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Modeling of La0.6Sr0.4Co0.2Fe0.

8O3- Using Electrochemical Impedance Spectroscopy

Stephanie Hare
Adler Research Group
Department of Chemical Engineering, University of Washington, Seattle , WA 98195

Introduction to EIS and NLEIS

Current Perturbation Voltage Response

Experimental Design
Current Perturbation Voltage Response

1st 2nd 3rd

Conduct frequency sweep of the range 100,000-0.1 Hz Obtain EIS spectra for an LSCF electrode at 1, 10, and 100% pO2

Characterizes impedance of electrochemical system as a function of frequency Only accurate for an amplitude range small enough such that the function can be approximated as linear

Results and Discussion

Separates the voltage response into harmonics


Valid over a wider range of amplitudes, dependence of voltage on current is not necessarily linear Reveals underlying non-linear phenomena

Structure of La0.6Sr0.4Co0.2Fe0.8O3- (LSCF)

Shows predominantly semi-conductor character, electronic conduction in the valence band Ionic conduction via diffusion of oxygen vacancies Manipulation of A and B-site compositions controls semi-conductor vs. metallic character, stability at a range of temperatures and pO2

Three Regions of Interest Perovskite Structure ABO3

A (La, Sr) B (Co, Fe) Oxygen Oxygen Vacancy
II. I. Offset - Electrolyte ohmic resistance - Constant with respect to pO2 1st arc - Interfacial kinetics - Approximately constant between different pO2 - Positive imaginary component at high frequency

Model Parameters
Rchem = diameter of semi-circular region ( ). chem = peak frequency ( ).

III. 2nd arc - Co-limitation of reaction - Gerischer (teardrop) shape defined only for 100% pO2 - Suggests lack of co-limitation for low pO2

SOFC Fabrication and Characteristics

Screen-Print Cathode and Anode Hand Paint Reference Electrode


O2 + 2e- O2Cathode Electrolyte Anode


Future Work
Develop electrochemical model from NLEIS spectra Addition of thermodynamic measurements to model Test SOFC at varying humidity


Gd-Doped Ceria Pellet


Highly efficient fuel oxidation at intermediate temperatures (500-800C) Can operate reversibly, allowing direct conversion between fuels and oxidized streams Currently, rate-limiting mechanism of the electrode is not well understood, motivating generation of a working model

SEM images of LSCF electrode

-Adler Group: TJ McDonald, Tim Geary -NSF Division of Materials Research, Ceramics Program -Ford Motor Company Fellowship

Screen-Print Cathode and Anode

Hand Paint Reference Electrode

Gd-Doped Ceria Pellet