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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
References
References
[1]Y.Wang,D.Wang,Q.Li,W.Guo,F.Zhang,Y.Yu,Y.Yang,GeneralSynthesisandLithiumStoragePropertiesofMetalOxides/MnO2HierarchicalHollowHybridSpheres,Part.Part.Syst.Charact.1700336（2017）3-8
[2]L.Li,L.Wang,M.Zhang,Q.Huang,L.Chen,F.Wu,High-performancelithium-ionbatteryanodesbasedonMn3O4/nitrogen-dopedporouscarbonhybridstructures,J.Alloy.Compd.775（2019）51-58.
[3]Y.Yang,H.Wang,W.Liu,J.Shi,G.Dong,H.Zhang,D.Li,G.Lu,Polymersalt-derivedcarbon-basednanomaterialsforhigh-performancehybridLi-ioncapacitors,J.Mater.Sci.54（2019）7811-7822.
[4]S.Xiang,Y.Shi,K.Zhang,Y.Chen,R.Ge,C.Wu,H.Sun,B.Yang,DesignandsynthesisofdodecahedralcarbonnanocagesincorporatedwithFe3O4,RSCAdv.7（2017）13257-13262.
[5]D.Su,H.Ahn,G.Wang,One-dimensionalmagnetiteFe3O4nanowiresaselectrodematerialforLi-ionbatterieswithimprovedelectrochemicalperformance,J.PowerSources244（2013）742-746.
[6]Y.Wang,X.Chen,Z.Liu,H.Wu,H.Zhao,H.Liu,Y.Zhang,Cycling-inducedstructurerefinementofMnOnanorodswrappedbyN-dopedcarbonwithinternalvoidspaceforadvancedlithium-ionanodes,Appl.Surf.Sci.479（2019）386-394.
[7]T.Feng,J.Wang,J.Yang,M.Wu,Investigationoforderedmesoporouscarbon@MnOcore–shellnanospheresasanodematerialforlithiumionbatteries,J.Mater.Sci.54（2019）6461–6470.
[8]Z.Xiangyang,B.Tao,Y.Juan,W.Kang,L.Chongwu,Synthesisofthree-dimensionalcross-linkedMnO@Ccompositeashigh-performanceanodematerialforlithium-ionbatteries,Ionics22（2016）779–788.
[9]P.Mu,W.Ma,Y.Zhao,C.Zhang,S.Ren,F.Wang,C.Yan,Y.Chen,J.H.Zeng,J.Jiang,FacilepreparationofMnO/nitrogen-dopedporouscarbonnanotubescompositesandtheirapplicationinenergystorage,J.PowerSources426（2019）33–39.
[10]H.Liu,J.Liu,Z.Yang,D.Tang,Controlledconstructionofhierarchicalhollowmicro/nanourchin-likeb-MnO2withsuperiorlithiumstorageperformance,J.Alloy.Compd.795（2019）336-342.
[11]D.Wang,Y.Wang,Q.Li,G.W,Guo.F.Zhang,S.Niu,Urchin-likeα-Fe2O3/MnO2hierarchicalhollowcompositemicrospheresaslithium-ionbatteryanodes,J.PowerSources393（2018）186–192.
[12]M.He,P.Zuo,H.Zhang,J.Hua,Y.Ma,C.Du,X.Cheng,Y.Gao,G.Yin,Polymericmultilayer-modifiedmanganesedioxidewithhollowporousstructureassulfurhostforlithiumsulfurbatteries,ElectrochimicaActa259（2018）440-448.
[13]X.Ma,Y.Zhai,N.Wang,J.Yang,Y.Qian,Mn3O4@Ccore–shellcompositesasanimprovedanodeforadvancedlithiumionbatteries,RSCAdv.5（2015）46829-46833.
[14]B.Sambandam,V.Soundharrajan,J.Song,S.kim,J.Jo,D.PTung,S.Kim,V.Mathew,J.Kim,Aspongenetwork-shapedMn3O4/Canodederivedfromasimple,one-potmetalorganicframework-combustiontechniqueforimprovedlithiumionstorage,Inorg.Chem.Front.3（2016）1609–1615.
[15]X.Gu,J.Yue,L.Li,H.Xue,J.Yang,X.Zhao,GeneralSynthesisofMnOx（MnO2,Mn2O3,Mn3O4,MnO）HierarchicalMicrospheresasLithium-ionBatteryAnodes,ElectrochimicaActa184（2015）250-256
[16]G.Luo,W.Liu,S.Zeng,C.Zhang,X.Yu,Y.Fang,L.Sun,HierarchalmesoporousSnO2@C@TiO2nanochainsforanodematerialoflithium-ionbatterieswithexcellentcyclingstability,ElectrochimicaActa184（2015）219–225.
[17]L.Liu,J.Peng,G.Wang,Y.Ma,F.Yu,B.Dai,X.Guo,C.Wong,SynthesisofmesoporousTiO2@C@MnO2multishelledhollownanosphereswithhighratecapabilityandstabilityforlithium-ionbatteries,RSCAdv.6（2016）65243–65251.
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