Elsevier

Electrochimica Acta

Volume 170, 10 July 2015, Pages 48-56
Electrochimica Acta

Evolution of the chemical bonding nature and electrode activity of indium selenide upon the composite formation with graphene nanosheets

https://doi.org/10.1016/j.electacta.2015.04.121Get rights and content

Highlights

  • In4Se2.85@graphene nanocomposite is easily prepared by high energy mechanical milling process.

  • The bond covalency of In4Se2.85 is notably changed upon the composite formation with graphene.

  • In4Se2.85@graphene nanocomposite shows promising anode performance for lithium ion battery.

Abstract

Evolution of the chemical bonding nature and electrochemical activity of indium selenide upon the composite formation with carbon species is systematically investigated. Nanocomposites of In4Se2.85@graphene and In4Se2.85@carbon-black are synthesized via a solid state reaction between In and Se elements, and the following high energy mechanical milling of In4Se2.85 with graphene and carbon-black, respectively. The high energy mechanical milling (HEMM) of In4Se2.85 with carbon species gives rise to a decrease of particle size with a significant depression of the crystallinity of In4Se2.85 phase. In contrast to the composite formation with carbon-black, that with graphene induces a notable decrease of (Insingle bondSe) bond covalency, underscoring significant chemical interaction between graphene and In4Se2.85. Both the nanocomposites of In4Se2.85@graphene and In4Se2.85@carbon-black show much better anode performance for lithium ion batteries with larger discharge capacity and better cyclability than does the pristine In4Se2.85 material, indicating the beneficial effect of composite formation on the electrochemical activity of indium selenide. Between the present nanocomposites, the electrode performance of the In4Se2.85@graphene nanocomposite is superior to that of the In4Se2.85@carbon-black nanocomposite, which is attributable to the weakening of (Insingle bondSe) bonds upon the composite formation with graphene as well as to the better mixing between In4Se2.85 and graphene. The present study clearly demonstrates that the composite formation with graphene has strong influence on the chemical bonds and electrode activity of indium selenide and the HEMM process with graphene nanosheet is fairly useful in exploring excellent electrode materials of metal chalcogenide–carbon nanocomposite for lithium ion batteries.

Introduction

An exploration of new efficient anode materials is one of the most important issues for the researches of lithium secondary batteries [1], [2], [3]. While the cathode material working at high potential should be operated in terms of intercalation–deintercalation mechanism, the low working potential of anode material allows the contributions of diverse working mechanisms such as conversion, alloying–dealloying, intercalation–deintercalation, etc [4], [5], [6]. As an alternative anode material for replacing currently-commercialized graphite, many kinds of inorganic materials such as metal elements and metal oxides are investigated because of their large theoretical capacity [7], [8], [9], [10], [11], [12], [13], [14], [15], [16]. Similarly large numbers of layered metal chalcogenides are explored as intercalation anode materials for lithium secondary batteries [17], [18], [19], [20]. However, there is still a plenty of room for the development of new efficient anode materials from non-layered metal chalcogenide operating in terms of non-intercalative mechanism, since only a few studies are carried out for this type of materials [21], [22], [23]. Despite their large theoretical discharge capacity, the electrode materials relying on non-intercalative mechanism suffer from severe capacity fading, which originates from remarkable volume change upon electrochemical cycling [4], [24]. Such drawbacks of these materials can be relieved by the formation of nanocomposites with carbon species [25], [26], [27]. In addition, a coupling with highly conductive carbon species is fairly effective in improving the rate characteristics of metal chalcogenide [28], [29], [30]. The composite formation with conductive carbon would be easily achieved by a facile mechanical milling between electrode material and carbon species [31]. Additionally, high energy mechanical milling (HEMM) process can induce an effective exfoliation of graphite into graphene, since the shear stress from the ball milling process can overcome the π–π stacking interaction between graphene layers [32]. To better understand the role of carbon species on the electrode performance of the resulting metal chalcogenide–carbon nanocomposite, it is quite important to elucidate the variation of chemical bonding nature of metal chalcogenide and carbon upon the composite formation. But at the time of the publication of the present study, we are aware of no systematic study about the synthesis of metal chalcogenide–carbon nanocomposites via mechanical milling method and the evolution of chemical bonding character upon the composite formation.

In the present study, the intimately-coupled nanocomposites of In4Se2.85@graphene and In4Se2.85@carbon-black are synthesized by the high energy mechanical milling (HEMM) of bulk In4Se2.85 crystal with graphene and carbon-black (super P). To improve the electrical conductivity and electrode activity of indium selenide phase, the self-doped composition of In4Se2.85 with Se deficiency is adopted for the synthesis of the present nanocomposites. In addition, the Se defect is supposed to act as active sites for interacting with hybridized carbon species. The effects of ball milling and composite formation on the crystal structure and morphology of In4Se2.85 are systematically investigated along with the accompanying variation of chemical bonding nature. The obtained nanocomposites are applied as anode materials for lithium secondary batteries to study the influence of composite formation with carbon species on the electrode activity of indium selenide.

Section snippets

Synthesis

The bulk crystal ingot of n-type In4Se2.85 was synthesized by conventional melting and annealing process with high purity In (>99.999%, CERAC) and Se granules (>99.999%, 5N Plus Materials Inc., USA). The raw materials in an evacuated quartz tube (under 10−4 Torr) were congruently melted by torch. Then, two-step annealing of the ingot was performed at 773 K for 48 h, and then at 733 K for 24 h in order to produce a homogenous In4Se2.85 phase. The anion deficiency in the In4Se3 phase was introduced to

Powder XRD measurements and elemental analysis

Fig. 1 represents the powder XRD patterns of the pristine In4Se2.85, the carbon-free ball-milled derivative, and the nanocomposites of In4Se2.85@graphene and In4Se2.85@carbon-black. The pristine In4Se2.85 material shows well-defined Bragg reflections of In4Se2.85 phase, indicating the successful formation of single-phase indium selenide through the two-step annealing process [34]. The carbon-free ball-milled In4Se2.85 material displays nearly identical XRD pattern to the pristine material with

Conclusions

In this study, we are successful in synthesizing new promising anode materials of the In4Se2.85@graphene and In4Se2.85@carbon-black nanocomposites via a facile HEMM process and in demonstrating the evolution of the chemical bonding nature of indium selenide and carbon upon the composite formation with graphene. Upon the composite formation with graphene, the pristine In4Se2.85 material experiences a marked weakening of bond covalency, which is negligible for the composite formation with

Supporting information

FE-SEM images of the precursor graphene nanopowder and carbon-black. Powder XRD patterns of the electrochemically-cycled materials.

Acknowledgments

This work was supported by the National Research Foundation of Korea Grant funded by the Korean Government (MEST)" (NRF-2010-C1AAA001-2010-0029065), by the Core Technology of Materials Research and Development Program of the Korea Ministry of Intelligence and Economy (grant No. 10041232), by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (<GN3>NRF-2014R1A2A1A10052809</GS3>), by the National Research Council of Science and Technology through the

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