8YSZ/(La0.8Sr0.2)0.95MnO3-δ cathode performance at 1-3 bar oxygen pressures

Pressurised operation of solid oxide fuel cells (SOFC) has been shown to significantly improve their performance (Singhal, 2000) [1], however little work has been done on the effects of pressure on SOFC cathodes. The effect of pressurised oxygen on the area specific polarisation resistance (ASRp) of (La_0.8Sr_0.2)_0.95MnO_3-δ/8YSZ SOFC cathodes was determined by electrochemical impedance spectroscopy (EIS). Pellets of 8YSZ were pressed and sintered at 1350 °C, and screen printed layers of LSM/8YSZ cathode and LSM current collector were applied and sintered at 1300 °C and 1200 °C respectively. EIS was carried out between 1 and 3 bar oxygen at 800-1000 °C. One process dominated the spectra, and was identified as process C, (Jorgensen and Morgensen, 2001) [2] by comparison of measured and reference frequency maxima, the dependence of polarisation resistance on P_O2, the capacitance, and the activation energy. It is suggested that this represents the physical process of dissociative adsorption of oxygen at the triple phase boundaries of the electrode. A second process, with a magnitude almost independent of P_O2, is observed, which may be process B [2], related to transport of oxygen ions in the YSZ.     

Preparation and electrochemical characterization of cobalt-manganese oxide as electrode materials for electrochemical capacitors

Cobalt-manganese oxide materials (CMOs) were prepared by chemical method and heat treated at 150, 400, 600, 800 and 1000 °C, respectively. The physical and electrochemical properties of the materials were characterized. The heat treatment process leads to the removal of water molecules adsorbed on the surface of CMO particles (below 400 °C) and the progressive reduction of Mn and Co ions from Mn⁴⁺ and Co³⁺ to Mn³⁺/Mn²⁺ and Co²⁺, respectively (440-1000 °C). CMOs obtained by treatment below 800 °C have poor crystallinity and a highly crystallized tetragonal phase by treatment at 1000 °C. The ratio of Mn and Co in CMOs is found by EDX analysis to be about 2:1. The electrochemical testing results indicate that the high crystallization of CMO is disadvantageous for the energy storage as electrode material of electrochemical capacitors. However, for CMOs with poor crystallinity, relatively high specific capacitances can be obtained. The incorporation of protons and ions into the CMO's lattice during electrochemical charge/discharge process leads to the distortion of crystal lattice and improvement of crystallinity of CMO. The XRD patterns show that negative electrode (NE) and positive electrode (PE) have tetragonal (Co, Mn)(Mn, Co)₂O₄ phase.     

Electrochemical synthesis of ammonia based on doped-ceria-carbonate composite electrolyte and perovskite cathode

Electrochemical synthesis of ammonia was investigated using a cobalt-free La_0.6Sr_0.4Fe_0.8Cu_0.2O_3-δ-Ce_0.8Sm_0.2O_2-δ (LSFCu-SDC) composite cathode and SDC-ternary carbonate composite electrolyte. La_0.6Sr_0.4Fe_0.8Cu_0.2O_3-δ and Ce_0.8Sm_0.2O_2-δ were prepared via combined EDTA-citrate complexing sol-gel and glycine nitrate processes, respectively, and characterised by X-ray diffraction (XRD). Ammonia was successfully synthesised from wet hydrogen and dry nitrogen under atmospheric pressure using Ni-SDC, SDC-carbonate and LSFCu-SDC composites as anode, electrolyte and cathode respectively. Ammonia formation was observed at 400, 425, 450 and 475 °C and the maximum rate of ammonia production was found to be 5.39 × 10⁻⁹ mol s⁻¹ cm⁻² at 450 °C and 0.8 V. The AC impedance measurements were recorded before and after the ammonia synthesis in the range of temperature 400-475 °C. The formation of ammonia at the N₂ side together with stable current at 450 °C under constant voltage demonstrates that SDC-(Li/Na/K)₂CO₃ composite electrolyte exhibits significant proton conduction at a temperature around 450 °C.     

Characterization of YSr2Fe3O8 − δ as electrode materials for SOFC

YSr₂Fe₃O_8 − δ was prepared by traditional solid state reaction method and characterized by X-ray diffraction, ac impedance, dc conductivity, dilatometry and thermogravimetric analysis for possible use in solid oxide fuel cells (SOFCs). YSr₂Fe₃O_8 − δ crystallizes with tetragonal symmetry in the space group P4/mmm and found to be stable at high temperatures under H₂ and air. Four probe dc electrical conductivity measurements show that the conductivity increases up to 745 K and then decreases with temperature; the highest conductivity σ_745K = 43.5 S cm^− 1. The n-type conductivity at low oxygen partial pressure (pO₂) changes to p-type at high pO₂. Polarization behavior was investigated measuring the ac impedance response in symmetrical cell arrangements in air with YSZ and GDC electrolytes. Cathodic area specific resistance (ASR) varies with firing temperature. The lowest area specific resistance was observed with a GDC electrolyte fired at 1000 °C. In case of YSZ, ASR increases and in case of GDC, ASR decreases in air when electrode firing temperature decreases. At 800 °C ASRs are 0.20 Ω cm² and 0.65 Ω cm² with GDC and YSZ electrolytes, respectively, in air. Fuel cell measurements with symmetrical electrodes were performed using a thin YSZ electrolyte under H₂ at anode and air at cathode, show that the power density is about 0.035 W/cm² at 900 °C.     

Investigations on the thermo-chemical stability and electrical conductivity of K-doped Ba3 − xKxCaNb2O9 − δ (x = 0.5, 0.75, 1, 1.25)

In this paper, we report the synthesis, crystal structure and electrical transport properties of new K-doped Ba₃CaNb₂O₉ (BCN) and investigate their chemical stability in H₂O and pure CO₂ at elevated temperature. The powder X-ray diffraction (PXRD) of Ba_2.5K_0.5CaNb₂O_9 − δ, Ba_2.25K_0.75CaNb₂O_9 − δ, Ba₂KCaNb₂O_9 − δ, and Ba_1.75K_1.25CaNb₂O_9 − δ showed the formation of a single-phase double perovskite (A₃BB^/₂O₉)-like cell with a lattice constant of a ∼ 2a_p (where a_p is a simple perovskite cell of ∼ 4 Å). Perovskite-like structure was found to be retained after treating with CO₂ at 700 °C and also after boiling H₂O for 120 h. The lattice constant of CO₂ and H₂O treated samples was found to be comparable to that of the corresponding as-prepared compound. The total electrical conductivity of all the investigated K-doped BCN increases with increasing K content in BCN in various atmospheres, including air, dry H₂, wet N₂ and wet H₂. The electrical conductivity in dry and wet H₂ atmospheres was found to be higher than that of air in the temperature range of 300-700 °C, while in wet N₂ a slightly lower value was observed. Among the compounds investigated in the present study Ba_1.75K_1.25CaNb₂O_9 − δ showed the highest total electrical conductivity of 1 × 10^− 3 S/cm in dry H₂ at 700 °C with an activation energy of 1.28 eV in the temperature range of 300-700 °C.     

Electrical properties of thin yttria-stabilized zirconia overlayers produced by atomic layer deposition for solid oxide fuel cell applications

Thin films of yttria-stabilized zirconia (YSZ) electrolyte were prepared by atomic layer deposition at 300 °C for solid oxide fuel cell (SOFC) applications. YSZ samples of 300-1000 nm thickness were deposited onto La_0.8Sr_0.2MnO₃ (LSM) cathodes. A microstructural study was performed on these samples and their electrical properties were characterised between 100 and 390 °C by impedance spectroscopy. A remarkable feature is that the as-deposited layers were already crystalline without any annealing treatment. Their resistance decreased when reducing the layer thickness; nevertheless, their conductivity and activation energy were significantly lower than those reported in the literature for bulk YSZ.     

Morphology Control of the Electrode for Solid Oxide Fuel Cells by Using Nanoparticles

LSM(La(Sr)MnO₃)/YSZ(Y₂O₃ stabilized ZrO₂) composite cathode for Solid Oxide Fuel Cells (SOFCs) was fabricated by using the composite particle consisting of well-dispersed nano-size grains of LSM and YSZ. The composite cathode had a porous structure as well as uniformly dispersed fine LSM and YSZ grains. Such unique morphology of the composite cathode led high electrochemical activity at 800°C. It suggests that the intermediate temperature (less than 800°C) operation of SOFCs will be achieved by using composite particles.     

Structural, transport and electrochemical properties of LiNi1 − yCoyMn0.1O2 and Al, Mg and Cu-substituted LiNi0.65Co0.25Mn0.1O2 oxides

LiNi_{1 - y − z}Co_yMn_zO₂ (y = 0.25, 0.35, 0.5, 0.6; z = 0.1, 0.2), LiNi_0.63Cu_0.02Co_0.25Mn_0.1O₂, LiNi_0.65Co_0.25Mn_0.08Al_0.02O₂, LiNi_0.65Co_0.25Mn_0.08Mg_0.02O₂ and LiNi_0.65Co_0.25Mn_0.08Al_0.01Mg_0.01O₂ cathode materials were synthesized by a soft chemistry EDTA-based method. Structural and transport properties of pristine and delithiated materials (Li_xNi_0.65Co_0.25Mn_0.1O₂, Li_xNi_0.55Co_0.35Mn_0.1O₂ and LiNi_0.63Cu_0.02Co_0.25Mn_0.1O₂ oxides) are presented. In the considered group of oxides there is no correlation between electrical conductivity and the a parameter (M-M distance in the octahedra layers). The results of electrochemical performance of cathode materials are presented. The best stability during first 10 cycles was obtained for Li/Li_xNi_0.63Cu_0.02Co_0.25Mn_0.1O₂ cell due to enhanced kinetics of intercalation process.     

Preparation of YSZ films by magnetron sputtering for anode-supported SOFC

YSZ films for anode-supported SOFCs were prepared by reactive sputtering method. It was found that the surface morphology of anode substrate has a very important effect on the quality of sputtered films. By applying an anode functional layer and making the anode surface smooth, dense and uniform YSZ films of 10 µm in thickness were successfully fabricated. The sintering behaviors of the sputtered YSZ films were also discussed. It is suggested that the optimized densification condition for the deposited YSZ films is sintering at 1250 °C for 4 h. Single cells with sputtered YSZ film as electrolyte and LSM-YSZ as active cathode materials were tested. 1.08 V open circuit voltage and a 700 mW/cm² maximum power density were achieved at 750 °C by using humidified H₂ as fuel and air as oxidant.     

A novel chemical synthesis and characterization of Mn3O4 thin films for supercapacitor application

Mn₃O₄ thin films have been prepared by novel chemical successive ionic layer adsorption and reaction (SILAR) method. Further these films were characterized for their structural, morphological and optical properties by means of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), field emission scanning electron microscopy (FESEM), wettability test and optical absorption studies. The XRD pattern showed that the Mn₃O₄ films exhibit tetragonal hausmannite structure. Formation of manganese oxide compound was confirmed from FTIR studies. The optical absorption showed existence of direct optical band gap of energy 2.30 eV. Mn₃O₄ film surface showed hydrophilic nature with water contact angle of 55°. The supercapacitive properties of Mn₃O₄ thin film investigated in 1 M Na₂SO₄ electrolyte showed maximum supercapacitance of 314 F g⁻¹ at scan rate 5 mV s⁻¹.     

A Ni/YSZ composite containing Ce0.9Ca0.1O2−δ particles as an anode for SOFCs

A composite material (hereafter referred to as NYC) containing Ni, Y₂O₃-stabilized ZrO₂ (YSZ) and Ce_0.9Ca_0.1O_2−δ (CC10) particles was prepared and used as the anode of solid oxide fuel cells (SOFCs). The performance of NYC was better than that of conventional Ni/YSZ anodes in terms of anodic overpotential and interface impedance. The additional CC10 particles improved the anode properties. XRD results suggest that a solid solution of YSZ and CC10 was produced. From impedance measurements, it is concluded that the solid solution exhibits substantial electronic conduction. Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ anodes exhibited the best properties over the experimental temperature range. A SOFC with an anode of Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ provided the maximum power density and current density. Addition of CC10 with an average particle size of 0.3 μm was more advantageous than that with an average size of 3 μm.     

Electrochemical properties of nanostructured lanthanum strontium manganite cathode fabricated by electrostatic spray deposition

Electrostatic spray deposition was applied to prepare nanoporous lanthanum strontium manganite (LSM) films with high specific surface area (37.34 m²/g) for the cathode application in solid oxide fuel cell (SOFC). The electrochemical characteristics were investigated at a temperature range from 546 to 777 °C and oxygen partial pressure from 0.01 to 1.0 atm. The diffusion of atomic oxygen and oxygen ion transfer from three-phase boundary to the YSZ electrolyte were found to be the rate-determining steps for oxygen reduction reaction on LSM cathode. The polarization resistance of the LSM prepared using electrostatic spray deposition decreased from 15 to 1.2 Ωcm² with increasing temperature from 546 to 777 °C and the activation energy was 0.81 eV. It was demonstrated that the ESD method offers a promising approach for the preparation of electrochemically active nanoporous layers, particularly applicable for solid oxide fuel cells.     

Investigating the formation and magnetic properties of the Dy0.75Fe1.25O3 orthoferrite prepared by sol-gel method

In this paper, the Dy_0.75Fe_1.25O₃ orthoferrite nanoparticles were synthesized successfully by sol-gel method. Dy_0.75Fe_1.25O₃ orthoferrite nanoparticles are obtained by calcining the flakes at 600 and 700 °C. The magnetic properties of the different samples are investigated using Quantum Design MPMS SQUID magnetometer and MS-500 Mössbauer spectrometer. Magnetic phase γ-Fe₂O₃ coexists in the samples calcined at 600 °C and orthoferrite phase is completely recovered in the samples calcined at 700 °C. Although excessive Fe³⁺ ions were introduced, none of these iron spins couple magnetically with Dy³⁺ ions.     

Characterization of scandia doped pressed cathode fabricated by spray drying method

Scandia doped pressed cathode was prepared by a new method of spray drying combined with two-step hydrogen reduction process. The Sc₂O₃ and barium-calcium aluminate co-doped powders have sub-micrometer size in the range of 0.1-1 μm and scandium oxide and barium-calcium aluminate are distributed evenly in the powders. The cathodes sintered by powder metallurgy at 1600 °C_b have a smooth surface and sub-micrometer grain structure with homogeneous distribution of scandium, barium, calcium and aluminum which are dispersed over and among the tungsten grains. This cathode has good emission, e.g., the current density of this cathode reaches 31.50 A/cm² at 850 °C_b. After proper activation, the cathode surface is covered by a Ba-Sc-O active substances layer with a preferable atomic ratio, leading to its good emission property. The evaporation activation energy of SDP cathode with 4.58 eV is the highest among the Ba-W, M-type and SDP cathodes, and the average evaporation velocity v_t of SDP cathode with 1.28 × 10⁻⁸ g cm⁻² s⁻¹ at 1150 °C_b is the lowest one.     

Investigations on Pr1.6Sr0.4NiO4-YSZ-Ag composite cathode for solid oxide fuel cells

Ag-network was successfully deposited by VA-EP (vacuum assisted electroless plating) method on Pr_1.6Sr_0.4NiO₄-YSZ cathode to form (1−x) wt% Pr_1.6Sr_0.4NiO₄−x wt% YSZ-Ag (x=0, 10, 20, 30, 40) (abbr. PYx-Ag) composite cathode. XRD results suggested that there was a good chemical stability between Pr_1.6Sr_0.4NiO₄ and YSZ at temperatures below 1050 °C. PY20-Ag cathode exhibited higher exchange current density, lower overpotential and ASR (Area Specific Resistance) than PY20 cathode. At 650 °C, the ASR of PY20-Ag cathode was 2.5 Ω cm², which was only about 42% of that of PY20, 5.9 Ω cm². PY20-Ag can be a promising candidate for SOFC cathode.     

Preparation and electrochemical performance of novel ruthenium-manganese oxide electrode materials for electrochemical capacitors

A series of novel ruthenium-manganese oxide (denoted as Ru_nMn_1−nO_x) has been formed by oxidative co-precipitating. The precursor was obtained by mixing Mn(VII) (potassium permanganate), Mn(II) (manganese acetate) and Ru(III) (ruthenium chloride) in neutral aqueous solution at room temperature. The powder of Ru_nMn_1−nO_x was obtained by calcinating the precursor at appropriate temperature. The crystalline structure and electrochemical performance of the powder have been studied as a function of the calcination temperature. At appropriate calcination temperature (e.g. 170 °C), the powder is in hydrous amorphous phase with a high specific capacitance. When the calcination temperature reaches up to 350 °C, the crystal form of α-MnO₂ is formed, but the ruthenium oxide still keeps amorphous structure, which will lead to the decrease of specific capacitance of the composite electrode materials. The X-ray photoelectron spectroscopy (XPS) analysis shows that the powder of Ru_nMn_1−nO_x prepared in this study belongs to the composite of RuO₂-MnO₂. The results from cyclic voltammetry (CV), chronopotentiometry and electrochemical impedance spectroscopy (EIS) indicate that the ruthenium weight density of 9 wt% in Ru_nMn_1−nO_x can improve the cost-performance of ruthenium-manganese composite electrode.     

Synthesis and characterization of lithium manganese oxides with core-shell Li4Mn5O12@Li2MnO3 structure as lithium battery electrode materials

By a facile LiNO₃ flux method, lithium manganese oxide composites (xLi₄Mn₅O₁₂? yLi₂MnO₃) were synthesized using a hierarchical organization precursor of manganese dioxide. Li₄Mn₅O₁₂ and Li₂MnO₃ have spinel and rocksalt structures, respectively. The lithiation and structural transformation from the precursor to the composites occurred topotactically from exterior toward interior in the precursor particle with the increase of reaction time, and the composites had core-shell spinel@rocksalt structures in addition to the original hierarchical core-shell organization. The electrochemical measurements at 50 °C after 50 cycles confirmed that a typical spinel@rocksalt cathode had higher capacity retention (87.1%) than that with the composition close to the stoichiometric spinel (64.6%), indicating the Li₂MnO₃ shell can improve cycling stability for the composite electrode at elevated temperature.     

Optical polarized properties related to the oxygen vacancy in the CaMoO4 crystal

The electronic structures, dielectric functions and absorption spectra for the CaMoO₄ (CMO) crystal with and without oxygen vacancy V_O²⁺ have been calculated using the CASTEP code with the lattice structure optimized. The calculated results indicate that the optical properties of the CMO crystal show anisotropy and its optical symmetry coincides with the lattice structure geometry of the CMO crystal. The calculated absorption spectra indicate that the perfect CMO crystal does not display absorption band in the visible and near-ultraviolet range. However, in this range, the absorption spectra of the CMO crystal containing V_O²⁺ exhibit one peak at about 1.84 eV (673 nm). It predicates that the 680 nm absorption band is related to the existence of V_O²⁺ in the CMO crystal.     

In situ XPS study of Pd(1 1 1) oxidation. Part 1: 2D oxide formation in 10 mbar O2

The oxidation of the Pd(1 1 1) surface was studied by in situ XPS during heating and cooling in 3 × 10⁻³ mbar O₂. A number of adsorbed/dissolved oxygen species were identified by in situ XPS, such as the two dimensional surface oxide (Pd₅O₄), the supersaturated O_ads layer, dissolved oxygen and the R 12.2° surface structure.Exposure of the Pd(1 1 1) single crystal to 3 × 10⁻³ mbar O₂ at 425 K led to formation of the 2D oxide phase, which was in equilibrium with a supersaturated O_ads layer. The supersaturated O_ads layer was characterized by the O 1s core level peak at 530.37 eV. The 2D oxide, Pd₅O₄, was characterized by two O 1s components at 528.92 eV and 529.52 eV and by two oxygen-induced Pd 3d_5/2 components at 335.5 eV and 336.24 eV. During heating in 3 × 10⁻³ mbar O₂ the supersaturated O_ads layer disappeared whereas the fraction of the surface covered with the 2D oxide grew. The surface was completely covered with the 2D oxide between 600 K and 655 K. Depth profiling by photon energy variation confirmed the surface nature of the 2D oxide. The 2D oxide decomposed completely above 717 K. Diffusion of oxygen in the palladium bulk occurred at these temperatures. A substantial oxygen signal assigned to the dissolved species was detected even at 923 K. The dissolved oxygen was characterised by the O 1s core level peak at 528.98 eV. The “bulk” nature of the dissolved oxygen species was verified by depth profiling.During cooling in 3 × 10⁻³ mbar O₂, the oxidised Pd²⁺ species appeared at 788 K whereas the 2D oxide decomposed at 717 K during heating. The surface oxidised states exhibited an inverse hysteresis. The oxidised palladium state observed during cooling was assigned to a new oxide phase, probably the R 12.2° structure.     

Epitaxial growth of YSZ buffer layer for YBa2Cu3O7−δ coated conductor by reel-to-reel pulsed laser deposition

Yttria-stabilized zirconia (YSZ) buffer layers were deposited on CeO₂ buffered biaxially textured Ni-W substrate by reel-to-reel pulsed laser deposition (PLD) for the application of YBa₂Cu₃O_7−δ (YBCO) coated conductor and the influence of substrate temperature and laser energy on their crystallinity and microstructure were studied. YSZ thin films were prepared with substrate temperature ranging from 600 to 800 °C and laser energy ranging from 120 to 350 mJ. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were used to investigate how thin film structure and surface morphology depend on these parameters. It was found that the YSZ films grown at substrate temperature below 600 °C or laser energy above 300 mJ showed amorphous phase, the (0 0 1) preferred orientation and the crystallinity of the YSZ films were improved with increasing the temperature, but the surface roughness increased simultaneously, the SEM images of YSZ films on CeO₂/NiW tapes showed surface morphologies without micro-cracks. Based on these results, we developed the epitaxial PLD-YSZ buffer layer process at the tape transfer speed of 3-4 m/h by the reel-to-reel system for 100 m class long YBCO tapes.