Enhancing the stability of power generation of single‐chamber microbial fuel cells using an anion exchange membrane

BACKGROUD: A decreased power density could be observed in a single‐chamber microbial fuel cell (MFC) with a cation exchange membrane (CEM), as a result of pH‐associated problem and a precipitated salt‐associated problem, due to the transport of cations other than protons through the membrane to the cathode. To inhibit cation transport and enhance the stability of power generation, an anion exchange membranes (AEM) was applied in a single‐chamber MFC. RESULTS: After 70 days' operation, the power density dropped 29% in the MFC with an AEM (AMFC), smaller than 48% in the MFC with a cation exchange membrane (CMFC). The reason for this difference lay in internal resistance development. Membrane resistance in the AMFC remained the same but that in the CMFC was increased by 67 Ω, and the cathode resistance increase in the AMFC was 54 Ω, while that in the CMFC was 123 Ω. The precipitated cations on the cathode catalyst surface in the CMFC, which accounted for the resistance increase, were up to 84 times larger than that in the AMFC. CONCLUSION: Because of its capacity for inhibiting cations, the AMFC possessed more stable membrane and cathode resistances; thus an enhanced power generation was obtained. Copyright © 2009 Society of Chemical Industry     

Electric field-assisted sintering anode-supported single solid oxide fuel cell

Cosintering (La_0.84Sr_0.16MnO₃ thin-film cathode/ZrO₂: 8 mol% Y₂O₃ thin-film solid electrolyte/55 vol.% ZrO₂:8 mol% Y₂O₃ + 45 vol.% NiO anode, ϕ = 12 × 1.5 mm thick pellet) was achieved by applying an electric field for 5 min at 1200°C. Impedance spectroscopy measurements of the anode-supported three-layer cell show an improvement of the electrical conductivity in comparison to that of a conventionally sintered cell. The scanning electron microscopy images of the cross-sections of electric field-assisted pressureless sintered cells show a fairly dense electrolyte and porous anode and cathode. Joule heating, resulting from the electric current due to the application of the AC electric field, is suggested as responsible for sintering. Dilatometric shrinkage curves, electric voltage and current profiles, impedance spectroscopy diagrams, and scanning electron microscopy micrographs show how anode-electrolyte-cathode ceramic cells can be cosintered at temperatures lower than the usually required.     

A high-performance solid oxide fuel cell with a layered electrolyte for reduced temperatures

The application of conventional zirconia-based electrolytes is limited to relatively high temperatures (ie > 750°C) due to their poor conductivities at low temperatures. Doped ceria has much higher conductivities; however, when exposed to fuel, electronic current develops within the material, which impairs cell performance and efficiency. Herein, we report a novel layered electrolyte structure consisting of a 10 µm samaria-doped ceria primary layer and a 2 µm scandia-ceria-stabilized zirconia protection layer on the fuel side. The cell had five layers and was fabricated using a tape casting and ultrasonic spraying technique. By carefully selecting the raw materials, the bilyer electrolyte was sintered to full density at a low temperature of 1250°C. The adverse interdiffusion and undesirable reactions between the two layers were largely avoided. A fuel cell with the layered electrolyte structure, operated on hydrogen fuel, produced a high open circuit voltage 1.07 V and a power density of 321 mW/cm² at 0.8 V and 600°C, 76% improvement compared to the fuel cell with a scandia-stabilized zirconia/samaria-doped ceria bilayer electrolyte reported in literature.     

Optimization of anode structure for intermediate temperature solid oxide fuel cell via phase‐inversion cotape casting

A functional layer and a porous support that together constitute an anode for a solid oxide fuel cell were simultaneously formed by the phase‐inversion tape casting method. Two slurries, one composed of NiO and yttria‐stabilized zirconia (YSZ) powders and the other of NiO, YSZ, and graphite were cocasted and solidified by immersion in a water bath via the phase‐inversion mechanism. The as‐formed green tape consisted of a sponge‐like thin layer and a fingerlike thick porous layer, derived from the first slurry and the second slurry, respectively. The former acted as the anode functional layer (AFL), while the latter was used as the anode substrate. The AFL thickness was varied between 20 and 60 μm by adjusting the blade gap for the tape casting. Single cells based on such NiO‐YSZ anodes were prepared with thin YSZ electrolytes and YSZ‐(La_0.8Sr_0.2)_0.95MnO_3?δ (LSM) cathodes, and their electrochemical performance was measured using air as oxidant and hydrogen as fuel. The maximum power densities obtained at 750°C were 720, 821, and 988 mW cm^?2 with the AFL thickness at 60, 40, and 20 μm, respectively. The satisfactory electrochemical performance was attributed to the dual‐layer structure of the anode, where the sponge‐like AFL layer provided plenty of triple‐phase boundaries for hydrogen oxidation, and the fingerlike thick porous substrate allowed for facile fuel transport. The phase‐inversion tape casting developed in this study is applicable to the preparation of other planar ceramic electrodes with dual‐layer asymmetric structure.     

An investigation of metal ion diffusion in ceria‐based solid oxide fuel cell with barium‐containing anode

Metal ion diffusion is an effective strategy to suppress the internal electronic short circuit in ceria‐based solid oxide fuel cells (SOFCs). This could be achieved by fabricating an electron‐blocking layer between the barium‐containing anode and ceria‐based electrolyte. In this paper, a 0.6NiO‐0.4BaZr_0.1Ce_0.7Y_0.2O_3‐δ (NiO‐BZCY) anode‐supported cell based on Gd_0.1Ce_0.9O_2‐δ (GDC) electrolyte was employed to evaluate the internal metal ion diffusion behavior. The high open circuit voltages of about 1 V obtained at 550‐700°C can be attributed to in situ formation of an electron‐blocking interlayer between NiO‐BZCY and GDC. Microstructural analyses of the interlayer grains obtained by traditional solid‐state reaction were carried out. Phase identification demonstrated that the electron‐blocking interlayer had a perovskite structure. SEM and TEM analyses indicated formation of a new compound in the interlayer, of which the composition was determined as Zr, Y, and Ni co‐doped BaCe_0.9Gd_0.1O₃ with orthorhombic structure.     

平板式直接内重整固体氧化物燃料电池的一维动态建模与仿真

This article aims to investigate the transient behavior of a planar direct internal reforming solid oxide fuel cell (DIR-SOFC) comprehensively. A one-dimensional dynamic model of a planar DIR-SOFC is first developed based on mass and energy balances, and electrochemical principles. Further, a solution strategy is presented to solve the model, and the International Energy Agency (IEA) benchmark test is used to validate the model. Then, through model-based simulations, the steady-state performance of a co-flow planar DIR-SOFC under specified initial operating conditions and its dynamic response to introduced operating parameter disturbances are studied. The dynamic responses of important SOFC variables, such as cell temperature, current density, and cell voltage are all investigated when the SOFC is subjected to the step-changes in various operating parameters including both the load current and the inlet fuel and air flow rates. The results indicate that the rapid dynamics of the current density and the cell voltage are mainly influenced by the gas composition, particularly the H2 molar fraction in anode gas channels, while their slow dynamics are both dominated by the SOLID (including the PEN and interconnects) tem-perature. As the load current increases, the SOLID temperature and the maximum SOLID temperature gradient both increase, and thereby, the cell breakdown is apt to occur because of excessive thermal stresses. Changing the inlet fuel flow rate might lead to the change in the anode gas composition and the consequent change in the current den-sity distribution and cell voltage. The inlet air flow rate has a great impact on the cell temperature distribution along the cell, and thus, is a suitable manipulated variable to control the cell temperature.     

固体氧化物燃料电池阳极材料Sr_2Fe_(1.5)Mo_(0.5)O_6(SFM)/Sm_(0.2)Ce_(0.8)O_(1.9)(SDC)的研究

采用机械混合法合成了Sr2Fe1.5Mo0.5O6(SFM)和Sm0.2Ce0.8O1.9(SDC)质量比为7∶3的SFM/SDC复合材料。用X射线衍射(XRD)、扫描电镜(SEM)、H2-TPR、EIS等表征手段对其进行了表征,并以SFM/SDC|La0.8Sr0.2Ga0.83Mg0.17O3(LSGM)|Ba0.5Sr0.5Co0.8Fe0.2O3(BSCF)为单电池片进行电化学测试,对其性能进行评价。结果表明,复合材料取得了较好的放电性能,即以氢气为燃料气,850、800、750℃时分别取得了630.6、548.4、426 mW/cm2最大功率密度;以甲醇为燃料,850、800、750℃时分别取得了551.6、426.8、335.3 mW/cm2最大功率密度。     

固体氧化物燃料电池阳极材料Ni-SDC的稳定性实验及热力学分析

以Ni-SDC作为固体氧化物燃料电池（SOFC）的阳极,研究了该阳极粉末在制备过程中以及5% H2S-N2硫化后的产物,并用热力学软件绘制相图对其在各种温度下的产物变化进行分析。结果表明：NiO-SDC在800 ℃煅烧和在850 ℃还原的产物与热力学分析结果是一致的。对比在5%的H2S-N2中硫化12 h前后的XRD表明Ni已经转化为NiS2,热力学分析验证了该结论。比较Ni-SDC和SDC硫化前后的Raman光谱和XRD结果得到：SDC硫化后主峰型没有发生明显变化,但强度变弱,说明粒径变大,可能因为有Ce-O-S键生成。     

Long‐term microstructural changes in solid oxide fuel cell anodes: 3D reconstruction

Microstructural changes in solid oxide fuel cell anodes after long‐term operation have been characterized by sequential sectioning with a focused ion beam, followed by scanning electron microscopy imaging and three‐dimensional reconstruction. The anodes were porous composites of Ni and Y₂O₃‐stabilized ZrO₂ (YSZ). The cells were operated at 800°C for 2, 4, and 8 kh, and at 925°C for 2 and 4 kh. For each specimen, the volume fraction, surface area, particle diameter, and tortuosity have been calculated for each phase (Ni, YSZ, and pores). The dependence of these microstructural parameters on the volume of sample analyzed was monitored; sufficiently large volumes were analyzed so as to eliminate any effect of sample volume. Gradients in volume fraction of Ni and porosity developed during fuel cell operation, with Ni fraction increasing, and pore fraction decreasing, at the electrolyte/anode interface. The magnitudes of these gradients increased with time.     

Microstructural characterization of spray-dried NiO-8YSZ particles as plasma sprayable anode materials for metal-supported solid oxide fuel cell

The plasma spray method is widely used to produce NiO-8YSZ (composed of nickel oxide (NiO) and 8 mol% yttria-stabilized zirconia) anode layers in metal-supported solid oxide fuel cell (SOFC). Flowability control of microsized particles is important for achieving consistent performance of the SOFC anode layer. When microsized particles are fabricated via spray drying and sintering, the most significant factors that influence flowability are their sizes, distribution, and surface conditions. Thus, the aim of this study is to analyze the fabrication conditions for microsized NiO-8YSZ cermet particles made from a nanoscale, sinterable NiO-8YSZ dispersion solution by using an appropriate spray-drying and sintering process. The characteristics of the as-sprayed and sintered NiO-8YSZ composite particles (such as size, distribution, roughness, and nanostructure) were analyzed via field emission scanning electron microscope (FE-SEM), energy dispersive spectroscopy (EDS), particle size distribution (PSD), Brunauer–Emmett–Teller (BET) surface area, and atomic force microscopy (AFM). The as-sprayed microsized NiO-8YSZ particles became smaller and more uniformly distributed as the rotational speed used for spray drying increased. As a result of sintering, the extent of shrinkage of as-sprayed microsized NiO-8YSZ particles generated at high RPMs was lower than that of particles formed at low RPMs. No significant difference was observed in the distribution of the nanosized NiO and 8YSZ particles at different rotational speeds. Furthermore, the highest BET surface areas were observed for particles generated at 8000 RPM before sintering at 13.74 m²/g. After sintering, the highest BET surface area was 0.94 m²/g for particles generated at 16,000 RPM. Differences in nanostructure and surface roughness between as-sprayed and sintered microsized NiO-8YSZ particles were identified via AFM. This study is expected to provide important fundamental information useful for optimizing SOFC efficiency by promoting flowability control during the production of SOFC anodes via plasma spraying.     

Polarization effects in electrolyte/electrode-supported solid oxide fuel cells

The effects of activation, ohmic and concentration polarization on the overall polarization in solid oxide fuel cells are presented. A complete analysis was conducted based on thermodynamic principles for the calculation of cell voltage. Treating the fuel cell as a control volume, the irreversibility term in a steady flow thermodynamic system was related to the overall polarization. The entropy production was calculated and related to the lost work of the fuel cell, while the heat loss from the cell was determined from the entropy balance. To generalize the cell voltage–current density expression, the Butler–Volmer model was used in the calculation of activation polarization and both ordinary and Knudsen diffusions were considered in the calculation of concentration polarization. The overall cell resistance was deduced from the generalized cell voltage–current density expression. The concentration resistance at the anode can be minimized by humidifying the hydrogen with an appropriate amount of water, depending on the thickness of the anode used. Comparison of polarization effects on the cell performance between the electrolyte-supported and anode-supported cells showed that the latter would give a better cell performance.     

Modeling the temperature field in the reforming anode of a button-shaped solid oxide fuel cell

A model predicting the temperature field in the porous reforming anode of a solid oxide fuel cell is presented herein. The model is based on mass, momentum, and heat balances of a chemically reacting mixture of gases within the porous matrix of the anode. The important novel characteristic of the model is the consideration of the both internal reforming and electrochemical reactions in the bulk of the porous anode. The electronic and ionic currents in the anodes are calculated utilizing the solution of the Poisson equations for the electric potentials in the porous medium. The transfer current density is described by the Butler–Volmer equation.The model is applied to investigate the temperature field and the reactive flow in button-shaped fuel cells with uniform and graded (multi-layer) anodes composed of Ni and YSZ particles with methane/water vapor mixture used as the fuel. The maximum temperature difference between the hot and cold spots of the anodes is found to reach up to 200 K. The results indicate that the generation of Joule heating caused by the current passing through the anode and the activation losses are the dominating heat sources compared to the gas-water shift and electrochemical reactions.     

Micro‐modeling of porous composite anodes for solid oxide fuel cells

A new anode micromodel for solid oxide fuel cells to predict the electrochemical performance of hydrocarbon‐fuelled porous composite anodes with various microstructures is developed. In this model, the random packing sphere method is used to estimate the anode microstructural properties, and the complex interdependency among the multicomponent mass transport, electron and ion transports, and electrochemical and chemical reactions is taken into account. As a case study, a porous Ni–YSZ composite anode operated with biogas fuel is simulated numerically and distributions of the current density, polarization, and mole fraction and rate of flux of the fuel components along the thickness of the anode are determined. The effect of the anode microstructural variables including the porosity, thickness, particle‐size ratio, and particle size and volume fraction of Ni particles on the anode electrochemical performance is also studied. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1893–1906, 2012     

硫化氢固体氧化物燃料电池研究进展

综述了H2 S固体氧化物燃料电池 (SOFC)的发展历史和研制现状 ,包括固体电解质薄膜如质子传导膜和氧离子传导膜的开发、电极催化材料尤其是阳极催化材料的研制、以及整个电池系统的性能研究。指出H2 SSOFC在工业化过程中所面临和必须解决的关键技术问题是 :电解质薄膜材料的研制及其制备 ,尤其是薄膜化的制备技术 ;电极材料的开发及制备 ,特别是阳极催化材料的选择与制备技术 ;膜 -电极三合一制备技术。并对H2 SSOFC的开发及工业应用前景作了展望     

Fabrication of apatite-type lanthanum silicate films and anode supported solid oxide fuel cells using nano-sized printable paste

Apatite-type lanthanum silicate based films have attracted significant interests to use as an electrolyte of solid oxide fuel cells (SOFCs) working at intermediate temperature. We have prepared Mg doped lanthanum silicate (MDLS) films on NiO–MDLS cermet substrates by spin coating and sintering of nano-sized printable paste made by beads milling. Changes in crystal structure and microstructure of the paste films with the sintering temperature have been investigated to show that porous network structure with a grain growth evolves up to 1300 °C, whereas densification occurred above 1400 °C. Anode supported SOFCs using the pasted MDLS films were successfully fabricated: an open circuit voltage of 0.91 V and a maximum power density of 150 mW cm⁻² measured at 800 °C were obtained with the electrolyte film sintered at 1500 °C.     

Nanostructured engineering of nickel cermet anode for solid oxide fuel cell using inkjet printing

A single-step wet-chemical synthesis of NiO-SDC (Sm³⁺ doped ceria) colloidal ink for the inkjet printing (IJP) of nanostructured anodic layers with enhanced catalytic activity for solid oxide fuel cells (SOFCs) is developed and characterized. Dynamic light scattering, scanning electron microscope, and Raman spectroscopy revealed stable nanoparticles with the main size of 11.85 nm within the ink solution. Rheology parameters were analyzed, and the anode was printed. Porous post-sintered Ni-cermet layer, with a thickness of 15?25 μm contained near-spherical nanoparticles of 40?80 nm, was obtained. X-ray diffraction confirmed the phase composition of the cermet layer. Electrical impedance spectroscopy demonstrated a significant reduction, by more than 80 %, in the area-specific resistance of the IJP half-cell in comparison with the Screen-printed half-cell. The microstructure engineering using IJP provides fabrication of the cermet NiO-SDC layer with a conjugated structure, which ultimately enhances the catalytic activity of the SOFC.     

Mathematical modeling of solid oxide fuel cells at high fuel utilization based on diffusion equivalent circuit model

Mass transfer and electrochemical phenomena in the membrane electrode assembly (MEA) are the core components for modeling of solid‐oxide fuel cell (SOFC). The general MEA model is simply governed with the Stefan‐Maxwell equation for multicomponent gas diffusion, Ohm's law for the charge transfer and the current‐overpotential equation for the polarization calculation. However, it has obvious discrepancy at high‐fuel utilization or high‐current density. An advanced MEA model is introduced based on the diffusion equivalent circuit model. The main purpose is to correct the real‐gas concentrations at the triple‐phase boundary by assuming that the resistance of surface diffusion is in series with that of the gaseous bulk diffusion. Thus, it can obtain good prediction of cell performance in a wide range by avoiding the decrement of effective gas diffusivity via unreasonable increment of the electrode tortuosity in the general MEA model. The mathematical model has been validated in the cases of H₂? H₂O, CO? CO₂ and H₂? CO fuel system. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

使用丙烷燃料的便携式固体氧化物燃料电池研究进展

阐述了丙烷燃料应用于固体氧化物燃料电池(solid oxide fuel cell,SOFC)的工艺及其原理,其中包括重整、部分氧化;综述了使用丙烷燃料SOFC阳极材料研究进展,现有的研究工作主要围绕着如何阻止积炭进行,主要途径是改善阳极性能和选用合适的阳极催化剂等;介绍了当今世界上针对便携式应用的各式SOFC的研究发展现状,特别介绍了单气室SOFC;对便携式SOFC的发展前景进行了展望。     

Biodiesel formulations as fuel for internally reforming solid oxide fuel cell

Biodiesel (alkyl ester of rapeseed oil) is prepared using various, methyl, ethyl and butyl alcohols through the transesterification process. Sodium hydroxide and sulfuric acid are used as catalyst for methyl alcohol, ethyl alcohol and butyl alcohol respectively. Biodiesel-water formulations are formulated using water and emulsifiers like sodium lauryl sulphate (SLS) and SPAN 80 in a high shear mixer. The formulations are tested at 800 °C as fuel for internal reforming in solid oxide fuel cells (SOFCs). The formulations based on methyl and butyl esters require the use of emulsifiers to prepare stable emulsions, while ethyl esters are able to form stable emulsions without emulsifiers. The decrease in the biodiesel concentration of formulation does not have any effect on the power density of the ethyl ester formulation. Fuel cells fuelled with 20% formulations lasted longer than 50% formulations in all the formulations tested as result of increase in steam carbon ratio resulting in effective removal of carbon deposited on the anode surface. Butyl ester formulations exhibited the worst performance in both types of formulation tests. The best performance was exhibited by 20% ethyl formulation in terms of life of the cell but 50% methyl ester formulations exhibit the highest power density.     

内部重整固体氧化物燃料电池发电系统的非线性预测控制

固体氧化物燃料电池（SOFC）发电系统运行除了电堆本体外还需要包含诸多其他辅助组件以期获得系统输出的最大效率,为了使SOFC电堆能够对纯氢以外的燃料具有更好的适用性,加入了燃料内部重整装置和燃烧室两个重要辅助组件。文中在对系统展开建模的基础上提出了采用非线性模型预测控制策略,能够更有效地使输出燃料气体的组分、温度、压力、浓度和流率满足燃料电池堆正常运行的需要,通过仿真分别论证了线性模型预测控制和非线性模型预测控制两种不同控制方案的有效性和适用性。