LSCF is a promising candidate for the cathode in SOFCs. Understanding the microstructural characteristics is crucial to its application because they predominately determine the performance and durability of the porous cathodes and hence of the SOFCs. To date little work has been reported on its mechanical properties and their correlation with the 3D microstructures. The main purpose of this research was to study the mechanical properties of both films and bulk samples, and to evaluate the effect of microstructural parameters, by means of both experimental and numerical methods. Room-temperature mechanical properties were investigated by nanoindentation. The elastic modulus of the bulk samples was found to increase from 33.8 to 174.3 GPa and hardness from 0.64 to 5.32 GPa as the porosity decreased from 0.45 to 0.05 after sintering at 900 to 1200C. It was shown that reliable measurements of the true properties of the films were obtained provided that the effects from both surface roughness and substrate were minimised to neglected levels within a certain range of indentation depth to film thickness ratio. The fracture toughnesses of bulk LSCF were determined to increase from 0.51 to 0.99 MPam0.5. The microstructures of films were characterised using FIB-SEM slice and view technique and the actual 3D microstructure models of the porous films were reconstructed based on the tomographic data obtained. Finite element modelling of the elastic modulus agreed well with the nanoindentation results. The 3D microstructures were numerically modified at constant porosity using cellular automaton method, so that the influence on elastic modulus of factors other than porosity could be evaluated. It was found that the heterogeneity of the pore structure has a significant influence on the elastic properties computed using mechanical simulation.
An organometallic powder (platinum (II) acetylacetonate) is decomposed in the post-discharge of an atmospheric RF plasma torch to deposit Pt nanoparticles on carbon black supports. The resulting nanohybrid materials are characterized by FEG-SEM and XPS techniques to highlight their high content in Pt, their oxidation degree, and the dispersion of the Pt nanoparticles on the substrate. ICP-MS and electrochemical characterizations in a single fuel cell (cyclic voltammetry, dynamic polarization curves) are also performed on electrodes realized by treating the powder mixture overlaid on gas diffus…
This report presents some of the key laboratory electrochemical battery testing methods that are used in fuel cell research. Methods such as voltammetry, chronoamperometry, chronopotentiometry, and electrochemical impedance spectroscopy are of major importance. All the electrochemical corrosion tests are performed through a tri-electrode polarization cell setup containing a reference electrode, a counter electrode, and the working electrode (metal sample of interest) in an electrolyte solution. All three electrodes are connected to a potentiostat. Corrosion of metal occurs through an oxidation…
The extent of irreversible deactivation of Pt towards hydrogen oxidation reaction (HOR) due to sulfur adsorption and subsequent electrochemical oxidation is quantified in a functional PEM fuel cell. At 70 °C, sequential hydrogen sulfide (H2S) exposure and electrochemical oxidation experiments indicate that as much as 6% of total Pt sites are deactivated per monolayer sulfur adsorption at open circuit potential of a PEM fuel cell followed by its removal. The extent of such deactivation is much higher when the electrode is exposed to H2S when the fuel cell is operating at a finite load, and is d…
The role of catalyst stability on the adverse effects of hydrogen peroxide (H2O2) formation rates in a proton exchange membrane fuel cell (PEMFC) is investigated for Pt, Pt binary (PtX, X = Co, Ru, Rh, V, Ni) and ternary (PtCoX, X = Ir, Rh) catalysts. The selectivity of these catalysts towards H2O2 formation in the oxygen reduction reaction (ORR) was measured on a rotating ring disc electrode. These measured values were used in conjunction with local oxygen and proton concentrations to estimate local H2O2 formation rates in a PEMFC anode and cathode. The effect of H2O2 formation rates on the m…
We report the performance of a hydrogen-chlorine electrochemical cell with a chlorine electrode employing a low precious metal content alloy oxide electrocatalyst for the chlorine electrode: (Ru_0.09Co_0.91)_3O_4. The cell employs a commercial hydrogen fuel cell electrode and transports protons through a Nafion membrane in both galvanic and electrolytic mode. The peak galvanic power density exceeds 1 W cm^-2, which is twice previous literature values. The precious metal loading of the chlorine electrode is below 0.15 mg Ru cm^-2. Virtually no activation losses are observed, allowing the cell t…
Characterizing electrochemical energy conversion devices during operation is an important strategy for correlating device performance with the properties of cell materials under real operating conditions. While operando characterization has been used extensively for low temperature electrochemical cells, these techniques remain challenging for solid oxide electrochemical cells due to the high temperatures and reactive gas atmospheres these cells require. Operando X-ray diffraction measurements of solid oxide electrochemical cells could detect changes in the crystal structure of the cell materi…
Development of materials for electrochemical energy conversion requires a deep understanding of the factors governing chemical and physical rates at submicron length scales. Many workers have sought to develop chemically sensitive in situ or operando imaging techniques targeting these length scales. However, current methods focus on steady-state or stepwise response. To probe electrode processes both spatially and temporally, we have developed a frequency-resolved implementation of X-ray absorption imaging (FR-XAS) that can measure local electrochemical response in operando during a global sin…
A combination of experimental measurements and numerical simulations are used to characterize the mechanical and electrochemical response of thin film amorphous Si electrodes during cyclic lithiation. Parameters extracted from the experiment include the variation of elastic modulus and the flow stress as functions of Li concentration; the strain rate sensitivity; the diffusion coefficient for Li transport in the electrode; the free energy of mixing as a function of Li concentration in the electrode; the exchange current density for the Lithium insertion reaction; as well as reaction rates and …
The process of creating an atomically defined and robust metallic tip is described and quantified using measurements of contact conductance between gold electrodes and numerical simulations. Our experiments show how the same conductance behavior can be obtained for hundreds of cycles of formation and rupture of the nanocontact by limiting the indentation depth between the two electrodes up to a conductance value of approximately $5G_{0}$ in the case of gold. This phenomenon is rationalized using molecular dynamics simulations together with density functional theory transport calculations which…
Solid-oxide fuel cells produce electric current from energy released by a spontaneous electrochemical reaction. The efficiency of these devices depends crucially on the microstructure of their electrodes and, in particular, on the three-phase boundary (TPB) length, along which the energy-producing reaction occurs. We present a systematic maximisation of the TPB length as a function of four readily-controllable microstructural parameters, for any given mean hydraulic radius, which is a conventional measure of the permeability to gas flow. We identify the maximising parameters and show that the …
A key cause of chemo-mechanical degradation in battery electrodes is that they undergo abrupt phase transformation during the charging/discharging cycle. This phase transformation is accompanied by lattice misfit strains that nucleate microcracks, induce fracture and, in extreme cases, amorphize the intercalation electrode. In this work, we propose a strategy to prevent the chemo-mechanical degradation of intercalation electrodes: we show that by engineering suitable film strains we can regulate the phase transformations in thin-film intercalation electrodes and circumvent the large volume cha…
Highly porous Pt/Al thin film electrodes on yttria stabilized zirconia electrolytes were prepared by dealloying of co-sputtered Pt/Al films. The oxygen reduction capability of the resulting electrodes was analyzed in a solid oxide fuel cell setup at elevated temperatures. During initial heating to 523 K exceptionally high performances compared to conventional Pt thin film electrodes were measured. This results from the high internal surface area and large three phase boundary length obtained by the dealloying process. Exposure to elevated temperatures of 673 K or 873 K gave rise to degradation…
In Li-ion batteries the electrochemical potential drives the redox reactions occurring at the interface between electrolyte and storage material, typically active particles for porous electrodes, allowing Li ions intercalation/extraction from electrodes. The limiting factor of the process is not solely related to the electrochemical affinity, but also to structural features as the morphology of the electrodes. In this note, the relevance of the electrodes architecture is investigated numerically, in terms of the electro-chemo-mechanical response of a battery cell with homogeneous electrodes an…
Amorphous/crystalline multilayer structures of Fe-P alloys were deposited electrochemically using the single bath technique. Hall-Petch behavior of microhardness with respect to sublayer thickness was observed down to a sublayer thickness of 15 nm. For thinner sublayers, a hardness plateau was obtained. The transition at a sublayer thickness of 15 nm coincides with the loss of the multilayer structure as observed in transmission electron microscopy. The transition is a possible result of a change in the amorphous to crystalline sublayer thickness ratio and the interface roughness development d…
Pt-Al and Pt-Y-Al thin film electrodes on yttria-stabilised zirconia electrolytes were prepared by dealloying of co-sputtered Pt-Al or Pt-Y-Al films. The selective dissolution of Al from the Pt-alloy compound causes the formation of a highly porous nanowire network with a mean branch thickness below 25 nm and a pore intercept length below 35 nm. The oxygen reduction capability of the resulting electrodes was analysed in a micro-solid oxide fuel cell setup at elevated temperatures (598-873 K). Here, we demonstrate that these nanoporous thin films excel "state-of-the-art" fuel cell electrodes in…
Uncovering microstructure evolution mechanisms that accompany the long-term operation of solid oxide fuel cells is a fundamental challenge in designing a more durable energy system for the future. To date, the study of fuel cell stack degradation has focused mainly on electrochemical performance and, more rarely, on averaged microstructural parameters. Here we show an alternative approach in which an evolution of three-dimensional microstructural features is studied using electron tomography coupled with topological data analysis. The latter produces persistent images of microstructure before …
A carbon corrosion model is developed based on the formation of surface oxides on carbon and platinum of the polymer electrolyte membrane fuel cell electrode. The model predicts the rate of carbon corrosion under potential hold and potential cycling conditions. The model includes the interaction of carbon surface oxides with transient species like OH radicals to explain observed carbon corrosion trends under normal PEM fuel cell operating conditions. The model prediction agrees qualitatively with the experimental data supporting the hypothesis that the interplay of surface oxide formation on c…
In this work we studied the influence of particle size and agglomeration in the performance of solid oxide fuel cell cathodes made with nanoparticles of La0.8Sr0.2MnO3. We followed two synthesis routes based on the Liquid Mix method. In both procedures we introduced additional reagents in order to separated the manganite particles. We evaluated cathodic performance by Electrochemical Impedance Spectroscopy in symmetrical (CATHODE/ELECTROLYTE/CATHODE) cells. Particle size was tuned by the temperature used for cathode sintering. Our results show that deagglomeration of the particles, serves to i…
We report in situ measurements of stress evolution in a silicon thin-film electrode during electrochemical lithiation and delithiation by using the Multi-beam Optical Sensor (MOS) technique. Upon lithiation, due to substrate constraint, the silicon electrode initially undergoes elastic deformation, resulting in rapid rise of compressive stress. The electrode begins to deform plastically at a compressive stress of ca. -1.75 GPa; subsequent lithiation results in continued plastic strain, dissipating mechanical energy. Upon delithiation, the electrode first undergoes elastic straining in the oppo…
This is the first quantitative analysis of mechanical reliability of all-solid state batteries. Mechanical degradation of the solid electrolyte (SE) is caused by intercalation-induced expansion of the electrode particles, within the constrain of a dense microstructure. A coupled electro-chemo-mechanical model was implemented to quantify the material properties that cause a SE to fracture. The treatment of microstructural details is essential to the understanding of stress-localization phenomena and fracture. A cohesive zone model is employed to simulate the evolution of damage. In the numerica…
Electrochemical devices such as solid oxide fuel cells (SOFC) may greatly benefit from the implementation of nanoengineered thin-film multifunctional layers providing, alongside enhanced electrochemical activity, improved mechanical, and long-term stability. In this study, an ultrathin (400 nm) bilayer of samarium-doped ceria and a self-assembled nanocomposite made of Sm0.2Ce0.8O1.9-La0.8Sr0.2MnO3-$δ$ was fabricated by pulsed laser deposition and is employed as a functional oxygen electrode in an anode-supported solid oxide fuel cell. Introducing the functional bilayer in the cell architecture…
A new Surrogate Microstructure Generator for Porous Materials with Applications to the Buffer Layer of TRISO Nuclear Fuel Particles
Laboratoire de Mécanique des Solides, Ecole Polytechnique, CNRS, Institut Polytechnique de Paris（固体力学实验室，巴黎综合理工学院，法国国家科学研究中心，巴黎理工学院）；Safran Tech（赛峰技术）；Department of Mathematics,Technical University of Munich（慕尼黑工业大学数学系）
Graphene has exceptional optical, mechanical and electrical properties, making it an emerging material for novel optoelectronics, photonics and for flexible transparent electrode applications. However, the relatively high sheet resistance of graphene is a major constrain for many of these applications. Here we propose a new approach to achieve low sheet resistance in large-scale CVD monolayer graphene using non-volatile ferroelectric polymer gating. In this hybrid structure, large-scale graphene is heavily doped up to 3{\times}1013 cm-2 by non-volatile ferroelectric dipoles, yielding a low she…
Lithium intercalation into graphite is the foundation for the lithium-ion battery, and the thermodynamics of the lithiation of graphitic electrodes have been heavily investigated. Intercalated lithium in bulk graphite undergoes structural ordering known as staging to minimize electrostatic repulsions within the crystal lattice. While this process is well-understood for bulk graphite, confinement effects become important at the nanoscale, which can significantly impact the electrochemistry of nanostructured electrodes. Therefore, graphene offers a model platform to study intercalation dynamics …
Rational combination holds the key for non-precious metal oxides and economic carbon materials to the creation of high performance air electrode materials. Carbon nanotubes (CNTs)-supported manganese oxides composite catalysts (CMnCs) were obtained by reacting commercial CNTs with MnO$_4^-$ in diluted H$_2$SO$_4$ with cancelling conventional hydrothermal processing or adding surfantant templates. CMnCs were then assembled into commercial air cathodes equipped in metal air fuel cells. CNTs demonstrated structurally much defective. Outer CNT walls were cracked into graphene nano pieces yet remai…
Portable electronic devices are already an indispensable part of our daily life; and their increasing number and demand for higher performance is becoming a challenge for the research community. In particular, a major concern is the way to efficiently power these energy-demanding devices, assuring long grid independency with high efficiency, sustainability and cheap production. In this context, technologies beyond Li-ion are receiving increasing attention, among which the development of micro solid oxide fuel cells (μSOFC) stands out. In particular, μSOFC provides a high energy density, high e…
Micro-solid oxide fuel cells based on thin films have strong potential for use in portable power devices. However, devices based on silicon substrates typically involve thin-film metallic electrodes which are unstable at high temperatures. Devices based on bulk metal substrates overcome these limitations, though performance is hindered by the challenge of growing state-of-the-art epitaxial materials on metals. Here, we demonstrate for the first time the growth of epitaxial cathode materials on metal substrates (stainless steel) commercially supplied with epitaxial electrolyte layers (1.5 {um (…
Hydrogen peroxide (H2O2) formation rates in a proton exchange membrane (PEM) fuel cell anode and cathode were estimated as a function of humidity and temperature by studying the oxygen reduction reaction (ORR) on a rotating ring disc electrode (RRDE). Fuel cell conditions were replicated by depositing a film of Pt/Vulcan XC-72 catalyst onto the disk and by varying the temperature, dissolved O2 concentration and the acidity levels in hydrochloric acid (HClO4). The HClO4 acidity was correlated to ionomer water activity and hence fuel cell humidity. The H2O2 formation rates showed a linear depend…
We report that 30-inch scale multiple roll-to-roll transfer and wet chemical doping considerably enhance the electrical properties of the graphene films grown on roll-type Cu substrates by chemical vapor deposition. The resulting graphene films shows a sheet resistance as low as ~30 Ohm/sq at ~90 % transparency which is superior to commercial transparent electrodes such as indium tin oxides (ITO). The monolayer of graphene shows sheet resistances as low as ~125 Ohm/sq with 97.4% optical transmittance and half-integer quantum Hall effect, indicating the high-quality of these graphene films. As …
A new dual plasma coating process to produce platinum-free catalysts for the oxygen reduction reaction in a fuel cell is introduced. The catalysts thus produced were analysed with various methods. Electrochemical characterisation was carried out by cyclic voltammetry, rotating ring- and rotating ring-disk electrode. The surface porosity of the different catalysts thus obtained was characterised with the nitrogen gas adsorption technique and scanning electron microscopy was used to determine the growth mechanisms of the films. It is shown that catalytically active compounds can be produced with…
We present a mechanistic theory for predicting void evolution in the Li metal electrode during the charge and discharge of all-solid-state battery cells. A phase field formulation is developed to model vacancy annihilation and nucleation, and to enable the tracking of the void-Li metal interface. This is coupled with a viscoplastic description of Li deformation, to capture creep effects, and a mass transfer formulation accounting for substitutional (bulk and surface) Li diffusion and current-driven flux. Moreover, we incorporate the interaction between the electrode and the solid electrolyte, …
