Chromium Poisoning of La 1-x Sr x MnO 3±δ Cathodes and Electrochemical Validation of Chromium Getters in Intermediate Temperature-Solid Oxide Fuel Cells

Heo, Su Jeong; Hong, Junsung; Aphale, Ashish; Hu, Boxun; Singh, Prabhakar

doi:10.1149/2.0931913jes

Title: Chromium Poisoning of La _1-x Sr _x MnO _3±δ Cathodes and Electrochemical Validation of Chromium Getters in Intermediate Temperature-Solid Oxide Fuel Cells

Abstract

The effect of chromium poisoning on electrochemical performance degradation has been studied at intermediate temperatures (550-650 degrees C) using La_1-xSr_xMnO_3±δ (LSM) cathode and an electrochemical cell configuration air/LSM//YSZ//Pt/air. A rapid increase in polarization resistance is observed in the presence of gaseous chromium species containing humid air (3% H₂O) at both 550 degrees C and 650 degrees C. Cross-sectional elemental mapping and high-resolution transmission electron microscopy of the LSM/YSZ interface show the presence of crystalline Cr₂O₃ and (Mn,Cr)₃O₄ phases indicating reduction of gaseous hexavalent-chromium species and deposition of solid reaction products. Subsequent experiments, performed under the above exposure conditions but in the presence of a chromium getter, showed stable polarization resistance. The electrochemical performance of half-cells in Cr-containing humid air atmosphere and in the presence of the chromium getter also remained stable during 100-h tests at 550 and 650 degrees C, respectively. The post-test structural and chemical analysis of the electrode, electrode-electrolyte interface and getter by scanning- transmission electron microscopy, energy dispersive X-ray and Raman spectroscopy showed that the cathode bulk and cathode- electrolyte interface remained free of chromium deposits whereas chromium species deposited near the air inlet region of the porous getter as crystalline SrCrO₄.

Authors:

Heo, Su Jeong;

; Aphale, Ashish; Hu, Boxun; Singh, Prabhakar

Publication Date:: Wed Aug 28 00:00:00 EDT 2019

Research Org.:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Fossil Energy (FE)

OSTI Identifier:: 1562978

Alternate Identifier(s):: OSTI ID: 1566053

Report Number(s):: NREL/JA-5K00-74917
Journal ID: ISSN 0013-4651; /jes/166/13/F990.atom

Grant/Contract Number:: FE 0023385; AC36-08GO28308; FE-0023385

Resource Type:: Journal Article: Published Article

Journal Name:: Journal of the Electrochemical Society

Additional Journal Information:: Journal Name: Journal of the Electrochemical Society Journal Volume: 166 Journal Issue: 13; Journal ID: ISSN 0013-4651

Publisher:: The Electrochemical Society

Country of Publication:: United States

Language:: English

Subject:: 30 DIRECT ENERGY CONVERSION; fuel cells; solid oxide fuel cells; chromium poisoning; poisoning mitigation; SOFC cathode

Citation Formats


                    Heo, Su Jeong, Hong, Junsung, Aphale, Ashish, Hu, Boxun, and Singh, Prabhakar. Chromium Poisoning of La 1-x Sr x MnO 3±δ Cathodes and Electrochemical Validation of Chromium Getters in Intermediate Temperature-Solid Oxide Fuel Cells.  United States: N. p., 2019. 
        Web.  doi:10.1149/2.0931913jes.

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                    Heo, Su Jeong, Hong, Junsung, Aphale, Ashish, Hu, Boxun, & Singh, Prabhakar. Chromium Poisoning of La 1-x Sr x MnO 3±δ Cathodes and Electrochemical Validation of Chromium Getters in Intermediate Temperature-Solid Oxide Fuel Cells.  United States.  https://doi.org/10.1149/2.0931913jes

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                    Heo, Su Jeong, Hong, Junsung, Aphale, Ashish, Hu, Boxun, and Singh, Prabhakar. 2019.  
        "Chromium Poisoning of La 1-x Sr x MnO 3±δ Cathodes and Electrochemical Validation of Chromium Getters in Intermediate Temperature-Solid Oxide Fuel Cells".  United States.  https://doi.org/10.1149/2.0931913jes.

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@article{osti_1562978,

  title        = {Chromium Poisoning of La 1-x Sr x MnO 3±δ Cathodes and Electrochemical Validation of Chromium Getters in Intermediate Temperature-Solid Oxide Fuel Cells},

  author       = {Heo, Su Jeong and Hong, Junsung and Aphale, Ashish and Hu, Boxun and Singh, Prabhakar},

  abstractNote = {The effect of chromium poisoning on electrochemical performance degradation has been studied at intermediate temperatures (550-650 degrees C) using La1-xSrxMnO3±δ (LSM) cathode and an electrochemical cell configuration air/LSM//YSZ//Pt/air. A rapid increase in polarization resistance is observed in the presence of gaseous chromium species containing humid air (3% H2O) at both 550 degrees C and 650 degrees C. Cross-sectional elemental mapping and high-resolution transmission electron microscopy of the LSM/YSZ interface show the presence of crystalline Cr2O3 and (Mn,Cr)3O4 phases indicating reduction of gaseous hexavalent-chromium species and deposition of solid reaction products. Subsequent experiments, performed under the above exposure conditions but in the presence of a chromium getter, showed stable polarization resistance. The electrochemical performance of half-cells in Cr-containing humid air atmosphere and in the presence of the chromium getter also remained stable during 100-h tests at 550 and 650 degrees C, respectively. The post-test structural and chemical analysis of the electrode, electrode-electrolyte interface and getter by scanning- transmission electron microscopy, energy dispersive X-ray and Raman spectroscopy showed that the cathode bulk and cathode- electrolyte interface remained free of chromium deposits whereas chromium species deposited near the air inlet region of the porous getter as crystalline SrCrO4.},

  doi          = {10.1149/2.0931913jes},

  url          = {https://www.osti.gov/biblio/1562978},
  journal      = {Journal of the Electrochemical Society},

  issn         = {0013-4651},

  number       = 13,

  volume       = 166,

  place        = {United States},

  year         = {Wed Aug 28 00:00:00 EDT 2019},

  month        = {Wed Aug 28 00:00:00 EDT 2019}

}

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Cited by: 14 works

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Figure 1: (a) Electrochemical performance (I-t curve) and impedance spectra of the half-cell in the presence of Cr vapors at (b) 650°C and (c) 550°C. SEM images of the cross-sections of the LSM/YSZ interface after the test in 3% H₂O/air in the presence of Cr vapor at (d) 650°C andmore »

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Title: Chromium Poisoning of La 1-x Sr x MnO 3±δ Cathodes and Electrochemical Validation of Chromium Getters in Intermediate Temperature-Solid Oxide Fuel Cells

Abstract

Citation Formats

Figures / Tables:

LSM–YSZ interactions and anode delamination in solid oxide electrolysis cells journal, November 2012

Lowering the Temperature of Solid Oxide Fuel Cells journal, November 2011

Comparison of chromium poisoning among solid oxide fuel cell cathode materials journal, September 2014

The effect of temperature on chromium vaporization and oxide scale growth on interconnect steels for Solid Oxide Fuel Cells journal, August 2015

Stability of strontium-doped lanthanum manganite cathode in humidified air journal, February 2014

Vaporisation of chromia in humid air journal, February 2005

Roles of humidity and cathodic current in chromium poisoning of Sr-doped LaMnO3-based cathodes in solid oxide fuel cells journal, August 2017

Time-Dependence of Surface Composition, Transport Properties Degradation, and Thermodynamic Consideration of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3- δ under Chromium Poisoning journal, January 2018

Recent Development of SOFC Metallic Interconnect journal, April 2010

Experimental and thermodynamic evaluation of La1−xSrxMnO3±δ and La1−xSrxCo1−yFeyO3−δ cathodes in Cr-containing humidified air journal, April 2017

H 2 O Absorption Assisted Sr-Segregation in Strontium Nickel Oxide Based Chromium Getter and Encapsulation with SrCO 3 journal, January 2019

A perspective on low-temperature solid oxide fuel cells journal, January 2016

Chromium poisoning and degradation at Gd0.2Ce0.8O2-impregnated LaNi0.6Fe0.4O3−δ cathode for solid oxide fuel cell journal, October 2012

Degradation phenomena in the cathode of a solid oxide fuel cell with an alloy separator journal, May 1995

Deposition of Chromium Species at Sr-Doped LaMnO[sub 3] Electrodes in Solid Oxide Fuel Cells. I. Mechanism and Kinetics journal, January 2000

Intermediate temperature solid oxide fuel cells journal, January 2008

Insight into surface segregation and chromium deposition on La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ cathodes of solid oxide fuel cells journal, January 2014

Chromium Vapor Species over Solid Oxide Fuel Cell Interconnect Materials and Their Potential for Degradation Processes journal, January 1996

Materials for Solid Oxide Fuel Cells † journal, February 2010

Air side contamination in Solid Oxide Fuel Cell stack testing journal, September 2011

Raman Spectroscopy Study of Chromium Deposition on La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ Cathode of Solid Oxide Fuel Cells journal, January 2014

Chromium-Related Degradation of Thin-Film Electrolyte Solid Oxide Fuel Cell Stacks journal, January 2015

In situ study of activation and de-activation of LSM fuel cell cathodes – Electrochemistry and surface analysis of thin-film electrodes journal, October 2012

Combined Cr and S poisoning in solid oxide fuel cell cathodes journal, March 2012

Preface—JES Focus Issue on Oxygen Reduction and Evolution Reactions for High Temperature Energy Conversion and Storage journal, January 2017

Synthesis and Stability of Sr x Ni y O z Chromium Getter for Solid Oxide Fuel Cells journal, January 2018

Chromium deposition and poisoning in dry and humidified air at (La0.8Sr0.2)0.9MnO3+δ cathodes of solid oxide fuel cells journal, March 2010

Title: Chromium Poisoning of La _1-x Sr _x MnO _3±δ Cathodes and Electrochemical Validation of Chromium Getters in Intermediate Temperature-Solid Oxide Fuel Cells

LSM–YSZ interactions and anode delamination in solid oxide electrolysis cells
journal, November 2012

Lowering the Temperature of Solid Oxide Fuel Cells
journal, November 2011

Comparison of chromium poisoning among solid oxide fuel cell cathode materials
journal, September 2014

The effect of temperature on chromium vaporization and oxide scale growth on interconnect steels for Solid Oxide Fuel Cells
journal, August 2015

Stability of strontium-doped lanthanum manganite cathode in humidified air
journal, February 2014

Vaporisation of chromia in humid air
journal, February 2005

Roles of humidity and cathodic current in chromium poisoning of Sr-doped LaMnO3-based cathodes in solid oxide fuel cells
journal, August 2017

Time-Dependence of Surface Composition, Transport Properties Degradation, and Thermodynamic Consideration of La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3- _δ under Chromium Poisoning
journal, January 2018

Recent Development of SOFC Metallic Interconnect
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Experimental and thermodynamic evaluation of La1−xSrxMnO3±δ and La1−xSrxCo1−yFeyO3−δ cathodes in Cr-containing humidified air
journal, April 2017

H ₂ O Absorption Assisted Sr-Segregation in Strontium Nickel Oxide Based Chromium Getter and Encapsulation with SrCO ₃
journal, January 2019

A perspective on low-temperature solid oxide fuel cells
journal, January 2016

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journal, October 2012

Degradation phenomena in the cathode of a solid oxide fuel cell with an alloy separator
journal, May 1995

Deposition of Chromium Species at Sr-Doped LaMnO[sub 3] Electrodes in Solid Oxide Fuel Cells. I. Mechanism and Kinetics
journal, January 2000

Intermediate temperature solid oxide fuel cells
journal, January 2008

Insight into surface segregation and chromium deposition on La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3−δ cathodes of solid oxide fuel cells
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Chromium Vapor Species over Solid Oxide Fuel Cell Interconnect Materials and Their Potential for Degradation Processes
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Materials for Solid Oxide Fuel Cells ^†
journal, February 2010

Air side contamination in Solid Oxide Fuel Cell stack testing
journal, September 2011

Raman Spectroscopy Study of Chromium Deposition on La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3-δ Cathode of Solid Oxide Fuel Cells
journal, January 2014

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