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
