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1.
The cathode reaction mechanism of porous Sm0.5Sr0.5CoO3−δ, a mixed ionic and electronic conductor (MIEC), is studied through a comparison with the composite cathode Sm0.5Sr0.5CoO3−δ/Sm0.2Ce0.8O1.9. First, the cathodic behaviour of porous Sm0.5Sr0.5CoO3−δ and Sm0.5Sr0.5CoO3−δ/Sm0.2Ce0.8O1.9 are observed for micro-structure and impedance spectra according to Sm0.2Ce0.8O1.9 addition, thermal cycling and long-term properties. The cathode reaction mechanism is discussed in terms of frequency response, activation energy, reaction order and electrode resistance for different oxygen partial pressures p(O2) at various temperatures. Three elementary steps are considered to be involved in the cathodic reaction: (i) oxygen ion transfer at the cathode-electrolyte interface; (ii) oxygen ion conduction in the bulk cathode; (iii) gas phase diffusion of oxygen. A reaction model based on the empirical equivalent circuit is introduced and analyzed using the impedance spectra. The electrode resistance at high frequency (Rc,HF) in the impedance spectra represents reaction steps (i), due to its fast reaction rate. The electrode resistance at high frequency is independent of p(O2) at a constant temperature because the semicircle of Rc,HF in the complex plane of the impedance spectra is held constant for different values of p(O2). Reaction steps (ii) and (iii) are the dominant processes for a MIEC cathode, according to the analysis results. The proposed cathode reaction model and results for a solid oxide fuel cell (SOFC) well describe a MIEC cathode with high ionic conductivity, and assist the understanding of the MIEC cathode reaction mechanism.  相似文献   

2.
A cobalt-free Ba0.5Sr0.5Fe0.9Ni0.1O3−δ–Sm0.2Ce0.8O1.9 (BSFN–SDC) composite was employed as a cathode for proton-conducting solid oxide fuel cells (H-SOFCs) using BaZr0.1Ce0.7Y0.2O3−δ (BZCY) as the electrolyte. The chemical compatibility between BSFN and SDC was evaluated. The XRD results showed that BSFN was chemically compatible with SDC after co-fired at 1100 °C for 5 h. The thermal expansion coefficient (TEC) of BSFN–SDC, which showed a reasonably reduced value (16.08 × 10−6 K−1), was effectively decreased due to Ce0.8Sm0.2O1.9 (SDC) added. A single cell of Ni–BZCY/Ni–BZCY/BZCY/BSFN–SDC with a 25-μm-thick BZCY electrolyte membrane exhibited excellent power densities as high as 361.8 mW cm−2 at 700 °C with a low polarization resistance of 0.174 Ω cm2. The excellent performance implied that the cobalt-free BSFN–SDC composite was a promising alternative cathode for H-SOFCs.  相似文献   

3.
We have studied a new composite SOFC cathode consisting of LaCo0.4Ni0.6O3−δ (LCN60) and Ce0.9Gd0.1O1.95 (CGO). The polarisation resistance (RP) at 750 °C and OCV was measured to 0.05 ± 0.01 Ω cm2 and the activation energy was determined to be about 1 eV. The impedance spectra were modelled with an EQC model consisting of a high frequency ZRQ circuit and a medium frequency Gerischer impedance, ZG. The resistance of ZG was found to decrease with approximately a factor of two as a consequence of infiltration of (La0.6Sr0.4)0.99CoO3 into the porous LCN60-CGO structure. RP of both infiltrated and non-infiltrated LCN60-CGO cathodes is substantially lower than that of LSM-YSZ and comparable with single phase LSC cathodes at low T due to its low EA. RP was also found to be stable at 750 °C and OCV. The cathodes were integrated onto ScYSZ based anode supported cells which were measured to have an ASR of 0.16-0.18 Ω cm2 at 750 °C.  相似文献   

4.
The mixed ionic and electronic conductors (MIEC) of La0.9Sr0.1Co0.8Ni0.2O3−δ (LSCN)-Ce0.8Sm0.2O1.9 (SDC) were investigated for potential application as a cathode material for solid oxide fuel cells (SOFCs) based on a SDC electrolyte. Electrochemical impedance spectroscopy (EIS) technique was performed over the temperature range of 600-850 °C to determine the cathode polarization resistance, which is represented by area specific resistance (ASR). This study systematically investigated the exchange current densities (i0) for oxygen reduction reaction (ORR), determined from the EIS data and high-field cyclic voltammetry. The 70LSCN-30SDC composite cathode revealed a high exchange current density (i0) value of 297.6 mA/cm2 at 800 °C determined by high-field technique. This suggested that the triple phase boundary (TPB) may spread over more surface of this composite cathode and revealing a high catalytically active surface area. The activation energies (Ea) of ORR determined from the slope of Arrhenius plots for EIS and high-field techniques are 96.9 kJ mol−1 and 90.4 kJ mol−1, respectively.  相似文献   

5.
This study investigates the microstructure and electrochemical properties of Sm0.5Sr0.5Co0.8Cu0.2O3−δ (SSC-Cu) cathode infiltrated with Ce0.8Sm0.2O1.9 (SDC). The newly formed nanosized electrolyte material on the cathode surface, leading the increase in electrochemical performances is mainly attributed to the creation of electrolyte/cathode phase boundaries, which considerably increases the electrochemical sites for oxygen reduction reaction. Based on the experiment results, the 0.4 M SDC infiltration reveals the lowest cathode polarization resistance (RP), the cathode polarization resistances (Rp) are 0.117, 0.033, and 0.011 Ω cm2 at 650, 750, and 850 °C, and the highest peak power density, are 439, 659, and 532 mW cm−2 at 600, 700, and 800 °C, respectively. The cathode performance in SOFCs can be significantly improved by infiltrating nanoparticles of SDC into an SSC-Cu porous backbone. This study reveals that the infiltration approach may apply in SOFCs to improve their electrochemical properties.  相似文献   

6.
A nanocrystalline powder with a lanthanum based iron- and cobalt-containing perovskite, La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF), is investigated for solid oxide fuel cell (SOFC) applications at a relatively low operating temperature (600-800 °C). A LSCF powder with a high surface area of 88 m2 g−1, which is synthesized via a complex method with using inorganic nano dispersants, is printed onto an anode supported cell as a cathode electrode. A LSCF cathode without a sintering process (in situ sintered cathode) is characterized and compared with that of a sintering process at 780 °C (ex situ sintered cathode). The in situ sintered SOFC shows 0.51 A cm−2 at 0.9 V and 730 °C, which is comparable with that of the ex situ sintered SOFC. The conventional process for SOFCs, the ex situ sintered SOFC, including a heat treatment process after printing the cathodes, is time consuming and costly. The in situ sinterable nanocrystalline LSCF cathode may be effective for making the process simple and cost effective.  相似文献   

7.
Perovskite Ba0.5Sr0.5Co0.8Fe0.1Ni0.1O3-δ (BSCFNi) oxide is synthesized and characterized as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The X-ray diffraction (XRD) spectra show that BSCFNi is chemical compatible with La0.9Sr0.1Ga0.83Mg0.17O2.865(LSGM) electrolyte below 950 °C, but weak reaction is observed between BSCFNi cathode and Sm0.2Ce0.8O1.9 (SDC) electrolyte after calcined at 950 °C for 10 h. The XPS results indicate that transition metal cations in BSCFNi sample exist two different valence states, i.e., Co4+/3+, Fe4+/3+ and Ni3+/2+. The average thermal expansion coefficient (TEC) of BSCFNi is 18.7 × 10?6 K?1 between 200 °C and 850 °C in air. The maximum electrical conductivity reaches 35.3 Scm?1 at 425 °C in air. The polarization resistance of BSCFNi cathode on LSGM and SDC electrolytes are 0.033 and 0.066 Ωcm2 at 800 °C, respectively. The maximum power density of LSGM electrolyte-supported single cell with BSCFNi cathode reaches 690 mWcm?2 at 800 °C. These primarily results indicate that BSCFNi is a candidate cathode material for IT-SOFCs.  相似文献   

8.
Solution impregnated La0.8Sr0.2Co0.8Ni0.2O3 + Gd-doped CeO2 (LSCN + GDC) cathodes for intermediate temperature solid oxide fuel cells (IT-SOFC) are prepared and their electrochemical properties are evaluated and compared with the conventional LSCN cathodes. The results indicate that the cathode performance can be enhanced by the presence of the nanosized microstructure produced with the solution impregnation method. It is determined that the amount of LSCN loading in the LSCN + GDC composite cathode needs to be higher than 35 wt% in order to achieve a performance superior to that of the conventional LSCN cathode. The optimum amount of LSCN loading is in the range of 45-55 wt% with an activation energy near 1.32 eV for oxygen reduction. At temperatures between 600 and 750 °C, the polarization resistance of the 55 wt% LSCN loaded LSCN + GDC cathode is in the range of 1.07 and 0.08 Ω cm2, which is only about one half of that for the conventional cathode.  相似文献   

9.
LaCo0.6Ni0.4O3−δ (LCN64) was prepared through the polymeric steric entrapment precursor route with Polyvinyl alcohol (PVA) as the entrapment agent and was evaluated as a contact material between the metallic interconnect and the cathode in planar intermediate temperature solid oxide fuel cell stacks (IT-SOFC). The ratio of PVA to metal nitrates and the calcination temperature of the precursor were optimized for the process. The electrical conductivity and thermal expansion coefficient (TEC) of the synthesized LCN64 and its chemical compatibility with SUS 430 were also characterized. The results indicate that 1:4 is a proper ratio of PVA to metal nitrates for process control and safety management; and calcination of the precursor at temperatures above 650 °C leads to formation of single perovskite phase LCN64. The conductivity of fully sintered LCN64 is above 1150 S cm−1 in the temperature range between 100 °C and 800 °C, which is higher than those of conventional contact materials La1−xSrxMnO3 (LSM) and LaNiyFe1−yO3 (LNF). The average TEC is 17.22 × 10−6 K−1 at temperatures below 900 °C, which is higher than those of the metallic interconnect and cell components. Mn and Cr elements contained in SUS 430 migrated into the porous LCN64 layer at 800 °C without chemically forming resistive phases.  相似文献   

10.
Lanthanum-based iron- and cobalt-containing perovskite is a promising cathode material because of its electrocatalytic activity at a relatively low operating temperature in solid oxide fuel cells (SOFCs), i.e., 700-800 °C. To enhance the electrocatalytic reduction of oxidants on La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF), nanocrystalline LSCF materials are successfully fabricated using a complexing method with chelants and inorganic nano dispersants. When inorganic dispersants are added to the synthesis process, the surface area of the LSCF powder increases from 18 to 88 m2 g−1, which results in higher electrocatalytic activity of the cathode. The performance of a unit cell of a SOFC with nanocrystalline LSCF powders synthesized with nano dispersants is increased by 60%, from 0.7 to 1.2 W cm−2.  相似文献   

11.
A Sm0.5Sr0.5CoO3−δ-Ce0.8Sm0.2O2−δ (SSC-SDC) composite is employed as a cathode for proton-conducting solid oxide fuel cells (H-SOFCs). BaZr0.1Ce0.7Y0.2O3−δ (BZCY) is used as the electrolyte, and the system exhibits a relatively high performance. An extremely low electrode polarization resistance of 0.066 Ω cm2 is achieved at 700 °C. The maximum power densities are: 665, 504, 344, 214, and 118 mW cm−2 at 700, 650, 600, 550, and 500 °C, respectively. Moreover, the SSC-SDC cathode shows an essentially stable performance for 25 h at 600 °C with a constant output voltage of 0.5 V. This excellent performance implies that SSC-SDC, which is a typical cathode material for SOFCs based on oxide ionic conductor, is also a promising alternative cathode for H-SOFCs.  相似文献   

12.
Porous La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) cathodes are coated with a thin film of Sm0.2Ce0.8O1.95−δ (SDC) using a one-step infiltration process. Examination of the microstructures reveals that small SDC particles are formed on the surface of LSCF grains with a relatively narrow size distribution. Impedance analysis indicates that the SDC infiltration has dramatically reduced the polarization of LSCF cathode, reaching interfacial resistances of 0.074 and 0.44 Ω cm2 at 750 °C and 650 °C, respectively, which are about half of those for LSCF cathode without infiltration of SDC. The activation energies of the SDC infiltrated LSCF cathodes are in the range of 1.42-1.55 eV, slightly lower than those for a blank LSCF cathode. The SDC infiltrated LSCF cathodes have also shown improved stability under typical SOFC operating conditions, suggesting that SDC infiltration improves not only power output but also performance stability and operational life.  相似文献   

13.
The perovskite La0.6Sr0.4Co0.8Cu0.2O3−δ (LSCCu) oxide is synthesized by a modified Pechini method and examined as a novel cathode material for low-temperature solid oxide fuel cells (LT-SOFCs) based upon functional graded anode. The perovskite LSCCu exhibits excellent ionic and electronic conductivities in the intermediate-to-low-temperature range (400-800 °C). Thin Sm0.2Ce0.8O1.9 (SDC) electrolyte and NiO-SDC anode functional layer are prepared over macroporous anode substrates composed of NiO-SDC by a one-step dry-pressing/co-firing process. A single cell with 20 μm thick SDC electrolyte on a porous anode support and LSCCu-SDC cathode shows peak power densities of only 583.2 mW cm−2 at 650 °C and 309.4 mW cm−2 for 550 °C. While a cell with 20 μm thick SDC electrolyte and an anode functional layer on the macroporous anode substrate shows peak power densities of 867.3 and 490.3 mW cm−2 at 650 and 550 °C, respectively. The dramatic improvement of cell performance is attributed to the much improved anode microstructure that is confirmed by both SEM observation and impedance spectroscopy. The results indicate that LSCCu is a very promising cathode material for LT-SOFCs and the one-step dry-pressing/co-firing process is a suitable technique to fabricate high performance SOFCs.  相似文献   

14.
The Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) cathode for solid oxide fuel cell has been prepared by glycine–nitrate combustion process. Crystal structure and chemical state of BSCF have been studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). XRD pattern indicates that a single cubic perovskite phase of BSCF oxide is successfully obtained after calcination at 850 °C for 2 h. XPS results show there exists a little amount of SrCO3 in the surface of BSCF. Co2p spectra indicate that some Co3+ ions have changed into Co4+ ions to maintain the electrical neutrality. O1s spectra present that adsorbed oxygen species appear in the surface BSCF oxide.  相似文献   

15.
Thermochemical compatibilities with Ce0.8Gd0.2O2−δ (GDC) electrolyte and electrochemical behaviors under the condition of anodic or cathodic current treatment are investigated for La0.8Sr0.2Co0.8Ni0.2O3−δ (LSCN) cathode of solid oxide fuel cell (SOFC). X-ray diffractometer (XRD) shows that cation exchange at 1150 °C leads to the formation of solid state solution between the cathode and electrolyte. Considering thermal expansion coefficient (TEC) and conductivity, La1−xSrxCo1−yNiyO3−δ with the composition of La0.8Sr0.2Co0.8Ni0.2O3−δ is indicated as a promising cathode for intermediate temperature SOFC. Electrochemical measurement reveals that the performance of LSCN cathode shows reversibility under anodic with subsequent cathodic current treatment. Further, the low frequency electrode process is strongly affected by anodic current. While the high frequency arc shows independent relationship with current polarization.  相似文献   

16.
The electrochemical properties of an Sm0.5Sr0.5CoO3−δ/Co3O4 (SSC/Co3O4) composite cathode were investigated as a function of the cathode-firing temperature, SSC/Co3O4 composition, oxygen partial pressure and CO2 treatment. The results showed that the composite cathodes had an optimal microstructure at a firing temperature of about 1100 °C, while the optimum Co3O4 content in the composite cathode was about 40 wt.%. A single cell with this optimized C40-1100 cathode exhibited a very low polarization resistance of 0.058 Ω cm2, and yielded a maximum power density of 1092 mW cm−2 with humidified hydrogen fuel and air oxidant at 600 °C. The maximum power density reached 1452 mW cm−2 when pure oxygen was used as the oxidant for a cell with a C30-1100 cathode operating at 600 °C due to the enhanced open-circuit voltage and accelerated oxygen surface-exchange rate. X-ray diffraction and thermogravimetric analyses, as well as the electrochemical properties of a CO2-treated cathode, also implied promising applications of such highly efficient SSC/Co3O4 composite cathodes in single-chamber fuel cells with direct hydrocarbon fuels operating at temperatures below 500 °C.  相似文献   

17.
The properties and performance of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) + Sm0.2Ce0.8O1.9 (SDC) (70:30 in weight ratio) composite cathode for intermediate-temperature solid-oxide fuel cells were investigated. Mechanical mixing of BSCF with SDC resulted in the adhesion of fine SDC particles to the surface of coarse BSCF grains. XRD, SEM-EDX and O2-TPD results demonstrated that the phase reaction between BSCF and SDC was negligible, constricted only at the BSCF and SDC interface, and throughout the entire cathode with the formation of new (Ba,Sr,Sm,Ce)(Co,Fe)O3−δ perovskite phase at a firing temperature of 900, 1000, and ≥ 1050 °C, respectively. The BSCF + SDC electrode sintered at 1000 °C showed an area specific resistance of ∼0.064 Ω cm2 at 600 °C, which is a slight improvement over the BSCF (0.099 Ω cm2) owing to the enlarged cathode surface area contributed from the fine SDC particles. A peak power density of 1050 and ∼382 mW cm−2 was reached at 600 and 500 °C, respectively, for a thin-film electrolyte cell with the BSCF + SDC cathode fired from 1000 °C.  相似文献   

18.
A cobalt-free composite Sm0.5Sr0.5Fe0.8Cu0.2O3−δ-Ce0.8Sm0.2O2−δ (SSFCu-SDC) is investigated as a cathode for proton-conducting solid oxide fuel cells (H-SOFCs) in intermediate temperature range, with BaZr0.1Ce0.7Y0.1Yb0.1O3−δ (BZCYYb) as the electrolyte. The XRD results show that SSFCu is chemically compatible with SDC at temperatures up to 1100 °C. The quad-layer single cells of NiO-BZCYYb/NiO-BZCYYb/BZCYYb/SSFCu-SDC are operated from 500 to 700 °C with humidified hydrogen (∼3% H2O) as fuel and the static air as oxidant. It shows an excellent power density of 505 mW cm−2 at 700 °C. Moreover, a low electrode polarization resistance of 0.138 Ω cm2 is achieved at 700 °C. Preliminary results demonstrate that the cobalt-free SSFCu-SDC composite is a promising cathode material for H-SOFCs.  相似文献   

19.
Mixed rare-earth (La, Pr)0.8Sr0.2FeO3−δ–Sm0.2Ce0.8O2−δ (LPSF–SDC) composite cathode was investigated for proton-conducting solid oxide fuel cells based on protonic BaZr0.1Ce0.7Y0.2O3−δ (BZCY) electrolyte. The powders of La0.8−xPrxSr0.2FeO3−δ (x = 0, 0.2, 0.4, 0.6), Sm0.2Ce0.8O2−δ (SDC) and BaZr0.1Ce0.7Y0.2O3−δ (BZCY) were synthesized by a citric acid-nitrates self-propagating combustion method. The XRD results indicate that La0.8−xPrxSr0.2FeO3−δ samples calcined at 950 °C exhibit perovskite structure and there are no interactions between LPSF0.2 and SDC at 1100 °C. The average thermal expansion coefficient (TEC) of LPSF0.2–SDC, BZCY and NiO-BZCY is 12.50 × 10−6 K−1, 13.51 × 10−6 K−1 and 13.47 × 10−6 K−1, respectively, which can provide good thermal compatibility between electrodes and electrolyte. An anode-supported single cell of NiO-BZCY|BZCY|LPSF0.2–SDC was successfully fabricated and operated from 700 °C to 550 °C with humidified hydrogen (∼3% H2O) as fuel and the static air as oxidant. A high maximum power density of 488 mW cm−2, an open-circuit potential of 0.95 V, and a low electrode polarization resistance of 0.071 Ω cm2 were achieved at 700 °C. Preliminary results demonstrate that LPSF0.2–SDC composite is a promising cathode material for proton-conducting solid oxide fuel cells.  相似文献   

20.
Perovskite structure Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) and La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) powders have been successfully synthesized by glycine–nitrate combustion process. A porous and crack-free BSCF cathode is obtained by spraying the slurry of BSCF powders and terpineol onto LSGM pellet. The oxygen reduction reaction mechanism has been investigated by AC impedance spectroscopy and cyclic voltammetry method. AC impedance spectroscopy analysis shows that there are two different processes in the cathode reaction which are related to oxygen dissociation/adsorption and bulk oxygen diffusion. And the molecular oxygen is involved in the rate-determining step. The polarization resistance decreases with an increase of temperature and the oxygen partial pressure. With an increase of the applied DC bias, the logarithm of the polarization resistance decreases linearly due to additional oxygen vacancies and the lowered chemical potential of oxygen at the BSCF/LSGM interface by the applied voltage. The exchange current density reaches to 182 mA cm−2 at 700 °C, suggesting that the ORR kinetics at the BSCF/LSGM interface is high due to the excellent mixed ionic and electronic conductivity of BSCF.  相似文献   

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