IV–22DOE Hydrogen and Fuel Cells Program FY 2014 Annual Progress Report

Donald L Anton (Primary Contact), Theodore Motyka, Bruce J Hardy, David A Tamburello and Claudio CorgnaleSavannah River National Laboratory (SRNL)Bldg. 999-2WAiken, SC 29808Phone: (803) 507-8551 Email: DONALD.ANTON@SRNL.DOE.GOV

DOE Managers Ned StetsonPhone: (202) 586-9995Email: Ned.Stetson@ee.doe.govJesse AdamsPhone: (720) 356-1421Email: Jesse.Adams@ee.doe.gov

Technical AdvisorRobert BowmanPhone: 818-354-7941Email: rcbjr1967@gmail.com

Subcontractors• PacificNorthwestNationalLaboratory(PNNL),

Richland, WA• UnitedTechnologiesResearchCenter(UTRC),

E. Hartford, CT• GeneralMotorsCorporation(GM),Dearborn,MI• FordMotorCorporation(Ford),Dearborn,MI• TheNationalRenewableEnergyLaboratory(NREL),

Golden, CO• Los Alamos National Laboratory (LANL), Los Almaos,

NM• TheJetPropulsionLaboratory(JPL),Pasadena,CA• TheUniversityofMichigan(UM),AnnArbor,MI• TheCaliforniaInstituteofTechnology(CalTech),

Pasadena, CA • OregonStateUniversity(OSU),Corvallis,OR• HexagonLincolnLLC,Lincoln,NB• UniversityofQuébec,TriosRivieres(UQTR),TroisRivieres,QC,Canada

ProjectStartDate:February1,2009 Project End Date: June 30, 2015

Overall Objectives Developsystemmodelsthatwilllendinsightintooverall•fuelcycleefficiency.

Compileallrelevantmaterialsdataforcandidatestorage•mediaanddefinefuturedatarequirements.

Developengineeringanddesignmodelstofurtherthe•understanding of onboard storage energy management requirements.

Developinnovativeonboardsystemconceptsformetal•hydride, chemical hydrogen storage, and adsorbent materials-based storage technologies.

Designcomponentsandexperimentaltestfixturesto•evaluate the innovative storage devices and subsystem designconcepts,validatemodelpredictions,andimprovebothcomponentdesignandpredictivecapability.

Design, fabricate, test, and decommission the subscale •prototypecomponentsandsystemsofeachmaterials-based technology (adsorbents, metal hydrides, and chemical hydrogen storage materials).

Fiscal Year (FY) 2014 Objectives

Management Work Scope

Coordinationandfacilitationofpartner’sactivities:•

Organize and conduct one face-to-face Center –Technical Meeting

OrganizeandparticipateinTechTeamReview –

Publish Integrated model on the HSECoE website –

CompleteconstructionofPhase3prototypes –

Updatedprototypesystemtestingplanforboth•adsorbent and chemical hydrogen systems

Technical Work Scope

Design and construct two hydrogen cryo-adsorbent test •stationscapableofevaluatingtheperformanceofa2-literprototypeoperatingbetween80-160Kand5-100bar.

TestStation#1–Flow-throughcoolingconceptwith –a resistance-based heater

TestStation#2–Isolated-fluidcooling/heating –concept

Design and construct two 2-liter adsorbent subscale •prototypes:

Hexagonalheatexchanger(HexCell)Design–Flow- –throughcoolingconceptwitharesistance-basedhexagonalheatexchangerdevelopedforpowderadsorbent

ModularAdsorptionTankInsert(MATI)Design– –Isolated-fluidcooling/heatingconceptdevelopedforcompactedadsorbent

Completetestmatrixforevaluationofthe2-liter•adsorbent system.

IV.B.1 Hydrogen Storage Engineering Center of Excellence (HSCoE)

IV–23FY 2014 Annual Progress Report DOE Hydrogen and Fuel Cells Program

IV.B Hydrogen Storage / Engineering – HSECoEAnton – Savannah River National Laboratory

Updatethecryo-adsorbentsystemmodelswithPhase•3performancedata,integratethemodelsintotheframework, document the models, and release them to thepublic.

Refinethedetailedmodels(validate)forscaleupand•alternativehydrogenstorageapplications.

Determineminimallyacceptableadsorbentmaterial•propertiestomeetthe2017andultimatesystemtargets.

Technical BarriersThisprojectaddressesthefollowingtechnicalbarriers

fromtheHydrogenStoragesectionoftheFuelCellTechnologiesOfficeMulti-YearResearch,Development,andDemonstration Plan:

(A) System Weight and Volume

(B) System Cost

(C) Efficiency

(D) Durability/Operability

(E) Charging/DischargingRates

(G) Materials of Construction

(H)Balance-of-Plant(BOP)Components

(J) Thermal Management

(K) SystemLife-CycleAssessments

(L) LackofTankPerformanceDataandUnderstandingofFailureMechanisms

(O) LackofUnderstandingofHydrogenPhysisorptionandChemisorption

(R) By-Product/SpentMaterialRemoval

Technical TargetsThisprojectdirectsthemodeling,design,build,and

demonstrationofprototypehydrogenstoragesystemsforeach material class (metal hydride, chemical hydrogen storage and hydrogen adsorbent) meeting as many of the DOE Technical Targets for light-duty vehicular hydrogen storage. The current status of these systems versus the Onboard Hydrogen Storage System Technical Targets as of the end of Phase 2 is given in Table 1.

Center Wide Accomplishments

The following are landmark innovations that the HSECoE can claim to have lead which have changed the way we think about hydrogen storage systems and the materials which are used in them. Overall, the DOE Technical Targets

P has e 2 HS E CoE Targets

(M ateria l)

P has e 2 HS E CoE Targets

(B O P only )

P has e 2 HS E CoE Targets

(S y s tem )

P has e 2 HS E CoE Targets

(M ateria l)

P has e 2 HS E CoE Targets

(B O P only )

P has e 2 HS E CoE Targets

(S y s tem )G ravam etric Capac ity k g H2/k g s y s tem 0.055 0.187 0.10 0.0352 0.0872 0.15 0.055

mass kg 102 16.1 159 102V olum etric Capac ity k g H2/L s y s tem 0.04 0.03 0.053 0.0175 0.078 0.132 0.049

Volumetric liters 140 16.9 320 114S y s tem Cos t $/k W h net 6 3.5 5.62 12.74

$ 1,119 1048 2376Fuel Cos t $/gge at pum p 2-6 4.89M in O perat ing Tem p °C -40 -40 -20M ax O perat ing Tem p °C 60 60 60M in Delivery Tem p °C -40 -40 -20M ax Delivery Tem p °C 85 85 85Cy c le Life Cy c les 1500 1500 1000M in Delivery P res s ure bar 5 5 5M ax Delivery P res s ure bar 12 12 12O nboard E ffic ienc y % 90 92 95W ell to P ower P lant E ffic ienc y % 60 39.2 37S y s tem F ill Tim e m in 3.3 3.3 2.9M in Full F low Rate (g/s /k W ) 0.02 0.02 0.02

g/s 1.6 1.6 1.6S tart Tim e to Full F low (20°C) s ec 5 5 1S tart Tim e to Full F low (-20°C) s ec 15 15 1Trans ient Res pons e s ec 0.75 0.75 0.5Fuel P urity % H2 99.97 99.99 99.97

P erm eation, Tox ic ity , S afety S c c /hM eets or E x c eeds

S tandardss s

Los s of Us eable Hy drogen (g/h)/k g H2 s tored 0.05 0.44 0.05

Projected System HSECoE Go/No-GoWhat could be built in the future

(full scale)

Target Units

2017 DO E G oal

(S y s tem )

Phase 2 Actual

(automotive scale)

Adsorbent System Chemical Systyem

Table 1. System Status vs. Technical Targets

Anton – Savannah River National Laboratory IV.B Hydrogen Storage / Engineering – HSECoE

IV–24DOE Hydrogen and Fuel Cells Program FY 2014 Annual Progress Report

wereprioritizedshowingthatvolumetricdensityismoreimportantthangravimetricdensitywhenrangeandspaceare considered. Integration of the hydrogen storage system modelsincludingthefuelcell,balanceofplant,andvehicledrivecycleswereusedtodeterminetheemptytankstatusundertheUS06drivecycle.

Formetalhydridestorage,ametalhydrideacceptabilityenvelopeshowingtheinterrelationshipoftheenthalpy,specificheat,thermalconductivity,andgravimetricdensityinapostulatedmaterial’sabilitytomeettherefuelingtargetwasaccomplished.Amicrochannelcatalyticburnerwasdemonstrated achieving a volumetric density record for oxidizinghydrogenandreturntheavailableheatinausefulform to the storage system.

ForchemicalhydrogenstoragetheHSECoEidentifiedthataslurrywasneededtotransportthehydrogencarriermaterialintoandoutofacontrolledtemperaturereactor.ThedefinitionofslurrystoragematerialcharacteristicsnecessarytomeettheDOETechnicalTargetswasidentified.An Auger reactor for slurries and a helical reactor for neat liquidsallowingtheuniformtransportofthechemicalhydrogen carrier into a thermally controlled reactor for dehydrogenation were shown. Demonstration of a viable 60 wt% alane slurry into an auger reactor with controlled hydrogen discharge.

ForadsorbentstoragetheHSECoEidentifiedtherequirementforaliquidnitrogenjackettankcoolingstrategywhichrapidlydissipatestheenthalpyofadsorptionand cools the adsorbent allowing achievement of the three minute refueling time technical target. Demonstration of a novellow-costflow-throughheatexchangerdesignwhichallowsfortherapidcoolingoftheadsorbentmediaduringrefuelingandevenheatdistributionduringoperationwasalsoshown.Combinedmetalorganicframework(MOF)compactionandaugmentationwiththermalconductivityenhancementsachievedhydrogenadsorptiondensities50%greaterthanconventionalpowderpackinghadpreviouslyachieved.Developmentofamicrochannelheatexchangerdesignallowingfortheuseofcompactedadsorbentmediaachievinga10%reductiontotalsystemvolume.DevelopmentoftheadsorbentacceptabilityenvelopeoutlinesthenecessaryadsorbentpropertiesusingtheUNILANmodelshowingthenecessityforadsorbedhydrogendensityof≥120mol/Kgandanisostericheatof4.6KJ/mol.

Technical Accomplishments

Small-scale(0.5-literflangedvesselwithaHexCellHX)experimentsandmodelsforpowderMOF-5:

Verificationthatphysicalprocessesareproperly –included/represented

Flow-throughcoolinghydrogenchargingexperiments –werecompletedandmodelswerevalidated

Resistive heating rod hydrogen discharging –experimentswerecompletedandmodelswerevalidated

Phase3HexCellexperimentsandmodelvalidation:•

PrototypeteststationatUQTRwasbuiltandtested –

2-liter vessel with resistive rod heater within a –hexagonalheatexchanger

Designcompleted -

AssembledandinstrumentedatUQTR -

Model for the 2-liter tank in three-dimensional –geometry with 90o symmetry

Modelrunningsuccessfullywithpreliminary -test cases

Leveragedpreviousexperiencefromthe -0.5-liter tank

Testmatrixcompleted –

PreliminaryexperimentsatUQTRhavebegun –

Phase3MATIexperimentsandmodelvalidation:•

PrototypedesignhasbeencompletedwithOSU –

PrototypeteststationatSRNLdesigncompleted –

Allcomponentspurchasedandonsite -

Test station is 80% assembled with electrical left -tocomplete

Preliminarytestmatrixcompleted –

G G G G G

InTroduCTIon The HSECoE brings together all of the materials and

hydrogen storage technology efforts to address onboard hydrogenstorageinlight-dutyvehicleapplications.Theeffortbeganwithaheavyemphasisonmodelinganddatagatheringto determine the state of the art in hydrogen storage systems. Thiseffortspannedthedesignspaceofvehiclerequirements,powerplantandbalanceofplantrequirements,storagesystemcomponents,andmaterialsengineeringefforts.Thesedataandmodelswillthenbeusedtodesigncomponentsandsub-scaleprototypesofhydrogenstoragesystemswhichwillbeevaluatedandtestedtodeterminethestatusofpotentialsystemsagainsttheDOE2017andUltimateFullFleetTechnical Targets for Hydrogen Storage Systems for Light-Duty Vehicles.

ApproACH A team of leading North American national laboratories,

universities, and industrial laboratories, each with a high

IV–25FY 2014 Annual Progress Report DOE Hydrogen and Fuel Cells Program

IV.B Hydrogen Storage / Engineering – HSECoEAnton – Savannah River National Laboratory

degreeofhydrogenstorageengineeringexpertisecultivatedthroughpriorDOE,international,andprivatelysponsoredprojectshasbeenassembledtostudyandanalyzetheengineeringaspectsofcondensedphasehydrogenstorageasappliedtoautomotiveapplications.Thetechnicalactivitiesof the HSCoE are divided into three System Architectures: adsorbent, chemical hydrogen storage and metal hydride matrixedwithsixtechnologyareas:PerformanceAnalysis,IntegratedPowerPlant/StorageSystemAnalysis,MaterialsOperatingRequirements,TransportPhenomena,EnablingTechnologiesandSubscalePrototypeConstruction,TestingandEvaluation.Theprojectisdividedintothreephases;Phase1:SystemRequirementsandNovelConcepts,Phase2:NovelConceptModelingDesignandEvaluation,andPhas3:Subscale System Design, Testing, and Evaluation.

rESulTSSRNLandUQTRtodatehavemetandorexceeded

theirFY2014objectivesforalloftheirmajortechnicalgoalswithin the HSECoE. These objectives fall within the areas of TransportPhenomena,AdsorbentSystemLevelModeling,MaterialOperatingRequirements,andSystemArchitecture.TransportPhenomenaandAdsorbentSystemModelingresults are shown below for adsorbent systems.

Transport phenomena

ComponentlevelexperimentsforMOF-5chargingand•dischargingina0.5-literflow-throughcoolingsystemwere conducted.

Flow-throughcoolingwasdemonstratedforthe –chargingprocess.

Heating via a resistance rod imbedded in an –aluminumhexagonwasusedforthedischargeprocess.

Heating(discharge)experimentsalongwith -computationalcomparisonscompletedformultipleconfigurationsincludingheatingexperimentswithemptyHexCells,heatingexperimentswithalumina-filledHexCells,andheatingexperimentswithMOF-5powder-filledHexCells.

Modelsdeveloped/appliedbySRNLreplicatethe•experimentalconditions

Validation of models against the 0.5-liter –experimentaldataforseveralflow-throughcoolingandresistanceheaterdesorptionexperimentstoverifythatthephysicalprocessesareproperlyincluded/represented.

Figure1showsrepresentativeresultsbetweenthe –experimentaldataandcomputationalmodelforpowderMOF-5,initiallyat3.5MPahydrogen,77Katvesselsurface,andnooutflow.

TheHexCellHXdistributesthermalenergy -well.

Resultsareshownforauniformheaterpower -profile;comparisonsarealsogoodforaparabolicheaterpowerprofile.

Bothexperimentalmeasurementsandnumerical –modelsoftheheating/dischargetechniqueshowedthattheHexCellHXdistributesthermalenergywell.

2-literHexCellprototypeexperimentsandmodels•

Designed and assembled vessel and internal –componentsofthe2-literprototype(asshowninFigure2)andtheHexCellprototypeteststand(asshowninFigure3).

Theprototypetestfacilityhasbeencompleted, -withcapabilitiesofhydrogenflowratesupto1,000splm.

Developedatestmatrix –

Conductedpreliminaryexperimentsinambient –temperatureandabove

Createdathree-dimensionalcomputationalmodel –geometry with a 90o symmetry (as shown in Figure2),whichissuccessfullyrunningandshowsgoodagreementwiththepreliminaryambienttemperatureexperiments.

Currently working on solutions for the 2-liter vessel –sealleakissueatcryogenictemperatures.

2-literMATIprototypeexperimentsandmodels•

AssistedOSUinthedesignofthe2-literprototype –anditsinternalcomponents(showninFigure4).

Designed and began assembly of the MATI –prototypeteststand,showninFigure4,withthefollowingcapabilities:

Gassupplies: -

H - 2at80Kand>100slpmLN - 2at~7barand80KN - 2at>373Kand>100slpm

Dataacquisition: -

Pressureandtemperatureatalltankinlets/ -outletsMassflowcontrolandmeasurementsofall -gas/liquidflows

BeganconstructionoftheMATIprototypetest –stand,withcompletionscheduledforAugust,2014.

Adsorbent System level Modeling

The MATLAB• ®-version of the cryo-adsorbent system modelshasbeenupdatedtoreflectthelatestinputfromallHSECoEpartnersforbothoftheHexCelland

Anton – Savannah River National Laboratory IV.B Hydrogen Storage / Engineering – HSECoE

IV–26DOE Hydrogen and Fuel Cells Program FY 2014 Annual Progress Report

Figure 1. 0.5-Liter Vessel Experimental Data and Model Comparison

Figure 2. 2-Liter HexCell Prototype Assembly and Computational Model

IV–27FY 2014 Annual Progress Report DOE Hydrogen and Fuel Cells Program

IV.B Hydrogen Storage / Engineering – HSECoEAnton – Savannah River National Laboratory

Awiderangeofthermo-physicalproperty –correlationsfor0.1bar<P<450barand20K<T<450K.

Excludingpressureandtemperature,thereare –atotalofover60,000systemparameteroptioncombinations.

The Simulink• ® version of the cryo-adsorbent system modelsisbeingupdatedfromtheMATLAB-versioninpreparationforitsinclusionin“ModelsontheWeb.”

ConCluSIonS And FuTurE dIrECTIonSMetal hydride efforts were terminated based on the

judgmentthatnoknownmaterialwascapableofmeetingeitherthe2017orultimatetargetsinasystemconfiguration.Ultimately,ametalhydrideisneededwhichwillhaveacapacityof10-11wt%hydrogenandanenthalpyof25-27KJ/moleH2toavoidtherequirementofconsumingasignificantportionofthestoredhydrogen.Nometalhydrideis currently foreseen that meets this very demanding target.

Chemical hydrogen storage efforts were centered on slurry/solventmaterialsutilizingflowthroughreactor

MATI system designs. Note that the system models havethefollowingcapabilities,withallsubroutineshavingexpansionabilitiesshouldadditionaloptions/improvementsbeavailable/desirable:

First-ordersystemandindividualcomponentcost –estimates.

Overall system ranks based on a value algorithm –developedbyFordthatincorporatesthesystemcost,gravimetriccapacity,andvolumetriccapacity.

Dubinin-Astakhovparametersforhydrogenstorage –within several cryo-adsorbents (single and multi-componentversionsareavailable).

Internaltankheatexchangerconcepts,wherethe –massandvolumeoftheheatexchangerisadaptablebasedontheproperties(andamount)ofthecryo-adsorbent.

A tank design algorithm, with a wide variety of –materialanddimensionaloptions,whichwasdevelopedbyPNNLwithinputfromSRNLandHexagonLincoln.

Figure 3. 2-Liter HexCell Prototype Test Stand

Anton – Savannah River National Laboratory IV.B Hydrogen Storage / Engineering – HSECoE

IV–28DOE Hydrogen and Fuel Cells Program FY 2014 Annual Progress Report

overallsystemperformanceprojections,theprojectedcosts,theprojectedinteractionwiththeforecourt,andthefuturedirection of adsorbent material research.

FuturetechnicalworkbySRNLintheadsorbentareawill include:

Continue to verify and determine solutions for the 2-liter •vesselsealleakissueatcryogenictemperatures.

PreliminarytestplanfortheHexCellprototype:•

Pressureteststhe2-litervesselwithouttheHexCell –structure inside the tank to check the characteristics of the tank (volume, thermal mass, etc.)

Performance evaluation of the heating rod –(temperatureprofiles)

Flow-throughcooling/chargingtestswithpowder –MOF-5

Heating/desorptiontestswithpowderMOF-5 –

Cycle testing, with charge-discharge-charge, etc. –

developmentwithdynamictemperaturecontrol,high-flowgasliquidseparationandimpuritytrapping.Furtherstudieswereconductedonendothermicvs.exothermicchemicalhydrogenstoragematerialswiththeidentificationofvariousstart-stopcyclesdeeplyinhibitingattainmentoftheonboardefficiencytarget.Ultimately,thechemicalhydrogenstoragematerials efforts were terminated based on the regeneration costs and other associated technology factors outside of the HSECoEscope.

Adsorbent system efforts are concentrated on Phase 3 prototypedesign,assembly,testing,andmodeling,includingteststationdesign,construction,andcapabilitiesverification.Twoprototypesarebeingtested(andmodeled)inPhase3;(1)powderMOF-5inaHexCellthatutilizesflow-throughcooling during refueling and resistance heating during dischargewillbetestedatUQTRandmodeledatSRNL,and(2)compactedMOF-5inaMATIutilizingisolatedliquidnitrogenduringrefuelingandisolatedhydrogenduring discharge will be tested at SRNL and modeled at OSU.Severalfactorsaffectedthisselection,includingthedetailedmodelanalyseswithexperimentalvalidation,the

Figure 4. 2-Liter MATI Prototype Test Stand

IV–29FY 2014 Annual Progress Report DOE Hydrogen and Fuel Cells Program

IV.B Hydrogen Storage / Engineering – HSECoEAnton – Savannah River National Laboratory

FY 2014 puBlICATIonS/prESEnTATIonS BY Srnl/uQTr 1.HardyB,CorgnaleC,TamburelloD,AntonD.“Acceptabilityenvelopeforadsorptionbasedhydrogenstorage”InvitedpresentationatMCARE2014,Clearwater(FL),USA.

2.PasiniJM,CorgnaleC,VanHasselB,MotykaT.,KumarS,SimmonsK.“Metalhydridematerialrequirementsforautomotivehydrogenstoragesystems”InternationalJournalofHydrogenEnergy, Volume 38, Issue 23, 2013, Pages 9755–9765

3.“HydrogenStorageMaterials:ASystemPerspectiveastoWhatIsNeededforTransportationApplications”,D.L.AntonInvitedPresentation at Gordon Conference 2013, Barga, Italy.

FY 2014 pATEnTS BY Srnl/uQTr 1.Tamburelloet.al.,HeatTransferUnitMethodforPrefabricatedVessel,61/905,557,12/12/2013.

Completeconstructionandcapabilitiesverificationofthe•MATIprototypeteststand.

PreliminarytestplanfortheMATIprototype:•

Pressure test the 2-liter vessel without the MATI –structure inside the tank to check the characteristics of the tank (volume, thermal mass, etc.)

PerformanceevaluationoftheMATI(temperature –profiles)

Cooling/adsorptiontestswithcompactedMOF-5 –

Heating/desorptiontestswithcompactedMOF-5 –

Cycle testing, with charge-discharge-charge, etc. –

UpdateSimulinkcryo-adsorbentsystemmodelsto•predictfull-scalesystemperformance.

Makeupdatedsystemmodelsavailablefor“models –ontheWeb.”