热电材料研究的现状与发展趋势_任志锋

323Vol.32No.3西华大学学报自然科学版JournalofXihuaUniversity·NaturalScience20135May20132013-03-10“”“SolidStateSolar－ThermalEnergyConversionCenterS3TEC”DE－SC0001299。1963－、、。·先进材料及能源·任志锋刘玮书77204。、。、、、。O472+.7A1673－159X201303－0001－09doi10．3969/j．issn．1673－159X．2013．03．001TheState-of-the-artandFutureTrendoftheStudyonThermoelectricMaterialsRENZhi-fengLIUWei-shuDepartmentofPhysicsandTcSUHUniversityofHoustonHoustonTexas77204USAAbstractThermoelectricmaterialsaregettinglotsofattentionsincetheyarethekeyforthethermoelectricpowergenerationfromwasteheatandsolarenergy．Recentlybreakthroughshappenedowingtothecontinuousadvancesinthenewsynthesistechniquefornanomaterialsandthenewunderstandingforthetransportmechanismoftheelectronsandphononsatnanoscale．Inthispaperwewillbrieflyintroducetheworkingprinciplesofthethermoelectricpowergeneratorsandreviewtheresearchprogressesofthethermoe-lectricmaterialsunderatomicscalenanoscaleandmicroscale．Finallywesuggestthatthatthepowerfactorimprovementfromin-creasingdegeneratebandstuningmicrostructureandformingresoantstateswillbethefuturefocusinthermoelectricresearch．Keywordsthermoelectricmaterialsnanoscaletransportmechanismlatticethermalconductivitypowerfactor1。2011122．7t、、87%1。50。、。netprimaryresourceconsumption55%2。、。、。、、。3×1024J7.2×105t。60003。·20130.2%10%。。。1234。、4－5。ThermoelectricPowerGenera-tion。238235。2006238“”238140W。。4.6%6。。。、GM、Bosch。2PN。PNther-mopower1。1heatengine。ZT1。φte=Th－TcTh1+＜ZT槡＞－11+＜ZT槡＞+TcTh1ThTc＜ZT＞TcThZT。ZT。ZTIoffe4SeebeckS、σ、κT2。ZT=S2σκT21ZTZT。3S、σ、κZT。S、σ、κZT。Eg。＜ZT＞1legef-ficiencyφmat。23。2300K7。、8%～15%。NPlegefficiency。Manhan8S、σ、κNP9。2300K7Pn3ZT3S、σ、κZT。、、。。BoltzmannS、σ、κm*、rμ。ZTβ10ZT=η－r+5/2βexpη－1+r+5/23β=5.745×10－6μm*/m03/2κlatT5/24ZTββZT。Nvm*m*bm*=Nv2/3m*b。EΔ＜5kBTm*11。μm*/m03/2κlat。、、。3.1Nv。Keyes12。。Slack|Δx|13。14－15。Gao16quantumstructurediagramQSD。QSDΔAΔX。QSD、。。BiSb、Bi2Te3PbTe。1994Slack3·201313。SkutteruditeRxCo4Sb17－1912ClathrateBa8Ga16Ge30Sr8Ga16Ge2030。2011ShiSkutterudite2aBa、LaYbZT1.7850K21。。ZT。Zn4Sb31.3at670K22、Yb14MnSb11～1.0at900℃23。Zn4Sb3～0.3W/mKZn。Zn。NaxCoO2CoO23Na1ZT124。naturalsuperlatticeZT。2009RhyeeIn4Se3－Se2ZT1.48705K25。20122627Cu2Se。β－Cu2Se111Se1Cu2。Cu2SeZT700℃1.627。Cu2SeCu。。。TlPbTe。PPbTeZT0．71.528。2012ZhangAlPbSeZT1.329。。NBi2Te3SeBi2Te3－xSexPBi2Te3SbBi1－xSbxTe3ZT30。ABAB。PbTeLNv=4ΣNv=12LCΔEC－L=0.3eVΣCΔEC－Σ=0.36eV31。ΔEC－ΣΔEC－L。450KΣLΔEC－Σ=ΔEC－LNv16m*。ΣLΔEC－Σ＜ΔEC－LΣL。PbTeSePbTe1－xSexΣLTcvgZT。2011PeiΣLTcvgPPbTe1－xSexZT～11.8850K32。2012LiuNMg2Si1－xSnxZT～11.3700K33。3.2。3.2.1纳米晶粒。70Wales43SiGe34－35。。。。。。。。SiGeWunderlichSiGe915℃1h36。9037－38。。。。。BMHP。3BM－HPSiGe39－40、Half-Heusler41－42Bi2Te43－453。SiGe、Half-HeuslerBi2Te3ZT。、。1PBi0.4Sb1.6Te4。1～310～30nm25abBi0.4Sb1.6Te346Zr0.5Hf0.5CoSb0.8Sn410.235cHf0.8Ti0.2CoSb0.8Sn0.2475dPbTePb48。。49－52。。S2σ。3BM－HPBi2Te3SiHalf-Heusler。abcd。4BM－HPPBi2Te3TEM465·20135aBi0.4Sb1.6Te346bZr0.5Hf0.5CoSb0.8Sn0.241cHf0.8Ti0.2CoSb0.8Sn0.247dPbTePb48。3.2.2第二相纳米颗粒。Zhang53TlNaPbTeSi2～3μm200～300nm～2W/mK1.2～1.3W/mK。Seebeck。Sb2Te3Pt54RyCo4Sb12InSb55GaSb56。3.2.3纳米析出相。4matrixencapsulation/nucleation/growtheutecticdecompositionspinodaldecomposition6。4。。6bPbTe－4%SbTEM57。PbBiPbTe。/123。23。6dPbTe－5.5%Ag2TeTEM58。。6faPbTe－SbbPbTe－4%SbTEMcPbTe－Ag2TedPbTe－5．5%Ag2TeTEMePbTe－Sb2Te3fPb2Sb6Te11PbTeSb2Te359gPbTe－PbShPbTe－8%PbSTEM60。6PbTe63Pb2Sb6Te11PbTeSb2Te3。6h。3.3、、、。ZT。2012“”7。ZT。。752。7a－ef－i7415～20。、、、。ZT2。、。。。1。2。3。1BPEB/OL．2012－12－20．http//．bp．com/statisticalreview．2Productionandend-usedatafromEnergyInformationAdminis-trationJ．AnnualEnergyReview2002145－503GrtzelM．SolarEnergyConversionbyDye-SensitizedPhotovol-taicCellsJ．InorganicChemistry20054468416851．4KajikawaT．CRCthermoelectrichandbookM．BocaRatonCRCPress201245－56．5YangJHStablerFR．CRCthermoelectrichandbookM．Bo-caRatonFLCRCPress200660－70．6KraemerDPoudelBFengHPetal．．HighperformanceflatpanelsolarthermoelectricgeneratorwithhighthermalconcentrationJ．NatureMaterials．2011．10532－538．7LiuWSYanXChenGetal．Recentadvancesinthermoelec-tricnanocompositesJNanoEnergy2012142－56．8MahanGD．InhomogeneousthermoelectricsJ．JournalAp-pliedPhysics1991704551－4554．9MaEnaneyKKraemerDRenZFChenG．Modelingofcon-centratingsolarthermoelectricgeneratorsJ．JournalofAppliedPhys-ics2011110074502．10GoldsmidHJ．IntroductiontothermoelectricityM．Heidel-7·2013bergSpringer201018－25．11LiuWSZhaoLDZhangBPetal．．Enhancedthermoelec-tricpropertiesoriginatingfromadditionalcarrierpocketinskutteruditecompoundsJ．AppliedPhysicsLetters200893042109．12KeyesRW．High－temperaturethermalconductivityofinsula-tingcrystalsrelationshiptothemeltingpointJ．PhysicsReview1959115564－567．13SlackGATsoukalaVG．SomePropertiesofSemiconductingIrSb3J．JournalofAppliedPhysics1994761665－1671．14KlemensPG．Thescatteringoflow－frequencylatticewavesbystaticimperfectionsJ．ProceedingsofthePhysicalSocietyALon-don1955681113－1128．15CallawayJVonBaeyerHC．EffectofpointimperfectionsonlatticethermalconductivityJ．PhysicsReview19601201149－1154．16GaoMRoweDM．“Quantumstructurediagram”asathermo-electricperformanceindicatorJ．JournalofMaterialsScienceLetters1997161339－1341．17SalesBCMandrusDWilliamsRK．Filledskutterduiteanti