Oxygen flux and dielectric response study of Mixed Ionic-Electronic Conducting (MIEC) heterogeneous functional materials
Date of Award
Open Access Dissertation
Kenneth L. Reifsnider
Dense mixed ionic-electronic conducting (MIEC) membranes consisting of ionic conductive perovskite-type and/or fluorite-type oxides and high electronic conductive spinel type oxides, at elevated temperature can play a useful role in a number of energy conversion related systems including the solid oxide fuel cell (SOFC), oxygen separation and permeation membranes, partial oxidization membrane reactors for natural gas processing, high temperature electrolysis cells, and others. This study will investigate the impact of different heterogeneous characteristics of dual phase ionic and electronic conductive oxygen separation membranes on their transport mechanisms, in an attempt to develop a foundation for the rational design of such membranes. The dielectric behavior of a material can be an indicator for MIEC performance and can be incorporated into computational models of MIEC membranes in order to optimize the composition, microstructure, and ultimately predict long term membrane performance. The dielectric behavior of the MIECs can also be an indicator of the transport mechanisms and the parameters they are dependent upon.
For this study we chose a dual phase MIEC oxygen separation membrane consisting of an ionic conducting phase: gadolinium doped ceria-Ce0.8Gd0.2O1.9 (GDC) and an electronic conductive phase: cobalt ferrite-CoFe2O4 (CFO). The membranes were fabricated from mixtures of Nano-powder of each of the phases for different volume percentages, sintered with various temperatures and sintering time to form systematic micro-structural variations, and characterized by structural analysis (XRD), and micro-structural analysis (SEM-EDS). Performance of the membranes was tested for variable partial pressures of oxygen across the membrane at temperatures from 850°C-1060°C using a Gas Chromatography (GC) system. Permeated oxygen did not directly correlate with change in percent mixture. An intermediate mixture 60%GDC-40%CFO had the highest flux compared to the 50%GDC-50%CFO and 80%GDC-20%CFO mixtures. Material characterization suggests the emergence of a third phase contributing to the behavior. Microstructural studies suggested changes in micro-structure of a given volume fraction for different sintering temperature and sintering time. Flux variation was observed for membranes with the same constituent volume fraction but different micro-structure indicating the effects of the micro-structure on the overall oxygen permeation.
To correlate the experimental flux measurement with a standard Wagner‟s flux equation, different microstructural characteristics were studied to incorporate them into a modified Wagner‟s flux equation.
In-situ broadband dielectric spectroscopy measurements over a temperature range of 850°C-1060°C and frequency range of (0.1Hz-1MHz) of the operating 60%GDC-40%CFO mixture oxygen separation membranes were measured using a NOVOCONTROL dielectric spectroscopy test system. Dielectric response of the operating membrane was studied to identify the charge transfer process in the membrane.
A computational model to study the dielectric impedance response of different microstructure was developed using a COMSOLTM Multiphysics qasi-static electromagnetic module. This model was validated using model materials with regular geometric shapes. To measure impedance of real micro/nano-structures of the membrane material, domains required for the COMSOL calculation were obtained from actual micro/nano structures by using 3D scans from X-ray nano and micro tomography. SimplewareTM software was used to generate 3D domains from image slices obtained from the 3D x-ray scans. Initial voltage distributions on the original microstructure were obtained from the computational model. Similarly, development of a primary model for simulating ionic/electronic species flow inside of an MIEC was also begun. The possibility of using broadband dielectric spectroscopy methods to understand and anticipate the flux capabilities of MIECs to reduce the cost and time of development of such material systems was explored.
Rabbi, F.(2014). Oxygen flux and dielectric response study of Mixed Ionic-Electronic Conducting (MIEC) heterogeneous functional materials. (Doctoral dissertation). Retrieved from https://scholarcommons.sc.edu/etd/2868