logo

Urchin-like FeOOH hollow microspheres decorated with MnO2 for enhanced supercapacitor performance

More info
  • ReceivedJun 14, 2017
  • AcceptedSep 15, 2017
  • PublishedOct 13, 2017

Abstract

Ultrathin MnO2 decorated hierarchical urchin-like FeOOH hollow micro-nanospheres have been designed and synthesized through a facile hydrothermal route. The microspheres are made of FeOOH nanofibers with a diameter of 10 nm. Due to the synergetic effect between the unique FeOOH hollow micro/nanostructures and ultrathin MnO2 layer, the as-fabricated FeOOH@MnO2 hybrid electrode exhibits a high specific capacitance of 1192 F g−1 at a current density of 1 A g−1. It also reveals high rate capabilities and superior stability. Moreover, the asymmetric supercapacitor (ASC) assembled from the FeOOH@MnO2 and the active carbon (AC) delivers a high energy density of 40.2 W h kg−1 at a power density of 0.78 kW kg−1, and the energy density could remain 10.4 W h kg−1 under a condition of high power density of 11.7 kW kg−1.


Funded by

the National Natural Science Foundation of China(21771137)

Shandong Provincial Natural Science Foundation(ZR2016BM12)

the Fundamental Research Funds for the Central Universities(15CX08010A)

and the starting-up fund from TJUT.


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21771137), Shandong Provincial Natural Science Foundation (ZR2016BM12), the Fundamental Research Funds for the Central Universities (15CX08010A), and the starting-up fund from TJUT.


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Du K designed and engineered the samples; Du K wrote the draft with discussion of Wei G, Zhao F, Li J, and An C. Wang H performed the SEM and XRD characterization. An CH supervised the projects and carefully reviewed and revised this manuscript. All authors contributed to the general discussion.


Author information

Kun Du is currently a Master student in materials science from China University of Petroleum. Her research interests include the synthesis, characterization, and explorations of efficient catalysts in the fields of clean energy production and environmental purification.


Changhua An received his PhD degree from the University of Science and Technology of China (USTC) in 2003. In 2013, he was promoted to full professor of materials science. Now he is a professor at Tianjin University of Technology. His research interests focus on the synthesis, characterization, and explorations of efficient catalysts in the fields of clean energy production and environmental purification.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


References

[1] Wang H, Dai H. Strongly coupled inorganic–nano-carbon hybrid materials for energy storage. Chem Soc Rev, 2013, 42: 3088-3113 CrossRef PubMed Google Scholar

[2] Zhang GQ, Wu HB, Hoster HE, et al. Single-crystalline NiCo2O4 nanoneedle arrays grown on conductive substrates as binder-free electrodes for high-performance supercapacitors. Energ Environ Sci, 2012, 5: 9453-9456 CrossRef Google Scholar

[3] Chu S, Majumdar A. Opportunities and challenges for a sustainable energy future. Nature, 2012, 488: 294-303 CrossRef PubMed ADS Google Scholar

[4] Miller JR, Simon P. Electrochemical capacitors for energy management. Science, 2008, 321: 651-652 CrossRef PubMed Google Scholar

[5] Wang Z, Jia W, Jiang M, et al. One-step accurate synthesis of shell controllable CoFe2O4 hollow microspheres as high-performance electrode materials in supercapacitor. Nano Res, 2016, 9: 2026-2033 CrossRef Google Scholar

[6] Zhang YQ, Li L, Shi SJ, et al. Synthesis of porous Co3O4 nanoflake array and its temperature behavior as pseudo-capacitor electrode. J Power Sources, 2014, 256: 200-205 CrossRef ADS Google Scholar

[7] Wu ZS, Zhou G, Yin LC, et al. Graphene/metal oxide composite electrode materials for energy storage. Nano Energ, 2012, 1: 107-131 CrossRef Google Scholar

[8] Liu M, Gan L, Xiong W, et al. Development of MnO2/porous carbon microspheres with a partially graphitic structure for high performance supercapacitor electrodes. J Mater Chem A, 2014, 2: 2555-2562 CrossRef Google Scholar

[9] Shang X, Chi JQ, Lu SS, et al. Carbon fiber cloth supported interwoven WS2 nanosplates with highly enhanced performances for supercapacitors. Appl Surf Sci, 2017, 392: 708-714 CrossRef ADS Google Scholar

[10] Li Y, Li Z, Shen PK. Simultaneous formation of ultrahigh surface area and three-dimensional hierarchical porous graphene-like networks for fast and highly stable supercapacitors. Adv Mater, 2013, 25: 2474-2480 CrossRef PubMed Google Scholar

[11] Wu S, Zhu Y. Highly densified carbon electrode materials towards practical supercapacitor devices. Sci China Mater, 2017, 60: 25-38 CrossRef Google Scholar

[12] Shinde SK, Dubal DP, Ghodake GS, et al. Nanoflower-like CuO/Cu(OH)2 hybrid thin films: synthesis and electrochemical supercapacitive properties. J Electroanal Chem, 2014, 732: 80-85 CrossRef Google Scholar

[13] Wei G, Du K, Zhao X, et al. Carbon quantum dot-induced self-assembly of ultrathin Ni(OH)2 nanosheets: a facile method for fabricating three-dimensional porous hierarchical composite micro-nanostructures with excellent supercapacitor performance. Nano Res, 2017, 10: 3005-3017 CrossRef Google Scholar

[14] Wang JG, Yang Y, Huang ZH, et al. Interfacial synthesis of mesoporous MnO2/polyaniline hollow spheres and their application in electrochemical capacitors. J Power Sources, 2012, 204: 236-243 CrossRef Google Scholar

[15] Xu J, Wang Q, Wang X, et al. Flexible asymmetric supercapacitors based upon Co9S8 nanorod//Co3O4@RuO2 nanosheet arrays on carbon cloth. ACS Nano, 2013, 7: 5453-5462 CrossRef PubMed Google Scholar

[16] Inagaki M, Konno H, Tanaike O. Carbon materials for electrochemical capacitors. J Power Sources, 2010, 195: 7880-7903 CrossRef ADS Google Scholar

[17] Yuan C, Li J, Hou L, et al. Ultrathin mesoporous NiCo2O4 nanosheets supported on Ni Foam as advanced electrodes for supercapacitors. Adv Funct Mater, 2012, 22: 4592-4597 CrossRef Google Scholar

[18] Zhou C, Zhang Y, Li Y, et al. Construction of high-capacitance 3D CoO@polypyrrole nanowire array electrode for aqueous asymmetric supercapacitor. Nano Lett, 2013, 13: 2078-2085 CrossRef PubMed ADS Google Scholar

[19] Deori K, Ujjain SK, Sharma RK, et al. Morphology controlled synthesis of nanoporous Co3O4 nanostructures and their charge storage characteristics in supercapacitors. ACS Appl Mater Interfaces, 2013, 5: 10665-10672 CrossRef PubMed Google Scholar

[20] Hu JS, Zhong LS, Song WG, et al. Synthesis of hierarchically structured metal oxides and their application in heavy metal ion removal. Adv Mater, 2008, 20: 2977-2982 CrossRef Google Scholar

[21] Cao M, Liu T, Gao S, et al. Single-crystal dendritic micro-pines of magnetic α-Fe2O3: large-scale synthesis, formation mechanism, and properties. Angew Chem Int Ed, 2005, 44: 4197-4201 CrossRef PubMed Google Scholar

[22] Zhang T, Zhang X, Ng J, et al. Fabrication of magnetic cryptomelane-type manganese oxide nanowires for water treatment. Chem Commun, 2011, 47: 1890-1892 CrossRef PubMed Google Scholar

[23] Zeng Y, Yu M, Meng Y, et al. Iron-based supercapacitor electrodes: advances and challenges. Adv Energ Mater, 2016, 6: 1601053 CrossRef Google Scholar

[24] Choi WS, Koo HY, Zhongbin Z, et al. Templated synthesis of porous capsules with a controllable surface morphology and their application as gas sensors. Adv Funct Mater, 2007, 17: 1743-1749 CrossRef Google Scholar

[25] Nie Z, Wang Y, Zhang Y, et al. Multi-shelled α-Fe2O3 microspheres for high-rate supercapacitors. Sci China Mater, 2016, 59: 247-253 CrossRef Google Scholar

[26] Huang M, Li F, Dong F, et al. MnO2-based nanostructures for high-performance supercapacitors. J Mater Chem A, 2015, 3: 21380-21423 CrossRef Google Scholar

[27] Reddy AE, Anitha T, Gopi CVVM, et al. Fabrication of a snail shell-like structured MnO2@CoNiO2 composite electrode for high performance supercapacitors. RSC Adv, 2017, 7: 12301-12308 CrossRef Google Scholar

[28] Cheng G, Xie S, Lan B, et al. Phase controllable synthesis of three-dimensional star-like MnO2 hierarchical architectures as highly efficient and stable oxygen reduction electrocatalysts. J Mater Chem A, 2016, 4: 16462-16468 CrossRef Google Scholar

[29] Zhu J, Tang S, Xie H, et al. Hierarchically porous MnO2 microspheres doped with homogeneously distributed Fe3O4 nanoparticles for supercapacitors. ACS Appl Mater Interfaces, 2014, 6: 17637-17646 CrossRef PubMed Google Scholar

[30] He Y, Chen W, Li X, et al. Freestanding three-dimensional graphene/MnO2 composite networks as ultralight and flexible supercapacitor electrodes. ACS Nano, 2013, 7: 174-182 CrossRef PubMed Google Scholar

[31] Yang P, Ding Y, Lin Z, et al. Low-cost high-performance solid-state asymmetric supercapacitors based on MnO2 nanowires and Fe2O3 nanotubes. Nano Lett, 2014, 14: 731-736 CrossRef PubMed ADS Google Scholar

[32] Wang H, Xu Z, Yi H, et al. One-step preparation of single-crystalline Fe2O3 particles/graphene composite hydrogels as high performance anode materials for supercapacitors. Nano Energ, 2014, 7: 86-96 CrossRef Google Scholar

[33] Lu X, Zeng Y, Yu M, et al. Oxygen-deficient hematite nanorods as high-performance and novel negative electrodes for flexible asymmetric supercapacitors. Adv Mater, 2014, 26: 3148-3155 CrossRef PubMed Google Scholar

[34] Yang S, Song X, Zhang P, et al. Self-assembled α-Fe2O3 mesocrystals/graphene nanohybrid for enhanced electrochemical capacitors. Small, 2014, 10: 2270-2279 CrossRef PubMed Google Scholar

[35] Lu XF, Wu DJ, Li RZ, et al. Hierarchical NiCo2O4 nanosheets@hollow microrod arrays for high-performance asymmetric supercapacitors. J Mater Chem A, 2014, 2: 4706-4713 CrossRef Google Scholar

[36] Chen YC, Lin YG, Hsu YK, et al. Novel iron oxyhydroxide lepidocrocite nanosheet as ultrahigh power density anode material for asymmetric supercapacitors. Small, 2014, 10: 3803-3810 CrossRef PubMed Google Scholar

[37] Chemelewski WD, Lee HC, Lin JF, et al. Amorphous FeOOH oxygen evolution reaction catalyst for photoelectrochemical water splitting. J Am Chem Soc, 2014, 136: 2843-2850 CrossRef PubMed Google Scholar

[38] Yu Q, Meng X, Wang T, et al. Hematite films decorated with nanostructured ferric oxyhydroxide as photoanodes for efficient and stable photoelectrochemical water splitting. Adv Funct Mater, 2015, 25: 2686-2692 CrossRef Google Scholar

[39] Barik R, Jena BK, Dash A, et al. In situ synthesis of flowery-shaped α-FeOOH/Fe2O3 nanoparticles and their phase dependent supercapacitive behaviour. RSC Adv, 2014, 4: 18827-18834 CrossRef Google Scholar

[40] Rao CNR, Sarma DD, Vasudevan S, et al. Study of transition metal oxides by photoelectron spectroscopy. Proc R Soc A-Math Phys Eng Sci, 1979, 367: 239-252 CrossRef ADS Google Scholar

[41] Wang Q, Liu B, Wang X, et al. Morphology evolution of urchin-like NiCo2O4 nanostructures and their applications as psuedocapacitors and photoelectrochemical cells. J Mater Chem, 2012, 22: 21647-21653 CrossRef Google Scholar

[42] Zhu Y, Wu Z, Jing M, et al. Porous NiCo2O4 spheres tuned through carbon quantum dots utilised as advanced materials for an asymmetric supercapacitor. J Mater Chem A, 2015, 3: 866-877 CrossRef Google Scholar

[43] Zhou H, Liu L, Wang X, et al. Multimodal porous CNT@TiO2 nanocables with superior performance in lithium-ion batteries. J Mater Chem A, 2013, 1: 8525-8528 CrossRef Google Scholar

[44] Wang M, Li Z, Wang C, et al. Novel core-shell FeOF/Ni(OH)2 hierarchical nanostructure for all-solid-state flexible supercapacitors with enhanced performance. Adv Funct Mater, 2017, 27: 1701014 CrossRef Google Scholar

[45] Chen J, Xu J, Zhou S, et al. Amorphous nanostructured FeOOH and Co–Ni double hydroxides for high-performance aqueous asymmetric supercapacitors. Nano Energ, 2016, 21: 145-153 CrossRef Google Scholar

[46] Wei W, Cui X, Chen W, et al. Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chem Soc Rev, 2011, 40: 1697-1721 CrossRef PubMed Google Scholar

[47] Liu J, Jiang J, Bosman M, et al. Three-dimensional tubular arrays of MnO2–NiO nanoflakes with high areal pseudocapacitance. J Mater Chem, 2012, 22: 2419-2426 CrossRef Google Scholar

  • Figure 1

    SEM images of FeOOH (a, b) and FeOOH@MnO2 (c, d).

  • Figure 2

    (a) XRD patterns of FeOOH and FeOOH@MnO2; (b) TEM image of a FeOOH microsphere; (c) low-magnification and (d) high-resolution TEM image of FeOOH@MnO2; (e–h) EDS elemental mapping from several hybrid nanofibers, and (i) EDS spectrum of the FeOOH@MnO2 nanofibers shown in (e).

  • Figure 3

    (a) XPS spectrum of α-FeOOH@MnO2 and high-resolution XPS spectra of (b) Fe 2p, (c) O 1s, and (d) Mn 2p.

  • Figure 4

    (a) Comparison of CV curves of the FeOOH and FeOOH@MnO2 electrodes at scan rate of 50 mV s−1; (b) comparison of GCD curves of the FeOOH and FeOOH@MnO2 electrodes at current density of 2 A g−1; (c) CV curves of FeOOH@MnO2 at various scan rates; (d) GCD curves of FeOOH@MnO2 electrode at different current densities of 1, 2, 3, 5, 10, and 20 A g−1, respectively; (e) variation in specific capacitance with current density, and (f) cycling performance of the FeOOH and FeOOH@MnO2 electrodes for 1000 cycles at 5 A g−1.

  • Figure 5

    (a) CV curves of the FeOOH@MnO2//AC ASC at various scan rates; (b) GCD curves of FeOOH@MnO2 at various current densities; (c) the Ragone of the energy densities and power densities of FeOOH@MnO2 and the inset is schematic showing ASC device construction using FeOOH@MnO2 and AC electrodes; (d) cycling performance of FeOOH@MnO2//AC ASC measured at a current density of 10 A g−1.

Copyright 2020 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有

京ICP备17057255号       京公网安备11010102003388号