10先进铅酸电池用高性能碳添加剂-------雷汉伟

PerformanceCarbonAdditivesforAdvancedLeadAcidBatteries先进铅酸电池用高性能碳添加剂HanweiLei(雷汉伟),PaolinaAtanassova,AurelienDuPasquier,MikiOljaca2014SinoLead-acidBatterySummitOct.30-31,2014,Xuzhou,ChinaOutline•CabotIntroduction•CabotPBXTMPerformanceAdditivesforAdvancedLead-AcidBatteries•GoalsandRequirementsforAdvancedLeadAcidBatteries•RoleofCarboninImprovingChargeAcceptanceandCycleLifeatPartialStateofCharge(PSoC)•HighRateDischargeandWaterLossinHighCarbonBatteries•Summary2014SINOLEAD-ACIDBATTERYSUMMIT2CabotCorporationmanufacturingsiteaffiliateregionalheadquarters•NYSE:CBTsince1968•Founded1882•Globalperformancematerialscompany•46manufacturingsitesinover20countries•Coretechnicalcompetenciesinfineparticlesandsurfacemodification•FY2013salesof$3.5B2014SINOLEAD-ACIDBATTERYSUMMIT3SegmentsandBusinessesPerformanceMaterialsFumedMetalOxidesMasterbatchSpecialtyBlacksReinforcementMaterialsRubberblacksPurificationSolutionsBatteryMaterialsSecurityInkjetAerogelElastomerCompositesAdvancedTechnologiesSpecialtyFluids2014SINOLEAD-ACIDBATTERYSUMMIT4LeadingPositionscarbonblackfumedmetaloxidesinkjetcolorantsactivatedcarboncesiumformate#1#2#1#1#12014SINOLEAD-ACIDBATTERYSUMMIT5CoreCompetency-DesignandManufactureParticleMaterialsConductiveLowviscosityadditiveReinforcingPigments2014SINOLEAD-ACIDBATTERYSUMMIT6VariousApplicationsNeedLeadAcidBatterieswithImprovedPerformanceAutomotiveMicrohybridCars(Start-Stop)StationaryTelecom,RenewablesMotiveForkLiftsE-BikesE-MotorBikes2014SINOLEAD-ACIDBATTERYSUMMIT7Start-StopStationary,E-bikesMotiveStateofcharge[%]C-rate[h-1]0.11102050100PBX*GradePBX*LoadingPBX*PasteFormulationVRLA,FloodedVRLAFloodedHRPSoCDifferentApplicationsMightRequireDifferentSolutions2014SINOLEAD-ACIDBATTERYSUMMIT8PBXTMProductsPerformanceOverviewPBX092014SINOLEAD-ACIDBATTERYSUMMIT9Mechanismofcarboneffectnotcompletelyunderstoodbutcertainaspectsareclear:IncreasednegativeelectrodeactivesurfaceareaDepolarizationofthenegativeelectrodeSupercapacitiveeffectforhighsurfaceareacarbonsAdditionalnucleationsitesCarbonfacilitatesthechargereactionPbSO4PbbyprovidingconductivesurfaceareaforPbnucleationModificationofnegativeelectrodemorphologyCarbonparticlesaffectthePb/PbSO4crystallizationSizeofcrystallitesPorosityofelectrodeOptimizationofexpanderandpasteformulationneededLignosulfonateloadingAdditionalwaterCarbonAdditivesEnableImprovementsinDynamicChargeAcceptance(DCA)andCycleLife2014SINOLEAD-ACIDBATTERYSUMMIT10CarbonsCouldActasSeedforPbSO4/PbCrystallitesGrowthandChangePbSizeandSurfaceAreaPbArea2m2/gPbAreaforControl,0.5m2/gPbArea1m2/gCarbon,9m2/g+=0.5m2/gBETarea=10m2/g(totalBETarea)+8m2/g=10m2/g(totalBETarea)2014SINOLEAD-ACIDBATTERYSUMMIT1112NAMSurfaceAreaDependsonCarbonTypeandLoadingPbPb0123456789100246810121416NAMBETmeasured[m2/g]Theoreticalcarbonsurfacearea[m2/g]1%PBX510.5%PBX510.25%PBX510.25%PBX511%PBX091%PBX1350.5%PBX1352014SINOLEAD-ACIDBATTERYSUMMIT0.000.250.500.751.000.20.40.60.81.01.21.41.6SoC80%60%40%20%0%Chargepower/Wg-1Carbonconcentration/wt.%5sec.ofchargeat2.50VPBX51PChargeAcceptanceAGMFlatPlate2VCell1%PBX09HRPSoCCyclingTestResultsin4.8AhAGMCell5%DODwith3Crate,1min@50%SOC;2.83V-1.7V1%PBX511%PBX09Control#cyclesControl2,329PBX51_1%15,104PBX09_1%6,5832014SINOLEAD-ACIDBATTERYSUMMIT1314NAMSurfacearea–micro,mesovs.macroporosity0.25%PBX512014SINOLEAD-ACIDBATTERYSUMMITPb1%PBX1350.5%PBX1350.25%PBX510.5%PBX511%PBX1351%PBX090.5%PBX51NitrogenNAMAreaHgNAMporearea0.25%PBX51WithoutcarbonadditiveWith0.5%CarbonBlackSEMImagesofNegativeActiveMass(NAM):DifferentSizePbCrystallitesCBPbPb2014SINOLEAD-ACIDBATTERYSUMMIT15RequirementsforLeadAcidBatteriesinMicroHybridApplicationsImprovedDynamicChargeAcceptance(DCA)Current/Powerat3-20secatfixedchargevoltageof14.4Vtypicallyat50-90%SOCStableaftercyclingatPSoCconditions–KardenDCAtestImprovedcyclelifeatPSoCcyclingVariabletestsdependingonOEMrequirementsColdcrankHighratedischargeat-18°CWaterlossOverchargetestat14.4V2014SINOLEAD-ACIDBATTERYSUMMIT16ConcentrationofLignosulfonateNeedstobeOptimizedforHighCarbonNAMPbArea2m2/gPbAreaforControl,0.5m2/gPbArea1m2/gLS/Pb:0.4/m2surfaceconcentrationofLSCarbon,9m2/gLS/Pb:0.2/m2surfaceconcentrationofLSonlead++LS/Pb:0.1/m2surfaceconcentrationofLSonlead8m2/g2014SINOLEAD-ACIDBATTERYSUMMIT1702468100.0-0.5-1.0-1.5-2.0-2.5-3.0-3.5NAMspecificsurfacearea/m2g-1Currentdensity/mAm-2g-1(NAM)-1.18-1.20-1.22-1.24-1.26-1.28-1.30Negativeplatepotential/VButler–Vollmerequationforhydrogenreduction:I=-A.i0.exp[-acnF/RT(E-Eeq)]I–cathodiccurrent;A–electrodesurfacearea;E–negativeplatepotentialButler–Vollmerequationforhydrogenreduction:I=-A.i0.exp[-acnF/RT(E-Eeq)]I–cathodiccurrent;A–electrodesurfacearea;E–negativeplatepotentialOriginofWaterLossDuringOverchargeatConstantVoltageOriginofWaterLossDuringOverchargeatConstantVoltage•IncreaseinNAMelectrochemicallyactivesurfaceareainherentlydepolarizesnegativeplateduetodecreaseincurrentdensity.•Depolarizationofthenegativeplatecouldaffectthegassingratesbothonleadandcarbonsurface.•Polarizationofthepositiveplatecouldleadtoincreasedoxygenevolution.•IncreaseinNAMelectro