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:
Design,FabricationandTest
SiddharthaP.Duttagupta
IndianInstituteofTechnologyBombay
_
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IITBEEMEMSOverview
Research, Education, Training, Collaboration:
Crossinstitution research: 2 microfluidics for electronics
, , ,
transceiver, Multiferroic RF inductor, Polymer accelerometer,
also activities in Suman Mashruwala Lab and Biosciences Dept
MEMS institute elective (EE701), also dept electives in
Mechanical (P Gandhi) and Biosciences (R Srivastava)
(May 2012)
Partners: IITB (Centre Res Nano Tech Science, Earth Sciences,
Mechanical, Physics, Systems & Control*), Mumbai Univ., VJTI,
Univ. Pune, CMET, Nanded Univ., SAMEER, IIT Hyderabad, NPCIL,
, , , ,
BITS(Dubai)*, Cal Univ*, Joint Science Academies SRF Programme*
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GreenEnergyManagementSystems
Integration
and
Optimization
SourceSolarPVSPV
FuelCellFC
Components
SolarPV
Array
DCDC
ACGridDC
AC
Converters
DC
to
DCDCtoAC
Fuel
Cell DCLoadDC
DC DC DC
StorageBattery
UltraCapacitorTidal
Storage
Battery,AC DC
DCsource
Onchip
LoadVariableDC
VariableAC
Power UltraCap
Generation Conversion Distribution
DC DC
Partners:VAgarwal,AGuha,MNGandhi,DRamakrishnan,AAgrawal,SGSingh(IITB),
KPRay
(SAMEER),
SA
Gangal (U
Pune),
GJ
Phatak (CMET
),
TCS,
CGL,
Datar ,
Sasken
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Motivation and Sco e
u purpose supp y rom on onven ona ources
MicroscaleEnergySourceforonchippower
DegradationMonitoringforlowsystemlifetimecost
ReliablePowerGenerationunderNonOptimalConditions
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Background- Fuel Cell
Electrochemical conversion
Device (Hydrogen Cell)
+Fuel (H2)
at Anode
Oxidant (O2)
at CathodeReactants_
Load
Bi Cubic
Fuel Cell
Stack
Other Fuels Hydrocarbons, Alcohols [1]
Other Oxidants Chlorine
Operational temp. < 1000C
ApplicationsFuel Cell vehicle create electricity using H2 fuel and O2 from air [1]
Uninterrupted power supply instant protection from momentary power failure
Emer enc ower s stems and Co eneration for small scale networks
[1] Fuel Cell Handbook, Fundamentals and Survey of Systems,John Wiley Publication, ISBN 0-471-49926-9 , 2003, Vol. 1, pp. ix 23
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Fuel Cell Operation
Ideal (thermodynamic)
Fuel Cell EMF at No Loadcm2
Act ivation Loss
Tafel Equation
tageV 1. ActivationRegion
3. Mass Transport or
Concentration Region
1.0
Density
W
Power Density Curve
0lnA
IV A I
CellVol
2. Ohmic Region0.5
CellPowerm c eg on
.R
V R I
Concentration EThermod namicall
Current Density A/cm2
I V CurvePolarization
Region
mnI
C mV mI e
predicted Fuel cell
Voltage o/p -
theoretically
A system constant
I0 current density where voltage starts to drop initially
R Ohmic resistance by polymer electrolyte membrane
-
Overall dependence between the
the voltage and the current density
,
Im start of non-linear region star t of mass transfer0 A R C
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Methodology I
Size, Power Density
Requirements
Field Test
Design
YES
CompactModelCellmeets
Application
Design
OK?
NO pecs
Fabrication LabTest
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Uniformdistributionof
fuel
and
oxidant
inside
cell
Uniformtemperaturedistributioninsidecell
Electricalcontactsvs.porosity(GDLinterfacewithelectrode)
Properselectionofmaterials(electrode,membrane)
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Ion Flux Map Micro-PEM Fuel Cell
es gn arac er s cs Cell length (L) 200 micron
Channel height 10 micron
Channel width 70 micron
Rib width 90 micron
GDL width 30 micron
orous e ectro e t c ness m cron
Membrane thickness 50 micron
GDL electric conductivity 1000 S/m Inlet H2 mass fraction (anode) 0.743
Inlet H2O mass fraction (cathode) 0.023
Inlet oxygen mass fraction (cathode) 0.228
.
Cathode inlet flow velocity 0.5m/s
Permeability (porous electrode) 2.36 E -12 m2
Membrane conductivity 10 S/m
AssumptionsMembrane is 100% humidified
No hydrogen cross over
9[3] Ramesh P.,S.S Dimble,V Agarwal, S.P Duttagupta ,Performance of miniature fuel cells with segmented contacts attached to the
GDL,International conference on Electric Power and Energy Systems, Sharjah, 2011
Reacting gases are ideal
Water produced is in gaseous state
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Conventional PEM Fuel Cell Components
Proton Exchange Membrane Fuel Cell PEMFC [1]
Fuel Cell Chemistry Anode
Anode Side2H2 => 4H+ + 4e-
Cathode Side Cathode
Conducts electrons freed fromhydrogen molecules so that the free
e- can be used in external circuitry
O2 + 4H+ + 4e- => 2H2O
Net Reaction
2H2 + O2 = 2H2o
Oxidant
O2
Catalyst,
PlatinumProtonExchange
Anode,
FuelH2
Channels etched on anode
disperses the hydrogen gas equally
over the surface of the catalyst
ParticlesMembrane,
ElectrolyteCathode
Conducts electrons back fromConducts only +ve ions and blocks electrons. Hydration Reqd.
Electro lyte (PEM)
ex erna c rcu ry o ca a ys w erethey recombine with O2 and H+
Channels etched on cathode
distribute the ox en to the surface
NAFION is most widely used proton conductor in fuel cells [[22]]
Not easily patterned using photolithography, not easy to integrate
of the catalystBonding with Si is challenging under working Fuel Cell conditions
[1] Fuel Cell Handbook, Fundamentals and Survey of Systems,John Wiley Publication, ISBN 0-471-49926-9 , 2003, Vol. 1, pp. ix 23
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Nano-Porous Si Membrane [2]
A) B)
Prime grade boron doped p type
double side polished Silicon Post-lithography
wafer with 100 mm diameter
and 0.02 ohm - cm resistivity
w n ows or 3 4 c ng
Si Membrane Thickness 100 -meter
C) D)
Each well area - 0.0625 cm2
Reactive Ion Etching with SF6 Plasma
selective removal of Si3N4
Deep Reactive Ion Etching of Siliconthrough wells to create Silicon Membrane
[2] Kaun-Lun Chu et al. , A Nanoporous Silicon Membrane Electrode Assembly for On-Chip Micro Fuel Cell Applications, IEEE, Journ. MEMS Syst., Vol .15, (2006) 671
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NP Si Membrane Formation [2]
Removal of native oxide by immersion of
Silicon Wafer in Buffered Oxide Etch Soln.
Deposition on both s ides of wafer
ICPCVD or LPCVD
AB) II AB) III
Applicat ion of photoresist coating
On Silicon Nitride surface Photolithography
Silicon Substrate Silicon Nitride Insulator Photoresist Photo Mask
[2] Kaun-Lun Chu et al. , A Nanoporous Silicon Membrane Electrode Assembly for On-Chip Micro Fuel Cell Applications, IEEE, Journ. MEMS Syst., Vol .15, (2006) 671
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SEM TOP View of Silicon WellFormed after DRIE of Substrate [2]
Low Magnification - 500 Micro Meters Side View of Well Walls in Silicon
High Magnification - 100 Nano Meters
[2] Kaun-Lun Chu et al. , A Nanoporous Silicon Membrane Electrode Assembly for On-Chip Micro Fuel Cell Applications, IEEE, Journ. MEMS Syst., Vol .15, (2006) 671
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NP Si Membrane Formation [2]Nanoporous Si membrane
E)
-
at wafer back for electrical contact generation.
AZ 4903 photoresist spin coated on Cr-Au
layer to protect from acid etching
- chemical etching.
Cr - Au and Photoresist still existing
G)
r - u ayer an otores st remove yPiranha solution and Chrome etchant
Piranha solution - 1:3 volume ratio of 30 wt. % H2O2 (aq.) : 98 wt.% H2SO4
AZ 4903 Photoresist Cr-Au Layer Porous Si licon Membrane
[2] Kaun-Lun Chu et al. , A Nanoporous Silicon Membrane Electrode Assembly for On-Chip Micro Fuel Cell Applications, IEEE, Journ. MEMS Syst., Vol .15, (2006) 671
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Setup for Nano Porous
Electrolyte is constantly stirred by magnetic rotor, constant current of 40 mA/cm2
PlatinumSilicon
Cathode
Electrolyte-
Nanopores are
formed by
Ethanol and
49wt.% HF 1:1
etching of Silicon
Membrane
[2] Kaun-Lun Chu et al. , A Nanoporous Silicon Membrane Electrode Assembly for On-Chip Micro Fuel Cell Applications, IEEE, Journ. MEMS Syst., Vol .15, (2006) 671
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Porous Silicon Membrane
[2] Kaun-Lun Chu et al. , A Nanoporous Silicon Membrane Electrode Assembly for On-Chip Micro Fuel Cell Applications, IEEE, Journ. MEMS Syst., Vol .15, (2006) 671
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Nano Porous (DFAFC)
This TiO la er makes anode
u l
5 M Formic Acid and
0.5 M H2SO4 is Fuel
catalyst layer surface hydrophilic.
Hence, fuel gets attracted tocatalyst to ease anode reaction
Reactions
Load Current
Silicon Bulk
Voltage
Silicon Nitride Insulator Gold Contact LayerPorous Silicon Membrane
Platinum Cathode Palladium AnodeInsulation (TiO2 or SiO2)
Prevents short circuit
between anode and cathode
[2] Kaun-Lun Chu et al. , A Nanoporous Silicon Membrane Electrode Assembly for On-Chip Micro Fuel Cell Applications, IEEE, Journ. MEMS Syst., Vol .15, (2006) 671
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Mi r F l ll T P r m r
Dynamic
Impedance
Spectroscopy
Ion uxmapping
Transient
impact,
fuel/oxidant
contaminants
Transientimpact,downstreampowerconverternoise
Degradation(fueldepletion,hotspotformation,catalystpoison)
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Fuel Cell Test Setup
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References PEMFC Design & Fabrication
[1] Fuel Cell Handbook , Fundamentals and Survey of Systems, John Wiley
, - - - , , . , .
[2] Kaun-Lun Chu et al. , A Nanoporous Silicon Membrane Electrode
Assembly for On-Chip Micro Fuel Cell Applications, IEEE, Journal of
Michroelectro-mechanical Systems, Vol.15, No.- 3, June 2006, pp. 671 -677
[3] Ramesh P., S.S Dimble, V. Agarwal, S.P Duttagupta, Performance ,
International conference on Electric Power and Energy Systems,
Sharjah, 2011
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Methodology-II
MEMSSensorNetworkforReliableOperation
MarkettrendinFCresearchistoreducecomponentcost
Researchcanreducesystemcostinthelongrunbyreverting
de radationinFCincreasesh brid sourceli etime
WSNbasedpredictivecontrolhelpstostabilizeFCpoweroutput
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FuelCellPerformanceParameters
Studyofoutputpowerdropbecauseof
Degradationof
electrode
and
ion
mass
transport
through
membrane
2
poisonsthenanoPtcrystalsofelectrodeirreversibledamage
CO contaminant
anode
reduces
O of
fuel
reversible
dama e
Impactofpowerconvertersonelectrodeelectrochemicalsurfacearea
LowfrequencyreverseripplefromDCACconverters
High
switching
frequency
and
load
fluctuation
of
DC
DC
converters
Localizedvariationinhumidityandtemperature(hotspots)
Impactsnearelectrodemembranemorphology(ionflow)
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Field Deployed Air PEMFC-Reliable Operation
air in
range sensing through
backscattering
air fuel cell
protecting chamberlaser
diodeCO sensor grid- proximity plume
tracking and
nozz e ap
control
air out
air
orecas ng
cell
CO sensor
compressed
electricheater
coil
vaporwater
2 s orage
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CO Estimation in Dynamic Smoke Plume
Assumption: No air velocity network of 8 CO sensors placed elliptically
vertical
profilehorizontalprofile
mean
CO Gaussian dispersion profile
- to be estimated
Localization of CO dispersion profile
- estimated using ML estimation
CO propagation constant determined experimentally 2.65
CO2 propagation constant 2.3 25 / 30
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Optimization of Proton Transport in Membrane
PerFluoroSulfonic polymer (NAFION) membrane in
NAFION in hydrophilic domain responsible for
proton transport
Membrane fully hydrated to maintain continuous
ionconductivity through hopping mechanism
reducing ion conductivity, lower fuel cell power output
Optimizationofmembranehumidityformaximum
ionconductivity
is
to
be
studied
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Multi-parameter FC Degradation
Fuel Cell
Power Density
water vapor mass
fraction at cathode CO2 mass fraction
at cathode
dynamicmembrane
impedance
dynamic change inelectrode impedance
for change in CO
densit at cathode air
time (minutes)
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References Fuel Cell Optimization1) S.Mitra,K.Tuckley,andS.P.Duttagupta,2DLocalizationandthreatestimationofnoxiousgassource
originatingfromburiedlandfills,ProceedingsofInternationalConference,USCUDAR2011,Prague,Czech
Republic,Sep.2011,pp.148 154.
2) S.Mitra,S.P.Duttagupta,K.Tuckley,andS.Ekram,Wirelesssensornetworkbasedlocalizationandthreat
estimationofhazardouslandfillgassource, InPressProceedingsofIEEEInternationalConference,ICIT
2012,
Athens,
Greece,
March
2012.3) S.Mitra,S.P.Duttagupta,K.Tuckley,andS.Ekram,3Dadhocsensornetworksbasedlocalizationandrisk
assessmentofburiedlandfillgassource,NAUN/WSEASInternationalJournalofCircuits,Systemsand
, . , , , . .
4) S.Mitra,Ramesh P.,M.Bhattacharyya,andS.P.Duttagupta,Multimodesensingtechniqueforcarbon
monoxideplumetrackingandforecastingforreliablefielddeployedairbreathingPEMfuelcelloperation,
InPressProceedingsofISPTS1,Pune,India,March2012.
5) M.W.Elis,M.R.VSpakovsky,D.J.Nelson,Fuelcellsystems:efficient,flexibleenergyconversionforthe21st
century,ProceedingsofIEEE,InvitedPaper,Vol.89,No.12,December2001,pp.18081818.
6) W.P.Teagan,J.Bentley,andB.Barnett,Costreductionsoffuelcellsfortransportapplications:fuelprocessing
options,JournalofPowerSources,Vol.71,No.12,1998,pp.8085.
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DrivesConference,
IEMDC
2001,
Cambridge,
America,
2001,
pp.
604611.
8) C.Changsong,D.Shanxu,Y.Jinjun,Researchofenergymanagementsystemofdistributedgenerationbased
onpowerforecasting,inProceedingofInternationalconferenceonElectricalMachinesandSystems,ICEMS
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. . c ae, . . u p, ac scattera sorpt ongas mag ng:anewtec n que orgasv sua zat on, ourna o
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References- II10) I.JSimpson,BorealforestfireemissionsinfreshCanadiansmokeplumes:C1C10volatileorganiccompounds
(VOCs),CO2,CO,NO2,NO,HCN,andCH3CN,JournalofAtmos.Chem.Phys.,Vol.11,2011,pp.64456463.
11) T.Zhou,H.Liu,A3DmodelforPEMfuelcellsoperatedonreformate,JournalofPowerSources,Vol.138,
2004,pp.101110.
12) A.Rodrigues,J.C.Amphlett,R.F.Mann,B.A.Peppley,P.R.Roberge,Carbonmonoxidepoisoningofproton
exchange
membrane
fuel
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Proceedings
of
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Intersociety,
IEEE
Energy
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, , . , , . .
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30 / 30
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Dr. M. Bhattacharyya, Dr. A.V. Kshirsagar,
Dr. S. Mehta (Post-doctoral Research Scholar)
B Patnaik, SS Dimble, Ramesh P, A Das,
U Chatterjee, R Rashmi, S Mitra, K Ghosh,, , , ,
B Somaiah, S Roy (Ph.D. Research Scholar)
S Shyamsundar, J Mohod, H Manaswala, N Patel,P Chafekar, D Soni (M.Tech. Research Scholar)