Synthesis and characterization of Ca3-xLaxCo4-yCuyO9+δ cathodes for intermediate temperature solid oxide fuel cells

The calcium cobaltite Ca_3-xLa_xCo_4-yCu_yO_9+δ with x and y = 0 and 0.1 were synthesized and the electrical, thermal, and catalytic behaviors for the oxygen reduction reaction (ORR) for use as air electrodes in intermediate-temperature solid oxide fuel cells (IT-SOFCs) were evaluated. X?ray diffraction confirms the Ca_3-xLa_xCo_4-yCu_yO_9+δ samples were crystallized in a monoclinic structure and scanning electron microscopic image shows lamella-like grain formation. Introduction of dopants decreases slightly the loss of lattice oxygen and thermal expansion co-efficient. The Ca_3-xLa_xCo_4-yCu_yO_9+δ samples exhibit good phase stability for long-term operation, thermal expansion, and chemical compatibility with the Ce_0.8Gd_0.2O_2-δ electrolyte. Among the studied samples, Ca_2.9La_0.1Co₄O_9+δ shows a maximum conductivity of 176 Scm^?1 at 800 °C. Although the doped samples exhibit a higher total electrical conductivity, an improved symmetrical cell performance is displayed by the undoped sample. Comparing the sintering temperatures, the composite cathode Ca₃Co₄O_9+δ + Ce_0.8Gd_0.2O_2-δ sintered at 800 °C exhibit the lowest area specific resistance of 0.154 Ω cm² at 800 °C in air. In the Ca_3-xLa_xCo_4-yCu_yO_9+δ + GDC composite cathodes, the charge-transfer process at high frequencies presents a major rate limiting step for the oxygen reduction reaction.     

PrBaFe2O5+δ promising electrode for redox-stable symmetrical proton-conducting solid oxide fuel cells

The proton conduction behavior and electrochemical performance of PrBaFe₂O_5+δ (PBF) are firstly studied for use as promising anode materials in symmetrical proton-conducting solid oxide fuel cells (PCFCs). This study focuses on the investigation of protonic defect formation in PBF and its properties as an electrode, including its chemical stability, electrochemical performance and redox stability. PBF is found to have proton conductivity at intermediate temperatures, which contributes to improved hydrogen oxidation reaction and water formation reaction at the anode and cathode, respectively. Hence, the symmetrical PCFC exhibits a peak power density of 301 mW?cm^?2 and total resistance of 0.77 Ω?cm² at 700 °C. Further, it shows excellent redox-cycle stability upon cycling between fuel and air under a current load. The electrochemical analysis and redox cycling tests of the PBF anode demonstrate that PBF is an attractive candidate for alternative material for symmetrical PCFCs.     

La0.5Sr0.5Fe0.9Mo0.1O3-δ-CeO2 anode catalyst for Co-Producing electricity and ethylene from ethane in proton-conducting solid oxide fuel cells

A La_0.5Sr_0.5Fe_0.9Mo_0.1O_3-δ-CeO₂ (LSFM-CeO₂) composite was prepared by impregnating CeO₂ into porous La_0.5Sr_0.5Fe_0.9Mo_0.1O_3-δ perovskite and was used as an anode material for proton-conducting solid oxide fuel cells (SOFCs). The maximum power densities of the BaZr_0.1Ce_0.7Y_0.2O_3-δ (BZCY) electrolyte-supported single cell with LSFM-CeO₂ as the anode reached 291 mW cm^?2 and 190 mW cm^?2 in hydrogen and ethane fuel at 750 °C, respectively, which are significantly higher than those of a single cell with only LSFM as the anode. Additionally, the ethylene selectivity and ethylene yield from ethane for the fuel cell at 750 °C were as high as 93.4% and 37.1%, respectively. The single cell also showed negligible degradation in performance and no carbon deposition during continuous operation for 22 h under an ethane fuel atmosphere. The improved electrochemical performance due to the impregnation of CeO₂ can be a result of enhanced electronic and ionic conductivity, abundant active sites, and a broad three-phase interface in the resultant composite anode. The LSFM-CeO₂ composite is believed to be a promising anode material for proton-conducting SOFCs for co-producing electricity and high-value chemicals from hydrocarbon fuels.     

Evaluation of bismuth doped La2-xBixNiO4+δ (x = 0, 0.02 and 0.04) as cathode materials for solid oxide fuel cells

Bismuth doped La_2-xBi_xNiO_4+δ (x = 0, 0.02 and 0.04) oxides are investigated as SOFC cathodes. The effects of Bi doping on the phase structure, thermal expansion, electrical conduction behavior as well as electrochemical performance are studied. All the samples exist as a tetragonal Ruddlesden-Popper structure. Bi-doped LBNO-0.02 and LBNO-0.04 have good chemical and thermal compatibility with LSGM electrolyte. The average TEC over 20–900°С was 13.4 × 10^?6 and 14.2 × 10^?6 K^?1 for LBNO-0.02 and LBNO-0.04, respectively. The electrical conductivity was decreasing with the rise of Bi doping content. EIS measurement indicates Bi doping can decrease the ASR values. At 750 °C, the obtained ASR for LBNO-0.04 is 0.18 Ωcm², which is 56% lower than that of the sample without Bi doping, suggesting Bi doping is beneficial to the electrochemical catalytic activity of LBNO cathodes.     

Screen printing of sol–gel-derived electrolytes for solid oxide fuel cell (SOFC) application

The idea of using the sol–gel technique for producing low-cost components for solid oxide fuel cell (SOFC) application has attracted great interest. Besides its economic advantages, the sol–gel technique additionally offers the chance to reduce either the thickness of the electrolyte and therefore to reduce ohmic resistances or to lower the sintering temperature of single components like the electrolyte layer, due to the clearly reduced particle sizes of colloidal distributed particles in the sol.The work presented here deals with the development of sols and their application in combination with yttria fully stabilized zirconia mixed-oxide powders for the preparation of screen-printing pastes. Besides physical, chemical and thermal characterization of the sols, variations of the composition of the sol as well as of the pastes composed of sol and mixed-oxide powder were evaluated for preparing dense, gas-tight layers sintered at various temperatures, resulting in sufficient gas-tightness to ensure high power density SOFCs. Additionally, technological screen-printing parameters were studied.Single cell tests (50 mm × 50 mm) revealed current densities of approx. 1 A/cm². These values are comparable to current densities obtained by cells based on normal electrolyte layers, which were prepared in parallel.     

Liquid-phase synthesis of SrCo0.9Nb0.1O3-δ cathode material for proton-conducting solid oxide fuel cells

A novel liquid-phase synthesis strategy is demonstrated for the preparation of the Nb-containing ceramic oxide SrCo_0.9Nb_0.1O_3-δ (SCN). In comparison with the traditional solid-state reaction (SSR) method, the liquid-phase synthesis route offers a couple of advantages, including a lower phase formation temperature and a smaller particle size of the SCN materials that are beneficial for applications as proton-conducting fuel cell cathode. With BaCe_0.4Zr_0.4Y_0.2O_3-δ (BCZY442) as the electrolyte and the SCN synthesized in this work as the cathode, a proton-conducting solid oxide fuel cell (SOFC) shows a peak power density of 348 mW cm^?2 at 700 °C, significantly higher than that of a SOFC fabricated with SCN cathode prepared using the SSR method, which can only deliver 204 mW cm^?2 at the same temperature. Additionally, this new synthesis strategy allows impregnation of Sr²⁺, Co³⁺and Nb⁵⁺ on the solid backbone in aqueous solution, further improving cell performance to reach a peak power density of 488 mW cm^?2 at 700 °C.     

Electrochemical performance of La2NiO4+δ cathode for intermediate-temperature solid oxide fuel cells

The application of the La₂NiO_4+δ (LNO), one of the Ruddlesden–Popper series materials, as a cathode material for intermediate temperature solid oxide fuel cells is investigated in detail. LNO is synthesized via a complex method using ethylenediaminetetraacetic acid (EDTA) and citric acid. The effect of the calcination temperature of the LNO powder and the sintering temperature of the LNO cathode layer on the anode-supported cell, Ni–YSZ/YSZ/GDC/LNO, is characterized in view of the charge transfer resistance and the mass transfer resistance. Charge transfer resistance was not significantly affected by calcination and sintering temperature when the sintering temperature was not lower than the calcination temperature. Mass transfer resistance was primarily governed by the sintering temperature. The unit cell with the LNO cathode sintered at 1100 °C with 900 °C-calcined powder presented the lowest polarization resistance for all the measured temperatures and exhibited the highest fuel cell performances, with values of 1.25, 0.815, 0.485, and 0.263 W cm⁻² for temperatures of 800, 750, 700, and 650 °C, respectively.     

Synthesis and characterization of fibrous La0.8Sr0.2Fe1-xCuxO3-δ cathode for intermediate-temperature solid oxide fuel cells

Aiming to offer a high-performance Co-free cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs), a series of La_0.8Sr_0.2Fe_1-xCu_xO_3-δ (LSFCux, x = 0.0–0.3) nanofiber cathodes were synthesized by the electrospinning method. The effects of various Cu doping amounts on the crystal structure, fiber morphology, and electrochemical performance of LSF nanofiber cathode materials were investigated. The results indicate that after being calcined at 800 °C for 2 h, the perovskite structure samples with a high degree of crystallinity are obtained. The morphology of electrospun nanofibers is continuous, and the average diameter of nanofibers is about 110 nm. In addition, the La_0.8Sr_0.2Fe_0.8Cu_0.2O_3-δ (LSFCu2) fiber cathode displays the optimal electrochemical performance, and the polarization resistance (R_p) is 0.674 Ω cm² at 650 °C. The doping of Cu transforms the main control step of the low-frequency band from dissociation of oxygen molecules to charge transfer on the electrode, and the maximum power density (P_m) of the Ni-SDC/SDC/LSFCu2 single cell reaches 362 mW cm^-2 at 650 °C.     

Synthesis and characterization of 10Sc1CeSZ powders prepared by a solid–liquid method for electrolyte-supported solid oxide fuel cells

10Sc1CeSZ is one of the most important electrolyte materials used for solid oxide fuel cells (SOFCs). A novel solid–liquid method (SLM) was adopted for the preparation of 10Sc1CeSZ nanopowder. High-purity, single-phase, homogeneous 10Sc1CeSZ powder was successfully prepared using this method. The resulting powders and ceramic pellets were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). A cubic structure was obtained when the value of the specific surface area (SSA) of the starting material ZrO₂ was greater than 60 m² g⁻¹. A conductivity of 0.14 S cm⁻¹ at 800 °C was achieved for the sintered pellets. The performance of the electrolyte-supported cell (ESC) NiO+GDC/10Sc1CeSZ /10Sc1CeSZ +LSM reached 0.66 W cm⁻² at 0.75 V and 850 °C.     

Synthesis and characterisation of MnGaxCr2−xO4 (0.1≤x≤1) spinels as potential electrode support materials for intermediate-temperature solid oxide fuel cells

MnGa_xCr_2−xO₄ (MGCO, x=0.1, 0.2, 0.4, 0.8, 1) oxides are synthesised using a citric acid nitrate combustion method. The influence of Ga substitution on the structure, electrical conductivity and electrochemical performance are systematically investigated. The chemical and thermal compatibility of MGCO materials with yttrium-stabilised zirconia (YSZ) are also studied. All the samples exhibit a single phase spinel structure. Thermal expansion coefficients (TECs) of the MGCO oxides are in the range of 9–12×10⁻⁶ K⁻¹, indicating a good thermal match with the YSZ electrolyte. No chemical reactions are detected between MGCO materials and YSZ, indicating their good chemical compatibility with YSZ. The magnitude of electrical conductivity of all the obtained samples is in the order of about 10⁻³ S cm⁻¹at 800 °C measured in air. The polarisation resistance reaches a value as low as 5.2 Ω cm² for x=0.4 at 800 °C. The preliminary results demonstrate that MGCO materials could be used as electrode support materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs).     

Highly active and stable BaCo0.8Zr0.1Y0.1O3-δ cathode for intermediate temperature solid oxide fuel cells

Developing cathode material with high performance and excellent stability is the ultimate goal for solid oxide fuel cells (SOFCs). Based on this consideration, we design a new simple perovskite oxide BaCo_0.8Zr_0.1Y_0.1O_3-δ (BCZY) as the cathode material of SOFC without any further modification, which has good oxygen reduction reaction (ORR) activity and excellent stability in air and CO₂ at an intermediate temperature range of 600 ℃? 800 ℃. The area specific resistance (ASR) of symmetrical cell with BCZY cathode is 0.041 Ω cm² at 700 ℃, moreover, BCZY cathode keeps good structural and catalytic stability during 100 h test in air. The electrolyte-supported single cell fabricated with BCZY as cathode delivers a maximum power density of 460 mW cm^?2 and a superior steady operation over 200 h at 700 ℃. The good thermal physical structure stability of BCZY is further demonstrated by in-situ X-ray diffraction (XRD), good ORR activity and excellent CO₂ tolerance are further confirmed by density functional theory (DFT) calculations. These results indicates that BCZY maybe a potential cathode material for intermediate temperature SOFCs (IT-SOFCs).     

Microwave-assisted synthesis and characterization of new cathodic material for solid oxide fuel cells: La0.3Ca0.7Fe0.7Cr0.3O3−δ

In this work, we examine the benefits of alternative powder processing methods, with a primary focus on microwave-based synthesis, that could both lower material manufacturing costs and further enhance cathode performance for solid oxide fuel cell applications. La_0.3Ca_0.7Fe_0.7Cr_0.3O_3−δ (LCFCr), formed using conventional solid-state methods, has been shown in earlier work to be a very promising catalyst for the oxygen reduction reaction. To further increase its performance, microwave methods were used to increase the surface area of LCFCr and to decrease the synthesis time. It was found that the material could be obtained in crystalline form in only 7 h, with the synthesis temperature lowered by roughly 300 °C as compared to conventional methods.     

In-situ exsolution of PrO2−x nanoparticles boost the performance of traditional Pr0.5Sr0.5MnO3-δ cathode for proton-conducting solid oxide fuel cells

By synthesizing the nominal Pr_xSr_0.5MnO_3-δ materials (x = 0.5, 0.6, 0.7, 0.8), new Pr_0.5Sr_0.5MnO_3-δ (PSM50)+PrO_2−x composite cathodes for proton-conducting solid oxide fuel cells (SOFCs) were developed. The structure analysis and morphology observations verified the exsolution of PrO_2−x particles, and the amount of exsolved PrO_2−x increased with the amount of Pr in Pr_xSr_0.5MnO_3-δ. An H-SOFC with a Pr_0.7Sr_0.5MnO_3-δ (PSM70) cathode enabled the highest reported fuel cell output for H-SOFCs with manganate cathodes. The construction of a PSM50/PrO₂ heterostructure interface can reduce the formation energy of oxygen vacancies, hence accelerating the cathode oxygen reduction reaction (ORR) kinetics, as confirmed by oxygen diffusion and surface exchange experiments. The excellent electrochemical performance was combined with its good chemical stability against CO₂ and H₂O, allowing a stable operation of the cell for over 100 h, indicating that PSM70, which was in fact PSM50 +PrO_2−x, was a highly efficient and durable cathode material for H-SOFCs.     

Electrochemical and microstructural characteristics of nanoperovskite oxides Ba0.2Sr0.8Co0.8Fe0.2O3−δ (BSCF) for solid oxide fuel cells

Nanoperovskite oxides, Ba_0.2Sr_0.8Co_0.8Fe_0.2O_3?δ (BSCF), were synthesized via the co-precipitation method using Ba, Sr, Co, and Fe nitrates as precursors. Next, half cells were fabricated by painting BSCF thin film on Sm_0.2Ce_0.8O_x (samarium doped ceria, SDC) electrolyte pellets. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical impedance spectroscopy (EIS) measurements were carried out on the BSCF powders and pellets obtained after sintering at 900 °C. Investigations revealed that single-phase perovskites with cubic structure was obtained in this study. The impedance spectra for BSCF/SDC/BSCF cells were measured to obtain the interfacial area specific resistances (ASR) at several operating temperatures. The lowest values of ASR were found to be 0.19 Ω cm², 0.14 Ω cm² 0.10 cm², 0.09 Ω cm² and 0.07 Ω cm² at operating temperatures of 600 °C, 650 °C, 700 °C, 750 °C and 800 °C, respectively. The highest conductivity was found for cells sintered at 900 °C with an electrical conductivity of 153 S cm^?1 in air at operating temperature of 700 °C.     

Improved electrochemical activity of Bi0.5Sr0.5FeO3-δ–Ce0.9Gd0.1O1.95composite cathode electrocatalyst for solid oxide fuel cells

Developing MIEC materials with high electrocatalytic performance for the ORR and good thermal/chemical/structural stability is of paramount importance to the success of solid oxide fuel cells (SOFCs). In this work, high-activity Bi_0.5Sr_0.5FeO_3-δ-xCe_0.9Gd_0.1O_1.95 (BSFO-xGDC, x = 10, 20, 30 and 40 wt%) oxygen electrodes are synthesized, and confirmed by XRD, SEM and EIS, respectively. The crystal structure, microstructure, electrochemical property and performance stability of the promising BSFO-xGDC composite cathodes are systematically evaluated. It is found that introducing GDC nanoparticles can obviously improve the electrochemical property of the porous composite electrode. Among all these composite cathodes, BSFO-30GDC composite cathode shows the best ORR activity. The peak power density of anode supported single cells employing BSFO-30GDC composite cathode reaches 709 mW cm^?2 and the electrode polarization resistance (R_p) of the BSFO-30GDC is about 0.14 Ω cm² at 700 °C. The analysis of the oxygen reduction kinetic indicates that the major electrochemical process of the GDC-decorated composite cathode is oxygen adsorption-dissociation. These preliminary results demonstrated that BSFO-30GDC is a prospective composite cathode catalyst for SOFCs because of its outstanding ORR activity.     

Fabrication and characterization of MOCVD (In1-xAlx)2O3 (0.1≤x≤0.6) ternary films

A series of (In_1-xAl_x)₂O₃ (0.1 ≤ x ≤ 0.6) films with tunable bandgap were grown on MgO (100) substrates by MOCVD. The influences of chemical compositions and growth temperatures on the film properties were studied systematically. XRD analyses indicated that the film quality degraded from crystalline to amorphous structure as Al concentration (x) increased. The (In_1-xAl_x)₂O₃ films prepared at 700 °C exhibited better film crystallinity than those of the ones grown at 600 °C. The films prepared at 700 °C with x = 0.1–0.3 showed an epitaxial In₂O₃ <111> orientation with the corresponding growth relationship of In₂O₃ (111)∥MgO (100). The film with x = 0.2 exhibited the best crystallinity and the largest grain size of 25.9 nm. The Hall mobilities and resistivities of the films were influenced evidently by Al concentrations. The Hall mobility showed a monotonous decrease from 12 to 1.1 cm²V^?1s^?1 as x increased from 0.1 to 0.6. The lowest resistivity of 9.2 × 10^?3 Ω cm was acquired for the film with x = 0.2. The average transmittances in the visible region for all the films were beyond 83%. The bandgap of the (In_1-xAl_x)₂O₃ films can be regulated in the range of 3.85–4.88 eV by changing Al concentrations from 0.1 to 0.6.     

Nanofiber-structured Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ-Gd0.2Ce0.8O1.9 symmetrical composite electrode for solid oxide fuel cells

In this research, nanofiber-structured Pr_0.4Sr_0.6Co_0.2Fe_0.7Nb_0.1O_3-δ (PSCFN) electrode scaffolds were impregnated with Gd_0.2Ce_0.8O_1.9 (GDC) nanoparticles to prepare PSCFN-GDC nanofiber-structured composite electrodes, which could function well as a novel electrode material for symmetrical solid oxide fuel cells (SSOFCs). The polarization resistances of PSCFN-GDC (1:0.56) composite electrodes as cathode and anode were 0.044 and 0.309 Ω cm² at 800 °C, respectively, indicating that the composite electrodes demonstrated excellent electrochemical performances for both oxygen reductions and fuel oxidation reactions. La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-δ (LSGM) electrolyte-supported single cells with the PSCFN-GDC symmetrical composite electrodes showed excellent long-term stability in wet H₂ (97% H₂-3% H₂O) and wet CH₄ (97% CH₄-3% H₂O) for 100 h with constant current density at 800 °C. A conversion electrode method was applied by interchanging the atmosphere of cathode and anode to solve the problem of PSCFN-GDC symmetrical single cell's carbon deposition in wet CH₄. After working three cycles for 384 h, carbon deposition was not found in the symmetrical electrode scaffold. Taken together, the results described above demonstrated that the PSCFN-GDC composite material acted as a promising symmetrical electrode for SSOFCs, and the conversion electrode method would make for a good application to process carbon deposition generated by hydrocarbon fuels.     

Comparative study on the electrochemical performance of Sr(Ti0.3Fe0.7)O3-δ fuel electrode in different fuel gases for solid oxide electrochemical cells

Sr(Ti_1-xFe_x)O_3?δ (STF) perovskite has been developed as one of the alternatives to Nickel-base fuel electrodes for solid oxide electrochemical cells (SOCs) that can provide good tolerance to redox cycling and fuel impurities. Recent results on STF fuel electrodes present excellent electrochemical performance and outstand stability both under H₂ fuel cell mode and H₂O electrolysis mode, however, the electrochemical characteristics in other fuel gases, such as CO, CO–H₂ mixture, CH₄, and CO–CO₂ mixture have not been investigated. Herein, we report the electrochemical performance of Sr(Ti_0.3Fe_0.7)O_3?δ fuel electrode on La_0.8Sr_0.2MnO_3?δ-Zr_0.92Y_0.16O_2?δ (LSM-YSZ) oxygen electrode supported SOCs with thin YSZ electrolyte using different fuel gases. At 800 °C, the peak power density slightly decreased from 0.9 W/cm² in wet H₂ to 0.68 W/cm² in wet CO under fuel cell mode. However, the cell only showed a peak power density of 0.27 W/cm² at 800 °C in wet CH₄, reaching 0.75 W/cm² at 850 °C, when the open-circuit voltage increased from 0.9 V to 1.02 V. STF fuel electrode exhibited much worse CO₂ electrolysis performance than steam electrolysis, especially in high CO₂ concentration due to the increased ohmic resistance and electrode polarization resistance.     

On the manufacturing of low temperature activated Sr0.9La0.1TiO3-δ-Ce1-xGdxO2-δ anodes for solid oxide fuel cell

Lanthanum doped strontium titanate–gadolinium doped cerium oxide (LST-GDC) anodic layers are sintered in air and further reduced in-situ at low temperature (750 °C) avoiding usually performed pre-reduction treatment at high temperature. The influence of various milling techniques and of powders with different specific surface area, on the microstructures of screen-printed anodes, is investigated. The combination of milling and sonication processes is efficient in reducing aggregation of the anode powders. The anode performance is improved when a planetary milling step is involved in the preparation of the screen printing inks. The use of gadolinium doped cerium oxide with high specific surface area decreases the polarization resistance. The rate of hydrogen oxidation is also enhanced by increasing porosity.     

Effects of mass fraction of La0.9Sr0.1Cr0.5Mn0.5O3-δ and Gd0.1Ce0.9O2-δ composite anodes for nickel free solid oxide fuel cells

The optimal anode mass fraction of La_0.9Sr_0.1Cr_0.5Mn_0.5O_3-δ (LSCM) and Gd_0.1Ce_0.9O_2-δ (GDC) is evaluated in this study. The anodes with GDC share of 30–100 wt.% are investigated. Initial polarization resistance decreased as the GDC share increased. However, anodes with GDC share over 80 wt.% significantly deteriorated in the degradation tests. Nano-scale cracks were observed in the GDC phase at the grain boundaries after the test. These nano-cracks were not observed in composite anodes, from which it is implied that LSCM has stabilization effect on GDC structure. The mass fraction of LSCM : GDC = 30 : 70 wt.% is found to be optimal in terms of initial electrochemical performance and stability. The optimal LSCM-GDC shows lower polarization resistance than conventional Ni-YSZ at low temperatures, which is comparable to Ni-GDC anode.