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
EIS
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

NLEIS
Separates the voltage response into harmonics

1
=
I II
III

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

Air

O2 + 2e- O2Cathode Electrolyte Anode

2e-

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

O2H2 CO
Fuel

Gd-Doped Ceria Pellet

H2O CO2

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

Acknowledgments
-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

II

III