Synthesis, Characterization, and Optimization of Novel Solid Oxide Fuel Cell Anodes

This dissertation presents research on the development of novel materials and fabrication procedures for solid oxide fuel cell (SOFC) anodes. The work discussed here is divided into three main categories: all-oxide anodes, catalyst exsolution oxide anodes, and Ni-infiltrated anodes. The all-oxide and catalyst exsolution anodes presented here are further classi?ed as Ni-free anodes operating at the standard 700-800°C SOFC temperature while the Ni-infiltrated anodes operate at intermediate temperatures (≤650°C).;Compared with the current state-of-the-art Ni-based cermets, all-oxide, Ni-free SOFC anodes offer fewer coking issues in carbon-containing fuels, reduced degradation due to fuel contaminants, and improved stability during redox cycling. However, electrochemical performance has proven inferior to Ni-based anodes. The perovskite oxide Fe-substituted strontium titanate (STF) has shown potential as an anode material both as a single phase electrode and when combined with Gd-doped ceria (GDC) in a composite electrode. In this work, STF is synthesized using a modified Pechini processes with the aim of reducing STF particle size and increasing the electrochemically active area in the anode. The Pechini method produced particles ? 750 nm in diameter, which is signi°Cantly smaller than the typically micron-sized solid state reaction powder. In the first iteration of anode fabrication with the Pechini powder, issues with over-sintering of the small STF particles limited gas di?usion in the anode. However, after modifying the anode firing temperature, the Pechini cells produced power density comparable to solid state reaction based cells from previous work by Cho et al.;Catalyst exsolution anodes, in which metal cations exsolve out of the lattice under reducing conditions and form nanoparticles on the oxide surface, are another Ni-free option for standard operating temperature SOFCs. Little information is known about the onset of nanoparticle formation, which presents opportunities for the new kinds of ex situ and in situ experiments performed in this thesis. Ex situ experiments involved reducing powder samples at SOFC operating temperatures under hydrogen gas and characterizing them via electron microscopy and X-ray diffraction (XRD). For the in situ experiments, powders were heated, then reduced at temperature, and catalyst exsolution was observed in real-time. Pechini-synthesized cerium oxide substituted with 2-5 mol% Pd was studied using in situ X-ray heating experiments at Argonne National Laboratory's Advanced Photon Source. In these experiments, the powder was subjected to several cycles of reduction and oxidation at 800°C, and Pd metal formation was confirmed through the appearance of Pd peaks in the X-ray spectra. Next, Fe- and Ru-substituted lanthanum strontium chromite (LSCrFeRu14) synthesized by solid state reaction was characterized with ex situ and in situ microscopy. Transmission electron microscopy (TEM) in situ heating experiments were conducted to observe Ru nanoparticle evolution under the reducing conditions of the TEM vacuum chamber. LSCrFeRu14 was heated to 750°C and observed over ∼ 90 min at temperature during which time nanoparticle formation, coarsening, and di?usion were observed. Experiments on both materials sought to understand the conditions and timing of nanoparticle formation in the anode, which is not necessarily apparent from electrochemical data.;Reducing the operating temperature of SOFCs from the current state-of-the-art range of 700-800°C to ≤ 650°C has many advantages, among them increased long-term stability, reduced balance of plant costs, fewer interconnect/seal material issues, and decreased start-up times. In order to maintain good performance at reduced temperature, these intermediate temperature SOFCs require new materials including highly active alternatives to micron-scale Ni-YSZ composite anodes. The present work focuses on the development of IT-SOFCs with Sr0.8La 0.2TiO3 (SLT) anode supports, thin La1--xSr x Ga0.8Mg0.2O3 (x = 0.1, 0.2) dense electrolytes, and porous LSGM anode functional layers. The SLT support and the LSGM functional layer are infiltrated with nanoscale Ni, creating extensive electrochemically active triple phase boundary area. The scope of the work presented here encompasses every step of cell development including powder synthesis, optimization of firing conditions, and long-term stability testing. Using an optimized fabrication process, cells with power density > 1.2 W cm-2 were fabricated. Dry pressing and colloidal de-position were used to make the first generation of these cells, and once suitable times and temperatures were determined, the process was shifted to tape casting to make larger batches of uniform cells. After obtaining initial results of low anode polarization resistance and high power density, the long-term stability of the Ni-infiltrated anodes was examined. A coarsening model was developed using the data from accelerated degradation tests to predict cell performance over a typical device lifetime. This thesis encompasses a broad range of novel SOFC anode materials, each of which has its own strengths and weaknesses. Presenting several possible avenues for SOFC development provides a complete picture of the ?eld and its current focuses. The wide scope of this work offers multiple solutions for the SOFC community and demonstrates that SOFCs are a strong candidate for meeting the United States' need for energy conversion and storage.