Synthesis and characterization of hierarchical porous LiNiCuZn-oxides as potential electrode materials for low temperature solid oxide fuel cells

Low temperature, 300–600 °C solid oxide fuel cell (LTSOFC) is one of the hot areas in recent fuel cell development. In order to develop high performance LTSOFCs, compatible electrodes are highly demanded. In this work, a lithium transition metal oxide electrode material with hierarchical porous structure was synthesized. The phase structure was analysed by XRD and microstructure was studied by SEM. The as-synthesized material was constructed to devices using the SDC (samarium doped ceria)-carbonate nanocomposite (NSDC) as the electrolyte to test the OCV (open circuit voltage), which indicates good catalytic performance for H₂ at 600 °C.     

Performance of fuel cells with proton-conducting ceria-based composite electrolyte and nickel-based electrodes

A ceria-based composite electrolyte with the composition of Ce_0.8Sm_0.2O_1.9 (SDC)–30 wt.% (2Li₂CO₃:1Na₂CO₃) is developed for intermediate temperature fuel cells (ITFCs). Two kinds of SDC powders are used to prepare the composite electrolytes, which are synthesized by oxalate coprecipitation process and glycine–nitrate process, respectively, and denoted as SDC(OCP) and SDC(GNP). Based on each composite electrolyte, two single cells with the electrolyte thickness of 0.3 and 0.5 mm are fabricated by dry-pressing technique, using nickel oxide as anode and lithiated nickel oxide as cathode, respectively. With H₂ as fuel and air as oxidant, all the four cells exhibit excellent performances at 400–600 °C, which can be attributed to the highly ionic conducting electrolyte and the compatible electrodes. The cell performance is influenced by the SDC morphology and the electrolyte thickness. More interestingly, such composite electrolytes are found to be proton conductors at intermediate temperature range for the first time since almost all water is observed at the cathode side during fuel cell operation for all cases. The unusual transport property, excellent cell performance and potential low cost make this kind of composite material a good candidate electrolyte for future cost-effective ITFCs.     

Electrical properties of SDC–BCY composite electrolytes for intermediate temperature solid oxide fuel cell

The electrolyte material Ce_0.85Sm_0.15O_1.92 (SDC) powders are synthesized by glycine–nitrate processes and BaCe_0.83Y_0.17O_3−δ (BCY) powders are synthesized by sol–gel processes, respectively. Then SDC–BCY composite electrolytes are prepared by mixing SDC and BCY. The SDC and BCY powders are mixed in the weight ratio of 95:5, 90:10 and 85:15 and named as SB95, SB90 and SB85, respectively. The electrical properties of SDC and SDC–BCY composites are investigated. The experimental results show that SDC–BCY composites exhibit the excellent conductivity and could significantly enhance the fuel cell performances. The behavior that SDC–BCY composites display hybrid proton and oxygen ion conduction is substantiated. Among these electrolytes, the maximum power density reaches as high as 159 mW cm⁻² for the fuel cell based on SB90 composite electrolyte at 600 °C.     

Microwave synthesis of mesoporous Cu-Ce0.8Sm0.2O2−δ composite anode for low-temperature ceramic fuel cells

In recent year, new nanocomposite electrolytes materials have been developed for low-temperature ceramic fuel cells (CFCs). To further improve the performance of CFCs based on the nanocomposite electrolyte, compatible active anode with sufficient low polarizations is needed. To improve the performance of anode, i.e. to enlarge tripe phase boundaries (TPB), anode materials with both porous structure and phase homogeneity of metal and ceramic are preferred. In the present study, we developed a novel microwave-assisted template-, surfactant-free synthesis route for mesoporous CuO–Ce_0.8Sm_0.2O_2−δ composite anode by homogeneous precipitation of microspherical precursor in aqueous solutions followed by calcination. The composite anode sample was characterized by thermogravimetry analysis, X-ray diffraction, SEM, EDX, etc. The characterization results indicated that CuO–SDC composite anode with mesoporous structure was prepared and both SDC and CuO phases were homogenously distributed. Fuel cells have been constructed using as-prepared composite as anodes and lithiated NiO as cathode based on the SDC–carbonate nanocomposite electrolyte. Fuel cell performance tests indicated that the cell with mesoporous Cu–SDC anode had better performance than conventional Cu–SDC anode prepared by solid-state method.     

Preparation and characterization of nanocrystalline Ce0.8Sm0.2O1.9 for low temperature solid oxide fuel cells based on composite electrolyte

Nanocrystalline Ce_0.8Sm_0.2O_1.9 (SDC) has been synthesized by a combined EDTA–citrate complexing sol–gel process for low temperature solid oxide fuel cells (SOFCs) based on composite electrolyte. A range of techniques including X-ray diffraction (XRD), and electron microscopy (SEM and TEM) have been employed to characterize the SDC and the composite electrolyte. The influence of pH values and citric acid-to-metal ions ratios (C/M) on lattice constant, crystallite size and conductivity has been investigated. Composite electrolyte consisting of SDC derived from different synthesis conditions and binary carbonates (Li₂CO₃–Na₂CO₃) has been prepared and conduction mechanism is discussed. Water was observed on both anode and cathode side during the fuel cell operation, indicating the composite electrolyte is co-ionic conductor possessing H⁺ and O²⁻ conduction. The variation of composite electrolyte conductivity and fuel cell power output with different synthesis conditions was in accordance with that of the SDC originated from different precursors, demonstrating O²⁻ conduction is predominant in the conduction process. A maximum power density of 817 mW cm⁻² at 600 °C and 605 mW cm⁻² at 500 °C was achieved for fuel cell based on composite electrolyte.     

Effects of salt composition on the electrical properties of samaria-doped ceria/carbonate composite electrolytes for low-temperature SOFCs

Samaria-doped ceria (SDC)/carbonate composite electrolytes were developed for low-temperature solid oxide fuel cells (SOFCs). SDC powders were prepared by oxalate co-precipitation method and used as the matrix phase. Binary alkaline carbonates were selected as the second phase, including (Li–Na)₂CO₃, (Li–K)₂CO₃ and (Na–K)₂CO₃. AC conductivity measurements showed that the conductivities in air atmosphere depended on the salt composition. A sharp conductivity jump appeared at 475 °C and 450 °C for SDC/(Li–Na)₂CO₃ and SDC/(Li–K)₂CO₃, respectively. However, the conductivities of SDC/(Na–K)₂CO₃ increase linearly with temperature. Single cells based on above composite electrolytes were fabricated by dry-pressing and tested in hydrogen/air at 500–600 °C. A maximum power density of 600, 550 and 550 mW cm⁻² at 600 °C was achieved with SDC/(Li–Na)₂CO₃, SDC/(Li–K)₂CO₃ and SDC/(Na–K)₂CO₃ composite electrolyte, respectively, which we attribute to high ionic conductivities of these composite electrolytes in fuel cell atmosphere. We discuss the conduction mechanisms of SDC/carbonate composite electrolytes in different atmospheres according to defect chemistry theory.     

The effect of electrode infiltration on the performance of tubular solid oxide fuel cells under electrolysis and fuel cell modes

The electrochemical performance of two different anode supported tubular cells (50:50 wt% NiO:YSZ (yttria stabilized zirconia) or 34:66 vol.% Ni:YSZ) as the fuel electrode and YSZ as the electrolyte) under SOFC (solid oxide fuel cell) and SOEC (solid oxide electrolysis cell) modes were studied in this research. LSM (La_0.80Sr_0.20MnO_3−δ) was infiltrated into a thin porous YSZ layer to form the oxygen electrode of both cells and, in addition, SDC (Sm_0.2Ce_0.8O_1.9) was infiltrated into the fuel electrode of one of the cells. The microstructure of the infiltrated fuel cells showed a suitable distribution of fine LSM and SDC particles (50–100 nm) near the interface of electrodes and electrolyte and throughout the bulk of the electrodes. The results show that SDC infiltration not only enhances the electrochemical reaction in SOFC mode but improves the performance even more in SOEC mode. In addition, LSM infiltrated electrodes also boost the SOEC performance in comparison with standard LSM–YSZ composite electrodes, due to the well-dispersed LSM nanoparticles (favouring the electrochemical reactions) within the YSZ porous matrix.     

Study on BaCo0.7Fe0.2Nb0.1O3−δ—SDC composite cathodes for intermediate temperature solid oxide fuel cell

BaCo_0.7Fe_0.2Nb_0.1O_3−δ(BCFN)/Ce_0.8Sm_0.2O_1.9(SDC) composite material was prepared and characterized as cathode for intermediate temperature solid oxide fuel cells. The X-ray diffraction result proved that there was no obvious reaction between the BCFN and SDC after calcination at 1000 °C for 10 h. AC impedance spectra based on La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ(LSGM) electrolyte measured at intermediate temperatures showed that a cathode with 30 wt% SDC exhibited the best electrochemical performance among the electrodes studied. The interfacial resistance value for BCFN/30SDC was as low as 0.0104, 0.017, 0.029, and 0.062 Ω cm² at 800, 750, 700 and 650 °C, respectively. The maximum power density of a single cell with BCFN/30SDC cathode, Ni_0.9Cu_0.1-SDC anode, and LSGM/SDC electrolyte was 209.7, 298.2, 407.1, 543.4 and 697.9 mW cm⁻² at 600, 650, 700, 750 and 800 °C.     

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.     

Study on GDC-KZnAl composite electrolytes for low-temperature solid oxide fuel cells

Development of low-temperature solid oxide fuel cells (LTSOFC) is now becoming a mainstream research direction worldwide. The advancement in the effective electrolyte materials has been one of the major challenges for LTSOFC development. To further improve the performance of electrolyte, composite approaches are considered as common strategies. The enhancement on ionic conductivity or sintering behavior ceria-based electrolyte can either be done by adding a carbonate phase to facilitate the utilization of the ionic-conducting interfaces, or by addition of alumina as insulator to reduce the electronic conduction of ceria. Thus the present report aims to design a composite electrolyte materials by combining the above two composite approaches, in order to enhance the ionic conductivity and to improve the long-term stability simultaneously. Here we report the preparation and investigation of GDC-KAlZn materials with composition of Gd doped ceria, K₂CO₃, ZnO and Al₂O₃. The structure and morphology of the samples were characterized by XRD, SEM, etc. The ionic conductivity of GDC-KAlZn sample was determined by impedance spectroscopy. The composite samples with various weight ratio of GDC and KAlZn were used as electrolyte material to fabricate and evaluate fuel cells as well as investigate the composition dependent properties. The good ionic conductivity and notable fuel cell performance of 480 mW cm⁻² at 550 °C has demonstrated that GDC-KAlZn composite electrolyte can be regarded as a potential electrolyte material for LTSOFCs.     

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.     

Preparation and characterization of Sm0.2Ce0.8O1.9/Na2CO3 nanocomposite electrolyte for low-temperature solid oxide fuel cells

Sm_0.2Ce_0.8O_1.9 (SDC)/Na₂CO₃ nanocomposite synthesized by the co-precipitation process has been investigated for the potential electrolyte application in low-temperature solid oxide fuel cells (SOFCs). The conduction mechanism of the SDC/Na₂CO₃ nanocomposite has been studied. The performance of 20 mW cm⁻² at 490 °C for fuel cell using Na₂CO₃ as electrolyte has been obtained and the proton conduction mechanism has been proposed. This communication demonstrates the feasibility of direct utilization of methanol in low-temperature SOFCs with the SDC/Na₂CO₃ nanocomposite electrolyte. A fairly high peak power density of 512 mW cm⁻² at 550 °C for fuel cell fueled by methanol has been achieved. Thermodynamical equilibrium composition for the mixture of steam/methanol has been calculated, and no presence of C is predicted over the entire temperature range. The long-term stability test of open circuit voltage (OCV) indicates the SDC/Na₂CO₃ nanocomposite electrolyte can keep stable and no visual carbon deposition has been observed over the anode surface.     

Synthesis of hierarchically porous LiNiCuZn-oxide and its electrochemical performance for low-temperature fuel cells

In this work, hierarchically porous composite metal oxide LiNiCuZn-oxide (LNCZO) was successfully synthesized through a sol–gel method with a bio-Artemia cyst shell (AS) as a hard template. The phase and morphology of the products were characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM). The as-synthesized material was used as symmetrical electrodes, anode and cathode, for the SDC-LiNaCO₃ (LNSDC) electrolyte based low temperature solid oxide fuel cell (LTSOFCs), achieving a maximum power density of 132 mW cm⁻² at 550 °C. Besides, a single-component fuel cell device was also demonstrated using a mixture of as-prepared LNCZO and ionic conductor LNSDC, and a corresponding peak power output of 155 mW cm⁻² was obtained, suggesting that the hierarchically porous product has high prospective in the single-component fuel cell.     

A high performance BaZr0.1Ce0.7Y0.2O3-δ-based solid oxide fuel cell with a cobalt-free Ba0.5Sr0.5FeO3-δ–Ce0.8Sm0.2O2-δ composite cathode

A cobalt-free Ba_0.5Sr_0.5FeO_3-δ–Ce_0.8Sm_0.2O_2-δ (BSF–SDC) composite is employed as a cathode for an anode-supported 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 BSF and SDC is evaluated. The XRD results show that BSF is chemically compatible with SDC after co-fired at 1000 °C for 6 h. A single cell with a 20-μm-thick BZCY electrolyte membrane exhibits excellent power densities as high as 792 and 696 mW cm⁻² at 750 and 700 °C, respectively. To the best of our knowledge, this is the highest performance reported in literature up to now for BZCY-based single cells with cobalt-free cathode materials. Extremely low polarization resistances of 0.030 and 0.044 Ωcm² are achieved at 750 and 700 °C respectively. The excellent performance implies that the cobalt-free BSF–SDC composite is a promising alternative cathode for H-SOFCs. Resistances of the tested cell are investigated under open circuit conditions at different operating temperatures by impedance spectroscopy.     

Pr2NiO4–Ag composite cathode for low temperature solid oxide fuel cells with ceria-carbonate composite electrolyte

Pr₂NiO₄–Ag composite was synthesized and evaluated as cathode component for low temperature solid oxide fuel cells based on ceria-carbonate composite electrolyte. X-ray diffraction analysis reveals that the formation of a single phase K₂NiF₄–type structure occurs at 1000 °C and Pr₂NiO₄–Ag composite shows chemically compatible with the composite electrolyte. Symmetrical cells impedance measurements prove that Ag displays acceptable electrocatalytic activity toward oxygen reduction reaction at the temperature range of 500–600 °C. Single cells with Ag active component electrodes present better electrochemical performances than those of Ag-free cells. An improved maximum power density of 695 mW cm⁻² was achieved at 600 °C using Pr₂NiO₄–Ag composite cathode, with humidified hydrogen as fuel and air as the oxidant. Preliminary results suggest that Pr₂NiO₄–Ag composite could be adopted as an alternative cathode for low temperature solid oxide fuel cells.     

Study on calcium and samarium co-doped ceria based nanocomposite electrolytes

Calcium co-doped SDC-based nanocomposite electrolyte (Ce_0.8Sm_0.2−xCa_xO_2−δ-Na₂CO₃) was synthesized by a co-precipitation method. The microstructure and morphology of the composite electrolytes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM), and thermal properties were determined with differential scanning calorimetry (DSC). The particle size, as shown by TEM imaging, was 5-20 nm, which is in a good agreement with the SEM and XRD results. The co-doping effect on both interfaces of the composite electrolyte and doped bulk effect inside the ceria was studied. The excellent performance of the fuel cell was about 1000 mW cm⁻² at 560 °C and at the very low temperature of 350 °C the power density was 200 mW cm⁻². This paper may give a new approach to develop functional nanocomposite electrolyte for low-temperature solid oxide fuel cell (LTSOFC).     

Thermal stability study of SDC/Na2CO3 nanocomposite electrolyte for low-temperature SOFCs

The novel core–shell nanostructured SDC/Na₂CO₃ composite has been demonstrated as a promising electrolyte material for low-temperature SOFCs. However, as a nanostructured material, stability might be doubted under elevated temperature due to their high surface energy. So in order to study the thermal stability of SDC/Na₂CO₃ nanocomposite, XRD, BET, SEM and TGA characterizations were carried on after annealing samples at various temperatures. Crystallite sizes, BET surface areas, and SEM results indicated that the SDC/Na₂CO₃ nanocomposite possesses better thermal stability on nanostructure than pure SDC till 700 °C. TGA analysis verified that Na₂CO₃ phase exists steadily in the SDC/Na₂CO₃ composite. The performance and durability of SOFCs based on SDC/Na₂CO₃ electrolyte were also investigated. The cell delivered a maximum power density of 0.78 W cm⁻² at 550 °C and a steady output of about 0.62 W cm⁻² over 12 h operation. The high performances together with notable thermal stability make the SDC/Na₂CO₃ nanocomposite as a potential electrolyte material for long-term SOFCs that operate at 500–600 °C.     

(La,Pr)0.8Sr0.2FeO3−δ–Sm0.2Ce0.8O2−δ composite cathode for proton-conducting solid oxide fuel cells

Mixed rare-earth (La, Pr)_0.8Sr_0.2FeO_3−δ–Sm_0.2Ce_0.8O_2−δ (LPSF–SDC) composite cathode was investigated for proton-conducting solid oxide fuel cells based on protonic BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) electrolyte. The powders of La_0.8−xPr_xSr_0.2FeO_3−δ (x = 0, 0.2, 0.4, 0.6), Sm_0.2Ce_0.8O_2−δ (SDC) and BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) were synthesized by a citric acid-nitrates self-propagating combustion method. The XRD results indicate that La_0.8−xPr_xSr_0.2FeO_3−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.     

Ni-SDC cermet anode fabricated from NiO–SDC composite powder for intermediate temperature SOFC

We report a cost-effective processing method for fabricating intermediate temperature solid oxide fuel cells (SOFCs) with Ni-samaria doped ceria (SDC) anode. First, SDC and NiO powders were mechanically treated to make their composite powder. Then, the composite powder was applied into a ceramic tape casting method to form a thick layer for the anode supporting. Finally, an anode supported single cell with a configuration of Ni-SDC/SDC/La_0.6Sr_0.4Co_0.2Fe_0.8O_3 − δ (LSCF) was prepared. Because of the usage of the composite powder, homogenous distribution and connection of each Ni and SDC were achieved. Peak power densities of 460, 750 and 910 mW cm⁻² were obtained on the single cell at 550, 600 and 650 °C, respectively.     

Sm0.5Sr0.5Co0.4Ni0.6O3−δ–Sm0.2Ce0.8O1.9 as a potential cathode for intermediate-temperature solid oxide fuel cells

The mixed ionic and electronic conductors (MIECs) of Sm_0.5Sr_0.5Co_0.4Ni_0.6O_3−δ (SSCN)–Sm_0.2Ce_0.8O_1.9 (SDC) were investigated for potential application as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs) based on an 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). To investigate the ORR mechanism, the impedance diagram for 70SSCN–30SDC was measured under applied cathodic voltage from E = 0.0 to E = −0.3 V. It indicated that the charge transfer dominated the rate-determining step at the temperature of 600 °C; whereas the diffusion or dissociative adsorption of oxygen dominated the rate-determining step at the temperature of 800 °C. In this study, the exchange current density (i₀) for oxygen reduction reaction (ORR) was determined from the EIS data. The i₀ value of 70SSCN–30SDC/SDC was 187.6 mA cm⁻² which is larger than the i₀ value of 160 mA cm⁻² for traditional cathode/electrolyte, i.e. LSM/YSZ at 800 °C, indicating that the 70SSCN–30SDC composite cathode with a high catalytically active surface area could provide the oxygen reduction reaction areas not only at the triple-phase boundaries but also in the whole composite cathode.