生物质定向气化制合成气—气化热力学模型与模拟

通过对气化炉内反应的热力学模型构建和模拟,探讨了实现生物质定向气化为合成气(H2∶CO=2∶1) 的条件,以便使用该合成气直接合成液体燃料—甲醇.在考虑气化过程中物质平衡、能量平衡和化学反应平衡的 基础上,建立了生物质气化模型,并使用PASICAL语言及其外挂DELPHI程序,编写了FBGB程序,用于模拟生物 质、水蒸气输入量与产气中各种气体组分含量之间的关系.通过模拟,发现水蒸气与生物质输入速率的比值 (S/B)是影响H2/CO值的关键参数.模拟结果显示当其它反应条件确定时,S/B与H2/CO呈线性递增关系,通 过调节S/B,H2与CO的比例可以得到控制.     

不同电池并联时利用电池能量的条件

一般情况下,在断开外电路时,不能将电动势不同的两个电源并联起来,因为在电池组未对外供电时,E1E2构成的回路中有电流通过,E1>E2,E2是反电动势,E1对E2充电。但不能由此得出电动势不等的电池不能并联起来使用,电动势小的电池不能对外提供电能的结论.在图1中若先闭合K1,使K2断开,     

Ni与钇稳定的氧化锆(111)表面相互作用以及界面活性的第一性原理研究

采用基于密度泛函理论的第一性原理方法, 系统研究了Ni原子在钇稳定的氧化锆(YSZ)(111)和富氧的YSZ(YSZ+O)(111)表面不同位置的吸附, 以及CO和O₂分子在Ni₁(单个镍原子)/YSZ和Ni₁/YSZ+O表面吸附的几何与电子结构特征. 结果表明: 1) 单个Ni原子倾向于吸附在O原子周围, 几乎不吸附在Y原子周围, 且Ni原子在氧空位上吸附最稳定; 2)和YSZ相比, 单个Ni原子在YSZ+O表面易发生氧化现象, Ni原子失去1.06 e电子, 被氧化成了Ni⁺, 吸附能力更强; 3)被氧化的Ni催化活性大幅下降, 大大减弱了表面对O₂和CO等燃料气体的吸附作用.     

平板式阳极支撑SOFC多场耦合数值模拟

建立了平板式固体氧化物燃料电池多场耦合数学模型,利用商业CFD软件FLUENT对包括阳极和阴极多孔介质、致密固体氧化物电解质、燃料流道、氧化剂流道、电流收集双极板、外壳的单电池三维整体计算区域进行了数值模拟,得到了流场、温度场、组分浓度场、电流密度场、Nernst电动势、活化过电势和欧姆过电势等重要物理量的详细分布,并分析了影响电池性能的主要因素。模拟结果与SOFC研制单位提供的实验数据基本符合。     

“电位計測电动势实驗”中的几个問题的討論

电位计是电测量中精确度高、用途广的重要仪器.在普通物理实验教学中,普遍采用的是结构简单直观的滑线电位计. 电位计测电动势是采用所谓“补偿法”,它是以被测电池的电动势与电阻上的已知电压降相互平衡这一原理作为基础的.图1为其原理性示意图,设l_s为相应于ε_s时的平衡长度,l_x为相应于ε_x时的平衡长度,则有     

新旧干电池混合使用一定不好吗？

许多教师在教学中都要告诫同学 ,新旧干电池不要混合使用 ,否则会造成新电池的浪费 .其实 ,这要具体情况具体分析 .设新电池的电动势为Ｅ ,内电阻为ｒ,旧电池的电动势为Ｅ′ ,内电阻为ｒ′ ,负载电阻为Ｒ ,当两节新电池串联供电时 ,路端电压为Ｕ =ＩＲ =2ＥＲ 2ｒＲ     

Ba0.98Ce0.8Tm0.2O3-α的离子导电性及其燃料电池性能

用高温固相反应法制备了Ba_0.98Ce_0.8Tm_0.2O_3-α钙钛矿型氧化物固溶体,粉末X射线衍射表明该固溶体为单相. 用交流阻抗谱技术和气体浓差电池方法研究了样品在500～900 oC、不同气体气氛中的导电性,以及该样品为固体电解质的氢-空气燃料电池性能. 该电池能稳定地工作,在900 oC时,电池的最大功率密度为110.2 mW/cm²,高于以Ba_xCe_0.8RE_0.2O₃^- (x≤1, RE=Y, Eu, Ho)为固体电解质的氢-空气燃料电池的功率密度     

电位差计实验中待测电源的改进

在用电位差计测量电源电动势实验中,常用1.5伏的普通电池作为待测电动势。由于普通电源在开始使用时电动势较高(最高可达1.6V),而在使用一段时间后电动势则会变小(可低至1.3V以下),这就给实验指导教师检查学生测量结果的正确性带来了困难。为解决这一问题,我们采用了在待测电池后面加一低压稳压电路的方法,实际效果较好。当待测电池的电动势在1.6V至1.3V     

光催化二氧化碳还原研究进展

21 世纪以来，随着CO2 为主的温室气体排放量不断增加，寻求新型能源来构建低碳型社会的诉求越来越迫切。其中以太阳能驱动转化CO2 为碳氢燃料的技术，可将CO2 转化成甲烷、甲醇、甲酸或C2+ 等高附加值的碳氢燃料，是实现全球碳平衡的有效途径之一，具有巨大潜力。半导体材料是决定光催化还原CO2 过程进行的重要因素之一，因此探索和开发高效光催化功能材料是当今研究的主要方向。本文综述了近几年来作者课题组在光催化还原CO2 为碳氢燃料方面的重要研究进展，主要涉及TiO2 基系列光催化材料，V、W、Ge、Ga、C3N4 基等系列光催化材料的结构组分调控。     

膨体聚四氟乙烯膜的亲水改性及其在微生物燃料电池中的应用

膨体聚四氟乙烯(ePTFE)膜以聚四氟乙烯为原料膨化拉伸而成,具有耐酸碱、强度高、生物适应性强、抗污染性高等优点。本文对已商品化的ePTFE膜进行亲水处理,并对无膜以及使用Nafion 117质子交换膜,未处理的ePTFE膜,亲水处理的ePTFE膜时的微生物燃料电池的性能进行了比较。实验发现ePTFE膜经过亲水处理后其与水的接触角从122°变化为64°;使用亲水性ePTFE膜的微生物燃料电池获得的最大功率密度为1303 mW/m~2,高于无膜(1170mW/m~2),使用Nafion 117(840 mW/m~2)和未处理ePTFE膜(678 mW/m~2)时的功率密度。结果表明ePTFE膜可以作为微生物燃料电池的分隔物,并且通过改善膜表面与水的接触角可以在增加质子传递效率的同时减小氧气的渗透,进而提高微生物燃料电池的电池性能。     

Measurement of electrode overpotentials for direct hydrocarbon conversion fuel cells

Cathodic and anodic overpotentials were measured using current interruption and AC impedance spectroscopy for two separate solid oxide fuel cells (SOFCs). The fuel cells used yttria-stabilized zirconia (YSZ) as the electrolyte, strontium-doped lanthanum manganite (LSM) as the cathode, and a porous YSZ layer impregnated with copper and ceria as the anode. The Cu/CeO₂/YSZ anode is active for the direct conversion of hydrocarbon fuels. Overpotentials measured using both current interruption and impedance spectroscopy for the fuel cell operating at 700 °C on both hydrogen and n-butane fuels are reported. In addition to providing the first electrode overpotential measurements for direct conversion fuel cells with Cu-based anodes, the results demonstrate that there may be significant uncertainties in measurements of electrode overpotentials for systems where there is a large difference between the characteristic frequencies of the anode and cathode processes and/or complex electrode kinetics.     

Samaria-doped Ceria Modified Ni/YSZ Anode for Direct Methane Fuel in Tubular Solid Oxide Fuel Cells by Impregnation Method

以NiO和8%(摩尔分数)氧化钇稳定的氧化锆为原料,采用注凝成型工艺制备了管状固体氧化物燃料电池阳极支撑体．用离子浸渍法对阳极支撑体进行表面修饰．用电化学工作站测单电池交流阻抗和输出性能并且用化学气相色谱仪对电池尾气进行分析．测试结果表明修饰后的阳极在通甲烷的情况下出现了一定程度的积炭,但是积炭现象在一定的测试时间内达到平衡,没有对电池造成破坏,并且显著地提高了电池阳极的电化学性能．单电池在通入氢气和甲烷的情况下最大输出功率密度分别达到了225和400 mW/cm²．     

Aging behavior and ionic conductivity of ceria-based ceramics: a comparative study

An understanding of high-temperature aging effects on the electrical properties of electrolytes is very important in selecting optimum compositions for practical applications. The aging behavior and mechanisms of doped zirconia ceramics have been extensively studied. However, little information is available regarding the aging behavior of ceria-based electrolytes. The present study has demonstrated that a high-temperature aging at 1000 °C has a significant effect on the ionic conductivity of the Y- or Gd-doped ceria (Ce_1−xY_xO_2−δ and Ce_1−xGd_xO_2−δ), especially in the case of the Gd doping. The aging behavior is characterized by a critical dopant concentration, above which the aging has a detrimental effect on the conductivity of the doped ceria ceramics. The aging behavior in the doped ceria cannot be explained using the aging mechanisms applied to the doped zirconia. Instead, the formation of the microdomains in the doped ceria has been acknowledged to be the main contribution to the aging behavior of the Y- or Gd-doped ceria ceramics. The formation ability of microdomains has been estimated to be in the order of La³⁺>Gd³⁺>Y³⁺, based on the degree of size mismatch between the dopant ion and Ce⁴⁺ ion. The critical dopant concentrations at which the microdomains start to form for La³⁺, Gd³⁺ and Y³⁺ in the doped ceria ceramics are x=0.15, 0.2 and 0.25, respectively. This critical dopant concentration is also an important indication: below which the conductivity is governed by only the association enthalpy, and above which the conductivity is dominated mainly by the microdomains rather than the association enthalpy.     

Ceria: Relation among thermodynamic,electronic hole and proton properties

The proton solubility and the hole conductivity of the rare earth doped ceria have been examined in their relations to the thermodynamic properties of doped ceria under the assumption that the hypothetical species, LnOOH and LnOO (Ln = Rare earth), can be regarded as constituents for representing protons and holes in the fluorite lattice. Focus is made on the dopant dependence, the host dependence and the temperature dependence in the rare earth doped zirconia(or ceria) fluorite lattice. The chemical potentials of the rare earth dopant are less stabilized in the ceria-based oxides than in the zirconia-based ones. The proton solubility in the ceria-based, zirconia-based, and ceria–zirconia solid solutions has been well interpreted in terms mainly of the hydroxidation energy and the stabilization energy of LnO_1.5 in the fluorite lattice. Since the dopant dependence of the stabilization energy of LnO_1.5 is stronger than the hydroxidation energy, the proton solubility becomes high in the smaller dopants. To account for less dopant-dependent behavior in the hole conduction, the peroxidation energy is assumed to have about the same dopant dependence as the stabilization energy. The calculated temperature dependences of proton solubility and hole concentration were compared with available experimental data; it has been suggested that holes and protons in ceria reach to saturation levels with lowering temperature. Some discussions are made on the possible explanation on recently observed anomalous hole conductivity in nano-size Ce_0.8Gd_0.2O_1.9 in terms of plausible effects of miscibility gap, associated Gd enrichment, and simultaneous formation of Ce³⁺ and holes.     

Fuel quality and operational issues for polymer electrolyte membrane (PEM) fuel cells

Polymer electrolyte membrane (PEM) fuel cells are susceptible to degradation due to the catalyst poisoning caused by CO present in the fuel above certain limits. Although the amount of CO in the fuel may be within the permissible limit, the fuel composition (% CO₂, CH₄, CO and H₂O) and the operating conditions of the cell (level of gas humidification, cell temperature and pressure) can be such that the equilibrium CO content inside the cell may exceed the permissible limit leading to a degradation of the fuel cell performance. In this study, 50 cm² active area PEM fuel cells were operated at 55–60 °C for periods up to 250 hours to study the effect of methane, carbon dioxide and water in the hydrogen fuel mix on the cell performance (stability of voltage and power output). Furthermore, the stability of fuel cells was also studied during operation of cells in a cyclic dead end / flow through configuration, both with and without the presence of carbon dioxide in the hydrogen stream. The presence of methane up to 10% in the hydrogen stream showed a negligible degradation in the cell performance. The presence of carbon dioxide in the hydrogen stream even at 1–2% level was found to degrade the cell performance. However, this degradation was found to disappear by bleeding only about 0.2% oxygen into the fuel stream.     

Nanostructure and conductivity study of yttria doped zirconia films deposited on samaria doped ceria

Yttrium doped zirconia (YSZ) film was deposited on poly-crystalline 10 at.% samaria doped ceria (SDC) and YSZ plate (doped with 8 at.% yttria) by electron beam evaporation deposition. For electrolyte application in solid oxide fuel cells, YSZ can be used with SDC and act as an electron barrier. The conductivity of YSZ and SDC was measured after sintering at 1000 °C. Results indicated that YSZ film became columnar structure, and a new layer formed between the YSZ film and SDC, due to the inter-diffusion between zirconium ions and cerium ions.     

Processing and microstructure characterization of ceria-doped yttria-stabilized zirconia powder and ceramics

Cubic stabilized zirconia is a promising material as target for the transmutation of actinides in nuclear reactors. In this concept, actinides are incorporated into an inert matrix (zirconia) to form a solid solution. The present work is focused on the synthesis of 8 mol% yttria-stabilized zirconia doped with 10 mol% ceria (10Ce–8YSZ) in which Ce is used to simulate the incorporation of tetravalent actinides. A wet chemical route powder synthesis method was applied to make homogeneous single-phase ceria-doped yttria-stabilized zirconia ceramics. The synthesis as well as the characterization of samples by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray emission Spectrometry (EDXS) and Rutherford Backscattering Spectroscopy (RBS) is presented.     

Different conduction behaviors of grain boundaries in SiO2-containing 8YSZ and CGO20 electrolytes

Both doped zirconia and ceria have been widely recognized as promising electrolytes in solid oxide fuel cells (SOFC). Total conductivity is an important parameter to evaluate solid electrolytes. It is well know that the contribution to the total conductivity by grain boundaries is especially pronounced for SiO₂-contaminated electrolytes. In this study, we report on the different conduction behaviors of grain boundaries (GB) found in SiO₂-containing (impure) 8YSZ (8 mol% Y₂O₃-doped ZrO₂) and CGO20 (10 mol% Gd₂O₃-doped CeO₂) ceramics. In the grain size range (∼ 0.5–10 μm) studied, the GB conductivity of impure CGO20 ceramics constantly decreases with increasing grain size, in contrast to that observed in impure 8YSZ electrolytes whose GB conductivity increases almost linearly with grain size. It is also found that the variation in GB conductivity versus grain size is different from case to case, depending on the sintering/annealing conditions used to fabricate the ceramics. Two mechanisms were proposed to explain the GB behaviors of the impure 8YSZ and CGO20 ceramics. For doped ceria, the GB phases are supposed to be inert, which do not react with or dissolve into the matrix. Increasing sintering temperature leads to not only grain growth but also change in viscosity and wetting nature of the GB phases. These two factors promote further propagation of the GB phases along the grain boundaries, leading to an increased GB coverage fraction. For doped zirconia, however, the major factor dominating the GB conduction is the further dissolution of SiO₂ into zirconia lattice as a result of increase in sintering temperature or/and time. In addition, we will also evaluate and discuss the validities of the three models that are widely used to analyze the GB conduction in solid electrolytes.     

生物柴油发动机非常规排放的FTIR检测

采用傅里叶变换红外光谱FTIR,研究了汽车发动机燃用生物柴油的非常规排放物。所用燃料分别为纯柴油、纯生物柴油、生物柴油掺混比为20%的B20混合燃料。结果表明,该机燃用纯柴油和B20燃油的甲醛排放差别不大,纯生物柴油的甲醛排放则明显高于柴油。燃用B20燃油的乙醛排放略低于纯柴油;纯生物柴油的乙醛排放在中低负荷低于纯柴油,在高负荷时高于柴油及B20燃油。燃用B20燃油和纯生物柴油的丙酮排放要高于柴油,但排放量均较低。随着生物柴油掺混比例的增加,发动机甲苯和二氧化硫均呈逐渐下降趋势,纯生物柴油的二氧化硫排放大幅降低。燃用生物柴油后,发动机的二氧化碳排放有所降低,表明了生物柴油有利于温室气体的控制。     

Improvement of Cu–CeO2 anodes for SOFCs running on ethanol fuels

Ethanol is considered to be an attractive green fuel for solid oxide fuel cells (SOFCs) due to several advantages. In this paper, we presented recent progress of our group in Cu–CeO₂ anodes for SOFCs with ethanol steam as a fuel. Cu–CeO₂–ScSZ (scandia stabilized zirconia)anodes with different ratios of copper versus ceria were fabricated and the impedance spectra of symmetric cells were measured to optimize the anode composition. Area specific resistance (ASR) of these anodes was examined to prove the thermal stability of them, and possible reasons for degradation were analyzed. Furthermore, a Ni–ScSZ interlayer was added between Cu–CeO₂–YSZ (yttria stabilized zirconia) anode and ScSZ electrolyte to improve the anode performance, and the three-layer structure was fabricated by acid leaching of nickel and wet impregnation method. The maximum power density of the single cell reached 604 mW cm^? 2 and 408 mW cm^? 2 at 800 °C in hydrogen and ethanol steam respectively, and the cell obtained stable output in ethanol steam over an operation period of 50 h.