固体氧化物燃料电池电解质材料的研究进展

介绍了固体氧化物燃料电池(SOFC)用萤石型、钙钛矿型及磷灰石型电解质材料的结构、导电机理、性能及研究进展。存在的离子电导率较低、化学组成及相组成不稳定等问题,主要通过氧化物共掺杂及不同材料之间的复合等方法来改善。材料的复合与电解质层结构的设计,将成为电解质研究的主要方向。

低温自蔓延法合成SOC金属连接体用锰钴氧化物

采用柠檬酸低温自蔓延法合成尖晶石锰钴氧化物(MnCo2O4)粉体,利用湿粉末喷涂在Crofer 22金属连接体上制备致密涂层,考察工艺条件对涂层的影响,用XRD、SEM分析涂层的相结构及形貌,并对电性能进行分析。在900℃下烧结的连接体涂层具有更好的性能,其在850℃时测得的面积比电阻(ASR)为6.5 mΩ·cm2。

固体氧化物燃料电池/电解池金属连接体涂层研究进展

可逆固体氧化物池(SOC)既可作为燃料电池(SOFC)发电,又可用作电解池(SOEC)制氢或合成气,用于清洁能源转换和存储。涂层制备技术对SOC电堆的发展尤为重要。本研究对SOC在不同操作模式下的工作环境进行了分析,对SOC电堆连接体可用的合金材料、涂层材料和涂层制备技术进行了综述。

镍-镓酸镧复合阳极的研究

制备了多种镍-镓酸镧(LaGaO3)复合阳极,并以Ni-LaGaO3为复合阳极,系列Sr、Mg和Co掺杂的LaGaO3为电解质,Sm0.5Sr0.5CoO3(SSC)-LaGaO3为复合阴极,组装单电池。用极化、交流阻抗等技术,对阳极电化学性能进行研究,测试了电池的功率输出特性。Ni-LaGaO3复合阳极的最佳焙烧温度约为1 200℃,焙烧温度显著影响阳极/电解质界面的欧姆电阻和极化电阻。Ni-LaGaO3复合阳极的性能,依赖于所负载电解质及电极中掺入的LaGaO3的性质。随着电解质中Co含量的增加,电池的欧姆电阻减小、电极活性增加,单电池的最大输出功率密度提高。Ni-La0.8Sr0.2Ga0.8Mg0.15Co0.05O3(LSGMC5)|La0.8Sr0.2Ga0.8Mg0.115Co0.085O3(LSGMC8.5)|SSC-LSGMC5电池在800℃、氢为燃料的条件下,最大输出功率密度达0.75 W/cm2;甲烷为燃料的条件下,最大输出功率密度达0.53 W/cm2。

Electricity Storage With High Roundtrip Efficiency in a Reversible Solid Oxide Cell Stack

We theoretically investigate the electricity storage/generation in a reversible solid oxide cell stack. The system heat is for the first time tentatively stored in a phase-change metal when the stack is operated to generate electricity in a fuel cell mode and then reused to store electricity in an electrolysis mode. The state of charge （H2 frication in cathode） effectively enhances the open circuit voltages （OCVs） while the system gas pressure in electrodes also increases the OCVs. On the other hand, a higher system pressure facilitates the species diffusion in electrodes that therefore accordingly improve electrode polarizations. With the aid of recycled system heat, the roundtrip efficiency reaches as high as 92% for the repeated electricity storage and generation.

Influence of CO2 on Oxygen Surface Exchange Kinetics of Mixed- Conducting Ba0.5 Sr0.5 Co0.8 Feo.2O3_δ Oxide

The poisoning effect of CO2 on the oxygen surface exchange kinetics of BSCF （Ba0.5 Sr0.5 Co0.8 Feo.2O3_δ） is investigated with a novel pulse isotopic exchange technique. The surface exchange rate of BSCF severely decreases after in situ exposure to CO2, which is ascribed to carbonate formation on the material surface. The detrimental effect of CO2 starts at a low temperature of 375 ℃ and concentration as low as 1%, and becomes more pro- nounced at higher temperatures. Degradation of the surface exchange kinetics is associated with a rapid loss of oxygen permeation performance of BSCF in CO2.

Ni doped La_(0.6)Sr_(0.4)FeO_(3-δ) symmetrical electrode for solid oxide fuel cells

The conventional Ni cermet anode suffers from severe carbon deposition and sulfur poisoning when fossil fuels are used. Alternative anode materials are desired for high performance hydrocarbon fuel solid oxide fuel cells （SOFCs）. We report the rational design of a very active Ni doped La0.6Sr0.4FeO3‐δ（LSFN） electrode for hydrocarbon fuel SOFCs. Homogeneously dispersed Ni‐Fe alloy nanoparticles were in situ extruded onto the surface of the LSFN particles during the operation of the cell. Sym‐metric SOFC single cells were prepared by impregnating a LSFN precursor solution onto a YSZ （yt‐tria stabilized zirconia） monolithic cell with a subsequent heat treatment. The open circuit voltage of the LSFN symmetric cell reached 1.18 and 1.0 V in humidified C3H8 and CH4 at 750？？, respective‐ly. The peak power densities of the cells were 400 and 230 mW/cm2 in humidified C3H8 and CH4, respectively. The electrode showed good stability in long term testing, which revealed LSFN has good catalytic activity for hydrocarbon fuel oxidation.

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

A porous NiO/yttria-stabilized zirconia was prepared by gel casting technique. anode substrate for tubular solid oxide fuel cells Nano-scale samaria-doped ceria （SDC） particles were formed onto the anode substrate to modify the anode microstructure by the impregnation of solution of Sm（NO3）3 and Ce（NO3）3. Electrochemical impedance spectroscopy, current-voltage and current-powder curves of the cells were measured using an electrochemical workstation. Scanning electron microcopy was used to observe the microstructure. The results indicate that the stability of the performance of the cell operated on humidified methane can be significantly improved by incorporating the nano-structured SDC particles, compared with the unmodified cell. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. In addition, it was found that a small amount of deposited carbon is beneficial to the performance of the anode. The cell showed a peak power density of 225 mW/cm^2 when it was fed with H2 fuel at 700 ℃, but the power density increased to 400 mW/cm^2 when the fuel was switched from hydrogen to methane at the same flow rate. Methane conversion achieved about 90%, measured by gas chromatogram with a 10.0 mL/min flow rate of fuel at 700 ℃. Although the carbon deposition was not suppressed absolutely, some deposited carbon was beneficial for performance improvement.

Composite Cathode based on Mn-doped Perovskite Niobate-Titanate for Efficient Steam Electrolysis

Redox-active Mn is introduced into the B site of redox-stable perovskite niobate-titanate to improve the electrocatalytic activity of composite cathode in an oxide-ion-conducting solid oxide electrolyzer. The XRD and XPS results reveal the successful partial replacement of Ti/Nb by Mn in the B site of niobate-titanate. The ionic conductivities of the Mndoped niobate-titanate are significantly improved by approximately 1 order of magnitude in reducing atmosphere and 0.5 order of magnitude in oxidizing atmosphere compared with bare niobate-titanate at 800 ℃. The current efficiency for Mn-doped niobate-titanate cathode is accordingly enhanced by ,-25% and 30% in contrast to the bare cathode with and without reducing gas flowing over the cathode under the applied voltage of 2.0 V at 800 ℃ in an oxide-ion-conducting solid oxide electrolyzer, respectively.

Effect of Gd_(0.2)Ce_(0.8)O_(1.9) nanoparticles on the oxygen evolution reaction of La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ) anode in solid oxide electrolysis cell

La（0.6）Sr（0.4）Co（0.2）Fe（0.8）O（3-δ）（LSCF） anodes were infiltrated by Gd（0.2）Ce（0.8）O（1.9）GDC） nanoparticles to improve the oxygen evolution reaction（OER） performance of solid oxide electrolysis cells（SOECs） in CO2 electroreduction. The effect of GDC loading was investigated, and 10 wt% GDC nanoparticle infiltration of the LSCF（10 GDC/LSCF） anode results in the highest OER performance. Electrochemical impedance spectra measurements indicate that the infiltration by GDC nanoparticles greatly decreases the polarization resistance of the SOECs with the 10 GDC/LSCF anodes. The following distribution of relaxation time analysis suggests that four individual electrode processes are involved in the OER and that all of them are accelerated on the 10 GDC/LSCF anode. Three phase boundaries, surface oxygen vacancies, and bulk oxygen mobility increased, based on scanning electron microscopy and temperature-programmed desorption of O2 characterizations, and contributed to the enhancement of the four electrode processes of the OER and electrochemical performance of SOECs.

Effect of H_2S Flow Rate and Concentration on Performance of H_2S/Air Solid Oxide Fuel Cell

A solid state H2S/air electrochemical cell having the configuration of H2S, (MoS2+NiS+Ag)/YSZ/Pt, air has been examined with different H2S flow rates and concentrations at atmospheric pressure and 750-850 ℃. Performance of the fuel cell was dependent on anode compartment H2S flow rate and concentration. The cell open-circuit voltage increased with increasing H2S flow rate. It was found that increasing both H2S flow rate and H2S concentration improved current-voltage and power density performance. This is resulted from improved gas diffusion in anode and increased concentration of anodic electroactive species. Operation at elevated H2S concentration improved the cell performance at a given gas flow rate. However, as low as 5% H2S in gas mixture can also be utilized as fuel feed to cells. Highest current and power densities, 17500mA·cm-2 and 200mW·cm-2, are obtained with pure H2S flow rate of 50ml·min-1 and air flow rate of 100ml·min-1 at 850℃.

Influence of Metal Sulfides as Anode Catalysts on Performance of H_2S SOFC

Two anode catalysts with Pt, MoS2 and composite metal sulfides (MoS2+NiS), are investigated for electrochemical oxidation of hydrogen sulfide in solid oxide fuel cell (SOFC) at temperatures 750-850℃. The catalysts comprising MoS2 and MoSa+NiS exhibited good electrical conductivity and catalytic activity. MoS2 and composite catalysts were found to be more active than Pt, a widely used catalyst for high temperature H2S/O2 fuel cell at 750-850℃. However, MoS2 itself sublimes above 450℃. In contrast, composite catalysts containing both Mo and transition metal (Ni) are shown to be stable and effective in promoting the oxidation of H2S in SOFC up to 850℃. However, electric contact is poor between the platinum current collecting layer and the composite metal sulfide layer, so that the cell performance becomes worse. This problem is overcome by adding conductive Ag powder into the anode layer (forming MoS2+NiS+Ag anode material) to increase anode electrical conductance instead of applying a thin layer of platinum on the top of anode.

Electromotive Force for Solid Oxide Fuel Cells Using Biomass Produced Gas as Fuel

The electromotive force （e.m.f.） of solid oxide fuel cells using biomass produced gas （BPG） as the fuels is calculated at 700-1,200 K using an in-house computer program, based on thermodynamic equilibrium analysis. Tour program also predicts the concentration of oxygen in the fuel chamber as well as the concentration of equilibrium species such as H2, CO, CO2 and CH4. Compared with using hydrogen as a fuel, the e.m.f. for cells using BPG as the fuels is relative low and strongly influenced by carbon deposition. To remove carbon deposition, the optimum amount of H2O to add is determined at various operating temperatures. Further the e.m.f, for cells based on yttria stabilized zirconia and doped ceria as electrolytes are compared. The study reveals that when using BPG as fuel, the depression of e.m.f, for a SOFC using doped ceria as electrolyte is relatively small when compared with that using Yttria stabilized zirconia.

Characteristic Analysis of the Solid Oxide Fuel Cell with Proton Conducting Ceramic Electrolyte

An electrolyte model for the solid oxide fuel cell (SOFC) with proton conducting perovskite electrolyte is developed in this study, in which four types of charge carriers including proton, oxygen vacancy (oxide ion), free electron and electron hole are taken into consideration. The electrochemical process within the SOFC with hydrogen as the fuel is theoretically analyzed. With the present model, the effects of some parameters, such as the thickness of electrolyte, operating temperature and gas composition, on the ionic transport (or gas permeation) through the electrolyte and the electrical performance, i.e., the electromotive force (EMF) and internal resistance of the cell, are investigated in detail. The theoretical results are tested partly by comparing with the experimental data obtained from SrCe0.95M0.05O3-α, (M=Yb, Y) cells.

Highly dispersed nickel species on iron‐based perovskite for CO_(2) electrolysis in solid oxide electrolysis cell

Feasible construction of cathode materials with highly dispersed active sites can extend the tri‐ple‐phase boundaries,and therefore leading to enhanced electrode kinetics for CO_(2) electrolysis in solid oxide electrolysis cell(SOEC).Herein,highly dispersed nickel species with low loading(1.0 wt%)were trapped within the La_(0.8)Sr_(0.2)FeO_(3)–δ‐Ce_(0.8)Sm_(0.2)O_(2)–δvia a facial mechanical milling ap‐proach,which demonstrated excellent CO_(2) electrolysis performance.The highly dispersed nickel species can significantly alter the electronic structures of the LSF‐SDC without affecting its porous network and facilitate oxygen vacancy formation,thus greatly promote the CO_(2) electrolysis perfor‐mance.The highest current density of 1.53 A·cm^(-2) could be achieved when operated under 800℃ at 1.6 V,which is about 91%higher than the LSF‐SDC counterpart.

Theoretical Aspects on Doped-Zirconia for Solid Oxide Fuel Cells:from Structure to Conductivity

Solid oxide fuel cells(SOFCs)are regarded to be a key clean energy system to convert chemical energy(e.g.H_(2) and O_(2))into electrical energy with high efficiency,low carbon footprint,and fuel flexibility.The electrolyte,typically doped zirconia,is the"state of the heart"of the fuel cell technologies,determining the performance and the operating temperature of the overall cells.Yttria stabilized zirconia(YSZ)have been widely used in SOFC due to its excellent oxide ion conductivity at high temperature.The composition and temperature dependence of the conductivity has been hotly studied in experiment and,more recently,by theoretical simulations.The characterization of the atomic structure for the mixed oxide system with different compositions is the key for elucidating the conductivity behavior,which,however,is of great challenge to both experiment and theory.This review presents recent theoretical progress on the structure and conductivity of YSZ electrolyte.We compare different theoretical methods and their results,outlining the merits and deficiencies of the methods.We highlight the recent results achieved by using stochastic surface walking global optimization with global neural network potential(SSW-NN)method,which appear to agree with available experimental data.The advent of machine-learning atomic simulation provides an affordable,efficient and accurate way to understand the complex material phenomena as encountered in solid electrolyte.The future research directions for design better electrolytes are also discussed.

Overcoming coke formation in high-temperature CO_(2)electrolysis

High-temperature CO_(2)reduction reaction(HT-CO_(2)RR)in solid oxide electrochemical cells(SOECs)features near-unity selectivity,high energy efficiency,and industrial relevant current density for the production of CO,a widely-utilized“building block”in today’s chemical industry.Thus,it offers an intriguing and promising means to radically change the way of chemical manufacturing and achieve carbon neutrality using renewable energy sources,CO_(2),and water.Albeit with the great potential of HT-CO_(2)RR,this carbon utilization approach,unfortunately,has been suffering coke formation that is seriously detrimental to its energy efficiency and operating lifetime.In recent years,much effort has been added to understanding the mechanism of coke formation,managing reaction conditions to mitigate coke formation,and devising coke-formation-free electrode materials.These investigations have substantially advanced the HT-CO_(2)RR toward a practical industrial technology,but the resulting coke formation prevention strategies compromise activity and energy efficiency.Future research may target exploiting the control over both catalyst design and system design to gain selectivity,energy efficiency,and stability synchronously.Therefore,this perspective overviews the progress of research on coke formation in HT-CO_(2)RR,and elaborates on possible future directions that may accelerate its practical implementation at a large scale.

Efficient Thickness of Solid Oxide Fuel Cell Composite Electrode

The efficient thickness of a composite electrode for solid oxide fuel cells was directly calculated by developing a physical model taking into account of the charge transfer process, the oxygen ion and electron transportation, and the microstructure characteristics of the electrode. The efficient thickness, which is defined as the electrode thickness corresponding to the minimum electrode polarization resistance, is formulated as a function of charge transfer resistivity, effective resistivity to ion and electron transport, and three-phase boundary length per unit volume. The model prediction is compared with the experimental reports to check the validity. Simulation is performed to show the effect of microstructure, intrinsic material properties, and electrode reaction mechanism on the efficient thickness. The results suggest that when an electrode is fabricated, its thickness should be controlled regarding its composition, particle size of its components, the intrinsic ionic and electronic conductivities,and its reaction mechanisms as well as the expected operation temperatures. The sensitivity of electrode polarization resistance to its thickness is also discussed.

Nonlinear modelling of a SOFC stack by improved neural networks identification

The solid oxide fuel cell (SOFC) is a nonlinear system that is hard to model by conventional methods. So far,most existing models are based on conversion laws,which are too complicated to be applied to design a control system. To facilitate a valid control strategy design,this paper tries to avoid the internal complexities and presents a modelling study of SOFC per-formance by using a radial basis function (RBF) neural network based on a genetic algorithm (GA). During the process of mod-elling,the GA aims to optimize the parameters of RBF neural networks and the optimum values are regarded as the initial values of the RBF neural network parameters. The validity and accuracy of modelling are tested by simulations,whose results reveal that it is feasible to establish the model of SOFC stack by using RBF neural networks identification based on the GA. Furthermore,it is possible to design an online controller of a SOFC stack based on this GA-RBF neural network identification model.

One-dimensional Dynamic Modeling and Simulation of a Planar Direct Internal Reforming Solid Oxide Fuel Cell

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 D1R-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） temperature. 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 density 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.