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  • NETL Meeting 06122017

    Materials and Approaches for the Mitigation of SOFC Cathode Degradation in SOFC Power Systems

    Prabhakar Singh

    Department of Materials Science and EngineeringCenter for Clean Energy Engineering, University of Connecticut, CT

    WORK PERFORMED UNDER AGREEMENT DE-FE 0023385 and 0027894

    18th Annual SOFC Program Review MeetingJune 12, 2017

  • NETL Meeting 06122017

    Technical Contributors

    UConn

    Prabhakar SinghRampi RamprasadSteven SuibBoxun HuAshish AphaleAman UddinSridevi KrishnanSu Jeong HeoJunkai HeYanliu DangJunHo SongJustin WebsterSeraphim Belko

    ProfessorProfessorProfessorAssistant Research ProfessorPost-doctoral fellowPost-doctoral fellowPost-doctoral fellowGraduate StudentGraduate StudentGraduate StudentGraduate StudentUndergraduate StudentUndergraduate Student

    Program Managers: Drs. Patcharin N. Burke and Jason Lewis, NETL

    UAlabama Manoj Mahapatra Assistant Professor

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    Outline• Accomplishments• Background• Experimental

    • Getter optimization, process scale up and stability evaluation• Evaluation of getter performance• Fabrication and long term testing of Cr Getter• Electrochemical testing – BOP & In-Cell simulation• Characterization-SEM-EDX, XRD, and FIB-TEM• High surface area (HSA) getter materials• Sensor Development for in-situ Cr monitoring

    • Results and Discussion• Future Work• Acknowledgements

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    Cathode DegradationOhmic losses

    Non-ohmic losses

    Mechanical changes

    Gas – Solid Reactions Solid – Solid Reactions

    Dopant exolution, Compound Formation, Surface Morphology Changes, Interface Diffusion

    Gas phase constituents and

    contaminants

    Solid state reaction and Inter-diffusion

    Long term SOFC Degradation – Role of Cathode A Universal Degradation Phenomena for HT Electrochemical Systems

    SOFCSOECOTM

    Gas Concentration

    Oxygen 20.9 v%

    Nitrogen 78 v%

    Water

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    Chromium Evaporation at Low & Intermediate TemperaturesOxidation and electrochemical poisoning

    Gaseous Cr species formation and transport remains a significant issue at lower temperatures similar to high temperature operation conditions. Presence of H2O in air will lead to high partial pressures of Cr species.

    Air + 3%H2O atmospherePO2 = 0.21 atm.PH2O = 0.03 atm.

    • Alloy oxidation rate increases.• Lowering of temperature

    doesnot significantly lower the Cr vapor pressure in humidified air as indicated by smaller slope.

    • Significant reduction will, however, be obtained in dry air as indicated by larger slope.

    -25

    -20

    -15

    -10

    -5

    400 450 500 550 600 650 700 750 800

    Log

    part

    ial p

    ress

    ure

    of C

    r vap

    ors (

    atm

    .)

    Temperature (°C)

    P CrO2(OH)2

    CrO2(OH)

    P CrO3

    P CrO(OH)2

    Paralinear oxidationElectrode poisoning

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    SrO

    CrO2(OH)2

    SrO

    CrO2(OH)2

    SrCrO4

    B. Hu, S. Krishnan, C. Liang, S. J. Heo, A. N. Aphale, R. Ramprasad., P. Singh, . Int J Hydrogen Energy , 2017

    Morphology evolution in the presence of water and chromium vapor

    Background – Chromium Poisoning of Cathodes

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    Project ObjectivesDevelop, Validate and Transfer Technology Related to Materials and Approaches

    for the Mitigation of SOFC Cathode Degradation in SOFC Power Systems

    Long Term Bulk, Interfacial and Surface Stability

    Dopants, Electric polarization, Gas phase contaminants (H2O, CO2, SO2, Cr-vapor species, stoichiometry)

    Compound formation (Solid-solid/solid-gas reactions) dopants exolution and oxides segregation at surface oxides and compounds at interface crystal symmetry microstructure Micro-cracking and/or delaminationTools: EIS, DC conductivity, XRD, SEM,

    X-ray absorption spectroscopy, XPS, SIMS, TEM, HTXRD

    Bulk, Interfaces, Surface Stability

    Electrode – Electrolyte / Electrode - IC

    Couple/ Symmetric / Full cell/ configurations

    Air side contaminants:Water,CO2, SO2, Oxide vaporsOther contaminants

    In-situ, Ex-situ Bench top tests

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    Accomplishments

    • Cr capture successfully demonstrated from BOP/ In-cell sources• Cr getter identified, synthesized, tested and characterized• Synthesis process scaled up to 1kg/batch using lab equipment• Design studies performed for 40,000 hrs. getter life• Cr getter provided to PNNL, LG, Cummins, Ceres for testing• Laboratory findings provided to SOFC industries• Cathode degradation mechanisms identified• Getter operation validated at low temperatures• Alternate HSA getter has been identified and synthesized.

    TRL1,2 5,6

    Concept validation:Materials, synthesis, testing,

    characterization

    Scale up, testing and validation, technology

    transfer

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    Accomplishments-Technical• Suitable metal oxides have been selected for co-getter materials using thermodynamic calculations. • Processes have been identified for the synthesis of HSA materials • As-synthesized HSA materials have been characterized using SEM, TEM and EDS techniques. • In-situ electrochemical and ex-situ transpiration tests have been conducted to validate co-getter

    efficacy for Cr and S capture.• Getter design is being further optimized by CFD computational analysis.• New sensor design have been examined to test the sensitivity of Cr.

    Developed chromium getter shows excellent affinity for capturing gaseous Cr 6+ . Experiments are in progress on validating the capture of Sulfur and Sulfur- chromium species, respectively.

    Pre- formed and “in-situ” getter preparation demonstrated Electrochemical and transpiration tests show excellent blockage of Cr vapor from entering into cathode

    electrode. Getter materials, support structure and HSA getter deposition processes are being developed and optimized.

    • Graduate / Undergraduate students being trained - 7• Post-doctoral fellows - 3• Outreach: Middle and High School, STEM, International academic institutions• Publications in peer reviewed journals

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    Cr getter critical property

    Performance of new Cr getter against baseline state of the art Cr getter

    Test conditions(Temp, time, atm)

    Phase Stability Superior: New Cr getter shows no phase changes and interactionwith humidity and CO2 present in air.

    RT-980C, Ambient air

    Reaction products As processed getters consist of several oxide phases containingSr and Ni (Sr9Ni7O21, Sr4Ni3O9 and Sr2Ni4O5).

    Powder synthesis process and transpiration,electrochemical testing at 850C for up to 500hrs in Air -3%H2O

    Microstructures Stable powder, coating and substrate microstructures obtainedNew Cr getter retains its microstructure after high temperatureexposures (850C) in humidified air. Literature review does notprovide background information on the SOTA.

    During processing up to 980C in airDuring bench top testing at 850C for up to500 hrs in humid air

    Thermochemistry Similar or Superior: Based on thermochemical models developed

    Physical Properties Similar or Superior: Based on resistance to ambient air(NAAQS)

    Product morphology Porous powder coating on ceramic substrates During processing up to 980C in airDuring bench top testing at 850C for up to500 hrs in humid air

    Cr Conc. profile Superior: Capture Cr in the first 1500 - 3000 micron.Reproducible results

    During bench top testing at 850C for up to500 hrs in humid air

    Substrate Configuration include honeycomb, foam and fibrous structure,Substrate materials include Cordierite, Mullite, zirconia andalumina.

    Ease of fabrication Conventional powder preparation and coating techniques pre-formed /In-situ getter formation

    A list of Cr getter properties against the state of the art Cr poisoning mitigation and getter materials

    Background: Getter

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    Design flexibility for integration in wide range of SOFC systems configuration Flexibility of operation from 600-900°C Use of conventional non-strategic and non-noble low cost metal oxides for getter synthesis Ease of getter synthesis and fabrication High Cr capture capacity through tailored high surface area powder and coatings Replaceable unit with getter health monitoring and sensing

    Novelty and Innovation

    The innovation will also find application in related high temperature electrochemical systems such asOTM and SOEC for the prevention of Cr assisted performance degradation. The proposed approach forCr capture can also be applied to oxycombustion and other advanced combustion techniques for thereduction of Cr vapor in the exhaust gas stream.

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    Getter Chemistry Optimization and Scale up

    Validation and testing

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    Materials Selection- Phase diagram

    SrO - NiO

    M. Zinkevich / Journal of Solid State Chemistry 178 (2005) 2818–2824

    SrO - MnOx

    JPEDAV (2004) 25:311-319

    Oxide solid solutions and mixtures from Alkaline earth and Transition metal group are preferred and considered over single phases due to chemical stability and resistance to interactions with gas phase impurities.

    MgO – Cr2O3

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    Large-Scale Getter Material SynthesisObjective: Produce a large batch of SNO for industrial applicationApproach: Scale up smaller 20g batches of SNO to produce 1kg batch.Rationale: Using results from initial 20g and 100g batches, 250g batch isprepared to produce SNO with desired composition. XRD results fromassay and temperature comparison of 20g batches were used to optimize250g batch.

    Previous Work : 20g batches wereused to optimize powdercomposition of large batch withrespect to initial assay and sintertemperature. Optimal compositionand temperature were found to be49:51 Sr to Ni ratio sintered at900°C as shown.

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    Alternate Synthesis Processes

    Synthetic Method Advantages DisadvantagesMicrowave Fast, high surface area Lack of affinity

    Sol-gel Simplicity, high surface area

    complex

    Impregnation Doped ions and form secondary coating layer

    Need two steps

    Hydrothermal Uniform crystal size Low surface area, high energy needed

    UCT Form porous thin layer with HSA

    complex

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    Process Flowchart

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    Synthesis Methods for High Surface Area Getter

    Microwave Method

    MOx nanofibers

    Hydrothermal method Impregnation Method

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    Honeycomb/ Foam Substrate Getters

    Schemes of Cr getter with honeycomb structuresurface-coated with SrNiOx

    High surface area and porous SrNiOx coating (10-30 µm)

    Before After

    a b

    Filter coated with SrNiOx: (a) before and (b) after

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    Coating Optimization: Slurry coating of honeycomb

    After 3rd coating, coating thickness: 40-60 µm. Coating is porous.

    After RT drying

    After 900C heat treatment for 5 hour

    After 900C heat treatment for 5 hour

    1st coating 2nd coating

    After 850C heat treatment for 5 hour

    3rd coating

    50-60µm40µm

    Coating #5SNO 10gDurban 1.2mlPVP 3gCement 1gSolvent50ml

    50%/50%Water/Ethanol

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    SEM images of the cross-section of the Cr getter and elemental analysis by EDS.

    Pores in the substrate (cordierite) contain Sr and NiIt is suggested that the SrNiOH penetrated into the holes cause strong adhesion betweenthe coated layer and the substrate.The SrNiO layer is ~10 – 15 µm in thickness.

    Cross section

    Element Atomic Ratio (%)

    MgAlSiSrFeNi

    016.8130.6216.85

    2.6333.10Cross-section

    Coating Optimization: Slurry coating of honeycomb

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    Stability of Getter Materials

    Before sintering

    1000˚C (20h)

    850˚C (20h)

    Sintering at 850˚C for 20h: No change in color and shape of the pellet Sintering at 1000˚C for 20h: Pellets became brown and the shape was intact immediately after

    removal from furnace at room temperature, but after 24h the pellets were pulverized completely.

    After sintering

    post sintering24h in air at RT

    Evaluate the stability of SrNiOx

    Validate in-cell getter to capture Cr from IC source

    • No/ negligible changes in morphology was observed for SNO sintered at 850oC for 20h• Particles agglomeration was observed for SNO sintered at 1000oC for 20h

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    Thermal stability

    No change in color and shape of the pellet after sintering at 850°C for 20h Sintering at 1000˚C for 20h leads to pulverization of SNO powders. Initially the pellets turn brown in color

    immediately after taking out of the furnace with changing to green and completely pulverized after 24h left in lab atmosphere.

    Pellets of SrNiOx sintered at 850°C and 1000°C for 20h1000oC

    850oC

    (a) (b)

    (d)

    PelletPowder

    (c)

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    Post sintering XRD characterization

    • The XRD pattern of 850 °C sintered SNO indicates presence of only SrxNiyOz phase with presence of minor SrCO3 phase

    • In contrast, XRD patterns of pulverized powder (1000°C) shows the presence of Sr(OH)2.H2O phase along with the strong peaks of SrCO3.

    • Strong peaks of NiO phase appear with absence of SrO phase in XRD patterns of the pulverized samples.

    XRD was conducted after sintering the pellets at 850°C and 1000°C and left in air for at least 24 hours

    850˚C (20h)

    1000°C (20h)

    Material Lattice Volume

    (Å3) Pattern

    SrO FCC 137.51 01-075-6979

    Sr(OH)2 Orthorhombic 237.27 00-027-0847

    SrCO3 Orthorhombic 259.07 00-005-0418

    Material Molar Mass

    (g/mol)Density(g/cm3)

    Molar Volume(cm3/mol)

    SrO 103.62 4.70 22.05

    Sr(OH)2 121.63 3.63 33.51

    SrCO3 147.63 3.74 39.47

    Lattice volume

    Molar volume

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    850˚C 900˚C

    950˚C 1000˚C

    Phase Stability has been studies by high temperature in-situ XRD performed on SrNiOx powder for up to 40h

    • SrNiOx demonstrated phase stability sintered at 850oC and 900oC.• SrNiOx sintered at 950oC and 1000oC dissociates into SrO and NiO phases.

    Getter Materials Stability

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    Endothermic peaks at 105and 489C indicatingrelease of H2O from SNOpowder samples sinteredat (a) 850C and (b) 1000C(20Hrs)

    TGA-DTA Analysis

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    Ni coarse

    & sulfide

    Cr poisoning&Sealing

    Compound formation

    In Stack Cr Capture

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    Half-cell configuration

    PtYSZLSM

    Getter Paste

    Anode Air

    Cathode Air

    ConditionsTemperature 850C

    Flowrate 150 sccm

    Cr Source Cr2O3Cr Getter SNO/ LSCF-SNO

    compositeBias -500 mV

    Half-cell fabrication procedure was maintained for all the half-cell fabrication LSM was screen printed and sintered at 1200 ˚C for 1h SNO or LSCF/SNO getter was brush coated and sintered at 850 ˚C for 20h Config-1: Getter paste is 5 mm apart form LSM and Config-2: Getter paste is in direct contact with LSM

    PtYSZLSM

    Anode Air

    Cathode Air

    (Ni-supported) Getter Paste

    5 mm

    Config-2Config-1

    Electrochemical Evaluation

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    LSCF-SNOLSM-SNO

    0.001

    0.01

    0.1

    1

    10

    100

    1000

    500 600 700 800 900

    Ele

    ctri

    cal c

    ondu

    ctiv

    ity (S

    /cm

    )

    Temperature (C)

    75 LSCF - 25 SNO

    50 LSCF - 50 SNO

    0 LSCF - 100 SNO0.001

    0.01

    0.1

    1

    10

    100

    1000

    500 700 900

    Ele

    ctri

    cal c

    ondu

    ctiv

    ity (S

    /cm

    )

    Temperature (C)

    100LSM-0 SNO75 LSM - 25 SNO50 LSM - 50 SNO0 LSM - 100 SNO

    Electrical conductivity of LSM is approximately 120 S/cm at 850˚C Electrical conductivity of SNO is approximately 1.2 S/cm at 850˚C Addition of SNO in LSM lowers the conductivity of LSM-SNO composites Electrical conductivity of LSCF is more than 800 S/cm at 850˚C1 LSCF-SNO composites display higher conductivity compared to LSM-SNO composites.

    1. Q. Xu et al, Journal of Alloys and Compounds 454 (2008) 460–465

    Electrical Conductivity

    Getter Materials Conductivity

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    0

    200

    400

    600

    800

    1000

    1200

    1400

    0 10 20 30 40 50 60 70 80 90 100

    I (m

    A/cm

    2 )

    Time (h)

    I-t data shows stable performance for 100h in all the half-cell configurations Config-1 shows higher performance because of no direct contact of getter with the LSM cathode 75LSCF-50SNO getter shows higher current density (~1100 mA/cm2) as compared to 50LSCF-50SNO getter (~700 mA/cm2)

    Config-1

    Config-2

    100 SNO (Ni-supported brush coated)

    100SNO (brush coated)

    50LSCF-50SNO (brush coated)

    50LSCF-50SNO (Screen printed)

    75LSCF-25SNO (Screen printed)

    I-t data

    Baseline (No Cr-No Getter)

    Cr-No Getter

    Electrochemical Evaluation

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    75LSCF-50SNO (Screen printed) Cross-section

    - Higher Cr concentration observed at the surface

    - Cathode/ electrolyte interface remained free from Cr

    Posttest characterization (SEM)

    Electrochemical Evaluation

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    75LSCF-25SNO (Screen printed)

    (a) (b)

    1μm 1μm

    1μm 1μm

    (d) (e)

    50LSCF-50SNO (Screen printed)

    (c)

    1μm

    1μm

    50LSCF-50SNO (Brush coated)

    (f)

    Surface

    Cross-Section

    Posttest characterization (SEM)

    All Cr are mostly captured at the surface of the cathode with faceted particle formation No Cr or product was found inside cathode or cathode-YSZ interface

    Electrochemical Evaluation

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    Getter reaction and Cr capture

    5 μm

    Air +3%H2O+Crv

    SrNiOx

    Product layerSrCrO4(s)

    SrNiOx

    Product layerSrCrO4

    Cr(g)

    Sr

    Solid-Gas interface

    CrO3 (g) + SrxNiyOz = SrCrO4+ NiO+ O2 (g) CrO2(OH)2 (g) + SrxNiyOz + O2 (g) = SrCrO4 + NiO + H2O (g)

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    YSZLSM

    LSM

    Getter

    Anode Lead

    Cat

    hode

    Lea

    d

    Reference Lead

    Air flow

    Cr2O3

    Pellets

    Airflow

    Airflow

    Airfl

    ow

    In-Situ Electrochemical CharacterizationTest assembly : Half cell configuration

    Temperature: 850°CCathode atmosphere: 3% H2O/air (balance), flow rate: 50 (500) sccmAnode atmosphere: dry air, flow rate: 150 sccmCathodic Bias vs reference: 0.5 VGetter: cordierite /alumina fiber supported SrNiOx

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    Thermodynamic Analysis

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    Cr poisoning in SOFC cathodes

    • Cr poisoning effects in SOFC cathodes• (La,Sr)MnO3• (La,Sr)(Co)O3

    • Ab-initio thermodynamic with a linear programming approach• Reaction Energetics of the SOFC cathodes with CrO3

    Thermodynamic Analysis

    * The structure of the LSCO and LSMO at different Sr concentration have been studied.* We have identified the minimum energy structures in each of the compositions and they agree well with experiments * Reaction energetics of CrO3 with the compounds La0.5Sr0.5CoO3 and La0.75Sr0.25MnO3were studied.* We find that while LSCO results in reactive products for the experimental window, the LSMO remains unreactive

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    Reaction energetics of La0.5Sr0.5CoO3 Cubic

    Based on the reaction energetics, the formation of these products: LaCoO3, Co3O4, SrCrO4, and O2 are energetically favored in the experimental window.

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    Based on the reaction energetics, the formation of Cr deposition products are not energetically favored in the experimental window.

    Reaction energetics of La0.75Sr0.25MnO3 Cubic

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    SrO

    CrO2(OH)2

    SrO

    CrO2(OH)2

    SrCrO4

    B. Hu, S. Krishnan, C. Liang, S. J. Heo, A. N. Aphale, R. Ramprasad., P. Singh, . Int J Hydrogen Energy , 2017

    Morphology evolution in the presence of water and chromium vapor

    Background – Chromium Poisoning of Cathodes

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    • Sr-Ni-O, Sr-Mn-O, Sr-Fe-O perovskite type compounds with relatively high electrical conductivity are the potential coating materials for getter application.

    • CaO and MgO are considered.• The oxidation of both Cr vapor and SO2

    occurs the most by SrO getter material over a wide temperature range.

    Co-oxidation of Cr and SO2 on metal oxides

    Co-stability calculated based on Gibbs free energy and equilibrium constant

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    Thermodynamic Calculations of pCr and pSO2 vapors at High Temperatures

    • SrO is better than CaO, and MgO as a getter material for Cr and S capture.• SrO is capable of forming SrCrO4 and SrSO4 compounds at extremely low

    concentrations of Cr and SO2 vapors, even below 1 ppb.

    Sr

    Ca

    Mg

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    • Sensor design:Planar sensor design to monitor the presence of chromium within the getter

    Design and fabrication

    • LSM sintered at 1200 oC in air and Pt sintered at 850 oC in air with the ramp rate of 3C/min for 1h

    • LSM and Pt ink was brush coated on the YSZ disk as sensing (SE) and reference electrode (RE)

    Airflow

    LSM PtYSZ

    Sensor Fabrication

    Sensor Validation

    (SE)LSM

    (RE)Pt ink

    Planar (2D) sensor

    YSZ

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    Validation

    Getter

    Outer tube (alumina)

    Cr pellets

    3% H

    2O Air

    EIS

    • S1 is inserted within the getter at about 2 mm from inlet• S2 is inserted about 8 mm from inlet of the getter • Observe the changes in polarization resistance and ohmic

    resistances to determine extent of Cr related degradation

    S1

    S2

    2mm

    8mm

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    Mass conservation equation: 𝜕𝜕𝜌𝜌𝜕𝜕𝜕𝜕

    + 𝛻𝛻. 𝜌𝜌𝐮𝐮 = 0

    Momentum conservation equation: 𝜕𝜕(𝜌𝜌𝐮𝐮)𝜕𝜕𝜕𝜕

    + 𝛻𝛻. 𝜌𝜌𝐮𝐮𝐮𝐮 = −𝛻𝛻𝑝𝑝 + 𝛻𝛻. 𝝁𝝁𝒆𝒆𝒆𝒆𝒆𝒆𝛻𝛻𝐮𝐮 + 𝜌𝜌𝐠𝐠

    Species conservation equation: 𝜕𝜕(𝐶𝐶𝐶𝐶𝐶𝐶)𝜕𝜕𝜕𝜕

    + 𝛻𝛻. 𝐮𝐮𝐶𝐶𝐶𝐶𝐶𝐶 = 𝛻𝛻. 𝑫𝑫𝛻𝛻CCr + S𝐶𝐶𝐶𝐶

    Boundary Conditions

    𝑢𝑢,𝐶𝐶𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝐶𝐶𝐶𝐶

    wall

    symmetry

    Pressure outlet

    S𝐶𝐶𝐶𝐶: sink term for Cr.

    43

    Governing Equations, Boundary Conditions, and Parameters

    • Set of equations is discretized using a finite-volume method.• Discretized equations are solved within the commercially available CFD software, Fluent, by

    customizing via user-defined functions. • The software utilizes the well-known SIMPLE algorithm.

    Numerical Procedure

    • Modeling Geometry: 50 mm long and 1mm width• Temperature: 850˚C• Cr partial pressure 0.1 Pa and 0.001 Pa• Air density: 0.3139 kg/m3 at 850˚C• Gas phase Cr diffusivity: 1.08775e-4 m2/s• Solid phase Cr diffusivity: 1e-19 m2/s• Solid phase Sr diffusivity: 1e-17 m2/s

    Modeling Parameters• Getter material: SrNiOx• SrNiOx density: 5406 kg/m3

    • SrNiOx molecular weight: 1.53542 kg/mol

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    Electrode poisoning at low temperatures

    In cell validation

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    0

    50

    100

    150

    200

    250

    300

    0 10 20 30 40 50 60 70 80 90 100

    mA

    (I)

    Time (h)

    The LSM/YSZ/Pt half-cell exposed to 3% H2O/air in the presence of Cr vapor shows a rapid drop in the current within the first few hours while the I-t curves from the standard cell (No Cr vapor) and the cell exposure to Cr and followed a chromium getter show similar curve with stable electrochemical performance.

    Electrochemical Performance at 650C

    w/Cr

    wo/Crw/Cr getter

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    0

    0.2

    0.4

    0.6

    0.8

    1

    1.2

    0 1 2 3 4 5

    -ImZ

    (ohm

    /cm

    2 )

    Re Z (ohm/cm2)

    1h

    5h

    10h

    60h

    100h

    0

    5

    10

    15

    20

    25

    0 20 40 60 80 100

    -Im Z

    (ohm

    /cm

    2 )

    Re Z (ohm/cm2)

    1h

    5h

    10h

    20h

    60h

    100h

    Exposure to Cr vapor No Cr vapor

    0

    0.1

    0.2

    0.3

    0.4

    0.5

    0.6

    0.7

    0.8

    0 1 2 3 4

    -ImZ

    (ohm

    /cm

    2 )

    Re Z (ohm/cm2)

    1h

    5h

    10h

    60h

    100h

    Exposure to Cr with getter

    Changes in EIS with/without Cr and Cr/getter

    Rp increases with time when cell was exposure to Cr while Rp keeps stable if no Cr species present.

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    Cr vaporNo Cr vapor

    LSM

    YSZ

    LSM

    YSZ

    Cr2O3

    Cr deposition in the cellObservations: Cr2O3 deposits at the LSM/YSZ interface at 650°C when cell was exposed to Cr vapor.

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    Summary

    • Cr capture has been successfully demonstrated from BOP/ In-cell sources• Cr getter materials have been identified and synthesis process have been

    developed and scaled up. • Synthesis process scaled up to 1kg/batch using lab equipment• Design studies have been performed to obtain 40,000 hrs. getter life• Fabricated Cr getter samples and materials have been provided to PNNL,

    LG, Cummins, Ceres and others for testing• Laboratory findings have been provided to SOFC industries• Cathode degradation mechanisms have been identified and published.• Getter operation has been validated at low (650C) temperature• Alternate HSA getter has been identified and synthesized.

    Getters can be provided to SOFC industries and research institutions for independent testing and validation

  • NETL Meeting 06122017

    Acknowledgements

    • Drs. Rin Burke, Jason Lewis and Shailesh Vora for guidance and encouragement• Dr. Jeff Stevenson, Matt Chou and Brian Koeppel (PNNL) for electrical testing and

    discussion• Mr. Rich Goettler (LGFCS), Dr. Amit Pandey (LGFCS), Dr. Hossain Ghezel-Ayagh

    (FCE), Dr. Shubi Mukherjee (CP), Dr. Charles Veseley (CPS), Dr. Lou Carreiro(NUWC) and Dr. Deodeshmukh (Haynes) for engineering and systems related discussion

    • Drs. Yu Zhong (FIU), Yoed Tsur(Technion) for thermochemical model• UConn for providing laboratory facility and support

  • NETL Meeting 06122017

    Thank you

  • NETL Meeting 06122017

    Composite with LSM – LSCF with SNO

    LSM/ LSCF pellets were sintered at 1200oC LSM/LSCF-SNO composite pellets were sintered at 950oC for 1h Pt electrodes were attached using Pt paste and sintered at 850oC Pellet: Dia: ~12.70mm, Thickness: ~2.07mm, ~Wt: 0.9655g 4-probe measurement method applied

    4 point probe method

    t

    75 LSM-25 SNO

    50 LSM-50 SNO

    25 LSM-75 SNO

    0 LSM-100 SNO

    Electrical conductivity measurement: In-cell getter

    Getter Materials Optimization

  • NETL Meeting 06122017

    Cr getter critical property

    Performance of new Cr getter against baseline state of the art Cr getter

    Test conditions(Temp, time, atm)

    Phase Stability Superior: New Cr getter shows no phase changes and interactionwith humidity and CO2 present in air.

    RT-980C, Ambient air

    Reaction products As processed getters consist of several oxide phases containingSr and Ni (Sr9Ni7O21, Sr4Ni3O9 and Sr2Ni4O5).

    Powder synthesis process and transpiration,electrochemical testing at 850C for up to 500hrs in Air -3%H2O

    Microstructures Stable powder, coating and substrate microstructures obtainedNew Cr getter retains its microstructure after high temperatureexposures (850C) in humidified air. Literature review does notprovide background information on the SOTA.

    During processing up to 980C in airDuring bench top testing at 850C for up to500 hrs in humid air

    Thermochemistry Similar or Superior: Based on thermochemical models developed

    Physical Properties Similar or Superior: Based on resistance to ambient air(NAAQS)

    Product morphology Porous powder coating on ceramic substrates During processing up to 980C in airDuring bench top testing at 850C for up to500 hrs in humid air

    Cr Conc. profile Superior: Capture Cr in the first 1500 - 3000 micron.Reproducible results

    During bench top testing at 850C for up to500 hrs in humid air

    Substrate Configuration include honeycomb, foam and fibrous structure,Substrate materials include Cordierite, Mullite, zirconia andalumina.

    Ease of fabrication Conventional powder preparation and coating techniques pre-formed /In-situ getter formation

    A list of Cr getter properties against the state of the art Cr poisoning mitigation and getter materials

    Background: Getter

  • NETL Meeting 06122017

  • NETL Meeting 06122017

    Cr getter

    Appearance

    Figure Cr getter coated withSrNiO (3 cm in diameter, 2 inchin length)2. Expectation from the appearance

    (1) Black color in all positions Uniformly coated(2) No clogging Uniform and ideal(3) No powder dust detached from the getter Strong adhesion

    Relatively, uniformlycoated without anyclogging

    1. Fabrication Process (coating x2): Coating with SrNi(OH)x sintering at 850oC for 1 h Coating with SrNi(OH)x sintering at 650 oC for 1 h

  • NETL Meeting 06122017

    • SNO does not dissociate into SrO or NiO - indicating phase stability. • LSCF remains stable throughout the 40h sintering process• After 40h sintering strontium iron oxide (SFeO)and lanthanum cobalt iron oxide (LCoFeO) appeared in smaller quantity.

    High temperature in-situ XRD performed on 75LSCF-25SNO powder for up to 40h at 850 C

    SNONiOLSCFSFeOLCoFeO

    RT

    0h

    40h

    Cool to RT

    Getter Materials Stability

  • NETL Meeting 06122017

    Figure 6. XRD patterns of SNO sintered at 850°C showing stability and showing the formation of Sr(OH)2 and SrCO3 compounds in the pulverized samples sintered at 1000°C for 20h.

  • NETL Meeting 06122017

    -0.15-0.1

    -0.050

    0.050.1

    0.15

    0.4 0.6 0.8 1 1.2 1.4

    -Im

    (Z) (

    Ω c

    m2)

    Re(Z) (Ω cm2)1h 20h 40h 60h 80h 100h

    -0.15-0.1

    -0.050

    0.050.1

    0.15

    0.4 0.6 0.8 1 1.2 1.4

    -Im

    (Z) (

    Ω c

    m2)

    Re(Z) (Ω cm2)1h 20h 40h 60h 80h 100h

    -0.25

    -0.15

    -0.05

    0.05

    0.15

    0.25

    0.4 0.6 0.8 1 1.2 1.4

    -Im

    (Z) (

    Ω c

    m2)

    Re(Z) (Ω cm2)1h 20h 40h 60h 80h 100h

    Nyquist plots

    SNO getter (Config-1) half-cell shows least ohmic resistance and polarization and remained stable throughout 75LSCF-25SNO and 50LSCF-50SNO getter with (Config-2) half-cell demonstrated decrease in the ohmic resistance

    as well as polarization resistance during first 20h and later remained stable 100 SNO getter (Config-2) based half-cell has consistent ohmic resistance as well as polarization resistances, 0.6

    and 1.5 ohms respectively

    100 SNO (brush coated)

    Config-1

    Config-250LSCF-50 SNO (brush coated)Config-2

    100 SNO (Ni supported) 50LSCF-50 SNO (Screen printed)Config-275LSCF-25 SNO (Screen printed)Config-2

    -0.05

    -0.03

    -0.01

    0.01

    0.03

    0.05

    0.35 0.4 0.45 0.5 0.55 0.6

    -Im

    (Z) (

    Ω c

    m2)

    Re(Z) (Ω cm2)1h 20h 40h 60h 80h 100h

    -0.05

    -0.03

    -0.01

    0.01

    0.03

    0.05

    0.35 0.4 0.45 0.5 0.55 0.6

    -Im

    (Z) (

    Ω c

    m2)

    Re(Z) (Ω cm2)1h 20h 40h 60h 80h 100h

    (a)

    0

    0.2

    0.4

    0.6

    0.8

    (a) (b) (c) (d) (e)

    Res

    ista

    nce

    (Ωcm

    2 ) RnpRp

    (b) (c)

    (d) (e) (f)

    Electrochemical Evaluation

  • NETL Meeting 06122017

    Future Work

    • Complete validation of 1 kg/ batch getter powder synthesis process• Use the above getter powder for coating getter support (foam, honeycomb)• Complete getter desgn• Test coated getters under SOFC system conditions• Test getters in the cell • Provide powder and fabricated getters to SOFC industry under DOE guidelines• Assist DOE in technology transfer

  • NETL Meeting 06122017

    I-t performance

    0

    0.1

    0.2

    0.3

    0.4

    0.5

    0.6

    0.7

    0.8

    0 5 10 15 20 25 30 35

    I(mA)

    Time (h)

    I-t data

    S1S2

    •Performance of S1 decreases continuously and S2 performance stabilizes after 5h

  • NETL Meeting 06122017

    Changes in Rp and Rnp

    -20

    0

    20

    40

    60

    80

    200 400 600

    I(mA)

    Time (h)

    S1

    0h10h20h30h 0

    10

    20

    30

    40

    50

    60

    200 300 400 500

    I(mA)

    Time (h)

    S2

    0h

    10h

    20h

    30h

    -10

    40

    90

    0 20 40% In

    crea

    se in

    R

    p

    Time (h)

    S1S2

    •Polarization resistance (Rp) of S1 continouslyincreases and within 30h, it increased by more than 60%•Increase in Rp of S2 is relatively stable over time. •No significant changes in Rnp for both sensor.•Continue to monitor the performance over longer time

  • NETL Meeting 06122017

    Design and Optimization of Chromium Getter through Computational Modeling

  • NETL Meeting 06122017

    Aman UddinCollaboration with PNNL

    Design and Optimization of Chromium Getter through Computational Modeling

  • NETL Meeting 06122017

    The overall objective is to design and optimize chromium getter to capture the chromium species originating from the metallic stack and BOP components. The objectives include:• Parametric study of getter to predict the effects of the key parameters such as geometric surface area,

    porosity, thickness of coating materials, etc. when:o Surface reaction is rate limitingo Solid state diffusion is rate limitingo Diffusion through porous product layer is rate limiting

    • Optimize design for higher utilization and low pressure drop requirement. • Fabricate and test getter according to the proposed model and validate

    63

    Objectives

    A transient, two dimensional model of chromium getter is developed to predict the utilization of getter with various rate limiting cases.

    In this model, cordierite substrate with 400 cpsi (cells per square inch) is considered as the getter support material for 1 kW SOFC system (4 SLPM flow rate), and the model is solved for high Cr partial pressure (1e-6 atm).

    In solid state diffusion case, Chromium front moves forward before reaching to maximum capacity because porosity of getter decreases due to product layer formation with time and diffusion is rate limiting.

    Chromium front moves faster in solid state diffusion case compared to reaction rate limited case. Current efforts are underway to optimize design for higher utilization and low pressure drop requirement.

  • NETL Meeting 06122017

    Hu et al. J. Power Source, 2016, submitted

    64

    Background• Cr poisoning is one of the major causes of cathode degradation in high temperature electrochemical

    systems such as SOFC.• A novel approach called Cr getter is developed to mitigate the Cr poisoning.• Cr getter contains SrNiOx getter material supported by various structure.• Support materials: cordierite, porous alumina. • Successfully captured Cr within 2-3mm of getter.

    air flow rate of 50 sccm for 100hr at 850˚C

    0 2500 5000 7500 20000 30000 40000

    0.0

    0.2

    0.4

    0.6

    0.8

    1.0

    Inten

    sity p

    ercen

    tage o

    f chr

    omium

    Distance from inlet (µm)

    Getter 1 Getter 2 Getter 3

    air flow rate of 300 sccm for 500hr at 850˚C.

    air flow rate of 50 sccm for 100hr at 850˚C

  • NETL Meeting 06122017

    Assumption: 10µm thick coating with 50% porosity Product layer reduces porosity of getter Solid State Diffusion

    Rate Limiting Step: Solid state diffusion

    S𝐶𝐶𝐶𝐶 = 𝐷𝐷𝑖𝑖 ∗𝐶𝐶𝑠𝑠𝐶𝐶δ 𝜕𝜕

    ∗𝐴𝐴𝑉𝑉

    Where, 𝐶𝐶𝑠𝑠𝐶𝐶=concentration of Strontium, De= Diffusion coefficient; δ(t)=thickness product layer, A/V= area to volume ratio

    00.20.40.60.8

    1

    0 10 20 30 40 50

    Cr c

    apac

    ity

    Channel length (mm)

    Chromium profile at 4 SLPM flow rate with 0.1 Pa Cr pressure

    28 hr

    56hr

    76hr

    00.10.20.30.40.50.6

    0 10 20 30 40 50

    Poro

    sity

    Channel length (mm)

    Porosity of getter

    0hr

    28hr

    56hr

    76hr

    SrCrO4NiO

    SrNiOxSr

    Chromium front moves forward before reaching to maximum capacity because porosity of getter decreases and diffusion is rate limiting.

    Chromium front moves faster in solid state diffusion case compared to reaction rate limited case.

    00.20.40.60.8

    1

    0 10 20 30 40 50

    Cr c

    apac

    ity

    Channel length (mm)

    Comparison (after 56hr)

    ReactionrateSolid statediffusion

  • NETL Meeting 06122017

    Electrochemical Performance (Baseline- No Cr-No Getter)

    • Results from 100 h I-t data shows stable performance• Polarization resistance remained stable at (Rp) ~60 Ω• Ohmic resistance also remains constant at (Rnp) ~80 Ω

    0

    1

    2

    3

    0 50 100

    I (m

    A)

    Time (h)

    I-t data

    Chart1

    82.447283.851383.833583.570483.342483.663783.723683.839884.279984.59684.4158

    82.13283.516183.457183.240383.045983.286583.401883.539383.938484.277484.2286

    81.880283.391683.219483.047982.743882.987783.181483.408383.688384.027883.9239

    81.627483.061382.99682.829882.570882.927583.02183.096783.480883.787683.837

    81.533682.97982.972982.697882.454382.705982.842482.899183.375183.728783.6025

    81.363882.84282.869882.669982.28481.5012382.766782.913683.256483.722883.5544

    81.364682.830282.845882.64182.28391.6232582.773782.904883.238183.603683.5227

    81.399882.784982.834182.60482.39771.8815482.779582.916783.255883.639583.5673

    81.364582.867482.84882.71982.35912.115772.0395582.939383.254683.569583.5379

    81.398182.919882.862282.732182.38632.3224783.000383.345783.760383.5914

    81.469982.98283.01282.738982.46442.492283.192283.382583.820183.6922

    81.617483.072583.024982.896282.56982.8062783.165183.539183.943383.8042

    81.749683.191783.196283.009282.6392.9698383.377883.74284.09883.9498

    81.82283.310183.32983.178182.87383.2384783.466683.867584.229884.151

    82.086883.555683.6283.345283.00683.4537183.650684.049784.343784.2763

    82.204683.688383.703583.532783.24133.6828583.824984.205384.552784.4413

    82.418183.831783.921583.660483.44773.940484.149384.45584.739984.6573

    82.590984.143984.176484.040483.71094.2858584.346984.662285.007284.9604

    82.839984.335284.372284.243784.01274.6246384.564584.964385.298285.2956

    83.160284.658284.71884.63984.27934.9852684.916985.322285.623485.5859

    83.462784.920184.969484.870884.57825.264885.22485.591485.92385.8975

    83.869985.351485.469385.260984.93865.6000185.486485.827686.342886.3249

    84.221385.673285.816785.63485.29685.9391485.963786.225386.644986.6914

    84.588986.084186.204886.016185.66446.3271186.337486.676687.140287.0453

    84.995486.44186.634686.5586.19846.6834986.869987.188587.550287.5158

    85.508986.734187.109287.064386.68397.0716287.292387.717488.031888.0103

    85.989987.286687.636487.483187.13917.4549487.933388.190788.611188.6463

    86.572887.707388.061188.155587.73067.7999788.465588.792589.181689.1603

    87.089788.133888.737588.756788.26588.1725889.139189.360389.805589.7558

    87.719488.682489.253889.469788.9428.6614789.81290.026790.45890.5148

    88.326289.188989.992690.15589.6659.0033990.549790.750591.169591.2901

    88.97689.632690.634190.926290.38639.3694891.271691.424491.900491.9595

    89.641990.204791.331491.731190.98819.7482392.287692.263192.857292.7644

    90.349390.815892.137692.546191.84610.026593.110893.18493.661393.6692

    90.980391.206392.799493.443592.672810.372994.046193.945794.558694.6111

    91.648191.766693.571694.33693.537810.668595.173394.993595.532795.598

    92.262292.212394.375495.334894.46110.950796.214396.063196.43196.6111

    92.956692.688495.202396.242395.371111.097597.318796.917997.47897.7243

    93.621893.365795.973897.341396.282311.262698.554898.062798.574898.7796

    94.260793.718896.907598.441997.164211.376799.901499.172299.6024100.001

    94.949494.273997.683999.348298.159111.5146101.117100.312100.719101.312

    95.413994.823398.4283100.34898.948711.4969102.247101.465101.814102.51

    95.969395.249899.2836101.41399.939211.5695103.794102.547102.916103.792

    96.532495.8066100.004102.493100.94711.5262105.006103.649104.055104.982

    97.163496.1821100.812103.301101.79611.3086106.236104.885105.149106.103

    97.620796.6565101.528104.461102.62111.165107.62105.878106.042107.258

    98.115197.3157102.244105.359103.52511.0332108.938107.144107.242108.609

    98.622597.699102.976106.316104.30110.7477110.041108.051108.126109.619

    99.148498.2198103.606107.183105.20110.6455111.149109.076108.995110.643

    99.66198.8338104.443108.12105.98910.4019112.327109.994110.001111.636

    100.12299.312105.134108.909106.76610.084113.461111.005110.836112.639

    100.72999.8692105.761109.663107.3719.95137114.349111.759111.67113.548

    101.182100.36106.4110.414108.1149.73157115.365112.449112.278114.429

    101.856100.916107.013111.224108.8079.42603116.138113.213113.074115.13

    102.385101.559107.791112.004109.3799.29755116.9113.921113.626115.787

    103.09102.174108.405112.68110.1299.17681117.72114.568114.326116.551

    103.79102.902109.213113.496110.6918.9767118.454115.286114.811117.259

    104.474103.61109.969114.079111.4318.72665119.168115.843115.366117.863

    105.218104.215110.64114.806111.9348.58065119.859116.418115.904118.271

    106.047105.071111.305115.508112.5468.59284120.314116.933116.41118.926

    106.872105.794112.13116.293113.2598.48861121.089117.5116.921119.408

    108.399106.52112.041116.243113.3688.86023120.843116.889117.119118.362

    108.799107.296113.682117.594114.3178.3689122.447118.475117.865120.369

    109.836108.343114.258118.621115.0618.41687122.453119.123118.05120.637

    110.806109.345115.442119.332115.7238.34409123.449119.441118.768121.238

    111.927110.326116.108119.934116.2228.61755123.966120.155119.038121.765

    113.339111.228117.086120.819117.1498.41917124.479120.37119.678122.281

    114.732112.177117.888121.761117.7958.36227125.057121.081120.129122.687

    115.665113.587119.006122.579118.5228.71012125.98121.775120.563123.13

    117.157114.882120.124123.261119.0249.13688126.915122.657121.136124.078

    117.894114.138120.936127.085122.876.99577125.547120.408123.672121.681

    120.919115.011120.96127.38122.3456.65163125.493121.108122.673123.779

    121.5118.05122.889126.487121.5518.78936128.228123.804122.858125.373

    123.006118.85123.912127.439122.5778.74809128.803124.248123.262126.086

    124.07120.366124.918128.003123.2248.98129129.774125.324124.205126.733

    125.31121.33125.967129.213124.4058.81422130.311125.861124.749127.139

    126.551122.756127.051129.763124.4899.29819131.719126.964125.197128.174

    127.978123.58127.66131.478125.859.03833131.834127.318126.047128.512

    128.533124.747128.742131.99126.7478.92626132.533128.111126.627129.24

    129.755125.534129.8133.326127.6058.54075133.386128.554127.511129.881

    130.488126.753130.701133.635128.2938.94871134.366129.777128.293130.667

    131.282127.651131.486134.087128.8578.70056135.395130.501128.829131.741

    132.514128.342132.314135.041129.6548.54092136.215131.272129.371132.419

    132.583129.301132.88135.628130.4548.18657136.961131.882130.082133.183

    132.841129.86133.803136.625131.6138.01048137.163132.622131.364133.548

    133.256130.148134.313137.051132.287.67909137.585133.051131.653134.204

    133.801131134.908137.586132.8827.39352138.598133.677132.166134.817

    133.953131.521135.513138.473133.3297.13968139.003134.205133.152135.101

    134.618132.043135.886138.862133.8796.65943139.45134.81133.165135.779

    134.576132.23136.645139.592134.4036.3442139.93134.837134.438135.736

    135.184132.479136.207139.664135.3815.78056139.918135.409134.156136.779

    135.436133.364136.991139.423134.8485.48079140.834136.031134.109137.112

    135.531133.347137.165140.113135.4545.17947140.868136.445134.757137.317

    135.801133.385137.671140.424135.8334.75167141.013136.402135.378137.414

    135.994133.973137.98140.335136.0024.60325141.594136.751135.323137.917

    135.838134.123137.886140.736136.5654.3293141.419136.883135.622137.89

    136.223134.198138.138141.118136.7844.40703142.448137.118135.757138.373

    135.884134.701138.274141.485136.9073.75659141.815137.515136.164138.478

    136.182134.396138.673141.599137.4243.76276142.272137.858135.97138.609

    136.247134.784138.912141.514137.2673.99789142.244137.702136.301138.63

    136.414134.933138.777142.21137.4873.86396142.526138.256136.729138.977

    136.404134.871139.203142.184138.0033.22909143.21138.063136.634138.682

    136.65135.061139.26141.998137.5693.25213143.099138.343136.742139.136

    136.199135.031139.211142.697138.2233.24701143.428138.381137.043139.024

    136.652134.556139.698142.513138.1262.87959143.245138.67137.546139.979

    136.84135.169139.353142.359138.2633.68767143.194139.678137.406139.601

    136.807134.842139.41142.79138.3583.63757144.056138.904137.967140.116

    1h

    10h

    20h

    30h

    40h

    50h

    60h

    70h

    80h

    90h

    100h

    Re(Z)/ Ohms

    Re(Z')/Omhs

    0.494727

    0.472539

    0.597226

    0.782135

    0.529543

    0.611446

    0.692537

    0.643508

    0.686226

    0.622545

    0.682025

    0.572571

    0.620662

    0.702983

    0.905794

    0.704005

    0.784049

    0.767187

    0.843966

    0.897567

    0.885664

    0.88957

    0.720493

    0.797988

    0.868157

    1.07109

    0.893787

    0.957952

    1.01676

    1.04483

    1.00332

    1.00998

    0.945116

    0.916967

    0.919978

    1.01342

    1.29598

    1.09413

    1.04405

    1.14838

    1.17563

    1.18236

    1.18073

    1.27541

    1.09328

    1.07655

    1.20673

    1.43667

    1.24843

    1.30249

    1.30314

    1.34939

    1.26637

    1.32696

    1.41729

    1.27517

    1.2068

    1.35634

    1.66508

    1.39369

    1.43584

    1.57641

    1.55044

    1.59003

    1.57027

    1.38752

    1.35098

    1.54214

    1.8234

    1.60013

    1.65832

    1.74983

    1.73903

    1.70229

    1.78256

    1.59804

    1.58753

    1.75892

    2.08319

    1.82003

    1.85011

    1.92433

    1.93232

    1.90311

    1.97533

    1.73237

    1.78632

    1.95337

    2.27496

    2.01287

    2.21016

    2.19574

    2.14015

    2.28439

    2.01483

    1.89327

    2.06908

    2.54182

    2.26602

    2.4214

    2.38614

    2.33793

    2.4747

    2.22285

    2.17355

    2.38355

    2.70431

    2.4617

    2.63357

    2.56567

    2.6381

    2.68534

    2.41943

    2.35592

    2.6533

    3.06679

    2.6586

    2.91756

    2.87434

    2.74763

    2.91396

    2.58693

    2.55196

    2.83208

    3.23286

    2.92383

    3.15649

    3.03452

    3.02725

    3.19311

    2.87915

    2.67715

    3.0352

    3.54186

    3.1599

    3.30172

    3.3591

    3.43902

    3.42467

    3.01395

    2.99537

    3.3093

    3.8109

    3.39727

    3.64982

    3.52977

    3.59353

    3.68293

    3.27689

    3.11716

    3.51554

    4.11824

    3.63229

    3.96165

    3.83698

    3.92757

    3.92241

    3.60677

    3.37571

    3.8909

    4.43866

    3.95775

    4.31717

    4.17185

    4.13715

    4.28538

    3.86744

    3.54973

    4.10286

    4.7234

    4.22662

    4.61994

    4.42333

    4.49099

    4.59388

    4.04839

    3.88338

    4.37706

    5.02344

    4.52443

    4.94761

    4.71322

    4.76737

    4.91884

    4.35403

    4.07175

    4.60335

    5.35896

    4.82071

    5.22411

    5.06031

    5.11109

    5.29179

    4.64771

    4.23281

    4.91908

    5.66392

    5.10529

    5.62094

    5.36579

    5.4357

    5.61393

    5.01287

    4.44669

    5.31535

    6.0852

    5.48657

    6.08096

    5.75909

    5.78265

    5.99794

    5.32691

    4.72612

    5.60104

    6.5595

    5.74518

    6.44318

    6.12531

    6.19599

    6.34327

    5.59681

    4.9659

    5.99843

    6.82373

    6.14034

    6.82418

    6.49877

    6.60032

    6.7673

    5.88329

    5.08247

    6.30833

    7.26084

    6.5309

    7.35611

    6.94879

    6.95307

    7.19397

    6.22286

    5.37145

    6.55165

    7.72736

    6.88919

    7.71293

    7.36593

    7.41222

    7.60871

    6.48139

    5.44464

    6.82131

    8.14618

    7.32253

    8.18946

    7.76326

    7.80045

    8.08105

    6.65835

    5.82219

    7.27903

    8.50756

    7.68265

    8.73148

    8.13293

    8.23213

    8.49521

    7.0191

    5.87377

    7.55486

    8.88843

    7.95489

    9.20761

    8.61834

    8.61797

    8.94056

    7.14779

    6.08501

    7.87483

    9.30368

    8.42767

    9.64221

    9.03312

    8.92319

    9.38232

    7.4358

    6.19095

    8.18673

    9.71091

    8.60211

    10.1834

    9.44815

    9.42122

    9.84683

    7.65074

    6.31099

    8.43694

    10.0862

    8.95709

    10.7587

    9.85062

    9.77857

    10.2582

    7.80832

    6.44049

    8.63931

    10.5152

    9.28144

    11.2622

    10.3389

    10.2189

    10.8401

    7.81971

    6.55792

    8.92814

    10.8029

    9.59346

    11.717

    10.7268

    10.5501

    11.192

    7.97853

    6.5791

    9.13306

    11.0794

    9.8856

    12.1937

    11.0992

    10.9014

    11.6333

    8.02637

    6.66065

    9.3446

    11.4731

    10.2538

    12.5696

    11.4174

    11.282

    12.006

    8.12609

    6.73288

    9.54836

    11.5969

    10.3631

    13.0767

    11.7001

    11.5478

    12.3552

    8.13356

    6.82012

    9.66306

    11.7763

    10.6236

    13.3952

    12.0458

    11.819

    12.6754

    8.06198

    6.79141

    9.73195

    11.9297

    10.7314

    13.711

    12.3338

    11.9926

    12.9808

    8.09877

    6.98243

    9.87941

    12.0944

    10.8148

    14.099

    12.4997

    12.1839

    13.2024

    8.09167

    6.96381

    9.87392

    12.091

    10.8495

    14.1272

    12.6752

    12.1832

    13.3399

    8.10387

    7.09113

    9.87388

    12.1018

    10.867

    14.5608

    12.855

    12.2733

    13.3182

    8.09625

    7.10078

    9.85468

    12.0335

    10.8808

    14.5164

    12.8528

    12.195

    13.5477

    8.14468

    7.20287

    9.7692

    12.0541

    10.8338

    14.4747

    12.7269

    12.2472

    13.4797

    8.2059

    7.2166

    9.86356

    11.948

    10.8282

    14.4296

    12.6787

    12.1434

    13.4025

    8.15758

    7.43605

    9.8001

    11.7958

    10.6617

    14.2854

    12.453

    11.9125

    13.1273

    8.24806

    7.50168

    9.83525

    11.5649

    10.5548

    14.1532

    12.3853

    11.702

    12.9458

    8.24899

    7.65716

    9.73634

    11.5369

    10.5042

    13.9066

    12.0428

    11.5161

    12.7506

    8.49393

    7.79196

    9.84362

    11.3906

    10.2741

    13.5511

    11.7523

    11.1463

    12.3638

    8.53667

    7.89808

    9.85397

    11.3428

    10.0847

    13.1968

    11.5091

    10.7515

    12.0783

    8.68647

    8.15283

    9.93849

    11.0638

    9.98176

    12.8402

    11.1248

    10.5173

    11.7112

    9.00717

    8.3471

    9.77706

    11.0166

    9.89441

    12.4595

    10.8055

    10.14

    11.3532

    9.05197

    8.50325

    9.94007

    10.8746

    9.75614

    12.0566

    10.4439

    9.77172

    10.8067

    9.44538

    8.76874

    9.93943

    10.7486

    9.57619

    11.6278

    10.1441

    9.50021

    10.4277

    9.7264

    9.07259

    10.0196

    10.7757

    9.50385

    11.2447

    9.90167

    9.16842

    10.2182

    9.92706

    9.23711

    10.0923

    10.7199

    9.39041

    10.8834

    9.58588

    8.90451

    9.80804

    10.2689

    9.50383

    10.151

    10.6438

    9.43588

    10.6769

    9.31166

    8.71139

    9.52651

    10.6777

    9.93639

    10.1487

    10.6603

    9.28827

    10.3186

    9.03032

    8.31998

    9.16529

    11.0596

    10.18

    10.4118

    10.5029

    9.33305

    10.0492

    8.82732

    8.17865

    8.98568

    11.4688

    10.4685

    10.545

    10.6202

    9.21673

    9.83681

    8.60071

    8.07734

    8.7242

    11.8545

    10.657

    10.7547

    12.1737

    9.36886

    9.67973

    8.53854

    7.9977

    8.56133

    10.8788

    12.2944

    9.56689

    10.5709

    10.7994

    7.89201

    9.6592

    6.14887

    7.17398

    12.695

    11.3249

    10.9532

    10.7071

    9.31853

    9.24318

    8.2891

    7.60799

    7.96263

    12.9805

    11.5626

    11.1239

    10.8019

    9.35345

    9.28599

    8.11787

    7.58032

    8.20631

    13.4744

    11.8554

    11.349

    10.8805

    9.44904

    9.07557

    8.05417

    7.61813

    7.97441

    13.5598

    12.2365

    11.4684

    10.92

    9.83994

    8.99015

    8.0953

    7.76188

    7.69786

    14.0239

    12.4043

    11.4193

    10.9817

    9.63706

    8.97302

    7.911

    7.5606

    7.84959

    14.1891

    12.7401

    11.7852

    11.2783

    9.64217

    9.1385

    8.16973

    7.64658

    7.84927

    14.2535

    12.6819

    11.797

    11.3088

    9.96399

    9.07294

    8.10306

    7.93836

    7.67351

    13.9946

    13.0075

    12.3193

    12.9508

    10.2843

    9.18029

    8.19758

    8.17218

    7.65769

    16.7021

    11.4718

    9.08858

    11.6003

    8.8709

    6.33393

    6.52577

    6.07961

    8.75474

    16.4171

    12.9803

    10.1049

    11.1274

    8.32906

    8.31145

    7.8971

    5.70545

    9.6505

    14.3247

    13.0726

    11.8654

    11.1104

    10.0271

    9.20608

    8.40431

    7.85374

    7.97274

    14.2597

    13.124

    11.6033

    11.3173

    10.1061

    9.23997

    8.4979

    7.94836

    8.25427

    13.6271

    12.7538

    11.7342

    10.926

    10.3053

    9.10328

    8.31174

    8.04348

    8.167

    13.68

    12.496

    11.4651

    10.6941

    9.86196

    9.10562

    8.56772

    8.01386

    8.28641

    12.2759

    12.5386

    11.7008

    10.3726

    10.133

    9.47727

    8.85044

    8.66517

    7.89267

    12.285

    12.1512

    10.9068

    10.2327

    9.80683

    9.07346

    8.77118

    8.04828

    8.55553

    11.7768

    11.7391

    10.7002

    10.0552

    9.8582

    9.19729

    8.39035

    8.05906

    8.52829

    11.2459

    11.501

    10.3641

    9.71801

    9.60005

    8.85255

    8.72517

    7.99634

    8.47697

    10.3318

    10.7395

    10.0433

    9.37466

    9.56834

    8.86705

    8.37667

    8.11183

    8.17973

    9.64554

    10.2446

    10.0575

    8.79252

    9.3433

    8.64724

    8.08074

    8.33926

    7.66273

    8.78255

    10.0831

    9.5378

    8.43351

    8.81507

    8.67782

    8.22193

    8.03528

    7.68732

    8.38928

    9.23413

    8.98563

    8.26354

    8.53627

    7.93524

    7.68683

    7.70616

    7.45349

    7.84827

    8.57398

    8.23376

    7.87742

    8.44358

    7.57876

    7.34237

    7.36286

    7.50884

    7.37746

    7.87058

    8.0079

    7.14252

    8.06744

    7.37486

    6.93209

    7.28011

    6.91013

    6.68165

    7.67319

    7.42091

    6.91581

    7.75354

    7.04955

    7.13718

    6.85675

    6.85989

    6.2405

    7.24123

    6.82634

    6.34155

    7.5853

    6.45136

    6.55381

    6.58727

    6.65536

    5.72127

    6.79222

    6.61771

    6.46076

    7.16925

    6.30561

    6.34912

    6.30599

    6.23435

    5.25217

    6.51486

    6.00674

    5.40148

    7.14397

    5.533

    6.10457

    5.92105

    6.17205

    5.41535

    5.82226

    5.6413

    5.4092

    6.27471

    5.62186

    5.52858

    5.25549

    5.84038

    4.25267

    5.57444

    5.84063

    4.93149

    5.55441

    5.5891

    5.23877

    5.40679

    5.00505

    4.19759

    4.97043

    4.87076

    5.076

    5.51003

    5.09161

    4.99281

    5.24874

    4.87202

    3.75181

    4.13271

    4.69905

    4.53319

    5.21469

    4.591

    4.32486

    4.8156

    4.50216

    3.36473

    4.37109

    4.60666

    4.08059

    4.90402

    4.57206

    4.41134

    4.54858

    4.60277

    3.32092

    3.63717

    4.07788

    4.13067

    4.81638

    4.3455

    4.19616

    4.07508

    4.19822

    2.74773

    3.87128

    4.06238

    3.80776

    4.64503

    3.54156

    4.17814

    4.02592

    3.92931

    2.94356

    3.15814

    3.697

    3.77532

    4.27986

    3.97668

    4.00011

    3.66894

    3.8147

    2.68659

    2.90321

    3.37654

    3.76141

    3.81542

    3.8073

    3.85368

    3.80331

    3.81503

    2.29741

    2.6878

    3.21185

    3.37722

    3.75402

    3.45554

    4.02701

    3.862

    3.85246

    1.90578

    2.44575

    3.18225

    3.23825

    3.89343

    3.80223

    3.51174

    3.58544

    3.03458

    2.26531

    2.67435

    2.62493

    3.25582

    3.59907

    3.5735

    3.40911

    3.78783

    3.63725

    1.91212

    1.93488

    3.06187

    2.78198

    3.44857

    3.47478

    3.74814

    3.33057

    3.49135

    1.75395

    1.92519

    2.11861

    2.70797

    3.23605

    3.62767

    3.20538

    3.60481

    3.65778

    1.32215

    2.19557

    2.47474

    2.84769

    3.13549

    3.51675

    3.64264

    3.61198

    3.09987

    1.66144

    1.81216

    2.05854

    2.13105

    2.32102

    3.50865

    3.73301

    3.04023

    3.49698

    1.56131

    1.71011

    1.93992

    2.49846

    3.17241

    3.40482

    3.72336

    4.38022

    It data

    C:\EIS data\Ashish\LSM1.2-NO Cr-No Getter\Corrected\Baseline 110316-LSM1_2-No getter-NoCr-50sccm air-250mv bias-850C 100h_04.mprC:\EIS data\Ashish\LSM1.2-NO Cr-No Getter\Corrected\Baseline 110316-LSM1_2-No getter-NoCr-50sccm air-250mv bias-850C 100h_04.mpr

    time/h/mA (-)time/h/mA (-)TIME

    0.01687992.061020.01687992.0610215.0168799

    0.03354662.088160.03354662.0881615.0335466

    0.05021322.088520.05021322.0885215.0502132

    0.06687992.081040.06687992.0810415.0668799

    0.08354662.069790.08354662.0697915.0835466

    0.1002132.055120.1002132.0551215.100213

    0.116882.038270.116882.0382715.11688

    0.1335472.019940.1335472.0199415.133547

    0.1502132.000720.1502132.0007215.150213

    0.166881.979370.166881.9793715.16688

    0.1835471.955470.1835471.9554715.183547

    0.2002131.932490.2002131.9324915.200213

    0.216881.907310.216881.9073115.21688

    0.2335471.884850.2335471.8848515.233547

    0.2502131.862620.2502131.8626215.250213

    0.266881.841850.266881.8418515.26688

    0.2835471.824830.2835471.8248315.283547

    0.3002131.808770.3002131.8087715.300213

    0.316881.795320.316881.7953215.31688

    0.3335471.78530.3335471.785315.333547

    0.3502131.78040.3502131.780415.350213

    0.366881.775890.366881.7758915.36688

    0.3835471.766430.3835471.7664315.383547

    0.4002131.758550.4002131.7585515.400213

    0.416881.753090.416881.7530915.41688

    0.4335471.754540.4335471.7545415.433547

    0.4502131.752170.4502131.7521715.450213

    0.466881.750370.466881.7503715.46688

    0.4835471.742160.4835471.7421615.483547

    0.5002131.738490.5002131.7384915.500213

    0.516881.737520.516881.7375215.51688

    0.5335471.734420.5335471.7344215.533547

    0.5502131.731170.5502131.7311715.550213

    0.566881.729590.566881.7295915.56688

    0.5835471.728640.5835471.7286415.583547

    0.6002141.723040.6002141.7230415.600214

    0.616881.721520.616881.7215215.61688

    0.6335471.720650.6335471.7206515.633547

    0.6502141.720640.6502141.7206415.650214

    0.666881.717910.666881.7179115.66688

    0.6835471.716910.6835471.7169115.683547

    0.7002141.71970.7002141.719715.700214

    0.716881.720720.716881.7207215.71688

    0.7335471.721290.7335471.7212915.733547

    0.7502141.719310.7502141.7193115.750214

    0.766881.720040.766881.7200415.76688

    0.7835471.719290.7835471.7192915.783547

    0.8002141.718490.8002141.7184915.800214

    0.816881.717870.816881.7178715.81688

    0.8335471.714850.8335471.7148515.833547

    0.8502141.715090.8502141.7150915.850214

    0.866881.716230.866881.7162315.86688

    0.8835471.716540.8835471.7165415.883547

    0.9002141.715750.9002141.7157515.900214

    0.916881.716110.916881.7161115.91688

    0.9335471.719340.9335471.7193415.933547

    0.9502141.719290.9502141.7192915.950214

    0.966881.717340.966881.7173415.96688

    0.9835471.715520.9835471.7155215.983547

    1.000131.713711.000131.7137116.00013

    1.000221.713381.000221.7133816.00022

    1.00031.714371.00031.7143716.0003

    1.000391.713391.000391.7133916.00039

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