Development and Validation of Chromium Getters for Solid Oxide Fuel Cell Power Systems

Summary

Cathode poisoning from airborne contaminants in trace levels remains a major concern for long-term stability of high-temperature electrochemical systems. We provide a novel method to mitigate the cathode degradations using getters, which capture airborne contaminants at high temperature before entering electrochemically active stack area.

Abstract

Degradation of cathode in solid oxide fuel cells (SOFC) remains a major concern for the long-term performance stability and operational reliability. The presence of gas phase chromium species in air has demonstrated significant cathode performance degradation during long-term exposure due to unwanted compound formation at the cathode and electrolyte interface which retards the oxygen reduction reaction (ORR). We have demonstrated a novel method to mitigate the cathode degradation using chromium getters which capture the gas phase chromium species before it is ingested in the cathode chamber. Low-cost getter materials, synthesized from alkaline earth and transition metal oxides, are coated on the cordierite honeycomb substrate for application in the SOFC power systems. As-fabricated getters have been screened by chromium transpiration tests for 500 h in humidified air atmosphere in presence of chromium vapor. Selected getters have been further validated utilizing electrochemical tests. Typically, electrochemical performance of SOFCs (lanthanum strontium manganite (LSM) ǁ yttria stabilized zirconia (YSZ) ǁ Pt) was measured at 850 °C in the presence and absence of Cr getter. For the 100 h cell tests containing getters, stable electrochemical performance was maintained, whereas the cell performance in the absence of Cr getters rapidly decreased in 10 h. Analyses of Nyquist plots indicated significant increase in the polarization resistance within the first 10 h of the cell operation. Characterization results from posttest SOFCs and getters have demonstrated the high efficiency of chromium capture for the mitigation of cell degradation.

Introduction

Solid oxide fuel cell (SOFC) power system, a high temperature direct electrochemical energy conversion device, offers an environmentally friendly pathway to generate electricity from a wide variety of fossil and renewable fuels. SOFC technology finds its applications in centralized as well as distributed power generation areas¹. This technology relies on electrochemical conversion of chemical energy stored in the fuels into electricity. Numerous advantages are offered by SOFCs in terms of high energy efficiency, high quality heat, ease of modularity, and no or negligible carbon footprints². Several individual SOFC cells ....

Protocol

1. Synthesis of chromium getter

1. Synthesize precursor powder using alkaline earth and transition metal oxide salts via conventional coprecipitation synthesis route as depicted in Figure 1¹⁶.
   1. Prepare a stock solution using 50.33 g of strontium nitrate Sr(NO₃)₂ and 43.97 g of nickel nitrate hexahydrate Ni(NO₃)₂.6H₂O in order to prepare 2.4 M solutions in 100 mL of de-ionized water. 
   2. Use 9 mL of 2.4 M Sr(NO₃)₂ and add with 7 mL of 2.4 M solution of Ni(NO₃)₂.6H₂O, followed....

Results

A Cr transpiration experiment is a screening test for the selection of Cr getters. Cr transpiration setup was utilized to validate the performance of chromium getter under the SOFC operating conditions. Experiments were conducted in the presence of a chromium getter operated at 850 °C in humidified (3% H₂O) air for 500 h. Visual observations during Cr transpiration tests indicated significant discoloration of the outlet elbow during 500 h in the absence of getter. However, plac.......

Discussion

The experimental results clearly demonstrate the effectiveness of chromium getters during long-term chromium transpiration tests and electrochemical tests. Presence of getters successfully mitigates the contamination of the electrode which otherwise would lead to rapid increase in polarization resistance and electrochemical performance degradation.

The formation of gas phase chromium species from chromia is favored and enhanced with an increase of water vapor concentration (humidity level)

Materials

List of materials used in this article

Name	Company	Catalog Number	Comments
Sr(NO3)2	Sigma-Aldrich	243426	Getter precursor material
Ni(NO3)2-6H2O	Alfa Aesar	A15540	Getter precursor material
NH4OH	Alfa Aesar	L13168	Getter precursor material
Pt ink	ESL ElectroScience	5051	Current collector paste
Pt wire	Alfa Aesar	10288	Current collector wire
Pt gause	Alfa Aesar	40935	Current collector
Cr2O3 powder	Alfa Aesar	12286	Chromium source
Nitric acid (HNO3)	Sigma-Aldrich	438073	Chromium extraction
Potassium permanganate (KMnO4)	Alfa Aesar	A12170	Chromium extraction
LSM paste	Fuelcellmaterials	18007	Cathode
YSZ electrolyte	Fuelcellmaterials	211102	Electrolyte
Alumina fiber board	Zircar	GJ0014	Getter substrate
Ceramabond paste	AREMCO	552-VFG	For cell sealing
ICP-MS (7700s)	Agilent	NA	For Cr analysis
Potentiostat (VMP3)	Biologic	NA	For EIS/I-t measurement
FIB (Helios Nanolab 460F1)	FEI	NA	For Nano-sample preparation
TEM (Talos F200X S/TEM)	FEI	NA	For composition analysis