新能源材料New-Energy-Materials课件

NewEnergyMaterials1NewEnergyMaterials

2025/3/18NewEnergyMaterials2Chapter1Introduction★BasicrequirementsImportanceandnecessityofdevelopingnewenergymaterialsCharacterizationofnewenergymaterialsClassificationofnewenergymaterialsApplication,researchanddevelopmentofnewenergymaterials★Emphases:CharacterizationofnewenergymaterialsClassificationofnewenergymaterials★Difficulty:Statusandchallengeofnewenergymaterialsinnationaleconomy2025/3/18NewEnergyMaterials31.1OverviewMaterial:oneofthemostimportanttechnologiesinthe21stcentury(Material,Information,Energy)Generally

MaterialMetallicInorganicNonmetallicOrganicPolymerCompositeEnergy:oneofthemostimportanttechnologiesinthe21stcentury(Material,Information,Energy)Fourclassificationtype:FormationPrimaryenergy(Coal,Oil,Gas,Solar)Secondaryenergy(Electricity,Steam)PropertyFuelenergy(Coal,Oil)Non-fuelenergy(Electricity,Solar)2025/3/18NewEnergyMaterials4Regeneration?Renewable(Hydrogenenergy)Non-renewable(Fossilfuel)AgeConventionalenergy(Coal,Oil)Newenergy(Hydrogenenergy)※HistoryandFutureoftheenergyusageforhuman￭Fire

燧人氏“钻木”发明人工取火（传说）北京猿人距今50万年以前使用天然火（雷火）赤铁矿石＋燧石碰撞取火－－人类最早发明的取火方法￭Coal2000yearsago,战国时代（《山海经》中的“石涅”，见煤炭开发史）18thcentury,Europe,KingofenergyduringthefirstIndustrialRevolutionperiod1850~1870,CoaloutputofGreatBritainincreasedfrom50to112millionton2025/3/18NewEnergyMaterials5￭Oil2000yearsago,我国西北地区人民用石油点灯1859,PennsylvaniaofUS,thefirstoilwellinthewesterncountries

Forinternal-combustionengine(ICE),thesecondclimaxofworldenergyrevolutionOrganizationofPetroleumExportingCountries(OPEC)ismoreandmoreimportant2003,IraqWar,forOil￭FutureTable1-1Ratioinworldenergyconsumptionandyearsforuseofnon-renewableenergyEnergytypeRatioinworldenergyconsumption(%)Timeforuse(years)FossilenergyCoal25.074.0220Oil32.040Naturalgas17.060Nuclearenergy4.0260Total78.0CallforNewandRenewableSourcesofEnergy(NRSE)2025/3/18NewEnergyMaterials6※ContinuousincreaseofenergyrequirementTable1-2Increaseratefortheprimaryenergyconsumptionintheworld1966~19731973~19791979~19851985~1990Worldaverage(%)Developedcountries(%)OECDcountries(%)Developingcountries(%)ChinaOthers5.14.95.06.35.46.82.72.01.16.06.75.50.90.1-0.34.03.44.32.21.31.85.04.65.2Ingeneral,theenergyconsumptionkeptincreasing.Ontheotherhand,theenergyconsumptionovergrossdomesticproductGDP(单位GDP能耗)isdecreasing.2025/3/18NewEnergyMaterials7Fig.1-1VariationoftheenergyconsumptionoverGDPofseveraldevelopedcountries(1985fixedprice)EnergyconsumptionoverGDPwasdecreasedfor20%~40%duringthe16yearsTheenergyconsumptionoverGDPofourcountryistwiceoverUSA※ChangeofenergystructureOilreplacedcoalastheprimaryenergyfrom1970sintheworldNaturalgaswasalsoincreased2025/3/18NewEnergyMaterials8Table1-3StructureofprimaryenergyintheworldYear19501960197019801990Primaryenergysupply(×108tstandardoil)Ratio(%):CoalOilNaturalgasWaterpowerNuclearenergy17.557.731.09.71.6028.946.037.814.22.0-48.530.548.718.62.10.162.728.348.619.92.30.980.327.338.621.66.75.8Inourcountry:coal75.0%,oil17.5%,naturalgas1.6%,waterpower5.9%in1996Highcapacitysecondarybatterybecomesmoreandmoreimportantinthedevelopmentofnewenergyduetothewideapplicationofmobilepowersources,suchasthinkpad,mobiletelephone,DC,DV.2025/3/18NewEnergyMaterials9※ExhaustionoffossilenergyTable1-4Forecastoffossilenergyfor1990~2020(unit:100milliontonstandardoil)OilNaturalgasCoalTotalKnownstorage(by1991)EstimatedincreaseTotalsourcesAccumulatedrequirement(1990~2020)13506502000100011401060220068052002880034000850770030500382002530※EnvironmentalpollutioncausedbyburningoffossilfuelFossilfuelburningSOxCO2CONOxSoot…GreenhousEffectTherarityofoilandnaturalgaswillbeacrucialissueinthe21stcentury!2025/3/18NewEnergyMaterials10Fig.1-2CO2emissionintheworldFig.1-3AverageCO2emissionofapersonindifferentarea2025/3/18NewEnergyMaterials11Wecanfind:(a)CO2emissionincreasedcontinuously:1990,5.9billiontonC;2020,8.4billiontonC.(b)Mostemissioncontributedbydevelopedcountries.(c)IncreaserateofCO2emissionfordevelopingcountrieswashigherthandevelopedcountriessince1980s.CO2concentrationintheatmosphereincreasedfrom280×10-4%(1000yearsago)to320×10-4%,whichwasresponsiblefortheglobalwarmanddangeroustohumanbeings.Allabovereasonsmakeusbelieveitisveryimportantandurgenttodevelopnewenergyandnewenergymaterials,whichshouldberesponsibleforthesustainabledevelopmentofthesociety!!!2025/3/18NewEnergyMaterials121.2

Classificationandpropertiesofnewenergymaterials1.2.1SolarenergyManystoriesaboutcatch“skyfire”inage-oldcountries,likeEgypt,GreeceandChina.Prometheus:ATitanwhostolefirefromOlympusandgaveittohumankind,forwhichZeuschainedhimtoarockandsentaneagletoeathisliver,whichgrewbackdaily.------GreekMythologyGenerallyspeaking,allenergyintheeartharedirectlyorindirectlycomefromsun!Theenergyreceivedbyearthisonly1/2000000000ofthetotalradiationproducedbythesunandabout1.7×1013kWcanreachtheland,whichisseveraltenthousandtimesoftheelectricitypowergeneratedeveryyearintheworld.NewenergySolarenergyHydrogenenergyWindenergyBio-energyOceanenergyGeothermicenergy2025/3/18NewEnergyMaterials13Majorapplicationsofsolarenergy:calefaction,heater,generateelectricitySolarcell:

basedonPhotovoltaicEffect(PV)Thepowergeneratedbysolarcellincreasedfrom88.5MWin1996to287.7MWin2000intheworldandisstillincreasingnow.Fig.1-4Solarenergy–Electricity–Hydrogenenergy–FuelCells2025/3/18NewEnergyMaterials14Fig.1-5Someexamplesofsolarenergysetting2025/3/18NewEnergyMaterials151.2.2HydrogenenergyWillonedaywaterbeemployedasafuel?(JulesVerne,TheMysteriousIsland,1874)Hydrogenistheidealandcleannewenergy,forwhichhasbeenearnestlylongedduringthedevelopmentofhumankind.Hydrogen:thelightestelementinthenature.However,onlyverysmallamountofH2existinthenature,mosthydrogenexistintheformofcompounds.ItisdifficulttogetnaturalH,whichrestrictstheuseofhydrogenenergy.Heatofburningveryhigh:120.4MJ/kgH2,3timesofgasolineHstorage:over75%intheuniverse;80%inthesun(byvolume);25%inthecrust(bywt)H:colorless,smellless,innocuous;diffuseveryquickly;Burningofhydrogen:nosmokeandchangetowater–nopollution.2025/3/18NewEnergyMaterials16Thehistoryofhydrogenenergy●Hydrogenasafuel:18thcentury,H2foundbyLavoisier拉瓦锡andCavendish卡文迪什.1766,CavendishfromEngland,metal+acid→H2●1818,England,H2O(electrolyze)→H2●1839,WilliamGrove,fuelcell●1920s,GermanandEngland,startedstudyofhydrogenfuel●1928,RudolphEJrren(German),thefirstpatentofhydrogenengine●Theendof1930s,German,trainpoweredbyhydrogen●1950s,hydrogenas“energycarrier”or“energymedium”●1970,GMTechnicalCenter,conceptof“hydrogeneconomy”●1974,foundationofInternationalAssociationforHydrogenEnergy(IAHE)

InternationalJournalofHydrogenEnergyWorldHydrogenEnergyConference(WHEC),everyoneyearHyforum(Hydrogen+Forum)startedfrom2000●2003,IPHEConferenceheldinWashington,Chinawasamemberamong15countries2025/3/18NewEnergyMaterials17●ThesymbolofsuccessofIPHE:thecostforhydrogenproductionwillbeoneofthechoicesfortransportationfuelby2020.Whyhydrogen?Hydrogenistheeternalenergyinthefutureformankind.●Abundantsources:watereverywhere“hydrogenmine”●Obtainedfrommanychannels:primaryenergy,secondaryenergy●Environmentfriendly:noCO2andNOxemission,nopollution●Storable:intheformofgas,liquidandsolid●Renewable●“Peaceful”energy:everycountryhaslargeamountof“hydrogenmine”,noopposeorwar,unlikeoilinMiddleEast.●Safeenergy:fastdiffusion,notoxicity,noradioactivity,nogreenhouseeffect,hydrogensensor2025/3/18NewEnergyMaterials18Hydrogenproduction●Water:electrolysis,thermochemistry,hightemperaturepyrogenation●Fossilenergy:coal,gassources(naturalgas),liquidfossilenergy(methanol,oil)●Bio-material:microbe,pyrogenation●NaBH4+2H2O→NaBO2+4H2

●xH2S→Sx+xH2●Watersplitbysolarenergy●OthersHydrogenstorage●Gaseous●Liquid●Metalhydride(MH)●Complex(NaAlH4,LiAlH4,Li-N-H)●Carbon(Carbonnanotube,Carbonnanofiber)●Others(Carbonaerogels,glassmicrospheres,hydrogenslurry,icecage)2025/3/18NewEnergyMaterials19IdealCleanRenewable2025/3/18NewEnergyMaterials20Althoughhydrogenhasthehighestenergydensityoftoday’sfuelsonaweightbasis,ithasthelowestenergydensityonavolumebasis.◆1Kgofhydrogencontainsthesameamountofenergyas—2.1Kgofnaturalgas—2.8Kgofgasoline◆Hydrogenpossesses2.36kWh/lasaliquid—Naturalgascontains5.8kWh/l—Gasolineregistersat8.76kWh/l2025/3/18NewEnergyMaterials21Hydrogenproduction2025/3/18NewEnergyMaterials22Gaseous:2M+xH22MHxElectrochemical:M+xH2O+xe-MHx+xOH-absorb

desorbchargedischargeHydrogenstoragebySWCN2025/3/18NewEnergyMaterials23Slurry2025/3/18NewEnergyMaterials24Howdoesafuelcellwork?2025/3/18NewEnergyMaterials25Hydrogentransportation2025/3/18NewEnergyMaterials26Ishydrogensafety?2025/3/18NewEnergyMaterials27Alternative-FueledVehiclesFuelCellVehicles2025/3/18NewEnergyMaterials282025/3/18NewEnergyMaterials292025/3/18NewEnergyMaterials30Whatisahydrogeneconomy?2025/3/18NewEnergyMaterials312025/3/18NewEnergyMaterials321.2.3Windenergy●Causedbysolarradiation:~2%ofsolarenergy●Global:2.74×109MWtotal,2×107MWcanbeutilized●Cleanenergy●Generateelectricity●Liftwater(Netherlands,“thecountryofwindmill”)●Cost:￥0.4~0.7/kWh●Globalcapacity:over25000MW●Globalproductionvalue:over$5billion/year2025/3/18NewEnergyMaterials331.2.4Bio-energy●Biomass:producedbyphotosynthesis●Storedinbiologyintheformofchemicalenergytransformedfromsolarenergy●Generateelectricity:burningdirectly,gasification,pyrogenation●Firedamp:CH4,CO2●Transformrouteofbiomass:thermochemistry,biochemistry,distill1.2.5Oceanenergy●Oceanarea:3.6×108km2,71%oftheearth●Tideenergy:~0.1billionkW●Waveenergy:~1billionkW●Oceancurrentenergy:~0.3billionkW●Differenceintemperature:~2billionkW●Differenceinsalt:~3billionkW●Mainutilizationform:generateelectricity2025/3/18NewEnergyMaterials341.2.6Geothermicenergy●Renewableheatenergycomesfromthedeepinearth●Origin:meltingmagmaanddisintegrationofradioactivematerials●Fivetypes:steam,hotwater,geostatic,xerothermicmagma,magma●Energycarrier:water●Applications:hotwell,greenhouse,heatpump,generateelectricity1.3ApplicationsofnewenergymaterialsNewenergymaterialsHydrogenstoragematerialsMH-NibatterymaterialsLi-ionbatterymaterialsFuelcellmaterialsSolarcellmaterials2025/3/18NewEnergyMaterials351.3.1Hydrogenstoragematerials●Metal(Alloy)

AB5type(LaNi5)1969,Philipslab,LaNi5,Hcontent1.4wt.%,forNi-MHbattery,rapiddegradation1984,Willims,CosubstitutionforNi,multi-alloying,cyclelifeimprovedgreatlyLaNi5-xMx(M=Al,Co,Mn,Cu,Ga,Sn,In,Cr,Fe)LapartialsubstitutedbyCe,Pr,Nb,Y,Sm,Mm,Ml,Zr,TiElectrochemicalcapacityover320mAh/g

AB2type(ZrM2,TiM2,M=Mn,Ni,V…)1966,Pebler,Zr-basedLavesphase1980s,Ti-Zr-Ni-M(M=Mn,V,Al,Co,Mo,Cr)1.8~2.4wt.%,over360mAh/g

ABtype(TiFe,TiNi)1974,ReillyandWiswall,1.86wt.%,lowcost,slowactivationTiFexMy(M=Ni,Cr,Mn,Co,Co,Mo,V),improvedtheactivationproperties2025/3/18NewEnergyMaterials36

A2Btype(Mg2Ni,Ti2Ni)1968,ReillyandWiswall,Mg2NiH4,3.6wt.%,light,lowcost,highcapacityDesorbhydrogenathighertemperature(>200℃),slowkineticsMechanicalalloying,ballmilling

BCCsolidsolution(V-based)V-Ti-Fe,V-Ti-Cr,V-Ti-Mn,etal.3.8wt.%,halfdesorbed,expensiveV3TiNiM,420mAh/g

AB3type(LaNi3,CaNi3)1/3AB5+2/3AB2~1.1wt.%AB2C9type(LaMg2Ni9,La2MgNi9,La-Mg-Ni-based)Highcapacity~400mAh/g

ComplexNaAlH4,Ti-basedcatalyst,5.6wt.%reversibleLi-N-based,~10wt.%2025/3/18NewEnergyMaterials37●Non-Metal(Hydrogenadsorption)Activatedcarbon5.3wt.%at77KCarbonnanotube>4.0wt.%,poorinreproductionCarbonnanofiber~10wt.%Glassmicrospheres~42wt.%,Highpressure(10~200MPa)Hightemperature(>200℃)●OrganicliquidBenzene,Toluene,Naphthalene,MCH(甲基环己烷）etal.Highcapacity~7wt.%1.3.2MH-NibatterymaterialsNegativeelectrodematerial:hydrogenstoragealloyEnergydensity:1.5~2timesofNi/CdbatteryNopollution,widelyusedinmobilecommunication,thinkpadanddevelopedinpowerbatteryResearchactivities:energydensity,powerdensity,cyclelife,highratedischargeability2025/3/18NewEnergyMaterials38●ImprovementinpositiveelectrodematerialsPropertiesofball-typeNi(OH)2

Studyinshape,chemicalcomposition,particledistribution,structuraldefectandsurfaceactivation,andsoon.●ImprovementinnegativeelectrodematerialsAB5typealloy,goodoverallelectrochemicalpropertiesResearchactivities:composition,structure,surfacetreatment,rapidsolidification,annealingtreatment,low-Co,non-Coalloy,hotchargingetal.●NovelhighcapacityhydrogenstorageelectrodealloyOvoniccompany,AB2type,~400mAh/gAmorphousMg-Nialloy,theoreticalcapacity~1000mAh/gV-basedsolidsolution,~500mAh/g●Regenerationofbattery

火法冶金、湿法冶金

Recycleofvaluableelements2025/3/18NewEnergyMaterials391.3.3Li-ionbatterymaterialsStudyofhighcapacitybatteryusedinEV,improvethepropertiesofsmalltypebattery,developinpolymerbattery●CarbonnegativeelectrodematerialHardcarbon,naturalgraphite…●Nano-alloymaterialsSn,SnSb,SnAgalloy,improvedcyclingproperties●PositiveelectrodematerialsLiCoO2:crystalstructure,chemicalcomposition,particlesize,particledistributionLiMn2O4,lowercost,poorpropertiesathightemperature●ElectrolyteNonaqueoussolventelectrolyteSO2,CO2addition,improvetheinitialchargeanddischargeefficiencyofcarbonmaterialsPolymerelectrolyte,thin-typebattery2025/3/18NewEnergyMaterials401.3.4FuelcellmaterialsImproveinefficiencyofgeneratingelectricity,workinglife●PEMFC(ProtonExchangeMembraneFuelCell)Ptcatalyst,highcost,blockitsapplicationPt/C,Pt-Ru/Ccatalyst,lowercostAdditionofNafioncolophonyintheelectrode,increasePtefficiencyPtcontentdecreasedto1/10~1/20●MCFC(MoltenCarbonateFuelCell)Highworkingtemperature,650℃,highvalueofresidualheatNiastheelectriccatalyst,nonoblemetalHighcostCathodematerial:NiO,LiCoO2,easytodissolveAnodematerial:sinteredNi,Ni-Cr,Ni-AlalloyBipolarboard:stainlesssteel,easytocorrosion2025/3/18NewEnergyMaterials41●SOFC(SolidOxideFuelCell)SolidelectrolyteBroadrangeoffuel,highefficiencyoffuelYSZ(Y2O3StabilizedZrO2)electrolytematerials1.3.5Solarcellmaterials●Developmaterialtechnics,improvetransformefficiencyPurification,crystalgrowth,filmpreparation,andsoon.SinglecrystallineSi23.7%,Poly-crystallineSi18.6%,GaAs30%●Developthinfilmcell,savematerials1~2μm,GaAs,CdTe,AmorphousSi●Large-scaleprocesstechnologyofmaterials200kgSicast,savecost●Combi