Abstract
Fe/Fe3O4@r-GO composite nanocages with a hollow porous heterostructure, which look like “flower cluster,” are prepared by a mild, simple, and flexible method, followed by a thermal treatment. Metal-organic framework Prussian blue (PB), used as a precursor of Fe3O4, possesses a special hollow porous morphology, which is able to shorten transmission path and relives the mechanical stress during charge/discharge cycles. Verified by SEM and TEM characterizations, the Fe/Fe3O4 nanocage coated with uniform graphene sheets is achieved. Furthermore, XRD and XPS analysis combined with TEM results also prove that the composite is mainly composed of Fe, Fe3O4, and C. A series of electrochemical tests show that Fe/Fe3O4@r-GO composite electrodes exhibit a superior reversible capacity, rate capability, and cycling stability. The composite delivers a high reversible capability of 1200 mAh g−1 after 160 cycles at a current density of 100 mA g−1. Especially, when the current density is increased to 1000 mA g−1, the composite delivers a capacity of 455 mAh g−1. Even at a current density of 2000 mA g−1, a capacity of 355 mAh g−1 is retained. The outstanding electrochemical performances are mainly attributed to the integrity of hollow porous nanocube structure and doping of moderate graphene, which enables to promote the conductivity of electrode and build a continue network between Fe/Fe3O4 nanocubes to further accelerate ion/electron migration rate and relieve mechanical stress during cycles.
Similar content being viewed by others
References
Xu X, Shen K, Wen M (2018) Facile synthesis of three-dimensional Cu/Fe3O4 nanowires as binder-free anode for lithium-ion batteries. Appl Surf Sci 450:356–363
Guo C, He J, Wu X (2018) Facile fabrication of honeycomb-like carbon network-encapsulated Fe/Fe3C/Fe3O4 with enhanced Li-storage performance. ACS Appl Mater Interfaces 10(42):35994–36001
Zhang Z, Wang F, An Q (2015) Synthesis of graphene@ Fe3O4@ C core–shell nanosheets for high-performance lithium ion batteries. J Mater Chem A 3(13):7036–7043
Jiang X, Yang X, Zhu Y (2015) Graphene/carbon-coated Fe3O4 nanoparticle hybrids for enhanced lithium storage. J Mater Chem A 3(5):2361–2369
Wang H, Xie J, Almkhelfe H (2017) Microgel-assisted assembly of hierarchical porous reduced graphene oxide for high-performance lithium-ion battery anodes. J Mater Chem A 5(44):23228–23237
Ma Y, Huang J, Lin L (2017) Self-assembly synthesis of 3D graphene-encapsulated hierarchical Fe3O4 nano-flower architecture with high lithium storage capacity and excellent rate capability. J Power Sources 365:98–108
Wei W, Yang S, Zhou H (2013) 3D graphene foams cross-linked with pre-encapsulated Fe3O4 nanospheres for enhanced lithium storage. Adv Mater 25(21):2909–2914
Bruck AM, Gannett CN, Bock DC (2017) The electrochemistry of Fe3O4/polypyrrole composite electrodes in lithium-ion cells: the role of polypyrrole in capacity retention. J Electrochem Soc 164(1):A6260–A6267
Min J, Kierzek K, Chen X et al (2017) Facile synthesis of porous iron oxide/graphene hybird nanocomposites and potential application in electrochemical energy storage[J]. New J Chem. https://doi.org/10.1039/C7NJ03416D
Shi X, Shuai Z, Chen X et al (2017) Effect of iron oxide impregnated in hollow carbon sphere as symmetric supercapacitors[J]. J Alloys Compd 726:466–473
Xu Y, Feng J, Chen X et al (2015) Beaded structured CNTs-Fe3O4@C with low Fe3O4 content as anode materials with extra enhanced performances in lithium ion batteries[J]. RSC Adv 5:28864–28869
Liu B, Zhang Q, Jin Z (2018) Uniform pomegranate-like nanoclusters organized by ultrafine transition metal oxide@ nitrogen-doped carbon subunits with enhanced lithium storage properties. Adv Energy Mater 8(7):1702347
Wang Y, Gao Y, Shao J (2018) Ultrasmall Fe3O4 nanodots within N-doped carbon frameworks from MOFs uniformly anchored on carbon nanowebs for boosting Li-ion storage. J Mater Chem A 6(8):3659–3666
Wang L, Wu J, Chen Y (2015) Hollow nitrogen-doped Fe3O4/carbon nanocages with hierarchical porosities as anode materials for lithium-ion batteries. Electrochim Acta 186:50–57
Jiang T, Bu F, Feng X (2017) Porous Fe2O3 nanoframeworks encapsulated within three-dimensional graphene as high-performance flexible anode for lithium-ion battery. ACS Nano 11(5):5140–5147
Zhang N, Chen C, Yan X (2017) Bacteria-inspired fabrication of Fe3O4-carbon/graphene foam for lithium-ion battery anodes. Electrochim Acta 223:39–46
Zhou S, Zhou Y, Jiang W (2018) Synthesis of Fe3O4 cluster microspheres/graphene aerogels composite as anode for high-performance lithium ion battery. Appl Surf Sci 439:927–933
Zhang M, Hou C, Halder A (2017) Interlocked graphene–Prussian blue hybrid composites enable multifunctional electrochemical applications. Biosens Bioelectron 89:570–577
Zhang L, Zhang A, Du D (2012) Biosensor based on Prussian blue nanocubes/reduced graphene oxide nanocomposite for detection of organophosphorus pesticides. Nanoscale 4(15):4674–4679
Zhao G, Feng JJ, Zhang QL (2005) Synthesis and characterization of Prussian blue modified magnetite nanoparticles and its application to the electrocatalytic reduction of H2O2. Chem Mater 17(12):3154–3159
Zhang L, Wu HB, Lou XW (2013) Metal–organic-frameworks-derived general formation of hollow structures with high complexity. J Am Chem Soc 135(29):10664–10672
Li Z, Li B, Yin L (2014) Prussion blue-supported annealing chemical reaction route synthesized double-shelled Fe2O3/Co3O4 hollow microcubes as anode materials for lithium-ion battery. ACS Appl Mater Interfaces 6(11):8098–8107
Liu L, Shi J, Wang R (2017) Fabrication of double-shelled Fe2O3/CeO2 boxes from CeO2-modified Prussian blue and their enhanced performances for CO removal and water treatment. J Alloys Compd 725:544–556
Ai Q, Yuan Z, Huang R (2019) One-pot co-precipitation synthesis of Fe3O4 nanoparticles embedded in 3D carbonaceous matrix as anode for lithium ion batteries. J Mater Sci 54(5):4212–4224
Zhang WM, Wu XL, Hu JS (2008) Carbon coated Fe3O4 nanospindles as a superior anode material for lithium-ion batteries. Adv Funct Mater 18(24):3941–3946
Ma M, Zhang J, Shen W, Guo S (2019) Cladding transition metal oxide particles with graphene oxide sheets: an efficient protocol to improve their structural stability and lithium ion diffusion rate. J Solid State Electrochem 23(10):2969–2977
Noerochim L, Wang JZ, Chou SL (2010) SnO2-coated multiwall carbon nanotube composite anode materials for rechargeable lithium-ion batteries. Electrochim Acta 56(1):314–320
He J, Zhao S, Lian Y (2017) Graphene-doped carbon/Fe3O4 porous nanofibers with hierarchical band construction as high-performance anodes for lithium-ion batteries. Electrochim Acta 229:306–315
Sathish M, Tomai T, Honma I (2012) Graphene anchored with Fe3O4 nanoparticles as anode for enhanced Li-ion storage. J Power Sources 217:85–91
Li L, Raji ARO, Tour JM (2013) Graphene-wrapped MnO2–graphene nanoribbons as anode materials for high-performance lithium ion batteries. Adv Mater 25(43):6298–6302
Zhu Y, Murali S, Cai W (2010) Graphene and graphene oxide: synthesis, properties, and applications. Adv Mater 22(35):3906–3924
Zheng GZ, Hui JY, Fei L (2011) Preparation of graphene oxide by ultrasound-assisted hummers method. Chinese J Inorg Chem 27:1753–1757
Shen X, Wu S, Liu Y (2009) Morphology syntheses and properties of well-defined Prussian blue nanocrystals by a facile solution approach. J Colloid Interface Sci 329(1):188–195
Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80(6):1339–1339
Wang Z, Luan D, Madhavi S (2012) Assembling carbon-coated α-Fe2O3 hollow nanohorns on the CNT backbone for superior lithium storage capability. Energy Environ Sci 5(1):5252–5256
Zhou G, Wang DW, Li F (2010) Graphene-wrapped Fe3O4 anode material with improved reversible capacity and cyclic stability for lithium ion batteries. Chem Mater 22(18):5306–5313
Xu Y, Wu Q, Sun Y (2010) Three-dimensional self-assembly of graphene oxide and DNA into multifunctional hydrogels. ACS Nano 4(12):7358–7362
Xiao L, Wu D, Han S (2013) Self-assembled Fe2O3/graphene aerogel with high lithium storage performance. ACS Appl Mater Interfaces 5(9):3764–3769
Wang R, Xu C, Sun J (2014) Three-dimensional Fe2O3 nanocubes/nitrogen-doped graphene aerogels: nucleation mechanism and lithium storage properties. Sci Rep 4:7171
Jin E, Lu X, Cui L (2010) Fabrication of graphene/prussian blue composite nanosheets and their electrocatalytic reduction of H2O2. Electrochim Acta 55(24):7230–7234
Liu XW, Yao ZJ, Wang YF (2010) Graphene oxide sheet–prussian blue nanocomposites: green synthesis and their extraordinary electrochemical properties. Colloids Surf B: Biointerfaces 81(2):508–512
Kaneti YV, Tang J, Salunkhe RR (2017) Nanoarchitectured design of porous materials and nanocomposites from metal-organic frameworks. Adv Mater 29(12):1604898
He Z, Wang K, Zhu S (2018) MOF-derived hierarchical MnO-doped Fe3O4@ C composite nanospheres with enhanced lithium storage. ACS Appl Mater Interfaces 10(13):10974–10985
Funding
This work is supported by Hubei Provincial Major Technology Innovation project of China (No. 2018AAA056) and the International Science & Technology Cooperation Program of China (2016YFE0124300).
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Wu, H., Ai, Q., Yang, C. et al. Preparation and electrochemical properties of Fe/Fe3O4@r-GO composite nanocage with 3D hollow structure. J Solid State Electrochem 25, 869–879 (2021). https://doi.org/10.1007/s10008-020-04865-y
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10008-020-04865-y