电致变色材料的研究进展及发展前景

344Vol.34No.4CHINESEJOURNALOFRAREMETALS20107Jul．20102009－11－282010－01－201984－*[e-mail]*210009。、、、。doi10．3969/j．issn．0258－7076．2010．04．026O484A0258－7076201004－0610－08ProgressandPotentialApplicationofElectrochromicMaterialsXuNaShenXiaodong*CuiShenCollegeofMaterialsScienceandTechnologyNanjingUniversityofTechnologyNanjing210009ChinaAbstractAsoneoftheintelligentmaterialswithhugepotentialapplicationselectrochromicmaterialswerewidelystudieddur-ingthepastseveraldecades．ThemainelectrochromicmaterialsnamelythetransitionmetaloxidesPrussianbluesystemsvi-ologensconductingpolymersandmetalphthalocyaninesweredescribed．Thestructureofelectrochromicdeviceswasintroduced．Theproblemsandresearchinterestsofelectrochromicmaterialsweresummarizedandthefutureofelectrochromicmaterialswasalsoprospected．Keywordselectrochromicmateialsdevicesapplication。。4、、1。2。。123。11969DebWO3。70804611“”3。、4。1．1。。WO3。WO3WⅥWⅤ。WO3。xM++xe－+WO3→MxWO3MH+Li+。Faughnan5WO31ae－M+WO3MxWO3。1be－M+。WO3ⅥB。1Fig．1SketchofintervalencechargetransfermodelⅧPtPtPdRuRh。IrO2NiO。ROH幑幐2ROOH+H++e－1ROH2+OH幑幐－ROOH+H2O+e－21H+2OH－。。6、7、-8、CVD9、10、11、12、。1．2PB13M″kM'CN6lM'M″kl－CN。PBFeIII4FeIICN63PBKFeIIIFeIICN614。EverittPWBerlinPG。PB+3。PBPB1516。Fe3+Fe3+CN6+e－→PrussianbrownFe3+Fe2+CN6PrussianbluePBPB612343Fe3+Fe2+CN6－→PrussianblueFe33+Fe3+CN62Fe2+CN6－+2e－PrussiangreenPGPBPX。PB17Fe3+Fe2+CN6－→PrussianblueFe3+Fe3+CN6+e－PrussianbrownEverittFe3+Fe2+CN6－+e－→PrussianblueFe2+Fe2+CN62－Prussianwhite。K+Fe3+Fe2+。KCl。20ms1×106。1．311'--44'-18。32ABC。ABC2。－R。23Fig．2Threecommonredoxstatesofviologens。。MV。。ll'-diheptyl-44'-bipyridyliumHV。HV2+。HV10～50ms1×10519。1．4、、、、20。pp。。1．4．1PPYπ321。、、、、。。3PPYπFig．3π-conjugatedstructureofpolypyrrolePPY4613λmax=670nmλmax=420nm22。。＞1μm。1．4．2、2324。———。。1．4．325。－0．2～0．7V、、。pH26。4。127～29。1．5。1970LuPc230531444。。1Table1Electrochromicpropertiesofseveralmajorcon-ductingpolymersPolymerAnionColouroffilmsOxidisedReducedReactiontime/msPolypyrroleClO4－BrownYellow20PolythiopheneClO4－BrownGreen45Poly3-MethylthiopheneBF4－BlueRed12Poly34-DimethylthiopheneClO4－BlueblackBlue60Poly22'-BithiopheneCF3SO3－Blue/grayRed40H+GreenBlue1PolyanilineCl－Green/blueYellow1004Fig．4Electrochromicreactionofpolyaniline5Fig．5Metalphthalocyanines61434LuT4APc2、CoT4APcNiT4APcPloyCoⅡT4APcblue-green+ne幑幐帯帯－PloyCoⅠT4APc－yellowish-brown+ne幑幐帯帯－PloyCoⅠT4APc2－reddish-brownordeeppinkPloyNiⅡT4APcgreen+ne幑幐帯帯－PloyNiⅠT4APc－Blue+ne幑幐帯帯－PloyNiⅠT4APc2－purpleLuPc25-。。LuPc2、5×106。22。3、。632。TransparentConductorTC3385%。ITO。ElectrochromicFilmECD。。IonStorageFilm/ECD。、。IonConductor≥1×10－7S·cm－1≥1×1012Ω·cm。。、6Fig．6Basicdesignofelectrochromicdevices2Table2ComparisonbetweeninorganicandpolymericelectrochromicmaterialsSerialnumberPropertyInorganicmaterialsPolymer1MethodofpreparationSophisticatedtechniquesSimplechemicalpolymerization2ProcessibilityofthematerialsPoorEasilybeprocessed3CostformakingdevicesHighLow4ColorsLimitednumberofcolorsLargenumberofcolors5ContrastModerateHigh6Switchingtime10～750ms10～120ms7Cycletime1×103～1×1051×104～1×1064615、。、、。3．134。。、、。3．2ECD、、、、、、。。。。、TiO2Viologen。。。35。Ntera。7Ntera50%。3．3。36。7Fig．7Nanoscaledelectrochromicdisplay3．4。。37。4。12。。、。138、39、40、412PEO423/。/、、61634。/43、-44、LB45。5。WO3。。。、。、、。、。1BamfieldP．TechnologicalApplicationsofColourChemistryM．RoyalSocietyofChemistryCambridge2002．2MonkPMSMortimerRJRosseinskyDR．ElectrochromismFundamentalsandApplicationsM．WeinheimVCH1995．3LampertCM．InnovativesolaropticalmaterialsJ．OpticalEngineering198423192．4RauhRD．ElectrochromicwindowsanoverviewJ．Electro-chimActa199944183165．5FaughnanBW．ElectrochromisminWO3amorphousfilmsJ．RCARev．1975361177．6EsraOzkanSe-HeeLeeCEdwinTracyJRolandPittsSatyenKDeb．Comparisionofelectrochromicamor-phousandcrystal-linetungstenoxidefilmsJ．SolarEnergyMaterials＆SolarCells200379439．7TokuroNanbaTadashiTakahashiJunTakadaAkiyoshiOsa-kaYoshinariMiuraItaruYasuiAkiraKishimotoTetsuichiKudo．CharacterizationofamorphoustungstentrioxidethinfilmspreparedbyRFmagnetronsputteringmethodJ．JournalofNon-CrystallineSolids1994178233．8NatarajanCOhkuboSNogamiG．Influenceoffilmprocess-ingtemperatureontheelectrochromicpropertiesofelectrode-posi-tednickelhydroxideJ．Rev．Chem．Miner．198421487．9BensonDK．OpticalmaterialstechnologyforenergyA．Effi-ciencyandSolarEnergyConversionVI．SPIEC．198772823．10RezraziMBohnkeOPagettiJ．ElectrochromicbehaviourofthinfilmsoftungstentrioxidepreparedbyanodicoxidationoftungstenwithpulsedcurrentJ．SolidStateIonics199686-882949．11DelicherePFalarasPFromentM．Preparationandphysico-chemicalpropertiesoffilmsinthevirginandcolouredstatesJ．ThinSolidFilms198816135．12HiroharuKawasakiTsuyoshiUedaYoshiakiSudaTamikoOhs-hima．PropertiesofmetaldopedtungstenoxidethinfilmsforNOxgasnsorsgrownbyPLDmethodcombinedwithsputteringprocessJ．SensorsandActuators2004B100266．13SharpeAG．TheChemistryofCyanoComplexesoftheTransi-tionMetalsM．NewYorkAcademicPress1976．14MortimerRogerJ．ElectrochromicmaterialsJ．Chem．Soc．Rev．199726147．15PrakashSomaniRadhakrishnanS．Chargetransportprocessesinconductingpolypyrrole/PrussianBluebilayersJ．MaterialsChemistryandPhysics20027615．16Pra