Characteristics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ–La0.9Sr0.1Ga0.8Mg0.2O3−δ composite cathode for solid oxide fuel cell

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ–La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ composite cathodes are prepared successfully using combustion synthesis method. Microstructure, chemical compatibility and electrochemical performance have been investigated and analyzed in detail. SEM micrographs show that a structure with porosity and well-necked particles forms after sintering at 1000 °C in the composites. Grain growth is suppressed by addition of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ phase and grain sizes decrease with increasing weight percent of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ phase in the composites. Phase analysis demonstrates that chemical compatibility between Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ and La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ is excellent when the weight percent of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ in the composite is not more than 40%. Through fitting ac impedance spectra, it is found that the ohmic resistance and polarization resistance decrease with increasing La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ content. The polarization resistance reaches a minimum at about 30 and 40 wt.% La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ in the composite.     

Performance of solid oxide electrolysis cells based on composite La0.8Sr0.2MnO3−δ – yttria stabilized zirconia and Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen electrodes

The electrochemical performance of solid oxide electrolysis cells (SOECs) having barium strontium cobalt ferrite (Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ) and composite lanthanum strontium manganite–yttria stabilized zirconia (La_0.8Sr_0.2MnO_3−δ–YSZ) oxygen electrodes has been studied over a range of operating conditions. Increasing the operating temperature (973 K to 1173 K) significantly increased electrochemical performance and hydrogen generation efficiency for both systems. The presence of water in the hydrogen electrode was found to have a marked positive effect on the EIS response of solid oxide cell (SOC) under open circuit voltage (OCV). The difference in operation between electrolytic and galvanic modes was investigated. Cells having BSCF oxygen electrodes (Ni–YSZ/YSZ/BSCF) showed greater performance than LSM-YSZ-based cells (Ni–YSZ/YSZ/LSM-YSZ) over the range of temperatures, in both galvanic and electrolytic regimes of operation. The area specific resistance (ASR) of the LSM-YSZ-based cells remained unchanged when transitioning between electrolyser and fuel cell modes; however, the BSCF cells exhibited an overall increase in cell ASR of ∼2.5 times when entering electrolysis mode.     

Oxygen reduction mechanism at Ba0.5Sr0.5Co0.8Fe0.2O3−δ cathode for solid oxide fuel cell

Perovskite structure Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) and La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−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.     

X-ray photoelectron spectroscopic studies of Ba0.5Sr0.5Co0.8Fe0.2O3−δ cathode for solid oxide fuel cells

The Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−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.     

Ceria interlayer-free Ba0.5Sr0.5Co0.8Fe0.2O3−δ–Sc0.1Zr0.9O1.95 composite cathode on zirconia based electrolyte for intermediate temperature solid oxide fuel cells

We synthesized Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) powders with a primary particle size of 20 nm using a Pechini type method. By using nanocrystalline BSCF powders, we were able to fabricate a ceria interlayer-free nanoporous cathode on a scandia stabilized zirconia (ScSZ) electrolyte at low temperatures. Cathodes sintered below 750 °C lacked sufficient mechanical adhesion to the electrolyte, while electrode was well adhered to the electrolyte when fired at 800 °C. The symmetrical BSCF-ScSZ|yttria stabilized zirconia (YSZ)|BSCF-ScSZ half-cell that we generated had an exceptionally low polarization resistance of 0.06 Ω·cm² at 700 °C. The maximum power density of the BSCF-ScSZ|ScSZ|Ni-ScSZ unit cell was over 1 W cm⁻² at 700 °C. We investigated the durability of the BSCF-ScSZ composite cathode by 30 thermo-cycles performed by varying the temperature from 200 to 700 °C. The polarization resistance after the test remained low at less than 0.08 Ω·cm².     

Cobalt-free oxide Ba0.5Sr0.5Fe0.8Cu0.2O3−δ for proton-conducting solid oxide fuel cell cathode

A cobalt-free perovskite oxide Ba_0.5Sr_0.5Fe_0.8Cu_0.2O_3−δ (BSFC) is employed as a cathode material for intermediate-temperature proton-conducting solid oxide fuel cells. Symmetrical electrochemical cell with the configuration of BSFC-BZCY/BZCY/BSFC-BZCY is applied for the impedance study. The single cell, consisting of BSFC-BZCY/BZCY/NiO-BZCY structure, is assembled and tested from 600 to 700 °C with humidified hydrogen (∼3% H₂O) as the fuel and the static air as the oxidant. A maximum power density of 430 mW cm⁻² is obtained at 700 °C for the single cell. Long-term stability of the BSFC-BZCY/BZCY/NiO-BZCY single cell at 600 °C for 40 h has also been studied. Preliminary results demonstrat that cobalt-free oxide BSFC is a very promising cathode for application in proton-conducting solid oxide fuel cells.     

Evaluation of Ba0.5Sr0.5Co0.8Fe0.2O3−δ as a potential cathode for an anode-supported proton-conducting solid-oxide fuel cell

The potential application of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) as a cathode for a proton-conducting solid-oxide fuel cell based on BaCe_0.9Y_0.1O_2.95 (BCY) electrolyte was investigated. Cation diffusion from BCY to BSCF with the formation of a perovskite-type Ba²⁺-enriched BSCF and a Ba²⁺-deficient BCY at a firing temperature as low as 900 °C was observed, the higher the firing temperature the larger deviation of the A to B ratio from unit for the perovskites. Symmetric cell tests demonstrated the impurity phases did not induce a significant change of the cathodic polarization resistance, however, the ohmic resistance of the cell increased obviously. Anode-supported cells with the electrolyte thickness of ∼50 μm were successfully fabricated via a dual-dry pressing process for the single-cell test. Under optimized conditions, a maximum peak power density of ∼550 and 100 mW cm⁻² was achieved at 700 and 400 °C, respectively, for the cell with the BSCF cathode layer fired from 950 °C. At 500 °C, the ohmic resistance is still the main source of cell resistance. A further reduction in membrane thickness would envisage an increase in power density significantly.     

Development of La0.6Sr0.4Co0.2Fe0.8O3−δ cathode with an improved stability via La0.8Sr0.2MnO3-film impregnation

Uniform, dense and continuous coatings of La_0.8Sr_0.2MnO_3−δ (LSM) have been successfully deposited on dense/porous La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) substrates via a one-step drop-coating process using a water-based solution in order to improve the operating stability of solid oxide fuel cell cathode. The processing conditions were optimized by precise control of the composition of infiltrating solution, including chelating agents (glycine, citric acid and ethylene glycol), surfactants (polyvinyl alcohol (PVA), polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP)) and pH values (5.25, 4.29, 3.01 and 2.09). Ethanol was found to improve the wetting ability of the water-based solution significantly, but unfortunately causing precipitation. The symmetrical and full cells tests demonstrated that both performance and stability of LSCF cathode can be enhanced by surface modification with an optimized LSM film coating, leading to ∼31% reduction in cathodic polarization resistance and ∼45% improvement in power density (without observable degradation) for almost 350 h operation at 750 °C under a constant voltage of 0.7 V.     

Palladium and ceria infiltrated La0.8Sr0.2Co0.5Fe0.5O3−δ cathodes of solid oxide fuel cells

La_0.8Sr_0.2Co_0.5Fe_0.5O_3−δ (LSCF) cathodes infiltrated with electrocatalytically active Pd and (Gd,Ce)O₂ (GDC) nanoparticles are investigated as high performance cathodes for the O₂ reduction reaction in intermediate temperature solid oxide fuel cells (IT-SOFCs). Incorporation of nano-sized Pd and GDC particles significantly reduces the electrode area specific resistance (ASR) as compared to the pure LSCF cathode; ASR is 0.1 Ω cm² for the reaction on a LSCF cathode infiltrated with 1.2 mg cm⁻² Pd and 0.06 Ω cm² on a LSCF cathode infiltrated with 1.5 mg cm⁻² GDC at 750 °C, which are all significantly smaller than 0.22 Ω cm² obtained for the reaction on a conventional LSCF cathode. The activation energy of GDC- and Pd-impregnated LSCF cathodes is 157 and 176 kJ mol⁻¹, respectively. The GDC-infiltrated LSCF cathode has a lower activation energy and higher electrocatalytic activity for the O₂ reduction reaction, showing promising potential for applications in IT-SOFCs.     

Characteristics of nano La0.6Sr0.4Co0.2Fe0.8O3−δ-infiltrated La0.8Sr0.2Ga0.8Mg0.2O3−δ scaffold cathode for enhanced oxygen reduction

The chemical compatibility and electrochemical properties of nanoLa_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)-infiltrated La_0.8Sr_0.2Ga_0.8Mg_0.2O_3−δ (LSGM) scaffold were manufactured and assessed for the application as a solid oxide fuel cell cathode with an LSGM electrolyte. When the LSCF and LSGM powder mixture was fired above 950 °C, the characteristic peaks of the two materials merged and an insulation peak (derived from LaSrGaO₄) was observed. To prevent reactions between LSCF and LSGM, an infiltration technique was utilized with the LSGM as a scaffold. Using this infiltration technique, nano LSCF particles (approximately 100 nm) can be uniformly coated on the LSGM scaffold surface. Good nano particle adhesion was observed at the LSGM/LSCF interface, even at relatively low firing temperatures (850 °C). The cathode polarization resistance (R_p) of the nano LSCF infiltrated LSGM scaffold cathode was lower than that of a conventional LSCF cathode. The improvement in performance of the nano LSCF-infiltrated cathode was attributed to an increase in the number of triple phase boundaries (TPB) as a result of the nano LSCF coating. In addition, the oxygen reduction reaction (ORR) paths were extended from the TPBs to the LSCF surface because LSCF particles are considerably smaller than the LSCF oxygen ion penetration depth (3–4 μm) over the temperature range of 700 °C–800 °C.     

Preparation and characterization of Ba0.5Sr0.5Fe0.9Ni0.1O3−δ–Sm0.2Ce0.8O1.9 compose cathode for proton-conducting solid oxide fuel cells

A cobalt-free Ba_0.5Sr_0.5Fe_0.9Ni_0.1O_3−δ–Sm_0.2Ce_0.8O_1.9 (BSFN–SDC) composite was employed as a cathode for proton-conducting solid oxide fuel cells (H-SOFCs) using BaZr_0.1Ce_0.7Y_0.2O_3−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 Ce_0.8Sm_0.2O_1.9 (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.     

Properties and performance of Ba0.5Sr0.5Co0.8Fe0.2O3−δ + Sm0.2Ce0.8O1.9 composite cathode

The properties and performance of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) + Sm_0.2Ce_0.8O_1.9 (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)O_3−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.     

La0.6Sr0.4Fe0.8Cu0.2O3−δ perovskite oxide as cathode for IT-SOFC

A La_0.6Sr_0.4Fe_0.8Cu_0.2O_3−δ (LSFCu) perovskite was investigated as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFC). The LSFCu material exhibited chemical compatibility with the Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte up to a temperature of 1100 °C. The electrical conductivity of the sintered sample was measured as a function of temperature from 100 to 800 °C. The highest conductivity of about 238 S cm⁻¹ was observed for LSFCu. The average thermal-expansion coefficient (TEC) of LSFCu was 14.6 × 10⁻⁶ K⁻¹, close to that of typical CeO₂ electrolyte material. The investigation of electrical properties indicated that the LSFCu cathode had lower interfacial polarization resistance of 0.070 Ω cm² at 800 °C and 0.138 Ω cm² at 750 °C in air. An electrolyte-supported single cell with 300 μm thick SDC electrolyte and LSFCu as cathode shows peak power densities of 530 mW cm⁻² at 800 °C.     

Silver-modified Ba0.5Sr0.5Co0.8Fe0.2O3−δ as cathodes for a proton conducting solid-oxide fuel cell

Electrochemical performance of silver-modified Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF-Ag) as oxygen reduction electrodes for a protonic intermediate-temperature solid-oxide fuel cell (SOFC-H⁺) with BaZr_0.1Ce_0.8Y_0.1O₃ (BZCY) electrolyte was investigated. The BSCF-Ag electrodes were prepared by impregnating the porous BSCF electrode with AgNO₃ solution followed by reducing with hydrazine and then firing at 850 °C for 1 h. The 3 wt.% silver-modified BSCF (BSCF-3Ag) electrode showed an area specific resistance of 0.25 Ω cm² at 650 °C in dry air, compared to around 0.55 Ω cm² for a pure BSCF electrode. The activation energy was also reduced from 119 kJ mol⁻¹ for BSCF to only 84 kJ mol⁻¹ for BSCF-3Ag. Anode-supported SOFC-H⁺ with a BZCY electrolyte and a BSCF-3Ag cathode was fabricated. Peak power density up to 595 mW cm⁻² was achieved at 750 °C for a cell with 35 μm thick electrolyte operating on hydrogen fuel, higher than around 485 mW cm⁻² for a similar cell with BSCF cathode. However, at reduced temperatures, water had a negative effect on the oxygen reduction over BSCF-Ag electrode, as a result, a worse cell performance was observed for the cell with BSCF-3Ag electrode than that with pure BSCF electrode at 600 °C.     

Electrochemical performance of novel cobalt-free oxide Ba0.5Sr0.5Fe0.8Cu0.2O3−δ for solid oxide fuel cell cathode

A novel cobalt-free perovskite oxide Ba_0.5Sr_0.5Fe_0.8Cu_0.2O_3−δ (BSFC) is employed as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The electrical conductivity of BSFC reaches the maximum value of 57 S cm⁻¹ at 600 °C. Symmetrical electrochemical cell with the configuration of BSFC/SDC/BSFC is applied for the impedance study and area specific resistance (ASR) of BSFC cathode material is as low as 0.137 Ω cm² at 700 °C. The single cell, consisting of BSFC/SDC/NiO-SDC structure, is assembled and tested from 550 to 700 °C with humidified hydrogen (∼3% H₂O) as the fuel and the static air as the oxidant. A maximum power density of 718 mW cm² is obtained at 700 °C for the single cell. Preliminary results demonstrate that the cobalt-free oxide BSFC is a very promising cathode material for application in IT-SOFCs.     

Investigation of cobalt-free cathode material Sm0.5Sr0.5Fe0.8Cu0.2O3−δ for intermediate temperature solid oxide fuel cell

A cobalt-free cubic perovskite oxide Sm_0.5Sr_0.5Fe_0.8Cu_0.2O_3−δ (SSFCu) was investigated as a novel cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). The thermal expansion coefficient (TEC) of SSFCu was close to that of Sm_0.2Ce_0.8O_1.9(SDC) electrolyte and the electrical conductivity of SSFCu sample reached 72–82 S cm⁻¹ in the commonly operated temperatures of IT-SOFCs (400–600 °C). Symmetrical electrochemical cell with the configuration of SSFCu/SDC/SSFCu was applied for the impedance study and area specific resistance (ASR) of SSFCu cathode material was as low as 0.085 Ω cm² at 700 °C. Laboratory-sized tri-layer cells of NiO-SDC/SDC/SSFCu were operated from 450 to 700 °C with humidified hydrogen (∼3% H₂O) as fuel and the static air as oxidant. A maximum power density of 808 mW cm² was obtained at 700 °C for the single cell.     

In situ sinterable cathode with nanocrystalline La0.6Sr0.4Co0.2Fe0.8O3−δ for solid oxide fuel cells

A nanocrystalline powder with a lanthanum based iron- and cobalt-containing perovskite, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−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.     

Fabrication and characterization of Sm0.2Ce0.8O2−δ-Sm0.5Sr0.5CoO3−δ composite cathode for anode supported solid oxide fuel cell

The Sm_0.5Sr_0.5CoO_3−δ (SSC) with perovskite structure is synthesized by the glycine nitrate process (GNP). The phase evolution of SSC powder with different calcination temperatures is investigated by X-ray diffraction and thermogravimetric analyses. The XRD results show that the single perovskite phase of the SSC is completely formed above 1100 °C. The anode-supported single cell is constructed with a porous Ni-yttria-stabilized zirconia (YSZ) anode substrate, an airtight YSZ electrolyte, a Sm_0.2Ce_0.8O_2−δ (SDC) barrier layer, and a screen-printed SSC-SDC composite cathode. The SEM results show that the dense YSZ electrolyte layer exhibits the good interfacial contact with both the Ni-YSZ and the SDC barrier layer. The porous SSC-SDC cathode shows an excellent adhesion with the SDC barrier layer. For the performance test, the maximum power densities are 464, 351 and 243 mW cm⁻² at 800, 750 and 700 °C, respectively. According to the results of the electrochemical impedance spectroscopy (EIS), the charge-transfer resistances of the electrodes are 0.49 and 1.24 Ω cm², and the non charge-transfer resistances are 0.48 and 0.51 Ω cm² at 800 and 700 °C, respectively. The cathode material of SSC is compatible with the YSZ electrolyte via a delicate scheme employed in the fabrication process of unit cell.     

Cathode reaction mechanism of porous-structured Sm0.5Sr0.5CoO3−δ and Sm0.5Sr0.5CoO3−δ/Sm0.2Ce0.8O1.9 for solid oxide fuel cells

The cathode reaction mechanism of porous Sm_0.5Sr_0.5CoO_3−δ, a mixed ionic and electronic conductor (MIEC), is studied through a comparison with the composite cathode Sm_0.5Sr_0.5CoO_3−δ/Sm_0.2Ce_0.8O_1.9. First, the cathodic behaviour of porous Sm_0.5Sr_0.5CoO_3−δ and Sm_0.5Sr_0.5CoO_3−δ/Sm_0.2Ce_0.8O_1.9 are observed for micro-structure and impedance spectra according to Sm_0.2Ce_0.8O_1.9 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 (R_c,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 R_c,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.