LSM-YSZ nano-composite cathode with YSZ interlayer for solid oxide fuel cells

Low temperature prepared(La_(0.8)Sr_(0.2))_(0.9)MnO_3-δ-Y_(0.15)Zr_(0.85)O_(1.93)(LSM-YSZ) nano-composite cathode has high three-phase boundary(TPB) density and shows higher oxygen reduction reaction(ORR) activity than traditional LSM-YSZ cathode at reduced temperatures. But the weak connection between cathode and electrolyte due to low sintering temperature restrains the performance of LSM-YSZ nano-composite cathode. A YSZ interlayer, consisted of nanoparticles smaller than 10 nm, is introduced by spinning coating hydrolyzed YSZ sol solution on electrolyte and sintering at 800 °C. The thickness of the interlayer is about 150 nm. The YSZ interlayer intimately adheres to the electrolyte and shows obvious agglomeration with LSM-YSZ nano-composite cathode. The power densities of the cell with interlayer are 0.83, 0.46 and 0.21 W/cm~2 under 0.7 V at 800, 700 and 600 °C, respectively, which are 36%, 48% and 50% improved than that of original cell. The interlayer introduction slightly increases the ohmic resistance but significantly decreases the polarization resistance. The depressed high frequency arcs of impedance spectra suggest that the oxygen incorporation kinetics are enhanced at the boundary of YSZ interlayer and LSM-YSZ nanocomposite cathode, contributing to improved electrochemical performance of the cell with interlayer.     

通过溅射与退火制备的用于固体氧化物燃料电池的氧化钆掺杂氧化铈电解质隔层

采用溅射或溅射与退火相结合的方法制备了一系列氧化钆掺杂的氧化铈（GDC）隔层,并考察了其对固体氧化燃料电池性能的影响. 结果表明,200 ℃下溅射获得了立方结构氧化钆掺杂的氧化铈均匀薄膜,在900-1100 ℃范围内的退火处理使得GDC薄膜致密,从而有效阻止了氧化钇掺杂的氧化锆电解质与阴极材料之间的反应,大幅度提高了电池的电化学性能.     

Model-guided design of a high performance and durability Ni nanofiber/ceria matrix solid oxide fuel cell electrode

Mixed ionic electronic conductors(MIECs)have attracted increasing attention as anode materials for solid oxide fuel cells(SOFCs)and they hold great promise for lowering the operation temperature of SOFCs.However,there has been a lack of understanding of the performance-limiting factors and guidelines for rational design of composite metal-MIEC electrodes.Using a newly-developed approach based on 3 D-tomography and electrochemical impedance spectroscopy,here for the first time we quantify the contribution of the dual-phase boundary(DPB)relative to the three-phase boundary(TPB)reaction pathway on real MIEC electrodes.A new design strategy is developed for Ni/gadolinium doped ceria(CGO)electrodes(a typical MIEC electrode)based on the quantitative analyses and a novel Ni/CGO fiber-matrix structure is proposed and fabricated by combining electrospinning and tape-casting methods using commercial powders.With only 11.5 vol%nickel,the designer Ni/CGO fiber-matrix electrode shows 32%and 67%lower polarization resistance than a nano-Ni impregnated CGO scaffold electrode and conventional cermet electrode respectively.The results in this paper demonstrate quantitatively using real electrode structures that enhancing DPB and hydrogen kinetics are more efficient strategies to enhance electrode performance than simply increasing TPB.     

Study of transition metal oxide doped LaGaO3 as electrode materials for LSGM-based solid oxide fuel cells

Transition metal oxide doped lanthanum gallates, La_0.9Sr_0.1Ga_0.8M_0.2O₃ (where M=Co, Mn, Cr, Fe, or V), are studied as mixed ionic-electronic conductors (MIECs) for electrode applications. The electrochemical properties of these materials in air and in H₂ are characterized using impedance spectroscopy, open cell voltage measurement, and gas permeation measurement. Three single cells based on La_0.9Sr_0.1Ga_0.8 Mg_0.2O₃ (LSGM) electrolyte (1.13 to 1.65 mm thick) but with different electrode materials are studied under identical conditions to characterize the effectiveness of the lanthanum gallate-based MIECs for electrode applications. At 800 °C, a single cell using La_0.9Sr_0.1- Ga_0.8Co_0.2O₃ as the cathode and La_0.9Sr_0.1Ga_0.8Mn_0.2O₃ as the anode shows a maximum power density of 88 mW/cm², which is better than that of a cell using Pt as both electrodes (20 mW/cm²) and that of a cell using La_0.6Sr_0.4CoO₃ (LSC) as the cathode and CeO₂-Ni as the anode (61 mW/cm²) under identical conditions. The performance of LSGM-based fuel cells with MIEC electrodes may be further improved by reducing the electrolyte thickness and by optimizing the microstructures of the electrodes through processing. Received: 9 January 1998 / Accepted: 1 May 1998     

Fabrication and characterization of large-size electrolyte/anode bilayer structures for low-temperature solid oxide fuel cell stack based on gadolinia-doped ceria electrolyte

Preliminary progress is reported in this communication in building a planar anode-supported low-temperature solid oxide fuel cell (SOFC) stack based on gadolinia-doped ceria (GDC) electrolyte, i.e. fabrication and characterization of a Ø80 planar bilayer structure composed of GDC electrolyte film and Ni–GDC anode substrate. The anode substrates were prepared from mixtures of NiO, GDC, and carbon black by die-pressing. After pre-firing to remove the carbon black, the anode substrates were deposited with a GDC layer using a spray coating technique. The green bilayers of anode substrate and electrolyte film were then co-sintered at 1500 °C for 3 h. Through proper control of the sintering process, bilayer structures with excellent flatness were achieved after co-sintering. Scanning electron microscopy (SEM) observation indicated that the electrolyte film was about 22 μm in thickness, highly dense, crack-free, and well-bonded to the anode substrate. Small disks which were cut out from the Ø80 bilayer structure were electrochemically examined in a single button-cell mode incorporating a (LaSr)(CoFe)O₃–GDC composite cathode. With humidified hydrogen as the fuel and air as the oxidant, the cell demonstrated an open-circuit voltage of 0.884 V and a maximum power density of 562 mW/cm² at 600 °C. The results imply that high-quality anode-supported electrolyte/anode bilayer structures were successfully fabricated. Based on them, planar anode-supported SOFC stacks will be assembled in the future.     

以椰壳生物质炭为燃料的直接炭固体氧化物燃料电池

通过热裂解制得椰壳炭,表征了其结构和组成,并将其用于电解质为钇稳定化氧化锆（YSZ）、电极材料为银和钆掺杂氧化铈（Ag-GDC）的固体氧化物燃料电池（SOFC）的燃料,对所构成的直接炭固体氧化物燃料电池（DC-SOFC）的性能进行了测试研究。结果表明,所制得的椰壳炭颗粒粒径在微米级别,具有介孔结构,而且椰壳炭中含有K、Ca等元素,可用作Boudouard反应催化剂。当使用椰壳炭作为DC-SOFC燃料时,在800 ℃下电池最大功率密度为255 mW/cm²;负载Fe催化剂后,最大功率密度提升为274 mW/cm²。以0.5 A/cm²的恒电流放电,0.5 g负载Fe椰壳炭燃料电池能够连续工作17.6 h,燃料利用率为39%,表明椰壳炭作为DC-SOFC燃料具有优异的性能和潜力。     

Crystallization kinetics of basalt-based glass-ceramics for solid oxide fuel cell application

Journal of Thermal Analysis and Calorimetry - Solid oxide fuel cell (SOFC) is a very efficient and clean source of energy. The glass and glass-ceramics are the most suitable and compatible sealing...     

Symmetrical solid oxide fuel cell with strontium ferrite-molybdenum electrodes

The work contains the results of studies of a promising composite material of Sr₂Fe_1.5Mo_0.5O₆ + Ce_0.8Sm_0.2O_1.9 for electrodes of symmetrical solid oxide fuel cells. It is shown that conductivity of the composite at 800°C is about 10 and 15 S/cm, for air and humid hydrogen, respectively, and polarization resistance of the electrodes in contact with the electrolyte based on doped lanthanum gallate under the same conditions is about 0.26 and 0.12 Ohm cm². Tests of a symmetrical fuel cell with a planar design and the supporting gallate electrolyte with the thickness of 300 μm show that the cell can develop the power of about 0.5 W/cm² at 800°C when air is supplied to the cathode and humid hydrogen is supplied to the anode. Analysis of polarization losses shows that the polarization of the oxygen electrode considerably exceeds the polarization of the anode.     

Raman spectroscopy as a probe of temperature and oxidation state for gadolinium-doped ceria used in solid oxide fuel cells

Raman spectroscopy is a noninvasive and highly sensitive analytical technique capable of identifying chemical compounds in environments that can mimic SOFC operating conditions. Here we demonstrate the use of Raman spectroscopy to perform local thermal and temporal measurements, both of which are essential if phase formation diagrams are to be mapped out and compared to thermodynamic phase stability predictions. We find that the time resolution of the Raman technique is more than sufficient to capture essential dynamic effects associated with a change of chemical composition.     

Novel nano-structured Pd+yttrium doped ZrO2 cathodes for intermediate temperature solid oxide fuel cells

Novel nano-structured Pd+yttrium doped ZrO₂ (YSZ) electrodes have been developed as cathodes of intermediate temperature solid oxide fuel cells (IT-SOFCs). Nano-sized Pd particles were introduced into the rigid and porous YSZ structure by PdCl₂ solution impregnation. The results show that Pd nanoparticles (20–80 nm) were uniformly distributed in the porous YSZ structure; and such nano-structured composite cathodes were highly active for the O₂ reduction reaction, with polarization resistances (R_E) of 0.11 and 0.22 Ω cm² at 750 and 700 °C and activation energy of 105 kJ mol⁻¹ that is significantly lower than those for the conventional perovskite-based cathodes (130–201 kJ mol⁻¹).     

Nanostructured anodes for solid oxide fuel cells

Solid oxide fuel cells (SOFC) have much promise as efficient devices for the direct conversion of the energy stored in chemical fuels into electricity. The development of highly robust SOFC that can operate on a range of fuels, however, requires improvements in the electrodes, especially the anode, where nanoscale engineering of the structure is required in order to maximize the number of sites where the electrochemical reactions take place. In this article we review the approaches that are currently being used to improve anode performance and microstructure with a focus on new materials and synthesis techniques.     

EPMA of interfaces applied to the solid oxide fuel cell

Chemical interactions at the phase boundaries of materials applied for the solid oxide fuel cell (SOFC) have been studied by EPMA. The chemical reactivity at the interface of La_y-xSr_xMnO₃/ZrO₂-Y₂O₃ is dependent on the stoichiometry (y) and the Sr content (x) of the perovskite. Typical reaction products (zirconates) and a diffusion zone in the ZrO₂–Y₂O₃ have been observed. The extension of cation release (Mn) is related to the increasing chemical activity of Mn oxide in the perovskite by the Sr substitution for La. The wettability of the metal/oxide interface in the anode cermet (Ni/ZrO₂–Y₂O₃) has been found to be influenced by chemical reactions resulting from the applied reducing atmosphere with high carbon activity. The disintegration of ZrO₂–Y₂O₃ in contact with molten Ni or Ni-Ti and Ni-Cr alloys leads to the redeposition of Y₂O₃-enriched oxides and also to Zr-rich intermetallic compounds and eutectics.     

固体氧化物燃料电池直接以焦炭为燃料的电性能

直接碳固体氧化物燃料电池（DC-SOFC）是一种潜在的固体碳燃料高效率、低污染发电技术。本研究报道了将工业焦炭直接用作管式DC-SOFC燃料的研究。制备了电极材料为Ag-GDC （钆掺杂氧化铈）的YSZ （钇稳定化氧化锆）电解质支撑型管式固体氧化物燃料电池（SOFC）。采用拉曼光谱、扫描电镜和X射线能谱仪对焦炭燃料进行了性质表征。结果表明,焦炭燃料呈微米级的颗粒状,并含有大量对Boudouard反应有利的缺陷结构。电池以纯焦炭为燃料在850℃取得的最大功率密度为149mW/cm²,在碳燃料表面负载能提高Boudouard反应速率的Fe催化剂后,最大功率密度提高至217mW/cm²。通过电化学测试和尾气表征,分析了恒电流放电过程中电池的性能衰减机制。测试结果证明了将焦炭直接用作全固态DC-SOFC的燃料产生电能的可行性。     

Quantitative three-dimensional microstructure of a solid oxide fuel cell cathode

Solid oxide fuel cells (SOFCs) are being actively developed world wide for clean and efficient electrical generation from fuels such as natural gas, hydrogen, coal, and gasoline. The cathode in state of the art SOFCs is typically a porous composite of electronically-conducting La_1?xSr_xMnO₃ (LSM) and ionically-conducting Y₂O₃-stabilized ZrO₂ (YSZ) that facilitates the critical oxygen reduction reaction. Here we describe the three-dimensional characterization and quantification of key structural parameters from an LSM-YSZ cathode, using imaging and volume reconstruction based on focused ion beam – scanning electron microscopy. LSM-YSZ-pore three-phase boundaries (TPBs) were identified. Approximately 1/3 of the TPBs were found to be electrochemically inactive, as they were on isolated LSM particles, yielding an active TPB density of 4.9 μm^?2. Cathode electrochemical modeling, which included a measured YSZ tortuosity of 3.4, yielded an effective TPB resistance of ≈2.5 × 10⁵ Ω cm at 800 °C.     

A direct-methane solid oxide fuel cell with a double-layer anode

A tubular anode-supported solid oxide fuel cell with a double-layer anode for the direct conversion of CH₄ has been prepared and operated at 800 °C successfully. The double-layer anode was composed of NiO–YSZ and CoO–NiO–SDC acting as supporting layer and active reforming layer, respectively. At 800 °C, a maximum power density of 350 mW cm⁻² was obtained with CH₄ as fuel and air as oxidant. The time-dependent impedance spectra of the tubular cell were examined and discussed. No carbon deposition was observed on the surface of the anode when the cell was operated at a constant current density of 250 mA cm⁻².     

Prediction of infiltrated solid oxide fuel cell cathode polarization resistance

The polarization resistance of La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF)-infiltrated Ce_0.9Gd_0.1O_1.95 cathodes was quantitatively explained using a simple model where the resistance scaled directly with the LSCF surface area, as estimated from cross-sectional fracture surfaces. The Tanner, Fung, Virkar composite cathode model was also applied and showed that ionic transport in these 25-μm-thick cathodes was not a significant limitation at 600 °C, but became more limiting at 700 °C. Calculated polarization resistances were within ～40% (without fitting parameters) of reported values.     

EPMA of interfaces applied to the solid oxide fuel cell

Chemical interactions at the phase boundaries of materials applied for the solid oxide fuel cell (SOFC) have been studied by EPMA. The chemical reactivity at the interface of La(y-x)Sr(x)MnO(3)/ZrO(2)-Y(2)O(3) is dependent on the stoichiometry (y) and the Sr content (x) of the perovskite. Typical reaction products (zirconates) and a diffusion zone in the ZrO(2)-Y(2)O(3) have been observed. The extension of cation release (Mn) is related to the increasing chemical activity of Mn oxide in the perovskite by the Sr substitution for La. The wettability of the metal/oxide interface in the anode cermet (Ni/ZrO(2)-Y(2)O(3)) has been found to be influenced by chemical reactions resulting from the applied reducing atmosphere with high carbon activity. The disintegration of ZrO(2)-Y(2)O(3) in contact with molten Ni or Ni-Ti and Ni-Cr alloys leads to the redeposition of Y(2)O(3)-enriched oxides and also to Zr-rich intermetallic compounds and eutectics.     

An optimization and fast load-oriented control for current-based solid oxide fuel cell system

Journal of Solid State Electrochemistry - One of the key problems for a solid oxide fuel cell (SOFC), which is a high-temperature power-generation plant, is the cooperative control of safe...