Supplementary Material.docx
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Supplementary Material.docx
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SupplementaryMaterial
SupplementaryInformation
ControlledsynthesisofFe3O4@C@manganeseoxides(MnO2,Mn3O4andMnO)hierarchicalhollownanospheresandtheirsuperiorlithiumstorageproperties
YongWang*a,ShunRaoa,PeiyuanMaoa,FanchaoZhanga,PandengXiaoa,LianPengbandQingshanZhu*b
aDepartmentofChemistry,CapitalNormalUniversity,Beijing100048,China.E-mail:
yongwang@(Y.Wang)
bStateKeyLaboratoryofMultiphaseComplexSystems,InstituteofProcessEngineering,ChineseAcademyofSciences,Beijing100190,China.E-mail:
qszhu@(Q.Zhu)
*Correspondingauthor.E-mail:
yongwang@(Y.Wang);qszhu@(Q.Zhu).
S1.HRTEMandTEMimagesofFe3O4hollownanospheres;FESEMandTEMimagesofFe3O4@Chollownanospheres(FCHNs).
Fig.S1.(a)HRTEMand(b-c)TEMimagesofFe3O4hollownanospheres;(d)FESEMand(e-f)TEMimagesofFe3O4@Chollownanospheres(FCHNs).
S2.MagnifiedHRTEMimageofFCMnO2s.
Fig.S2.MagnifiedHRTEMimageofFCMnO2s.
S3.MagnifiedHRTEMimageofFCMn3O4s.
Fig.S3.MagnifiedHRTEMimageofFCMn3O4s.
S4.MagnifiedHRTEMimageofFCMnOs.
Fig.S4.MagnifiedHRTEMimageofFCMnOs.
S5.XRDpatternsofsamplesaftercalcinationat800℃
Fig.S5.XRDpatternsofsamplesaftercalcinationat800℃:
(a)FCHNs,(b)FCMnO2s,FCMnOsandFCMn3O4s.(Fe2O3,JCPDScardNo.13-0534,signal$;Mn3O4,JCPDScardNo.24-0734,signal&)
S6.Mn2pXPSspectraofFCMnO2s,FCMn3O4sandFCMnOs.
FromtheMn2pspectruminFigureS3a,aspin-energyseparationofMn2p1/2(653.3eV)andMn2p3/2(641.4eV)peaksis11.9eV,suggestingthepresentenceofMn4+(MnO2)[1].Thehigh-resolutionspectrumofMn2pinFig.S3bshowstwodistinctpeaksat~653.3eVand~641.7eV,whicharerespectivelyascribedtoMn2p1/2andMn2p3/2,andthesplittingwidth(11.6eV)isingoodagreementwiththereportedresultsofMn3O4.Moreover,theMn2pXPSspectrumexhibitsthreecharacteristicpeaksat640.8eV,642.1eVand643.6eV,correspondingtospin-orbitpeaksofmanganesewithmixedvalencestatesof+2,+4and+3,respectively[2].InFigureS3c,Mn2ppeakcanbespiltintoMn2p1/2(653.4eV)andMn2p3/2(641.8eV),indicatingtheexistenceofMnO.TheMn2p3/2centeredat641.8eVcanbedividedintothreepeakscenteredat640.9,642.0,and643.5eV.ThethreepeaksrepresenttheoxidationstateofMn(II),furtherconfirmingtheexistenceofMn+2[3].
Fig.S6.Mn2pXPSspectraof(a)FCMnO2s,(b)FCMn3O4sand(c)FCMnOs.
TableS1.ThecontentofcomponentsinthesamplesonthebasisofTGandICP-MS.
Fe3O4@C
Fe3O4@C@MnO2
Fe3O4@C@Mn3O4
Fe3O4@C@MnO
C
27.4%
20.3%
20.9%
21.3%
Fe3O4
72.6%
53.7%
55.5%
56.4%
MnOX
\
26.0%
23.6%
22.3%
S7.TheequivalentcircuitofEIS
Fig.S7.TheequivalentcircuitofEIS.
S8.TEMimagesofFe3O4@Chollownanospheresafter150cycles
Fig.S8.TEMimagesofFe3O4@Chollownanospheresafter150cyclesat0.1Ag-1.
S9.HRTEMimagesofFCMnO2s,FCMn3O4sandFCMnOsafter150cycles.
InHRTEMimageofFig.S5,itcanbeseenthatthestripespacingsof0.277nmand0.248nmcorrespondtothe(103)and(211)planeofMn3O4,respectively,whilethestripespacingof0.253nmisattributedtothe(311)planeofFe3O4,indicatingtheconversionofthreehollownanocompositestoFe3O4@C@Mn3O4nanocompositesafterintensecycles.
Fig.S9.HRTEMimagesofFCMnO2s,FCMn3O4sandFCMnOsafter150cycles.
TableS2.ComparisonoftheElectrochemicalPropertiesofFe3O4@C@MnOx(MnO2,Mn3O4,MnO)withsomereportedFe3O4/C,MnOx,MnOx/CandotherTMO@C@TMOcompositeanodematerialsforLIBs
No.
Sample
Currentdensity(mAg−1)
1st(mAhg-1)
no.ofcycles
capacity
(mAhg−1)
Refs
1
Fe3O4/Ccarbonnanocages
100
1370
60
584
[4]
2
Fe3O4nanowires
500
1868
100
503
[5]
3
carbon-wrappedMnOnanorods
1000
600
570
[6]
4
mesoporouscarbon@MnO
500
1000
572
[7]
5
Cross-linkedMnO@C
200
100
615
[8]
6
MnO/Nitrogen-DopedPorousCarbonNanotubes
100
\
250
652
[9]
500
\
250
512
7
micro/nanohollowurchin-MnO2
20
100
455.12
[10]
8
MnO2hierarchicalhollowspheres
100
1232
150
420
[11]
9
S@MnO2@PMcomposites
0.2C
1000
481
[12]
10
Mn3O4@Ccore–shell
500
100
765
[13]
11
Mn3O4/C
200
1186
100
768
[14]
12
MnO2microspheres
0.5C
\
100
240
[15]
Mn2O3microspheres
0.5C
\
100
396
[15]
Mn3O4microspheres
0.5C
\
100
271
[15]
MnOmicrospheres
0.5C
\-
100
810
[15]
13
mesoporousSnO2@C@TiO2
100
807
100
369
[16]
14
mesoporousTiO2@C@MnO2
0.3C
100
506.8
[17]
3C
200
278.7
15
Fe3O4@C
100
1140
150
634
Thiswork
500
1038
500
387
Fe3O4@C@MnO2
100
1138
150
708
Thiswork
500
1067
500
609
Fe3O4@C@Mn3O4
100
1233
150
833
Thiswork
500
1143
500
780
Fe3O4@C@MnO
100
996
150
670
Thiswork
500
1010
500
523
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