SOFC内部重整反应与电化学反应耦合机理

以经过预重整反应的混合气为原料的固体氧化物燃料电池（SOFC）内部,甲烷蒸气重整反应与电化学反应同时发生在阳极多孔介质中,二者受到不同的操作与设计参数的影响,对电池总体性能起着决定性作用。编制了三维数值模拟程序,对由多孔阳极层、气体流动管道、固体支撑平板构成的单个复合管道进行了研究。结果显示：重整反应主要发生在多孔材料靠近流动管道的薄层内,只有靠近管道入口处才能在较深处进行;电化学反应发生在多孔层与电解质的交界面处;重整反应生成的H2、CO扩散到多孔材料底部参加电化学反应;电化学反应生成的热量供重整反应使用。说明研究范围内,SOFC阳极复合通道具有较好的传热、传质性能,化学/电化学反应存在较好的耦合关系。     

Electrolytic preparation of magnesium perchlorate

The electrochemical preparation of magnesium perchlorate from magnesium chlorate employing a platinum anode and a rotating stainless steel cathode is described. The effect of electrolyte concentration, cathode and anode current densities, pH and temperature of the electrolyte and cathode rotation on current efficiency for the preparation of magnesium perchlorate was studied. A maximum current efficiency of 65–72% was achieved. Based on the results obtained on the laboratory scale, a 100 A cell was designed, fabricated and operated.     

电化学法制备辛酸亚锡新工艺

采用电化学法代替传统的复分解法制备辛酸亚锡,研究了电解质、搅拌速度、电流密度、电压、温度、电极材料及抗氧化剂等诸多因素对辛酸亚锡产品质量的影响,并获得了最佳工艺参数。实验结果表明,在以浓度为 6 mol/L氯化钠为电解质、以金属锡为阳极、以钛板为阴极、阳极电流密度为100～120 A/m2、阴极电流密度为800～ 1 000 A/m²、搅拌转速为100 r/min、电解液温度为60～70 ℃,同时加抗氧化剂的情况下,可制备得到亚锡质量分数为28.32%、全锡质量分数为29.23%的辛酸亚锡产品。     

SOFC中低浓度干甲烷在Ni/YSZ阳极上的反应

固体氧化物燃料电池(SOFC)趋向于直接使用甲烷天然气为燃料,确定甲烷在固体氧化物燃料电池阳极发生的化学与电化学反应非常重要.以Ni/YSZ为阳极、YSZ板做电解质、LSM为阴极,用涂浆法制作电解质支撑的电池,研究低浓度干甲烷在固体氧化物燃料电池中的反应.改变甲烷浓度、电池工作温度、电解质厚度,用在线色谱测量不同电流密度下,阳极出口气体产生速率.根据阳极出口气体产生速率变化,分析干甲烷在阳极的反应变化.通过氧消耗计算和转移电子数的分析,说明甲烷在电池阳极发生不同类型的反应.电流密度小时,甲烷发生部分氧化反应.电流密度大时,发生氢氧化和CO氧化,部分甲烷发生总反应为完全氧化的反应.部分甲烷发生完全氧化反应的同时,部分甲烷仍发生部分氧化反应,但其反应速率随电流密度增加逐渐降低.甲烷浓度和试验温度增加,甲烷开始发生完全氧化的电流密度增加.     

Modeling and Scaleup of Galvanic Deoxidation of Molten Metals Using Solid Electrolyte Cells

Argon and induction stirred copper melts were deoxidized at different temperatures by short-circuiting a solid electrolyte cell. The solid electrolyte cell consisted of an yttria-stabilized zirconia tube closed at one end. The tube interior was flushed with a reducing gas and the tube was immersed in the copper melt. A layer of porous Ni-ZrO₂ cermet deposited on the inner wall of the tube served as the anode while the copper melt was the cathode. The deoxidation experiments were modeled as a function of mass transfer in the melt, temperature, electronic and ionic conductivity of the electrolyte, short-circuit resistance, and flow rate of the reducing gas. The deoxidation model was used to discuss process optimization and scaleup.     

A Study of Polymer Electrolyte Fuel Cells by the Measurement of AC Impedance,Current Interrupt,and Dew Points: 2. Effect of Cell Temperature

The effect of cell temperature on the performance of a polymer electrolyte fuel cell was examined in the present study. Measurements using the current interrupt and AC impedance methods showed that membrane resistance increased as the cell temperature was reduced. The charge transfer resistance, determined by the AC impedance method, also increased with decreasing cell temperature. The results of electrochemical analysis showed that the temperature of the cell strongly affected the performance of the membrane–electrode assembly in the cell. In addition, the water balance calculated from dew points of fuel gases changed with cell temperature. At a cell temperature of 80 °C, ca. 80% of the water generated on the cathode passed through the membrane to the anode, while at a cell temperature of 40 °C, only ca. 20% of the water on the cathode passed through the membrane to the anode.     

Calculation of reversible electrode heats in the proton exchange membrane fuel cell from calorimetric measurements

A calorimeter was used to measure the heat production in polymer electrolyte membrane (PEM) fuel cells operated on hydrogen and oxygen at 50 °C and 1 bar. Two cells were examined, one using a 35 μm thick Nafion membrane and a catalyst loading of 0.6/0.4 mg Pt cm⁻², for the cathode and anode layer, respectively, the other using a 180 μm thick Nafion membrane and loading of 0.4/0.4 mg Pt cm⁻². The cells investigated thus had different membranes and catalyst layers, but identical porous transport layers and micro-porous layers. The calorimeter is unique in that it provides the heat fluxes out of the cell, separately for the anode and the cathode sides. The corresponding cell potential differences, ohmic cell resistance and current densities are also reported. The heat fluxes through the current collector plates were decomposed by a thermal model to give the contributions from the ohmic and the Tafel heats to the total heat fluxes. Thus, the contributions from the reversible heat (the Peltier heats) to the current collectors were determined. The analysis suggests that the Peltier heat of the anode of these fuel cell materials is small, and that it is the cathode reaction which generates the main fraction of the total heat in a PEM fuel cell. The entropy change of the anode reaction appears to be close to zero, while the corresponding value for the cathode is near −80 J K⁻¹ mol⁻¹.     

SOFC Cell Design Optimization Using the Finite Element Method Based CFD Approach

Fuel cells are hopeful for future energy systems, because they are energy efficient and able to use renewable fuels. A coupled computational fluid dynamics approach based on the finite element method, in three‐dimensions, is used to illustrate a planar intermediate‐temperature solid oxide fuel cell. Governing equations for momentum, gas‐phase species, heat, electron and ion transport are implemented and coupled to kinetics describing electrochemical reactions. Three different cell designs are compared in a parametric study. The importance of the cathode support layer is revealed, because this layer significantly decreases the oxygen gas‐phase resistance within the cathode (at positions under the interconnect ribs) in the direction normal to the cathode/electrolyte interface as well as the electron resistance inside the cathode (at positions under the air channel) in the same direction. It is concluded that wider and thinner gas channels enable a more compact design with only a slightly decreased cell current density (per cross‐sectional electrode/electrolyte interface area), i.e. a considerably increased volumetric cell current can be achieved.     

Quasi Three–Dimensional Modelling of the PEM Fuel Cell: Comparison of the Catalyst Layers Performance

The results of the first quasi three dimensional modelling of a polymer electrolyte membrane fuel cell with meander–like gas channels are reported. The model resolves the catalyst layers and takes into account feed gas consumption in the channels. The results show that in both catalyst layers the rate of electrochemical reaction in front of the channels is higher, than in front of the current collectors. The overpotential is almost constant across the cathode catalyst layer and varies rapidly (exponentially) across the anode catalyst layer. A current on the anode side is produced in a thin sub–layer adjacent to the membrane, where the overpotential is close to its maximum value. A simple formula for optimal thickness of the anode catalyst layer is derived and compared with numerical results.     

电化学合成纳米α—Fe2O3的工艺研究

采用金属铁为“牺牲”阳极,不锈钢片为阴极,在无隔膜电解槽中,用电化学一步法合成纳米氧化铁。讨论了温度、水的质量分数、电解质浓度对电流强度的影响,并通过IR、XRD及粒径分布等测试方法对所得的纳米粒子进行了表征和分析。实验表明：在电解反应中,反应最适宜温度应控制在55～65℃之间,水的最适宜质量分数为0．02,四丁基溴化铵的最适宜浓度为0．08mol／L;电解所得产物经540℃煅烧3h后,可得到α—Fe2O3纳米粒子,其平均粒径为35．3nm。     

Polyaniline as cathodic material for electrochemical energy sources: The role of morphology

Polyaniline layers of different morphologies ranging from open and “sponge-like” structures to compact and “pebble-like” surfaces were synthesized from perchlorate solutions and employed as cathode in the galvanic cell with Zn anode and NH₄Cl/ZnCl₂ electrolyte. Cathodic properties of synthesized layers were investigated by the constant current charging/discharging method in 500 cycles. Specific charge capacities and specific energies obtained form the current-time curves strongly depend on the morphology of investigated layers and discharge conditions. The results unambiguously show that charging/discharging reaction of polyaniline layers is limited to relatively thin layer at polymer/solution boundary. Specific charge capacities are inversely related to both the polymer thickness and the discharge current density. In the limit of zero current densities the specific charge capacity as high as 245 A h kg⁻¹ could be achieved for porous structures of polyaniline layers. Specific capacitance higher than 400 F g⁻¹ obtained at 2 mA cm⁻² current density makes polyaniline a promising material for the application in electrochemical supercapacitors. The electrochemical behaviour of the layers was investigated by cyclic voltammetry and electrochemical impedance spectroscopy before and after 500 cycles of charging/discharging experiments. Both, cyclic voltammetry and electrochemical impedance spectroscopy showed that some polyaniline layers develop an increased charged transfer resistance at the carbon support/polymer interface during charging/discharging process. The increased charge transfer resistance does not affect the overall specific charge of the layers. The low-frequency capacities in impedance spectra are attributed to charging/discharging of polymer/electrolyte interface and seem to be related to the specific charge capacities obtained by extrapolation to zero current density discharge reaction.     

采用泡沫铜电极的热再生氨电池性能数值模拟

以采用泡沫铜电极的热再生氨电池(thermally regenerative ammonia-based battery,TRAB)为研究对象,建立了多孔介质内物质传输与电化学反应耦合的稳态模型,计算获得了电池性能及多孔电极内物质传输特性,并研究了电解质浓度和电极孔隙率对电池性能的影响。研究结果表明,从主流区界面到多孔电极内部,阳极氨和阴极铜离子浓度逐渐降低,存在一定的浓度梯度,而且随着反应电流的增大,浓度梯度明显增大。在一定的范围内分别增大阳极氨浓度和阴极铜离子浓度,从主流区向多孔电极内物质传输增强,电池性能均能不断提升;随着硫酸铵浓度的增大,电解质电导率增大,电池性能逐渐提升,但增幅逐渐减小。此外,多孔电极孔隙率也会影响电池性能,本研究中TRAB在电极孔隙率为0.6时获得最高的最大功率(15.3 mW)。     

A Performance Prediction Tool for Solid Oxide Fuel Cells after Single Redox Cycle

The effects of anode support fabrication parameters on the cell performance and the redox behavior of the cell are investigated experimentally and theoretically. In the experimental program, an yttria stabilized zirconia based anode supported membrane electrode group (MEG) is developed via the tape casting, co‐sintering and screen printing methodologies. For comparison, various anode supported cells with different electrolyte thickness and anode support porosities are also fabricated. In the theoretical study, a mathematical model is developed to represent the fluid flow, the heat transfer, the species transport and the electrochemical reaction in solid oxide fuel cells. In addition, a redox model representing the mechanical damage in the electrochemical reaction zones due to redox cycling is developed by defining a damage function as a function of strain and a damage coefficient. The effects of anode support porosity and the electrolyte thickness on the cell performance and redox stability of the cells are numerically investigated. The experimental results are compared with the numerical results to validate the mathematical model. Finally, a predictive tool, which is valid for the ranges of the cell fabrication parameters investigated, is developed to estimate the electrochemical performance after single redox cycle.     

应用离子交换膜通过电化学氧化合成氯甲苯

以钛网为阳极,镍网为阴极,饱和的NaCl溶液为阳极电解质,应用离子交换膜通过阳极氧化甲苯的方法合成氯甲苯。讨论了阳极电解质质量分数、电流密度、电解液温度、反应时间等反应条件的选择。结果表明：在反应温度25 ℃,阳极、阴极电解液分别为25％NaCl和10％NaOH溶液,电流密度为10～15 A/dm2条件下电解,并在4.5 h左右结束反应,氯甲苯的产率最高,可达55.5％,电流效率为51.5％。     

Computational fluid dynamics study on the anode feed solid polymer electrolyte water electrolysis

A steady-state two-dimensional model for the anode feed solid polymer electrolyte water electrolysis (SPEWE) is proposed in this paper. Finite element procedure was employed to calculate the multicomponent transfer model coupled with fluid flow in flow channels and gas diffusion layers and electrochemical kinetics in catalyst reactive surface. The performance of the anode feed SPEWE predicted by this model was compared with the published experimental results and reasonable agreement was reached. The results show that oxygen mass fraction increases because of the water oxidation when water flows from the import to the export on the anode side. On the cathode side, hydrogen mass fraction varies little since hydrogen and water mix well. The flux of water across the electrolyte increased almost linearly with the increase of the applied current density. Since the ohmic overpotential loss increasing as the solid polymer electrolytes’ thickness increasing, the performance of the anode feed SPEWE with Nafion 112, 115, 117 decreases at the same applied current density.     

Inert substrate-supported microtubular solid oxide fuel cells based on highly porous ceramic by low-temperature co-sintering

Inert substrate-supported microtubular solid oxide fuel cells (MT-SOFCs) are attractive due to their advantages, including high reduction–oxidation (redox) cycling stability and thermal cycling tolerance. A method involving sequential dip-coating, leaching, and co-sintering was developed and applied to fabricate inert substrate-supported MT-SOFCs through acid leaching nickel from the conventional Ni–yttria-stabilized zirconia (YSZ) anode. A thin current collector was deposited onto the support surface to minimize the current collection losses by collecting current from the entire surface area of the anode. A dense electrolyte could be obtained at a co-sintering temperature of 1250?°C. The produced MT-SOFC with the configuration of porous zirconia support/Ni–Scandia-stabilized zirconia (SSZ) anode current collector/Ni-SSZ anode/SSZ electrolyte/strontium-doped lanthanum manganite (LSM)-SSZ cathode/LSM cathode current collector was evaluated by electrochemical characterization tests. The inert substrate-supported MT-SOFC exhibited the maximum power densities of 616, 542, 440, and 300?mW?cm^?2 at 800, 750, 700, and 650?°C, respectively using dry hydrogen and air. In addition, the thermal cycling stability of the MT-SOFC was evaluated. The cell survived from thermal cycling tests and came out intact after 50 thermal cycles between 700?°C and 400?°C during an operation time of 50?h.     

操作条件对质子交换膜燃料电池电化学阻抗动态行为的影响

应用交流阻抗谱法（electrochemical impedance spectroscopy,EIS）研究温度、湿度和阴、阳极过量系数4种操作条件对质子交换膜燃料电池（proton exchange membrane fuel cell,PEMFC）电化学阻抗的影响,并应用复合阻容并联等效电路对实验结果进行等效拟合。实验结果表明,PEMFC单电池的电流密度为1400 mA/cm²时,阴极过量系数对PEMFC单电池高频阻抗的影响最大,温度和湿度次之,阳极过量系数影响最小;不同操作条件的改变对高频阻抗谱中的欧姆阻抗的影响非常小,主要通过影响阴阳极法拉第阻抗来影响PEMFC单电池的输出性能;等效结果和实验结果在不同频率段的阻抗表现出一致的变化规律,各阻抗的误差值能够控制在2mΩ以内,可以有效地等效替代实验结果。     

Electrochemical sulfur dioxide concentrator for flue-gas desulfurization

A small test cell has been designed to investigate the electrochemical removal and concentration of sulfur dioxide from stack gases. The cell is a high temperature molten-salt cell which uses the ternary eutectic of lithium, potassium and sodium sulfates as the electrolyte. Simulated flue-gas having a composition similar to that resulting from burning 3.5% sulfur coal is fed to the cathode, where sulfur dioxide and oxygen are converted to sulfate ion. At the anode, the reverse reaction occurs resulting in a small volume of gas containing up to 50% sulfur oxides.     

Investigation of electrode composition of polymer fuel cells by electrochemical impedance spectroscopy

In order to optimize the electrode composition and performance of Polymer Fuel Cells and to reduce the production cost of membrane electrode assemblies (MEAs), different MEAs using different catalyst powders, carbon supported and unsupported catalysts with different proton conducting electrolyte powder (Nafion) content were produced by using a dry powder spraying technique developed at German Aerospace Research Center (DLR, Deutsches Zentrum fuer Luft- und Raumfahrt). The electrochemical characterization was performed by recording current-voltage curves and electrochemical impedance spectra (EIS) in the galvanostatic mode of operation at 500 mA cm⁻². The evaluation of the measured impedance spectra with an adequate equivalent circuit shows that the cathode of the fuel cell is very sensitive to the electrode composition whereas the contribution of the anode is very small and invariant to the electrode composition. Furthermore, it could be shown for the first time using electrolyte powder in the electrodes that the charge transfer of the cathode decreasing monotonically with increasing electrolyte content in the cathode. These findings suggest that with increasing electrolyte content in the electrodes, in particular in the cathode, the utilization degree of the catalyst increasing linearly with increasing electrolyte content in the electrode.