Fabrication and characterization of In doped Li13.9Sr0.1Zn(GeO4+δ)4 electrolytes for proton-conducting solid oxide fuel cells

Li_13.9Sr_0.1Zn(GeO_4+δ)₄ (LSZG) materials can exhibit proton conduction by Li⁺/H⁺ ion exchange in hydrogen atmosphere. It can be used in solid oxide fuel cells (SOFCs) as an electrolyte. In this study, In³⁺ doped LSZG powders are synthesized by sol-gel method. X-ray diffraction, scanning electron microscopy, thermal gravimetric analyzer, and electrochemical impedance spectroscopy are used to investigate the effects of In doping on LSZG. All Li_13.9-xIn_xSr_0.1Zn(GeO_4+δ)₄ (LISZG, 0 ≤ x ≤ 0.3) ceramics exhibit the same phase with LSZG. The dopant of In promotes the sintering activity and Li⁺/H⁺ ion exchange rate of LSZG. The optimum doping of In is x = 0.2. At 600 °C, Li_13.7In_0.2Sr_0.1Zn(GeO_4+δ)₄ (0.2LISZG) shows a proton conductivity of 0.094 S/cm under 0.9 V direct current bias voltage. In addition, the single cell based on 0.2LISZG electrolyte is prepared, and it has been demonstrated that the practical utilization of 0.2LISZG in IT-SOFCs is feasible.     

Electrocatalytic activity of LaSr3Fe3O10 and LaSr3Fe3O10-GO towards oxygen reduction reaction in alkaline medium

Oxygen reduction reaction(ORR) plays a critical role in many energy conversion and storage processes.Therein, a comparative study of the electrocatalytic activity for ORR in 0.1 mol/L KOH solution was conducted using layered perovskite-like LaSr_3 Fe_3 O_(10) and LaSr3 Fe_3 O_(10)-graphene oxide(GO) composite as electrodes. Linear sweep voltammetry(LSV) results show that the LaSr3 Fe_3 O_(10)-GO hybrid exhibits higher current density, a more positive onset potential(-0.15 V vs. Hg/HgO) in comparison with LaSr_3 Fe_3 O_(10).The value of the overall transferred electrons for both catalysts implies a dominant two electron process for ORR. Both catalysts under alkalic conditions exhibit a two-step Tafel slope, suggesting a change in the reaction mechanism for ORR. The composite electrode exhibits a higher ORR current density, but inferior durability performances in relative to the LaSr_3 Fe_3 O_(10) electrode.     

Boosting the activity of FeOOH via integration of ZIF-12 and graphene to efficiently catalyze the oxygen evolution reaction

Transition metal oxyhydroxides have been used as promising electrocatalysts for water splitting however, their catalytic activity is restricted due to low surface area and poor conductivity. Herein, we report novel composite FeOOH@ZIF-12/graphene composite as electrocatalyst for water oxidation, whereby ZIF-12 provide extra surface for the FeOOH dispersion whilst graphene act as excellent electron mediator. The composite shows a low overpotential value of 291 mV to attain a current density of 10 mA cm^?2 and a low Tafel slope value of 78 mV dec^?1. The catalyst offers a maximum current density of 101 mA cm^?2, while it gives a turnover frequency (TOF) value of 0.031 s^?1 at an overpotential of 291 mV only. The excellent activity and remarkable stability of composite is attributed to highly conductive and porous support.     

Charge injection in metal/organic/metal structures with ZnO:Al/organic interface modified by Zn1−xMgxO:Al layer

Aluminum-doped zinc oxide (ZnO:Al, AZO) electrodes were covered with very thin (∼6 nm) Zn_1−xMg_xO:Al (AMZO) layers grown by atomic layer deposition. They were tested as hole blocking/electron injecting contacts to organic semiconductors. Depending on the ALD growth conditions, the magnesium content at the film surface varied from x = 0 to x = 0.6. Magnesium was present only at the ZnO:Al surface and subsurface regions and did not diffuse into deeper parts of the layer. The work function of the AZO/AMZO (x = 0.3) film was 3.4 eV (based on the ultraviolet photoelectron spectroscopy). To investigate carrier injection properties of such contacts, single layer organic structures with either pentacene or 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine layers were prepared. Deposition of the AMZO layers with x = 0.3 resulted in a decrease of the reverse currents by 1–2 orders of magnitude and an improvement of the diode rectification. The AMZO layer improved hole blocking/electron injecting properties of the AZO electrodes. The analysis of the current-voltage characteristics by a differential approach revealed a richer injection and recombination mechanisms in the structures containing the additional AMZO layer. Among those mechanisms, monomolecular, bimolecular and superhigh injection were identified.     

Investigation of LSM-8YSZ cathode within an all ceramic SOFC. Part I: Chemical interactions

This work focuses on a novel, co-sintered, all-ceramic solid oxide fuel cell (SOFC) concept. The objective is the understanding of interaction and degradation mechanisms of the cathode and current collector layers within the design during co-sintering. Half cells consisting of silicate mechanical support, lanthanum strontium manganite (LSM) current collector, LSM mixed with 8 mol% yttria-stabilized zirconia (8YSZ) composite cathode and 8YSZ electrolyte were co-sintered at 1150 °C < T < 1250 °C. Crystallographically stable LSM compositions within the design were identified. However, the cathode and silicate/electrolyte interacted by interdiffusion of Zn (gas diffusion) and Mn (solid diffusion), and by the formation of several reaction phases (between silicate and cathode only). Introducing silicate poisoning decreased the electrochemical performance of the cell by around 40%. This is likely due to the formation of the Zn- and Mn-rich phase in the cathode, but may also be caused by a higher ohmic resistance of the current collector.     

La0.6Sr0.4Co0.2Fe0.8O3-δ nanofiber cathode for intermediate-temperature solid oxide fuel cells by water-based sol-gel electrospinning: Synthesis and electrochemical behaviour

Water-based sol-gel electrospinning is employed to manufacture perovskite oxide La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) nanofiber cathodes for intermediate-temperature solid oxide fuel cells. LSCF fibrous scaffolds are synthesized through electrospinning of a sol-gel solution employing water as the only solvent. Morphological characterizations demonstrate that the LSCF fibers have highly crystalline structure with uniform elemental distribution. After heat treatment, the average fiber diameter is 250 nm and the porosity of the nanofiber tissue is 37.5 %. The heat treated LSCF nanofibers are applied directly onto a Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte disk to form a symmetrical cell. Electrochemical characterization is carried out through electrochemical impedance spectroscopy (EIS) in the temperature range 550?°C–950?°C, and reproducibility of the electrochemical performance for a series of cells is demonstrated. At 650?°C, the average measured polarization resistance R_p is 1.0 Ω cm². Measured performance decay is 1 % during the first 33?h of operation at 750?°C, followed by an additional 0.7 % over the subsequent 70?h.     

Synergistic flame retardant effects of activated carbon and molybdenum oxide in poly(vinyl chloride)

The synergistic effects of activated carbon (AC) and molybdenum oxide (MoO₃) in improving the flame retardancy of poly(vinyl chloride) (PVC) were investigated. The effects of AC, MoO₃ and their mixture with a mass ratio of 1:1 on the flame retardancy and smoke suppression properties of PVC were studied using the limiting oxygen index and cone calorimeter tests. It was found that the flame retardancy of the relatively cheaper AC was slightly weaker than that of MoO₃. In addition, the incorporation of AC and MoO₃ greatly reduced the total heat release and improved smoke suppressant property of PVC composites. When the total content of AC and MoO₃ was 10 phr, PVC/AC/MoO₃ had the lowest peak heat release rate and peak smoke production rate values of 173.80 kW m^?2 and 0.1472 m² s^?1, which represented reductions of 47.3 and 59.9%, respectively, compared with those of PVC. Furthermore, thermogravimetric analysis and gel content tests were used to analyze the flame retardant mechanism of AC and MoO₃, with results showing that AC could promote early crosslinking in PVC. Char residue left after heating at 500 °C was analyzed using scanning electron microscopy and Raman spectroscopy, and the results showed that MoO₃ produced the most compact char, with the smallest and most organized carbonaceous microstructures. © 2017 Society of Chemical Industry     

Hierarchical Ni-BDC coated FeOOH nanosheets: A coordination tuning synergistic electrocatalyst with enhanced activity for water oxidation

Hierarchical composites represent a class of efficient electrocatalysts for renewable energy storage and conversion technologies owing to the porous structure and additional exposure of metal sites. Herein, a Ni-based metal organic frameworks (MOFs) (marked as Ni-BDC, BDC stands for 1,4-benzenedicarboxylic acid) nanosheet is successfully fabricated on hydroxyl iron oxide (FeOOH) array with carbon fiber cloth (CFC) as substrate. Benefit from the coordination tuning synergistic effect of the distinct chemical composition and the hierarchical structure for fast mass transportation, the as-obtained FeOOH@Ni-BDC illustrates excellent catalytic ability for electrochemical water oxidation with low overpotential of 270 mV to reach 10 mA/cm² current and good durability in alkaline electrolyte. The novelty of this work lies in the modulation of electronic structure of the FeOOH with Ni-BDC through coordination effect to enhance the activity of the hierarchical composite electrocatalyst. This work is expected to guide the preparation of efficient electrocatalyst for new type alternative energy sources exploitation in near future.     

Enhanced graphitic domains of unreduced graphene oxide and the interplay of hydration behaviour and catalytic activity

Previous studies indicate that the properties of graphene oxide (GO) can be significantly improved by enhancing its graphitic domain size through thermal diffusion and clustering of functional groups. Remarkably, this transition takes place below the decomposition temperature of the functional groups and thus allows fine tuning of graphitic domains without compromising with the functionality of GO. By studying the transformation of GO under mild thermal treatment, we directly observe this size enhancement of graphitic domains from originally ≤40 nm² to >200 nm² through an extensive transmission electron microscopy (TEM) study. Additionally, we confirm the integrity of the functional groups during this process by a comprehensive chemical analysis. A closer look into the process confirms the theoretical predicted relevance for the room temperature stability of GO and the development of the composition of functional groups is explained with reaction pathways from theoretical calculations. We further investigate the influence of enlarged graphitic domains on the hydration behaviour of GO and the catalytic performance of single atom catalysts supported by GO. Additionally, we show that the sheet resistance of GO is reduced by several orders of magnitude during the mild thermal annealing process.