Oxide ion and proton conduction in doped ceria–carbonate composite materials

The direct current four-probe method has been employed to investigate the conduction of oxide ion and proton in a doped ceria–carbonate composite electrolyte for fuel cells. The measurements are conducted in oxygen and in hydrogen atmospheres in the temperature range of 425–650 °C. The conductivities of both of O²⁻ and H⁺ increase with the increase of carbonate content above the melting point of the carbonate. The ionic conductivities of the composite electrolytes have also been simulated using the effective medium percolation theory. The deviations between experimental results and simulated values of O²⁻ conductivity are caused by the associating effect of ceramic and carbonate phases, which leads to a higher O²⁻ migration energy through the phase interface. According to the comparison of experimental data and simulated values, the conduction mechanisms of O²⁻ and H⁺ have been proposed.     

Novel doped barium cerate–carbonate composite electrolyte material for low temperature solid oxide fuel cells

A composite of a perovskite oxide proton conductor (BaCe_0.7Zr_0.1Y_0.2O_3−δ, BCZ10Y20) and alkali carbonates (2Li₂CO₃:1Na₂CO₃, LNC) is investigated with respect to its morphology, conductivity and fuel cell performance. The morphology shows that the presence of carbonate phase improves the densification of oxide matrix. The conductivity is measured by AC impedance in air, nitrogen, wet nitrogen, hydrogen, and wet hydrogen, respectively. A sharp increase of the conductivity at certain temperature is seen, which relates to the superionic phase transition at the interface phases between oxide and carbonates. Single cell with the composite electrolyte is fabricated by dry-pressing technique, using nickel oxide as anode and lithiated nickel oxide as cathode, respectively. The cell shows a maximum power density of 957 mW cm⁻² at 600 °C with hydrogen as the fuel and oxygen as the oxidant. The remarkable proton conductivity and excellent cell performance make this kind of composite material a good candidate electrolyte for low temperature solid oxide fuel cells (SOFCs).     

Durability study of an intermediate temperature fuel cell based on an oxide–carbonate composite electrolyte

It was reported that ceria–carbonate composites are promising electrolyte materials for intermediate temperature fuel cells. The conductivity stability of composite electrolyte with co-doped ceria and binary carbonate was measured by AC impedance spectroscopy. At 550 °C, the conductivity dropped from 0.26 to 0.21 S cm⁻¹ in air during the measured 135 h. At a constant current density of 1 A cm⁻², the cell performance keeps decreasing at 550 °C, with a maximum power density change from 520 to 300 mW cm⁻². This is due to the increase of both series and electrode polarisation resistances. Obvious morphology change of the electrolyte nearby the cathode/electrolyte interface was observed by SEM. Both XRD and FT-IR investigations indicate that there are some interactions between the doped ceria and carbonates. Thermal analysis indicates that the oxide–carbonate composite is quite stable at 550 °C. The durability of this kind of fuel cell is not good during our experiments. A complete solid oxide-carbonate composite would be better choice for a stable fuel cell performance.     

Synthesis of ZIF-8 derived porous carbon/NiS hexahedral composite and its application in improving the electrochemical hydrogen storage properties of Co–P material

Thermal treatment of zinc-based MOF (ZIF-8) is conducted to prepare ZIF-8 derived porous carbon (ZIF-8-C). ZIF-8-C/NiS hexahedral composites with different C/Ni mole ratios (C@NiS-2, C@NiS-4 and C@NiS-6) are synthesized by solvothermal method. Co–P hydrogen storage material is prepared via mechanical alloying. Then, composites of Co–P coated with NiS, ZIF-8-C and C@NiS are obtained by ball-milling. Eventually, C@NiS-4 coated Co–P electrode exhibits higher discharge capacity of 624.8 mAh/g than separate NiS or ZIF-8-C modified Co–P and original Co–P electrodes. The HRD, corrosion resistance and kinetics properties of Co–P are also improved after C@NiS-4 loading. The enhanced kinetics performance and electrochemical activities of Co–P + C@NiS-4 may be due to the synergistic effect between flexible porous carbon ZIF-8-C and active NiS nanosheets, which can further accelerate the hydrogen diffusion during the charging/discharging processes.     

The electrochemical performances of Ti–V-based hydrogen storage composite electrodes prepared by ball milling method

In order to overcome the inherent disadvantages of Ti–V-based hydrogen storage alloys, such as poor activation behavior and low high-rate dischargeability, the novel composites Ti_0.17Zr_0.08V_0.35Cr_0.1Ni_0.3–x wt.% La_0.7Mg_0.3Ni_2.75Co_0.75 (x = 0, 5, 10 and 20) were successfully synthesized by ball milling method in the present study. And the structure and overall electrochemical properties of as-prepared composites are investigated systemically. The electrochemical studies show that the maximum discharge capacity of the composite electrodes displays no variation with the increase of La_0.7Mg_0.3Ni_2.75Co_0.75 content, whereas the high-rate dischargeability (HRD) and the activation behavior are distinctly improved with increasing x. The electrochemical hydrogen kinetics of composite electrodes is also studied by means of electrochemical impedance spectroscopy (EIS), linear polarization (LP), anodic polarization (AP) and potential-step measurements. It is found that the charge-transfer reaction resistance R_ct is decreased with increasing the amount of La_0.7Mg_0.3Ni_2.75Co_0.75 while exchange current density I₀, limiting current density I_L and hydrogen diffusion coefficient D are all increased with increasing the amount of La_0.7Mg_0.3Ni_2.75Co_0.75. These results suggest that the formation of composite with La_0.7Mg_0.3Ni_2.75Co_0.75 alloy is a promising strategy for improving the HRD, activation behavior and electrochemical kinetics of Ti–V-based alloy electrodes.     

Synthesis and electrochemical characterization of Li1.02Mg0.1Mn1.9O3.99S0.01 using sol–gel method

To improve the cycle performance of spinel LiMn₂O₄ as the positive electrode of 4 V lithium secondary batteries, the spinel oxysulfide Li_1.02Mg_0.1Mn_1.9O_3.99S_0.01 is synthesized by a sol–gel method using adipic acid as a chelating agent. The structural and electrochemical properties of the synthesized material are examined. Highly crystallized Li_1.02Mg_0.1Mn_1.9O_3.99S_0.01 is synthesized at 750°C in an oxygen atmosphere. Both cation and anion doping of spinel lithium manganese oxides are very effective for improving the cycle performance of lithium batteries.     

The effect of ceria content in nickel–ceria composite anode catalysts on the discharge performance for solid oxide fuel cells

Optimum ceria content in nickel–ceria composite anode catalyst from the point of discharge performance is discussed. The ohmic loss increased when the ceria content was higher than 30 mol%. Even though the electrical conductivity of the anode decreased with increasing ceria content in the anode catalyst in association with decreasing nickel content, the ohmic loss was kept low until the ceria content was ≤30 mol% because the semiconducting ceria compensated for the decreased current path owing to the decreasing nickel content. The lowest activation loss was observed when the ceria content in the nickel anode catalyst was 30 mol% and the maximum activation loss was obtained for ceria content of 2 mol%. Ceria content in nickel anode influenced microstructure of the anode matrix. When the CeO₂ content was 2 mol%, sintering of anode catalyst was evident and the porosity of anode matrix was almost 57% - highest in this study. Whereas sintering of anode catalyst was not evident and the porosity of anode matrix was 46% when the ceria content in the nickel anode catalyst was 30 mol%. Activation loss was strongly influenced by microstructure of anode matrix, and highest activation loss when the CeO₂ content was 2 mol% was owing to the inappropriate microstructure for electrochemical reaction: sintering of the anode catalyst and excessive porosity of the anode.     

Preparation and electrochemical properties of composite LaNix/Ni–S–Co alloy film

The composite LaNi_x/Ni–S–Co film with considerable stability and high HER activity (η₁₅₀ = 70 mV, 353 K) was obtained by molten salt electrolysis combined with aquatic electrodeposition. LaNi_x film was prepared by galvanostatic electrolysis at 100 mA cm⁻² under 1273 K. The results showed that the La³⁺ ions could be reduced on the nickel cathode and the LaNi_x film could form, i.e. La³⁺ + 3e + xNi = LaNi_x (x = 5 or 3) at ca. −0.6 V, which is much lower than that of the decomposition potential of lanthanum, due to the strong depolarization effect of nickel. Furthermore, compared with the traditional amorphous Ni–S film, the composite LaNi_x/Ni–S–Co film could absorb large amount of H atoms, which would be oxidized and avoid the dissolution of the Ni–S–Co film under the state of open-circuit effectively and increase the HER activity.     

Effects of manganese nitrate concentration on the performance of an aluminum substrate β-PbO2–MnO2–WC–ZrO2 composite electrode material

An Al/conductive coating/α-PbO₂–CeO₂–TiO₂/β-PbO₂–MnO₂–WC–ZrO₂ composite electrode material was prepared through electrochemical oxidation co-deposition on an Al/conductive coating/α-PbO₂–CeO₂–TiO₂ substrate. The effects of manganese nitrate concentration on the chemical composition, electrocatalytic activity, and stability of the composite anode material were investigated using energy dispersive X-ray spectroscopy, anode polarization curves, quasi-stationary polarization curves, electrochemical impedance spectroscopy, scanning electron microscopy, and X-ray diffraction. Results revealed that the WC and nano-ZrO₂ content in the β-PbO₂–MnO₂–WC–ZrO₂ composite coatings increased with increasing manganese nitrate concentration. Moreover, the highest values of 6.61 wt% and 3.51 wt%, respectively, were achieved at 80 g L⁻¹ manganese nitrate. PbO₂ content decreased and MnO₂ content increased with the increasing manganese nitrate concentration; both the descending and ascending trends were nonlinear. The Al/conductive coating/α-PbO₂–CeO₂–TiO₂/β-PbO₂–MnO₂–WC–ZrO₂ composite electrode obtained at 80 g L⁻¹ manganese nitrate concentration in plating solution exhibited reduced overpotential for oxygen evolution (0.610 V at 500 A m⁻²), highest electrocatalytic activity, longest service life (360 h at 40 °C in 150 g L⁻¹ H₂SO₄ solution at 2 A cm⁻²), and lowest cell voltage (2.75 V at 500 A m⁻²). Furthermore, the composite coating obtained with 80 g L⁻¹ manganese nitrate had uniform crystal grains. The deposit formed was flat, dense, and crackless.     

Ni–CeO2 composite cathode material for hydrogen evolution reaction in alkaline electrolyte

In this work, nickel-based electrodes were prepared using composite electrodeposition technique in a nickel sulphamate bath containing suspended micro- or nano-sized CeO₂ particles. The prepared Ni–CeO₂ composite electrodes exhibit an enhanced high catalytic activity toward hydrogen evolution reaction (HER) in alkaline solutions. X-ray diffraction patterns indicated that the CeO₂ particles have been successfully incorporated into the Ni matrix and altered the texture coefficient (TC) of the Ni layer. The morphology of the obtained coatings was characterized by Scanning Electron Microscopy, and the CeO₂ content was determined by coupled energy dispersive X-ray spectrometry. The thermal stability of the composite electrodes was analyzed by thermogravimetric and differential scanning calorimetry, showing a good thermal stability. The catalytic activity of the composite electrodes for HER was measured by steady-state polarization and electrochemical impedance spectroscopy techniques in 1.0 M NaOH solution at room temperature. The exchange current density of HER on the Ni–CeO₂ composite electrodes was much higher than that on Ni electrode. EIS results suggested that a synergetic effect on HER may exist between CeO₂ particles and Ni matrix. Compared to nano-CeO_2, the micro-CeO₂ derived composite electrodes showed higher electrochemical activity. The possible correlation among particle size, content and catalytic activity is discussed.     

Photo-electrochemical characteristics of a cobalt–air cell using an anode active material–semiconductor (Co–GaP) hybrid electrode

An anode active material–semiconductor hybrid electrode was prepared by combining electroplated Co and a GaP single crystal. This hybrid electrode acts not only as an active material for a cobalt–air cell but also as a photo-electrode for storing light energy. We studied the photo-electrochemical properties of the hybrid electrode, and confirmed that the electrode’s oxidized Co layer was reduced by the electrons generated when the GaP side was illuminated. We assembled a GaP–Co|KOH|O₂ cell with only two electrodes: the above hybrid electrode and an air electrode (oxygen catalyst). The photo-electrochemical characteristics of the Co–GaP hybrid electrode and cobalt–air cell showed that this cell can be charged by illuminating it and discharged by using the oxygen in the air.     

Improved hydrogen storage properties of LiBH4 doped Li–N–H system

Remarkable improvement of hydrogen sorption properties of Li–N–H system has been obtained by doping with a small amount of LiBH₄. The starting and ending temperatures of hydrogen desorption shift to lower temperatures and the release of NH₃ is obviously restrained by 10 mol% LiBH₄ doping. The kinetics of hydrogen desorption and absorption of Li–N–H system became faster by the addition of LiBH₄. About 4 wt.% H₂ can be released within 30 min and ∼4.8 wt.% H₂ can be reabsorbed within 2 min by LiBH₄ doped sample at 250 °C, while only 1.44 wt.% H₂ is released and 2.1 wt.% is reabsorbed for pure Li–N–H system. The quaternary hydride (LiNH₂)_x(LiBH₄)_(1−x) formed by the reaction between LiBH₄ and LiNH₂ may contribute to the enhancement of the hydrogen sorption performances by yielding a ionic liquid phase and transferring LiNH₂ from solid state to molten state with a weakened N–H bond.     

Fabrication and testing of a H2–O2 fuel cell using MoxRuySez

We report the results obtained in the preparation and characterization of Mo_xRu_ySe_z electrocatalysts for oxygen reduction reaction and the design, construction and characterization of a H₂–O₂ fuel cell using Mo_xRu_ySe_z. The catalysts were characterized with respect to their electrocatalytic properties. The fuel cell was designed and built with Mo_xRu_ySe_z supported on carbon as cathode, Pt supported on carbon as anode, and H₂SO₄ as the electrolyte. The fuel cell was tested at room temperature and atmospheric pressure. The H₂–O₂ cell showed an efficiency in the order of 30%.     

Cooling performance investigation of electronics cooling system using Al2O3–H2O nanofluid

In this study, the cooling performance of Al₂O₃–H₂O nanofluid was experimentally investigated as a much better developed alternative for the conventional coolant. For this purpose the nanofluid was passed through the custom-made copper minichannel heat sink which is normally attached with the electronic heat source. The thermal performance of the Al₂O₃–H₂O nanofluid was evaluated at different volume fraction of the nanoparticle as well as at different volume flow rate of the nanofluid. The volume fraction of the nanoparticle varied from 0.05 vol.% to 0.2 vol.% whereas the volume flow rate was increased from 0.50 L/min to 1.25 L/min. The experimental results showed that the nanofluid successfully has minimized the heat sink temperature compared to the conventional coolant. It was noticed also that the thermal entropy generation rate was reduced via using nanofluid instead of the normal water. Among the other functions of the nanofluid are to increase the frictional entropy generation rate and to drop the pressure which are insignificant compared to the normal coolant. Given the improved performance of the nanofluid, especially for high heat transportation capacity and low thermal entropy generation rate, it could be used as a better alternative coolant for the electronic cooling system instead of conventional pure water.     

Numerical solution for the hyperbolic heat conduction problems in the radial–spherical coordinate system using a hybrid Green's function method

The hyperbolic heat conduction problems in the radial–spherical coordinate system are investigated by the hybrid Green's function method. The present method combines the Laplace transform for the time domain, Green's function for the space domain and ?-algorithm acceleration method for fast convergence of the series solution. Three different examples problems have been analyzed by the present method. It is found that the present method does not exhibit numerical oscillations at the wave front and the numerical solutions are stable.     

Effect of plastic deformation on ionic conduction in pure AgI and AgIAl2O3 composite solid electrolytes

The ionic conductivities of pure silver iodide and silver iodide-(10–40 mol%) alumina composites used as solid electrolytes are determined at room temperature by a.c. impedance spectroscopy as a function of compression pressure and annealing temperature. The ionic conductivities of both the pure and the composite silver iodide specimens increase with increasing compression pressure. This suggests that structural defects acting as conduction paths are generated in abundance by the plastic deformation. The mechanical strength of the as-deformed pure silver iodide specimen is decreased drastically by annealing at 413 K, whereas that of the as-deformed composite specimens remains virtually, unchanged. This indicates that the deformation-induced defects are present largely as dislocations. The ionic conductivity of the as-deformed pure silver iodide specimen determined during annealing at 323 K decreases with annealing time, whereas the conductivities of the as-deformed composite specimens are practically unchanged. It is concluded that the removal of the deformation-induced dislocations during annealing is impeded by dispersed alumina particles.     

Improved hydrogen production performance of Ni–Al2O3/CaO–CaZrO3 composite catalyst for CO2 sorption enhanced CH4/H2O reforming

Bifunctional composite catalysts are very intrigued to produce hydrogen via CO₂ sorption enhanced CH₄/H₂O reforming. However, their hydrogen production performance declined over multiple cycles, owing to the structure collapse and the sintering of active component under high-temperature regeneration. This work reported the facile synthesis of long-lasting Ni–Al₂O₃/CaO–CaZrO₃ composite catalysts with less inert components (36 wt%) for stable hydrogen production over the multiple cycles of CO₂ sorption enhanced CH₄/H₂O reforming. The effects of reaction and regeneration temperature on the hydrogen production performance of Ni–Al₂O₃/CaO–CaZrO₃ were explored. Ni–Al₂O₃/CaO–CaZrO₃ demonstrated high activity and stability while fixing reaction temperature as 600 °C and regeneration temperature as 750 °C. Of particular importance, H₂ concentration was 98 vol% even after 10 hydrogen production cycles due to the inert component CaZrO₃ having a cross-linked structure. The distribution of CaZrO₃ in the composite as a coral-like structure inhibited the sintering of CaO through high Taman temperature and physical separation. Moreover, it provided the skeleton support and pore volume for the repeated expansion and contraction process of CaO to CaCO₃ during the cycling process. Finally, the sintering of Ni slowed down in appropriate regeneration temperature to maintain the structure of the composite catalyst, which further improved the catalyst's stability over multiple cycles.     

Enhanced reversible hydrogen storage performance of NbCl5 doped 2LiH–MgB2 composite

2LiBH₄ + MgH₂ system is considered as an attractive candidate for reversible hydrogen storage with high capacity and favorable thermodynamics. However, its reaction kinetics has to be further improved for the practical application. In this work, we investigated the effect of NbCl₅ additive on the de/hydrogenation kinetics and microstructure refinement in 2LiH–MgB₂ composite systematically. The hydrogenation and dehydrogenation kinetics of 2LiH–MgB₂ composite can be significantly enhanced with the increase of NbCl₅ content. The 3 mol% NbCl₅ doped 2LiH–MgB₂ composite exhibits the superior reversible hydrogen storage performance, which requires 50 min to uptake 9.0 wt% H₂ at 350 °C and release 8.5 wt% H₂ at 400 °C, respectively. In contrast, the undoped 2LiH–MgB₂ sample uptakes 6.2 wt% H₂ and releases 3.1 wt% H₂ under identical measurement conditions. Moreover, the 3 mol% NbCl₅ doped 2LiH–MgB₂ composite can release more than 9.0 wt% H₂ within 300 min at 400 °C without obvious degradation of capacity over the first 10 cycles. Microstructure analyses clearly indicate that NbCl₅ additive first reacts with LiH to form Nb and LiCl during ball-milling process, and then NbH is formed after the first hydrogenation and stabilized upon further de/hydrogenation cycling. The well-distributed NbH active species play an important role in the improvement of de/hydrogenation kinetics for Li–Mg–B–H system through facilitating hydrogen diffusion rapidly as well as prevent the particles from further growth in the subsequent hydrogenation and dehydrogenation processes.     

Fabrication and characterization of a YSZ/YDC composite electrolyte by a sol–gel coating method

The compatibility of a composite electrolyte composed of a yttria stabilized zirconia (YSZ) film and a yttria-doped ceria (YDC) substrate in a solid oxide fuel cell (SOFC) that can be operated under 800 °C was evaluated. The YSZ film coated on a YDC substrate was derived from a polymeric YSZ sol using a sol–gel spin coating method followed by heat-treatment at 1400 °C for 2 h. The SEM and XRD analysis indicated that there were no cracks, pinholes, or byproducts. The composite electrolyte comprising a YSZ film of 2 μm thickness and a YDC substrate of 1.6 mm thickness was used in a single cell performance test. A 0.5 V higher value of open circuit voltage (OCV) was found for the composite electrolyte single cell compared with an uncoated YDC single cell between 700 and 1050 °C and confirmed that the YSZ film was an electron blocking layer. The maximum power density of the composite electrolyte single cell at 800 °C, 122 mW/cm² at 285 mA/cm², is comparable with that of a YSZ single cell with the same thickness at 1000 °C, namely 144 mW/cm² at 330 mA/cm². The hypothetical oxygen partial pressure at the interface between the YSZ film and the YDC substrate for the composite electrolyte with the same thickness ratio at 800 °C is 5.58×10⁻¹⁸ atm which is two orders of magnitude higher than the equilibrium oxygen partial pressure of Ce₂O₃/CeO₂, 2.5×10⁻²⁰ atm, at the same temperature.