Elsevier

Electrochimica Acta

Volume 116, 10 January 2014, Pages 467-474
Electrochimica Acta

One-dimension MnCo2O4 nanowire arrays for electrochemical energy storage

https://doi.org/10.1016/j.electacta.2013.11.081Get rights and content

Highlights

  • MnCo2O4 nanowire array is prepared by a fast and facile hydrothermal method.

  • MnCo2O4 nanowire array exhibits noticeable pseudocapacitive properties.

  • The as-prepared nanowire array is also a promising material for Li-ion batteries.

Abstract

One-dimension MnCo2O4 nanowire arrays are synthesized on nickel foam by a facile hydrothermal method. The MnCo2O4 nanowires are highly crystalline with an average diameter of 70 nm and exhibit excellent properties for electrochemical energy storage. Impressively, the MnCo2O4 nanowire array exhibits noticeable pseudocapacitive performance with a high capacitance of 349.8 F g−1 at 1 A g−1 and 328.9 F g−1 at 20 A g−1 as well as excellent cycling stability. As an anode material for Li-ion batteries, the MnCo2O4 nanowire array delivers an initial specific discharge capacity of 1288.6 mAh g−1 at 100 mA g−1, with reversible capacity retention of 92.7% after 50 cycles. The outstanding electrochemical performances are mainly attributed to its nanowire array architecture which provides large reaction surface area, fast ion and electron transfer and good structure stability.

Introduction

Under the circumstance of energy and resources crisis, one of the most serious problems need to be solved is to search for high-power, low-cost and environmentally friendly energy storage devices. Among varies energy storage devices, supercapacitors and Li-ion batteries (LIBs) are most widely used [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], [13], [14], [15], [16]. Metal oxide nanostructures are promising electrode materials for lithium ion batteries and supercapacitors because of their high specific capacity/capacitance, typically 2–3 times higher than that of the carbon/graphite based materials [17].

Nowadays, many binary transition-metal oxides with spinel structure, such as NiFe2O4 [18], CuCo2O4 [19], MgCo2O4 [20], ZnCo2O4 [21], [22], NiCo2O4 [23], [24], [25], [26], [27], ZnMn2O4 [28], [29], and CoMn2O4 [30], etc, have been investigated as electrodes for supercapacitors and LIBs because of their low cost, environmentally friendly property and excellent electrochemical performances. Among them, there are few works about MnCo2O4 [31]. P. Lavela prepared the MnxCo3-xO4 spinel oxide series (x= 1, 1.5, 2, 3) used as anode materials for LIBs, capacities of higher than 400 mAh g−1 was sustained after 50 cycles [32]. The MnCo2O4 quasi-hollow microsphere anode materials for LIBs possessed reversible capacity of 755 mAh g−1 at a current density of 200 mA g−1 after 25 cycles [33]. However, most of the researches of MnCo2O4 focus on powder materials or compact films; there still exist several drawbacks, such as relatively low conductivity, low utilization of active materials and inferior structure stability.

One-dimension nanowire arrays have attracted intense attention for their excellent physical and chemical properties and are promising electrode materials for both supercapacitors and LIBs. The nanowire array architecture, just as the sphere-like particle, is one of the architectures which can provide large specific area, resulting in high utilization of active materials. And the nanowire array architecture can also alleviative the stress caused by volume changes during electrochemical processes. In a previous work [34], single-crystalline Co3O4 nanowire arrays grown on nickel foam were prepared by hydrothermal synthesis method for supercapacitor application, which exhibited noticeable pseudocapacitive performance with a high capacitance of 754 F g−1 at 2 A g−1 and 610 F g−1 at 40 A g−1, as well as excellent cycling performance. Besides, Co(OH)2 [35], MnO2 [36], LiMn2O4 [37], CoO [38], Na2V6O16 [39], ZnV2O6 [40] and polyanilineand [41], with nanowire structure were all widely investigated.

The hydrothermal method is one of the most widely used methods to fabricate nanostructured materials [42], [43], [44], [45], [46], [47], because the size, morphology, and crystal structure of the products can be easily controlled [48], and the reaction temperatures are also lower than other preparation methods. In this present work, we investigate the electrochemical properties of MnCo2O4 nanowire array prepared by a facile hydrothermal method coupled with an annealing treatment. The MnCo2O4 nanowire array electrode grown directly on nickel foam avoids the use of polymer binders and conducting additives so that ensures good mechanical adhesion and electrical connection. Through electrochemical measurements, the MnCo2O4 nanowire array is found to be a promising pseudocapacitive material with high specific capacitance and great rate capability. What's more, as an anode material for LIBs, the MnCo2O4 nanowire array also shows excellent electrochemical properties.

Section snippets

Preparation of materials

All the reagents used in the experiment were of analytical grade. The cobalt nitrate, manganese nitrate, urea and ammonium fluoride were obtained from Shanghai Chemical Reagent Co. All aqueous solutions were freshly prepared with high purity water (18 MΩ resistance).

MnCo2O4 nanowire arrays were prepared by a facile hydrothermal synthesis method according to our previous work [49], [50]. The reaction solution was obtained by mixing 1 mmol of Mn (NO3)2, 2 mmol of Co (NO3)2, 6 mmol of NH4F and 15 mmol

Characterization

Fig. 1a shows the XRD pattern of the product after annealing treatment. The standard XRD patterns of Ni and MnCo2O4 are included in the graph too. Expect for the peaks of Ni foam substrate (PDF No. 65-2865), all the diffraction peaks can be indexed as a spinel structure phase of space group Fd3 m MnCo2O4 (PDF No. 23-1237). No additional peaks for other phases are observed. The BET surface area of the MnCo2O4 product is 41.22 m2 g−1 (Fig. 1b).

Fig. 2 shows the SEM images of the as-prepared MnCo2O4.

Conclusions

We have illustrated a fast and facile hydrothermal method for the growth of MnCo2O4 nanowire array. The MnCo2O4 nanowire array exhibits noticeable pseudocapacitive performance with a high capacitance of 349.8 F g−1 at 1 A g−1 and 328.9 F g−1 at 20 A g−1 as well as excellent cycling stability. As an anode material for LIBs, the MnCo2O4 nanowire array delivers an initial specific discharge capacity of 1288.6 mAh g−1 at 100 mA g−1, with capacity retention of 92.7% after 50 cycles. The excellent

Acknowledgement

This work was supported by the Key Science and Technology Innovation Team of Zhejiang Province (2010R50013).

References (56)

  • H. Xia et al.

    MnO2 nanotube and nanowire arrays by electrochemical deposition for supercapacitors

    J. Power Sources

    (2010)
  • E. Hosono et al.

    Synthesis of single crystalline spinel LiMn2O4 nanowires for a lithium ion battery with high power density

    Nano Lett.

    (2009)
  • Y. Sun et al.

    Ultralong monoclinic ZnV2O6 nanowires: their shape-controlled synthesis, new growth mechanism, and highly reversible lithium storage in lithium-ion batteries

    RSC Adv

    (2012)
  • J.W. Lee et al.

    A facile and template-free hydrothermal synthesis of Mn3O4 nanorods on graphene sheets for supercapacitor electrodes with long cycle stability

    Chem. Mater.

    (2012)
  • J.F. Qian et al.

    Template-free hydrothermal synthesis of nanoembossed mesoporous LiFePO4 microspheres for high-performance lithium-ion batteries

    J. Phys. Chem. C

    (2010)
  • X.Y. Liu et al.

    Self-assembled porous NiCo2O4 hetero-structure array for electrochemical capacitor

    J. Power Sources

    (2013)
  • X.H. Xia et al.

    Freestanding Co3O4 nanowire array for high performance supercapacitors

    RSC Adv.

    (2012)
  • Y.Q. Zhang et al.

    Self-assembled synthesis of hierarchically porous NiO film and its application for electrochemical capacitors

    J. Power Sources

    (2012)
  • L. Zhou et al.

    Double-shelled CoMn2O4 hollow microcubes as high-capacity anodes for lithium-ion batteries

    Adv. Mater.

    (2012)
  • J.R. Miller et al.

    Electrochemical capacitors for energy management

    Science

    (2008)
  • X.H. Xia et al.

    High-quality metal oxide core/shell nanowire arrays on conductive substrates for electrochemical energy storage

    ACS Nano

    (2012)
  • P. Simon et al.

    Materials for electrochemical capacitors

    Nat. Mater.

    (2008)
  • X.C. Dong et al.

    3D graphene–cobalt oxide electrode for high-performance supercapacitor and enzymeless glucose detection

    ACS Nano

    (2012)
  • X.H. Xia et al.

    Porous hydroxide nanosheets on preformed nanowires by electrodeposition: branched nanoarrays for electrochemical energy storage

    Chem. Mater.

    (2012)
    M.Y. Ge et al.

    Porous doped silicon nanowires for lithium ion battery anode with long cycle life

    Nano Lett.

    (2012)
  • L. Wang et al.

    Interface chemistry engineering for stable cycling of reduced GO/SnO2 nanocomposites for lithium ion battery

    Nano Lett.

    (2013)
  • S. Ko et al.

    Mesoporous CuO particles threaded with CNTs for high-performance lithium-ion battery anodes

    Adv. Mater.

    (2012)
  • D. Rangappa et al.

    Ultrathin nanosheets of Li2MSiO4 (M = Fe, Mn) as high-capacity Li-ion battery electrode

    Nano Lett.

    (2012)
  • A. Brandt et al.

    A study about the use of carbon coated iron oxide-based electrodes in lithium-ion capacitors

    Electrochim. Acta

    (2013)
  • Cited by (0)

    View full text