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Carbon-covered Fe3O4 hollow cubic hierarchical porous composite as the anode material for lithium-ion batteries

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Abstract

In this work, Prussian blue nanocrystals, a kind of cubic metal-organic frameworks, was firstly covered by a uniform layer of resorcinol-formaldehyde (RF) resin, and then followed with heat treatment at different pyrolysis temperatures. The effects of pyrolysis temperature on the morphologies, phase, pore size, and electrochemical performance of the pyrolysis products were studied in this work. The composite generated at 600 ∘C, FexC600, was a hollow cubic composite of Fe3O4 covered by a thin RF-derived carbon layer. The carbon layer on FexC600 was a robust and conductive protective layer, which can accommodate Fe3O4 NPs and withstand the huge volume change of Fe3O4 during the process of discharge and charge. When used as anodes for lithium-ion batteries, FexC600 showed excellent electrochemical performance. It delivered a discharge capacity of 1126 mAh g−1 with a coulombic efficiency of 98.8% at the current density of 100 mA g−1 after 100 times discharge/charge cycling. It even delivered a capacity of 492 mAh g−1 at the current density of 500 mA g−1. This cubic hollow composite would be a promising alternative anode material for lithium-ion batteries.

A Prussian blue derived carbon-covered Fe3O4 composite was fabricated and severed as the anode material for lithium-ion batteries.

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References

  • An K, Kwon SG, Park M, Na HB, Baik SI, Yu JH, Kim D, Son JS, Kim YW, Song IC, Moon WK, Park HM, Hyeon T (2008) Synthesis of uniform hollow oxide nanoparticles through nanoscale acid etching. Nano Lett 8:4252–4258

    Article  Google Scholar 

  • Chen J, Zou YC, Zhang F, Zhang YC, Guo FF, Li GD (2013a) Superior electrode performance of LiFePO4/C composite prepared by an in situ polymerization restriction method. J Alloys Comp 563:264–268

    Article  Google Scholar 

  • Chen L, Wang ZY, He CN, Zhao NQ, Shi CS, Liu EZ, Li JJ (2013b) Porous graphitic carbon nanosheets as a high-rate anode material for lithium-ion batteries. ACS Appl Mater Interf 5:9537–9545

    Article  Google Scholar 

  • Chen S, Wu J, Zhou R, Zuo L, Li P, Song Y, Wang L (2015) Porous carbon spheres doped with Fe3C as an anode for high-rate lithium-ion batteries. Electrochimica Acta 180:78–85

    Article  Google Scholar 

  • Duan L, Huang Y, Jia D, Wang X, Guo Z (2012) Fe3O4 fuzzy spheroids as anode materials for lithium-ion batteries. Mater Lett 71:151–153

    Article  Google Scholar 

  • Grishechko LI, Amaral-Labat G, Fierro V, Szczurek A, Kuznetsov BN, Celzard A (2016) Biosourced, highly porous, carbon xerogel microspheres. RSC Adv 6:65,698–65,708

    Article  Google Scholar 

  • Gu S, Liu Y, Zhang G, Shi W, Liu Y, Zhu J (2014) Fe3O4/carbon composites obtained by electrospinning as an anode material with high rate capability for lithium ion batteries. RSC Adv 4:41,179–41,184

    Article  Google Scholar 

  • Guo C, Wang L, Zhu Y, Wang D, Yang Q, Qian Y (2015) Fe3O4 nanoflakes in an N-doped carbon matrix as high-performance anodes for lithium ion batteries. Nanoscale 7:10,123–10,129

    Article  Google Scholar 

  • Hu M, Belik AA, Imura M, Mibu K, Tsujimoto Y, Yamauchi Y (2012) Synthesis of superparamagnetic nanoporous iron oxide particles with hollow interiors by using Prussian blue coordination polymers. Chem Mater 24:2698–2707

    Article  Google Scholar 

  • Huang B, Bartholomew CH, Woodfield BF (2014) Improved calculations of pore size distribution for relatively large, irregular slit-shaped mesopore structure. Micropor Mesopor Mater 184:112–121

    Article  Google Scholar 

  • Huang X, Chen J, Lu Z, Yu H, Yan Q, Hng HH (2013) Carbon inverse opal entrapped with electrode active nanoparticles as high-performance anode for lithium-ion batteries. Sci Rep 3:2317

    Article  Google Scholar 

  • Huang Y, Dong Z, Jia D, Guo Z, Cho WI (2011a) Electrochemical properties of α-Fe2O3 /mwcnts as anode materials for lithium-ion batteries. Solid State Ionics 201:54–59

    Article  Google Scholar 

  • Huang Y, Dong Z, Jia D, Guo Z, Cho WI (2011b) Preparation and characterization of core-shell structure Fe3O4/C nanoparticles with unique stability and high electrochemical performance for lithium-ion battery anode material. Electrochim Acta 56:9233–9239

    Article  Google Scholar 

  • Hwang YK, Choi JN, Cho JH, Kwon H, Huh S (2012) Fe3O4-nanoparticle-embedded multifunctional hollow mesoporous silica capsules. Eur J Inorg Chem 2012:3379–3383

    Article  Google Scholar 

  • Jiang H, Zhang W, Chen P, Zhang W, Wang G, Luo X, Luo S (2016) Equipping an adsorbent with an indicator: a novel composite to simultaneously detect and remove heavy metals from water. J Mater Chem A 4:11897– 11,907

    Article  Google Scholar 

  • Kim HS, Baek SH, Jang MW, Sun YK, Yoon CS (2012) Fe-Fe3O4 composite electrode for lithium secondary batteries. J Electrochem Soc 159:A325–A329

    Article  Google Scholar 

  • Laruelle S, Grugeon S, Poizot P, Dolle M, Dupont L, Tarascon JM (2002) On the origin of the extra electrochemical capacity displayed by MO/Li cells at low potential. J Electrochem Soc 149:A627–A634

    Article  Google Scholar 

  • Lei C, Han F, Sun Q, Li WC, Lu AH (2014) Confined nanospace pyrolysis for the fabrication of coaxial Fe3O4@C hollow particles with a penetrated mesochannel as a superior anode for li-ion batteries. Chem - A Eur J 20:139–145

    Article  Google Scholar 

  • Lei D, Lee DC, Magasinski A, Zhao E, Steingart D, Yushin G (2016) Performance enhancement and side reactions in rechargeable nickel-iron batteries with nanostructured electrodes. ACS Appl Mater Interf 8:2088–2096

    Article  Google Scholar 

  • Leventis N, Chandrasekaran N, Sadekar AG, Mulik S, Sotiriou-Leventis C (2010) The effect of compactness on the carbothermal conversion of interpenetrating metal oxide/resorcinol-formaldehyde nanoparticle networks to porous metals and carbides. J Mater Chem 20:7456–7471

    Article  Google Scholar 

  • Li D, Li X, Wang S, Zheng Y, Qiao L, He D (2014) Carbon-wrapped Fe3O4 nanoparticle films grown on nickel foam as binder-free anodes for high-rate and long-life lithium storage. ACS Appl Mater Interf 6:648–654

    Article  Google Scholar 

  • Li G, Wu B, Li L (2016a) Facile synthesis of nitrogen and sulfur dual-doped graphitized carbon microspheres and their high performance in the oxygen reduction reaction. RSC Adv 6:38,880–38,886

    Article  Google Scholar 

  • Li H, Yu H, Zhang X, Guo G, Hu J, Dong A, Yang D (2016b) Bowl-like 3C-SiC nanoshells encapsulated in hollow graphitic carbon spheres for high-rate lithium-ion batteries. Chem Mater 28:1179–1186

    Article  Google Scholar 

  • Liu B, Zhang X, Shioyama H, Mukai T, Sakai T, Xu Q (2010) Converting cobalt oxide subunits in cobalt metal-organic framework into agglomerated Co3O4 nanoparticles as an electrode material for lithium ion battery. J Power Sour 195:857–861

    Article  Google Scholar 

  • Liu N, Lu Z, Zhao J, McDowell MT, Lee HW, Zhao W, Cui Y (2014) A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nat Nanotechnol 9:187–192

    Article  Google Scholar 

  • Liu Y, He X, Hanlon D, Harvey A, Khan U, Li Y, Coleman JN (2016a) Electrical, mechanical, and capacity percolation leads to high-performance MoS2/nanotube composite lithium ion battery electrodes. ACS Nano 10:5980–5990

    Article  Google Scholar 

  • Liu Z, Pulletikurthi G, Endres F (2016b) A prussian blue/zinc secondary battery with a bio-ionic liquid-water mixture as electrolyte. ACS Appl Mater Interf 8:12,158–12,164

    Article  Google Scholar 

  • Ma S, Zhan S, Jia Y, Zhou Q (2015) Superior antibacterial activity of Fe3O4-TiO2 nanosheets under solar light. ACS Appl Mater Interf 7:21,875–21,883

    Article  Google Scholar 

  • Ma Y, Huang Y, Wang X, Jia D, Tang X (2014) One-pot synthesis of Fe3O4/C nanocomposites by PEG-assisted co-precipitation as anode materials for high-rate lithium-ion batteries. J Nanopart Res 16:2614

    Article  Google Scholar 

  • Mitchell E, Gupta RK, Mensah-Darkwa K, Kumar D, Ramasamy K, Gupta BK, Kahol P (2014) Facile synthesis and morphogenesis of superparamagnetic iron oxide nanoparticles for high-performance supercapacitor applications. N J Chem 38:4344–4350

    Article  Google Scholar 

  • Ong QK, Lin XM, Wei A (2011) Role of frozen spins in the exchange anisotropy of core-shell Fe@Fe3O4 nanoparticles. J Phys Chem C 115:2665–2672

    Article  Google Scholar 

  • Park DY, Myung ST (2014) Carbon-coated magnetite embedded on carbon nanotubes for rechargeable lithium and sodium batteries. ACS Appl Mater Interf 6:11,749–11,757

    Article  Google Scholar 

  • Qin X, Zhang H, Wu J, Chu X, He YB, Han C, Miao C, Wang S, Li B, Kang F (2015) Fe3O4 nanoparticles encapsulated in electrospun porous carbon fibers with a compact shell as high-performance anode for lithium ion batteries. Carbon 87:347–356

    Article  Google Scholar 

  • Sun Y, Hu X, Luo W, Xia F, Huang Y (2013) Reconstruction of conformal nanoscale MnO on graphene as a high-capacity and long-life anode material for lithium ion batteries. Adv Funct Mater 23:2436–2444

    Article  Google Scholar 

  • Wang JZ, Zhong C, Wexler D, Idris NH, Wang ZX, Chen LQ, Liu HK (2011) Graphene-encapsulated Fe3O4 nanoparticles with 3D laminated structure as superior anode in lithium ion batteries. Chem Eur J 17:661–667

    Article  Google Scholar 

  • Wang L, Wu J, Chen Y, Wang X, Zhou R, Chen S, Guo Q, Hou H, Song Y (2015) Hollow nitrogen-doped Fe3O4/carbon nanocages with hierarchical porosities as anode materials for lithium-ion batteries. Electrochim Acta 186:50–57

    Article  Google Scholar 

  • Wang R, Xu C, Sun J, Gao L, Lin C (2013) Flexible free-standing hollow Fe3O4/graphene hybrid films for lithium-ion batteries. J Mater Chem A 1:1794–1800

    Article  Google Scholar 

  • Xie W, Li S, Wang S, Xue S, Liu Z, Jiang X, He D (2014) N-doped amorphous carbon coated Fe3O4/SnO2 coaxial nanofibers as a binder-free self-supported electrode for lithium ion batteries. ACS Appl Mater Interf 6:20,334–20,339

    Article  Google Scholar 

  • Xu H, Sun Y, Li J, Li F, Guan X (2016) Aging of zerovalent iron in synthetic groundwater: X-ray photoelectron spectroscopy depth profiling characterization and depassivation with uniform magnetic field. Environ Sci Technol 50(15):8214–8222

    Article  Google Scholar 

  • Xu JS, Zhu YJ, Chen F (2013) Solvothermal synthesis, characterization and magnetic properties of α-Fe2O3 and Fe3O4 flower-like hollow microspheres. J Solid State Chem 199:204–211

    Article  Google Scholar 

  • Yamashita T, Hayes P (2008) Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Appl Surf Sci 254(8):2441–2449

    Article  Google Scholar 

  • Yu WJ, Liu C, Hou PX, Zhang L, Shan XY, Li F, Cheng HM (2015) Lithiation of silicon nanoparticles confined in carbon nanotubes. ACS Nano 9:5063–5071

    Article  Google Scholar 

  • Zeng G, Shi N, Hess M, Chen X, Cheng W, Fan T, Niederberger M (2015) A general method of fabricating flexible spinel-type oxide/reduced graphene oxide nanocomposite aerogels as advanced anodes for lithium-ion batteries. ACS Nano 9:4227–4235

    Article  Google Scholar 

  • Zhang J, Wang K, Guo S, Wang S, Liang Z, Chen Z, Fu J, Xu Q (2014a) One-step carbonization synthesis of hollow carbon nanococoons with multimodal pores and their enhanced electrochemical performance for supercapacitors. ACS Appl Mater Interf 6:2192–2198

    Article  Google Scholar 

  • Zhang L, Wu HB, Madhavi S, Hng HH, Lou XW (2012) Formation of Fe2O3 microboxes with hierarchical shell structures from metal-organic frameworks and their lithium storage properties. J Amer Chem Soc 134:17,388–17,391

    Article  Google Scholar 

  • Zhang S, Zhu L, Song H, Chen X, Zhou J (2014b) Enhanced electrochemical performance of MnO nanowire/graphene composite during cycling as the anode material for lithium-ion batteries. Nano Energy 10:172–180

    Article  Google Scholar 

  • Zhang W, Li X, Liang J, Tang K, Zhu Y, Qian Y (2016) One-step thermolysis synthesis of two-dimensional ultrafine Fe3O4 particles/carbon nanonetworks for high-performance lithium-ion batteries. Nanoscale 8:4733–4741

    Article  Google Scholar 

  • Zhao B, Zheng Y, Ye F, Deng X, Xu X, Liu M, Shao Z (2015) Multifunctional iron oxide nanoflake/graphene composites derived from mechanochemical synthesis for enhanced lithium storage and electrocatalysis. ACS Appl Mater Interf 7:14,446–14,455

    Article  Google Scholar 

  • Zhao X, Xia D, Zheng K (2012) Fe3O4/Fe/carbon composite and its application as anode material for lithium-ion batteries. ACS Appl Mater Interf 4:1350–1356

    Article  Google Scholar 

  • Zhou H, Nanda J, Martha SK, Adcock J, Idrobo JC, Baggetto L, Veith GM, Dai S, Pannala S, Dudney NJ (2013) Formation of iron oxyfluoride phase on the surface of nano-Fe3O4 conversion compound for electrochemical energy storage. J Phys Chem Lett 4:3798–3805

    Article  Google Scholar 

  • Zhou J, Qin J, Zhang X, Shi C, Liu E, Li J, Zhao N, He C (2015) 2D space-confined synthesis of few-layer MoS2 anchored on carbon nanosheet for lithium-ion battery anode. ACS Nano 9:3837–3848

    Article  Google Scholar 

  • Zhu J, Wang T, Fan F, Mei L, Lu B (2016) Atomic scale control of silicon expansion space as ultra-stable battery anodes. ACS Nano 10:8243–8251

    Article  Google Scholar 

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (21165010, 21465014 and 21465015), Science and Technology Support Program of Jiangxi Province (20123BBE50104 and 20133BBE50008), Natural Science Foundation of Jiangxi Province (20142BAB203010 and 20143ACB21016), The Ministry of Education by the Specialized Research Fund for the Doctoral Program of Higher Education (20133604110002), and the Ground Plan of Science and Technology Projects of Jiangxi Educational Committee (KJLD14023).

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  1. College of Chemistry and Chemical Engineering, Jiangxi Normal University, 99 Ziyang Road, Nanchang, 330022, People’s Republic of China

    Shouhui Chen, Rihui Zhou, Yaqin Chen, Yuanyuan Fu, Ping Li, Yonghai Song & Li Wang

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  1. Shouhui Chen
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  2. Rihui Zhou
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Correspondence to Shouhui Chen.

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Chen, S., Zhou, R., Chen, Y. et al. Carbon-covered Fe3O4 hollow cubic hierarchical porous composite as the anode material for lithium-ion batteries. J Nanopart Res 19, 127 (2017). https://doi.org/10.1007/s11051-017-3794-x

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