Anwendung in-situ diagnostischer Methoden für die ...¤chs._BZ_Tag_Leipzig_G._Schiller.pdf · 4. Sächsischer Brennstoffzellentag, Leipzig, 10. November 2011 Alteration of the Gas

4. Sächsischer Brennstoffzellentag, Leipzig, 10. November 2011

Anwendung Anwendung inin--situsitu diagnostischer Methoden fdiagnostischer Methoden füür die r die Untersuchung oxidkeramischer BrennstoffzellenUntersuchung oxidkeramischer Brennstoffzellen

G. Schiller, H. Ax, W. Bessler, C. Christenn, Z. Ilhan, P. Szabo, C. Willich

Deutsches Zentrum für Luft- und Raumfahrt, Institut für Technische ThermodynamikPfaffenwaldring 38-40, D-70569 Stuttgart

4. Sächsischer Brennstoffzellentag, Neue Messe Leipzig, 10.November 2011


SOFC SOFC Activities at Activities at

DLRDLR

Characterization of Short Stacks and

Stacks (ASC, MSC)

Development of Metal Supported Cells (MSC)

System TechnologySOFC Diagnostics

Fuelgas Air

SOFC Modeling

H2H2/CO

CH4

H2OCO2

anode

electrolyte

cathode

O2/N2N2

interconnect

interconnect

Ri Resistor Si Switch, Ii Local current

Segmentvoltage,impedance

UlocalZlocal

Segmentcurrent

UIZ

Detailed 2D model of MEA, channel, interconnector

R1 R3 R4R2

R5 R7 R8R6

S1 S3 S4S2

S5 S7 S8S6

I4I3I2I1

Detailed 2D model of MEA, channel, interconnector

R1 R3 R4R2

R5 R7 R8R6

S1 S3 S4S2

S5 S7 S8S6

I4I3I2I1

Cell current,voltage,

impedance


„„SophisticatedSophisticated““ ((nonnon--traditionaltraditional) ) InIn--situsitu DiagnosticsDiagnostics

•• ElectrochemicalElectrochemical impedanceimpedance spectroscopyspectroscopy on on stacksstacks

•• SpatiallySpatially resolvedresolved measuringmeasuring techniquestechniques forfor currentcurrent, , voltagevoltage, , temperaturetemperature

and gas and gas compositioncomposition

•• OpticalOptical imagingimaging

•• OpticalOptical spectroscopyspectroscopy

•• AcousticAcoustic emissionemission detectiondetection

•• XX--rayray tomographytomography


OutlineOutline

•• IntroductionIntroduction

•• Experimental Experimental setupsetup forfor spatiallyspatially resolvedresolved measurementsmeasurements

•• ExemplaryExemplary resultsresults of of spatiallyspatially resolvedresolved measurementsmeasurements::

•• MSC MSC cellcell

•• ASC ASC cellcell withwith high high fuelfuel utilizationutilization

•• ASC ASC cellcell withwith reformatereformate as as fuelfuel gasgas

•• RamanRaman spectroscopyspectroscopy

•• ConclusionConclusion


MotivationMotivation

Problems in planar cell technology: Problems in planar cell technology: •• Strong local variation of gas Strong local variation of gas

composition, temperature, andcomposition, temperature, andcurrent densitycurrent density

•• Distribution of electrical and Distribution of electrical and chemical potential dependent onchemical potential dependent onlocal concentrationslocal concentrations

This may lead to:This may lead to:•• Reduced efficiencyReduced efficiency•• Thermo mechanical stressThermo mechanical stress•• Degradation of electrodesDegradation of electrodes

Effects are difficult to understand due to the strong interdepenEffects are difficult to understand due to the strong interdependence of dence of gas composition, electrochemical performance and temperaturegas composition, electrochemical performance and temperature


MeasurementMeasurement Setup Setup forfor SegmentedSegmented CellsCells

•• 16 16 galvanicallygalvanically isolated segmentsisolated segments•• Local and global iLocal and global i--V characteristicsV characteristics•• Local and global impedance Local and global impedance

measurementsmeasurements

•• Local temperature measurementsLocal temperature measurements•• Local fuel concentrationsLocal fuel concentrations•• Flexible design: substrateFlexible design: substrate--, anode, anode--, ,

and electrolyteand electrolyte--supported cellssupported cells•• CoCo-- and counterand counter--flowflow


SegmentedSegmented CellsCells

•• Anode supported cells: Anode supported cells: Segmented cathode Segmented cathode ((H.C.Starck/InDECH.C.Starck/InDEC))

•• Electrolyte supported cells: Electrolyte supported cells: Segmented cathode and Segmented cathode and anodeanode


Test Test RigRig


Power Power DensityDensity and and TemperatureTemperature Distribution of a Distribution of a Plasma Plasma SprayedSprayed CellCell

FuelAir•• P und T distribution at standard gas flow P und T distribution at standard gas flow

rates: 12,5/12,5//80 smlpm/cmrates: 12,5/12,5//80 smlpm/cm²²HH22/N/N22//Air, 800//Air, 800°°C, 0.7 V, C, 0.7 V,

13 14 15 16

9 10 11 12

5 6 7 8

1 2 3 4

Air Flow Fuel Flow


OCV OCV VoltageVoltage MeasurementMeasurement forfor Determination of Determination of HumidityHumidity

•• Voltage distribution at standard flow rates:Voltage distribution at standard flow rates:•• 50% H50% H22, 50% N, 50% N22 + 3% H+ 3% H22O, 0.08 SlpM/cmO, 0.08 SlpM/cm²² airair

13 14 15 16

9 10 11 12

5 6 7 8

1 2 3 4

fuel gas air

22

20 lnHO

OHrevrev pp

pzFRTUU

Nernst Nernst equationequation::

ProducedProduced waterwater::S4: 0.61%, S8: 0.72%, S4: 0.61%, S8: 0.72%, S12: 0.78%, S16: 3.30%S12: 0.78%, S16: 3.30%


Power Power DensityDensity DistribututionDistributution underunder ConditionsConditionsof High of High FuelFuel UtilizationUtilization

Counter-flow

Anode: 33% H2, 1% H2O,

66% N2

Cathode: air

T = 800 °C

Cell voltage: 0.59 V

Fu = 80%

Lit.: Fuel Cells, 10 (3), 411-418 (2010)


AssessmentAssessment of of LocalLocal Performance Performance withwith SegmentedSegmented SOFCsSOFCs

ExperimentExperiment

ModelModelUlocalZlocal

UIZ

UlocalZlocal

UIZ

16segments

Global Global behaviorbehavior

LocalLocalbehaviorbehavior

CellCell cancan bebe locallylocally in in criticalcritical conditionsconditions!!


Alteration of Alteration of thethe Gas Gas CompositionComposition at at 435 mA/cm435 mA/cm²²

0

0,05

0,1

0,15

0,2

0,25

0,3

Segment 9 Segment 10 Segment 11 Segment 12

Gas

konz

entra

tion

/ %

H2 CO CH4 CO2 H2O

Con

cent

ratio

n/ %

H2

10 11 12

CO

CH4

H2O

CO2

9


Alteration of Alteration of thethe Gas Gas CompositionComposition at at 100 mA/cm100 mA/cm²²

0

0,05

0,1

0,15

0,2

0,25

0,3

Segment 9 Segment 10 Segment 11 Segment 12

Gas

konz

entra

tion

/ %

H2 CO CH4 CO2 H2O

KS4X050609-7 in Metallischem Gehäuse; Substrat: Anodensubstrat, aktive Zellfläche:73,78 cm²,A: 542 µm NiO/YSZ, E: 14 µm YSZ + YDC,

K: 28 µm LSCF, Kontaktierung: 30 µm LSP16+Pt3600,Integral, Gasflüsse: 0,552 A/cm² Stromdichteäquivalent (54,9% N2, 16,7% H2,

16,5% CO, 6,6%CH4, 2,2%CO2, 3,2% H20) // 0,08 SlpM/cm² Luft, 800 °C, 100 mA/cm²

Metallic housing, anode substrate, active area 73.78 cm²Anode: 542 µm NiO/YSZ, Electrolyte: 14 µm YSZ + YDC,Cathode: 28 µm LSCFOperation conditions: 0.10 A/cm² - Anode = 5.52(54.9% N2, 16.7% H2, 16.5% CO, 6.6% CH4, 2.2% CO2, 3.2% H2O0.08 Nlpm/cm² Air, 800°C)

Con

cent

ratio

n/ %

9 10 11 12

H2

CO

H2O CO2CH4


Potential Potential forfor OpticalOptical SpectroscopiesSpectroscopies

Raman spectroscopyRaman spectroscopyLaser Doppler Anemometry (LDA)Laser Doppler Anemometry (LDA)Particle Image Particle Image VelocimetryVelocimetry (PIV)(PIV)FastFast--Fourier Infrared (FTIR)Fourier Infrared (FTIR)Coherent AntiCoherent Anti--Stokes Raman Spectroscopy (CARS)Stokes Raman Spectroscopy (CARS)Electronic Speckle Pattern Electronic Speckle Pattern InterferometryInterferometry (ESPI)(ESPI)

Digital CCD camera

Distance microscope(resolution1 µm)

Quarz window

Transparentflow field

Imagingspectrograph

Lenses/filter

Pulsed Nd:YAG laser(532 nm, 10 ns)

Open tube(5 mm)

a) In situ microscopy b) In situ Raman laser diagnostics

15 cm

Heat & radiation shield

SOFC


1D Laser Raman Scattering: Experimental Arrangement1D Laser Raman Scattering: Experimental Arrangement

Simultaneous detection of CH4, O2, N2, CO, H2, CO2, H2O

spectrograph forwavelength separation

fuel cell channellense

achromaticrelay optics

camera

posi

tion

wavelength

laser beam


Raman Spectrum from FlameRaman Spectrum from Flame

wavelength [nm]

Inte

nsity

CO2 O2 N2CO CH4 H2O H2

Raman bands are partly overlapped (cross talk)


Setup Setup forfor 1D1D--Raman Raman SpectroscopySpectroscopy

3 double pulse 3 double pulse Nd:YAGNd:YAG PIV 400 PIV 400 laserlaser systemssystemsλλ = 532 nm= 532 nmRepetition rate: 10 HzRepetition rate: 10 HzSingle pulse: E Single pulse: E ≤≤ 350 mJ / 350 mJ / ~~7 ns7 nsPulse Pulse energyenergy: 6 x 300 mJ : 6 x 300 mJ Pulse Pulse lengthlength: : ~380 ns ~380 ns

(temporal (temporal resolutionresolution))


Transparent Transparent FlowfieldFlowfield forfor SOFCSOFC

Top view

Side view


Experimental Setup Experimental Setup forfor RamanRaman SpectroscopySpectroscopy MeasurementsMeasurements


CellCell HousingHousing withwith Transparent Transparent FlowfieldFlowfield in Hot in Hot FurnaceFurnace


RamanRaman SpectraSpectra of Hof H22 and Hand H22O O ConcentrationsConcentrationsAlongAlong thethe FlowFlow ChannelChannel

HH2 2 + 3% H+ 3% H22O; 0,112 NL/min H2, 1,06 NL/min air, 850 O; 0,112 NL/min H2, 1,06 NL/min air, 850 °°CC

2800 3000 3200 3400 3600 3800 4000 4200 4400 4600-0.2

-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

Signal Fit H2O Fit H2

Sig

nal [

w.E

.]

Raman-Verschiebung [cm-1]


IV IV CharacteristicsCharacteristics of ESC of ESC CellCell


RamanRaman SpectraSpectra of an ESC of an ESC CellCell OperatedOperated at 5 Aat 5 A

H2O H2

35 mm


RamanRaman Signals of HSignals of H22 as a as a FunctionFunction of Distanceof DistanceAlongAlong thethe FlowFlow ChannelChannel

0 5 10 15 20 25 30 350.0

0.2

0.4

0.6

0.8

1.0

1.2

0 A 1 A 3 A 5 A 7 A

rel.

Inte

nsity

[-]

length [mm]


RamanRaman Signals of HSignals of H22O as a O as a FunctionFunction of Distanceof DistanceAlongAlong thethe FlowFlow ChannelChannel

0 5 10 15 20 25 30 350

1

2

3

4

5

6

0 A 1 A 3 A 5 A 7 A

rel.

Inte

nsity

[-]

length [mm]


Setup Setup forfor InIn--SituSitu OpticalOptical MicroscopyMicroscopy


ConclusionConclusion

•• InIn--situsitu diagnosticdiagnostic techniquestechniques allowallow forfor a a largelylargely extendedextended insightinsight intointo fuelfuelcellcell processesprocesses (fundamental (fundamental understandingunderstanding, , optimizationoptimization of of flowflow fieldfield))

•• TheThe potential of potential of spatiallyspatially resolvedresolved diagnosticsdiagnostics was was demonstrateddemonstrated withwith somesomeexemplaryexemplary resultsresults

•• TheThe obtainedobtained datadata cancan bebe usedused forfor modelingmodeling and and simulationsimulation forfor identificationidentification of of criticalcritical operatingoperating conditionsconditions

•• StrongStrong gradientsgradients of gas of gas concentrationsconcentrations and and currentcurrent densitydensity particularlyparticularly at at operationoperation withwith high high fuelfuel utilizationutilization maymay resultresult in in locallylocally criticalcritical operatingoperatingbehaviorbehavior

•• Qualitative Qualitative resultsresults of Laser of Laser RamanRaman SpectroscopySpectroscopy measurementsmeasurements havehave beenbeenshownshown, quantitative , quantitative measurementsmeasurements areare in in progressprogress..

Documents

Anwendung in-situ diagnostischer Methoden für die ...¤chs._BZ_Tag_Leipzig_G._Schiller.pdf · 4. Sächsischer Brennstoffzellentag, Leipzig, 10. November 2011 Alteration of the Gas