钙掺杂的氧化铈用于中温SOFCs阳极材料研究

作为一种混合的离子-电子导体材料,掺杂的氧化铈已逐渐被用来作为SOFCs阳极材料或其组成部分之一加以研究,但主要以稀土掺杂剂为主,为了进一步降低采用阳极支撑构型的SOFCs的成本,研究了钙掺杂的氧化铈(CCO)。结果表明,掺杂20%钙的材料(20CCO)的电导率最高,850℃时在氢气气氛下的电导率可以达到0.209S·cm-1,远大于在空气气氛中的电导率。800℃时在空气中的电导率为0.041S·cm-1,比同样温度下阳极中经常采用的钐掺杂的氧化铈(SDC)的电导率低了约0.04S·cm-1。但这并不影响单电池的输出性能,分别以Ni-20CCO作为阳极,Sm0.5Sr0.5Co-SDC作为阴极,SDC作为电解质(厚约35μm)的单电池在650℃,氢气气氛下的最大输出功率可以达到623mW·cm-2。     

掺杂F-,Sr2+的氧化铈紫外屏蔽和氧化催化性研究

采用沉淀法合成F-,Sr2+单掺杂和共掺杂的氧化铈,探讨了不同掺杂离子对氧化铈紫外屏蔽性能和氧化催化性能的影响.XRD结果表明,F-,Sr2+单掺杂或共掺杂的CeO2均为立方萤石结构,但衍射峰因掺杂离子的不同而稍有偏移.UV-Vis光谱表明,F-,Sr2+单掺杂和共掺杂的氧化铈的紫外屏蔽性能均优于纯氧化铈.共掺杂氟锶后的氧化铈的氧化催化性明显比纯氧化铈的弱,但是,单掺杂氟离子或锶离子的氧化铈的氧化催化性比纯氧化铈的强.     

天然气中温SOFC阳极材料铒掺杂的氧化铈的制备与性能研究

采用溶胶-凝胶法合成了新型中温固体氧化物燃料电池(IT-SOFC)阳极材料Ce_1-xEr_xO_y(x=0.00,0.10,0.15,0.20,0.25,0.30)(EDC),并采用共压-共烧结法制备了以NiO-EDC复合阳极为支撑、以Ce_0.8Gd_0.2O_2-δ(GDC)为电解质、以La_0.8Sr_0.2Co_0.8Fe_0.2O_3-δ(LSCF)-GDC为复合阴极的单电池。利用XRD和SEM等方法对阳极材料EDC进行了晶相结构、微观形貌和化学相容性等分析。在400~700 ℃范围内,以加湿天然气(3% H₂O)为燃料气,氧气为氧化气测试了电池的电化学性能。结果表明：EDC阳极材料具有良好的孔道结构;11种不同阳极组成的单电池中50%(质量分数)NiO-50%(质量分数)Ce_0.85Er_0.15O_y(E15C85)阳极支撑的单电池具有最佳的电化学性能,在650 ℃时其最大电流密度为117.84 mA·cm^-2和最大比功率为24.37 mW·cm^-2。     

利用钐掺杂氧化铈提高燃料电池阳极活性

用浸渍法制备并采用交流阻抗、极化等技术考察了不同组成的Ni-Sm3＋掺杂的CeO2(SDC) 复合镍阳极的电化学性能及相应电池的功率输出性能.结果表明，SDC掺入镍阳极后,阳极极化过电位及电池的欧姆电阻显著减小.其中阳极过电位的减小与SDC掺入镍电极引起的三相界扩展有关，但SDC的掺入同时引起了电极反应活化能的增加,造成低温下Ni-SDC的极化过电位大于纯Ni电极.高温下,Ni-SDC阳极的阻抗谱由两个半圆组成，其中高频半圆随着SDC掺入量的增加而减小,而低频环与SDC的掺入量基本无关.低温下只观察到一个高频环.高频环可能对应三相界反应,而低频环可能对应氢的解离吸附及扩散.75％（w）Ni-25％（w）SDC/La0.9Sr0.1Ga0.8Mg0.2O3(LSGM)/Sm0.5Sr0.5CoO3(SSC)在所研究的电池中具有最大功率输出密度，其值在1073、973、873 K下分别达到1.1、0.43、0.14 W•cm－2.     

水热法合成氧化亚钴纳米粒子/石墨烯复合材料及其储锂性能研究

针对目前的锂离子电池负极材料存在比容量低、循环稳定性差等问题,本工作发展了简单、有效的方法合成氧化亚钴纳米粒子与石墨烯的复合材料（CoO/RGO）.采用氧化石墨（GO）和Co（NO₃）₂作为原料,先用水热路线制备了前驱体,再将其在氮气气氛下热处理,最终得到CoO/RGO复合材料.存在于石墨烯表面的CoO纳米粒子可以有效地阻止石墨烯片层的聚集,同时石墨烯片层的相互连接能够形成三维的空间网络,提高复合材料的导电性.将合成的CoO/RGO复合材料作为负极,以锂片作为正极,组装成纽扣电池.电化学测试表明,在电流密度为100 mA·g^-1的条件下,初始比容量放电比容量高达1312.6 mAh·g^-1,在10000 mA·g^-1的大电流密度下,经过300圈循环后,其比容量仍然可以达到557.4 mAh·g^-1.这表明CoO/RGO复合材料具有高的比容量、优异的倍率性能及循环稳定性,这归因于3D网状结构能够避免在锂离子的嵌入/脱出过程中材料的结构被严重破坏.     

Electrical Properties of Sm‐doped Ceria (SDC) and SDC Carbonate Composite

This study prepared a dense Sm‐doped ceria (SDC) and an SDC carbonate composite (abbreviated as SDC‐C). The latter was prepared by immersing porous SDC with a formula of (Ce_0.8Sm_0.2)O_1.9 and a relative density of approximately 65‐70% into a molten mixture of carbonates containing 1:1 molar ratio of Li₂CO₃ and Na₂CO₃ at 500 °C. The relative density of the SDC‐C was close to 100%. In addition, SDC oxide without carbonates, which also has a relative density of close to 100%, was heat treated at 1600 °C. At 500 °C, the electrical conductivity and ionic transference number (t_i) of the SDC oxide were 1.79(5) × 10^?3 S·cm^?1 and 0.99(2), respectively, such that electronic conduction could be disregarded. Increasing the temperature caused a gradual decrease in the t_i of SDC. Following the addition of carbonates to SDC, the electrical conductivity reached 1.23(9) × 10^?1 S·cm^?1 at 500 °C. After 14 days (340 h), the electrical conductivity of the SDC‐C at 490 °C, leveled off at about 6 × 10^?2 S·cm^?1. SDC‐C could be used as a potential electrolyte in solid oxide fuel cells (SOFCs) at temperatures below 500 °C.     

LSGMC5含量对于二甲醚燃料电池复合Ni-Fe阳极性能的影响

用浸渍法制备了掺杂不同质量分数的La0.8Sr0.2Ga0.8Mg0.15Co0.05O3-δ (LSGMC5)粉末的Ni8-Fe2-LSGMC5复合阳极, 并采用交流阻抗和直流极化技术考察了以氢气和二甲醚为燃气时该复合阳极的电化学性能及相应电池的功率输出特性. 结果表明, 在电极中掺入LSGMC5 粉末, 能显著地改善电极的形貌和电极/电解质界面结构, 减小欧姆电阻和极化电阻. 电极中LSGMC5 粉末含量对于氢气及二甲醚电化学氧化性能的影响显著不同. 以二甲醚为燃气时, 电极极化电阻随LSGMC5 粉末含量的增加而减小, 其中LSGMC5 掺杂量为30%的复合阳极具有最高的电化学性能, 相应电池在1073、1023、973 K 时的输出功率分别为1.00、0.61、0.40 W·cm-2; 以氢气为燃气时, LSGMC5 掺杂量为20%的复合阳极具有最好的电化学性能, 随着LSGMC5 掺杂量的进一步增加, 电极极化电阻显著增大.     

焙烧温度对Mg(Al)O复合物结构和表面酸碱性质影响的研究

分别在673、873和1073K分解Mg/Al摩尔比为3的水滑石生成Mg(Al)O复合物.XRD测定均显示MgO物相.873K以上焙烧的样品同时存在MgAl2O4尖晶石物相.微量吸附量热测定其表面酸碱中心的强度和密度,发现碱中心强度和密度顺序为:MAO-2＞MAO-3≈MAO-1,而酸中心强度和密度顺序是:MAO-1＞MAO-3≈MAO-2.红外光谱表明,Mg(Al)O复合物表面酸碱中心主要存在L酸,碱中心是氧阴离子.焙烧温度对表面碱中心类型几乎没有影响.固态MAS27Al核磁共振结果展示,这些样品呈现出显著的Al3+配位情况的变化.     

掺钇纳米NiO的制备及其超大电容性能研究

应用化学共沉淀法制备掺Y的纳米N iO.XRD分析表明,Y的添加不改变N iO的晶体结构,但晶粒尺寸有所减小.利用恒流充放电、循环伏安和交流阻抗等测试方法对Y-N iO电极材料在5 mo.lL-1KOH溶液中作电化学性能测试.结果表明,化学掺杂提高了电极的比容量,当N iO与Y2O3的质量比为1∶0.1时,单电极放电比容量可达到363 F.g-1,比纯氧化镍电极提高了2.02倍.交流阻抗测试显示,Y掺杂降低了电解液在电极中的扩散阻力,提高了质子扩散能力,从而表现了更好的电容性能.     

Ceria Particles as Efficient Dopant in the Electrodeposition of Zn-Co-CeO2 Composite Coatings with Enhanced Corrosion Resistance: The Effect of Current Density and Particle Concentration

Novel Zn-Co-CeO₂ protective composite coatings were deposited successfully from chloride plating solutions. Two different types of ceria sources were used and compared: commercial ceria powder and home-made ceria sol. Electrodeposition was performed by a direct current in the range of 1–8 A dm⁻². Two different agitation modes were used and compared, magnetic stirring and ultrasound-assisted stirring (US). The influence of magnetic stirring on the stability of the related plating baths was evaluated via a dynamic scattering method. The results pointed to better stability of the prepared ceria sol. The morphology of the composite coatings was examined by scanning electron microscopy (SEM), and particle content was determined by energy-dispersive X-ray spectroscopy (EDS). The results showed that the increase in the deposition current density was not beneficial to the coating morphology and particle content. The corrosion behavior of the Zn-Co-CeO₂ composite coatings was analyzed and compared by electrochemical impedance spectroscopy and polarization resistance. The ultrasound-assisted electrodeposition at small current densities was favorable for obtaining composite coatings with enhanced corrosion stability. The protection was more effective when US was applied and, additionally, upon utilization of ceria sol as a particle source, which was revealed by higher polarization resistance and greater low-frequency impedance modulus values for sol-derived composite coatings deposited under ultrasound.     

Electron Microscopy Study of Nickel and Nickel Composite Electrocoatings

 It has been proved that the electrolysis parameters strongly influence the structural properties of nickel electrodeposits, mainly the crystalline growth, preferred orientation and surface morphology. To determine the structural characteristics of nickel and composite nickel matrix electrocoatings, prepared under either direct current or pulse current conditions, the electron microscopy techniques have proved very important tools. In particular, investigation of the distribution and percentage of microparticles incorporated in the metallic matrix during preparation of nickel composite electrocoatings demands the use of techniques such as energy dispersion spectroscopy (EDS) or image analysis.     

The Influence of Oxygen Plasma on Methylammonium Lead Iodide (MAPbI3) Film Doped with Lead Cesium Triiodide (CsPbI3)

In recent years, the study of organic–inorganic halide perovskite as an optoelectronics material has been a significant line of research, and the power conversion efficiency of solar cells based on these materials has reached 25.5%. However, defects on the surface of the film are still a problem to be solved, and oxygen plasma is one of the ways to passivate surface defects. In order to avoid destroying the methylammonium lead iodide (MAPbI₃), the influence of plasma powers on film was investigated and the cesium triiodide (CsPbI₃) quantum dots (QDs) were doped into the film. In addition, it was found that oxygen plasma can enhance the mobility and carrier concentration of the MAPbI₃ film.     

The Determination of Methanol Using an Electrolytically Fabricated Nickel Microparticle Modified Boron Doped Diamond Electrode

A nickel modified boron doped diamond (Ni‐BDD) electrode and nickel foil electrode were used in the determination of methanol in alkaline solutions. The Ni‐BDD electrode was electrodeposited from a 1 mM Ni(NO₃)₂ solution (pH 5), followed by repeat cycling in KOH. Subsequent analysis utilised the Ni(OH)₂/NiOOH redox couple to electrocatalyse the oxidation of methanol. Methanol was determined to limits of 0.3 mM with a sensitivity of 110 nA/mM at the Ni‐BDD electrode. The foil electrode was less sensitive achieving a limit of 1.6 mM and sensitivity of 27 nA/mM. SEM analysis of the electrodes found the Ni‐BDD to be modified by a quasi‐random microparticle array.     

碳酸钙/镍复合导电材料的原位合成及其抗静电性能

利用胶棉膜作为活性模板,制备出方解石型碳酸钙组装球,在其表面上将镍进行原位还原反应,首次成功获得了碳酸钙/镍复合导电材料,通过TEM、XRD、FT-IR和TG-DTA等测试技术对产物结构及性能进行了表征,并将产物应用于抗静电领域,制备成的抗静电涂料与用纯镍粉制备的涂料具有同等抗静电性能(电阻率为1.2×106 Ω·cm),并可以节省60%的镍。 该复合材料在导电和抗静电等领域具有应用前景,能够节省对镍的消耗。     

梯度Cu-CeO2-Ni-YSZ复合阳极直接甲烷SOFC的制备与性能

采用三层共压-共烧结法, 并涂覆La_0.8Sr_0.2MnO₃ (LSM)阴极, 制备了梯度Ni-YSZ阳极结构的固体氧化物燃料电池(SOFC)(大孔Ni-YSZ|微孔Ni-YSZ|YSZ|LSM) (YSZ: Y₂O₃稳定的ZrO₂; LSM: Sr 掺杂的LaMnO₃).通过浸渍法在大孔Ni-YSZ 基底中沉积占总重量约1%的Cu-CeO₂抗积碳催化剂, 形成梯度Cu-CeO₂-Ni-YSZ复合阳极. 分别以CH₄和H₂为燃料, 空气为氧化剂, 测定了构造的SOFC输出电性能和长期稳定性. 结果表明,三层共压-共烧结法制备的梯度阳极SOFC, 层间结合紧密无缺陷, 阳极梯度孔结构明显, YSZ膜致密无缺陷.在850℃下操作, 以梯度Ni-YSZ 阳极制备的SOFC, 燃料由H₂切换为甲烷时, 最大功率密度由284 mW·cm^-2下降到143 mW·cm^-2; 而以Cu-CeO₂-Ni-YSZ 复合阳极构造的SOFC出现相反趋势, H₂切换为甲烷后最大输出由176 mW·cm^-2增加到196 mW·cm^-2. 在250 mA·cm^-2负荷下, 梯度Ni-YSZ阳极支撑的直接甲烷SOFC仅稳定运转10 h 便出现明显衰减, 阳极中积碳严重; 但Cu-CeO₂-Ni-YSZ 复合阳极支撑SOFC连续运转50 h, 输出电压与输出功率密度基本不变, 电镜观察不到积碳.     

制备方法及焙烧温度对Co3O4/CeO2催化剂上CO低温氧化反应的影响

 分别采用沉淀氧化法、均匀沉淀法及络合燃烧法制备了Co3O4/CeO2复合氧化物催化剂,并在干燥及湿气条件下进行了CO氧化反应. 结果表明,采用沉淀氧化法经538 K焙烧制得的Co3O4/CeO2催化剂具有优异的CO低温氧化活性和较高的抗湿性能. 在196 K条件下,该催化剂上CO氧化的转化率为99%, 并且可连续保持400 min以上; 当温度上升到298 K时,经过 2400 min反应后, CO的转化率仍可达到94%; 当反应气中含3.1%湿气,温度为383 K时,经过2400 min反应后, CO的转化率仍保持在79%. 实验表明, Co3O4/CeO2催化剂的制备方法及焙烧温度对Co3O4与CeO2之间的相互作用有显著的影响,进而影响催化剂催化CO低温氧化的活性.     

碱土金属双掺杂的Ce_(0.9)Ca_(0.1-x)Sr_xO_(1.9)中温固体电解质的性能与应用

以固相反应方法合成了碱土 (Ca ,Sr)双掺杂的氧化铈基固溶体材料Ce0 .9Ca0 .1 -xSrxO1 .9(x =0 ,0 0 4,0 0 5 ,0 0 6 ,0 1)。结构研究表明 :碱土双掺杂的CeO2 呈立方萤石结构。利用阻抗谱研究了材料的离子导电性 ,发现碱土双掺杂有利于提高材料离子导电率 ,掺杂两种碱土金属离子的等效半径接近临界离子半径时导电率最高。将此系列材料作为电解质进行了燃料电池试验 ,发现电池的输出功率高于YSZ电解质及碱土单掺杂氧化铈 ,且电池输出开路电压亦高于单掺杂的情况。     

聚碳酸亚丙酯-聚醚聚氨酯的合成与性能

本文报道用CO2与环氧丙烷共聚产物聚碳酸亚丙酯和环氧丙烷均聚物来制备聚氨酯（PPCPOPU）弹性体。探讨了这类弹性体的最佳合成方法，考察了异氰酸酯基与羟基的比值；扩链交联剂用量等因素对弹性体的力学性能的影响。研究了弹性体的形态结构及其性能对配比的依赖关系。发现聚碳酸亚丙酯的耐热性因聚氨酯的形成而得到较大的改善，并发现该类弹性体具有优异的耐水性能。     

The Fabrication and Characterization of a Nickel Nanoparticle Modified Boron Doped Diamond Electrode for Electrocatalysis of Primary Alcohol Oxidation

We report the fabrication of a Ni nanoparticle modified BDD electrode and its application in the electrocatalysis of primary alcohol electrooxidation. Modification was achieved via electrodeposition from Ni(NO₃)₂ dissolved in sodium acetate solution (pH 5). Characterization of the Ni‐modified BDD (Ni‐BDD) was performed using ex situ atomic force microscopy (AFM) and high resolution scanning electron microscopy (SEM) coupled with energy dispersive X‐ray spectroscopy (EDX). Large nanoparticles of nickel were observed on the BDD surface ranging 5 to 690 nm in height and 0.18 μm^?3 in volume, and an average number density of ca. 13×10⁶ nanoparticles cm^?2 was determined. The large range of sizes suggests progressive rather than instantaneous nucleation and growth. Electrocatalysis of ethanol and glycerol, was conducted in an alkaline medium using an unmodified BDD, Ni‐BDD and a bulk Ni macro electrode. The Ni‐BDD electrode gave the better electrocatalytic performance, with glycerol showing the greatest sensitivity. Linear calibration plots were obtained for the ethanol and glycerol additions over concentration ranges of 2.8–28.0 mM and 23–230 μM respectively. This gave an ethanol limit of detection of 1.7 mM and sensitivity of 0.31 mA/M, and the glycerol a limit of detection of 10.3 μM with a sensitivity of 35 mA/M.     

钒-铜复合氧化物催化碳酸二甲酯和苯酚酯交换合成碳酸二苯酯

采用共沉淀法制备了一种用于碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的新型钒-铜复合氧化物催化剂.考察了V/Cu配比对催化剂性能的影响以及催化剂的重复使用效果,并用X射线衍射对催化剂的结构进行了表征.结果发现,在焙烧温度为550℃,V∶Cu摩尔比为4∶1条件下制得催化剂的活性最高,该催化剂上苯酚的转化率为37.0%,甲基苯基碳酸酯及碳酸二苯酯的总选择性为96.8%.由X射线衍射表征结果可知,该催化剂的物相组成为V2O5和CuV2O6.催化剂使用三次后苯酚转化率从37.0%降至23.7%,多次重复使用后的催化剂在空气气氛中焙烧即可再生,再生催化剂的催化性能几乎和新鲜催化剂相当,其苯酚转化率达到36.2%.