Effect of preparative methods on electrical and electrochemical performance of lanthanum strontium manganite

The electrochemical performance of La_0.8Sr_0.2MnO₃:Ce_0.8Gd_0.2O₂ composite cathode was investigated for solid oxide fuel cell applications. Sol–gel, combustion, and solid-state syntheses yielded rhombohedral La_0.8Sr_0.2MnO₃, whereas mechanochemical process gave cubic structure. X-ray diffraction results established good chemical stability of La_0.8Sr_0.2MnO₃ with Ce_0.8Gd_0.2O₂ composite cathode. Combustion synthesis was found best among all preparative methods on the basis of lowest area specific resistance 0.70 Ω cm² at 800 °C. The activation energy E _a = 1.09 ± 0.01 eV indicated absorption of O₂ and was the rate-limiting process of cathode.     

Electrochemical characteristics of cathodes based on perovskites modified by ceria

A system consisting of a solid oxide electrolyte of the Ce_0.9Gd_0.1O_{2 − x} (CGO) composition in contact with a two-layer cathode based on a nonstoichiometric composition (La_0.8Sr_0.2)_0.95MnO_{3 ± δ} (LSM1) and a stoichiometric perovskite La_0.8Sr_0.2MnO_{3 ± δ} (LSM2) is prepared by the tape-casting process. It was shown that the best electrochemical characteristics are achieved for a three-layer system LSM2/{CGO-LSM1}/CGO sintered at 1410°C. The use of Ce-modified perovskites La_0.8Sr_0.2MnO_{3 ± δ} and La_0.6Sr_0.6CoO_{3 ± δ} as the collector layer of two-layer electrodes allows the electrochemical characteristics at moderately high temperatures (600–750°C) to be improved.     

(La0.8Sr0.2)0.9MnO3–Gd0.2Ce0.8O1.9 composite cathodes prepared from (Gd, Ce)(NO3) x -modified (La0.8Sr0.2)0.9MnO3 for intermediate-temperature solid oxide fuel cells

Development of high performance cathodes with low polarization resistance is critical to the success of solid oxide fuel cell (SOFC) development and commercialization. In this paper, (La_0.8Sr_0.2)_0.9MnO₃ (LSM)–Gd_0.2Ce_0.8O_1.9(GDC) composite powder (LSM ~70 wt%, GDC ~30 wt%) was prepared through modification of LSM powder by Gd_0.2Ce_0.8(NO₃) _x solution impregnation, followed by calcination. The electrode polarization resistance of the LSM–GDC cathode prepared from the composite powder was ~0.60 Ω cm² at 750 °C, which is ~13 times lower than that of pure LSM cathode (~8.19 Ω cm² at 750 °C) on YSZ electrolyte substrates. The electrode polarization resistance of the LSM–GDC composite cathode at 700 °C under 500 mA/cm² was ~0.42 Ω cm², which is close to that of pure LSM cathode at 850 °C. Gd_0.2Ce_0.8(NO₃) _x solution impregnation modification not only inhibits the growth of LSM grains during sintering but also increases the triple-phase-boundary (TPB) area through introducing ionic conducting phase (Gd,Ce)O_2-δ, leading to the significant reduction of electrode polarization resistance of LSM cathode.     

The effect of phase composition on the transport properties of composites La0.8Sr0.2Fe0.7Ni0.3O3 ? δ-Ce0.9Gd0.1O1.95

Full conductivity, diffusion and oxygen exchange processes in composites (100 − x)La_0.8Sr_0.2Fe_0.7Ni_0.3O_{3 − δ}−xCe_0.9Gd_0.1O_1.95 (x is the volume fraction, 0 ≤ x ≤ 71.1%) at 700°C over the oxygen partial pressure range from 0.2 to 3 × 10⁻³ atm are studied by the electrical conductivity relaxation method. The composites’ conductivity was shown to decrease monotonically with the increasing of Ce_0.9Gd_0.1O_1.95 fraction, while the oxygen chemical diffusion coefficient increased. The oxygen exchange constant is higher for the composites than for the individual phases of La_0.8Sr_0.2Fe_0.7Ni_0.3O_{3 − δ} and Ce_0.9Gd_0.1O_1.95. Possible reason of the dependence of the parameters D _chem and k _chem on the temperature, oxygen pressure, and the composite composition is the effect of the interface on the oxygen transfer processes. Most effective oxygen transfer occurs in the composites whose composition approaches La_0.8Sr_0.2Fe_0.7Ni_0.3O_{3 − δ}-Ce_0.9Gd_0.1O_1.95 (x = 71%).     

High performance anode-supported intermediate temperature solid oxide fuel cells (IT-SOFCs) with La0.8Sr0.2Ga0.8Mg0.2O3−δ electrolyte films prepared by electrophoretic deposition

Remarkable power density was obtained for anode-supported solid oxide fuel cells (SOFCs) based on La_0.8Sr_0.2Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte films, fabricated following an original procedure that allowed avoiding undesired reactions between LSGM and electrode materials, especially Ni. Electrophoretic deposition (EPD) was used for the fabrication of 30 μm-thick electrolyte films. Anode supports were made of La_0.4Ce_0.6O_2−x (LDC). The LSGM powder was deposited by EPD on an LDC green tape-cast membrane added with carbon powder, both as pore former and substrate conductivity booster. A subsequent co-firing step at 1490 °C produced dense electrolyte films on porous LDC skeletons. Then, a La_0.8Sr_0.2Fe_0.8Co_0.2O_3−δ (LSFC) cathode was applied by slurry-coating and calcined at 1100 °C. Finally, the porous LDC layer was impregnated with molten Ni nitrate to obtain, after calcination at 900 °C, a composite NiO–LDC anode. Maximum power densities of 780, 450, 275, 175, and 100 mW/cm² at 700, 650, 600, 550, and 500 °C, respectively, were obtained using H₂ as fuel and air as oxidant, demonstrating the success of the processing strategy. As a comparison, electrolyte-supported SOFCs made of the same materials were tested, showing a maximum power density of 150 mW/cm² at 700 °C, more than 5 times smaller than the anode-supported counterpart.     

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.     

Effect of infiltration material on a LSM15/CGO10 electrochemical reactor in the electrochemical oxidation of propene

The effect of infiltrating on a La_0.85Sr_0.15MnO₃/Ce_0.9Gd_0.1O_1.95 11-layer electrochemical reactor with CeO₂ and Ce_0.8Pr_0.2O_2?δ was studied in propene oxidation at open-circuit voltage and under polarization as a function of reaction temperature. This work outlined the importance of catalytic and electrochemical properties of infiltrated material on the ability to increase propene conversion under polarization with good faradaic efficiency. Electrochemical impedance spectroscopy was used to study the effect of infiltration material on electrode properties. The infiltration of a mixed ionic and electronic conductor, like Ce_0.8Pr_0.2O_2?δ , increased the electrode performance at low temperature but decreased the lifetime of the oxygen ion promoters on the catalyst/electrode surface, reducing the faradaic efficiency of the reaction. The infiltration of CeO₂ provided high propene conversion at open circuit and high effect of polarization associated with good faradaic efficiency, especially at low temperature.     

High-performance Fe–Co-based SOFC cathodes

With the aim of reducing the temperature of the solid oxide fuel cell (SOFC), a new high-performance perovskite cathode has been developed. An area-specific resistance (ASR) as low as 0.12 Ωcm² at 600 °C was measured by electrochemical impedance spectroscopy (EIS) on symmetrical cells. The cathode is a composite between (Gd_0.6Sr_0.4)_0.99Fe_0.8Co_0.2O_3-δ (GSFC) and Ce_0.9Gd_0.1O_1.95 (CGO10). Examination of the microstructure of the cathodes by scanning electron microscopy (SEM) revealed a possibility of further optimisation of the microstructure in order to increase the performance of the cathodes. It also seems that an adjustment of the sintering temperature will make a lowering of the ASR value possible. The cathodes were compatible with ceria-based electrolytes but reacted to some extent with zirconia-based electrolytes depending on the sintering temperature.     

Oxygen permeability of mixed-conducting composite membranes: effects of phase interaction

Composite ceramic membranes, based on selected combinations of ionic conductors ((La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3-δ—LSGM or Ce_0.8Gd_0.2O_2-δ—CGO) and electronic/mixed conductors (La₂Ni_0.8Cu_0.2O_4+δ—LNC, La_0.8Sr_0.2Fe_0.8Co_0.2O_3-δ—LSFC, La_0.7Sr_0.3MnO_3-δ—LSM, and SrCoO_3-δ – Sr₂Fe₃O_6.5±δ—SCSF), were processed and characterized aiming at the identification of key features to be considered in the design and optimization of materials performance as mixed conductors. Although after almost complete reaction between constituents, the best permeability was observed for the LSGM/LSFC combination processed under moderate firing conditions. Ceria-based composites, while preserving a typical composite microstructure, and suffering small compositional changes due to interaction between constituents, behaved always below the result of an ideal combination of the best characteristics of the individual components. Materials interaction, from modest compositional changes to formation of new phases, with deep changes in nominal composition, can be understood both as a challenge requiring proper identification of ideal processing conditions for phase preservation, but also as an opportunity for the development of entirely new composites and materials with compositional heterogeneities at grain size level.     

Nano-sized La0.8Sr0.2MnO3 as oxygen reduction catalyst in nonaqueous Li/O2 batteries

Nano-sized La_0.8Sr_0.2MnO₃ prepared by the polyethylene glycol assisting sol–gel method was applied as oxygen reduction catalyst in nonaqueous Li/O₂ batteries. The as-synthesized La_0.8Sr_0.2MnO₃ was characterized by X-ray diffraction (XRD), scanning electron microscopy, and Brunauer–Emmet–Teller measurements. The XRD results indicate that the sample possesses a pure perovskite-type crystal structure, even sintered at a temperature as low as 600 °C, whereas for solid-state reaction method it can only be synthesized above 1,200 °C. The as-prepared nano-sized La_0.8Sr_0.2MnO₃ has a specific surface area of 32 m² g⁻¹, which is much larger than the solid-state one (1 m² g⁻¹), and smaller particle size of about 100 nm. Electrochemical results show that the nano-sized La_0.8Sr_0.2MnO₃ has better catalytic activity for oxygen reduction, higher discharge plateau and specific capacity.     

中温固体氧化物燃料电池La1.6Sr0.4Ni1-xCuxO4阴极材料的制备及电化学性能

采用甘氨酸-硝酸盐法合成了中温固体氧化物燃料电池阴极材料La_1.6Sr_0.4Ni_1-xCu_xO₄ (x=0.2, 0.4, 0.6,0.8), 利用X射线衍射(XRD)和扫描电子显微镜(SEM)对其结构和微观形貌进行了表征. 结果表明, 该阴极材料与固体电解质Ce_0.9Gd_0.1O_1.95(CGO)在1000 °C烧结时不发生化学反应, 且烧结4 h 后, 二者之间可形成良好的接触界面. 利用电化学交流阻抗谱技术对阴极材料的电化学性能进行研究, 结果显示, 当Cu离子掺杂量(x)为0.6 时, La_1.6Sr_0.4Ni_0.4Cu_0.6O₄阴极具有最小的极化电阻, 在空气中当测试温度为750 °C时, 极化电阻为0.35 Ω·cm². 在不同氧分压条件下电化学阻抗谱分析结果表明, 电极上的两个氧还原反应主要包含氧离子从三相界面向电解质CGO 转移的过程和电荷的迁移过程, 其中电荷的迁移过程为电极反应的速率控制步骤.La_1.6Sr_0.4Ni_0.4Cu_0.6O₄电极在空气中700 °C和阴极电流密度为45 mA·cm^-2时, 阴极过电位为45 mV. 本研究的初步结果表明La_1.6Sr_0.4Ni_1-xCu_xO₄材料是一种电化学性能较为优良的新型中温固体氧化物燃料电池(IT-SOFC)阴极材料.     

Fabrication by Co-extrusion and electrochemical characterization of micro-tubular hollow fibre solid oxide fuel cells

A phase inversion process was used to co-extrude cerium–gadolinium oxide (Ce_0.9Gd_0.1O_1.95)/NiO–CGO dual-layer hollow fibres (HF), which were then sintered to form, respectively, the electrolyte and high porosity anode precursor of a solid oxide fuel cell (SOFC) with anode inner diameter of 0.8 mm. Graded CGO–lanthanum strontium cobalt ferrite (La_0.6Sr_0.4Fe_0.8Co_0.2O₃) cathode layers were then painted onto the CGO electrolyte to form a micro-tubular HF-SOFC. With a carefully designed anode current collector, this produced maximum power densities of 1186–5864 W m^? 2 at 450–570 °C. High magnification imaging analysis revealed large three-phase boundary regions within the anode, a dense electrolyte layer and clearly highlighted the multiple CGO–LSCF cermet and pure LSCF cathode layers. The performance of the HF-SOFC with a twenty millimetre active length showed no degradation after four thermal cycles between 300 °C and 570 °C.     

固-溶法制备中温固体氧化物燃料电池高性能La0.8Sr0.2MnO3-Ba0.5Sr0.5Co0.8Fe0.2O3阴极

研究了新型固溶法合成La_0.8Sr_0.2MnO₃（LSM）包覆Ba_0.5Sr_0.5Co_0.8Fe_0.2O₃（BSCF）复合粉体（LSM-BSCF）,并探讨了其作为中温固体氧化物燃料电池阴极材料的电化学性能。LSM-BSCF阴极结合了LSM和BSCF阴极的优点,不仅增大了三相界面,而且稳定了微观结构。当温度为600-750℃时,其极化阻抗为0.61-0.09 Ω·cm²。与溶液注入法制备的高性能电极相比,极大地提高了性能稳定性。     

The ionic conductivity, thermal expansion behavior, and chemical compatibility of La0.54Sr0.44Co0.2Fe0.8O3-δ as SOFC cathode material

In this paper, the ionic conductivities of La_0.54Sr_0.44Co_0.2Fe_0.8O_3-δ and La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ were measured by electron-blocked alternating current impedance analysis technique. The results show that the oxygen ion conductivity of La_0.54Sr_0.44Co_0.2Fe_0.8O_3-δ is nearly five times higher than that of La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ, which makes La_0.54Sr_0.44Co_0.2Fe_0.8O_3-δ cathode more conductive than YSZ electrolyte. Consequently, the electrochemical reaction region is extended from the interface between the cathode and the electrolyte to the whole surface of the cathode grains, with a result of the cathode polarization overpotential being decreased and the cell electrical performance being improved. Besides, the XRD results show that both La_0.54Sr_0.44Co_0.2Fe_0.8O_3-δ and La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ begin to react with 8YSZ([Y₂O₃]_0.08·[ZrO₂]_0.92) at 850 °C, but La_0.54Sr_0.44Co_0.2Fe_0.8O_3-δ with a faster reaction rate. The thermal expansion experiments manifest that the two LSCFs have approximate thermal expansion coefficients, being about 14 × 10⁻⁶–15 × 10⁻⁶ K⁻¹ from 500 °C to 700 °C, which is moderately higher than that of 8YSZ.     

Preparation and Characterization of Single-Phase Perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ

Single-phase perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ has been successfully prepared by using citrate-EDTA complexation method at relatively low calcination temperature. The structure and thermal decomposition process of the complex precursor have been investigated by means of differential scanning calorimetry-thermal gravimetric analysis (DSC/TGA), X-ray diffraction (XRD), and Fourier transform infrared spectroscopic (FT-IR) measurements. The precursor decomposed completely and started to form perovskite-type oxide above 420℃ according to the differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) results. Single-phase perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ obtained has been confirmed from the XRD pattern, and no peak of SrCO3 was found by XR.D of the oxides synthesized at a relatively low temperature of 800 ℃. The reducibility of La0.6Sr0.4Co0.8Fe0.2O3-δ was also characterized by the temperature programmed reduction (TPR) technique. Disk shaped dense La0.6Sr0.4Co0.8Fe0.2O3-δ membrane was prepared by the isostatical pressing method. The oxygen flux rate of dense La0.6Sr0.4Co0.8Fe0.2O3-δ membrane was (2.8-18)×10-8 mol/(cm2·s) in the temperature range of 800-1 000℃.     

Sr2NiMoO6−δ as anode material for LaGaO3-based solid oxide fuel cell

The double-perovskite Sr₂NiMoO_6−δ (SNMO) was investigated as an anode material of a solid oxide fuel cell (SOFC). With a 300 μm thick La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−σ (LSGM) disk as electrolyte and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ as the cathode, the SNMO anode showed power densities of 819 mW cm⁻² in hydrogen at 1123 K. Moreover, there was no buffer layer between anode and electrolyte, which would reduce design techniques and save design cost. After test no chemical reaction was discovered between anode and electrolyte. The anode exhibited good conductivity and the value was around 60 S cm⁻¹ in H₂. Also it had almost linear thermal expansion from room temperature to 1253 K and the average thermal expansion coefficient was about 12.14 × 10⁻⁶ K⁻¹, which was quite close to that of La_0.9Sr_0.lGa_0.8Mg_0.2O₃ (12.17 × 10⁻⁶ K⁻¹) electrolyte.     

Composite cathode for IT-SOFC: Sr-doped lanthanum cuprate and Gd-doped ceria

Composite cathodes were synthesized via a citrate combustion method followed by an organic precipitation method. The cathodes were of K₂NiF₄-type crystal structure with x wt.% Ce_0.9Gd_0.1O_1.95 (CGO)–(100 ? x) wt.% La_1.96Sr_0.04CuO_4 + δ (LSC), where x = 0, 10, 20 and 30. The individual structural phases of the composite cathodes were characterized using a third-generation synchrotron source beamline powder X-ray diffractometer (XRD). The porous grain morphology of the CGO–LSC cathode composite for a symmetrical half-cell was determined from cross-sectional scanning electron microscopy images and elemental line profiles. The composite cathode was made of 20 wt.% CGO–80 wt.% LSC (CL20–80) and was coated onto a Ce_0.9Gd_0.1O_1.95 electrolyte. It showed the lowest area specific resistance (ASR) of 0.07 Ω cm² at 750 °C. An electrolyte-supported (300 μm thick) single-cell configuration of CL20–80/CGO/Ni-CGO attained a maximum power density of 626 mW cm^? 2 at 700 °C. The unique composite composition of CL20–80 demonstrates enhanced electrochemical performance and good chemical compatibility with the CGO electrolyte, as compared with the pure LSC (CL0–100) cathode for IT-SOFCs.     

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     

Activation of a single-chamber solid oxide fuel cell by a simple catalyst-assisted in-situ process

Initialization is a critical processing step that has thus far limited the application of the single-chamber solid oxide fuel cell (SC-SOFC). In-situ initialization of a SC-SOFC with a nickel-based anode by methane–air mixtures was investigated. Porous Ru–CeO₂ was used as a catalyst layer over a Ni-ScSZ cermet anode. Catalytic testing demonstrated Ru–CeO₂ had high activity for methane oxidation. The Ru in the catalyst layer catalyzed the formation of syngas, which successfully reduced the nickel oxide to metallic nickel in the anode. Single cells with a La_0.8Sr_0.2MnO₃ (LSM) cathode, initialized by this in-situ reduction method, delivered peak power densities of 205 and 327 mW cm⁻² at 800 °C and 850 °C, respectively. Such performances were better than those of the cell without the Ru–CeO₂ catalyst layer that was initialized by an ex-situ reduction method were.     

Composite electrodes for proton conducting electrolyte of CaZr<Subscript>0.95</Subscript>Sc<Subscript>0.05</Subscript>O<Subscript>3 – δ</Subscript>

A new method of obtaining gastight ceramic based on CaZr_0.95Sc_0.05O_{3 – δ} is presented. The microstructure and electric properties of the obtained samples, same as the behavior of composite electrodes in contact with this electrolyte, are studied for application of the obtained results in the technology of formation of electrochemical devices. The design of bilayer electrodes is suggested, in which the materials tested as the functional layer were layered lanthanum nickelate La2NiO_{4 + δ} and substituted lanthanum nickelate La_1.7Ca(Sr,Ba)_0.3NiO_{4 + δ} in combination with the electrolyte components of Ce_0.8Sm_0.2O_{2 – δ} and BaCe_0.89Gd_0.1Cu_0.01O_{3 – δ}. The collector layer used was lanthanum nickelate–ferrite LaNi_0.6Fe_0.4O_{3 – δ} and manganite La_0.6Sr_0.4MnO_{3 – δ} that are characterized by high electron conductivity, low layer resistance and are close by their values of coefficient of linear thermal expansion to the materials of functional layers. Electrochemical activity of the obtained electrodes are compared with the characteristics of composite electrodes based on lanthanum ferrite–cobaltite La_0.6Sr_0.4Fe_0.8Co_0.2O_{3 – δ} and deficient lanthanum manganite La_0.75Sr_0.2MnO_{3 – δ}.