NorthEast CenterforChemicalEnergyStorage(NECCES)M.StanleyWhittingham(BinghamtonUniversity)

EFRCmissionstatement

Developanunderstandingofhowkeyelectrodereactionsoccur,andhowtheycanbecontrolledtoimproveelectrochemicalperformance,fromtheatomisticleveltothemacroscopiclevelthroughoutthelife-timeoftheoperatingbattery.

(Focusisonintercalationelectrodesandonlithium)

http://necces.binghamton.edu

TheNECCESTeambringstogetherthenecessarymultidisciplinaryskills(experiment,theory,characterization)toachieveourmission

2

AssociateMembers TechnicalandAdminSupportStaff

NorthEast Center for Chemical Energy Storage h"p://necces.binghamton.edu

DirectorM.StanleyWhi:ngham

Thrust1Intercala2on:M.StanleyWhi:ngham

Understandingtheintercala=onmaterialitself

(bulkmaterial)

FIT1.1BeyondOlivines:Coordinator:M.S.Whi:ngham

Goal1:A"ainreversiblemul=-

electrontransferinacathode

materialusinglithium

Thrust3Cross-Cu?ngDiagnos2cs:KarenaChapman

Developtheessen=alcharacteriza=ontoolsto

supportThrusts1and2

AssociateDirectorGlennAmatucci

Thrust2ElectrodeTransport:GlennAmatucci

Understandperformancelimi=ngtransportat

theelectrodelevel

InternalScienceAdvisoryBoard:

ClareGrey&GerbrandCeder

FIT1.2Oxides:Coordinator:Y.ShirleyMeng

Goal2:Closethegapbetweenthetheore=calandprac=calenergy

densityforintercala=oncompounds

FIT2-1:LocalLevelEvolu2onofIonicandElectronicTransport:Coordinator:GlennAmatucci

FIT2-2:Transport;mesoscalethroughmacro:

Coordinator:Yet-MingChiang

ExternalScienceAdvisoryBoard(SAB):

BillBushong/Rayovac,GeorgeCrabtree/ANL,Claude

Delmas/Inst.ofSolidStateChemistry,LindaNazar/U.of

Waterloo,DanielScherson/CaseWesternReserveU.&

VenkatSrinivisan/LBNL

EFRCmissionstatementDevelopanunderstandingofhowkeyelectrode

reac2onsoccur,andhowtheycanbecontrolledtoimproveelectrochemicalperformance,fromthe

atomis2cleveltothemacroscopiclevelthroughoutthelife-2meoftheopera2ngbaRery.(Focusison

intercala2onelectrodesandonlithium)

Goal3:Understandperformancelimi=ngtransportinposi=veelectrode

structuresfromthelocalthroughthemesotothemacroscale.

Informalongoingadvice

Formalannualreviewofscien4fic

progress

Focusonin-situandoperando,Na4onalUserFacili4esplayanessen4alrole

Atomiclevel Par4clelevel Electrodelevel

Grey,CambridgeMRI

Chupas,ArgonneX-raytomography

Meng,UCSD&Cabana,UICStrainandchemicalmapping

withCXDI&X-raymicroscopies

Zhou,Binghamton&Batson,RutgersSurfaceandchemicallysensi=veTEM

X-raytools NMRChapman,Chupas,ArgonneXRD,PDF,XAS:

AMPIXcell

Grey,CambridgeNMR:auto-tuning

probe

Ong,UCSDtheory

Whi?ngham,ChernovaBinghamton

synthesis,TEM,electrochemistry

Piper,Binghamtonspectroscopy(XPS,XAS)

Chapman,ArgonneXRD,PDF

VanderVenUCSBtheory

ZhouBinghamton/BNL

EnvironmentalTEM

Meng,UCSDelectrochemistry,

XRD,ND,CXDI

GreyCambridge

NMR

Cabana,UICX-ray

microscopy

ChapmanArgonneXRD

Amatucci,Pereira,Rutgerssamplefabrica=on,XRD,

electrochemistry,microcalorimetry

Ceder,UCBtheory

Piper,Binghamtonsurface

characteriza=on

Batson,CosandeyRutgersHRTEM-EELS

Chiang,MITelectronicandionic

transportmeasurements

Thornton,Michiganmodelingacross

mul=plelengthscales

Modelcompoundε-LixVOPO4 ModelcompoundLiNi0.8Co0.15Al0.05O2(NCA)

ThismaterialisbaseduponworksupportedaspartofNECCES,anEnergyFron?erResearchCenterfundedbytheU.S.

DepartmentofEnergy,OfficeofScience,OfficeofBasicEnergySciencesunderAwardNumberDE-SC0012583.

Cross-cu:ng

characteriza=on

atalllengthscales

Howdosurfacereac2onsinducetransportissues?•  Surfaceoxygenloss− Newphasesincreaseimpedance

•  Theorydefiningsurfacestates•  Electrolyteiskeyplayer

ModelcompoundsfromThrust1:currentlyLiNi0.8Co0.15Al0.05O2(NCA)andvariantsWheredoesimpedancegrowthoriginate?• Interfacialreac=onislimi=ngathighSOC

• Exchangecurrentvariesby10xathighSOC• Meso/microscalesimula=onsconcur

• Newsinglepar=clemeasurementcapability

• ε-LiVOPO4reversiblyintercalatesLi

• Itisa1Ddiffuser• Synthesiscri=cal• VOPO4reactsslowly

• IsLi2VOPO4unstable?

•  1-2%NionLisite.•  PO2affectsphasechanges•  Two-phaseinNCAevolving•  Highdefectdensityatsinglepar=cle

a

b

c

shell(V3+)shell(V4+)core(V5+)

Atomistic Phases 2Theta

Defects P"="400"mTorr"

RT,"vacuum"

RT,"oxygen"150"°C"

200"°C"

250"°C"300"°C"

350"°C"

400"°C"

RT,"vacuum"

RT,"oxygen"150"°C"

200"°C"

300"°C"

P"="0.2"mTorr"

250"°C"

350"°C"400"°C"

O Activity

NCAparticle

Tungsten Pt

3

NorthEast CenterforChemicalEnergyStorage(NECCES)Four-YearResearchGoalsFocusonIntercalationCathodes

Today’sbatteriesAttainonlyaround25%oftheirtheoreticalcapacity.

EFRCresearchgoals

1. Attainreversiblemulti-electron transferinacathodematerialusinglithium,focusedonthemodelcompound,LixVOPO4.

2. “Closethegap” betweenthetheoreticalandpracticalenergydensityforintercalationcompounds,focusedonthemodelcompound,LiNi0.8Co0.15Al0.05O2.

3. Understandperformancelimitingtransportinpositiveelectrodestructuresfromthelocalthroughthemeso tothemacroscale.

KineticsvsThermodynamicsBeyondLiFePO4:LixVOPO4 a2electronsystem

TheOlivineLiFePO4• Behavesasasinglephasesystem,LixFePO4

• WhenreactionrateisgreaterthantimeforLiionstoorder• Theoreticalmodel,designedexperimentsandoperandostudies

Goal:Attainreversiblemulti-electron transferinacathodematerial• Focusonaphosphatematerialand2Liintercalation?

• Modelcompound,LixVOPO4.• SevenphasesofVOPO4 known• Thermodynamics,kineticsofreaction,phasesnowunderstood

• Kineticsarecomplexandcontrolphasesformed• Goalattained

• Synergistictheory,experimentandoperandocriticaltosuccess• Stillmuchtounderstandandcontrol

H-VOPO4

C/25

a

b

c

Characterizationandcontrolofmatterawayfromequilibrium?Goal:“ClosingtheGap”onthelayeredoxides.LiMO2

Modelcompound:NCA- LiNi0.85Co0.1Al0.05O2• RoleofAluminumandpseudophasetransitionsidentified

• HeterogeneityatNCAmateriallevelisthetruereasonforthepseudophasetransitionatlowvoltage

• AldistributionisuniforminthebulkanditsroleathighvoltageiscomplexGoal:Attainoptimum0.9MLi(>250mAh/g) inthelayeredoxidecathodematerials

• Focusonthebulkstructuralfactorsandsurface/interfacialphenomenaKineticlimitationofLitransportcanlimittheutilizationoffullenergydensity.

• Bulkintergranular crackingatsecondaryparticlelevelobserved• LocalenvironmentofdopedAlundergoescomplexchangesathighvoltagerange

Goalattained• SynergybetweenFIT1.2(Bulk)andFIT2.1(Interface)criticaltosuccess• ApplywhatwelearnttoNMCclassofcathodes- controlphase

transitionsandinterfacialstability

Pushingthefrontiersofoperandocharacterization.KeyroleofNationalLabstounderstandourmodelcompounds

SynchrotronX-raycapabilities:Visualizereactionheterogeneity• Expandedoperandocapabilities(AMPIX)tomultiplemonthstoidentify

changesintheatomic-scale reactionmechanismlinkedtocapacityfade• Operandospectromicroscopic imagingrevealsthepropagationofreactions

withinsecondarycathodeparticles.• Depthprofilestudiesofreactionprogress

demonstrateshowheterogeneitydevelopsinthickelectrodes

NMR• Combined17ONMRandfirstprinciplescalculationsforthefirsttimeto

probeOenvironmentsinparamagneticlayeredcathodessuchasNCA.• DevelopedanautomatictuningNMRprobethattunestheresonantcircuit

duringoperandomeasurements,improvingsignaltonoiseandfacilitatesoperandostudiesofbroadresonances(7Liand31PinLiVOPO4)

Goalattained• Synergistictheoryandoperandoexperimentcriticaltosuccess• Understandingandcontrollingheterogeneityatmultiplescalesis

criticaltoperformance

NECCESPresentationsthisweekdemonstratesynergisticinteractionbetweenexperiment,theoryandcharacterization

TALKS• INTEGRATED EXPERIMENTAL-COMPUTATIONAL INVESTIGATION OF TRANSPORT KINETICS IN

POLYCRYSTALLINE BATTERY-ELECTRODE PARTICLES - YET-MING CHIANG – M-D-2:30PM• THE MATERIALS PHYSICS OF LITHIUM (DE)INTERCALATION IN LAYERED OXIDE CATHODES – MAX

RADIN – T-D-2:30PM• ADVANCES IN NMRMETHODOLOGY OF PARAMAGNETIC LI-ION BATTERY CATHODE MATERIALS –

IEUAN SEYMOUR – T-D-9:50AM• THERMODYNAMIC STABILITY,VOLTAGE AND DIFFUSION KINETICS OF LIXVOPO4 (X=0,1,2)VANADYL

PHOSPHATE POLYMORPHS:JOINT FIRST-PRINCIPLES AND EXPERIMENTAL – YUH-CHIEH LIN,MARCHIDALGO AND SHAWN SALLIS (STUDENT-POSTDOC COMPETITION) – T-D-8:30AM

POSTERS• IDENTIFYING THE CHEMICAL AND STRUCTURAL IRREVERSIBILITY IN LINI0.8CO0.15AL0.05O2 - A MODEL

SYSTEM FOR CLASSICAL LAYERED INTERCALATION – SHIRLEY MENG – M-D-5:00PM• ELECTROCHEMICALLY INITIATED SURFACE CHEMISTRIES INHIBITING THE REALIZATION OF

THEORETICAL CAPACITY OF LINI0.8CO0.15AL0.05O2 – GLENN AMATUCCI – M-D-5:00PM• NEXT GENERATION OF VANADIUM-BASED MULTI-ELECTRON CATHODE MATERIALS – NATASHA

CHERNOVA – M-D-5:00PM• INSIGHT INTO REALIZING THE FULL 2LI+ CAPACITY OF MULTI-ELECTRON LIXVOPO4 – LOUIS PIPER• ADVANCING OPERANDO TOOLS TO PROBE MULTISCALE COMPLEXITY IN CHEMICAL ENERGY

STORAGE – KARENA CHAPMAN – T-D-3:30PM