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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
NETL Meeting 06122017
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
NETL Meeting 06122017
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
NETL Meeting 06122017
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
NETL Meeting 06122017
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
NETL Meeting 06122017
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
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
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
NETL Meeting 06122017
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
NETL Meeting 06122017
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
NETL Meeting 06122017
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
NETL Meeting 06122017
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
NETL Meeting 06122017
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
NETL Meeting 06122017
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.
NETL Meeting 06122017
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
NETL Meeting 06122017
• 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
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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
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Thank you
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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
1.000471.714151.000471.7141516.00047
1.000551.713771.000551.7137716.00055
1.000641.71511.000641.715116.00064
1.000721.714011.000721.7140116.00072
1.00081.712491.00081.7124916.0008
1.000891.714181.000891.7141816.00089
1.000971.714091.000971.7140916.00097
1.001051.713461.001051.7134616.00105
1.001141.715281.001141.7152816.00114
1.001221.715171.001221.7151716.00122
1.001311.714611.001311.7146116.00131
1.001391.713991.001391.7139916.00139
1.001471.714491.001471.7144916.00147
1.001561.714371.001561.7143716.00156
1.001641.715091.001641.7150916.00164
1.001721.715061.001721.7150616.00172
1.001811.715091.001811.7150916.00181
1.001891.714281.001891.7142816.00189
1.001971.714131.001971.7141316.00197
1.002061.714211.002061.7142116.00206
1.00211.714051.00211.7140516.0021
1.002191.712421.002191.7124216.00219
1.002231.712651.002231.7126516.00223
1.002311.7151.002311.71516.00231
1.002361.714811.002361.7148116.00236
1.002451.714541.002451.7145416.00245
1.00251.715071.00251.7150716.0025
1.002561.715581.002561.7155816.00256
1.002691.714891.002691.7148916.00269
1.002751.714851.002751.7148516.00275
1.002821.714911.002821.7149116.00282
1.002881.715121.002881.7151216.00288
1.002951.715551.002951.7155516.00295
1.003011.715561.003011.7155616.00301
1.003141.714331.003141.7143316.00314
1.00321.714091.00321.7140916.0032
1.003271.713971.003271.7139716.00327
1.003331.713761.003331.7137616.00333
1.00341.713421.00341.7134216.0034
1.003461.71381.003461.713816.00346
1.003531.714061.003531.7140616.00353
1.003591.714141.003591.7141416.00359
1.003661.714271.003661.7142716.00366
1.003721.714311.003721.7143116.00372
1.003781.714131.003781.7141316.00378
1.003851.714221.003851.7142216.00385
1.003911.714061.003911.7140616.00391
1.003981.713511.003981.7135116.00398
1.004041.713681.004041.7136816.00404
1.004111.714391.004111.7143916.00411
1.004171.714611.004171.7146116.00417
1.004241.714381.004241.7143816.00424
1.00431.714051.00431.7140516.0043
1.004371.714021.004371.7140216.00437
1.004431.714111.004431.7141116.00443
1.00451.714471.00451.7144716.0045
1.004561.714091.004561.7140916.00456
1.004631.713851.004631.7138516.00463
1.004691.713561.004691.7135616.00469
1.004761.713951.004761.7139516.00476
1.004821.714111.004821.7141116.00482
1.004891.713581.004891.7135816.00489
1.004951.713761.004951.7137616.00495
1.005021.714191.005021.7141916.00502
1.005081.714051.005081.7140516.00508
1.005151.713891.005151.7138916.00515
1.005211.713941.005211.7139416.00521
1.005281.714441.005281.7144416.00528
1.005341.714251.005341.7142516.00534
1.005411.713981.005411.7139816.00541
1.005471.713611.005471.7136116.00547
1.005541.713631.005541.7136316.00554
1.00561.713711.00561.7137116.0056
1.005671.71421.005671.714216.00567
1.005731.714081.005731.7140816.00573
1.005791.713531.005791.7135316.00579
1.005861.713491.005861.7134916.00586
1.005931.714161.005931.7141616.00593
1.005991.714131.005991.7141316.00599
1.006061.713591.006061.7135916.00606
1.006141.713611.006141.7136116.00614
1.006191.71421.006191.714216.00619
1.006261.713651.006261.7136516.00626
1.006331.713481.006331.7134816.00633
1.006411.713781.006411.7137816.00641
1.006461.713791.006461.7137916.00646
1.006511.713541.006511.7135416.00651
1.006571.714271.006571.7142716.00657
1.006631.713971.006631.7139716.00663
1.006711.713871.006711.7138716.00671
1.006791.713931.006791.7139316.00679
1.006881.714291.006881.7142916.00688
1.006981.714141.006981.7141416.00698
1.007091.714151.007091.7141516.00709
1.007211.714211.007211.7142116.00721
1.007351.71391.007351.713916.00735
1.007511.713711.007511.7137116.00751
1.007691.713051.007691.7130516.00769
1.007881.713281.007881.7132816.00788
1.00811.71381.00811.713816.0081
1.008351.713831.008351.7138316.00835
1.008621.713451.008621.7134516.00862
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