Fabrication and structural characterization of interdigitated thin film La1 − x Sr x CoO 3 (LSCO) electrodes

For the prospective use as micro-Solid Oxide Fuel Cell (μ-SOFC) cathodes and for the investigation of reaction kinetics, La1 − xSrxCoO3 (LSCO) mixed ionic electronic conducting thin films were deposited by DC and RF sputtering onto a number of different substrate materials and characterized. Standard photolithographic and wet chemical etching methods were utilized to microstructure the LSCO films and XRD, SEM, AFM, WDS, and RBS were used to characterize their structure, topography, and chemistry. Sputtering resulted in very homogeneous and smooth thin crystalline films with Sr deficiency and submicron sized grains. Hydrochloric acid was found to readily etch LSCO with the etching quality strongly dependent on substrate material. LSCO films were most easily etched when deposited directly on silicon substrates, etched at intermediate rates when deposited on Gd:CeO2 films, and most resistant to etching after deposition onto single crystal yttria stabilized zirconia (YSZ) substrates. Imperfect etching was attributed to interface formation and the presence of impuritie

Tailoring the performance of ZnO for oxygen evolution by effective transition metal doping

In the quest for active and inexpensive (photo)electrocatalysts, atomistic simulations of the oxygen evolution reaction (OER) are essential for understanding the catalytic process of water splitting at solid surfaces. In this paper, we study the enhancement of the OER by first-row transition-metal (TM) doping of the abundant semiconductor ZnO, using density functional theory (DFT) calculations on a substantial number of possible structures and bonding geometries. The calculated overpotential for undoped ZnO is 1.0 V. For TM dopants in the 3d series from Mn to Ni, the overpotentials decrease from 0.9 V for Mn, and 0.6 V for Fe, down to 0.4 V for Co, and rise again to 0.5 V for Ni and 0.8 eV for Cu. We analyze the overpotentials in terms of the binding to the surface of the species involved in the four reaction steps of the OER. The Gibbs free energies associated with the adsorption of these intermediate species increase down the series from Mn to Zn, but the difference between OH and OOH adsorption (the species involved in the first, respectively the third reaction step) is always in the range 3.0-3.3 eV, despite a considerable variation in possible bonding geometries. The bonding of the O intermediate species (involved in the second reaction step), which is optimal for Co, and to a somewhat lesser extend for Ni, then ultimately determines the overpotential. These results imply that both Co and Ni are promising dopants for increasing the activity of ZnO-based anodes for the OER.</p

Photoelectrochemical properties of plasma-induced nanostructured tungsten oxide

Helium (He)-induced nanostructured tungsten sheets were synthesized by He plasma irradiation under different plasma exposure durations. After calcination, nanostructured tungsten oxide samples were used as photoelectrodes to test photoelectrochemical (PEC) performance. The results showed that nanostructured WO3 photoanodes have higher PEC performance compared to the sample without nanostructures. The 15 min irradiated sample had the highest photocurrent density of 3.5 mA/cm2 under the thermodynamic potential of water oxidation (1.23 V vs. RHE). It was found that the oxide layer thickness and exposed crystal facet have a significant impact on PEC performance. The plasma synthesis technique has proved to be an effective method for preparing nanostructured WO3 photoelectrodes.</p

Micro-solid oxide fuel cells: status, challenges, and chances

Abstract: Micro-solid oxide fuel cells (micro-SOFC) are predicted to be of high energy density and are potential power sources for portable electronic devices. A micro-SOFC system consists of a fuel cell comprising a positive electrode-electrolyte-negative electrode (i.e. PEN) element, a gas-processing unit, and a thermal system where processing is based on micro-electro-mechanical-systems fabrication techniques. A possible system approach is presented. The critical properties of the thin film materials used in the PEN membrane are discussed, and the unsolved subtasks related to micro-SOFC membrane development are pointed out. Such a micro-SOFC system approach seems feasible and offers a promising alternative to state-of-the-art batteries in portable electronics. Graphical abstract: Graphical Abstract tex

Role of Excess Bi on the Properties and Performance of BiFeO₃ Thin-Film Photocathodes

BiFeO3 (BFO) has recently been identified as a promising photocathode material for photoelectrochemical (PEC) water splitting due to its light absorption and photoelectrochemical properties. The performance-limiting factors, in particular the impact of stoichiometry on the performance, still need to be understood. The effect of the ratio of Bi/Fe in the precursor solution for sol-gel synthesis on the properties and performance of BFO thin films is investigated in this study. Thin films with a stoichiometric Bi/Fe ratio and with a 10% excess of Bi are prepared on fluorine-doped tin-oxide substrates. While bulk characterization techniques show the formation of phase-pure BFO, surface characterization techniques indicate Bi enrichment on the surface. Light absorption and band gap do not change with excess Bi, whereas the current density is two times higher for Bi excess films compared to stoichiometric films at 0.6 V vs RHE. Electrochemical impedance spectroscopy attributes this improved performance of excess Bi thin films to a lower recombination rate and a lower charge transfer resistance. The lower recombination rate is attributed to fewer Bi and O vacancies, which can act as recombination centers. Therefore, adjusting the Bi/Fe ratio is an effective strategy to enhance the PEC performance of BFO photocathodes.</p

Syngas generation from n-butane with an integrated MEMS assembly for gas processing in micro-solid oxide fuel cell systems

An integrated system of a microreformer and a carrier allowing for syngas generation from liquefied petroleum gas (LPG) for micro-SOFC application is discussed. The microreformer with an overall size of 12.7 mm × 12.7 mm × 1.9 mm is fabricated with micro-electro-mechanical system (MEMS) technologies. As a catalyst, a special foam-like material made from ceria-zirconia nanoparticles doped with rhodium is used to fill the reformer cavity of 58.5 mm3. The microreformer is fixed onto a microfabricated structure with built-in fluidic channels and integrated heaters, the so-called functional carrier. It allows for thermal decoupling of the cold inlet gas and the hot fuel processing zone. Two methods for heating the microreformer are compared in this study: a) heating in an external furnace and b) heating with the two built-in heaters on the functional carrier. With both methods, high butane conversion rates of 74%–85% are obtained at around 550 °C. In addition, high hydrogen and carbon monoxide yields and selectivities are achieved. The results confirm those from classical lab reformers built without MEMS technology (N. Hotz et al., Chem. Eng. Sci., 2008, 63, 5193; N. Hotz et al., Appl. Catal., B, 2007, 73, 336). The material combinations and processing techniques enable syngas production with the present MEMS based microreformer with high performance for temperatures up to 700°C. The functional carrier is the basis for a new platform, which can integrate the micro-SOFC membranes and the gas processing unit as subsystem of an entire micro-SOFC system

Micro-solid oxide fuel cells running on reformed hydrocarbon fuels

Micro‐solid oxide fuel cell (micro‐SOFC) systems are predicted to have a high energy density and specific energy and are potential power sources for portable electronic devices. A micro‐SOFC system is under development in the frame of the ONEBAT project [1‐3]. In this presentation, we report on the fabrication and characterization of a sub‐system assembly consisting of a startup heater and a micro‐reformer bonded to a Si chip with electrochemically‐active micro‐SOFC membranes. A functional carrier including fluidic channels for gas feed and integrated heaters was bonded to a microreformer with an overall size of 12.7 mm x 12.7 mm x 1.9 mm [4‐7]. As a catalyst, a foam‐like material made of ceria‐zirconia nanoparticles doped with rhodium was used to fill the 58.5 mm3 reformer cavity. This micro‐reformer allows for high methane and butane conversion of > 90 % with a hydrogen selectivity of > 80 % at 550 °C in the reformer [7, 8]. A silicon chip with 30 free‐standing micro‐SOFC membranes (390 μm x 390 μm) with a thickness of less than 500 nm was bonded to the carrier‐reformer assembly described above. The micro‐SOFC membrane consisted of an yttria‐ stabilized zirconia thin film electrolyte. Both Pt‐based and ceramic‐based electrode materials were tested regarding the thermal stability and carbon poisoning at temperatures below 600 °C. The functional‐carrier mirco‐reformer micro‐SOFC assembly was electrochemically tested with hydrocarbon fuel between 300 °C and 600 °C. The fuel cell performance and the microstructural evolution of the anode are discussed as well