Cathodes based on (La,Sr)MnO<Subscript>3</Subscript> modified with PrO<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>

The electrochemical characteristics of composite cathodes made of (La, Sr) MnO₃-(Zr, Sc)O₂ (LSM-SSZ), modified with PrO_{2 − x} additive, and designed for application in solid oxide fuel cells at moderately high temperatures were studied. The relationship between activity of catalytically modified composite LSM-SSZ cathodes and dispersity of electrocatalyst was revealed. The boundaries of the temperature range with the maximum dispersity of electrocatalyst and electrochemical activity of cathodes were found. The composite LSM-SSZ cathodes modified with PrO_{2 − x} were shown inert with respect to oxidation reactions of hydrocarbon fuel (methane) and highly active electrochemically with respect to oxygen reaction in non-equilibrium gas mixture of CH₄ and O₂. In cells with (Ce, Sm)O₂ (SDC) and (Zr, Y)O₂ (YSZ) electrolytes, their overvoltage is below 80 mV at the current density about 0.5 A/cm² and temperature of 600°C. These electrodes can be used as cathodes in single-chamber fuel cells. Long-term experiments were carried out to study time stability of characteristics of the said composite cathodes. The studied electrodes show parabolic or damped exponential time curves of polarization resistance if contacting with YSZ or SDC electrolyte, respectively. According to the forecast based on the experimental regularities, the polarization resistance of LSM-SSZ cathodes in 10,000 h will not exceed 0.4 or 0.13 Ohm cm², respectively, if YSZ or SDC electrolyte is used.     

Effect of the Copper Oxide Sintering Additive on the Electrical and Electrochemical Properties of Anode Materials Based on Sr<Subscript>2</Subscript>Fe<Subscript>1.5</Subscript>Mo<Subscript>0.5</Subscript>O<Subscript>6–δ</Subscript>

The effect of introducing 1–3 wt % copper oxide sintering additive on the electrical and electrochemical characteristics of promising anode materials for solid oxide fuel cells based on Sr₂Fe_1.5Mo_0.5O_6–δ was studied. The total conductivity increases with increasing amount of copper oxide. The maximum conductivity in humid hydrogen at 800°C, 45 S cm^–1, was reached on introducing 3 wt % CuO. The sintering additive enhances the electrochemical activity of Sr₂Fe_1.5Mo_0.5O_6–δ and Sr₂Fe_1.5Mo_0.5O_6–δCe_0.8Sm_0.2O_1.9 anodes. A decrease in the sintering temperature of the anodes containing CuO with the electrolyte based on lanthanum gallate directly correlates with the electrochemical activity of the anodes. The minimum value of the polarization resistivity, 0.15 Ω cm² at 800°С in a humid hydrogen atmosphere, was obtained for the composite anode with 3 wt % CuO sintered at a temperature of 1050°С.     

Effects of CuO addition to anode on the electrochemical performances of cathode-supported solid oxide fuel cells

A cathode-supported electrolyte film was fabricated by tape casting and co-sintering techniques. (La_0.8Sr_0.2)_0.95MnO₃ (LSM95), LSM95/Zr_0.89Sc_0.1Ce_0.01O_2?x (SSZ), and SSZ were used as materials of cathode substrate, cathode active layer, and electrolyte, respectively. CuO–NiO–SSZ composite anode was deposited on SSZ surface by screen-printing and sintered at 1250 °C for 2 h. The effects of CuO addition to NiO–SSZ anode on the performance of cathode-supported SOFCs were investigated. CuO can effectively improve the sintering activity of NiO–SSZ. The assembled cells were electrochemically characterized with humidified H₂ as fuel and O₂ as oxidant. With 4 wt.% CuO addition, the ohmic resistance decreased from 3 to 0.46 Ω cm², and at the same time the polarization resistance decreased from 3.4 to 0.74 Ω cm². In comparison with the cell without CuO, the maximum power density at 850 °C increased from 0.054 to 0.446 W cm^?2 with 4 wt.% CuO addition.     

Electrochemical properties of La0.8Sr0.2FeO3 − δ –La0.45Ce0.55O2 − δ composite cathodes for intermediate temperature SOFC

The electrochemical properties of La_0.8Sr_0.2FeO_3???δ (LSF)–La_0.45Ce_0.55O_2???δ (LDC) composite cathodes coated on LSGM electrolyte were studied by electrochemical impedance spectroscopy and cathodic polarization technique. Results showed that the composite cathodes possessed superior electrochemical performance compared to that of pure LSF cathode. The cathodic overpotential of Cathode C was only 100 mV at 0.3 A cm^?2, and the charge transfer resistance and the gas phase diffusion resistance were decreased to 0.105 Ω cm² and 0.257 Ω cm², respectively at 800 °C. The improvement of the electrochemical performance is contributed to the increase of the triple-phase boundary, enlargement of the effective area for electrode reaction, and increase of the porosity of the cathode by adding LDC to the cathode material.     

Influences of synthesis route and preparation process on the electrochemical properties of Fe-doped strontium cobaltite

SrCo_0.8Fe_0.2O_3-δ (SCF), as a promising cathode material for intermediate temperature solid oxide fuel cells, possesses a high catalytic activity for the reduction of O₂ to 2O²⁻. The SCF powder was successfully synthesized by the solid state reaction method and Pechini method and characterized using XRD, particle analysis, and electrochemical performance measurements. Smaller-particle-size SCF materials (SCF-P) with single phase are obtained at lower synthesis temperature by the Pechini method and possess better electrochemical performance as compared with those prepared by the solid state reaction method. The reason is that the Pechini method involves the mixing of elements at atomic level, so pure SCF phase formation can be accelerated and showed high electrocatalytic activity. The preparation procedure of SCF cathode was firstly investigated using electrochemical impedance spectroscopy. Results show that the total polarization resistance and the low-frequency resistance decrease gradually with the reduction of the calcination temperature for the SCF cathodes. The SCF-P cathode sintered at 1,000 °C possesses the highest porosity and the best electrochemical performance. It is the result of a comprehensive function of three-phase boundary length, porosity of cathode, and the adhesion between cathode and electrolyte. The charge-transfer process, together with the adsorption, dissociation, and diffusion of oxygen, has a strong influence on the whole reaction process of the cathode. The influence of binder amounts on the performance of the SCF-P cathodes was also studied.     

Cobalt-free cathode material SrFe0.9Nb0.1O3−δ for intermediate-temperature solid oxide fuel cells

A cobalt-free cubic perovskite oxide, SrFe_0.9Nb_0.1O_3?δ (SFN) was investigated as a cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). XRD results showed that SFN cathode was chemically compatible with the electrolyte Sm_0.2Ce_0.8O_1.9 (SDC) for temperatures up to 1050 °C. The electrical conductivity of SFN sample reached 34–70 S cm^?1 in the commonly operated temperatures of IT-SOFCs (600–800 °C). The area specific resistance was 0.138 Ω cm² for SFN cathode on SDC electrolyte at 750 °C. A maximum power density of 407 mW cm^?2 was obtained at 800 °C for single-cell with 300 μm thick SDC electrolyte and SFN cathode.     

Silver migration at the Ag|Sm0.2Ce0.8O1.9 interface

The behavior of a silver electrode contacting Ce_0.8Sm_0.2O_1.9 (samaria-doped ceria or SDC) electrolyte under external cathodic polarization in the temperature range 350–700 °C was examined by means of long-term polarization experiments, scanning electron microscopy, and electrochemical impedance spectroscopy. A silver deposit is formed around the silver cathode via a surface migration mechanism without the occurrence of the gas-phase transport phenomenon during polarization. This results in an increase in both the electrode-electrolyte contact area and the triple-phase boundary length, which in turn causes decreases in charge transfer resistance and electrolyte resistance.     

Activation,microstructure, and polarization of solid oxide fuel cell cathodes

Activation effect can be defined as the enhancement of the electrochemical performance or activity of the solid oxide fuel cell cathodes such as Sr-doped LaMnO₃ (LSM) with the polarization/current passage treatment under fuel cell operation conditions. In this paper, the activation effect of the cathodic polarization/current passage on the O₂ reduction reaction of the LSM-based cathodes is reviewed. In addition to the activation effect, cathodic polarization/current passage also has a significant effect on the microstructure of the LSM electrodes and the morphology between the LSM electrode and Y₂O₃-ZrO₂ electrolyte interface. A mechanism involving the incorporation of SrO species into the LSM lattice and the formation of oxygen vacancies is proposed for the activation effect of the polarization.     

复合阴极材料La1-xSrxCuO3-δ-SDC的制备及电学性能

合成具有单相正交钙钛矿结构的La1-xSrxCuO3-δ(x=0.15, 0.2, 0.3, 0.4)系列样品, 碘量滴定法实验结果表明, 随着Sr掺入量的增加, Cu3+离子的含量逐渐增加. 电学性能研究结果表明, La0.7Sr0.3CuO3-δ电导率最高, 与La0.6Sr0.4CoO3-δ相比, La0.7Sr0.3CuO3-δ具有更好的电化学性能, 可作为一种新的中温固体氧化物燃料电池(IT-SOFC)阴极材料. 将La0.7Sr0.3CuO3-δ与不同质量比的中温电解质Ce0.85Sm0.15O2-δ(SDC) 固相混合, 制备复合阴极材料, 电化学性能测试结果表明, 掺入适量的SDC有利于降低La0.7Sr0.3CuO3-δ电极的极化, 获得性能更优越的IT-SOFC阴极材料, 提高在中温区单电池的输出功率.     

Improved electrochemical performance of SrCo0.8Fe0.2O3−δ–La0.45Ce0.55O2−δ composite cathodes for IT-SOFC

The performance of the SrCo_0.8Fe_0.2O_3−δ(SCF)–La_0.45Ce_0.55O_2−δ(LDC) composite cathodes was studied in this paper. The composite cathodes were prepared by screen-printing, and then sintered at 1200 °C for 2 h. Electrochemical impedance spectroscopy (EIS) and cathodic polarization test were carried out to investigate the electrochemical properties of the composite cathodes. The results showed that the composite cathodes had superior electrochemical performance compared to that of the pure SCF cathodes. Through optimizing the structures of composite cathodes, the cathodic overpotential of triple-layer SCF–LDC composite cathodes was only 23 mV at 0.3 A cm⁻². The specific ohmic resistance, charge transfer resistance and gas phase diffusion resistance of the triple-layer SCF–LDC cathodes were the lowest for the SCF–LDC composite cathodes, and they were 0.1 Ω cm², 0.01 Ω cm² and 0.1 Ω cm² respectively at 800 °C. The changes were attributable to the enlargement of triple phases boundary (tpb) and enhancement of the adhesion between electrode and electrolyte by adding LDC to the cathode material.     

(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.     

Composite cathode materials Ag-Ba0.5Sr0.5Co0.8Fe0.2O3 for solid oxide fuel cells

Silver-Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) cathodes were prepared in two ways. In the first method, Ag-BSCF composite powder was prepared in ethanol solution, where Ag nanoparticles serving as a component in the preparation of Ag-BSCF composite cathodes had been previously obtained via one-step synthesis in absolute ethanol using a neutral polymer (polyvinylpyrrolidone). To the best of our knowledge, this is the first study to use a Ag sol obtained by the above method for preparation of Ag-BSCF composite powder. Then, a paste containing this powder was screen-printed on a Sm_0.2Ce_0.8O_1.9 electrolyte and sintered at 1,000 °C. In the second technique, an aqueous solution of AgNO₃ was added to a previously sintered BSCF cathode, which was then sintered again at 800 °C. The oxygen reduction reaction at the quasi-point BSCF cathode on the Sm_0.2Ce_0.8O_1.9 electrolyte was tested by electrochemical impedance spectroscopy at different oxygen concentrations in three electrode setup. The continuous decrease of polarization resistance was observed under polarization ?0.5 V at 600 °C. The comparative studies of both obtained composite Ag-BSCF materials were performed in hydrogen-oxygen IT-SOFC involving samaria-doped ceria as an electrolyte and Ni-Gd_0.2Ce_0.8O_1.9 anode. In both cases, the addition of silver to the cathode caused an increase in current and power density compared with an IT-SOFC built with the same components but involving a monophase BSFC cathode material.     

Improved electrochemical performance of Ca2Fe1.4Co0.6O5–Ce0.9Gd0.1O1.95 composite cathodes for intermediate-temperature solid oxide fuel cells

The performance of Ca₂Fe_1.4Co_0.6O₅–Ce_0.9Gd_0.1O_1.95 (CFC–CGO) composite cathode has been investigated for potential application in intermediate-temperature solid oxide fuel cells (IT-SOFCs). The composite cathodes are prepared and characterized by XRD and SEM, respectively. The electrochemical properties of the composite cathodes are investigated using AC impedance and DC polarization methods from 500 to 700 °C under different oxygen partial pressures. The polarization resistance (R _p) decreases with the increase of CGO content in the composite electrode. The addition of 40 wt.% CGO in CFC results in the lowest R _p of 0.48 Ω cm² at 700 °C in air. Oxygen partial pressure dependence study indicates that the charge-transfer process is the rate limiting step for oxygen reduction reaction. CFC-40CGO composite cathode exhibits the lowest overpotential of about 67 mV at a current density of 85 mA cm⁻² at 700 °C in air.     

Effect of Bi0.75Y0.25O1.5 electrolyte additive in collector layer to properties of bilayer composite cathodes of solid oxide fuel cells based on La(Sr)MnO3 and La(Sr)Fe(Co)O3 compounds

The sintering features, electroconductivity, and electrochemical characteristics of bilayer electrodes with functional composite layers based on La(Sr)MnO₃ (LSM) and La(Sr)Fe(Co)O₃ with LSM collector layer and Bi(Y)O_1.5 (YDB) electrolyte additive in contact with Ce (Sm)O₂(SDC), La(Sr)Ga(Mg)O₃, and Zr(Sc)O₂ electrolytes were studied. YDB additive to the electrode collector layer was shown to produce a positive effect to the properties of the studied electrode systems. The maximum electrochemical activity and electroconductivity was observed for the electrodes with 5 wt % of YDB electrolyte additive in the collector layer. Thus, electroconductivity of electrodes is almost doubled and 100 mV cathode overvoltage current density is increased by 30% at the temperatures of 800 to 900°C and up to 10-fold at 650 to 700°C. The collector layer sintering temperature of bilayer electrodes can be reduced from 1150 to 1000°C without loss of electrochemical activity. The service life tests (about 1200 h) of composite electrodes with LSM2-SDC functional layer and 90% LSM2 + 10% YDB collector layer in contact with SDC electrolyte showed the time dependences of polarization resistance tending to saturation and described with damped exponent. Original Russian Text ? N.M. Bogdanovich, D.I. Bronin, G.K. Vdovin, I.Yu. Yaroslavtsev, B.L. Kuzin, 2009, published in Elektrokhimiya, 2009, Vol. 45, No. 4, pp. 486–494.     

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.     

Thin film nonstoichiometric chromium oxide-based cathode material for rechargeable and primary lithium batteries

The application of nonstoichiometric chromium oxide-based thin film cathodes in lithium rechargeable and primary batteries operating at high rates has been demonstrated. Films of varying composition have been obtained by anionic Cr (VI) species electrodeposition on a 1X18N10Т grade stainless steel cathode from fluoride-containing electrolytes. The effect of film doping by Li⁺ ions during its electrosynthesis has been сonsidered. As-prepared films were studied by scanning and transmission electron microscopies, 3D optical profiler, thermogravimetric analysis, chemical analysis, and X-ray diffraction (XRD). The main phase components of the electrodeposited films regardless of Li⁺ in an electrolyte are Cr₂O₃, α-CrOOH, β-CrOOH, and metallic chromium as shown by XRD pattern refinement. The electrochemical reduction rate in a non-aqueous electrolyte (1 M LiClO₄ in PC/DME) correlates with the chromium oxide-hydroxide component content of film. Primary CrO _x -Li CR2325 mock-up cathode coating can be discharged in a pulsed mode at 10 Ω external resistance with 80–84 mA cm^?2 current densities for 10–100 ms. Thin film cathodes electrodeposited in the presence of lithium ions become rechargeable when the lithium content of the film reaches 0.02 wt.%. Mock-ups of CR2325 coin battery with a thin film cathode doped with lithium ions can be discharged more than 40 times with 136 mAh g^?1 specific capacity, 461 Wh kg^?1 specific energy and 154 W kg^?1 power density at 30 kΩ external resistance. The simplicity of thin film preparation makes this technology promising for thin film lithium batteries.     

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。     

Characteristics of the La0.6Sr0.4Fe0.8Co0.2O3 − δ electrode in contact with the lanthanum gallate-based electrolyte

Lowering the working temperature of solid oxide fuel cells (SOFCs) is the main trend in their development, which requires selection of materials for electrolyte and electrodes. A highly conducting lanthanum gallate-based electrolyte is a promising material for creating medium-temperature SOFCs. The electrochemical characteristics of the La_0.6Sr_0.4Fe_0.8Co_0.2O_{3 ? δ} cathode that contacted with the La_0.88Sr_0.12Ga_0.82Mg_0.18O_2.85 electrolyte subject to electrode formation temperatures have been investigated. It was found that at optimum bake-on temperatures of 1200–1250°C, the cathode polarization resistance at 800°C was ～0.08 Ohm cm², which is comparable to the world’s best achievements.     

EDTA-甘氨酸法制备SmBaCo2O5+δ阴极材料及其性能

采用EDTA-甘氨酸法(EGP)合成了中温固体氧化物燃料电池(IT-SOFC)的阴极材料SmBaCo2O5+δ(SBCO).通过热重-差热分析(TG-DTA),X射线衍射(XRD),透射电镜(TEM),扫描电镜(SEM),直流四极法及交流阻抗技术分析材料的性能.结果表明,初始粉体在850°C煅烧5 h形成钙钛矿结构单相.EGP制备的SBCO粉体颗粒细小、分散性好、粒径分布均匀,其与Sm0.2Ce0.8O1.9(SDC)电解质材料具有良好的高温化学相容性.SBCO的电导率在500-800°C时达到668-382 S cm-1.以SDC为电解质,SBCO为阴极制备对称半电池,其界面结合良好,颗粒连接充分,形成好的三相界面,具有高的阴极催化活性,750°C时阴极极化电阻为0.0688Ωcm2,远低于固相法(SSR)的值,活化能(Ea)为122.21 kJ mol-1.     

Electrochemical performances of LaBaCuFeO5+x and LaBaCuCoO5+x as potential cathode materials for intermediate-temperature solid oxide fuel cells

Layered perovskite-structure oxides LaBaCuFeO_5+x (LBCFO) and LaBaCuCoO_5+x (LBCCO) were prepared and the electrical conductivity and electrochemical performance were investigated as potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The electrical conductivity of LBCCO is much higher than that of LBCFO. Area specific resistances of LBCFO and LBCCO cathode materials on Ce_0.8Sm_0.2O_1.9 (SDC) electrolyte are as low as 0.21 Ω cm² and 0.11 Ω cm² at 700 °C, respectively. The maximum power density of the LBCFO/SDC/Ni-SDC and LBCCO/SDC/Ni-SDC cells with 300 μm thick electrolytes attains 557 mW cm^?2 and 603 mW cm^?2 at 800 ^oC, respectively. Preliminary results demonstrated that the layered perovskite-structure oxides LBCFO and LBCCO are very promising cathode materials for application in IT-SOFCs.