IV–29FY 2013 Annual Progress Report DOE Hydrogen and Fuel Cells Program

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: [email protected]

DOE Managers Ned StetsonPhone: (202) 586-9995Email: [email protected] AdamsPhone: (720) 356-1421Email: [email protected] Technical AdvisorRobert BowmanPhone: (818) 354-7941Email: [email protected]

Subcontractors:• PacificNorthwestNationalLaboratory(PNNL),

Richland, WA• UnitedTechnologiesResearchCenter(UTRC),E.

Hartford, CT• GeneralMotors(GM),Detroit,MI• FordMotorCompany.(FMC),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: March 31, 2015

Overall Objectives Developsystemmodelsthatwilllendinsightintooverall•fuelcycleefficiency.

Compileallrelevantmaterialsdataforcandidatestorage•mediaanddefinefuturedatarequirements.

Developengineeringanddesignmodelstofurtherthe•understanding of onboard storage energy management requirements.

Developinnovativeonboardsystemconceptsformetal•hydride,chemicalhydrogenstorage,andadsorptionhydride 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) 2013 Objectives

Hydrogen Storage Engineering Center of Excellence (HSECoE) Management

Coordinationandfacilitationofpartner’sactivities•

OrganizeandconductoneF2FCenterTechnical –Meeting.

Publish two metal hydride models on the HSECoE –website.

CompletePhase3Go/No-Gorequirements. –

Completebalanceofplant(BOP)andcostanalysisfor•adsorbentsystem(performanceandcostanalysis).

Completebalanceofplantandcostanalysisforchemical•hydridesystem(performanceandcostanalysis).

Completeprototypesystemtestingplanforboth•adsorbent and chemical hydride systems (integrated powerplantandstoragesystemmodeling).

Demonstrateadsorbentsystemheating(transport•phenomena).

Demonstratestableflow-throughreactordesignfor•slurryammoniaborane(AB)(transportphenomena).

Identifyscale-upmethodsforslurryAB(materials•operatingrequirements).

Identifyoptimumadsorbentpackingstrategies(materials•operatingrequirements).

Submitforpublicationtwopeerreviewedjournal•articlesoutliningtherequiredmaterialspropertiesneeded to meet the DOE System Technical Targets for adsorbentsandchemicalhydrides(materialsoperatingrequirements).

IV.B.1 Hydrogen Storage Engineering Center of Excellence

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

IV–30DOE Hydrogen and Fuel Cells Program FY 2013 Annual Progress Report

Demonstratestablegasliquidseparatordesign(enabling•technologies).

Completemanufacturinganalysistodetermineadsorbent•systemdown-selectpriority(enablingtechnologies).

Identify and design one adsorbent system to go forward •with in Phase 3.

Identify and design one chemical hydride system to go •forward with in Phase 3.

SRNL HSECoE Technical Work Scope

DesignapparatusforheatingtheadsorbenttoyieldH2•dischargeonanappropriatetimescaleandcompatiblewithflow-throughcooling.

IdentifyformofMOF-5tobeusedinprototypeandsub-•scaleprototypetests.

Apply/developsystemmodelsto:•

Determinebestperformingmetal-organic –framework(MOF)form.

Determineconsumptionofstoredhydrogenfor –heatingandotherprocesses.

Identifyoptimalsystemdesignconcepts. –

Evaluatecoolingprocessesotherthanflow-through –cooling.

Developconceptofcooledtankwalltoreduceexhaust•H2requiredforflow-throughcooling.

Evaluatealternativemethodstoflow-throughcooling:•

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) System Life Cycle Assessments

(L) LackofTankPerformanceDataandUnderstandingofFailureMechanisms

(O) LackofUnderstandingofHydrogenPhysisorptionandChemisorption

(R) By-Product/SpentMaterialRemoval

Technical TargetsThisprojectdirectsthemodeling,design,build,and

demonstrationofprototypehydrogenstoragesystemsforeach metal hydride, chemical hydrogen storage, and hydrogen adsorptionmaterialmeetingasmanyoftheDOETechnicalTargets 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.

FY 2013 Accomplishments

Center Wide Accomplishments

CompletedPhase3Go/No-Gorequirements.•

Completedassessmentofchemicalhydrogenstorage•materials and systems. Will terminate work on these systemsduetolowprobabilityofidentifyingmaterialsthatmeet8.5wt%fluidgravimetricrequirementsandregenerationefficiencies.

Developeda6wt%H2liquidphasechemicalhydrogen•storage media having a viscosity before and after dehydrogenation below 1,500 cP.

Developeda45wt%ABslurryhavingaviscosityless•than 1,500 cP.

Developedaflow-throughreactorcapableofdischarging•0.8g/sH2froma40wt%ABfluid-phasecompositionhaving a mass of no more than 2 kg and a volume of no more than 1 liter.

Developedanammoniascrubberresultinginaminimum•ammoniaoutletconcentrationof0.1ppm(inletconcentration=500ppm)havingamaximummassof1.2kgandamaximumvolumeof1.6liters.

Designed a chemical hydrogen storage system based on •50%AB/Sioilhavingamassof137kgandavolumeof147 liters.

DemonstratedacompositeMOF-5adsorbentmonoliths•havingH2effectivekineticsequivalentto5.6kgusableH2overthreeminutesandpermeationinpackedandpowderparticlebedswithflowrateof1m/ssuperficialvelocityandpressuredropof5bar.

Completedassessmentofadsorbentstoragesystem.•Down-selectedboththeHexcelandmodularadsorbenttankinsert(MATI)heatexchangerdesignsforsubscaleprototypeadsorbentsystemstobeevaluatedinPhase3.

CompletedcompositeMOF-5adsorbentmonolithswere•demonstratedhavingH2effectivekineticsequivalentto

IV–31FY 2013 Annual Progress Report DOE Hydrogen and Fuel Cells Program

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

5.6kgusableH2overthreeminutesandpermeationinpackedandpowderparticlebedswithflowrateof1m/ssuperficialvelocityandpressuredropof5bar.

Completedcryogenicpressurevesselbursttesting•ofbothTypeIandIVcompositestanksat77Kandpressuresexceedingdesignlimits,provingtheefficacyofcompositecryogenic/compositepressurevessels.

Demonstratedaninternalflow-throughtheheat•exchangersystembasedoncompactedmediawasdemonstratedcapableofallowinglessthanthreeminutescaled refueling time and H2 release rate of 0.02 g H2/(sec.kW)withamasslessthan6.5kgandavolumeless than 6 liters.

Identifiedsystemconceptshavebeenidentifiedhavinga•mass less than 137 kg and a volume less than 279 liters meeting all of the HSECoE drive cycles.

Achievedawell-to-powerplantefficiencyof39.9%for•the80K/60-barsystemwhichis65%oftheultimatetargetof60%efficiency.

SRNL Technical Accomplishments

Demonstratedademonstrationofaflow-throughcooling•systemandvalidateddetailedmodelsforbothpowderMOF-5andcompactedMOF-5pellets.

Developedanadsorbentacceptabilityenvelope(AAE)•thatidentifiescoupledmaterialpropertiesandsystemdimensionsthataffectgravimetriccapacity,volumetriccapacity,chargingrates,andcharging/dischargingrates.

Designed, evaluated, and demonstrated heat transfer •technologies for cooling the adsorbent during the charge phaseandheatingitduringthedischargephase.

Charging is best achieved using LN – 2-assistedflow-through cooling.

WhilepelletizedMOF-5offerssomeimprovement –involumetriccapacity,thetimetochargeandthemassofthesystembothincreasecomparedtopowderMOF-5systems.

Down-selectedpowderMOF-5afterdetailedcomponent•andsystemlevelperformanceformodifiedformsincludingpelletsatdifferentlevelsofcompactionandamendedMOF-5containingadditivestoenhancethermal conductivity.

Developedafullycustomizablecryo-adsorbentsystem•modeltocomparepossiblefull-scalesystems.

Parametricstudy:reducedover½billionpossible –adsorbent system models down to two adsorbent systemsthatwillbeevaluatedasprototypesinPhase 3.

Table 1. System Status vs. 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 95Well to Power Plant Efficiency % 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

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

IV–32DOE Hydrogen and Fuel Cells Program FY 2013 Annual Progress Report

Projectedfuturesystemdesignsassumingpossible –system,component,and/ormaterialimprovementstoidentifysystemsthatcouldmeetorsurpasstheDOE 2017 Technical Targets.

G G G G G

INTRoduCTIoN The HSECoE brings together all of the materials and

hydrogen storage technology efforts to address onboard hydrogenstorageinlight-dutyvehicleapplications.Theeffortbeganwithaheavyemphasisonmodelinganddatagathering to determine the state of the art in hydrogen storage systems.Thiseffortspannedthedesignspaceofvehiclerequirements,powerplantandBOPrequirements,storagesystemcomponents,andmaterialsengineeringefforts.Thesedataandmodelswillthenbeusedtodesigncomponentsandsub-scaleprototypesofhydrogenstoragesystemswhichwillbeevaluatedandtestedtodeterminethestatusofpotentialsystem against the DOE 2017 light-duty vehicle technical targets for hydrogen storage systems.

AppRoACH A team of leading North American national laboratories,

universities, and industrial laboratories, each with a high degreeofhydrogenstorageengineeringexpertisecultivatedthroughpriorDOE,international,andprivatelysponsoredprograms,hasbeenassembledtostudyandanalyzethe

engineeringaspectsofcondensedphasehydrogenstorageasappliedtoautomotiveapplications.Thetechnicalactivitiesof the Center are divided into three system architectures; adsorbent, chemical hydrogen storage, and metal hydride, andarematrixedwithsixtechnologiesareas:PerformanceAnalysis,IntegratedPowerPlant/StorageSystemAnalysis,MaterialsOperatingRequirements,TransportPhenomena,EnablingTechnologiesandSubscalePrototypeConstruction,TestingandEvaluation.Theprojectisdividedintothreephases:Phase1:SystemRequirementsandNovelConcepts;Phase2:NovelConceptModelingDesignandEvaluationPhase; 3: Subscale System Design, Testing and Evaluation.

RESuLTSSRNLanditssubrecipientUQTRtodatehavemetand

orexceededtheirFY2013objectivesforalloftheirmajortechnical goals within the HSECoE. These objectives fall withintheareasofTransportPhenomena,AdsorbentSystemLevelModeling,MaterialOperatingRequirementsandSystemArchitecture.TransportPhenomenaandAdsorbentSystem Modeling results are shown below for adsorbent systems.

Transport phenomena

DevelopedanAAEthatidentifiescoupledmaterial•propertiesandsystemdimensionsthataffectgravimetriccapacity,volumetriccapacity,chargingrates,anddischargingrates.Figure1providesafunctionaldiagramof the AAE.

Figure 1. Functional diagram of the AAE.

IV–33FY 2013 Annual Progress Report DOE Hydrogen and Fuel Cells Program

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

TheAAEutilizescoupled,lumpedparameter, –transient energy, and mass balances that are solved numerically, accounting for the adsorbent material properties,theheatofadsorption,internalheatexchangerconcepts,storagevesseldesigns,andtheassumed BOP.

The AAE can be used to either evaluate adsorbents –withknownproperties(isotherms,thermalconductivity,specificheat,etc.)ortodeterminetheadsorbentpropertiesrequiredtomeetperformancetargets.

Carriedoutexperimentsfordifferentflow-through•coolingadsorbentsystems,withexperimentalconditionsanddatameasured.Theflow-throughcoolingconcept,whichappliestobothpowderandpelletbasedsystems,wastestedusingaspeciallydesignedreservoirwithaninternal diameter of 0.05 m and a length of 0.3 m. A two-dimensionalsketchofthereservoirisreportedinFigure2.

Detailed numerical models were validated against •dataforseveralflow-throughcoolingexperimentalconfigurations.Figure3providesanexampleoftheseexperimentalandcomputationalcomparisons.

MOF-5powderwithnointernalheatexchanger. –

MOF-5pelletswithinaHexcelinternalheat –exchanger,usingMaxSorbpowderasfillerinthevoidspacesaroundthepellets.

MOF-5powderwithinaHexcelinternalheat –exchanger.

Bothexperimentalmeasurementsandnumericalmodels•oftheflow-throughcoolingtechniqueshowedthattheperformanceofpowder-formadsorbentswassuperiortothatofpellet-form,asshowninFigure4.

Adsorbent System Level Modeling

The MatLAB• ® version of the cryo-adsorbent system modelshasbeenupdatedtoreflectthelatestinputfromallHSECoEpartnersforbothoftheprimarydesigns.Figure5showsthelatestversionoftheflow-throughcoolingwithaHexcelresistanceheaterdesign,whileFigure6showsthelatestversionoftheMATI-isolatedLN2/H2heatexchangerdesign.

Createdcryo-adsorbentsystemmodelimprovement•projections(usingtheMatLAB® versions) based on alteredversionsof“powderMOF-5”(changedtheDubinin-Astakhovparametersand/ormaterialpropertiesin“whatif”scenarios).Figure7showsexamplesoftheseprojections.

Both the Simulink• ® and MatLAB® versions of the cryo-adsorbentsystemmodelshavebeenupdatedtoincludethefollowingoptions,withadditionaltesting,debugging,andupdatesongoing.Notethatallsubroutineshaveexpansionabilitiesshouldadditionaloptions/improvementsbeavailable/desirable:

Firstordersystemandindividualcomponentcost –estimates.

Figure 2. Inside view of the reservoir used for pellet and powder-form experiments.

Teflon is a registered trademark of E. I. du Pont de Nemours and Company

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

IV–34DOE Hydrogen and Fuel Cells Program FY 2013 Annual Progress Report

regeneration costs and other associated technology factors outsideoftheHSECoEscope.

Adsorbent system efforts concentrated on material, subcomponent,andsystemcharacterizationandvalidationleadinguptothesystemselectionforprototypetestinginPhase3.Twoprevailingdesignswereidentified:1)powderMOF-5inahexagonalstructure(Hexcel)thatutilizesflow-through cooling during refueling and resistance heating duringdischarge,and2)compactedMOF-5inaMATIutilizing isolated-LN2 during refueling and isolated-H2 during discharge. Several factors affected this selection, includingthedetailedmodelanalyseswithexperimentalvalidation,theoverallsystemperformanceprojections,theprojectedcosts,theprojectedinteractionwiththeforecourt,and the future direction of adsorbent material research.

FuturetechnicalworkbySRNLintheadsorbentareawill include:

Validating,tuning,andrefiningthesystemmodel•estimatesoftheprototypeadsorbentsystemsinPhase3.

Validating,tuning,andrefiningthedetailedmodelsof•thePhase3Hexcelprototypedesign,whichusespowderMOF-5inanaluminumhexagonwithflow-through

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.

CoNCLuSIoNS ANd FuTuRE dIRECTIoNSChemicalhydrideeffortswerecenteredonslurry/

solventmaterialsutilizingflowthroughreactordevelopmentwithdynamictemperaturecontrol,high-flowgasliquidseparationandimpuritytrapping.Studieswerecontinuedonendothermicandexothermicchemical.Ultimately,thechemical hydride efforts were terminated based on the

Figure 3. Experimental data versus numerical simulations of MOF-5 powder with no internal heat exchanger.

Teflon is a registered trademark of E. I. du Pont de Nemours and Company

IV–35FY 2013 Annual Progress Report DOE Hydrogen and Fuel Cells Program

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

2. Gross K, Hardy B. Recommended Best Practices for CharacterizingEngineeringPropertiesofHydrogenStorageMaterials. V148: November 20, 2012. National Renewable Energy Laboratory Contract No. 147388.

3. Hardy B, Corgnale C. Adsorbent Based Hydrogen Storage SystemModels.Invitedpaperatthe2012WorldHydrogenEnergyConference Toronto, Ontario, Canada.

4. Anton D, Hardy B, Motyka T, Pasini JM, Van Hassel B, Corgnale C, Kumar S, Simmons K. Metal Hydride Hydrogen StorageforAutomotiveApplications:MaterialsandSystemChallenges. 2012 World Hydrogen Energy Conference, Toronto, Ontario, Canada.

cooling during refueling and resistance heating during discharge.

Buildinganexperimentaltestingfacility,designing,•fabricatingandevaluatingasubscaleprototypeflowthoughadsorptionsystemutilizingtheHexceldesign.

Buildinganexperimentaltestingfacilityandtestingthe•Phase3MATIprototypedesign,whichusescompactedMOF-5intheMATIwithisolated-LN2 cooling during refueling and isolated-H2 during discharge.

FY 2013 puBLICATIoNS/pRESENTATIoNS 1. Corgnale C, Hardy B, Anton D. Structural Analysis of Metal Hydride-Based Hybrid Hydrogen Storage Systems. International Journal of Hydrogen Energy, Vol. 37, Issue 19, 2012, Pages 14223-14233.

Figure 4. Computational analysis of MOF-5 pellet flow-over cooling versus MOF-5 powder flow-through cooling.

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

IV–36DOE Hydrogen and Fuel Cells Program FY 2013 Annual Progress Report

Figure 6. Overall system diagram for the MATI isolated-LN2/H2 heater design.

Figure 5. Overall system diagram for the flow-through cooling with a Hexcel resistance heater design.

IV–37FY 2013 Annual Progress Report DOE Hydrogen and Fuel Cells Program

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

Figure 7. Possible changes/improvements in the total system mass, total system volume, and estimated total system cost for an 80 K, 100 bar, Hexcel cryo-adsorbent system.