2008 MAFALDA project ANR PAN H OK ?· Cycles application Cycles réels Cycles réels simplifiés Analyse…

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  • Cyc

    les

    app

    licat

    ion

    Cycles rels Cycles relssimplifis

    An

    alys

    est

    atis

    tique

    Cycles relsmodifis

    4 TESTSrf.

    Modificationdes motifs

    Modification de la squencedes motifs

    4 tests par cycle modifi 16 TESTS

    OUI

    Nouveauxessais

    Suggestion de stratgies de

    fonctionnement

    Validationexprimentale

    Cyc

    les

    sim

    ple

    s

    Modification des conditions opratoires :- Tpile (Tmin, Tmax),- P (PH2max/Pair, PH2/Pairmax),- st (stH2max, stair max)

    6 tests par cycle modifi 24 TESTS

    20 TESTS

    Conditions opratoiresmodifies

    MODELISATION

    Impact des Impact des conditionsconditionsde cyclagede cyclage

    Impact des Impact des conditionsconditionsopratoiresopratoires

    MODELISATION Valid ?

    NON

    Lien avec les autres projets : DECODE, DVD-AME, SPACT-80

    Cycles simples, conditions opratoires de lapplication

    Cyc

    les

    app

    licat

    ion

    Cycles rels Cycles relssimplifis

    An

    alys

    est

    atis

    tique

    Cycles relsmodifis

    4 TESTSrf.

    Modificationdes motifs

    Modification de la squencedes motifs

    4 tests par cycle modifi 16 TESTS

    OUI

    Nouveauxessais

    Suggestion de stratgies de

    fonctionnement

    Validationexprimentale

    Cyc

    les

    sim

    ple

    s

    Modification des conditions opratoires :- Tpile (Tmin, Tmax),- P (PH2max/Pair, PH2/Pairmax),- st (stH2max, stair max)

    6 tests par cycle modifi 24 TESTS

    20 TESTS

    Conditions opratoiresmodifies

    MODELISATION

    Impact des Impact des conditionsconditionsde cyclagede cyclage

    Impact des Impact des conditionsconditionsopratoiresopratoires

    MODELISATION Valid ?

    NON

    Lien avec les autres projets : DECODE, DVD-AME, SPACT-80

    Cycles simples, conditions opratoires de lapplication

    Fix-

    +

    Fix-

    Fix-

    Fix-

    Fix-

    Fix-

    ++++

    HH++CoCo2+2+

    Compact layerCompact layer

    )),,(( txr

    ),( tr

    0=x

    Diffuse layerDiffuse layer

    Lx =

    ir

    Oxide (Oxide (----O)O)

    Intermediate reaction Intermediate reaction speciesspecies

    Adsorbed water Adsorbed water dipolesdipoles

    Surface catalyst layerSurface catalyst layerInner layer Inner layer

    )),(( trFix-

    OO22

    ++

    ++

    OH 2

    ++++

    ++++

    ++++

    ++++

    ++++

    ++++

    PtPt2+2+

    ++++

    ee--

    PtPtzz++, , CoCoyy++

    PtPtzz++, , CoCoyy++

    CC--supportsupport

    IonomerIonomer

    WaterWater

    GDL Channels

    Catalyst nano-particle

    Membrane

    e+

    H

    22 OOH +

    22 OOH +

    Carbon support

    OH 2

    e

    e

    e

    +2Co

    Cathode electrode

    e

    2O

    2O

    2O

    e

    e

    Impregnated ionomer

    +2Pt

    CutCut viewview

    ElectrodeElectrode

    Dr. Alejandro A. FrancoDr. Alejandro A. Franco11**, Dr. Olivier Lemaire, Dr. Olivier Lemaire11, Dr. Laure Guetaz, Dr. Laure Guetaz11, , RomainRomain CoulonCoulon11, Rodrigo Ferreira de Morais, Rodrigo Ferreira de Morais1,41,4, , Dr. Serge Dr. Serge GambarelliGambarelli22, Dr. Vincent Maurel, Dr. Vincent Maurel22, , Dr. Nicolas FouquetDr. Nicolas Fouquet33, Dr. Franck Masset, Dr. Franck Masset33, Dr. David Loffreda, Dr. David Loffreda44, Prof. Philippe Sautet, Prof. Philippe Sautet44

    11CEACEA--Grenoble/LITEN, Grenoble/LITEN, 22CEACEA--Grenoble/INAC, Grenoble/INAC, 33PSA Peugeot CitroPSA Peugeot Citron, n, 44ENS de LyonENS de Lyon--CNRS/CNRS/LaboratoireLaboratoire de de ChimieChimie*Contact: *Contact: alejandro.franco@cea.fralejandro.franco@cea.fr

    A.A. Franco et al., A.A. Franco et al., A Dynamic Mechanistic Model of an A Dynamic Mechanistic Model of an Electrochemical InterfaceElectrochemical Interface, , J. Electrochem.Soc.J. Electrochem.Soc., , 153153, A1053 (2006)., A1053 (2006).

    A.A. Franco et A.A. Franco et al.,al.,AA multimulti--scale dynamic mechanistic model for scale dynamic mechanistic model for transient analysis of PEFCtransient analysis of PEFC Fuel CellsFuel Cells, , 77, 99 (2007). , 99 (2007).

    MAFALDA ProjectMAFALDA Project (Feb09(Feb09--Jan12)Jan12)Experimental and Experimental and MModelingodeling AAnalyses nalyses ffor the or the

    PEFC PEFC AActive ctive LLayers ayers DDegradation egradation AAssessmentssessment

    MEMEPhysMEMEPhys: Invited lectures and oral presentations in about : Invited lectures and oral presentations in about 6464 international conferences international conferences (e.g. (e.g. americanamerican ElectrochemElectrochem. Soc.. Soc., , Int. Soc. ElectrochemistryInt. Soc. Electrochemistry)) all around the world all around the world (e.g. Qu(e.g. Qubec 2005, Vienna 2006, Chicago 2007, Miami 2007, Phoenix 2008, Vbec 2005, Vienna 2006, Chicago 2007, Miami 2007, Phoenix 2008, Vancouver 2008, Seville 2008, San Francisco 2009ancouver 2008, Seville 2008, San Francisco 2009). ). Invited seminars on Invited seminars on MEMEPhysMEMEPhys in high level institutes, e.g. Heidelberg University (2006), Stin high level institutes, e.g. Heidelberg University (2006), Stanford University (2007), British Columbia University (2008), Saanford University (2007), British Columbia University (2008), Santa Barbara (2009). nta Barbara (2009). 5656 publications on publications on MEMEPhysMEMEPhys in peerin peer--reviewed journals (reviewed journals (J. J. ElectrochemElectrochem. Soc.. Soc., , ElectrochemElectrochem. Soc. Trans.. Soc. Trans., , ElectrochimElectrochim. . ActaActa, , Fuel CellsFuel Cells) and proceedings + ) and proceedings + 153153 citationscitations 11 invited book in preparation by Dr. Franco (publisher: Pan Stanfinvited book in preparation by Dr. Franco (publisher: Pan Stanford) +ord) + 11 patent filled from the patent filled from the modelingmodeling results within MAFALDAresults within MAFALDA

    Publications, communications, patents

    OurOurapproachapproach

    advantagesadvantages

    More realistic description More realistic description of of electrocatalysiselectrocatalysis: :

    account for the nonaccount for the non--equilibriumequilibriumphysicochemical environment physicochemical environment

    Feedback instantaneous Feedback instantaneous performance performance degradationdegradation((prediction of durability as function prediction of durability as function of the materials and compositionsof the materials and compositions))

    Bridging spatiotemporal scales with Bridging spatiotemporal scales with reasonable reasonable

    computational efforts computational efforts

    Fast integration of new Fast integration of new physicochemical phenomena physicochemical phenomena

    ((study of study of synergies/synergies/interplayingsinterplayings))

    HydrogenHydrogen atomatom

    Equilibrated PtEquilibrated Pt--RhRh nanonano--structures in vacuum and structures in vacuum and in a Hin a H--rich environment:rich environment:

    reconstruction phenomenareconstruction phenomena

    IT

    PA, PCRHA, RHC

    instantaneous Ucell(t)

    Instantaneous cumulative materials losses

    instantaneous local operatingconditions

    instantaneousnano-micro-structure

    Co

    nro

    lpar

    amet

    ers Coupled no-aging

    phenomena

    Coupled aging phenomena

    Coupled agingCoupled agingphenomenaphenomena

    Coupled no agingCoupled no agingphenomenaphenomena

    Transient elementary Transient elementary kineticskinetics

    and electrochemical and electrochemical double layer effectsdouble layer effects

    (MF elementary kinetics + Monte Carlo)(MF elementary kinetics + Monte Carlo)

    Transient transfer phenomena Transient transfer phenomena --charges, Ocharges, O22, water, water--

    MEMEPhysMEMEPhys: : multiscalemultiscale mechanisticmechanistic model of the PEMFC electrochemical processes, scaling up model of the PEMFC electrochemical processes, scaling up abab initio initio concepts into anconcepts into an irreversible thermodynamics framework, accounting for:irreversible thermodynamics framework, accounting for:

    the MEA the MEA physicochemistryphysicochemistry at spatial NANO and MICRO scales (elementary kinetic approach at spatial NANO and MICRO scales (elementary kinetic approach nono ButlerButler--VolmerVolmer equations are used hereequations are used here).). the intrinsic MEA the intrinsic MEA nanomaterialsnanomaterials degradation and couplings between aging mechanismsdegradation and couplings between aging mechanisms

    Coupled agingCoupled agingphenomenaphenomena

    E.g. E.g. elementaryelementary kinetickinetic description of description of Pt Pt electrochemicalelectrochemical agingaging processesprocesses

    E.g. E.g. elementaryelementary kinetickineticdescription of HOR/ORRdescription of HOR/ORR

    PEMFC MEA durability prediction in automotive conditions: engineering challenges

    PEMFC are nonPEMFC are non--equilibrium electrochemical equilibrium electrochemical systems!systems! In PEMFC electrochemistry is dominated by In PEMFC electrochemistry is dominated by nanoscalenanoscale (quantum and interfacial) effects(quantum and interfacial) effects The The nanomaterialsnanomaterials reconstruct even without reconstruct even without polarization!polarization!

    Engineering requirement: Engineering requirement: improvement of PEMFC improvement of PEMFC nanomaterialsnanomaterials in terms of cost, in terms of cost, performance and durability.performance and durability. Physical modeling of the Physical modeling of the nanomaterialsnanomaterials properties and properties and behavior is crucial to suggest behavior is crucial to suggest new operating conditions filling new operating conditions filling these requirements. the