Optimizing Solid Oxide Fuel Cell Performance to Re-evaluate Its Role in the Mobility Sector.

A sustainable, interconnected, and smart energy network in which hydrogen plays a major role cannot be dismissed as a utopia anymore. There are vast international and industrial ambitions to reach the envisioned system transformation, and the decarbonization of the mobility sector is a central pillar comprising a huge economic share. Solid oxide fuel cells (SOFCs) are one of the most promising technologies in the brigade of clean energy devices and have potentially wide applicability for transportation, due to their high efficiencies and impurity tolerance. To uncover future pathways to boost the cell's performance, we propose a detailed multiscale modeling methodology to evaluate the direct impact of cell materials and morphologies on commercial-scale system performance. After acquiring intrinsic electrokinetics decoupled from mass and charge transport of different anode and cathode materials via a half-cell model, a full cell model is employed to identify the most promising electrode combination. Subsequently, a scale-up to the system level is performed by coupling a 3-D kW-stack model to the balance of plant components while focusing on morphological optimization of the membrane electrode assembly (MEA). On optimally tailoring the MEA, model results demonstrate that an advanced cell design comprising a Ni fiber-CGO matrix structured anode and a LSCF-infiltrated CGO cathode could reach a stack power density of 1.85 kW L-1 and a net system efficiency of 52.2% for operation at <700 °C, with manageable stack temperature gradients of <14 K cm-1. The model-optimized power density is substantially higher than those of commercial stacks and surpasses industrial targets for SOFC-based range extenders. Thus, with further cell and stack development targeting the performance limiting processes elucidated in the paper, commercial SOFCs could, alongside range extenders, also act as prime movers in larger scale transport applications such as trucks, trains, and ships.

Understanding the Coarsening and Degradation in a Nanoscale Nickel Gadolinia-Doped-Ceria Electrode for High-Temperature Applications.

Nanostructure engineering is an effective approach to enhance the electrochemical performance of energy devices. While the high surface area of nanoparticles greatly enlarges the density of reaction sites, it often also leads to relatively rapid degradation as the particles tend to coarsen to reduce their high surface energy. Therefore, a nickel/gadolinia-doped-ceria (CGO) cermet electrode is studied, with a novel porous nanostructure consisting of nanoscale Ni (100 nm) and CGO (50 nm) crystallites, cosintered from nanocomposite precursor agglomerate particles. This electrode combines both high performance and excellent durability, with a total area-specific resistance (ASR) of 0.11 Ω cm2 at 800 °C and a stable ASR with up to 170 h ageing in humidified 5% H2-N2. Post-test analysis by 3D tomography shows that nickel coarsens and is responsible for the initial increase in ASR. However, the subsequent electrochemical performance is stable because reaction at the double phase boundaries (DPBs) on the surfaces of nanoscale CGO becomes dominant and is resistant to ageing. At this stage, the coarsened Ni network is also stabilized by the surrounding nanostructure. The dominant role of the DPB reaction is supported quantitatively using a continuum model with geometrical parameters obtained from 3D tomography.

Hierarchical dual-porosity nanoscale nickel cermet electrode with high performance and stability.

Nano-structured metal-ceramic materials have attracted attention to improve performance in energy conversion applications. However, they have poor long-term stability at elevated temperatures due to coarsening of the metal nanoparticles. In this work we show that this can be mitigated by a novel design of the nano-structure of Ni cermet fuel electrodes for solid oxide cells. The strategy is to create a dual porosity microstructure, without the use of fugitive pore-formers, with micron-size pores to facilitate gas transport and nanoscale pores to control nano-particle coarsening. This has been achieved using a continuous hydrothermal synthesis and two-stage heat treatments to produce electrodes with micron size agglomerates of nano-structured porous Ni-Yttria-Stabilised-Zirconia (YSZ). This unique hierarchical microstructure combines enhanced electrochemical reaction in the high activity (triple phase boundary density 11 µm-2) nanoscale regions with faster gas diffusion in the micron-sized pores. The electrodes are aged at 800 °C in humidified 5% H2-N2 for up to 600 h. The electrochemical reaction resistance is initially 0.17 Ω cm2 but later reaches a steady long-term value of 0.15 Ω cm2. 3-D reconstruction of the electrodes after 10 h and 100 h of ageing reveals an increase in YSZ network connectivity and TPB percolation. This improvement is well-correlated to the 3-D tomography parameters using a physical model adapted from mixed conducting SOC air electrodes, which is also supported, for the first time, by numerical simulations of the microstructural evolution. These also reveal that in the long term, nickel coarsening is inhibited by the nanoscale entanglement of Ni and YSZ in the hierarchical microstructure.

Strategies for Carbon and Sulfur Tolerant Solid Oxide Fuel Cell Materials, Incorporating Lessons from Heterogeneous Catalysis.

Solid oxide fuel cells (SOFCs) are a rapidly emerging energy technology for a low carbon world, providing high efficiency, potential to use carbonaceous fuels, and compatibility with carbon capture and storage. However, current state-of-the-art materials have low tolerance to sulfur, a common contaminant of many fuels, and are vulnerable to deactivation due to carbon deposition when using carbon-containing compounds. In this review, we first study the theoretical basis behind carbon and sulfur poisoning, before examining the strategies toward carbon and sulfur tolerance used so far in the SOFC literature. We then study the more extensive relevant heterogeneous catalysis literature for strategies and materials which could be incorporated into carbon and sulfur tolerant fuel cells.

The effect of Mg location on Co-Mg-Ru/γ-Al2O3 Fischer-Tropsch catalysts.

The effectiveness of Mg as a promoter of Co-Ru/γ-Al2O3 Fischer-Tropsch catalysts depends on how and when the Mg is added. When the Mg is impregnated into the support before the Co and Ru addition, some Mg is incorporated into the support in the form of MgxAl2O3+x if the material is calcined at 550°C or 800°C after the impregnation, while the remainder is present as amorphous MgO/MgCO3 phases. After subsequent Co-Ru impregnation MgxCo3-xO4 is formed which decomposes on reduction, leading to Co(0) particles intimately mixed with Mg, as shown by high-resolution transmission electron microscopy. The process of impregnating Co into an Mg-modified support results in dissolution of the amorphous Mg, and it is this Mg which is then incorporated into MgxCo3-xO4. Acid washing or higher temperature calcination after Mg impregnation can remove most of this amorphous Mg, resulting in lower values of x in MgxCo3-xO4. Catalytic testing of these materials reveals that Mg incorporation into the Co oxide phase is severely detrimental to the site-time yield, while Mg incorporation into the support may provide some enhancement of activity at high temperature.

Proxy-based accelerated discovery of Fischer-Tropsch catalysts.

Development of heterogeneous catalysts for complex reactions such as Fischer-Tropsch synthesis of fuels is hampered by difficult reaction conditions, slow characterisation techniques such as chemisorption and temperature-programmed reduction and the need for long term stability. High-throughput (HT) methods may help, but their use has until now focused on bespoke micro-reactors for direct measurements of activity and selectivity. These are specific to individual reactions and do not provide more fundamental information on the materials. Here we report using simpler HT characterisation techniques (XRD and TGA) along with ageing under Fischer-Tropsch reaction conditions to provide information analogous to metal surface area, degree of reduction and thousands of hours of stability testing time for hundreds of samples per month. The use of this method allowed the identification of a series of highly stable, high surface area catalysts promoted by Mg and Ru. In an advance over traditional multichannel HT reactors, the chemical and structural information we obtain on the materials allows us to identify the structural effects of the promoters and their effects on the modes of deactivation observed.

Comprehensive study of DNA binding on iron (II,III) oxide nanoparticles with a positively charged polyamine three-dimensional coating.

Iron (II,III) oxide Fe3O4 nanoparticles (25 and 50 nm NPs) are grafted with amine groups through silanization in order to generate a positively charged coating for binding negatively charged species including DNA molecules. The spatial nature of the coating changes from a 2-D-functionalized surface (monoamines) through a layer of amine oligomers (diethylenetriamine or DETA, about 1 nm in length) to a 3-D layer of polyamine (polyethyleneimine or PEI, thickness ≥3.5 nm). These Fe3O4-PEI NPs were prepared by binding short-chain PEI polymers to the iodopropyl groups grafted on the NP surface. In this work, the surface charge density, or zeta potential, of the nanoparticles is found not to be the only factor influencing the DNA binding capacity, which also seems not to be affected by their buffering capacity profile in the range of pH 4-10. This study also allows the investigation of this 3-D effect on the surface of a nanoparticle as opposed to conventional 2-D amine functionalization. The flexibility of the PEI coating, which consists of only 1, 2, and 3° amines, on the nanoparticle surface has a significant influence on the overall DNA binding capacity and the binding efficiency (or N/P ratio). These polyamine-functionalized nanoparticles can be used in the purification of biomolecules and the delivery of drugs and large biomolecules.

High-throughput continuous hydrothermal synthesis of an entire nanoceramic phase diagram.

A novel High-Throughput Continuous Hydrothermal (HiTCH) flow synthesis reactor was used to make directly and rapidly a 66-sample nanoparticle library (entire phase diagram) of nanocrystalline Ce(x)Zr(y)Y(z)O(2-delta) in less than 12 h. High resolution PXRD data were obtained for the entire heat-treated library (at 1000 degrees C/1 h) in less than a day using the new robotic beamline I11, located at Diamond Light Source (DLS). This allowed Rietveld-quality powder X-ray diffraction (PXRD) data collection of the entire 66-sample library in <1 day. Consequently, the authors rapidly mapped out phase behavior and sintering behaviors for the entire library. Out of the entire 66-sample heat-treated library, the PXRD data suggests that 43 possess the fluorite structure, of which 30 (out of 36) are ternary compositions. The speed, quantity and quality of data obtained by our new approach, offers an exciting new development which will allow structure-property relationships to be accessed for nanoceramics in much shorter time periods.

Instant nano-hydroxyapatite: a continuous and rapid hydrothermal synthesis.

Nano-particle hydroxyapatite (HA) rods, were rapidly synthesised using a three pump continuous hydrothermal process (using a water feed at up to 400 degrees C and at 24 MPa): the product was obtained as a highly crystalline and phase pure material, without the need for an ageing step or subsequent heat treatment.