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.     

Hydrogen-storage property characterization of Mg–15 wt%Ni–5 wt%Fe2O3 prepared by reactive mechanical grinding

Mg–15 wt%Ni–5 wt%Fe₂O₃ (Mg155) was prepared by reactive mechanical grinding (RMG). Mg155 exhibited high hydriding and dehydriding rates even at the first cycle, and its activation was completed after only two hydriding–dehydriding cycles. The activated Mg155 absorbed 5.06 and 5.38 wt% of hydrogen, respectively, for 5 and 60 min at 573 K under 12 bar H₂. It desorbed 1.50 and 5.28 wt% of hydrogen, respectively, for 5 and 60 min at 573 K under 1.0 bar H₂. The initial hydrogen absorption rate decreased, but the hydrogen desorption rate increased rapidly with an increase in temperature from 563 K to 603 K. The rate-controlling step for the dehydriding reaction in a range from F ? 0.20 to F ? 0.75 is considered to be the chemical reaction at the Mg hydride/α-solid solution interface. The absorption and desorption PCT curves exhibited two plateaus at 573 K. The hydrogen-storage capacity of the activated Mg155 was about 6.43 wt% at 573 K.     

Rb掺杂Li4Ti5O12作为锂离子电池负极材料的合成及电化学性能

合成了不同Rb掺杂量的钛酸锂（Li_4-xRb_xTi₅O₁₂; x = 0.010, 0.015, 0.020）作为锂离子电池的负极材料。测试结果显示,Rb离子掺杂有效增强了钛酸锂的电子电导率。相同的测试条件下,相比于未掺杂样品和高Rb含量掺杂样品（x = 0.015, 0.020）,适量的Rb掺杂钛酸锂（Li_3.99Rb_0.01Ti₅O₁₂; x = 0.010）表现出最优的电化学性能。Li_3.99Rb_0.01Ti₅O₁₂材料表现出161.2 mA∙h/g的初始容量,且在1 C下经过1000次循环后容量保持率可达90.9%。此外,全电池Li_3.99Rb_0.01Ti₅O₁₂ // LiFePO₄在0.5 C条件下首次放电容量为144 mA∙h/g,经过150次循环后,容量保持率为78.8%。     

Assessment of PrBaCo2O5+δ + Sm0.2Ce0.8O1.9 composites prepared by physical mixing as electrodes of solid oxide fuel cells

The performance of PrBaCo₂O_5+δ + Sm_0.2Ce_0.8O_1.9 (PrBC + SDC) composites as electrodes of intermediate-temperature solid oxide fuel cells is investigated. The effects of SDC content on the performance and properties of the electrodes, including thermal expansion, DC conductivity, oxygen desorption, area specific resistance (ASR) and cathodic overpotential are evaluated. The thermal expansion coefficient and electrical conductivity of the electrode decreases with an increase in SDC content. However, the electrical conductivity of a composite electrode containing 50 wt% SDC reaches 150 S cm⁻¹ at 600 °C. Among the various electrodes under investigation, an electrode containing 30 wt% SDC exhibits superior electrochemical performance. A peak power density of approximately 1150 and 573 mW cm⁻² is reached at 650 and 550 °C, respectively, for an anode-supported thin-film SDC electrolyte cell with the optimal composite electrode. The improved performance of a composite electrode containing 70 wt% PrBC and 30 wt% SDC is attributed to a reduction in the diffusion path of oxygen-ions within the electrode, which is a result of a three-dimensional oxygen-ion diffusion path in SDC and a one-dimensional diffusion path in PrBC.     

Monoclinic zirconia-supported Fe3O4 for the two-step water-splitting thermochemical cycle at high thermal reduction temperatures of 1400–1600 °C

Two-step thermochemical water-splitting using monoclinic ZrO₂-supported Fe₃O₄ (Fe₃O₄/m-ZrO₂) for hydrogen production was examined at high thermal reduction temperatures of 1400–1600 °C. After thermal reduction of Fe₃O₄/m-ZrO₂, the reduced sample was quenched in liquid nitrogen, and was subsequently subjected to the water-decomposition step at 1000 °C. Quenching of the solid sample was conducted for analysis of the chemical reactions, such as phase transitions, occurring at high-temperature. The hydrogen productivity of Fe₃O₄ on a m-ZrO₂ support and the conversion of Fe₃O₄ to FeO were significantly enhanced with higher thermal reduction temperatures. The Fe₃O₄-to-FeO conversion reached 60% when the Fe₃O₄/m-ZrO₂ was thermally reduced at 1600 °C. The phase transition of m-ZrO₂ support to tetragonal ZrO₂ (t-ZrO₂) did not occur during the thermal reduction at 1400–1500 °C, but it did proceed slightly at 1600 °C. Fe ions from Fe₃O₄ did not enter the ZrO₂ lattice during high-temperature thermal reduction. Thus, the Fe₃O₄ loaded on a m-ZrO₂ support can continuously contribute as a Fe₃O₄–FeO redox reactant for thermochemical water-splitting at high-temperatures of 1400–1600 °C.     

Performance of SrSc0.2Co0.8O3−δ + Sm0.5Sr0.5CoO3−δ mixed-conducting composite electrodes for oxygen reduction at intermediate temperatures

In order to improve the electrical conductivity of the SrSc_0.2Co_0.8O_3−δ (SrScCo) electrode, a composite of 70 wt% SrSc_0.2Co_0.8O_3−δ and 30 wt% Sm_0.5Sr_0.5CoO_3−δ (SrScCo + SmSrCo) was prepared and investigated for electrochemical oxygen reduction at intermediate temperatures. The phase reaction between SrScCo and SmSrCo and its effect on the electrical conductivity, oxygen vacancy concentration and oxygen mobility were examined by XRD, 4-probe DC conductivity measurement, iodometry titration and O₂-TPD experiment, respectively. The results showed that the composite reached a maximum conductivity around 123 S cm⁻¹ at 600 °C, nearly five times that of SrScCo. AC impedance results showed that the electron charge-transfer process was greatly improved by forming the composite electrode, while the oxygen-ion charge-transfer process was somewhat deteriorated. By firing at 1000 °C for 2 h, a SOFC with the SrScCo + SmSrCo cathode and thin-film SDC electrolyte delivered peak power densities of 1100 and 366 mW cm⁻² at 600 and 500 °C, respectively, which were only modestly lower than those of a similar cell with a pure SrScCo cathode.     

Microstructure and hydrogen storage characteristics of nanocrystalline Mg + x wt% LaMg2Ni (x = 0–30) composites

The nanocrystalline Mg + x wt% LaMg₂Ni (x = 0, 5, 10, 20, 30) composites were prepared by reactive ball-milling, their microstructure and hydrogen storage characteristics were investigated. The results show that the addition of LaMg₂Ni improves the hydriding rate and capacity. The hydriding capacity of the Mg + x wt% LaMg₂Ni (x = 5, 10, 20, 30) composites are all above 4.1 wt% at 120 °C and above 4.3 wt% at 180 °C within 6000 s. Moreover, the addition of LaMg₂Ni also improves the dehydriding performance of the composites. The main reason for the improvement of hydriding/dehydriding properties investigated by XRD and SEM shows that the synergistic effect among the multiphase nanocrystalline Mg-based structures make hydrogen easily absorbed/desorbed on the interface of the matrix.     

Ag/Al2O3(Li2O)/g-C3N4光催化乙醇制取环氧乙烷

本文制备了一系列Ag/Al₂O₃(Li₂O)/g-C₃N₄复合催化剂,考察了其可见光催化乙醇制取环氧乙烷的性能。Li₂O可调变Al₂O₃表面的酸性,从而降低了主要副产物乙醛的选择性。Ag/Al₂O₃(Li₂O) 在g-C₃N₄上的负载量对产物环氧乙烷的选择性有较大影响,当Ag/Al₂O₃(Li₂O) 负载量为5wt%时,乙醇具有较高的转换率,且环氧乙烷的选择性高达100%。     

Characterization of perovskite-type cathode,La0.75Sr0.25 Mn0.95−xCox Ni0.05O3+δ (0.1 ≤ x ≤ 0.3), for intermediate-temperature solid oxide fuel cells

Phase evolution, structure, thermal property, morphology, electrical property and reactivity of a perovskite-type cathode system, La_0.75Sr_0.25 Mn_0.95−xCo_xNi_0.05O_3+δ (0.1 ≤ x ≤ 0.3), are reported. The samples are synthesized using metal acetates by the Pechini method. A perovskite-type phase is formed after calcination at ∼700 °C and a rhombohedral symmetry of R – 3c space group is stabilized at ∼1100 °C. An increase in x decreases the unit cell volume linearly, accompanying with a linear decrease in bond lengths and tilt angle. The differential thermal analysis suggests the phase stabilization for a temperature range, 50–1100 °C. The thermo-gravimetric, thermal expansion, and electrical and ionic conductivities studies suggest presence of a Jahn–Teller transition at ∼260–290 °C. The samples with x = 0.1 mol exhibit electrical conductivity of ∼55 S cm⁻¹ at ∼600 °C, activation energy of ∼0.13 eV, coefficient of thermal expansion of ∼12 × 10⁶ °C⁻¹, crystallite size of ∼45 nm, Brunauer–Emmett–Teller (BET) surface area of 1.26 m² g⁻¹ and average particle size of ∼0.9 μm. A fairly high ionic conductivity, 5–9 × 10⁻² S cm⁻¹ makes the sample with x = 0.1 mole suitable for intermediate-temperature solid oxide fuel cell cathode applications. The experimental results are discussed with the help of the defect models proposed for La_1−xSr_xMnO_3+δ.     

Microwave synthesis of novel high voltage (4.6 V) high capacity LiCuxCo1−xO2±δ cathode material for lithium rechargeable cells

Layered LiCu_xCo_1−xO_2±δ (0.0 ≤ x ≤ 0.3) has been synthesized using microwave method. This method possesses many advantages such as homogeneity of final product and shorter reaction time compared to other conventional methods. The structure and electrochemical properties of the synthesized materials are characterized through various methods such as XRD, SEM, FTIR, XPS and galvanostatic charge/discharge studies. The XRD patterns of LiCu_xCo_1−xO_2±δ confirm the formation of single-phase layered material. SEM images show that the particles are agglomerated and the average particle size decreases with increasing amount of copper. Electrochemical cycling studies are carried out between 2.7 and 4.6 V using 1 M LiPF₆ in 1:1 EC/DEC as electrolyte. The charge/discharge cycling studies of layered material with LiCu_0.2Co_0.8O₁₉ exhibit an average discharge capacity of ∼150 mAh g⁻¹ over the investigated 50 cycles.     

Electrical conductivity of Ce0.8Gd0.2−xDyxO2−δ (0 ≤ x ≤ 0.2) co-doped with Gd and Dy for intermediate-temperature solid oxide fuel cells

High-quality nano-sized Ce_0.8Gd_0.2−xDy_xO_2−δ (0 ≤ x ≤ 0.2) powders are synthesized by a solution combustion process. The calcined powders are composed of a ceria-based single phase with a cubic fluorite structure and are nanocrystalline nature, i.e., 15-24 nm in crystallite size. The addition of an intermediate amount of Dy³⁺ (0.03 ≤ x ≤ 0.16) for Gd³⁺ in Ce_0.8Gd_0.2O_2−δ decreases the electrical conductivity. On the other hand, the doping of a small amount of Dy³⁺ (0.01 ≤ x ≤ 0.02) and of a large amount of Dy³⁺ (0.17 ≤ x ≤ 0.19) leads to an increase in conductivity. The Ce_0.8Gd_0.03Dy_0.17O_2−δ shows the highest electrical conductivity (0.215 S cm⁻¹) at 800 °C.     

Nanospheres and nanorods structured Fe2O3 and Fe2−xGaxO3 photocatalysts for visible-light mediated (λ ≥ 420 nm) H2S decomposition and H2 generation

This article reports our investigation on H₂ generation from visible light (λ ≥ 420 nm) photodecomposition of H₂S by nanomaterial catalysts, α-Fe₂O₃ and its chemically modified Fe_2−xGa_xO₃ (Ga substitution at x = 0.6, FeGaO₃-I and x = 1.0, FeGaO₃-II). Simple template-free hydrothermal technique was employed to synthesize the three photocatalysts. XRD study reveals rhombohedral nanocrystalline structure and FESEM shows nanospheres morphology for Fe₂O₃ and nanosticks/nanorods for both FeGaO₃-I, and FeGaO₃-II. In H₂ generation, Fe₂O₃ and FeGaO₃-II perform moderate and almost same activities in the fresh and used conditions (quantum yield, QY = 6.0–6.8% at 550 nm). Contrarily, fresh FeGaO₃-I exhibits a greater activity (11.2% QY) and the activity is further enhanced (QY = 15.3%) on regeneration and reuse. The intricacy, as resolved by XRD and FESEM, appears to take place through morphology transformation. The present work, thus, successfully demonstrates H₂ generation from H₂S by nanostructured photocatalysts involving morphology dependent activity enhancement.     

Preparation and characterization of La0.9Sr0.1Ga0.8Mg0.2O3 − δ thin film on the porous cathode for SOFC

A dense and crack-free La_0.9Sr_0.1Ga_0.8Mg_0.2O_3 − δ thin film has been prepared by RF magnetron sputtering. The XRD, FESEM, XPS and four-probe technique are employed to characterize the La_0.9Sr_0.1Ga_0.8Mg_0.2O_3 − δ film. Results show that after annealing at 1000 °C, the La_0.9Sr_0.1Ga_0.8Mg_0.2O_3 − δ film presents a polycrystalline perovskite structure with grain size of 100–300 nm. XPS data show that both La and Ga are in their +3 state. Sr element has two chemical states which are related to Sr²⁺ in the perovskite lattice and SrO_1 − δ suboxide. The O 1s spectrum also shows two chemical states which can be assigned to molecularly adsorbed O₂ species and O²⁻ in the lattice. The electrical conductivity reaches to 0.093 S cm⁻¹ at 800 °C. The microstructure and conductivity analysis indicates that the La_0.9Sr_0.1Ga_0.8Mg_0.2O_3 − δ thin film prepared by RF magnetron sputtering is suitable for intermediate temperature Solid oxide fuel cell.     

Desirable performance of intermediate-temperature solid oxide fuel cell with an anode-supported La0.9Sr0.1Ga0.8Mg0.2O3 − δ electrolyte membrane

An anode-supported La_0.9Sr_0.1Ga_0.8Mg_0.2O_3 − δ (LSGM) electrolyte membrane is successfully fabricated by simple, cost-effective spin coating process. Nano-sized NiO and Ce_0.8Gd_0.2O_3 − α (GDC) powders derived from precipitation and citric-nitrate process, respectively, are used for anode support. The dense and uniform LSGM membrane of ca. 50 μm in thickness is obtained by sintering at relatively low temperature 1300 °C for 5 h. A single cell based on the as-prepared LSGM electrolyte membrane exhibits desirable high cell performance and generates high output power densities of 760 mW cm⁻² at 700 °C and 257 mW cm⁻² at 600 °C, respectively, when operated with humidified hydrogen as the fuel and air as the oxidant. The single cell is characterized by field-emission scanning electron microscope (FESEM), X-ray diffraction (XRD) and electrochemical AC impedance. The results demonstrate that it is feasible to fabricate dense LSGM membrane for solid oxide fuel cell by this simple, cost-effective and efficient process. In addition, optimized anode microstructure significantly reduces polarization resistance (0.025 Ω cm² at 700 °C).     

A new solid-state process for synthesis of LiMn1.5Ni0.5O4−δ spinel

A new two-step solid-state process was developed for synthesis of a pure phase 4.7 V LiMn_1.5Ni_0.5O_4−δ (LMNO) spinel of good electrochemical properties. This process which was based on formation of stable Ni_1−xMn₂O_4−δ (x ≤ 0.33) spinel followed by subsequent lithiation, demonstrated the emerging of LiMn_1.5Ni_0.5O_4−δ frame work at temperatures of as low as 350 °C. During this lithiation process, migration of metal ions (Ni/Mn) from partially occupied tetrahedral 8a sites (in Ni_0.67Mn₂O_4−δ) toward octahedral 16d site occurred. The resultant spinel material displayed low irreversible loss, a 97% columbic efficiency and 6% loss in discharge capacity after 100 cycles at 60 °C.     

Novel Nd2WO6-type Sm2−xAxM1−yByO6−δ (A = Ca, Sr; M = Mo, W; B = Ce, Ni) mixed conductors

In the present work, we have explored novel Nd₂WO₆-type structure Sm_2−xA_xM_1−yB_yO_6−δ (A = Ca, Sr; M = Mo, W; B = Ce, Ni) as precursor for the development of solid oxide fuel cells (SOFCs) anodes. The formation of single-phase monoclinic structure was confirmed by powder X-ray diffraction (PXRD) for the A- and B-doped Sm₂MO₆ (SMO). Samples after AC measurements under wet H₂ up to 850 °C changed from Nd₂WO₆-type structure into Sm₂MoO₅ due to the reduction of Mo^VI that was confirmed by PXRD and is consistent with literature. The electrical conductivity was determined using 2-probe AC impedance and DC method and was compared with 4-probe DC method. The total electrical conductivity obtained from these two different techniques was found to vary within the experimental error over the investigated temperature of 350-650 °C. Ionic and electronic conductivity were studied using electron-blocking electrodes technique. Among the samples studied, Sm_1.8Ca_0.2MoO_6−δ exhibits total conductivity of 0.12 S cm⁻¹ at 550 °C in wet H₂ with an activation energy of 0.06 eV. Ca-doped SMO appears to be chemically stable against reaction with YSZ electrolyte at 800 °C for 24 h in wet H₂. The ionic transference number (t_i) of Sm_1.9Ca_0.1MoO_6−δ in wet H₂ at 550 °C (pO₂ = 10^−25.5 atm) was found to be about 0.012 after subtraction of electrical lead resistance from the 2-probe AC data and showed predominate electronic conductors.     

Thermochemical transformations in 2MNH2–3MgH2 systems (M = Li or Na)

Thermochemical reactions between alkali metal amides and magnesium hydride taken in 2:3 molar ratios have been investigated using pressure-composition-temperature, X-ray powder diffraction and residual gas analysis measurements. The thermally induced reactions in both title systems are stoichiometric and proceed as a following solid state transformation: 2MNH₂ + 3MgH₂ → Mg₃N₂ + 2MH + 4H₂↑. A total of 6.45 wt.% of hydrogen is released by the 2LiNH₂–3MgH₂ system beginning at 186 °C, and a total of 5.1 wt.% H₂ is released by the 2NaNH₂–3MgH₂ system starting at 130 °C. Combined structure/property investigations revealed that the transformation in the lithium containing system proceeds in two steps. In the first step, lithium amide reacts with MgH₂ to form Li₂Mg(NH)₂ and hydrogen. In the second step, reaction between Li₂Mg(NH) and MgH₂ leads to the formation of the Mg₃N₂ nitride, lithium hydride and additional gaseous hydrogen. The transformation in the sodium containing system appears to proceed through a series of competing solid state processes with formation of Mg(NH₂)₂ and NaMgH₃ intermediates. Partial rehydrogenation in 190 bar hydrogen pressure leading to formation of the MgNH imide was observed in the dehydrogenated 2NaNH₂–3MgH₂ system at 395 °C.     

Ln0.6Sr0.4Co1−yFeyO3−δ (Ln = La and Nd; y = 0 and 0.5) cathodes with thin yttria-stabilized zirconia electrolytes for intermediate temperature solid oxide fuel cells

The electrochemical performances of the solid oxide fuel cells (SOFC) fabricated with Ln_0.6Sr_0.4Co_1−yFe_yO_3−δ (Ln = La, Nd; y = 0, 0.5) perovskite cathodes, thin yttria-stabilized zirconia (YSZ) electrolytes, and YSZ–Ni anodes by tape casting, co-firing, and screen printing are evaluated at 600–800 °C. Peak power densities of ∼550 mW cm⁻² are achieved at 800 °C with a La_0.6Sr_0.4CoO_3−δ (LSC) cathode that is known to have high electrical conductivity. Substitution of La by Nd (Nd_0.6Sr_0.4CoO_3−δ) to reduce the thermal expansion coefficient (TEC) results in only a slight decrease in power density despite a lower electrical conductivity. Conversely, substitution of Fe for Co (La_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ or Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ) to reduce the TEC further reduces the cell performance greatly due to a significant decrease in electrical conductivity. However, infiltration of the Fe-substituted cathodes with Ag to increase the electrical conductivity increases the cell performance while preserving the low TEC.     

Evaluation of A-site cation-deficient (Ba0.5Sr0.5)1−xCo0.8Fe0.2O3−δ (x > 0) perovskite as a solid-oxide fuel cell cathode

A-site cation-deficient (Ba_0.5Sr_0.5)_1−xCo_0.8Fe_0.2O_3−δ ((BS)_1−xCF) oxides were synthesized and evaluated as cathode materials for intermediate-temperature solid-oxide fuel cells (ITSOFCs). The material's thermal expansion coefficient, electrical conductivity, oxygen desorption property, and electrocatalytic activity were measured. A decrease in both the electronic conductivity and the thermal expansion coefficient was observed for increasing values of the stoichiometric coefficient, x. This effect was attributed to the creation of additional oxygen vacancies, the suppression of variation in the oxidation states of cobalt and iron, and the suppression of the spin-state transitions of cobalt ions. The increase in A-site cation deficiency resulted in a steady increase in cathode polarization resistance, because impurities formed at the cathode/electrolyte interface, reducing the electronic conductivity. A single SOFC equipped with a BS_0.97CF cathode exhibited peak power densities of 694 and 893 mW cm⁻² at 600 and 650 °C, respectively, and these results were comparable with those obtained with a Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ cathode. Slightly A-site cation-deficient (BS)_1−xCF oxides were still highly promising cathodes for reduced temperature SOFCs.     

Effects of Co3O4 as additive on the performance of metal hydride electrode and Ni–MH battery

In this paper, the performance of metal hydride electrodes prepared with different amounts of tricobalt tetraoxide (Co₃O₄) and AA size cylindrical Ni–MH battery with the capacity of 1500 mAh prepared with Co₃O₄ as negative additive has been investigated. The investigation reveals that the charge and discharge efficiency at 1400 mA g⁻¹ at room temperature, and the discharge efficiency at 140 mA g⁻¹ at −20 °C of metal hydride electrode are increased from 82.2% to 92.4%, from 55.1% to 84.7%, and from 30.2% to 68.8%, respectively, by adding proper amounts of Co₃O₄. Furthermore, it is also found that the high-rate and low-temperature discharge ability, overcharge endurance ability, cycle life, inner pressure of battery are greatly improved by adding Co₃O₄. These results can be attributed to the high electrocatalytic activity and extended hydride storage capability of Co₃O₄, the improvement of gas consumption ability and the restraining of oxidation of electrode alloys by adding Co₃O₄.