的研究RuAl的金属合金化及其氧化物Al_2O_3和RuO_2两相组的氧化关系,揭示其抗氧化性能机理。方法采用密度泛函理论的第一性原理,建立RuAl掺杂金属原子X及其间隙添加O原子的RuAl-X-O晶胞模型与其氧化产物Al_2O_3和RuO_2的晶胞模型。结果计算的Al_2O_3和RuO_2氧化能结果显示,Al_2O_3的氧化能(-11.43 eV/O_2)比RuO_2的氧化能(-2.28 eV/O_2)小,RuO_2的氧化能值与0值较为接近,在高温下结构稳定性较差,比较容易发生分解,RuAl的抗氧化能力主要依靠氧化产物Al_2O_3来进行。金属X合金化后,RuAl的氧化产物Al_2O_3和RuO_2的氧化能都增加,氧化能差值(eV/O_2)从大到小依次为Zr(0.29)Ce(0.28)Sn(0.22)Sr(-0.49),其中,金属Zr合金化对提高RuAl抗氧化能力的效果最好。计算的氧间隙形成能和电荷密集数等结果显示,金属X原子对RuAl的合金化降低了RuAl中的O固溶度,从而导致RuAl中内氧化速度降低。结论金属X原子对RuAl的合金化,阻碍RuAl表面的O向其内部扩散,障碍"内氧化"的生成条件,在RuAl表层界面的横向方向上容易形成连续、致密的Al_2O_3氧化层,提高RuAl的抗氧化性能。     

Electrochemical and microstructural characterization of cyclic redox behaviour of SOFC anodes

The oxidation of Ni to NiO in solid oxide fuel cell (SOFC) anode will result in large bulk volume change, which may change the interfaces of the two phases in the anode cermet and thus may cause significant performance degradation. The reduction and oxidation (redox) of the Ni/YSZ cermet were studied at 800 ℃. Anodic polarization measurements were performed before and after redox cycles. The anode current density at an overpotential of 100 mV kept decreasing during the whole redox treatment. It decreased from 19.11 to 7.95 mA·cm-2 after two redox cycles. Anode supported unit cell was assembled for cell's discharge measurements. Cell performance declined after each redox cycle. The maximum power density decreased from 126.28 to 40.32 mW·cm-2 . The microstructural changes after redox cycling were recorded using scanning electron microscopy (SEM). The results reveal that after re-oxidation, the Ni gets coarse and has a higher porosity; the nickel network structure turns to be desultory.     

Influence of characteristics of stabilized zirconia electrolyte on performance of cermet supported tubular SOFCs

Ni-Al2O3 cermet supported tubular SOFC was fabricated by thermal spraying. Flame-sprayed Al2O3-Ni cermet coating plays dual roles of a support tube and an anode current collector. 4.5mol.% yttria-stabilized zirconia (YSZ) and 10mol.% scandia-stabilized zirconia (ScSZ) coatings were deposited by atmospheric plasma spraying (APS) as the electrolyte in present study. The electrical conductivity of electrolyte was measured using DC method. The post treatment was employed using nitrate solution infiltration to densify APS electrolyte layer for improvement of gas permeability. The electrical conductivity of electrolyte and the performance of single cell were investigated to optimize SOFC performance. The electrical conductivity of the as-sprayed YSZ and ScSZ coating is about 0.03 and 0.07 S·cm-1 at 1000 ℃, respectively. The ohmic polarization significantly influences the performance of SOFC. The maximum output power density at 1000 ℃ increases from 0.47 to 0.76 W·cm-2 as the YSZ electrolyte thickness reduces from 100 μm to 40 μm. Using APS ScSZ coating of about 40 μm as the electrolyte, the test cell presents a maximum power output density of over 0.89 W·m-2 at 1000 ℃.     

Solid-state synthesis and electrochemical properties of SmVO4 cathode materials for low temperature SOFCs

A new cathode material fabricated by solid state reaction method was reported. The SmVO4 powder was obtained by firing the mixture of Sm2O3 and V2O5 powders in the temperature range of 700-1200 ℃. Its structure was identified by X-ray diffraction method and the electrochemical properties of SmVO4 as cathodes for solid oxide fuel cells (SOFCs) were investigated in single unit cell at the temperature ranged from 450-550 ℃. The results of the single fuel cell unit show that the maximum current densities are 641, 797, 688 mA·cm-2 and the maximum power output are 165, 268, 303 mW·cm-2 and the open circuit voltage are 1.04,0.96,0.92Vat 450, 500 and 550 ℃, respectively.     

TiO2组元对RuO2+SnO2+TiO2/Ti阳极涂层微观结构的影响

通过溶胶凝胶(Sol-gel)过程制备了添加TiO2的RuO2 SnO2／Ti纳米涂层钛阳极，并通过X射线衍射(XRD)、差热分析(DTA)、透射电子显微镜(TEM)分析了TiO2组元对RuO2 TiO2 SnO2／Ti电极涂层的微观结构和晶粒尺寸的影响。结果表明：涂层组成物主要为(Ru，Sn，Ti)O2固溶体，在TiO2含量增加、退火温度升高时，该固溶体仍可稳定存在；添加TiO2细化晶粒的效果不显著，但随退火温度的升高，TiO2相对含量较高的涂层中晶粒长大速率较低，即TiO2具备稳定晶粒尺寸的作用；添加TiO2的涂层晶粒外观呈较理想的等轴状。     

W合金化对RuAl抗氧化性能影响的计算研究

基于密度泛函理论的第一性原理,建立Al_2O_3和RuO_2晶胞模型,计算了Ru Al合金氧化物Al_2O_3和RuO_2的氧化能,结果显示:Al_2O_3的氧化能为–11.43 e V,RuO_2的氧化能为–2.28 e V,Al_2O_3比RuO_2的结构稳定性更好。通过态密度、Bander电荷密度等分析,发现W合金化提高RuAl抗氧化性能的根本原因是:由于W对O的吸附作用,使W周围的Al-O和Ru-O成键强度降低,Al_2O_3和RuO_2的氧化能减少,从而降低其结构稳定性。其中,Al_2O_3结构稳定性降低更加明显。同时,W合金化可降低RuAl合金体系基体内部的Al_2O_3结构稳定性,阻碍生成内氧化过程的生成条件,减少了垂直于表层界面的Al_2O_3的形成,促使表层界面的横向方向上Al_2O_3氧化层的成长,形成连续性致密的Al_2O_3氧化层,提高Ru Al抗氧化性。     

固体氧化物燃料电池(SOFC)用NiMOCr金属连接体氧化行为研究

金属作为固体氧化物燃料电池(SOFC)连接体材料已成为可能并成为研究热点.本论文对SOFC用NiMoCr合金分别在SOFC阴极和阳极气氛条件下的高温氧化性能作了详细的研究.结果表明:阳极(燃料极)条件下氧化所形成的是MnCr2O4尖晶石;阴极(空气极)条件下氧化所形成的是不含Cr的致密NiMnO4型尖晶石,能有效抑制C...     

SO2大气中AZ91D镁合金的腐蚀规律

通过室内模拟实验,研究了含体积分数4×10-6SO2大气中AZ91D镁合金的腐蚀行为。利用原子力显微镜、金相显微镜和扫描电镜观察腐蚀形貌,用XRD分析腐蚀产物。AZ91D镁合金腐蚀1200h的增重变化分为2个阶段,第1阶段符合线性增加规律,第2阶段符合指数衰减规律。腐蚀过程中,β相作为阴极,α相作为阳极,在其上形成颗粒状腐蚀产物,产物不断增多蔓延,直至完全覆盖镁合金表面。同时,在这层产物的裂纹处出现大颗粒产物。腐蚀产物主要为MgO,Mg(OH)2,MgSO3·6H2O,MgSO4·6H2O,随着腐蚀时间的延长,MgO与Mg(OH)2的量减少,而MgSO3·6H2O和MgSO4·6H2O的量增加。