Micro-tubular Solid Oxide Fuel Cells with Nickelate Cathode-support

The shortage of natural resources, rising energy demands and global warming have created an urgent need for more efficient energy conversion devices and different energy resources to achieve a more sustainable and efficient economy. Solid Oxide Fuel Cells (SOFC) are one of the most promising devices for the direct conversion from chemical to electrical energy in conjunction with high system efficiencies. Micro-tubular SOFC have been investigated since roughly 15 years. In contrast to planar systems, which produce electricity in the kW to MW range and target utilisation in stationary applications such as CHP plants, micro-tubular SOFC systems can be envisaged for mobile application due to quick start-up/shutdown operation. While most micro-tubular cells are mechanically supported by the electrolyte or anode, only few researches have investigated cathode-supported cells due to challenging fabrication. In this work, the new cathode material neodymium nickelate (NNO), Nd1.95NiO4+δ, was used as mechanical support, which is a novelty of this work, for micro-tubular SOFC. Different fabrication routes were used to create small tubes of 2-6 mm diameter. These tubes were evaluated with respect to their gas-diffusion properties by a new, self-manufactured diffusion setup and a complementary permeation setup. In order to achieve an economical fabrication process, the low-cost dip-coating method was investigated for the deposition of thin films from wet-chemical suspensions to create entire SOFC single cells. As SOFCs require gas-tight electrolyte layers, cofiring of tubular substrates and thin films must be executed to allow sufficient shrinkage of the deposited electrolyte thin layers to full density. Various electrolyte and electrode powders were characterised in different solvents, dispersants and binders with respect to low-temperature sintering feasibility. The shrinkage of scandia-stabilised zirconia (ScSZ) powder was decreased to 18% to still deliver sufficient sintered density by optimisation of the green density (usually zirconia requires shrinkage of 25% and more for densification). The cofiring temperature depends on the densification behaviour of powders but also on reactivity between adjacent layers. The reactivity between gadolinia-doped ceria (GDC)-interlayers and different zirconia materials was tested and showed lower compatibility of yttria-stabilised zirconia (YSZ) with GDC than for ScSZ/GDC reaction couples, which has not been reported so far. The interface of NNO cathodes and GDC interlayers was analysed by reactivity mapping and quantitative phase analysis. The performance optimisation of NNO/GDC interfaces by exchange current density measurement of NNO-cathodes sintered at different temperatures on GDC pellets is a further contribution of this work. The reactivity and performance investigations provide clear guidelines for maximum allowable cosintering temperature. Some electrochemical single cell tests showed competitive area-specific resistances (ASR) of ca. 1 Ωcm2 but were limited unfortunately by the counterelectrode microstructure and current collection methods, which were not the focus of this work. Open-circuit voltages (OCV) were 0.6-1.1 V at 700 °C in dry hydrogen atmosphere for tubes prepared by extrusion but only 0.3 V for tubes prepared by slip-casting. The electrochemical performances were modest with only 0.035 W/cm2 power density at 700 °C for tubes prepared by extrusion due to the elevated resistances of the counterelectrode and current collection.

Reversible solid-oxide cell stack based power-to-x-to-power systems: Comparison of thermodynamic performance

Philippe Aubin, Tzu-En Lin, François Maréchal, Maria del Mar Perez Fortes, Jan Van Herle, Ligang Wang, Yumeng Zhang

The increasing penetration of variable renewable energies poses new challenges for grid management. The economic feasibility of grid-balancing plants may be limited by low annual operating hours if they work either only for power generation or only for power storage. This issue might be addressed by a dual-function power plant with power-to-x capability, which can produce electricity or store excess renewable electricity into chemicals at different periods. Such a plant can be uniquely enabled by a solid-oxide cell stack, which can switch between fuel cell and electrolysis with the same stack. This paper investigates the optimal conceptual design of this type of plant, represented by power-to-x-to-power process chains with x being hydrogen, syngas, methane, methanol and ammonia, concerning the efficiency (on a lower heating value) and power densities. The results show that an increase in current density leads to an increased oxygen flow rate and a decreased reactant utilization at the stack level for its thermal management, and an increased power density and a decreased efficiency at the system level. The power-generation efficiency is ranked as methane (65.9%), methanol (60.2%), ammonia (58.2%), hydrogen (58.3%), syngas (53.3%) at 0.4 A/cm2, due to the benefit of heat-to-chemical-energy conversion by chemical reformulating and the deterioration of electrochemical performance by the dilution of hydrogen. The power-storage efficiency is ranked as syngas (80%), hydrogen (74%), methane (72%), methanol (68%), ammonia (66%) at 0.7 A/cm2, mainly due to the benefit of co-electrolysis and the chemical energy loss occurring in the chemical synthesis reactions. The lost chemical energy improves plant-wise heat integration and compensates for its adverse effect on power-storage efficiency. Combining these efficiency numbers of the two modes results in a rank of round-trip efficiency: methane (47.5%) > syngas (43.3%) ≈ hydrogen (42.6%) > methanol (40.7%) > ammonia (38.6%). The pool of plant designs obtained lays the basis for the optimal deployment of this balancing technology for specific applications.

2020

Chemical and electrochemical promotion of supported rhodium catalyst

Olena Baranova

The chemical and electrochemical promotion of highly dispersed nanofilm Rh catalysts (dispersion: about 10 %, film thickness: 40 nm) has been investigated for the first time. To this end Rh metal was sputter-deposited, either on a purely ionic conductor (8 % Y2O3-stabilized ZrO2) or on a mixed ionic-electronic conductor (TiO2), the latter being a highly dispersed layer of TiO2 (4 µm) deposited on YSZ. These catalysts are designated as Rh/YSZ and Rh/TiO2/YSZ, respectively. It was established analytically that both in the Rh/YSZ and in the Rh/TiO2/YSZ system, the catalyst films have a nanoparticle-size grain structure. The Rh supported on titania is rather porous, exhibiting a higher dispersion and surface area than Rh on YSZ. Both after reduction (H2, T=400 °C) and after oxidation (O2, T=400 °C), Rh supported on TiO2 was found to be in a more highly reduced state than Rh on YSZ. After reducing treatment, the Rh/TiO2/YSZ samples contain a larger amount of weakly bonded oxygen, which can be attributed to oxygen "backspillover" from the TiO2. A major feature of this research was the electrochemical characterization of the oxygen/Rh/solid electrolyte three-phase boundary by steady-state polarization measurements and by impedance spectroscopy. These are powerful techniques for extracting experimental trends and details that are useful for an understanding of the electrochemical promotion principles. It was shown that the exchange current densities at the Rh/solid electrolyte interface are lower on account of the TiO2 layer. The exchange current densities are more than twice lower at Rh/TiO2(4 µm)/YSZ than at Rh/YSZ, demonstrating that the former interface is much more polarizable. The mechanism of oxygen exchange occurring close to equilibrium (O2/O2- couple) was investigated for the first time at Rh catalyst electrodes interfaced with solid electrolyte. The processes of cathodic oxygen reduction and anodic oxygen evolution are not symmetric, but they are similar in the two systems, Rh/YSZ and Rh/TiO2(4 µm)/YSZ. The cathodic process consists of three steps: dissociative adsorption of oxygen at the gas-exposed Rh surface, atomic oxygen diffusion to the electrochemical reaction sites (ERS), and a two-electron transfer to this oxygen on the ERS. The cathodic process is limited by interfacial diffusion of oxygen atoms from the gas-exposed metal surface to the ERS. The anodic process includes two steps: two-electron transfer reaction, which is the rate-determining step, and oxygen desorption to the gas phase. With data obtained from impedance spectroscopy at the equilibrium potential, it was possible to confirm the reaction scheme proposed. It was demonstrated that Rh nanofilm catalysts interfaced with YSZ or TiO2/YSZ can be electrochemically promoted for the reaction of ethylene oxidation. Small anodic currents cause periodic oscillations in catalytic rate and potential of the Rh/YSZ catalyst, while at Rh/TiO2/YSZ they give rise to a stable and reversible rate enhancement by up to a factor 80. The increase in ethylene oxidation rate is up to 2000 times larger than the electrochemical rate, I/2F, of O2- oxidation. The pronounced electrochemical promotion behavior that has been observed is due to the anodically controlled migration of O2- species from the electrolyte to the Rh/gas interface. At the Rh surface, these species destabilize the formation of rhodium surface oxide (Rh2O3). The existence of backspillover oxygen species has been confirmed by impedance measurements under positive applied potential. Another significant result for heterogeneous catalysis is the finding that thick as well as thin films of Rh/TiO2/YSZ catalyst are open to chemical promotion of ethylene oxidation and partial methane oxidation, ie, they offer a higher catalytic activity and stability than the Rh/YSZ catalysts. The modification of catalytic activity observed for Rh/TiO2/YSZ was attributed to either a "long-range" electronic-type SMSI mechanism or to a self-driven electrochemical promotion mechanism. In both cases, the ultimate cause of promotion are different work functions of catalyst and support. Equilibration of the work functions of two solids in contact induces surface charging, a migration of O2- ions to the catalyst/gas interface, and a weakening of the Rh-O chemisorptive bonds. It facilitates reduction of oxidized surface sites. Another important achievement of the present work was that of exploring and confirming the possibilities of current-assisted activation of Rh/TiO2/YSZ catalysts. In partial methane oxidation using close to stoichiometric gas compositions (CH4 : O2 = 2 : 1) at 550 °C, the inactive (oxidized) Rh/TiO2/YSZ catalyst was successfully activated by applied currents, either positive or negative. This phenomenon is an example of "permanent" electrochemical promotion furnishing a permanent rate enhancement ratio of γ = 11. The activation by negative currents is explained in terms of an electrochemical reduction of rhodium surface oxide, while the activation by positive currents can be explained by the mechanism of electrochemical promotion.

EPFL2005

Microfabricated solid oxide fuel cells

Samuel Rey-Mermet

Micro-fabricated solid oxide fuel cells (µSOFCs) are finding an increasing interest as potential power sources for portable devices such as MP3 players or laptops. The aim of this work was to fabricate a µSOFC demonstrator that works at 500°C and is fuelled by hydrogen. This thesis was divided into two parts. The first one was devoted to the development of an electrolyte and electrodes in form of sputtered thin films with electrical and mechanical properties suitable for the implementation in a real cell. YSZ and CGO electrolyte have been reactively sputtered from metallic targets. Both films are dense and have a columnar microstructure. The ionic conductivity of these films was of 0.5 S/m at 550°C for the CGO and of 5.5 x 10-3 S/m at 500°C for the yttria stabilized zirconia (YSZ) . Albeit the ceria doped gadolinia (CGO) was a better ionic conductor at low temperature, it was not possible to obtain an open circuit voltage (OCV) with a CGO electrolyte film. Most likely, the reduction of the Ce+4 ion into Ce+3 in a hydrogen atmosphere creates an electrical leakage. Better results were obtained with YSZ layers. Single, (111) textured columnar films showed OCV's of 200 mV. Best results were obtained with a double layer of two different microstructures. The first one exhibited a dense, columnar microstructure with (111) texture. The second layer was porous with nanocrystalline grains and preferential (200) orientation. The improved properties are ascribed to the absence of film crossing grain boundaries. Of special interest is the mechanical stress behaviour upon heating to the operation temperature. The stress was investigated as a function of temperature up to 700°C. An anomalous, hysteretic behaviour was found during the first heating cycle in YSZ as well as CGO thin films. This phenomenon could be modelled as an oxygen uptake to fill up excess oxygen vacancies created during the sputtering process. The model allowed to derive a diffusion activation energy of 0.6 eV for these excess vacancies in YSZ. Annealing in air at 700 °C permits to reduce stress and to stabilize the YSZ membrane. As electrode materials, sputter deposited, porous platinum, porous Ni-CGO composites and dense LaxSr1-xCoO3-y (LSCO) thin films were developed and characterized. The PEN (Positive electrode-Electrolyte-Negative electrode) layer processes were combined with Micro Electro Mechanical System (MEMS) process technology to fabricate µSOFC test devices. The PEN membranes were liberated by deep silicon dry etching. The cell diameter was varied between 0.5 and 5 mm, the electrolyte thickness between 500 and 700 nm. A nickel grid grown by electroplating was used to support the electrolyte layer and to serves as current collector for the anode. The cell with a 5 mm diameter shows a very good mechanical stability up to 600°C in SOFC operating conditions and for several heating cycles. The functionality of the fuel cell with two 20 nm thick porous platinum electrodes and a YSZ bilayer electrolyte (500 nm) has been demonstrated. An OCV of 850 mV was measured at 500°C with hydrogen fuel. Unfortunately, a too high cathode contact resistance reduced the current to very low values. The achieved maximal power density was only 19 µW/cm2. A simple design change should remedy the problem.

EPFL2008