FSECsProcedures ForPerformingPEMSingleCellTesting

TestprotocolforCellPerformanceTests WorkPerformedUnder DOEContract#DEFC3606GO16028 April8,2009

EXECUTIVESUMMARY
This document defines, in detail, a test protocol for performing proton exchange membrane (PEM) single cell testing. Development of this test protocol is a part of the requirements of FSECs Task 5, Characterize MEA Performance, under DOE Contract #DEFC3606GO16028. ThistestprotocolhasbeenevaluatedandisusedatFSECforsinglecelltesting. Under this contract, FSEC will perform singlecell tests to assess the relative merits of the candidate membranes that are submitted by the Task 1 team members. These tests will be conducted at operating conditions that are of interest to the DOE and, where appropriate, will be run using identical procedures on all testedcells. Task 1 team members that arecontinuing beyond the Go No Go milestone are requested to review this document and identify conditions that are of concern. FSEC will iterate with these Task 1 team members to resolve theseconcerns Researchers following the test protocol will be able to reproduce results that have been obtainedbyFSEC.

Contents
1.OverviewofFSECsProceduresforPerformingPEMSingleCellTesting ................................... 6 1.1IntroductionToTheTestProtocolforPEMCellScreeningTest.......................................... 6 1.2ComponentstobeDelivered ............................................................................................... 6 1.3DetailsoftheCell ................................................................................................................. 6 1.4Membrane,CCM,andGDLThicknessMeasurement .......................................................... 8 1.5CellAssembly. ...................................................................................................................... 9 1.6PreTestIntegrityTest........................................................................................................ 10 1.7TestsPerformedonEachCell ............................................................................................ 10 1.7.1LinearSweepVoltammetry,CyclicVoltammetry,AndCellConditioning ................. 10 1.7.2PerformanceVerificationTest ................................................................................... 13 1.7.3PosttestIntegrityTest ............................................................................................... 15 1.7.4PosttestAnalysis ....................................................................................................... 15 1.7.5CellDataReport ......................................................................................................... 16 1.8FuelCellHydrogenSafetyPlan .......................................................................................... 16 2.DaybyDayPEMMEATestSequence ....................................................................................... 19 2.1AssembletheCell............................................................................................................... 19 2.2Day1................................................................................................................................... 19 2.3Day2................................................................................................................................... 20 2.4Day3................................................................................................................................... 20 2.5Day4(at1.5atm)............................................................................................................... 20 2.6Days5,6,and7(at1.5atm) .............................................................................................. 21 2.7Day8(at1.5atm)............................................................................................................... 21 2.8Day9................................................................................................................................... 22 AppendixA:GurleyNumberProcedure ....................................................................................... 23 A1ReferenceMaterials............................................................................................................ 23 A2Introduction ........................................................................................................................ 23 A3MaterialsandEquipment ................................................................................................... 24 A3.1Materials ..................................................................................................................... 24 A3.2Equipment................................................................................................................... 24 A3.3QualityControl ............................................................................................................ 25 A4MainGasketPreparation.................................................................................................... 25 A5PreparationofSubgaskets .................................................................................................. 25 A6PreparationofGasDiffusionLayerSamples ...................................................................... 26 A7CleaningofFuelCellComponents ...................................................................................... 26 A8AssemblyProcedure ........................................................................................................... 26 A9LeakingCheckProcedure.................................................................................................... 29 A10DataProcess...................................................................................................................... 29 A10.1DataSheetGurleyNumberCalculations .................................................................. 30 A11Acceptance........................................................................................................................ 30

AppendixB:PEMFuelCellUnitCellAssemblyProcedure ........................................................... 31 B1ReferenceMaterials............................................................................................................ 31 B2BillofMaterials ................................................................................................................... 31 B2.1Materials ..................................................................................................................... 31 B2.2Equipment ................................................................................................................... 31 B3Objectives............................................................................................................................ 32 B4GeneralInstructions............................................................................................................ 32 B5PreparationforCellAssembly.......................................................................................... 32 B6AssemblingtheCellFuelCellTechnology(FCT)HardwareSet. ...................................... 32 AppendixCProcedureforLeakTestingaSingleCellAfterAssembly .......................................... 34 C1ExternalLeakTest ............................................................................................................... 34 C1.1Procedure .................................................................................................................... 34 C2InternalLeakTest................................................................................................................ 35 C2.1ProcedureforInternalLeakTest................................................................................. 35 AppendixDPEMFCUnitCellTest ................................................................................................. 37 D1ReferenceMaterials ........................................................................................................... 37 D2BillofMaterials................................................................................................................... 37 D2.1Materials ..................................................................................................................... 37 D2.2Equipment................................................................................................................... 37 D3Objectives ........................................................................................................................... 37 D4GeneralInstructions ........................................................................................................... 38 D4.1FuelCellSystemConfiguration ................................................................................... 38 D4.2ExplanationoftheTestStation................................................................................... 38 D4.3HardwareSpecifications ............................................................................................. 39 D4.4DataFilingNamingConventions................................................................................. 39 D4.6NomenclatureofTestConditionTemperatures......................................................... 39 D4.7HandlingofGasTanks................................................................................................. 40 D5Day1Test ........................................................................................................................... 40 D5.1SetupCellHardwareontheTestStation.................................................................... 40 D5.2PreparationofCellTestontheTestStation............................................................... 40 D5.3OperationofComputertoStartUpCell ..................................................................... 40 D5.4CrossoverandCyclicVoltammetryTestsat25/25/25 ............................................... 42 D5.5HumidificationoftheMembrane ............................................................................... 44 D5.6OperationoftheCellinBreakInMode...................................................................... 45 D5.7CoolDownProcedure................................................................................................. 45 D6Day2Test ........................................................................................................................... 46 D6.1CrossoverandCyclicVoltammetryTestsat25/25/25 ............................................... 46 D6.2PolarizationCurveMeasurementat80/80/73(Air/O2Alternating) .......................... 46 D6.3CrossoverandCyclicVoltammetryTestsat80/80/73 ............................................... 48 D6.4Holdat400mA/cm2Overnight .................................................................................. 49 D7Day3Test ........................................................................................................................... 49 D7.1PerformanceMeasurementat80/80/73(Air/O2Alternating,1.5atm)..................... 49 3

D7.2PerformanceMeasurementat100/90/90(Air,1.5atm) ........................................... 49 D7.3HoldOvernightat400mA/cm2 .................................................................................. 49 D8Day4Test ........................................................................................................................... 49 D8.1PerformanceMeasurementat100/90/90(O2/AirAlternating,1.5atm)................... 49 D8.2CrossoverandCyclicVoltammetryTestsat120/90/90 ............................................. 49 D8.3PerformanceMeasurementat120/90/90(Air/O2Alternating,1.5atm) .................. 49 D8.4HoldOvernightat400mA/cm2 .................................................................................. 49 D9Day5Test ........................................................................................................................... 49 D9.1CrossoverandCyclicVoltammetryTestsat100/90/90 ............................................. 49 D9.2PerformanceMeasurementat100/90/90(Air/O2Alternating,1.5atm)................... 49 D9.3StabilityTest(Days5,6,and7).................................................................................... 50 D10Day8Test....................................................................................................................... 50 D10.1CrossoverandCyclicVoltammetryTestsat100/90/90 ........................................... 50 D10.2PerformanceTestat100/90/90(Air/O2Alternating,1.5atm)................................. 50 D10.3CoolDown................................................................................................................. 50 D11Day9Test ......................................................................................................................... 51 D11.1CrossoverandCyclicVoltammetryTestsat25/25/25 ............................................. 51 D11.2LeakTest ................................................................................................................... 51 D11.3ResistanceTest ......................................................................................................... 51 D11.4ShutDownandRemovefromTestStand................................................................. 51 D11.5PostTestAnalysis ..................................................................................................... 51 D15Troubleshooting:HardwareProblems ............................................................................. 51 D16ChartSummarizingDaytoDayActivities......................................................................... 53 AppendixEFluorideConcentrationMeasurementsTestProcedure ........................................... 54 E1CheckingElectrodeOperation.......................................................................................... 54 E1.1SuggestedEquipment.................................................................................................. 54 E1.2Procedure .................................................................................................................... 54 E2FluorideConcentrationMeasurements.............................................................................. 54 E2.1DirectCalibration......................................................................................................... 54 E2.2CalibrationCurve......................................................................................................... 55 E2.3MeasuringSampleswithConcentrationsGreaterthan1ppm .................................. 56 E2.4MeasuringSampleswithConcentrationsLessthan1ppm ........................................ 57 E3ElectrodeCleaningandStorage .......................................................................................... 58 E3.1ElectrodeCleaningI..................................................................................................... 58 E3.2ElectrodeCleaningII ................................................................................................. 58 E3.3ElectrodeStorageI ...................................................................................................... 58 E3.4ElectrodeStorageII ..................................................................................................... 58 AppendixFSafetyPlan ................................................................................................................. 59 F1ScopeofWork ..................................................................................................................... 60 F2IdentificationofSafetyVulnerabilities................................................................................ 61 F3RiskMitigationPlan............................................................................................................. 62 F3.1OrganicVaporExposure .............................................................................................. 62 4

F3.2CatalystHandling......................................................................................................... 62 F3.3HydrogenLeaks ........................................................................................................... 62 F3.4StandardOperatingProcedures.................................................................................. 63 F3.5PreviousExperienceWithHydrogen........................................................................... 64 F3.6SafetyPerformanceMeasurementandManagementofChangeReviews................ 64 F3.7EmployeeTraining ....................................................................................................... 64 F3.8EquipmentIntegrity..................................................................................................... 65 F3.9MaintenanceofSafetyDocumentation ...................................................................... 65 F4CommunicationPlan ........................................................................................................... 66 F4.1EmergencyResponsePlan........................................................................................... 66 F4.2IncidentReportingandLessonsLearned .................................................................... 66 F5SampleHandlingandTransport.......................................................................................... 67 F6References........................................................................................................................... 67 AppendixGFacilitiesandInstrumentation .................................................................................. 68 G1MembraneFabrication........................................ 68 G2MembraneElectrodeAssemblyFabrication ................................................... 68 G3ElectrochemicalCharacterization.................................................................... 68 G4MaterialsCharacterization .............................................................................. 68

1.1

Introduction to the Test Protocol for PEM Cell Tests

PEM singlecell testing for performance, durability and accelerated stress is conducted on a Fee for Service basis at a number of government as well as commercial laboratories. These services are available for the individual Task 1 team members with customerspecific protocols to meet their individual testing requirements. This document defines the PEM test procedures thatwillbeusedatFSECforconductingthescreeningteststhatarerequiredunderFSECsTask 5 Characterize performance of MEA of the DOE program DEPS366095020. The purpose of this testing is to assess the relative merits of the candidate membranes that are submitted by the Task 1 team members. These tests will be conducted at operating conditions that are of interesttotheDOE.Thegoalistoshowthecurrentcapabilityofthesemembranesratherthan simply to provide a Go/No Go rating against the Program Requirements. A further objective of this protocol is to clearly define the operating conditions to which the individual membranes will be subjected. This allows the details to be understood by the DOE; and, with this information, each team member can set limits of processing and operation based on the capabilities of their individual membranes. To the extent that all membranes are tested to the same protocol, the results provide a fair and accurate evaluation of the performance capabilities of each configuration. It is understood that the fabrication history for the membranes, as well as the characteristics of the interfacing cell components, the cell assembly procedures, and the cell operating history can have a significant impact on the cell performance. The impact of these histories is normalized in this protocol by using identical proceduresonallthecells. FSEC has followed this protocol on numerous cells and this test protocol produced repeatable results.

1.2ComponentstobeDelivered
Task 1 team members deliver sample membranes developed under this DOE program. A sufficientnumberofpiecessized12cmby12cm(4inchesby4inches)willbesubmittedto enabletheteststobecompleted.Thesemembranes,alongwiththefabricatorsconstraintsfor further processing, are represented to the DOE as the Task 1 team members best effort of performanceunderthisprogram.

1.3DetailsoftheCell
The test CCM is fabricated using membranes provided by the Task 1 team members. Prior to fabricationoftheCCM,membranesampleswillbeexaminedforuniformity(nobubbles,debris, fogginess, stretches, cracks, and thickness variations), gas crossover, and flexibility to ensure themembranesaresuitablefortesting.Samplepieceswillbecutfromthemembraneandsent to Bekktech, LLC and Scribner Associates for conductivity testing and to Material Scienceat the University of Central Florida for SEM/EDAX characterization. A diagram depicting how each supplied membrane will be used is shown in Figure 1.1. The CCM is fabricated by spraying a catalyst ink(ionomer, Pt/C, methanol mixture)on a membrane to achieve a nominal loading of 0.4 mg Pt/cm2 of TEC10E50E Pt 50 wt% catalyst supported on a high surface area carbon (SA = 800 m2/g) supplied by TKK. FSEC has achieved baseline performance by mixing the catalyst 6

with 32% 1100 EW Nafion using methanol and then spraying using a nitrogendriven spray gun, which is carried by a numericallycontrolled X/Z plotter. The CCM is then dried at 100 oC, heattreatedat136oCandcompressivelypressed5.1atm(75psi)compressivepressureforfive minutes,andthenprotonatedusinga0.5Msulfuricacidsolutionandwashedindistilledwater. A second CCM and two coupons are made at the same time, with identical processing. This second CCM and one coupon will be returned to the membrane fabricator untested for their evaluation and analysis. FSEC will communicate with the team members about the fabrication constraints for each membrane and an attempt will be made to accommodate the membrane requirements and the supplier wishes, while still achieving comparable results. Depending on the membrane composition and the supplier requirements, it may be necessary to adjust the typeofionomer,ionomerloading,dryingtemperature,hotpresstemperatures,andsolvent.

4 cm

8 cm

Coupon
4 cm

CCM
8 cm

Extra

12 cm

5 cm

5 cm

Conductivity #1
4 cm

Conductivity #2
4 cm

12cm
Figure1.1.Depictionofmembranesamplepieces.CCMandcouponpieceswillbesprayedatthesame time.ConductivitypieceswillbesenttoScribnerandAssociatesandBekktechfortesting.

The singlecell hardware (25 cm2) used for this program was manufactured by Fuel Cells Technologies Incorporated (FCT) www.fuelcellstechnologies.com. It consists of a pair of graphitebipolarplateswithaserpentineflowpattern,goldcoatedcurrentcollectorplates,and aluminum pressure plates. The design of the anode bipolar plate flow field has been rotated 90 to give a cross flow pattern and the dimensions of the serpentine flow field for both anode and cathode have been modified (width and depth) to decrease pressure drop. All other aspectsofthishardwareareasoriginallydesignedbyFCT.

 Figure1.2.Bipolarplates(anode,leftandcathode,right)showingsingleserpentineflowfield.

All the MEAs for these cells use type 10BB gasdiffusion layers purchased from SGL Carbon (Sigracet) Each of these gasdiffusion layers were tested for throughplane permeability prior to use, following the procedure in Appendix A. The minimum acceptable permeability for the cathode GDL is given by a Gurley Number of 0.024 L/min/cm H2O/cm2. The anode GDL permeability is allowed to be much lower. The cell seals are made of a stackup of Teflon gaskets with the thickness of the gaskets thinner than the cell assembly giving a pinch of 230 to250m (910mils).

1.4Membrane,CCM,andGDLThicknessMeasurement
The thickness of the membrane, CCM, and GDLs are measured using a Mitutoyo Gauge (Figure 1.3).Componentthicknessesaredefinedusingaverageofatleastninereadingsevaluatedover the entire component at locations shown on the template in Figure 1.4. The membrane, CCM, or GDL is sandwiched between thin sheets of Teflon of known thickness when making the measurements. The template is used to maintain the consistency of the location of successive measurements. The Teflon sheets aremeasured firstandthen the membrane, CCM, or GDL is insertedbetweenthemandasecondsetofreadingsistaken.Subtractingthefirstreadingfrom thesecondprovidesthecomponentthickness.

Figure1.3.MitutoyoGaugeformeasuringthicknessofmembranes,CCMs,MEAs,andGDLs

X X X

X X X

X MeasureeachMembranein9places Taketheaverage X X

Figure1.4.Templateformeasuringthicknessofmembrane,CCM,GDL,andMEA

1.5CellAssembly
Figure 1.5 shows an expanded view of a complete PEM fuel cell hardware. The design of the hardwareisfor25cm2cells.Forthisprogram,cellsareassembledbyhandusingbipolarplates, load plates, and end plates purchased from FCT. Prior to assembly, GDLs are tested for permeability, and cut to the required size. Teflon sheets are also die cut to size, and the membraneisspraycoatedwithamixtureofTKKplatinumoncarboncatalysttoformtheCCM. CCMshave0.4mg/cm2catalystoneachelectrodeforthescreeningtests;howevertheycanbe fabricated with catalyst loadings down to 0.05 mg/cm2 by the same processing equipment. After all components have been prepared, cleaned and documented, cells are assembled as defined in the Assembly Procedure included as Appendix B. Cell pinch, which establishes the compressive load on the active area of the MEA is controlled by selecting Teflon sealing gaskets that are thinner than the sum of the component thicknesses in the active area of the cell. This pinch is a critical parameter for cell assembly and is controlled by selecting Teflon gasketsofappropriatethicknessasshowninFigure1.6.

1 2 3 4 5 6 5 4 3 2 1 7

1. 2. 3. 4. 5. 6. 7.

EndPlate Goldcoatedcopperplate BipolarPlate TeflonGasket GasDiffusionLayer MEA M6Bolt

Figure1.5.ExpandedviewofPEMfuelcellhardware

GDL GDLTh Thi ickness

15.65 15.85 398 402 15.6 396 15.65 15.95 398 15.75 405 400 15.75 398 400 15.75 15.65 400 15.95 398 15.65 395 15.55 Anode 405 15.95 406 16 400 16.15 405 15.85 409 16.1 402 404 15.9

CCM CCMTh Thi ickness

2.2 56 2.25 57 2.45 62 62 2.45 70 2.75 74 2.9 70 2.75

Cathode
2.45 62 64 2.5

Pi Pin nch
9.4 239 245 9.65 246 9.7 9.35 237 10 254 9.8 249 241 9.5 254 10.4 254 10

All numbers are in m.

Thegasketswereeach310 m Measureeachcomponentin9places Buildcellwith229254mpinch Pinch=TGDL(Anode) +TGDL(Cathode) +TCCM TGaskets

Figure1.6.Schematicshowingsamplecalculationofpinchbymeasuringthicknessesofeach componentusingthetemplate.

1.6PreTestIntegrityTest
After the cell is built and before it is delivered to the test stand, it is externally leaktested, internally leaktested, and electrically isolationtested, each according to the procedures in AppendicesCandD.Thesetestsaretoensurethatthecellintegrityissufficienttowarrantthe test effort and to establish a pretest baseline database. After the cell is mounted in the test stand, the external leaktest of the cell and the stand, and the resistance tests of the cell and

10

the stand are repeated to validate test readiness. Allowable limits for these tests have been established by a combination of FSECs cumulative test experience and an impact analysis of the worstcase level of leakage and cell resistance on cell performance. These levels were also verifiedbythecurrentFSECdatabase.

1.7TestsPerformedonEachCell
1.7.1 Linear Sweep Voltammetry, Cyclic Voltammetry (CV), and Cell Conditioning Prior to performance evaluation, electrochemical active area (ECA) and H2 crossover (CO) tests are performed on the cell at ambient pressure at room temperature and 100% RH, 80 oC and ~100%RH, 100 oC and 69%RH, and 120 oC and 35% RH. The cathode is the working electrode and the anode, using hydrogen, is the counter as well as the reference electrode. Flows of 0.4 L/min of hydrogen and nitrogen are introduced to the anode and cathode side of the cell, respectively. The CV is conducted at a scan rate of 30 mV/s between zero and 0.8 V to determine the ECA. Hydrogen crossover is measured by the limiting current density method with H2 flowing on the anode and nitrogen on the cathode. The cell potential is scanned potentiodynamically at 4 mV/s from zero to 0.8 V. A PAR 263A potentiostat and CorrWare software is used to control the potential. The crossover test shows both the level of gas diffusion through the membrane and any electrical short. The level of diffusion is given by the flat portion of the curve and the level of short is calculated from the sloping linear relationship between the applied voltage and the measured current, specifically the measured current between 0.3 V and 0.8 V. Shorts must be less than the equivalent of 10 mA to be allowable, and to clarify the CV data, the linear slopes resulting from these electrical shorts are removed from the data. Figure 1.7 shows sample CO data and Figure 1.8 shows sample ECA data as a function of cell temperature. In the CV data, the hydrogen desorption peaks can easily be observed at room temperature. CV and CO tests were repeated before each test condition to providedatainsupportofthecellanalysis.
0.015

Crossover
0.010

0.005

Indicativeofashort

i / mA cm

-2

0.000 0.0 -0.005 0.2 0.4 0.6 0.8 1.0

25/25/25 0.28 mA/cm2 (pretest) 80/80/73 0.76 mA/cm2 100/90/90 0.73 mA/cm2

-0.010

120/90/90 1.98 mA/cm2 25/25/25 196 Ohm cm2 (post-test)

-0.015

E/V

Figure 1.7. CO data at different cell temperatures. Linear sweep voltammogram of FSEC1; scan rate = 2 mV/s, 0.4 L/min (H2/N2), Tcell = 25, 80, 100, 120 oC,working electrode = cathode, counter/reference = anode.

11

0.01

ECA
0.005 0 0 -0.005 -0.01 -0.015 -0.02 0.2 0.4 0.6 0.8 1

-2 i / mA cm

25/25/25 39.3 m2/g 80/80/73 35.6 m2/g 100/90/90 22.3 m2/g

E/V

Figure 1.8. ECA data as a function of cell temperature. Cyclic Voltammogram of FSEC1; scan rate = 30 mV/s,0.4L/min(H2/N2),Tcell=25,80,100oC,workingelectrode=cathode,counter/reference=anode.

Analysis of the cyclic voltammogram provides a measure of the electrochemical surface area (ECA) of the cathode. Periodically repeating this test during the program provides a history of the changes in cathode ECA for sample MEAs as a function of a fixed test history. Analysis of thesetestresultsshowscomparativemeritsofthesubmittedmembranes. It is recognized that the initial testing of CO/CV prior to conditioning the CCM does not represent the full potential of the cell, but these tests provide important data about the initial conditionofthecell.Inaddition,thisdataisrequiredasinputfortheanalysisofthecellduring operation. After the CO/CV test, the cell is heated to 80 oC and the saturators are heated to 80oC for the anode and 73 oC for the cathode, and the cell is conditioned for operation by adding water to the electrolyte. This is a twostep procedure, where water is first added as a vapor from saturated gases (hydrogen on the anode and nitrogen on the cathode), and second by operation of the cell at a fixed voltage of 0.55 V and run on hydrogen/air. Each step is for threehours,which,forNafion,hasproventobesufficienttowetuptheelectrolyte. After the electrolyte has been wetup, a series of performance curves are run at ambient pressure and high stoichiometry. These tests are run at near 100% RH with the cell at 80oC. The air dew point is a few degrees lower than the cell temperature to avoid flooding the cathode. Performance sweeps are taken on H2/Air, H2/O2, and H2/Air out to ILim. or IMax. The limiting current, ILim, is the current when the cell voltage becomes 0.3 V. This value is used rather that 0Vtoavoid damagetothecell.Themaximumcurrent,IMax,isbased ontheteststandreactant 12

flow capability at 2000 mA/cm2. The repeat of the H2/Air sweeps allows performance between the two tests to be compared to show that the cell has reached a stable starting performance point,andtoindicatethatthedifferencesbetweentheairandtheoxygenperformanceisbeing measured accurately. Test points are held for five minutesduring this testing as a compromise betweenfullystabledataandareasonableamountoftotaltesttime. The cell is then held at these same conditions (80 oC, 80 oC, 73 oC) while the initial test data is reviewed and the cell integrity is judged to be sufficient to proceed with the remainder of the testing.Ifthecellperformanceisnotadequate,itiscooledtoroomtemperature,theCO/CVis repeatedandfurtherdataanalysisisconductedtodeterminethenextsteps. 1.7.2 Performance Verification Test The purpose of the Performance Verification Test is to provide data on cells operating at a series of conditions that are at the DOE goals or that represent significant progress toward those goals and show the relative merits of each of the candidate membranes at those conditions. Having conditioned the cell and verified its integrity, the Performance Verification Testisstartedwithoutshuttingdown.Thecellispressurizedto1.5atmosphereswhileholding the cell temperature and the anode and cathode saturator temperatures at 80 oC, 80 oC, 73oC respectively; and a series of H2/Air, H2/O2, H2/Air performance sweeps are taken at high stoichiometry (above 3 to minimize the effects of reactant utilization). Following these tests, thecellandsaturatorsareheatedto100oC,90oC,90oC,whichchangestheinletRHatthecell to 69%. The three performance sweeps are taken and the temperatures are increased again to 120 oC, 90 oC, 90 oC to further reduce the relative humidity to 35%. In all cases, the cell is returned to 100 oC, 90 oC, 90 oC and held at 400 mA/cm2 overnight to evaluate the stability between the different sets of lower relative humidity tests. Cell temperatures are held at 100oC,90oC,90oCinpreparationforthestabilitytest. 1.7.2.1 Polarization Curve Figure 1.9 shows typical performance data, which shows three characteristic regions. The first (low current density region) is dominated by activation overpotential losses, the second (mid currentdensity)isdominatedbyresistancelosses,andthethird(highcurrentdensityregion)is dominated by mass transport losses. Analysis of these curves, and the changes to the various regionsofthecurves,asthetestingprogresses,provideskeyinsightsintotheperformanceand stabilityofthemembraneaswellasthecatalystlayerandthecatalystmembraneinterface. Fuel Utilization and air Utilization have significant impacts on the shape of these curves. Although utilizations used are higher than the goal values, this data is valuable in comparing performance with lower fuel and air flows. The highest obtainable current density is ILim, which isanimportantinputtotheanalysisoftheinternalresistanceofthecathode.

13

FSEC1 CCM @ 120o C _1.5atm Catalyst: TKK 45.5 Pt% 0.4mgPt/cm 2

1.0 0.9 0.8 0.7 Cell Voltage (V) 0.6 0.5 0.4 0.3 0.2 0.1 0.0 1 10 100 Current Density(mA/cm )
2

y = -0.0353Ln(x) + 1.0085 2 R = 0.9985

Air Vcell Air_iR_Free O2_iR_Free Air_Cathod Resistance Corrected O2_Cathode Resistance Corrected Air_Ilim Correct O2_Ilim Correct

1000

10000

Figure1.9.Typicalperformanceforaloadcalibrationsweep

1.7.2.2 Stability Test A 64hour endurance test is run on the 25cm2 fuel cell under H2/Air. The operating conditions are 400 mA/cm2, 100 oC, 1.5 atm, and 69% RH for both the H2 and air reactants. The cell is maintained at a constant current while cell performance and resistance are measured. Initial and final electrochemical active area, fuel crossover, and performance are determined at cell operating temperature. Water from the exit streams is condensed, collected, and analyzed for fluorideionconcentration. Typical cell voltage and cell resistance stability curves are shown in Figure 1.10. The voltage and resistancearebothexpectedtobestablethroughoutthestabilitytest.Anychangeinperformance orresistanceisaresultofMEAdegradationduetochemicalandmechanicalstress.

14

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 20 40 Time / h

Voltage / V Voltage /V

Resistance /

100/90/90 -1 400 mA cm

250 200 150 100

Voltage Resistance

50 0

60

80

Figure1.10.Typicalperformanceandcellresistancestabilitycurve.VoltageandresistanceofFSEC3,0.2 L/min(H2/Air),Tcell=90oC,%RH=30,i=400mA/cm2.

1.7.3 Post-Test Integrity Test After the cell is tested, and before it is removed from the test stand, the external leaktest of the cell and the stand, and the resistance tests of the cell and the stand are repeated to quantify the endoftest condition. In addition, before the cell is disassembled, it is externally leaktested, internally leaktested, and electrical isolation tested on the bench, each according to the procedures in Appendices C and D. Bolt torque is also measured. These tests are to determine the changes in the cell integrity as a result of the protocol testing. These tests providedataonsomeofthechangestothemembraneaswellasdataexternaltotheMEAthat isneededtosupportthecellanalysis. 1.7.4 Post-test Analysis FSEC has developed and verified a process to evaluate sources of polarization, mainly associated with the cathode, in hydrogen/air proton exchange membrane fuel cells and is currently using this process to analyze cell performance and guide development efforts. This process quantifies the six sources of polarization using data from the standardized test program. Nonelectrode ohmic overpotential, electrode ohmic overpotential, nonelectrode concentration overpotential, electrode concentration overpotential, activation overpotential from the Tafel slope, and activation overpotential from catalyst activity are analytically separatedintotheirdistinctelements.Theanalysisisbasedonhydrogen/airpolarizationcurves ofaninhousemembraneelectrodeassembly(MEA)usinghydrogen/oxygenpolarizationcurves as a diagnostic tool. The analysis results compare three cell temperature/relative humidity /oxygenpartialpressure(pO2,atm)conditions:80C/100%RHanode/75%RHcathode,100C/69%RH, and 120C/35% RH, which represent near fullyhumidified, moderately humidified, and low humidified conditions, respectively, at 1.5 atm operating pressure. The technique is useful for

mOhm cm
15

diagnosing the main sources of loss in MEA development work, especially for high temperature/low relative humidity operation where several sources of loss are present simultaneously.Thefollowingverificationtestdataandanalysisisreported. 1.7.5 Cell Data Report The experimental testing of a new membrane will result in the following data to enable the evaluationofmembraneperformanceinacell: Cellbuildverificationtestdata o Electronicresistanceforshortdetermination o Externalleakagerate o Internalleakagerate Cellcharacterizationatstartup o Cyclicvoltammetryat25oCtoenableelectrochemicalareadetermination o Linear sweep voltammetry at 25 oC for crossover and electronic resistance determination Performancetestdata o Cellvoltageandcellresistance(OCVto0.3V)atthefollowingconditions: H2/O2andH2/Airreactantsat1.5atm,80oC/80oC/73oC(100%RH) H2/O2andH2/Airreactantsat1.5atm,100oC/90oC/90oC(69%RH) H2/O2andH2/Airreactantsat1.5atm,120oC/90oC/90oC(35%RH) o AtabulationofcellcurrentdensityandresistanceusingH2/Airreactantsat0.7V for the above three conditions (This tabulation is provided to enable rapid membranecomparisons.) Stabilitytestdata o Cellvoltageandresistancefor100hoursatthefollowingconditions: H2/Airreactantsat400mA/cm2,150kPa,100oC,69%RH o Cyclicvoltammetrytoenableposttestelectrochemicalareadetermination o Linear sweep voltammetry for posttest crossover and electronic resistance determination o Fluoridepresentinexhaustcondensate

1.8FuelCellHydrogenSafetyPlan
Florida Solar Energy Center (FSEC) complies with the University of Central Florida (UCF) ChemicalHygienePlan(CHP),asrequiredbyOSHA.Thisplananditsassociateddocumentation (Safety Standards for Hydrogen and Hydrogen Systems SSHHS) provides a written description of safety policies and procedures that all university laboratory personnel must follow.Allfacultyresearchers,studenttraineesandvisitingscientistsandengineersworkingat FSEC's hydrogen research laboratories are provided with training and a copy of SSHHS document. SSHHS document contains guidelines for hydrogen system design, material selection, operation, storage, handling and transportation. Furthermore, FSEC's hydrogen laboratories and field facility meet and/or exceed the design and safety requirements imposed bytheFloridaStateFireMarshallandallthestateandfederalcodes(NFPA45StandardonFire Protection for Laboratories Using Chemicals, NFPA 50A Standard for Gaseous Hydrogen 16

Systems at Consumer Sites, and NFPA 70 National Electric Code) for handling large volumes of hazardous and flammable gases and chemicals including both gaseous and liquid hydrogen. In addition, FSECs hydrogen field facility has been upgraded with explosion proof electrical systemsandmeetsNFPA50BCodeLiquefiedHydrogenSystemsatConsumerSites. Before each new research activity is initiated, the personnel safety at and near the facility is reviewed and emergency procedures implemented at the earliest planning and design stages. Advance planning for a variety of emergencies such as fires and explosions are conducted and proper procedures developed and implemented. All hydrogen systems will be instrumented andcheckedfor: i. Processmonitoringandcontrol. ii. Collectionofperformancedata. iii. Providingwarningsand/oralarmsforoutoflimitsconditions. iv. Earlydetectionofhazardouscondition(s). v. Compatibilitywithhydrogenservice. vi. Establishmentoflocaland/orremoteoperationandmonitoringofthehydrogensystem. vii. Havingappropriaterange,accuracy,andresponsetime. The Safety Assessment Review shall be updated anytime a system or process is changed. An annualfacilityinspectionshallbeconductedanddocumented.AformalOperatingandSupport Hazard Analysis shall be performed as directed by the UCF Environmental Health and Safety Office.Significanthazardsidentifiedshallbeeliminatedorreducedtoacceptablerisklevels. Mr. Randy Fowler is the FSEC's Hydrogen R&D Laboratories' operational and safety manager. Hehasattendedandcompletedthefollowingsafetyrelatedcoursesandtrainingactivities: i. A full day course on HazMat and received his certification on spill control and respirators. ii. HassuccessfullycompletedNASAHydrogenSafetyclass. iii. AttendedtheLabSafetyBasicsandBeyondatPITTCON. iv. Taken and passed UCF's Chemical Safety and Environmental Management for Laboratoriesclass. v. HaspostsecondaryvocationalcertificategivenbytheBrevardCommunityCollegeon ChemicalLaboratorySpecialist,Decemberof2002. Mr. Fowler oversees the enforcement of all hydrogen and chemical safety procedures and trainingofthegraduateresearchstudentsworkinginFSEC'shydrogenlaboratories.Inaddition, a comprehensive safety plan will be developed and submitted to DOE at the time of contract award.Inpreparationforthisplan,thefollowingstepswillalsobetaken: The Chemical Hygiene Plan (CHP) will be reevaluated, modified as needed and periodicallycheckedforcompliance. Astandardoperatingprocedure(SOP)willbeestablishedforallexperimentsand operationstakingintoaccounthazardlevelofmaterialstobeused. 17

ProcedureswillbedevelopedforreportinganyeventsordeviationsfromSOP. Failure risk mitigation plan will be developed based on vulnerabilities identified byModesandEffectsAnalysis.

18

2.DaybyDayPEMMEATestSequence

2.1AssembletheCell
TheSampleMEA - Fromteammemberstwopieces12cmx12cm(4.75x4.75) AnodeandCathodeCatalyst - TKK46%Ptcatalyst - 0.4mg/cm2 - 32wt%Nafion1100binder - Spray - 136oCheattreat - Protonation - Twoidentical:Onetested/Onereturneduntested GDL - SGL10BB Pinch0.25mm+/ 0.02mm(0.01+/ 0.001) TeflonGasketLayup FCTCell - HardwareSinglepassserpentine - Crossflowcathodehorizontal - FSECbarandgroovedimensions BoltLoad - Starpattern - 4.5Nmtorque(40inchpounds) PretestConductivity TestedatBekkTech Measuremechanicalcrossover - <1mAeq.isacceptable MeasureExternalLeakage - <20mAeq.isacceptable CellResistanceacceptablelimits - AnodetoGround>100Ohms - CathodetoGround>100Ohms - AnodetoCathode>30Ohms Mountinteststand - ResistanceAnode/Cathodetoground>100Ohmsacceptable RoomtemperatureCOandCV WetUp - 80/80/73 H2/N23hNoLoad H2/Air~3h0.55V 19

2.2Day1

2.3Day2

Cooldowntoroomtemperature - HoldonN2/N2

RoomtemperatureCOandCV Heatup - H2/N2 - 80/80/73oC - Ambientpressure Measure - Opencircuitvoltage(OCV), - Performance(voltsvs.current)curve(VI) - Cellresistance(bycurrentinterrupt) Stoichiometry Anode3,Cathode3.6 H2/Air H2/O2 H2/Air COandCVat80/80/73oC Holdovernightat400mA/cm2

2.4Day3
Pressurizeto1.5atm Measureat80/80/73oC - OCV,VIcurve,cellresistance Stoichiometry Anode3,Cathode3.6 H2/Air H2/O2 H2/Air Heatto100/90/90oC COandCVat100/90/90oC Measure - OCV,VIcurve,cellresistance Stoichiometry Anode3,Cathode3.6 H2/Air Holdovernightat400mA/cm2

2.5Day4(at1.5atm)
RunVIcurveat100/90/90oC - Stoichiometry Anode3,Cathode3.6 - H2/Air

20

- H 2/O2 - H2/Air
Heatto120/90/90oC RecordCOandCVat120/90/90oC Measure - OCV,VIcurve,cellresistance Stoichiometry Anode3,Cathode3.6 H2/Air H2/O2 H2/Air Coolto100/90/90oC Holdovernightat400mA/cm2

2.6Day5,6,7(at1.5atm)StabilityTest
RecordCOandCVat100/90/90oC Measure - OCV,VIcurve,cellresistance Stoichiometry Anode3,Cathode3.6 H2/Air H2/O2 H2/Air Startstabilitytest - 1.5atm - 100/90/90oC - H2/Air - 400mA/cm2 Stoichiometry - Anode3,Cathode3.6 Measureduringstabilitytest Cellvoltage Fluorideemissionrate(FER)inreactantexhausts

2.7Day8(at1.5atm)
RecordCOandCVat100/90/90oC Measure - OCV,VIcurve,cellresistance Stoichiometry Anode3,Cathode3.6 H2/Air H2/O2 H2/Air 21

2.8Day9

Cooldowntoroomtemperature H2/N2

RoomtemperatureCOandCV Resistancetest - Anodetoground - Cathodetoground Removethecell Measuremechanicalcrossover - <1mAeq.desired Measureexternalleakage - <20mAeq.desired Measurecellresistance - AnodetogroundRecordOhms - CathodetogroundRecordOhms - AnodetocathodeRecordOhms Posttest - Measureboltload - Disassemblecell - Conductvisualinspection - BagandSealComponents Dataanalysis - Deltacellresistance - DeltaCO - DeltaCV - Deltaactivationloss - DeltaTafelslope - Deltadiffusion - DeltaIlim - Deltaconductivity - FER

22

AppendixA:GurleyNumberTest Procedures
DocumentNumberWP0012WPQRS A1.Referencematerials
A1.1MinKyuSong,PEMFCUnitCellAssemblyforNTMembraneandETEKElectrode,March 13,2001,Uconn A1.2B.Mueller,E.DeCastroetc.,CARBONCLOTHGASDIFFUSIONBACKINGSFORHIGH PERFORMANCEPEFCCATHODES,ElectrochemicalSocietyProceedingsVolume9827

A2.Introduction
For porous and/or fibrous gas filtration media, resistance to flow is often used as a characteristic measure for quality control and performance. Gurley Number basically measures gaspermeationratethroughthegasdiffusionbackingsamples. The Gurley number represents the gas flow rate (in LPM) for a Gas Diffusion Layer sample at a fixedpressuredifference(incmofH2O)throughafixedareaofsample(cm2),andthusindicates theresistancetogasflow. Samples of gas diffusion layers were cut and fitted into a manifold of main gaskets and sub gaskets, such that the uncoated side of the backing is oriented towards the nitrogen inlet and that there is no pinch on the Gas Diffusion Layer. The total gasket thickness has considerable influence on the pressure distribution pattern over the active area on both inlet and outlet sides. Therefore, it is very important to employ enough thickness gaskets to get relatively uniformpressuredistribution,resultinginmoremeaningfulGurleynumbers. Priortoevaluationofabackingsample,thesysteminherentresistancetogasflowisevaluated bymeasuringpressuredropacrossthecelloverarangeofflowrates.Thissystemresistanceto flowisusedasacorrectioninthesubsequentmeasurementofbackinggasflowcharacteristics. TheconfigurationofthesystemisillustratedasinFigureA1.

23

FlowMeter Needle Valve Cell Assembly Digital Meter

SlantPressure Guage

FigureA1.ApparatusforMeasuringGurleyNumber

A3.MaterialsandEquipment
A3.1 Materials Teflonfilm(0.25mm(10mil)thickness) Krytox(Dupontperformancelubricants,TeflonGrease) GasDiffusionLayers SnoopLiquidLeakDetector Ethyl Alcohol 200 Proof, Absolute (Dehydrated) USP Grade, Pharmco Products INC DeionizedWater(From153FuelCellsLaboratory ERI) A3.2 Equipment ElectronicDigitalMicrometer(Mitutoyo) CARVERHydraulicPress(UnitModel#3912) ClickerDies TorqueWrench(05.6Nm,0to50inlbs) 3/8inchNutDriver NutPlate Tweezers Knife SingleCellParts GraphiteFlowChannel GoldPlatedCopperPlates InsulatorSleeves M6Bolts/M6Nuts FlatWashers 24

A3.3. Quality control (test and criteria) QS0012GasPermeability,GasDiffusionLayer.

A4.MainGasketPreparation
To ensure sealing over the gas diffusion layer edges, the main gasket thickness should be at least 51 m(2 mil) thinner than thegas diffusion layer thickness. In general, thecarbon papers andcarbonclothsfallintherangebetween356and457m(14and18mil).Inthiscase,a254 m (10 mil)thick Teflonmain gasket would be appropriate. However, itis important to keepin mindthatweshouldalwaysusealittlethinnermaingasketthangasdiffusionlayers. Using clicker die and hydraulic press, make a normal size gasket, then make it 6.5 mm (1/4) largeroneachside.Usinga25cm2cellasanexample,anormalgasketwouldbelikeinFigA2a. Aftermadelarger,thegasketwouldlooklikeinFigA2b. OriginalGasket EnlargedGasket

Outsidedimension:9.5x9.5cm2 Insidedimension:5.2x5.2cm2 a

Outsidedimension:9.5x9.5cm2 Insidedimension:6.5x6.5cm2 b

FigureA2.PreparationofMainGaskets(5.25.2cm2cellsize)

A5.PreparationofSubgaskets
Subgasketsaredesignedwitha5.8cmx5.8cminsidedimensionandtheoutsidedimensionis the same as for normal gaskets. However, it is very important to prepare enough thick gaskets to guarantee that we can have a uniform pressure distribution on the active area, which will lead to a meaningful Gurley Number. The correct total thickness depends on the active area, andonthephysicalpropertiesofgasdiffusionlayers. It is also important to alternate thin and thick gaskets in the final assembly to ensure proper sealingbythegaskets.

25

From experience, for 5 cm2, 6.25 cm2, and 25 cm2 cells, 3810 m (150 mil) of total gasket thickness is enough to generate a uniform pressure distribution. Suppose the thickness of the main gasket is 254 m (10 mil). Wecould use seven 254 m (10 mil) gaskets, then one 254 m (10mil)maingasket.Thetotalgasketthicknesswouldbe1778+1778+254=3810m(70+70 +10=150mil).

A6.PreparationofGasDiffusionLayersamples
Gas Diffusion Layers should be strictly cut according to the size of the main gasket (Figure A2b, 6.5x6.5cm).Toensurepropersealingontheedgesofthegasdiffusionlayer,itisimportantto makesurethatthesampleandthemaingasketmatchesnicely.

A7.CleaningofFuelCellComponents
i. Rinse the gold plated copper plate, graphite flow channel block and Teflon gaskets with deionizedwaterbysoftbrushing. ii. Washthemwithethanol. iii. Drythematroomtemperature.

A8.AssemblyProcedure
Note.AllpartsshouldbeorientedasshowninFigureA3. i.LubricatethesurfaceofthreadofM6BoltsusingKrytoxTeflongrease. Note.VerifynutsturnfreelyonM6boltsbeforeplacingboltinthenutplate. ii.PlaceM6boltsheaddownintheNutPlate. iii.PutflatwashersonthroughtheNuts. iv.PlaceInsulationSleevesonthroughtheNuts. v.PlaceGoldPlatedCopperAlloyPlateon. vi.PutBipolarPlateon. vii.Put1778m(70mil)Teflon subgasketon(7layers,254mor10milforeach). Note.Alignnotchesineachgasket. viii.Putthemaingasket(254mor10milthick)onandalignsubgasketsandmain gasket. ix.Putthegasdiffusionlayeronthemaingasket.Makesuretheyfitnicelyandthe coatedsidefacesup. x.Putanother254m(70mil)Teflonsubgasketontop(7layers,254mor10milfor each). Note.Alignnotcheswithfirstsevengasketlayers(step7). xi.Puttheotherbipolarplateon. xii.Puttheothergoldplatedcopperalloyplateon. xiii.Putinsulationsleevesin. xiv.Putflatwasherson. xv.PlaceNutson.TightennutsusingaTorqueWrenchandNutDriverinthesequence1 to8asshowninFigureA4.Apply2.8Nm(25inlb)torqueforeachbolt. Note.Nutsmustturnfreelybyhandbeforeapplyingtorque.

26

Note.Besuretoputthecellontothenutplatetotightennuts.Afterthat,itcanbehardtotake the cell off. In this case, put a screwdriver between the cell and the nuts plate and gently move the screwdriver upward (on both sides), the cell will be easily taken out of the nut plate.Also,usenutplatetoloosenthenuts. xvi.ConnectgastubesasinFigureA3.

ToSlantGauge LowPressure End N2 In

FigureA3.CellConnectionsinGurleyTest

N2 Out

ToSlantGaugeHigh PressureEnd

27

1 7 4 6 2

5 8

M6Nuts GoldPlated CopperPlate BipolarPlate

Teflon SubGasket

GasDiffusionLayer andMainGasket

Teflon SubGaskets

BipolarPlate

GoldPlated CopperPlate M6Bolt

NutPlate

FigureA4.CellAssemblyExplosionViewinGurleyTest

28

A9.LeakingCheckProcedure
Every connection shown in Figure A3 should be leak tested before taking measurements. For the cell itself, the gasket side should be tested to make sure there is no leak in between the gaskets.Theleaktestprocedureisasfollows: i. Verify that the pressure drop meter is in horizontal position (that should be checked usingalevel),andtheslantliquidlevelisat0positionwithnopressureapplied. Note.Verifyneedlevalveisclosed. ii. OpenN2gas,keeppressure~0.68atm(10psi). iii. Adjust pressure drop at 0.05 inch H2O. Open valve slowly, make sure that pressure dropcanbeheldat0.05inchslantliquidexactly. iv. HoldSnooptubeendatconnectionandsqueezeuprightbottletoapplysolidstream ofSnoopliquidleakdetector.Bubblesformifconnectionleaks.Bubblesizeindicates approximateleaksize. Note. For different size gaskets and different gas diffusion layers, pressure drop across the cell mayvarytremendouslywhenmeasuringGurleyNumber.Sincepressuresdropandflowrate haveanearlylinearrelationship,ingeneral,pressuredropcanbeusedasacontrolfactorto takeflowratemeasurements. v. FillreservoirwithSnoopLeakdetectorSolutionifitisnotenough. vi. TurnOnDigitalFlowmeter,pressballgently,andmakesurethatonesinglebubbleis generatedatonetime. vii. Repeat until the flow rate is relatively constant ( 0.03 L / min.), and the surface of flowmeteriswetenough.Recordtheflowrateresultontheform(below). viii. Adjustpressuredropat0.1,0.15and0.2inchH2O,repeatsteps(12).

A10.Dataprocess
i.CalculateGurleyNumberwiththeaverageofflowratewithequation1. FlowRate( LPM ) GurleyNumber = . Pr essureDrop * 2.54 * ActiveArea ActiveAreaistheareaofsubgasketopeningarea,for25cm2cellis5.85.8cm2. ii. Calculate Average Gurley Number (GN), if the Percent Relative Standard Deviation (% RSD)ofGurleyNumber>10%,atallpressuredrop,needREDOit.
n 1 100% , (2) x where x GN average, xi measured GN at adjust pressure drop at 0.05, 0.1, 0.15 and 0.2 inch H2O. RSD =

(1)

(x x )
i

29

A10.1 Data sheet Gurley number calculations: Samplenumber:GDL Date: LPM LPM1 LPM2 LPM3 LPM4 LPM5 Avr.LPM GurleyNumber (GN) RSD RSDAccept RSDReject GDLAccept GDLReject 0.05 Pressure 0.1 % <10% >10% 0.100.18 <0.10or >0.18 Drop 0.15 0.2

GNAverage

A11.Acceptance
InspectinaccordancewithQS0012GasPermeability,GasDiffusionLayer.

30

AppendixB:PEMFuelCellUnitCell AssemblyProcedure 25cm2

DocumentNumberWPxyz B1Referencematerials
J.C.Lin,PreparationandCharacterizationofCompositeProtonExchangeMembranesforFuel CellApplication,Ph.D.Thesis,UConn(2000).

B2BillofMaterials
B2.1 Materials i. Acatalystcoatedmembrane(CCM)consistingof Apieceofmembrane(eitherFSEC1,FSEC3,NRE211,NRE212,Nafion112,etc.) Acathodecatalystlayerononeside(~0.4mg/cm2),activeareaof25cm2. Ananodecatalystsprayedontotheotherside(~0.4mg/cm2),activeareaof25cm2. ii. One piece of gas diffusion layer, 5.8 x 5.8 cm2, with Gurley number of at least 0.024 L/min/cmH2O/cm2forCATHODEGDL iii. One piece of gas diffusion layer, 5.8 x 5.8 cm2, with Gurley number of at least 0.01 L/min/cmH2O/cm2forANODEGDL iv. Teflonfilm(25.4m(1mil)thickness) v. Krytox(Dupontperformancelubricants,TeflonGrease) vi. DeionizedWaterandethanolforwashing B2.2 Equipment i. Asinglecellhardwareset AFuelCellTechnology(FCT)hardwaresetconsistsof: Twouniquelymachinedgraphiteflowfields(withFSEClowdeltaPserpentine grooves) Twoaluminumendplates1.27cm()thickness Twogoldplatedcurrentcollectors0.32cm(1/8)thickness Fourplasticrubbertubes0.95cm(3/8)long,0.2mmindiameter(calledlineup pins) Fourblackrubberorings(tosealallthelineuppins) EightStainlessscrews Eightblackrubberinsulatingsocks(oneforeachscrew) ii. DigitalBalance(METTLERAE240,S/NG56273) iii. ElectronicDigitalMicrometer(Mitutoyo) iv. TorqueWrench(0to5.6Nmor0to50inlbs)

31

B3Objectives:
To describe how to assemble a PEM fuel cell unit cell (called Membrane Electrode Assembly, MEA)usingaNafionbasedmembraneandSGL10BBGDLs.

B4GeneralInstructions

Lubricate the bolts every two cells to make certain the right amount of torque is applied to thecell(notthefrictionforce) Alignment of all components vertically is VERY CRITICAL. Take care to ensure good alignment (even if it means STARTING OVER, if you feel unsure). Misalignment will cause thecelltofailandwastealltheeffortoftheCCMpreparation.

B5PreparationforCellAssembly
Checkthatthehardwaresetcontainsalltheparts.Separatethecathodepartsand anodepartsaslabeled. ii. Clean the surface of the two graphite flow fields with ethanol. Take care not to leaveexcessethanolinflowfieldspriortoassembly. iii. Measure the thicknessof the CCM by placing it between two 1mil Teflon films (for surface protection) and measure the overall thickness with a Mitutoyo caliper. Then subtract off the Teflon film thickness. Measure AT LEAST 9 VALUES and obtain an averagevalue. iv. RepeatStepiiiforcathodeGDLandanodeGDL. v. Setthedesiredamountofpinchinthiscase,229254m(910mils) vi. CalculatethetotalthicknessofneededTeflongasketsby: Totalthicknessofthegaskets=(Tccm+TGDL,C,+TGDL,A)Pinch Totalthicknessofeachside(CathodeandAnode)=Totalthicknessofthegaskets/2 Note 1. If the total thickness of the gaskets is an ODD number, make total cathode gasket thicknessLESSthantotalanodegasketthickness. Note2.Usually(Tccm+TGDL,C,+TGDL,A)isintheorderof762889m(3035mils) vii. Prepare different combinations of Teflon gaskets (available as 25, 51, 76, 127, and 254mor1,2,3,5and10mil)forthecathodeandanodesides. Note.Cuteachgasketusinganappropriatelydesigneddiespecifictoeachhardwaredesign. viii. Cut both GDLs to the size that will fit PERFECTLY (within 0.3 mm) inside the middle opening of the prepared gaskets. The opening is slightly bigger (12 mm) than the cellactivearea). i.

B6AssemblingtheCellFuelCellTechnology(FCT)hardwareset
RefertoFigureB1. i. Placefourboltsthroughthecathodeendplateforalignmentofcellparts. ii. Placethecathodeendplatewithboltsatthebottomonasturdysurface. iii. Placethecathodegoldplatedcurrentcollectorplateontopofthecathodeend plate. iv. Placethetwolineuptubesandtwooringsintolineupholesofthecathodeend platetoaligntheendplatewiththecathodegoldplatedcurrentcollector.

32

v. vi.

vii. viii. ix. x. xi. xii. xiii. xiv.

xv.

Placethecathodegraphiteflowfieldontopofthecathodegoldplatedcurrent collector(withthegroovedsideup). Placethesetofcathodegasketsontop.MakeSUREitalignswellwithallthebolt holes.Usea1cmlongpieceofscotchtapetoattachthegasketstotheflowfield platetoensurealignmentinthecell,IFNECESSARY. PlacethecathodeGDLinthemiddleofthesetofgaskets(microporouslayerside UP). PlacetheCCMontop(ANODEsideUP);alignthecatalystactiveareainthemiddle ofthegasketmiddleopening. Placethesetofanodegasketsontop.MakeSUREitalignswellwithallthebolt/nut holes. PlacetheanodeGDLontop,alignitwiththeanodeGDL(microporouslayerside DOWN). Placetheanodeflowfieldplateontop(groovesideDOWN). Placetheanodegoldplatedcurrentcollectorplateontop. Placetheanodeendplateontop(withthetwoplasticlineuptubesandoringsin place. Tightenalltheboltsinacrosswiseorstarpattern.Insixcycles: A. Tightenlooselybyhand(avoidovertighteningandapplyingtoomuchtorque) B. Tightenwithatorquewrench,setto1.1Nm(10inlbs),byfeelingtheclick C. Tightenwithatorquewrench,setto2.3Nm(20inlbs),byfeelingtheclick D. Tightenwithatorquewrench,setto3.4Nm(30inlbs),byfeelingtheclick E. Tightenwithatorquewrench,setto4.5Nm(40inlbs),byfeelingtheclick F. Recheckallboltswiththetorquewrenchsetat4.5Nm(40inlbs),byfeelingthe click Theassembledcellisnowreadyforasinglecellperformancetest.

1 2 3 4 5 6 5 4 3 2 1 7

1. 2. 3. 4. 5. 6. 7.

EndPlate Goldcoatedcopperplate BipolarPlate TeflonGasket GasDiffusionLayer MEA M6Bolt

FigureB1.Expandedviewofassembledfuelcell

33

AppendixC:ProcedureforLeakTestinga SingleCellafterAssembly
DocumentNo.WP0023andWP0024 C1ExternalLeakTest
C1.1 Procedure i. SetupperFigureC1 ii. ConnectN2tohydrogensidewithaflowmeterfollowedbyanisolationvalve. iii. Connectgasoutlinetohydrogenside,withaninlettotheair/O2side iv. Connectgasoutlinetoair/O2sidewitha0to0.39atm(0to300mmHg)pressure gaugefollowedbyanisolationvalve. v. Pressurizethehydrogenandair/oxygensidesto0.03,0.07,0.14,0.2atm(0.5,1,2, 3psi)withnitrogen,respectively. vi. Recorddataoftheflowmeter. vii. LeakcheckwithDIwater,writedownwherethebubblescomefrom.Canuse Snooponplumbingconnection,notoncell. viii. Ifnoleakcanbeobservedandflowmeterremainsatzero,closethevalve,record pressuredropin5min. N2 Supply 0300 mmHg Flowmeter

P Vent
Valve

Valve

SingleCell

FigureC1.SetupforExternalLeakTest

34

C2InternalLeakTest
C2.1 Procedure for Internal Leak i. Verifythatexternalcellleakagesatisfiestherequirements ii. SetupFigureC2 iii. ConnectN2inlettothehydrogenside,withaflowmeterfollowedbyanisolation valve iv. Connectgasoutlettothehydrogensidewitha00.39atm(0300mmHg)pressure gaugefollowedbyanisolationvalve v. Connectbubblemetertoairside vi. Closethehydrogenventandpressurizethehydrogensideto0.03,0.07,0.14,0.2 atm(0.5,1,2,3psig)withN2,respectively vii. Checktheflowrateattheair/oxygenventwiththebubbleflowmeterandflow meter,recorddataondatasheet viii. Ifnoleakcanbefoundandflowmeterremainsatzero,closethevalveandrecord pressuredropin5min. C2.2 Procedure for Internal Leak i. SetupFigureC2 ii. ConnectN2inlettotheair/oxygenside,withaflowmeterfollowedbyanisolation valve iii. Connectgasoutlettoair/oxygenside,witha00.39atm(0300mmHg)pressure gaugefollowedbyanisolationvalve,otheroutletshouldbeclosed iv. Connectbubblemetertohydrogenside v. Closetheair/oxygenventandpressurizethehydrogensideto0.03,0.07,0.14,0.2 atm(0.5,1,2,3psig)withN2,respectively vi. Checktheflowrateatthehydrogenventwiththebubbleflowmeterandflow meter,recorddataondatasheet vii. Ifnoleakcanbefoundandflowmeterremainsatzero,closethevalveandrecord pressuredropin5min.

35

SingleCellAssembly
Valve N2 Supply Flowmeter Vent Bubble Meter

Singlecell

0 300mmHg

P Valve Vent

FigureC2:SetupforInternalLeakTest

36

AppendixD:PEMFCUnitCellTest
D1.Referencematerials
i. ii. iii. iv. v. vi. vii. FuelCellTestSystemConfiguration,ScribnerAssociates,Inc. FuelCellforWindows:FuelCellTestSoftware,ScribnerAssociate,Inc. Operating Manual of Fuel Cell for Windows, Fuel cell Test Software, Scribner Associatesmodel890loadsystems,Version2.0 ScribnerAssociatesInc.850CFuelCellTestSystemOperatingManual ConfigurationandApplicationManualofFuelcellTestSystemConfiguration Operating Manual of CorrWare for Windows, Electrochemistry/Corrosion Software, ScribnerAssociatesInc.,Version2.2 The Princeton Applied Research Potentiostat/Galvanostat Model 263A Operating Manual

D2.BillofMaterials
D2.1 Materials D2.1.1Gases i.Nitrogen ii.Oxygen iii.Air iv.Hydrogen D2.1.2Deionizedwater

Ultrahighpurity(99.999%),AirgasN.E. ZeroGrade(99.8%),AirgasN.E. ZeroGrade(90%),Compressed,AirgasN.E. Ultrahighpurity(99.999%),AirgasN.E. FacilityDIwater

D2.2 Equipment i.FuelCellTestStation ii.FuelCellTestLoadBox iii.ScribnerSeries890Bor850CElectronicLoadandDataAcquisitionSystem iv.ScribnerModel871ReformateSimulator(optionalnotactive) v.IBMPCwithNationalInstrumentsGPIPPCIInterfaceandGPIBCable vi.CellCableSets vii.Potentiostat/GalvanostatModel263,PrincetonAppliedResearch viii.Insulationjacket(Cloth) ix.Aplasticjack x.Wrench(13mm) xi. Multimeter, OMEGA, HHM25 KIT, OMEGA ENGINEERING INC. STAMFORD CT, U.S.A. xii.Plasticbottlefordeionizedwater

D3Objectives
TodescribetheperformancetestprocedureofaPEMfuelcell.

37

The overall objective of this test sequence is to determine the performance characteristics of a single,benchscale,protonexchangemembranefuelcelloverarangeoftemperaturesfrom80 o Cto120oC.Thecellactiveareais25cm2.

D4GeneralInstructions
Before the cell is mounted in the test stand, a review should be performed of the procedures described below and a check made of the availability of all of the materials and facilities to performthetestprogram. D4.1 Fuel Cell System Configuration

Bypass

Solenoid valve
Check valve

Massflow controller Humidifier

Heater
Vent

O
Air

3way valve
5

Condenser Backpressure regulator

Vent

Cathode Outlet Fuel Cell Anode Outlet

Solenoid valve

Check valve N2
5

Condenser
Massflow controller
5

Load

Solenoid

valve

Humidifier

IBM

Heater H2 Reformate
Figure D1. Schematic of Fuel Cell System Configuration

TestStation

D4.2 Explanation of the test station Gasesflowthroughmassflowcontrollerandhumidifiertothefuelcell. GasflowrateiscontrolledbyMKS1179Amassflowcontrollers Gastemperatureandhumidityareadjustedbyspargingthegasesthroughstainlesssteel humidifiertanks.

38

Thehumidifiedgasesareintroducedtothefuelcellhardware. Thegasesdiffusetotheelectrodesthroughgasdiffusionlayerwhiletheyarecirculating alongthegaschannel. Theexhaustedgasespassthroughthebackpressureregulatorandthentothevent.

D4.3 Hardware Specifications D4.3.1ElectronicLoadSystem: LoadCurrentRange 10,25,100A,fullscale LoadVoltage 20Vmax. LoadPowerRange 100W MinLoadResistance 0.5to1m IRMeasurement CurrentInterruptmethod CurrentMeasurement HallEffectDevice LoadCooling Forcedair,oneorthreefans

D4.3.2PowerRequirementsandPhysical 90125VAC,5060Hz,4A MainPower 17W10H21D(432553mm) LoadandDataUnit 3550lbs(1623kg) Weight 8W3H10D SystemInterfaceBox

D4.4 Data File Name Convention ThedatafilenamingconventionisBxxxDyyRzzAA,where BstandsforBUILD xxx represents the cell number that is assigned by the database upon entry of the cell assemblyrecordinformation DstandsforDAY yyrepresentsthenumberofdaysthatthecellhasbeentested (Do not count days elapsed, only the days that the cell has been operated: the first day that you operate the cell YY=1, if you operate the cell the next day, or any number of dayslater,thenYY=2,thethirddaythecellisoperated,YY=3,andsoon.) RstandsforRUN zzrepresentsthenumberoftherunduringday AArepresentthetypeofdatacollectedUsepropernomenclatureasfollows: COstandsforcrossover(toestimatehydrogencrossover) CVstandsforcyclicvoltammetry(toestimateECAelectrochemicalsurfacearea) VIstandsforvoltagecurrent(performanceorpolarizationcurve) CCstandsforconstantcurrent(constantcurrentoperation) D4.6 Nomenclature of the test condition (temperatures) is B/C/D: BreferstoTcellinoC Creferstoanodehumidifiercontrollertemperatures(bothtopandbottom)inoC Dreferstocathodehumidifiercontrollertemperatures(bothtopandbottom)inoC

39

Whenusercontrolsgaslines,theyarealways10oChigherthanTcell.

D4.7 Handling of gas tanks At the beginning of EACH day, verify that all gas (N2, H2, Air, and O2) cylinders have enoughpressure(Above13atmor200psi). At the beginning of Day 1, OPEN gas tanks for N2, H2, and Air (all gases used that day). Seteachgasregulatorat3.4atm(50psi).

D5Day1Test
D5.1 Setup Cell Hardware on the Test Station Timerequiredforthisstep:~30minutes i. Use a multimeter to measure the resistance between two graphite plates (anode and cathode).Waituntilthevalueisstabilizedandrecordtheexactvalue. Note. This step is to see that the resistance value is high enough (~50 ohm) that there is no indicationofshort.Iftheresistanceislowerthan10ohm,rebuildthecell. ii.Connectfourgastubestothefuelcellhardware Note1.MakesurethatanodeandcathodeplatescorrespondtothoseoftheMEAinside. Note2.MakesurethereisnoleakontheINLETGASLINES.Checkwithsoapywater. D5.2 Preparation of cell test on the test station Timerequiredforthisstep:~5minutes i. Insert the outside thermocouple into the end of a little hole on the graphite plate of the cellhardwareformeasuringthecellstemperature. Caution:Makesurethatthethermocouplestaysattheendoftheholeandusethescotchtape to keep it in place, if needed. If the thermocouple is not in place, the cell will be OVERHEATED tomaintainasetpointtemperature(acellfailure). ii. SwitchboththecathodeandanodegasvalvesontheteststationtoN2gas. D5.3 Operation of computer to start up cell Timerequiredforthisstep:~5minutes i. TurnonComputer1ANDFuelCellLoadUnit1. ii. SelecttheiconforFuelCellsoftwareonMSWindowsandopenit. AmenuboxtitledSETUPCELL(SeeFigureD2)willpopup.Setcellsurfaceareaas iii. APPROPRIATEfortheMEAtested(usually25cm2).Setcelltemperatureat25oC Note. If the Beep box is checked, FuelCell software program will produce a beep from the computerspeakerwhentheMinorMaxlimitsareexceeded.

40

FigureD2.SetupCellMenu

iv. AnothermenuboxtitledSetupFuelFlow(SeeFigureD3)willpopup. Settheflowratesat: Anode - MinimumFlow:0.4L/min - Loadbasedflow:0L/min/cell+0.023L/min/Amp/cell(notusedinthiscase) - Temperature:25oC Cathode: - MinimumFlow:0.4L/min - Loadbasedflow:0L/min/cell+0.066L/min/Amp/cell(notusedinthiscase) Temperature:25oC

41

FigureD3.SetupFuelMenu

D5.4 Crossover and Cyclic Voltammetry Tests Timerequiredforthisstep:~40mins Note.Thisisaseriesofteststodeterminethebasicsoundnessofthecelltoseeifitmeets minimumrequirements. i. Onthesideoftheteststation,switchANODEgasvalvetoH2andCATHODEgasvalve toN2. ii. ConnectWORKINGandSENSEelectrodestotheCATHODEandtheCOUNTERand REFERENCEelectrodestotheANODE.(SeeFigureD4) iii. TurnonthePrincetonAppliedResearch263A(ConnectedtoComputer3). iv. TurnonComputer3,whichisusedformeasuringshortcircuit,crossovercurrent andcyclicvoltammetry. v. SelecttheiconforCorrWare2softwareonthemainscreen,anddoubleclickitto activatetheprogram. vi. RightclickatPotentiodynamicandselectSetupcelloption vii. Setcellsurfaceareato25cm2andthenclickOK(seeFigureD5) viii. RightclickatPotentiodynamicandselectSetupinstrumentoption.Set bandwidthtohighstability

42

DoubleclickPotentiodynamictowaituntiltheOCPbecomeslowerthan0.1V. NamefileaccordingtotheIonomemDatabasefiles(SeeSectionD4.4)andselect whereitwillbesaved.Select4mV/sasthescanrate. Note.Thisopencircuitvoltagevaluewouldbeshownattheupperrightcornerofthemenu panel x. SelectPotentiodynamicfromexperimenttypesandclickthebuttonforMeasure Selectedintoolbarandbeginthismeasurement Note.Thisgreenlabelisshowninthetoolbarofthemenupanel. xi. RightclickatCyclicVoltammogramandselectSetupinstrumentoption.Set bandwidthtohighspeed. xii. DoubleclickCyclicVoltammogramandnamefileaccordingtotheIonomem Databasefiles(SeeSectionD4.4)andselectwhereitwillbesaved.Select30mV/sas thescanrate. xiii. SelectCyclicVoltammogramfromexperimenttypes. xiv. ClickatthebuttonforMeasureSelectedintoolbarandbeginthismeasurement; xv. TurnoffthePAR263Awhenfinished. xvi. Disconnecttheelectrodes(working,counter,sense,andreference)fromthecell hardwareplates
Working Electrode Counter Electrode

ix.

Cathode

Anode
FigureD4.ConnectionofElectrodewithFuelCellHardwareforCO/CVMeasurements

43

FigureD5.CorrWareSetupCellMenu

D5.5 Humidification of the Membrane Timerequiredforthisstep:~3.5hours Note.Thisstepisperformedtointroducewaterintothemembranetoimproveitsionic conductivityandreactantpermeability. i. SwitchtheANODEgasvalvetoH2andCATHODEgasvalvetoN2. ii. ConnecttheLOADLINEStothefuelcellhardware: Connect the cathode load line (red line) directly with the cathode metal plate of the fuel cell. Connecttheanodeloadline(blackline)directlywiththeanodemetalplateofthefuelcell. Caution:Beverycertainthattheconnectionistight! iii. InserttheSENSELEADSintotheholesoftheleadsonthefuelcellhardware: Insert the cathode sense lead (red line) directly into the hole in the red line attached to the cathodegraphiteplate Insert the anode sense lead (black line) directly into the hole in the black line attached to theanodegraphiteplate Caution: Never connect the sense leads to the test fixture without the large LOAD connections beingmadefirst.Failuretodothiswiththeloadunitactivemayresultindamagetotheload. iv. ChangeallsetpointstotheHEATUPStep(40/50/50condition) Setcelltemperatureat40oC Set anode and cathode gas lines at 50 oC (If applicable). (Recall 10 oC higher than cell temperature) Setanodeandcathodehumidifiercontrollersat50oC. v. Afterthetemperaturesreachthesetpoints,holdittherefor5to10min. vi. Changeallsetpointstothe80/80/73condition: Setcelltemperatureat80oC

44

Set anode and cathode gas lines at 90 oC (If applicable). Anode and cathode gas line temperaturesare510oChigherthancelltemperature(Tcell). Onthetestpanel,setanodehumidifiercontrollersat80oC(100%RH) Onthetestpanel,setcathodehumidifiercontrollersat73oC(75%RH) vii. Settheflowratesat: Anode - MinimumFlow:0.17L/min - Loadbasedflow:0L/min/cell+0.021L/min/cell(for3stoichiometryofH2) Cathode: - MinimumFlow:0.17L/min - Loadbasedflow:0L/min/cell+0.066L/min/cell(for4stoichiometryofAir) viii. Maintainatthiscondition(H2/N2,80/80/73)tohumidifytomembranefor3hours.

D5.6 Operation of the Cell in a Break-In Mode Timerequiredforthisstep:~3hoursminimum Note. This test is performed to let the cell come to a steady state while operating in a benign wayasafuelcell. i. SettheconditiontoH2/N2,80/80/73oCcondition(maintainpreviousstep). ii. On the side of the test station, keep the ANODE gas valve on H2 and switch the CATHODEgasvalvetoAir. iii. Wait until the cell voltage (which is the open circuit voltage at this point) stabilizes.(~3minutes).Thenrecordtheexactopencircuitvoltage. Note1.Thevalueofopencircuitvoltagewillincreasewiththetime.Justwaituntilitisstable. Note 2. NEVER leave the cell at the OCV (Open Circuit Voltage) for more than 5 minutes. Platinum and carbon will corrode and cause performance decay. While changing conditions with fuel (hydrogen) and oxidant (air/O2) present, always apply load at 100 400 mA/cm2. This istonotleavethecellatOCVtoavoidcellcorrosion. iv. ClickApplyFuelandApplyLoadbuttons. v. Setthecellvoltageat0.55V.RecordtheTOTALcurrentdensitytoValue#1(t=0 hours). vi. Holditforonehour,recordtheTOTALcurrenttoValue#2(t=1hour) vii. Holditforanotherhour,recordtheTOTALcurrenttoValue#3(t=2hours). viii. Repeat the recording every hour until the TWO last current values are within 5% ofeachother.(Usuallytakes35hours) D5.7 Cool-Down Procedure Timerequiredforthisstep:~1hour i. Setthecelltemperatureto80/60/60oC Note 1. The cell temperature must be about 1020 oC above the saturator temperatures during cooldown. Note 2. Water can be added to the saturators, and insulation can be removed from the cell to promotecooldown. ii. While waiting for temperatures to reach the first set points, disconnect the positive loadcable,toprotectfromcurrentleak.

45

iii. iv. v. vi. vii. viii. ix. x. xi. xii. xiii.

Settheminflowrateontheanodeandthecathodeat0.2L/min. SwitchthecathodevalveonthesideofthestationtoN2forpurgingthecell. Wait until the voltage falls to 0.4 V, then switch the anode valves in the front panel ofthestationtoN2forpurgingthecell. After the temperature reaches 80/60/60 oC, set it to 60/50/50, then 50/40/40, then 0/0/0. Wait until the cell temperature, the humidifier temperatures, and the gas line temperaturesareallbelow50oC. Turnoffthepowerofheaterforhumidifiers. Settheanodeandcathodeflowratebacktozero. Click"Exit"toclosetheFuelCellsoftware. TurnofftheFuelCellLoadUnit Closeallvalvesofthegascylinders. Closeanodeandcathodevalvesoftheteststation.

D6Day2Test
D6.1 Crossover and Cyclic Voltammetry Tests Timerequiredforthisstep:~0.5hour RepeattheprocedureformeasuringCOandCVonday1. D6.2 Polarization curve measurement at 80 oC (Air/O2 alternating) Timerequiredforthisstep:~7hours(Air/O2/Air) Note.Thistestisperformedtodeterminethecellperformance at atmospheric pressure, which istheconditionwheretheelectrolyteisnearsaturation. i. Settheflowratesasdoneforthehumidification. ii. Keep the ANODE gas valve on H2 and switch the CATHODE gas valve to Air (1st Air run). iii. LetthecellreachOCV(~23min).RecordOCV. iv. ClicktheApplyFuelbuttononthemainwindowasshowninFigureD6. v. ClicktheApplyLoadbuttononthemainwindowasshowninFigureD6. vi. Apply400mA/cm2load.Maintainuntilvoltageisconstant. vii. If no experiments are listed under the Setup Experiments panel, click on New button on the right of the panel, and select Arbitrary control. If there are experimentslistedintheSetupExperimentspanel,doubleclickoneofthem. viii. ThemenuboxtitledSetupArbitraryControlExperimentwillpopup ix. Chooseanameandlocationforthedatafile(filewiththeresultsoftheexperiment). x. Selectanappropriatecontrolsetupfilefortheexperiment,thenclickOK Note.ControlSetupfilesaretextfiles(i.e..txtfiles)thatareusedtocontroltheload.Weare currently testing the following loads: 0, 10, 20, 40, 60, 80, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 mA/cm2, held at eachpointfor5minutes. xi. ClicktheRunCellButtononthemainwindow

46

xii. xiii. xiv. xv. xvi.

xvii. xviii. xix.

Select Graphs in menu bar, then click vs Time command and click Voltage as showninFigureD7. ThemenuboxtitledGraphs#1willpopup. Change Background data to Experiment data at the upperright corner of this menubox SoftwarestartsdataacquisitionforaCellVoltagevs.Timeplot Wait until the experiment is finished. While the experiment is in progress, check regularlythatthewaterlevelinthehumidifierisnotbelowtheminimumlevel.Also checkthattheexperimentisprogressingwithoutjumpingtoOCV. After the experiment is finished, the load should return to whatever load was being usedpriortotheexperiment,inthiscase400mA/cm2. SwitchthecathodevalveonthesideofstationtoO2andwaituntilvoltagestabilizes. RepeatthemeasurementinO2(atthesametemperature). After the measurement on O2 is finished, switch the cathode valve back to Air. Repeatthemeasurementforair(2ndAirrun).

FigureD6.MainWindowforFuelCellsoftware

47

FigureD7.ChooseVoltagevs.Timegraph

D6.3 Crossover and Cyclic Voltammetry Tests at 80/80/73 Timerequiredforthisstep:~0.5hour Repeatthecrossoverandcyclicvoltammetryprocedurefromday1at80/80/73.

D6.4 Hold at 400 mA/cm2 overnight

D7Day3Test
D7.1 Performance Measurement at 80/80/73 (Air/O2 Alternating, 1.5 atm) Timerequiredforthisstep:~6hours i. Pressurizecellto1.5atm. ii. Runthecellatthe80/80/73conditionwithH2/Air. iii. Waituntilthewholesweepmeasurementisfinishedthenrepeatwithoxygenandagain withair. D7.2 Performance Measurement at 100/90/90, Air, 1.5 atm Timerequiredforthisstep:~2hours i. Changethetemperaturestothe100/90/90condition(usingH2/Air) Setcelltemperatureat100oC

48

 ii. iii.

Setanodeandcathodegaslinesat110oC,ifapplicable Setanodehumidifiercontrollersat100oC Apply400mA/cm2ofload,andwaituntiltemperaturesandvoltagestabilize StartthemeasurementoftheperformanceusingH2/air Waituntilthewholesweepmeasurementisfinished.

D7.3 Hold over night at 400 mA/cm2

D8Day4Test
D8.1 Performance Measurement at 100/90/90 (O2/Air Alternating, 1.5 atm) Timerequiredforthisstep:~3hours i. Runtheperformancetestatthe100/90/90conditionwithH2/O2 ii. Waituntilthewholesweepmeasurementisfinishedthenrepeatwithair. D8.2 Crossover and Cyclic Voltammetry Tests at 120/90/90 Timerequiredforthisstep:~1hour i. Releasepressureoncelltoambient ii. Changethetemperaturestothe120/90/90condition Setcelltemperatureat120oC Setanodeandcathodegaslinesat125oC(NOT10oChigherthanTcellasusual) Onthetestpanel,setanodehumidifiercontrollersat90oC(sameasprevious) iii. RepeattheCO/CVprocedureofDay2 D8.3 Performance Measurement at 120/90/90 (Air/O2 Alternating, 1.5 atm) Timerequiredforthisstep:~3hours i. Pressurizecellto1.5atm. ii. Changecathodegastoair iii. Apply400mA/cm2ofloadandwaituntilvoltagestabilizes iv. StartthemeasurementoftheperformanceusingH2/Air v. SwitchtoO2,apply400mA/cm2whilewaiting vi. RuntheperformancetestwithH2/O2thenwithH2/Air D8.4 Reduce Cell temperature to 100C and hold overnight at 400 mA/cm2

D9Day5Test
D9.1 Crossover and Cyclic Voltammetry Tests at 100/90/90 Timerequiredforthisstep:~1hour i. Releasepressureoncelltoambient ii. Changetemperatureto100/90/90condition iii. RepeatthecrossoverandcyclicvoltammetryprocedureofDay1 D9.2 Performance Measurement at 100/90/90 (Air/O2 Alternating) Timerequiredforthisstep:~6hoursminimum(Air/O2) i. Pressurizecellto1.5atm

49

ii. iii. iv. v. vi. vii. viii.

Changecathodegastoair Apply400mA/cm2ofloadandwaituntilvoltagestabilizes StartthemeasurementoftheperformanceusingH2/Air Whenmeasurementisfinished,switchtoO2andapply400mA/cm2whilewaiting RuntheperformancetestwithH2/O2. Whenmeasurementisfinished,switchtoairandapply400mA/cm2whilewaiting RuntheperformancetestwithH2/Air.

D9.3 Stability Test at 100/90/90 (H2/Air, 400 mA/cm2, 1.5 atm, Days 5, 6, and 7) UnderSetupexperimentsclickonNewbuttonontherightofthepanelandselect Constantcurrent Savethefileunderanappropriatenameandinputtesttime(~70h)andcurrent(400 mA/cm2) Collectcondensatewaterfromanodeandcathodeexhausteachmorningandevening, inseparate,labeledvials(endupwith12vialstotal).Analyzecondensatewaterfor fluorideionsaccordingtoAppendixE.

D10Day8Test
D10.1 Crossover and Cyclic Voltammetry Tests at 100/90/90 Timerequiredforthisstep:~0.5hour i. Releasepressureoncelltoambient ii. RepeatthecrossoverandcyclicvoltammetryprocedureofDay2 D10.2 Performance Test at 100/90/90 (Air/O2 Alternating, 1.5 atm) Timerequiredforthisstep:~6hours i. Pressurizecellto1.5atm ii. RepeatPerformancemeasurementat100/90/90fromday5 D10.3 Cool-down i. Setthecelltemperatureto80/60/60. Note 1. The cell temperature must be about 1020 oC above the saturator temperatures during cooldown. Note 2. Water can be added to the saturators, and insulation can be removed from the cell to promotecooldown. ii. While waiting for temperatures to reach the first set points, disconnect the positiveloadcable,toprotectfromcurrentleak. iii. Settheminflowrateontheanode(H2)andthecathode(air)at0.2L/min. iv. Switch the cathode valve in the front panel of the station to N2 for purging the cell. v. Waituntil the voltage falls to 0.4 volts, then switch the anode valves in the front panelofthestationtoN2forpurgingthecell. vi. Afterthetemperaturereaches80/60/60,setitto60/50/50,then50/40/40,then 25/25/25.

50

vii.

Wait until the cell temperature, the humidifier temperatures, the saturated gas water,andthegaslinetemperaturesareallbelow50oC.

D11Day9Test
D11.1 Repeat the crossover and cyclic voltammetry procedure of Day 2 (at room temperature) D11.2 Leak test per Appendix C D11.3 Resistance Test per Section D5.1 D11.4 Shut-down and Remove from the test stand i. Turnoffthepowerofheaterforhumidifiers(ifapplicable). ii. Settheanodeandcathodeflowratebacktozero. iii. Click"Exit"toclosetheFuelCellsoftware. iv. TurnofftheFuelCellLoadUnit v. Shutdowncomputer. vi. Closeallvalvesofthegascylinders. vii. Closeanodeandcathodevalvesoftheteststation. viii. Disconnectgastubingandelectricallinefromthecellhardware. D11.5 Post-test i. Measureboltload ii. DisassembletheCell iii. ConductvisualInspection iv. BagandSealComponentsWith10dropsofDIWaterineachBag

D12Troubleshooting:Hardwareproblems
INDICATION
yNopowerwhenunitis turnedON yACPowernotavailableto model890 yNoheaterpoweravailable foroneormoreofthe temperaturecontroller

CAUSE

CORRECTION

yFuseonrearpanelof yReplacewith4A,slowblow3AG thecontrolunitmaybe typefuse blown

yCheckinternalfusesthatprotect thetempcontrolleroutput.

51

yAlarmswhenFUELON buttonispressedinsoftware

yFuelGasunitcables notconnected yModel890Fuel System InterfaceBoxnot properlyconnected

yCheckgaspressuresandlow pressuresafetyswitchwiring. yLowgaspressurealarmswitches mustbeclosedforalarmstobeoff.

yNoloadcurrentwhenloadis yLoadcablesnot turnedON connected ySenseleadsnot connectedorreversed ySenseleadprotection fuse(internalfuse) blown

yRemoveallpowertosystemand disconnectanodecellleadand anodesenseleadfirst yResistanceshouldmeasure between10and15W yIfincorrect,removetheunit coverandcheckthefuseby removingitfromitssocket. yCheckcoolingrestrictions yProlongedovertemperature operationmaydamagetheload electronics.

yInadequatecoolingairflow causingovertemperatureshut down

52

D13ChartSummarizingDaytoDayActivities
Day 1 1 1 1 2 2 2 2 2 3 3 3 3 3 4 4 4 4 4 4 5 5 5 5 5 6 7 8 8 8 8 8 9 9 9 Time(h) 0.5 3.5 3 1 8h 0.5 2.5 2 2 0.5 7.5h 2 2 2 1 2 9h 2 2 1 1 1.5 1 8.5h 0.5 2 2 2 .25 6.75h 6070h 0.5 2 2 2 1 7.5h 0.5 1 0.25 Temp RT 80/80/73 80/80/73 25/25/25 80/80/73 80/80/73 80/80/73 80/80/73 80/80/73 80/80/73 80/80/73 100/90/90 100/90/90 100/90/90 100/90/90 120/90/90 120/90/90 120/90/90 120/90/90 100/90/90 100/90/90 100/90/90 100/90/90 100/90/90 100/90/90 100/90/90 100/90/90 100/90/90 100/90/90 100/90/90 25/25/25 GasA N/A H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 GasC N/A N2 Air N2 N2 Air O 2 Air N2 Air O 2 Air N2 Air O 2 Air N2 Air O 2 Air N2 Air O 2 Air Air Air Air N2 Air O 2 Air N2 N2 Action Setup Humidify Breakin Cooldown CO/CV IV IV IV CO/CV IV IV IV CO/CV IV IV IV CO/CV IV IV IV CO/CV IV IV IV Stability Stability Stability CO/CV IV IV IV Cooldown CO/CV LeakandResistanceTests DisassembleCell Notes Includesleaktest,resistance,etc. At0.55V 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm 1.5atm,400mA/cm2 1.5atm,400mA/cm2 1.5atm,400mA/cm2 1.5atm 1.5atm 1.5atm

53

AppendixE:FluorideConcentration MeasurementsTestProcedure
E1CheckingElectrodeOperation
Note1.CheckElectrodeOperationeverydaybeforebeginningmeasurements Note2.Atalltimesuseastirringplateandbar. Note3.BeforeandaftereachmeasurementrinseelectrodeinDIwater
E1.1 Suggested Equipment i. 2 250mLbeakers(1formeasurementand1torinseelectrode) ii. 1 10mLmeasuringcylinder iii. 2 50mLmeasuringcylinders(1forDIwaterandoneforTISABII) iv. 1 2000mLbeaker(forwaste) v. 1 DIwaterwashbottle vi. 1 glasspipettewithbulb E1.2 Procedure i. Mix50mLofDIwaterwith50mlofTISABII. ii. ImmerseElectrodeintosolution iii. Pipette1mLofeither0.1Mor100ppmFstandardintothemixture.Recordthe equilibratedreading(mV). iv. Add10mLmoreofthesamestandardtothemmixtureandagainrecordthe equilibratedreading(mV). v. Thedifferencebetweenthetworeadingsshouldbeintherangeof5460 mV/decadeat25C.IfthatisnotthecaserefertoTROUBLESHOOTING.

E2FluorideConcentrationMeasurements
Note1.Atalltimesuseastirringplateandbar. Note2.BeforeandaftereachmeasurementrinseelectrodeinDIwater
E2.1 Direct Calibration Note1.Forsamplewithconcentrationsgreaterthan1ppm. Note2.Calibrateeverydaybeforebeginningmeasurements Note3.Usethreestandardsthatcoverthewholerangeoftheconcentrationsofthesamples thataremeasured(e.g.1,10and100ppm) E2.1.1 Suggested Equipment i. 4250mLbeakers(3forstandardsand1torinseelectrode) ii. 250mLmeasuringcylinders(1forTISABIIandoneforDIwater) iii. 12000mLbeaker(forwaste)

54

iv.

1DIwaterwashbottle

E2.1.2 Procedure i. Mix50mLofthemostdilutestandardand50mLofTISABII(for1,2and100ppm thestandardsarealreadymixedwithTISABIIandareusedasgiven) ii. InsertelectrodeintosolutionandpressCalibrate.Waitforanequilibratedreading (inppm)andsetthevaluetothevalueofthestandard(e.g.1ppm). iii. InsertelectrodeintonextstandardandpressCalibrate.Waitforanequilibrated reading(inppm)andsetthevaluetothevalueofthestandard(e.g.10ppm). iv. Repeatwithfinalstandard(e.g.100ppm) v. PressMeasure.Recordslopethatisgiven(mV) Theelectrodeisnowcalibratedfortherangeof1to100ppm.Checkingtheelectrodeagainst thestandardsduringmeasurementisrecommended. E2.2 Calibration Curve Note1.Forsampleswithconcentrationslesserthan1ppm Note2.Makeacalibrationcurveeverydaybeforebeginningmeasurements Note3.UselowlevelTISAB(LLTISAB,madeinhouseusingprocedureinE2.2.1)forall measurements E2.2.1 Making LL-TISAB
Useverypurereagentsavoidmetalioncontamination,especiallyaluminumandironastheyform complexeswithfluoride

E2.2.1.1 Suggested Equipment i. 12000mLbeaker(forbulksolution) ii. 1100mLmeasuringcylinder iii. 1calibratedpHelectrode iv. 1250mLbeaker(forrinsingelectrode) v. 1glasspipettewithbulb vi. 1DIwaterwashbottle vii. 12000mLvolumetricflask(forLLTISAB) viii. 1500mLvolumetricflask(forNaOH) E2.2.1.2 Procedure i. Addca.1000mLofDIwatertothelargebeaker ii. Add114mLofpureglacialaceticacid iii. Add116gofpuresodiumchlorideandstir iv. Weigh100gofsodiumhydroxideintovolumetricflaskandmakeupto500mlwith water(cooliniceifnecessary) v. Immerseelectrodeintolargebeakerandadd5MNaOHuntilapHof5.05.5is achieved(makesureallsolutionsareatthesametemperature) 55

vi.

PutLLTISABintovolumetricflaskandmakeupto200ml

E2.2.2 Making Standard ThisstandardisusedtomaketheCalibrationCurve

E2.2.2.1 Suggested Equipment: i. 1400mLbeaker ii. 15mLpipettewithpump iii. 250mLmeasuringcylinders E2.2.2.2 Procedure: i. Measure5mLof100ppmFstandardintoameasuringcylinderandmakeup to50mL ii. Measure50mLofLLTISABandcombinethetwosolutionsinthebeaker
E2.2.3 Making Calibration Curve TheCalibrationCurveisneededtoconvertfrommVtoppm

E2.2.3.1 Suggested Equipment: i. 2 250mLbeakers(1formeasurementand1torinse electrode) ii. 1 1mLpipettewithpump iii. 2 50mLmeasuringcylinders(1forLLTISABandoneforDI water) E2.2.3.2 Procedure: i. Measure50mLofDIwaterand50mLofLLTISABintoabeaker ii. Rinse,immerseelectrodeintosolutionandrecordthereading(mV) iii. Add1mLofthestandard,leavetoequilibrateandrecordthereading(mV) iv. Repeat3untilallexpectedconcentrationsofFarecovered(atleast15mL arerecommended) v. PlotasemilogarithmicgraphofmVagainstppm Note.Additionof1mLofstandardisca.0.1ppm,5mLofstandardisca.0.47ppmand10mL ofstandardis0.9ppm
E2.3 Measuring Samples with Concentrations Greater than 1 ppm Note.Forsampleswithconcentrationsgreaterthan1ppm,directcalibrationofelectrodeis required.UseTISABIIforallmeasurements. E2.3.1 Suggested Equipment: i. 1 5mLpipettewithpump(forsamples)

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ii. iii. iv. v. vi. vii.

2 250mLbeakers(1formeasurementand1torinseelectrode) 2 50mLmeasuringcylinders(1forDIwaterandoneforTISABII) 1 2000mLbeaker(forwaste) 2 1000mLbeakers(1forDIwaterandoneforTISABII) 1 glasspipettewithbulb(forTISABII) 1 DIwaterwashbottle

E2.3.2 Procedure: i. Measure5mLofsampleintomeasuringcylinderandmakeupto50mLwith DIwater ii. Measure50mLofTISABIIandcombinebothcylindersinabeaker iii. Rinseelectrode,immerseinbeaker,leavetoequilibrateandrecordthe reading(ppm) iv. Repeatwithothersamples

InputalldataintoExcel,converttomoles/(cm2h)(equation:ppmx2/(25x19))andplotvs hours.
E2.4 Measuring Samples with Concentrations Less than 1 ppm Forsampleswithconcentrationslesserthan1ppm,uselowlevelTISAB(LLTISAB)forall measurements E2.4.1 Suggested Equipment: ii. 1 5mlpipettewithpump(forsamples) iii. 2 250mLbeakers(1formeasurementand1torinseelectrode) iv. 2 50mLmeasuringcylinders(1forDIwaterandoneforLLTISAB) v. 1 2000mLbeaker(forwaste) vi. 2 1000mLbeakers(1forDIwaterandoneforLLTISAB) vii. 1 glasspipettewithbulb(forLLTISAB) viii. 1 DIwaterwashbottle E2.4.2 Procedure: i. Measure5mLofsampleintomeasuringcylinderandmakeupto50mLwithDI water ii. Measure50mLofLLTISABandcombinebothcylindersinabeaker iii. Rinseelectrode,immerseinbeaker,leavetoequilibrateandrecordthereading (mV) iv. Repeatwithothersamples

UseCalibrationCurvetodeterminetheppmvaluesforeachmVreading.Inputalldatainto Excel,converttomoles/(cm2h)(equation:ppmx2/(25x19))andplotvshours.

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E3ElectrodeCleaningandStorage
E3.1 Electrode Cleaning I
Note.Ifelectrodeisnotfunctioningproperly,e.g.wrongslopeordriftingofvalues,thenitmayhelpto cleantheelectrode

i. ii.

Holdelectrodeinonehandandusethumbtopresscapdown,therebydrainingthe electrode RinseanddrainwithDIwaterandthenrefilltojustbelowtheholewithElectrode FillingSolution

E3.2 Electrode Cleaning II Iftheabovedoesnothelpthisisknowntohelp: i. UsingarubbergloveorKimWiperubtheelectrodeforaminutewithsomeordinary toothpaste(actsasaslightabrasive) ii. RinsethoroughlywithDIwaterandsoakinDIwaterforanhour iii. Ifdesired,refillthefillingsolutionasabove E3.3 Electrode Storage I Note.Thisisforwhentheelectrodewillbeusedwithinaweek

Iftheelectrodewillnotbeinuseforaweekorless,storetheelectrodeinthelowest concentrationstandard(i.e.1ppmF)
E3.4 Electrode Storage II Note.Thisisforwhentheelectrodewillnotbeusedwithinaweek i. Iftheelectrodewillnotbeusedforalongerperiodoftime,drainandrinsethe electrodewithDIwaterasdescribedinA1andleavetodry. ii. Putcaponelectrodeandstorydryinasafeplace.

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AppendixF:SafetyPlan
Contract Number: DE-FC36-06GO16028

Prepared By: Darlene Slattery Date: June 30, 2006 Modified: May 1, 2007

Approvals

James R. Fowler, FSEC CHO

Ali T-Raissi, HRD Division Director

James M. Fenton, FSEC Director

James Uhlir , UCF EH&S Director

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Project Title: LeadResearchandDevelopmentActivityforDOEsHighTemperature,Low

RelativeHumidityMembraneProgram Contract Number: DEFC3606GO16028 Prepared By: DarleneSlattery Date: June30,2006 Project Officer: DavidPeterson

F1ScopeofWork
Florida Solar Energy Center (FSEC), a research institute of the University of Central Florida, has been designated as the lead organization for DOEs High Temperature, Low Relative Humidity Membrane Program. As such, FSECs research and development team will prepare and evaluate new polymeric electrolyte phosphotungstic acid composite membranes. Additionally, FSEC will develop standardized experimental methodologies to 1) measure conductivity (in plane and throughplane) 2)characterize mechanical,mass transport, and surface properties of the membranes and 3) predict durability of the membranes and their membrane electrode assemblies. Work to stabilize and reduce particle size of the phosphotungstic acid that has lead to the highest conductivity membranes and highest performance membrane electrode assemblies, which surpass Nafion, at 100 120 oC and low relative humidity will continue. NonNafion based poly[perfluorosulfonic acids] (PFSAs) of equivalent weight lower than 1100; sulfonated poly(ether ether ketone)s (SPEEKs) with various sulfonation degrees; sulfonated poly(ether ketone ketone) (SPEKK) as the protonconducting component in a blend with either poly(ether sulfone) (PES) or SPEKK with different sulfonation levels will be fabricated into new composite membranescontainingsmallparticlestabilizedphosphotungsticacid.Thisteam,workingwith the fuel cell community, will develop standardized experimental methodologies to 1) measure conductivity as a function of relative humidity and mechanical properties of membranes, 2) characterize mechanical, mass transport, and surface properties of the membranes, and 3) predict durability of the membranes and their membrane electrode assemblies fabricated by the team for both the inhouse research program and for membranes provided by the High Temperature,LowRelativeHumidityMembraneWorkingGroup(HTMWG)members.FSECwill provide the HTMWG with standardized tests and methodologies and short course education offerings on these test methodologies along with membrane electrode assembly fabrication techniques so that at the end of three years all research program members will be able to perform this work in their own facility. An easilyimplemented protocol and rapid test apparatus for evaluating the throughthickness conductivity (or resistance) of membranes over a broad range of conditions will be developed. FSEC will use its experience in developing accredited standardized test methods for the solar thermal, photovoltaic and building energy efficiencyindustriestosupportthisactivity. ThisprogramwillbeconductedwithintheHydrogenR&DDivisionattheFloridaSolarEnergy Center,locatedinCocoa,Florida.Thefacilitieswithinthedivisioninclude:

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 HydrogenLabI 2,000squarefootchemicallab HydrogenLabII1,800squarefootchemicallab IntegratedFuelCellTestBed(IFCT)facilitya900squarefootfuelcelllab Researchactivitiesinthesefacilitiesinclude: Alternativefuels Fuelcells Highpressure,hightemperaturereactions Hydrogenenergysystems Hydrogenmembraneseparation Hydrogenproductionandstorage Materialfailuredetermination Materialpropertydetermination Nanosynthesisandmaterialsdevelopment Photoandthermocatalyticreactionandreactorengineering Photocatalyticandphotoelectrochemicalprocesses Pollutantdetoxification Sensorsanddetectors Synthesisofmetalhydridesandchemicalhydrides Thermalimaging
The researchers in the Division are scientists and engineers with extensive backgrounds in all aspects of hydrogen research. Nine of the staff researchers have Ph.D.s and three have M.S. degrees.Theyareassistedbyanumberofstudents,whichvariesforanygivensemester. Ultimate responsibility for meeting deliverables will rest with the project PI. However, he has appointed a Project Manager who will be responsible for oversight of the day to day tasks involved in the project. The Project Manager will work closely with the FSEC Chemical Hygiene Officer(CHO)toensurethatalltasksarecarriedoutinasafeandresponsiblemanner.

F2IdentificationofSafetyVulnerabilities
The University of Central Florida has a Chemical Hygiene Plan that the Florida Solar Energy Centerfollowsforallprograms. Underthatplan,theDepartmentofEnvironmentalHealthand SafetyChemicalHygieneOfficer(CHO)istaskedwithreviewingcontractproposalstodetermine the inclusion of hazardous chemicals or procedures. When they are identified, EH&S consults with the proposals Principal Investigator (PI) to ascertain the level of risk. It is the responsibility of the PI to choose the best method for project analysis. FSEC also has its own CHOwhoassiststheFSECPIswithchemicalhygieneandcompliance,andwhomaintainsFSECs chemicalsafetydocumentation. To fulfill the requirements of this contract, researchers will prepare polymer solutions and modify them by the addition of phosphotungstic acid and/or via sulfonation. Membranes will be cast and tested. Tests will include inplane and throughplane conductivity, swelling, 61

mechanicalstrength,chemicalstrengthandglasstransition temperature. Membranesdeemed worthy of additional analysis will be catalyst coated and developed as a membrane electrode assembly,MEA. Safety vulnerabilities are identified using a What if analysis. A process flow chart for the project was developed and each area was reviewed by the research team. Vulnerabilities thus identified include exposure to organic vapors during membrane fabrication; fire resulting from improper preparation or handling of catalysts; hydrogen leakage from a cylinder, regulator, or system;andlossofventilationbecauseofpowerfailureinfacility.

F3RiskMitigationPlan
F3.1 Organic Vapor Exposure Anumberofsolventswillbeusedinthepreparationofthemembranes.Becauseoftheimpact ofhumidityonthemembranes,itwasdeterminedthatmembranepreparationwasbestcarried out in the controlled environment of a glove box. A glove box dedicated to this process along with the appropriate personal protective equipment, PPE, will protect the membranes while ensuringthatthescientistisnotexposedtothesolventsduringthecastingprocess. F3.2 Catalyst Handling The finely divided catalysts on support material are known to be flammable when an alcohol is added to the dry material (SOP). A procedure, that includes the addition of water before the alcoholic solvent is added, which has been verified in earlier programs, will be used. Additionally, catalyst spraying will be carried out in a fume hood to limit worker exposure. Organic materials, such as paper toweling, will not be used in the hood where catalysts are beingsprayed. F3.3 Hydrogen Leaks Hydrogen leaks will be determined with both a hand held detector for checking systems and with an area detector in the area most prone to the presence of hydrogen. Hydrogen that flows through a fuel cell unreacted will be vented directly to a fume hood. In the event of a facility power failure that would result in a system shutdown, a valve will automatically shutdown the flow of hydrogen to the system. Gas cylinders not currently in use hydrogen as well as other gases will be capped and removed to the storage area that is separate from the laboratory. Before every procedure involving the use of hydrogen, the entire system will be checkedforleaksusingthehandheldleakdetector.

Maximumamountsofhydrogentobeusedhavebeencalculatedonthepremisethatalltest standsaresimultaneouslyinuse.Insuchaninstance,therewouldbelessthan8L/minof hydrogenflowing.Thiswasdeterminedbaseduponthefollowing: 1.SingleCell: Assuming 25cm2MEA

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80oCoperation H2Stoichiometry=3 1.5A/cm2max H2flow=9.01mL/min@1Ax25x3x1.5=1014mL/min 2).EnduranceTestCell=1014mL/minmax 3).DiagnosticTestCell=1014mL/minmax 4).4CellStack=4x1014mL/min=4056mL/minmax 5).ConductivityTestCell:500mL/min Add1)through5)gives =1014+1014+1014+4056+500=7598mL/min=7.958litre/min
F3.4 Standard Operating Procedures Before initiating any activity, a standard operating procedure (SOP) will be identified. If none has been identified for the particular activity, it will be developed in collaboration with the teammembermostfamiliarwiththeprocess.Oncedeveloped,theSOPwillbeapprovedbyan internal HR&D Procedures Committee, headed by the Project Manager, before it is put into practice. Any changes to an SOP must be put in writing, with justifications and possible ramifications and approved by the committee. All SOPs will be signed by the developer, dated and, once approved by the Procedures Committee; a copy will be placed at the point of use. AdditionalcopieswillbeavailableintheCHOsofficeandonCDineachlaboratory.

CurrentSOPsinclude: Preparationofmembranesolutions Manufactureofmembranes Protonationofmembranes HeattreatmentofMEAs Membraneleaktest PEMFCunitcelltest Catalystdeposition AdditionalSOPscurrentlyunderdevelopmentinclude Inplaneconductivitytest Throughplaneconductivitytest Wateruptakemeasurement Glasstransitiontemperaturedetermination In addition to SOPs for individual tests, under the Chemical Hygiene Plan, all researchers in the laboratory are required to wear safety goggles, lab coats and, when handling chemicals, the

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correct gloves. They are also required to wear closed toed shoes and no food or drink is allowedanywhereinthelabs.
F3.5 Previous Experience with Hydrogen All researchers in the Hydrogen R&D Division have extensive experience with hydrogen. While thejuniormembershaveasfewas35yearsofhydrogenrelatedexperience,seniormembers have as much as 30 years of experience. In addition to experience in assembling and testing of fuel cells and fuel cell components, various researchers within the group are experts in cryogenics, hydrogen storage in metal hydrides, chemical hydrides and complex hydrides, hydrogen production via electrolysis, photocatalytic water splitting, and several reformation processesandseparationprocessesusinghydridesandmembranematerials.Asaresultofthis experience, all are qualified in the safe handling of hydrogen and systems, which use or producehydrogen.

In the 17 years that FSECs hydrogen laboratories have existed, only four incidents have occurred, three of which were very minor and none of which resulted in injuries. Only one was directlyrelatedtohydrogenandwastheresultofafailedOringinasystem.Allincidentswere thoroughly reviewed, weaknesses identified and procedures modified. Each incident emphasizedthatsafetyprecautionsinplaceminimizeddamagetothesurroundings.
F3.6 Safety Performance Measurement and Management of Change Reviews Checklists have been developed and will be used to record accomplishment of the steps in a procedure. These checklists will be filed in binders kept at the location of each activity. Periodic monitoring of the checklists will be conducted by the project manager to ensure that proceduresarebeingfollowed.

The FSEC CHO will make monthly laboratory inspections to determine the presence of any hazard. Identified hazards will be corrected in cooperation with the project PI, the researcher and the CHO and any necessary changes to procedures will be made. To minimize repeat hazards,remedialtraininginsafepracticeswillbeprovided,ifnecessary. A checklist of the inspection will be made and filed in a binder in the CHOs office. The checklists will be reviewed periodically to determine the need to make procedure changes to eliminaterepeathazards. Before changes are made to any equipment or procedures and before any new activities are initiated, a review will be conducted with the researcher(s) involved, the project manager, the CHOandothersasdeemednecessarybytheprojectmanager.
F3.7 Employee Training The University of Central Floridas Environmental Health and Safety Department, EH&S, requires all laboratory personnel to take a Chemical Safety and Environmental Management course.Thiscourseisgivenatthebeginningofeachtermonthemaincampusoftheuniversity orcanberequestedatanytimeforgroups.Inadditiontotheinitialcoursefornew employees, allemployeesarerequiredtotakearefreshercourseyearly.

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In addition to the EH&S provided training, training videos on a variety of subjects have been obtainedandmadeavailabletoallemployees.Newemployeesarerequiredtoviewthevideos and complete the corresponding worksheet, which is filed by the CHO. Topics of these videos include general lab practices such as the use of glassware and balances, and a general safety videothatincludesuseoffireextinguishersandhandlingofgascylinders. The topics of this course include basic lab practices, chemical hygiene, waste management,and fire safety. More specific training is provided by EH&S for other areas such as Radiation safety and Biohazard Safety. The CHO or the individual researcher is responsible for training on specific instruments or any specialized apparatus or equipment in the laboratory. The FSEC CHO and the PI train new personnel on the safe handling of hydrogen and other flammables to be used for a project. Training includes proper handling of gas cylinders, leak checking, proper venting and purging of systems and materials compatibility. Refresher training requirements are determined by the CHO or PI based upon employee performance. The CHO maintains electronic and hard copies of the training history of all laboratory personnel as part of the ChemicalHygienePlan.

F3.8 Equipment Integrity Much of the testing of the membranes will be accomplished using 850C Compact Test Stations from Scribner Associates. These test stations feature automatic shutdown and N2 purge with under voltage, over current, over temperature, loss of supply pressures, low water, communicationsfailureorexternalalarm.Additionally,thereisamanualswitchforemergency shutdown. The test stands were installed and qualified by Scribner Associates. Routine inspection of these units will be carried out by the researchers who will be using them. Any maintenanceoftheunitswillbedoneinconsultationwithScribnerAssociates. NewequipmentorsystemsthatareinstalledwillbereviewedbytheCHOandProjectManager beforebeingcertifiedforusage.Tobecertified,aWhatifanalysiswillbeconductedandany safetyvulnerabilitiesidentifiedandproceduresdevelopedtomitigatethevulnerabilities. Routine maintenance of the laboratory safety equipment is conducted by the lab manager/CHO. Eye wash stations and showers are tested monthly and results recorded. The face velocity of fume hoods is verified semiannually by UCF EH&S personnel and results indicated on each hood. Fire extinguishers are checked periodically by the State Fire Marshall, whilesprinklersystemsandfirealarmsarecheckedbyFSECOperationspersonnel. F3.9 Maintenance of Safety Documentation TheChemicalHygienePlaninmaintainedbytheFSECCHOandacopyisavailabletostaffinhis office,whichislocatedwithinHydrogenLabI.Itisadditionallyavailableonlineviathe UniversityEH&Swebsite.Seethereferencesectionfordetails.

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MaterialSafetyDataSheets,MSDS,arefiledinasetofbindersandareavailableforall substancescurrentlyintheinventoryorusedpreviouslywithinthelabs.TheCHOisresponsible forobtainingandfilingtheMSDSandtheyarecontinuouslyavailableinhisoffice.Additionally, MSDSmaybeaccessedfromageneralusecomputerinthelaboratory.

F4CommunicationPlan
F4.1 Emergency Response Plan UCF has an Emergency Management Plan, available on the web at http://www.ehs.ucf.edu/Emergency/EMP%2020062007.pdf. This plan outlines the procedure for minor emergencies, such as a spill of less than 4 L of a chemical that is not acutely hazardous or an unknown. In this Plan, employees are advised to notify the laboratory manager or the principal investigator, PI, and use the available spill kits to clean up under the supervisionofthePI. In the event of a major emergency, such as a fire, explosion or a spill of more than 4 L or one that involves a chemical that is acutely hazardous, FSEC personnel have been instructed to leavethelabanddial911immediatelyfromasafelocation.Inaddition,BrevardCounty(where FSEC is located) has a Special Response Team for hazardous materials that is available 24/7 and is trained to deal with chemical spills or other incidents. Their number is posted by laboratory telephonesbuttheymayalsobesummonedbyrequeststo911. Each laboratory has posted on the door a list of phone numbers of individuals to call in the event of an incident within that laboratory. Nonemergency issues are reported to these contact individuals. Laboratories have spill kits, fire extinguishers, fire alarms, safety showers and eye wash stations. Most FSEC labs also have glass view panels in the walls for quick visual assessmentofphysicalconditionsin thelab. F4.2 Incident Reporting and Lessons Learned All incidents are reported to the individual supervisor and FSECs laboratory manager/CHO. Incidents that result in damage or injury must be written up for submission to the Environmental Health and Safety Department on the main campus. If damage or injury has occurred, the incident is presented to and is discussed at the next FSEC Executive Committee Meetingandadecisionismadeonfurtheraction. At a minimum, the individual involved and his/her supervisor reviews the activities leading up to the incident, determines a probable cause and modifies procedures and/or the setup in ordertoavoidarecurrence AsrequiredinSection4.3oftheCommunicationsPlanoftheDOEGuidanceforSafetyAspects ofProposedHydrogenProjects,allincidentsandnearmissesmustbereportedtoDOE.

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F5SampleHandlingandTransport
The materials that are expected to be transported will be membranes fabricated by other members of the HTMWG and shipped to us for testing. These are not considered hazardous materialsand,therefore,theirtransportisnotanissue. UCF and FSEC have procedures for shipping materials that are considered hazardous. A member of the EH&S Department is qualified to package such materials for shipment. When the need arises for such shipments, packing materials that meet DOT guidelines are obtained andtheEH&SemployeecomestoFSECandpreparesthepackage.

F6References
UCFEnvironmentalHealth&Safety www.ehs.ucf.edu ChemicalSafetyInformation,CHP www.ehs.ucf.edu/chemical/main.html EmergencyInformation,UCF www.ehs.ucf.edu/emergency/main.html CityofCocoa,Florida(Police&Fire) www.cocoafl.org/City%20Services/ BrevardCounty,Florida(Hazmat) www.brevardcounty.us/fire_rescue/

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AppendixG FacilitiesandInstrumentation
Facilities exist at FSEC and the University of Central Floridas Material Characterization Facility Advanced Materials Processing and Analysis Center to allow complete fabrication and characterizationofmembranesandmembraneelectrodeassemblies.

G1MembraneFabrication
i. ii. iii. Controlled temperature and humidity fabrication stations containing several levellingtables Ovenequippedwithavacuum(IsotempVacuumOvenModel281A) Balances

G2MembraneElectrodeAssemblyFabrication
i. ii. iii. iv. v.

Ultrasonicblender(FisherScientificGen1000Homogenizer) XZSpraysystem ScreenprintingMachine Hotpress(CarverAccustamp) Oven(FisherScientificIsotempOven)

G3ElectrochemicalCharacterization
i. ii. 4teststations(ScribnerAssociatesFuelCellTestSystems850C(3)and890(1)),with MEADScomingsoon(ScribnerAssociates8cellteststation) 3Potentiostats(PrincetonAppliedResearch263A(2)and273(1))

G4MaterialsCharacterization
i. ii. iii. iv. v. vi. vii. viii. ix. x. xi. xii. XRayDiffraction TransmissionElectronMicroscopy ScanningElectronMicroscopy(withEnergyDispersiveXrayAnalysis) XRayPhotoelectricSpectroscopy AugerSpectroscopy DifferentialScanningCalorimetry ThermalGravimetricAnalysis FourierTransformInfraredSpectroscopywithAttenuatedTotalReflectance MechanicalTensileStrengthTesting FluorideIonElectrodeAnalysis IonChromatography GasChromatographywithMassSpectrometry

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