Copper oxide and ordered mesoporous carbon composite with high performance using as anode material for lithium-ion battery

https://doi.org/10.1016/j.micromeso.2011.03.001Get rights and content

Abstract

A composite of leaf-shaped copper oxide (CuO) nanoparticles mainly covered on the ordered mesoporous carbon CMK-3 is synthesized by a facile precipitation method. This material (CuO/CMK-3) has been characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen sorption. Electrochemical analyses show that the material possesses excellent cycling stability and high rate capability with an average discharge capacity of 171 mAh g−1 at 25 C using as the anode material for lithium-ion battery.

Graphical abstract

A composite of CuO nanoparticles mainly covered on porous CMK-3 possesses excellent cycling stability and high rate capability with an average discharge capacity of 171 mAh g−1 at 25 °C using as the anode material for lithium-ion battery.

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Highlights

► We prepare CuO/CMK-3 composite by a facile precipitation method. ► The nanosized CuO are mainly covered outside mesoporous carbon CMK-3. ► Good electrical contacts of CuO/CuO and CuO/C form in the composite. ► The composite possesses excellent cycling stability and high rate capability. ► More active composites are possible for assembling the real Li-ion battery.

Introduction

Along with the development of communication technology, electric vehicles and hybrid electric vehicles, the demand of electronic devices with high capacity and rate capability is increasing urgently and rechargeable lithium-ion battery has attracted attention as one of the most promising energy storage systems [1], [2]. Carbons such as graphite, carbon nanotubes, carbon nanofibers, graphene, mesoporous carbon, as well as large porous carbon monoliths have been widely utilized as anode materials for the lithium-ion battery owing to their low cost, high capacity, and innocuousness [3]. The storage of Li in carbons can be described as: 6C + x Li+ + xe  LixC6. The storage of one Li atom among every six C atoms is only valid for graphite, in which the stoichiometric factor x is about 1.0, indicating a relatively low theoretical capacity of 372 mAh g−1. For nongraphitic carbon, x is in the range of 0.5–0.8 with lower capacity or 1.2–3.0 with higher capacity [3], [4]. Recently, ordered mesoporous carbon CMK-3 prepared by using ordered mesoporous silica molecular sieve SBA-15 as the template and sucrose as the carbon source [5] has been considered as possible anode materials with high Li-ion storage capacity and combined with other materials to improve the electrochemical property. Zhou et al. [4] reported a reversible capacity of 850–1100 mAh g−1 in 20 cycles for CMK-3 at a current of 100 mA g−1. However, the initial coulombic efficiency was only 34% attributed to the formation of solid electrolyte interface (SEI) films. Zhao et al. [6] loaded SnO2 in the channels of CMK-3 by an infusing method and the first discharge capacity of the composite was 520 mAh g−1, which dropped to about 249 mAh g−1 after the 20th cycle. Zhang et al. [2] loaded CoO nanoparticles in the channels of CMK-3 by an infusing method and the reversible capacity of the composite was more than 700 mAh g−1 at a current density of 100 mA g−1. 3d transition metal oxides (MO, M = Co, Ni, Cu and Fe) have attracted increasing attention as the promising anode materials for lithium-ion battery due to their high reversible capacities and good safety [7], [8]. The storage of Li in CuO can be expressed as: CuO + 2Li+ + 2e  Cu + Li2O, corresponding to a high theoretical capacity of 670 mAh g−1, which is 2–3 times larger than that of commercial graphite anode material [9], [10], [11]. In addition, CuO has become a promising candidate for anode materials of Li-ion batteries since it is inexpensive, non-toxic and easily produced [12]. However, the electrochemical property of CuO depends greatly on its morphology and size, bulk CuO only showed a sustained reversible capacity of 400 mAh g−1 [10], [13]. In order to decrease the irreversible capacity of CMK-3 and improve its rate capability at high rates, CuO/CMK-3 composite was synthesized by a facile precipitation method, the formation mechanism is discussed, and the electrochemical performance is investigated.

Section snippets

Preparation of the CuO/CMK-3 composite

CMK-3 was prepared using SBA-15 as template [14], [15]. In a typical synthesis [5], [16], [17], 1.0 g of SBA-15 was impregnated with aqueous solution obtained by dissolving 1.3 g of sucrose and 0.14 g of H2SO4 in 5.0 g of deionized water. The mixture was then dried at 100 °C for 6 h, and 160 °C for another 6 h. The obtained powder was treated again at 100 and 160 °C for 6 h, respectively, after the addition of 0.8 g of sucrose, 0.09 g of H2SO4 and 5.0 g of deionized water. The carbonization was completed by

Structure and morphology

Small- and wide-range XRD patterns of the CMK-3 and CuO/CMK-3 composite are given in Fig. 1. The ordered arrangement of carbon channels in the CMK-3 gave rise to the small-angle XRD peaks with two theta at 1.1°, 1.8° and 2.1° (Fig. 1a), which can be assigned to (1 0 0), (1 1 0) and (2 0 0) diffractions of two dimensional (2-D) hexagonal space group (p6mm). Small-angle XRD peaks of the CuO/CMK-3 composite apparently reduced compared with those of the CMK-3 even though about 11.49 wt.% of CuO (Table 1)

Conclusions

In summary, we prepared a kind of CuO/CMK-3 composite by the facile precipitation method. The leaf-shaped CuO nanoparticles are mainly covered outside ordered mesoporous carbon CMK-3. The combination of CuO on the surface of CMK-3 results in the appropriate reductions of the surface area and numbers of the active sites, which reduces the irreversible reactions for the capacity loss. The CuO particles are not easy to break and detach. The CMK-3 with excellent mechanical property and well

Acknowledgements

This work was financially supported by the National Basic Research Program of China (973 Program, No. 2011CB935700), Chinese National Science Foundation (No. U0734002), and Shanghai Basic Key Program (No. 09JC1415100).

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