Confining SnSe nanobelts in 3D rGO aerogel for achieving stable and fast lithium storage

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Highlights

Abstract

Tin selenide (SnSe) shows great potential as a promising anodic candidate of commercial graphite in Li-ion batteries (LIBs), but its practical application is hampered by huge volume change-induced poor cycle span. Herein, a gel-enabled selenization route has been developed for uniformly confining SnSe nanobelts within reduced graphene oxide aerogel (SnSe NB@rGO framework). These unique structural and compositional features make the SnSe NB@rGO framework electrode to show high revisable capacities (620 mA h g−1 after 200 cycles at 0.1 A g−1), high rate capability (626 and 551 mA h g−1 at 0.5 and 1 A g−1, respectively) and ultralong cycle span (412 mA h g−1 after 800 cycles at 1 A g−1).

Introduction

Li-ion batteries (LIBs) have been widely used in portable electronics, electric vehicles, and grid-scale storage in renewable energy systems [1], [2]. To satisfy the continuous demands for large-scale energy storage, the overall performance of LIBs need to be further improved via employing advanced electrode materials [3], [4], [5]. Tin-based materials including metallic tin, tin oxides, and tin chalcogenides have been intensively studied and considered to be ideal anodic candidates for next-generation LIBs [5], [6], [7], [8], [9], [10]. Among them, tin selenide (SnSe) is a semiconductor with a layered structure and has been widely used as photovoltaic, optoelectronic and thermoelectric materials [11], [12], [13]. As the same time, SnSe shows great potential as a promising anode by virtue of its high theoretical capacity (895 mA h g−1 in LIBs), natural abundance, and low toxicity [14], [15], [16], [17], [18], [19], [20], [21], [22], [23]. However, this material still suffers from enormous volume change during repeated lithium insertion/extraction processes, causing progressive electrode pulverization and fast capacity fading.

In order to improve cyclic life, much research effort has been devoted to accommodating the volume variations of SnSe anodes through the structural and compositional design [14], [15], [16], [17], [18], [19], [20], [21], [22], [23]. Among them, nanostructuring and hybridizing SnSe anodes with carbon matrices has been considered to be an effective and versatile strategy to improve the overall electrochemical performance of the hybrid anodes [15], [16], [17], [18], [19]. For example, zero-dimensional (0D) carbon black [16], [19], 1D carbon nanofiber [15], [18] and carbon nanotube [17] hybridized nanosized SnSe anodes have been reported to manifest markedly improved Li-storage performances owing to the enhanced strain accommodation and charge transport capabilities. Compared with these 0D and 1D matrices, 2D graphene possesses exceptional physicochemical features including outstanding mechanical flexibility and high electrical conductivity, and thus could serve as an ideal buffering and conducting matrix for electrodes in LIBs [24], [25], [26], [27]. Therefore, graphene-hybridized nano-SnSe anodes are anticipated to exhibit further improved cyclic life and enhanced rate capability and thus serve as promising anodic candidates in advanced LIBs.

Motivated by this, a novel type of graphene-hybridized nano-SnSe, i.e., SnSe nanobelts uniformly confined within 3D reduced graphene oxide (rGO) aerogel, SnSe NB@rGO framework, has been designed and constructed through a gel-enabled selenization route using GO hydrogel-wrapped Sn nanorods (Sn NR@GO) as a precursor. Compared with SnSe nanobelts, the SnSe NB@rGO framework manifests significantly enhanced lithium storage performance in term of reversible capacities, cyclic life, and rate capability.

Section snippets

Synthesis of the Sn NR@GO hydrogel and aerogel

Sn nanorods were obtained by a template-directed route using SnCl4 as a tin precursor and poly(diallyldimethylammonium chloride) (PDDA) as a soft template [28], [29], [30]. Graphene oxide (GO) was prepared by a modified Hummer's method. Solution A was 2 mg mL−1 polyvinyl pyrrolidone (PVP) aqueous solution containing well dispersed 10 mg mL−1 Sn nanorods. Solution B was aqueous solution containing fully dispersed 10 mg mL−1 GO. The Sn NR@GO hydrogel was prepared through simply mixing solutions A

Results and discussion

Fig. 1 schematically illustrates the synthetic route for the formation of the SnSe NB@rGO framework. As observed, Sn nanorods are in situ immobilized within GO hydrogel, and then the hybrid hydrogel is transformed into Sn NR@GO aerogel after a freeze-drying process. Subsequently, the Sn nanorods are in situ selenized within GO aerogel, and GO is then thermally reduced to rGO component, yielding the final SnSe NB@rGO framework.

The gelation of GO can be proceeded by adding small organic

Conclusions

To summarize, we propose a facile gel-enabled selenization route to realize uniform immobilization of SnSe nanobelts within 3D rGO aerogel for boosting energy storage of SnSe-based anodes. Sn nanorods are in situ selenized within the hybrid aerogel, and thus the SnSe nanobelts are uniformly attached to and confined in rGO aerogel. Thanks to the unique structural and compositional features, the SnSe NB@rGO framework manifests significantly enhanced lithium storage performance in term of

Acknowledgments

The authors appreciate the financial supports from National Natural Science Foundation of China (51401110), Natural Science Foundation of Jiangsu Higher Education Institutions of China (16KJB150023), and a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

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