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:1999201214:(A2762):(1970-),,,,Biography:LENGYong2jun,(1970-),male,lecture,PhD.1,1,1,2,1,2(1.,200240;2.,310027):2Ni(OH)2,,Fe,FeFe,XRD,Fe,Fe19.1%,;Fe1.9%,Fe6.4%12%,,,,IR,,CO2-3:Fe;;:TM910.3;TM912:A:10022087X(2000)0120032204Preparation,structureandelectrochemicalperformanceofiron2substitutednickelhydroxidePartStructureanalysisLENGYong2jun1,MAZi2feng1,ZHANGCun2gen1,ZHANGJian2qing2,WUYi2hua1,CAOChu2nan2(1.CollegeofChemistryandChemicalTechnology,ShanghaiJiaotongUniversity,Shanghai200240,China;2.ChemistryDepartment,ZhejiangUniversity,HangzhouZhejiang310027,China)Abstract:2Ni(OH)2isofgreatinterestsinceitislikelytohavehighspecificcapacity,moreover,mini2mizestheproblemsofnickelexpansion.Iron2substitutednickelhydroxideshavebeenpreparedbychemicalco2precipitationwithironsubstitutionratesrangingfrom0to0.40.Effectofironsubstitutiononphasestructurewasinvestigatedindetail.XRDanalysisshowsthatwithdifferentamountofironsubstitution,differentphasespresent.Whentheamountofironsubstitutionexceeds19.1%,only2phase,withwhichnickelhydroxidesarestableinstrongalkalinesolution,presentsinthesample.Onthecontrary,whentheamountofironsubstitutionisaslowas1.9%ornon,only2phasepresentsinthesample.Whiletheamountofironsubstitutionis6.4%or12%,both2phaseand2phasepresent.However,2phasedomi2natesinthesamplewiththeformersubstitutionamountaswellas2phasedoesinanothersample.IRstudyshowsthatitisnecessarytointercalatesomeanion,suchasCO2-3,betweenNi(OH)2slabsinordertokeepthephasestable.Keywords:Fe2substitutednickelhydroxide;phasestructure;electrochemicalperformance2Ni(OH)2/2NiOOH,2Ni(OH)2,2Ni(OH)2,2Ni(OH)2,2Ni(OH)22Ni(OH)2,Ni(OH)2,,23ChineseJournalofPowerSourcesVol.24No.1Feb.20002Ni(OH)2,,,Co[15]Mn[68]Fe[911]Al[12],NiFe,(pH),FeNi1-xFex(OH)2(CO3)x/2nH2O(Ni2FeLDHs),Fe[13],1FeNi2FeLDHs[13],2mol/LKOH,XIRX(XRD),RigakuD/max2B;(IR),ShimazuIR2408Cu,,20/min;40kV,30mAIR:(1)FeNi(OH)2;(2)FeNi(OH)222.1X(XRD)Fe:(a)19.1%,(b)12%,(c)6.4%,(d)1.9%,(e)Ni(OH)21FeNi2FeXRDFig.1PowderXRDpatternsofNi2FeLDHsandsphericalNi(OH)2sampleswithdifferentcontentsofFe1FeNi2Fe(LDHs)Ni(OH)2X(XRD)Ni(OH)219.22,33.0638.54,2Ni(OH)2FeXRD:(1)Fe19.1%,11.30,22.66,34.6038.00,,Fe19.1%XRD[12]2Ni(OH)2,,a=0.317nm,c=2.466nm;2Ni(OH)2(c=0.46nm)(2)Fe1.9%,,XRD,2Ni(OH)2(3)Fe6.4%12%,,Fe12%,;Fe6.4%,2FeNi2Fe(LDHs)X(XRD)X(XRD),FeNi2Fe(LDHs)X(XRD),FeNi2FeLDHs2Ni(OH)2,,2Ni(OH)2,2Ni(OH)22Ni(OH)2Fe:(a)19.1%,(b)12%,(c)6.4%,(d)1.9%2FeNi2FeXRDFig.2PowderXRDpatternsofalkali2agedNi2FeLDHssamplewithdifferentcontentsofFe3FeNi2FeLDHs3(f)2Ni(OH)2,:(1)3650cm-1,OH(OH);(2)520cm-1,OH(OH);(3)440cm-1,Ni2OFeNi2FeLDHs2Ni(OH)2Fe19.1%:(1)3450cm-11610cm-1,H2O(H2O)(H2O),H2O,H2O;33ChineseJournalofPowerSourcesVol.24No.1Feb.2000(2)3650cm-1,OH,;(a)19.1%Fe(b)12%Fe(c)6.4%Fe(d)1.9%Fe(e)0%Fe(f)2Ni(OH)23FeNi2FeIRFig.3IRspectraofNi2FeLDHsandsphericalNi(OH)2sampleswithdifferentcontentsofFe(3)1360cm-1710cm-1,D3hCO2-334,3CaCO2,(1429cm-11492cm-1),[10],CO2-3,4[10]780cm-1,,Fe19.1%2Ni(OH)2,[12]2Ni(OH)2,Fe19.1%2Ni(OH)20.78nm,CO2-3NiO20.78nm,SO2-4Co2Ni(OH)2,SO2-40.9nm[11],Fe19.1%1100cm-1620cm-1SO2-4(Td)34IRFe1.9%FeNi2FeLDHs4(CO2-3),Fe,CO2-33,2Ni(OH)2XRD,Fe1.9%FeNi2FeLDHsIR2Ni(OH)2Fe12%6.4%Ni2FeLDHs,Fe12%Ni2FeLDHsFe19.1%,3(CO2-3)4(CO2-3),3450cm-12Ni(OH)2;Fe6.4%Ni2FeLDHs3450cm-1H2O(H2O),710cm-14(CO2-3),IR2Ni(OH)24FeIRXRD,,Ni2Fe(LDHs)IRIR,FeNi2FeLDHs2Ni(OH)2,(a)19.1%Fe(2)12%Fe(c)6.4%Fe4FeNi2FeIRFig.4IRspectraofalkali2agedNi2FeLDHssamplewithdifferentcontentsofFe2.3XRDIR,Ni2Fe(LDHs),2Ni(OH)2(),2Ni(OH)2()Fe,Fe19.1%,;Fe1.9%,;Fe6.4%12%,,,5Fe3+Ni2FeLDHsFe3+Ni2+,,(CO2-3)NiO2,c,Fe20%,,Fe43:ChineseJournalofPowerSourcesVol.24No.1Feb.2000,,,Ni2+,,Ni3+Ni4+Ni2+,,,,,,,,,Fe12%19.1%Fe1.9%,,Fe19.1%Fe12%Fe34.5%,,,Ni(OH)2,Fe1.9%6.4%,,Fe,,,,,Fe19.1%34.5%200,Fe12%200,3,;Fe1.9%6.4%5Fe3+ZFig.5SchematicrepresentationofthestructuralmodificationofFe3+substitutedstable2phasesampleinvolvinginelectrochemicalcyclingbetweentheandphases3FeNi2FeLDHsFe,,20%,2Ni(OH)2,2Ni(OH)2:[1]FAUREC,DELMASJ,WILLMANNP.Electrochemicalbe2haviorof2cobaltednickelhydroxideelectrodes[J].JPowerSources,1991,36:497.[2]DELMASC,FAUREC,BORTHOMIEUY.Theeffectofcobaltonthechemicalandelectrochemicalbehaviourofthenickelhydroxideelectrode[J].MaterSci&Eng,1992,B13:89.[3]FAUREC,DELMASC,FOUASSIERM,etal.Preparationandcharacterizationofcobalt2substituted2nickelhydroxidesstableinKOHmediumPart.2Hydroxidewithanorderedpacking[J].JPowerSources,1991,35:249.[4]FAUREC,DELMASC,WILLMANNP.Preparationandcharacterizationofcobalt2substituted2nickelhydroxidesstableinKOHmediumPart.2Hydroxidewithaturbostraticstruc2ture[J].JPowerSources,1991,35:263.[5]FAUREC,BORTHOMIEUY,DELMASC,etal.Infraredcharacterizationofturbostratic2andwellcrystallized32cobal2tednickelhydroxides[J].JPowerSources,1991,36:113.[6]GUERLOU2DemourguesL,DENAGEC,DELMASC.Newmanganese2substitutednickelhydroxidesPart.Crystalchem2istryandphysicalcharacterization[J].JPowerSources,1994,52:269.[7]GUERLOU2DemourguesL,DELMASC.Newmangnese2substi2tutednickelhydroxidesPart.Interstratificationprocessuponageing[J].JPowerSources,1994,52:275.[8]GUERLOUDemourguesL,DELMASC.Electrochemicalbe2haviorofthemang