Potentialities of the sol-gel route to develop cathode and electrolyte thick layers Application to SOFC systems

In this work, we report the potential of sol–gel process to prepare cathode and electrolyte thin and thick layers on anodic NiO-YSZ supports which were also made from powders prepared by sol–gel route. YSZ and La2 − xNiO4 + δ, La4Ni3O10 were synthesized as electrolyte and cathode materials for SOFC applications. For electrolyte shaping, yttria stabilized zirconia (YSZ, 8% Y2O3) thick films were cast onto porous NiO-YSZ composite substrates by a dip-coating process using a new suspension formulation. Part of the YSZ precursor colloidal sol was added in the suspension to ensure both homogeneity and adhesion of the electrolyte on the anodic substrate after thermal treatment at 1400 °C for 2 h. By precisely controlling the synthesis parameters, dense and gas-tight layers with thicknesses in the range of 10–20 μm have been obtained. Gas-tightness was confirmed by He permeation measurements. Concerning cathode processing, a duplex microstructured cathode consisting of both La2 − xNiO4 + δ ultra-thin films (few nanometers) and La2 − xNiO4 + δ and/or La4Ni3O10 thick layers (few micrometers) was prepared on YSZ substrates by the dip-coating process, with the thickness being dependent on the nature of the dip-coated solution (polymeric sol or adequate suspension). The derived cathode microstructure, related to the number/thickness of layers and type of architecture, was correlated to the good cell electrochemical performances. Concerning cathode processing, a duplex microstructured cathode consisting of both La2 ? xNiO4 + ? ultra-thin films (few nanometers) and La2 ? xNiO4 + ? and/or La4Ni3O10 thick layers (few micrometers) was prepared on YSZ substrates by the dip-coating process, with the thickness being dependent on the nature of the dip-coated solution (polymeric sol or adequate suspension). The derived cathode microstructure, related to the number/thickness of layers and type of architecture, was correlated to the good cell electrochemical performances

Development of lanthanum nickelate as a cathode for use in intermediate temperature solid oxide fuel cells

The performance of lanthanum nickelate, La2NiO4+δ (LNO), as a cathode in IT-SOFCs with the electrolyte cerium gadolinium oxide, Ce0.9Gd0.1O2−δ (CGO), has been investigated by AC impedance spectroscopy of symmetrical cells. A significant reduction in the area specific resistance (ASR) has been achieved with a layered cathode structure consisting of a thin compact LNO layer between the dense electrolyte and porous electrode. This decrease in ASR is believed to be a result of contact at the electrolyte/cathode boundary enhancing the oxygen ion transfer to the electrolyte. An ASR of 1.0 Ω cm2 at 700 °C was measured in a symmetrical cell with this layered structure, compared to an ASR of 7.4 Ω cm2 in a cell without the compact layer. In addition, further improvements were observed by enhancing the cell current collection and it is anticipated that a symmetrical cell consisting of a layered structure with adequate current collection would lower these ASR values further

Laser induced densification of cerium gadolinium oxide: application to single-chamber solid oxide fuel cells

International audienceIn single-chamber solid oxide fuel cells (SC-SOFC), anode and cathode are placed in a gas chamber where they are exposed to a fuel/air mixture. Similarly to conventional dual-chamber SOFC, the anode and the cathode are separated by an electrolyte. However, as in the SC-SOFC configuration the electrolyte does not play tightness role between compartments, this one can be a porous layer. Nevertheless, it is necessary to have a diffusion barrier to prevent the transportation of hydrogen produced locally at the anode to the cathode that reduces fuel cell performances. This study aims to obtain directly a diffusion barrier through the surface densification of the electrolyte Ce0.9Gd0.1O1.95 (CGO) by a laser treatment. KrF excimer laser and Yb fiber laser irradiations were used at different fluences and number of pulses to modify the density of the electrolyte coating. Microstructural characterizations confirmed the modifications on the surface of the electrolyte for appropriate experimental conditions showing either grain growth or densified but cracked surfaces. Gas permeation and electrical conductivities of the modified electrolyte were evaluated. Finally SC-SOFC performances were improved for the cells presenting grain growth at the electrolyte surface

Anode supported single chamber solid oxide fuel cells operating in exhaust gases of thermal engine

International audienceThis project deals with the development and the electrochemical characterization of anode supported single chamber SOFC in a simulated environment of thermal engine exhaust gas. In the present work, a gas mixture representative of exhaust conditions is selected. It is composed of hydrocarbons (HC: propane and propene), oxygen, carbon monoxide, carbon dioxide, hydrogen and water. Only oxygen content is varied leading to different gas mixtures characterized by three ratios R = HC/O2. Concerning the cell components, a cermet made of nickel and an electrolyte material, Ce0.9Gd0.1O1.95 (CGO) is used as anode and two cathode materials, La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) and Pr2NiO4+δ (PNO), are evaluated. The prepared cells are investigated in the various gas mixtures for temperatures ranging from 450 °C to 600 °C. Ni-CGO/CGO/LSCF-CGO cell has delivered a maximum power density of 15 mW cm−2 at 500 °C with R = HC/O2 = 0.21, while lower power densities are obtained for the other ratios, R = 0.44 and R = 0.67. Afterwards, LSCF and PNO cathode materials are compared and LSCF is found to deliver the highest power densities. Finally, by improving the electrolyte microstructure, some cells presenting a maximum power density of 25 mW cm−2 at 550 °C are produced. Moreover, up to 17% of initial HC are eliminated in the gas mixture

Tunable architecture for flexible and highly conductive graphene-polymer composites

International audiencePrinted electronics, particularly on flexible and textile substrates, raised a strong interest during the past decades. This work presents a good candidate for conductive inks based on a graphene/polymer nanocomposite material that gathers three main benefits that are 1 - neither clogging nor flocculation, 2 - spontaneous film formation around room temperature, 3 - high conductivity. Nanosized Multilayered Graphene (NMG) is produced through a solvent-free procedure, using a grinding process in water. These NMG suspensions are used to elaborate conductive composite materials through physical blending with emulsifier-free latex. The nanocomposite microstructure exhibits a well-defined cellular architecture that highlights the formation of continuous paths of fillers throughout the material. The conductivity behavior of the nanocomposite material was efficiently described using a percolation model: the conductivity can be tuned by changing the NMG content and the latex size. A low percolation threshold (0.1 vol%) was obtained and the electrical conductivity reached 217 S m−1 for 6 vol% NMG. Efficient film forming occurs at room temperature leading to continuous and deformable materials, which is adequate for printing on flexible and textile substrates. The applicability in electronics is demonstrated by the use of the nanocomposite material in replacement of copper wires in a LED setup

Elaboration of metallic compacts with high porosity for mechanical supports of SOFC

The development of third generation Solid Oxide Fuel Cells (SOFC) with metallic mechanical supports presents several advantages over that of ceramic stacks by offering a lower cost and longer lifetime of the stacks. As a consequence, it is necessary to prepare metallic porous compacts that remain stable at the operating temperature of the SOFC (700–800 C) under reductive atmosphere. This paper presents an innovative process to elaborate iron, nickel and cobalt porous compacts. The process is based on the thermal decomposition of metal oxalate precursors with controlled morphology into metallic powders with coralline shape. Uniaxial compaction of such powders (without binder addition to the powders) under low uniaxial pressures (rising from 20 to 100 MPa) gave rise to green compacts with high porosity and good mechanical properties. After annealing at 800 C under H2 atmosphere, the compacts still present interconnected porosity high enough to allow sufficient gas flow to feed a SOFC single cell in hydrogen: the porosity rises from 25 to 50% for iron compacts, from 20 to 50% for cobalt compacts, and is higher than 40% for nickel compacts. Results from physicochemical characterization (XRD, SEM, gas permeation, Hg porosimetry) corroborated the process for SOFC application

Functionalization of APTES modified tin dioxide gas sensor

Communication présentée dans la session "Metal Oxide Gas Sensor".International audienceSummary In the present work, commercial SnO2 powder was used for sensor thick film fabrication. The film was produced using screen printing technology. The SnO2 functionalization was done with 3-aminopropyltriethoxysilane (APTES) in liquid phase as an intermediate step, followed by functionalization using hexanoyl chloride exhibiting an alkyl end functional (CH3) group. The SnO2 sensor modified with alkyl end group was found to be sensitive to ammonia gas at 100°C. The advantages are the reduction of the power consumption by decreasing the operating temperature, and the enhancement of the selectivity and sensitivity to the gas with respect to pure SnO2 sensor.MotivationMolecularly modified metal oxide gas sensors have shown to be promising devices for selective gas sensor related to disease diagnosis. Those sensors can be used to detect the gas emanated from the human body for breath analysis application. Tin dioxide sensors have lack of selectivity and work at high temperature (350-500°C). The need of selective sensors with high sensitivity at low gases concentration pushes us to modify SnO2 sensing element in order to change its interactions with gas. The modification with organic functional groups with different polarities change the sensor response to specific gases depending on their polarity. A SnO2 functionalization based on APTES combined with hexanoyl chloride was investigated. Another objective is to reduce the power consumption by decreasing the operating temperature

SOFC long term operation in pure methane by gradual internal reforming

International audienceA solid oxide fuel cell was designed to be operated in pure methane, without reforming or carrier gas. The fuel cell was built up from conventional NiO-YSZ anode supported cell with a specific Pt screen-printed anodic collecting system and a Ir-CGO catalytic layer. The operation principle is based on Gradual Internal Reforming. After an initiation in H2 for 30 minutes, the cell was operated for almost 2000 hours in pure and dry CH4 with a fuel utilization rate of 30 %. Intrinsic gradual degradation of 15 %/1000 h was observed, but no coking occurred at the anodic side

Effect of Catalyst Layer and Fuel Utilization on the Durability of Direct Methane SOFC

International audienceSolid oxide fuels cells with and without anodic catalytic layer and specific anodic current collectors were developed in order to be fueled by dry methane. Due to the cell architecture integrating a 0.1wt% Ir-CGO catalyst layer onto the anode, platinum, gold and cupper screen-printed meshes were designed and optimized to ensure efficient current collection between the anode surface and the catalyst membrane. Current density and ageing in H2 and in pure dry CH4 respectively were compared to conventional pressed grid collecting systems. Similar performances were achieved using bulk grids or gold, platinum and copper screen-printed meshes. Operation in pure dry methane is compared with and without the catalytic layer as a function of the fuel utilization. It is demonstrated that long term operation is possible provided that sufficient faradic efficiency is achieved