Flexible Bismuth Selenide /Graphene composite paper for lithium-ion batteries

doi:10.1016/j.ceramint.2016.10.110

Ceramics International

Volume 43, Issue 1, Part B, January 2017, Pages 1437-1442

https://doi.org/10.1016/j.ceramint.2016.10.110 Get rights and content

Abstract

A flexible Bi₂Se₃/Graphene (BSG) composite paper has been prepared through a simple vacuum filtration method and a thermal reduction together. The BSG composite paper was directly used as anode electrode for lithium-ion batteries, without using any polymer binders or conduction additives. In contrast to the pure Bi₂Se₃, the BSG exhibits high reversible lithium ion storage capacities and superior cyclic capacity retention. It proposed that the superior lithium storage performances would be attributed to the special construction of the as-prepared BSG paper, in which the graphene can not only act as conductive network for electrodes, but also act as a frame to alleviate volume expansion or aggregation of Bi₂Se₃ nanosheets during lithiation/delithiation. The as-prepared BSG paper shows a great potential as an anode materials for flexible Li-ion batteries.

Introduction

In recent decades, lithium-ion batteries (LIBs) has been widely applied to portable electronics and electric/hybrid devices because of its high energy density, high rate capability and environmentally friendly properties [1], [2], [3]. And with recent advances in the technology of various types of soft portable electronic instrument, there remains a strong market demand for ultra-thin and flexible Li-ion batteries to offer power [4], [5], [6]. However, due to the lack of material, which possess electronically superior conductivity, high mechanical flexibility and high electrochemical stability, hence, most materials are inappropriate as a flexible electrodes [7].

Graphene, a one-atom-thick two-dimensional (2D) carbon material, has gained high attention due to its high surface area, structural flexibility and chemical stability [8]. In addition, graphene oxide (GO) paper and graphene paper have been successfully fabricated by filtration of individual GO or graphene sheet [9], [10]. What's more, recent program demonstrated that graphene paper have an excellent lithium cycle performance when used as an advanced anode material in LIBs [5], [11], [12], [13] However, when the graphene paper directly as anode material for Li-ion batteries, the capacities are very poor, although they show a good cycling stability. It indicates that the graphene paper is not suitable for the application as the anode material for Li-ion batteries by itself [14].

Bismuth selenide (Bi₂Se₃), crystallizes in a layered structure, and the Li ion can be inserted into its gaps, making it can applicable in Li-ion batteries [15], [16], [17]. For example sheet-like and microrods structure showed discharge capacity of 725.6 and 870 mAh g⁻¹ in fist cycle, but the capacity loss rapid [18], [19]. In addition, Yang et al. [20] reports Bi₂Se₃ nanosheet and Bi₂Se₃-S_X with a discharge capacity of 123.4 and 235.1 mAh g⁻¹ after 30 cycles. Zou et al. [21] and Li et al. [22] synthesis In-Bi₂Se₃ and Bi₂Se₃-S hierarchical nanostructures with a 163.3 mAh g⁻¹ after 50 cycles and 109.4 mAh g⁻¹ after 100 cycles, respectively. However, owing to the poor cycle performance of Bi₂Se₃, it is unsuitable to practical application as anode Recently, graphene has been used to form composite materials (like SnO₂ [23], [24], TiO₂ [25], Si [26] and ect) as electrode materials, and exhibited a better cycling stability because of the hybridizing with graphene which has excellent mechanical strength and elasticity, high surface area, and superior electronic conductivity. So, integrating Bi₂Se₃ with the graphene paper is a practical way to fabricate flexible free-standing Bi₂Se₃/Graphene composite paper, and improve the capacity of Bi₂Se₃ based Li-ion batteries. However, to our best knowledge, there are no reports about Bi₂Se₃/graphene composite paper as anode for Li-ion battery.

In the present work, we have successfully prepared flexible free-standing Bi₂Se₃/Graphene composite paper through a simple vacuum filter method. When directly served as anode electrode for lithium batteries, it delivered a high cycle stability 203 mAh g⁻¹ after 100 cycles. The composite paper showed an excellent electrochemical discharge/charger performance, indicating their potential applications in Li-ion batteries.

Section snippets

Preparation of Bi₂Se₃ nanosheets

Bi₂Se₃ nanosheets were prepared by a hydrothermal exfoliation method based on our previous work [27], [28]. In a typical procedure, 0.23 g Bi₂Se₃ and 0.2 g LiOH was added into 30 ml ethylene glycol, after that the mixture was constantly stirred about 1 h. Then the solution was transferred into a 50 ml Teflon-lined autoclave under 200 °C for 24 h. The resulting products were collected after washing with acetone and deionized water for several times, then dried in vacuum.

Preparation of Bi₂Se₃/Graphene composite paper

Graphene oxide (GO) was

Results and discussion

The details of synthesis procedure are described in Fig. 1. Firstly, the GO dispersed into Bi₂Se₃ aqueous solution by sufficient ultrasound to obtain a stable dark brown suspension. Secondly, the composite suspension was filtered through an Anodisc membrane filter (47 mm diameter, 0.2 µm pore size, Whatman). Finally, the composite paper was peeled off from the filter membrane and then anneal.

Fig. 2(a) shows the photographs of as-prepared BSG paper, it is clear that the composite paper was

Conclusion

In summary, we rationally designed a flexible BSG paper by a simple vacuum filtration. The binder-free BSG electrode exhibits a high reversible capacity of 203mAh g⁻¹ after 100 cycles under 50 mA g⁻¹. Compared with the pure Bi₂Se₃ nanosheets, the BSG paper exhibits a higher capacity because of the hybridizing with excellently flexible and conductive graphene. Our work has used a simple vacuum filtration technique to incorporate these two functional materials into one entity. In addition our

Acknowledgments

This work was supported by the Grants from National Natural Science Foundation of China (No. 11504312), Scientific Research Fund of Hunan Provincial Education Department (No. 15C1322), Provincial Natural Science Foundation of Hunan (No. 2016JJ2132), Open Fund based on innovation platform of Hunan Colleges and Universities (No. 15K128), as well as the Program for Changjiang Scholars and Innovative Research Team in University (IRT13093).

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Flexible Bismuth Selenide /Graphene composite paper for lithium-ion batteries

Abstract

Introduction

Section snippets

Preparation of Bi2Se3 nanosheets

Preparation of Bi2Se3/Graphene composite paper

Results and discussion

Conclusion

Acknowledgments

Appl. Surf. Sci.

Ceram. Int.

J. Membr. Sci.

Ceram. Int.

Ceram. Int.

J. Solid State Chem.

Solid State Ion.

J. Power Sources

Ceram. Int.

J. Power Sources

Electrochim. Acta

Electrochim. Acta

Building better batteries

Nature

ChemInform Abstract: graphene-based Materials for Flexible Supercapacitors

Chem. Soc. Rev.

Graphene and Graphene-Based Materials for Energy Storage Applications

Small

Deposition SnO(2)/nitrogen-doped graphene nanocomposites on the separator: a new type of flexible electrode for energy storage devices

Acs Appl. Mater. Interfaces

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Nature

Organic solvent-based graphene oxide liquid crystals: a facile route toward the next generation of self-assembled layer-by-layer multifunctional 3D architectures

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Preparation of Bi₂Se₃ nanosheets

Preparation of Bi₂Se₃/Graphene composite paper

Deposition SnO₍₂₎/nitrogen-doped graphene nanocomposites on the separator: a new type of flexible electrode for energy storage devices