Barium carbonate nanoparticle as high temperature oxygen reduction catalyst for solid oxide fuel cell

BaCO₃ nanoparticles are demonstrated as outstanding electrocatalysts to enhance the high temperature oxygen reduction reaction (ORR) in solid oxide fuel cells (SOFCs). BaCO₃ nanoparticles are formed from thermal decomposition of barium acetate, Ba(Ac)₂ infiltrated to porous cathode skeleton and shows good chemical compatibility with cathode materials. BaCO₃ nanoparticles can greatly reduce the area specific resistance (ASR) of typical SOFC cathode materials, including La_0.8Sr_0.2FeO_3 -δ (LSF), La_0.6Sr_0.4Co_0.2Fe_0.8O_3 -δ (LSCF) and La_0.8Sr_0.2MnO_3 -δ (LSM). For example at 700 °C, ASR for LSF on yttria-stabilized zirconia (YSZ) electrolyte decreases from 2.95 Ω cm² to 0.77 Ω cm² when 12.9 wt.% BaCO₃ nanoparticles are deposited on the surface of the porous LSF electrode. Impedance spectra analysis shows that the decrease in ASR mainly comes from the reduction of the low frequency resistance. Furthermore, BaCO₃ nanoparticles are found to greatly enhance the oxygen chemical exchange coefficient. Most importantly, it has been found that the catalytic activity of BaCO₃ nanoparticles is even higher than those of the precious metals such as Pd, Rh, Pt and Ag, infiltrated into LSF, LSCF and LSM electrodes supported on YSZ electrolytes.     

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

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

Enhancement of electrochemical performance and thermal compatibility of GdBaCo2/3Fe2/3Cu2/3O5+δ cathode on Ce1.9Gd0.1O1.95 electrolyte for IT-SOFCs

Transition-metal doped double-perovskite structure oxides GdBaCo_2/3Fe_2/3Ni_2/3O_5+δ (FN-GBCO), GdBaCo_2/3Fe_2/3Cu_2/3O_5+δ (FC-GBCO), GdBaCoCuO_5+δ (C-GBCO) and pristine GdBaCo₂O_5+δ (GBCO) were synthesized via a citrate combustion method. The thermal-expansion coefficient (TEC) and electrochemical performance of the oxides were investigated as potential cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The TEC exhibited by the FC-GBCO cathode up to 900 °C is 14.6 × 10^?6 °C^?1, which is lower than the value of GBCO (19.9 × 10^?6 °C^?1). Area specific resistances (ASR) of 0.165 Ω cm² at 700 °C and 0.048 Ω cm² at 750 °C were achieved for the FC-GBCO cathode on a Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte. An electrolyte supported (300 μm thick) single-cell configuration of FC-GBCO/CGO/Ni-CGO attained a maximum power density of 435 mW cm^?2 at 700 °C. The unique composition of GBCO co-doped with Fe and Cu ions in the Co sites exhibited reduced TEC and enhancement of electrochemical performance and good chemical compatibility with CGO, and this composition is proving to be a potential cathode for IT-SOFCs.     

High-performance bilayered electrolyte intermediate temperature solid oxide fuel cells

The ESB/GDC bilayer electrolyte concept has been proved to improve open circuit voltage and reduce the effective area specific resistance of SOFCs utilizing a conventional single-layer GDC electrolyte. However, high performance from such bilayer cells had not yet been demonstrated. The main obstacles toward this end have been fabrication of anode-supported thin-film electrolytes and the reactivity of ESB with conventional cathodes. Recently, an ESB-compatible low area specific resistance cathode was developed: microstructurally optimized Bi₂Ru₂O₇-ESB composites. In addition, we recently developed a novel anode functional layer which can significantly enhance the performance of SOFC utilizing GDC electrolytes. This study combines these recent achievements in SOFC studies and shows that exceptionally high performance of SOFC is possible using ESB/GDC bilayer electrolytes and Bi₂Ru₂O₇-ESB composite cathodes. The result confirms that the bilayer electrolyte and the Bi₂Ru₂O₇-ESB cathode can increase the open circuit potential and reduce the total area specific resistance. The maximum power density of the bilayered SOFC was improved to 1.95 W cm^?2 with 0.079 Ω cm² total cell area specific resistance at 650 °C. This is the highest power yet achieved in the IT range and we believe redefines the expectation level for maximum power under IT-SOFC operating conditions.     

Electrode properties of Sr doped La2CuO4 as new cathode material for intermediate-temperature SOFCs

High performance La_2−xSr_xCuO_4−δ (x = 0.1, 0.3, 0.5) cathode materials for intermediate temperature solid oxide fuel cell (IT-SOFCs) were prepared and characterized. The investigation of electrical properties indicated that La_1.7Sr_0.3CuO₄ cathode has low area specific resistance (ASR) of 0.16 Ω cm² at 700 °C and 1.2 Ω cm² at 500 °C in air. The rate-limiting step for oxygen reduction reaction on La_1.7Sr_0.3CuO₄ electrode changed with oxygen partial pressure and measurement temperature. La_1.7Sr_0.3CuO₄ cathode exhibits the lowest overpotential of about 100 mV at a current density of 150 mA cm⁻² at 700 °C in air.     

Composite cathode for IT-SOFC: Sr-doped lanthanum cuprate and Gd-doped ceria

Composite cathodes were synthesized via a citrate combustion method followed by an organic precipitation method. The cathodes were of K₂NiF₄-type crystal structure with x wt.% Ce_0.9Gd_0.1O_1.95 (CGO)–(100 ? x) wt.% La_1.96Sr_0.04CuO_4 + δ (LSC), where x = 0, 10, 20 and 30. The individual structural phases of the composite cathodes were characterized using a third-generation synchrotron source beamline powder X-ray diffractometer (XRD). The porous grain morphology of the CGO–LSC cathode composite for a symmetrical half-cell was determined from cross-sectional scanning electron microscopy images and elemental line profiles. The composite cathode was made of 20 wt.% CGO–80 wt.% LSC (CL20–80) and was coated onto a Ce_0.9Gd_0.1O_1.95 electrolyte. It showed the lowest area specific resistance (ASR) of 0.07 Ω cm² at 750 °C. An electrolyte-supported (300 μm thick) single-cell configuration of CL20–80/CGO/Ni-CGO attained a maximum power density of 626 mW cm^? 2 at 700 °C. The unique composite composition of CL20–80 demonstrates enhanced electrochemical performance and good chemical compatibility with the CGO electrolyte, as compared with the pure LSC (CL0–100) cathode for IT-SOFCs.     

Novel nano-structured Pd+yttrium doped ZrO2 cathodes for intermediate temperature solid oxide fuel cells

Novel nano-structured Pd+yttrium doped ZrO₂ (YSZ) electrodes have been developed as cathodes of intermediate temperature solid oxide fuel cells (IT-SOFCs). Nano-sized Pd particles were introduced into the rigid and porous YSZ structure by PdCl₂ solution impregnation. The results show that Pd nanoparticles (20–80 nm) were uniformly distributed in the porous YSZ structure; and such nano-structured composite cathodes were highly active for the O₂ reduction reaction, with polarization resistances (R_E) of 0.11 and 0.22 Ω cm² at 750 and 700 °C and activation energy of 105 kJ mol⁻¹ that is significantly lower than those for the conventional perovskite-based cathodes (130–201 kJ mol⁻¹).     

A high performance nano-structure conductive coating on a Crofer22APU alloy fabricated by a novel spinel powder reduction coating technique

A nano-structure conductive coating was fabricated on a Crofer22APU alloy interconnect by an original coating strategy using Mn_0.9Y_0.1Co₂O₄ (MYC) novel spinel nanocrystalline powder. A unique treatment method by which the spinel powder was reduced was used to prepare the green coating. The resulting coating was about 12 μm in thickness, and was composed of MYC nanocrystalline with an average particle size of about 100 nm. The coating was well adhered with the substrate alloy. Less than 4 mΩ cm² of the area specific resistance (ASR) was obtained, and no obvious degradation was observed for a coated alloy (whose coating thickness was about 30 μm) after operated at 800 °C for 538 h under seven thermal cyclings. The coated alloy exhibited excellently electrical performance and long-term stability compared with the uncoated one. The exploration of the novel spinel powder reduction coating technique for alloy interconnect to obtain cheap coatings with excellent microstructure and performance showed a promising prospect for the practical application of solid oxide fuel cells (SOFCs).     

Fabrication by Co-extrusion and electrochemical characterization of micro-tubular hollow fibre solid oxide fuel cells

A phase inversion process was used to co-extrude cerium–gadolinium oxide (Ce_0.9Gd_0.1O_1.95)/NiO–CGO dual-layer hollow fibres (HF), which were then sintered to form, respectively, the electrolyte and high porosity anode precursor of a solid oxide fuel cell (SOFC) with anode inner diameter of 0.8 mm. Graded CGO–lanthanum strontium cobalt ferrite (La_0.6Sr_0.4Fe_0.8Co_0.2O₃) cathode layers were then painted onto the CGO electrolyte to form a micro-tubular HF-SOFC. With a carefully designed anode current collector, this produced maximum power densities of 1186–5864 W m^? 2 at 450–570 °C. High magnification imaging analysis revealed large three-phase boundary regions within the anode, a dense electrolyte layer and clearly highlighted the multiple CGO–LSCF cermet and pure LSCF cathode layers. The performance of the HF-SOFC with a twenty millimetre active length showed no degradation after four thermal cycles between 300 °C and 570 °C.     

Prediction of infiltrated solid oxide fuel cell cathode polarization resistance

The polarization resistance of La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF)-infiltrated Ce_0.9Gd_0.1O_1.95 cathodes was quantitatively explained using a simple model where the resistance scaled directly with the LSCF surface area, as estimated from cross-sectional fracture surfaces. The Tanner, Fung, Virkar composite cathode model was also applied and showed that ionic transport in these 25-μm-thick cathodes was not a significant limitation at 600 °C, but became more limiting at 700 °C. Calculated polarization resistances were within ～40% (without fitting parameters) of reported values.     

Development of high-performance cathodes for IT-SOFCs through beneficial interfacial reactions

We propose a new way to develop high-performance cathodes for IT-SOFCs by utilizing the interfacial reactions. SrCoO_x was selected as the starting electrode material, which took a vacancy-ordered 2H BaNiO₃-type structure and showed negligible ionic conductivity and low electrical conductivity. Phase reactions between SrCoO_x and Sm_0.2Ce_0.8O_1.9 happened at 900 °C or higher, resulting in the incorporation of Sm and Ce into its lattice structure. This promoted the phase transition to a cubic perovskite and led to substantial increase in the electrical conductivity and oxygen mobility of the electrode. By utilizing such phase reactions, the SrCoO_x + Sm_0.2Ce_0.8O_1.9 composite was developed into a high performance electrode with a low area specific resistance of 0.08 Ω cm^?2 at 650 °C. An anode-supported cell with such electrode delivered a peak power density of 795 mW cm^?2 at 600 °C.     

Poly(ether amine) and cross-linked poly(propylene oxide) diacrylate thin-film polymer electrolyte for 3D-microbatteries

This paper presents a novel thin-film electrolyte of a 2:1 blend of polyetheramine (glyceryl poly(oxypropylene)) and cross-linked oligomeric poly(propylene oxide) diacrylate with LiTFSI. The polyetheramine acts as a surfactant, and can thereby be applied as a conformal coating on complex surfaces—here demonstrated for porous LiFePO₄ cathodes—making it useful for 3D-microbatteries. The poly(propylene oxide) diacrylate blends with the surfactant and is easily UV cross-linked, thereby ensuring good mechanical stability. Electrolytes, ~ 2 μm thick, were casted onto LiFePO₄ cathodes and cycled against metallic lithium, displaying stable discharge capacities of ~ 8 mAh/g at room temperature and ~ 120 mAh/g at 60 °C. The electrolyte showed conductivities of 3.45 × 10^? 6 and 5.80 × 10^? 5 S cm^? 1 at room temperature and 60 °C, respectively.     

Electrochemical characterisation of MBaCo3ZnO7+δ (M = Y,Er, Tb) as SOFC cathode material with low thermal expansion coefficient

The electrochemical oxygen activation at high temperature was studied on a new class of oxygen-store material based on the system YBaCo₄O_7+δ. Three different porous layers made of YBaCo₃ZnO_7+δ, ErBaCo₃ZnO_7+δ and TbBaCo₃ZnO_7+δ were electrochemically tested as oxygen activation coatings and showed a very promising activity. The envisaged applications for these materials are principally as SOFC cathodes and as catalytic layer on oxygen membranes. The electrochemical performance followed the order Tb ? Y > Er at any tested temperature. Area specific resistance for the best performing material (TbBaCo₃ZnO_7+δ) ranges from 30 mΩ cm² at 850 °C to 0.46 Ω cm² at 650 °C. High temperature XRD showed that the thermal expansion coefficient (25–900 °C) in air of TbBaCo₃ZnO₇ is 9.45 × 10^?6 K^?1, which evidences the good thermochemical compatibility of this cobalt-rich electrocatalyst with YSZ/GDC electrolytes.     

Infiltrated Sr2Fe1.5Mo0.5O6/La0.9Sr0.1Ga0.8Mg0.2O3 electrodes towards high performance symmetrical solid oxide fuel cells fabricated by an ultra-fast and time-saving procedure

Herein, the Sr₂Fe_1.5Mo_0.5O₆ (SFM) precursor solution is infiltrated into a tri-layered “porous La_0.9Sr_0.1Ga_0.8Mg_0.2O₃ (LSGM)/dense LSGM/porous LSGM” skeleton to form both SFM/LSGM symmetrical fuel cells and functional fuel cells by adopting an ultra-fast and time-saving procedure. The heating/cooling rate when fabricating is fixed at 200 °C/min. Thanks to the unique cell structure with high thermal shock resistance and matched thermal expansion coefficients (TEC) between SFM and LSGM, no SFM/LSGM interfacial detachment is detected. The polarization resistances (Rp) of SFM/LSGM composite cathode and anode at 650 °C are 0.27 Ω·cm² and 0.235 Ω·cm², respectively. These values are even smaller than those of the cells fabricated with traditional method. From scanning electron microscope (SEM), a more homogenous distribution of SFM is identified in the ultra-fast fabricated SFM/LSGM composite, therefore leading to the enhanced performance. This study also strengthens the evidence that SFM can be used as high performance symmetrical electrode material both running in H₂ and CH₄. When using H₂ as fuel, the maximum power density of “SFM-LSGM/LSGM/LSGM-SFM” functional fuel cell at 700 °C is 880 mW cm^− 2. By using CH₄ as fuel, the maximum power densities at 850 and 900 °C are 146 and 306 mW cm^− 2, respectively.     

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

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

Cost-effective solid oxide fuel cell prepared by single step co-press-firing process with lithiated NiO cathode

A cost-effective cell fabrication process was developed for intermediate temperature solid oxide fuel cells (IT-SOFCs). Co-doped ceria Ce_0.8Gd_0.05Y_0.15O_1.9 (GYDC) was synthesized by carbonate co-precipitation method. Lithiated NiO was prepared by glycine-nitrate combustion method and adopted as cathode material for IT-SOFCs. Single cell was fabricated by one-step dry-pressing and co-firing anode, anode functional layer (AFL), electrolyte and cathode together at 1200 °C for 4 h. The cell presented decent performance and an overall electrode polarization resistance of 0.54 Ω cm² has been achieved at 600 °C. These results demonstrate the possibility of using lithiated NiO as cathode material for ceria-based IT-SOFCs and the development of affordable fuel cell devices is encouraged.     

Development of micro-tubular SOFCs with an improved performance via nano-Ag impregnation for intermediate temperature operation

Micro-tubular solid-oxide fuel cell consisting of a 10-μm thick (ZrO₂)_0.89(Sc₂O₃)_0.1(CeO₂)_0.01 (ScSZ) electrolyte on a support NiO/(ScSZ) anode (1.8 mm diameter, 200 μm wall thickness) with a Ce_0.8Gd_0.2O_1.9 (GDC) buffer-layer and a La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)/GDC functional cathode has been developed for intermediate temperature operation. The functional cathode was in situ formed by impregnating the well-dispersed nano-Ag particles into the porous LSCF/GDC layer using a citrate method. The cells yielded maximum power densities of 1.06 W cm⁻² (1.43 A cm⁻², 0.74 V), 0.98 W cm⁻² (1.78 A cm⁻², 0.55 V) and 0.49 W cm⁻² (1.44 A cm⁻², 0.34 V), at 650, 600 and 550 °C, respectively.     

Impact of reforming catalyst on the anodic polarisation resistance in single-chamber SOFC fed by methane

This paper emphasises the electrochemical and catalytic properties of a Ni–10% GDC (10% gadolinium-doped ceria) cermet anode of a single-chamber solid oxide fuel cell (SC-SOFC). Innovative coupling of electrochemical impedance spectroscopy with gas chromatography measurements was carried out to characterise the anode material using an operando approach. The experiments were conducted in a symmetric anode/electrolyte/anode cell prepared by slurry coating resulting in 100 μm-thick anode layers. The electrochemical performance was assessed using a two-electrode arrangement between 400 °C and 650 °C, in a methane-rich atmosphere containing CH₄, O₂ and H₂O in a 14:2:6 volumetric ratio. The insertion of a Pt–CeO₂ based catalyst with high specific surface area inside the cermet layer was found to promote hydrogen production from the Water Gas Shift reaction and consequently to improve the electrochemical performances. Indeed, a promising polarisation resistance value of 12 Ω cm² was achieved at 600 °C with a catalytic loading of only 15 wt.%.     

Fabrication of needle-type micro SOFCs for micro power devices

We report the world smallest tubular solid oxide fuel cell – needle-type micro SOFCs applicable to micro power devices. The anode-supported cell was prepared using cost effective, conventional extrusion and dip-coating techniques. The diameter of the needle-type cell is 0.4 mm, consisting of NiO-Gd doped Ceria (GDC) for anode (under 100 μm thick), GDC for electrolyte (8 μm thick), and (La, Sr) (Co, Fe)O₃ – GDC for cathode. The cell performances of 80, 160 and 300 mW cm⁻² at 450 °C, 500 °C, and 550 °C, respectively, were obtained using a simple current collection method with wet H₂ fuel. Impedance analysis indicated that the SOFC has a potential to be improved by optimizing the current collection method. Bundle concept using the SOFCs with the packing density of 100 cells in 1 cm³ was also proposed.     

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

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