Carbon nanotube-graphene nanosheet conductive framework supported SnO2 aerogel as a high performance anode for lithium ion battery
Graphical abstract
Introduction
During the past decades, a large amount of effort has been devoted to developing rechargeable lithium-ion batteries (LIBs) with high energy density, high safety and long cycling performance for various applications such as smart electronics, electric vehicles, and large scale energy storage system [1], [2]. However, rapid development of market, especially the increasing demand for high-energy-density LIBs to be deployed in hybrid electric vehicles has prompted the consideration of electrode material candidates for LIBs [3], [4]. Among those anode materials under being explored, tin oxide (SnO2) based material is regarded as a promising anode candidate due to its high theoretical reversible Li+ storage capacity (782 mAh g−1), low cost, and facile synthesis technology [5], [6]. However, the practical use of tin based materials is greatly hampered by its huge volume change (∼300%) during the lithiation of Sn, leading to pulverization of particles as well as exfoliation of electrode materials. It is recently reported that designing the tin based materials of nanostructures, such as 1D tin dioxide nanowires [7], nanotubes [8], [9], 2D tin nanosheets [10], 3D hollow sphere [11], hollow submicroboxes [12], or porous nanosphere [13], is proved to be an effective strategy to enhance the capacity of tin based anode. However, some technical challenges still exist in pure tin based anode for LIBs. For example, the volume expansion of electrode materials cannot be effectively suppressed by some nanostructure design. In addition, the large surface area of nanoparticles gives rise to serious parasitic side reactions, and aggravates the formation and fracture of unstable solid electrolyte interphase (SEI) film, resulting in continuing capacity degradation.
To address those issues, some positive methods have been made to introduce carbon buffer matrix for tin based anodes to improve their electrochemical properties in LIBs [14], [15], [16], [17], [18]. Among those carbonaceous materials, graphene exhibiting several inherent advantages, such as excellent conductivity, superior flexibility and chemical stability, has been investigated as a carbon matrix to fabricate of SnO2/graphene hybrid anode materials [19], [20], [21], [22], [23]. Firstly, graphene play an important role in promoting the electron transfer during the lithiation and delithiation process. Moreover, the flexibility of graphene can help release the residual stress arising from the volume change of SnO2 particles. Owing to these merits, various preparation methods have been conducted to construct SnO2/graphene composite, including solution-based synthesis [24], [25], [26], hydrothermal synthesis [27], [28], self-assembly synthesis [29], [30] and so on. A representative example can be found in anchoring SnO2 nanocrystals into 3D macroscopic frameworks built up by graphene, which can provide abundant interconnected porous structure with large surface area [27], [31]. These 3D frameworks avoid the π−π restacking of graphene nanosheets, significantly enhancing the accessible surface area and strengthening the electrochemical reaction kinetics. Therefore, improved capacity of SnO2/graphene composites has been achieved. However, the low electrical conductivity in the graphene-based aerogel structures may result in low rate capability (below 500 mAh g−1 at 2 A g−1) [32], [33], [34], which is primarily due to the inadequate conductive frameworks established in these porous structures. Therefore, it is greatly important to effectively construct a conductive structure as a bridge to connect the relatively independent porous graphene aerogel. To realize these aims, different kinds of tin based/graphene composites for LIBs have been focused on adopting a second carbon precursor, such as glucose, dopamine, polyvinyl alcohol to form a supporting layer on the surface of tin oxide [35], [36], [37]. The double conductive layer can offer fast electron transportation and enough Li+ ion diffusion pathway, which enables improved rate performance for LIBs [38]. However, it is still a big challenge to control the uniformity of coating layer on the tin matrix and the optimal thickness of coating layer for those tin dioxide/carbon-graphene composites.
In this study, we have fabricated carbon nanotube-graphene nanosheet (CNT-GN) conductive framework supported SnO2 aerogel composites by one-pot hydrothermal process. CNT is chosen as a conductive additive agent to build interconnected conductive framework. A systematic electrochemical analysis discloses that the 3D CNT-GN framework could suppress the volume expansion/shrinkage due to the synergistic effect of high mechanical property of CNT and flexibility of graphene, which increase the reversibility and kinetic behaviors of the composite. Thus, the as-prepared tin oxide/carbon nanotube-graphene nanosheet (SnO2/CNT-GN) composite exhibits a higher reversible capacity, better cycling stability and significantly enhanced rate capability as compared to its SnO2/GN counterpart.
Section snippets
Materials
Graphene oxide (GO) (GO, 99 wt%; Thinkness, 0.55–3.58 nm; layer number <10) and carbon nanotube (CNT, >95 wt%; OD, >50 nm; Length, 10–20 um; −OH content, 0.71 wt%) were purchased from Daying Juneng Technology and Development Co., Ltd without further purification. Stannic chloride pentahydrate (SnCl4∙5H2O >99.0%) and polyvinylpyrrolidone K30 (PVP) were purchased from Chengdu Kelong Chemical Reagent Factory (China).
Synthesis of SnO2/CNT-GN composite
The SnO2/CNT-GN composite was prepared by a facile hydrothermal process followed by the
Results and discussion
Fig. 1 illustrates the synthesis procedure of the SnO2/CNT-GN composites. The SnO2/CNT-GN composites were fabricated by one pot hydrothermal route. CNT was homogeneously distributed in a solution of graphene oxide (GO) by the assistance of PVP as surfactant. During the hydrothermal process, Sn4+ ions can be anchored onto the surface of GO as the function of electrostatic attraction by the abundant functional groups such as hydroxyl, carboxyl, and epoxy groups. Meanwhile, the GN anchored with SnO
Conclusions
CNT-GN 3D conductive framework supported SnO2 aerogel composites have been successfully synthesized by one-pot hydrothermal treatment followed by freeze drying and pyrolysis process. The design sufficiently takes advantages of porous structure by reconstructing graphene nanosheet, where a large amount of SnO2 nanocrystals are anchored. The introduction of CNT increases the connection of relatively independent graphene sheets, which provide much faster charge transfer pathways at the SnO2
Acknowledgements
This work was supported by the National Natural Science Foundation of China (grant No. 51502250, 51604250, 51474196, 51302232), the Science & Technology Department of Sichuan Province (grant no. 2015JY0089, 2016RZ0071), and Education Department of Sichuan Province (No. 16ZB0085).
References (48)
- et al.
Li-ion battery materials: present and future
Mater. Today
(2015) - et al.
Graphene/metal oxide composite electrode materials for energy storage
Nano Energy
(2012) - et al.
Synthesis of SnO2 nano hollow spheres and their size effects in lithium ion battery anode application
J. Power Sources
(2013) - et al.
Amorphous SnO2/graphene aerogel nanocomposites harvesting superior anode performance for lithium energy storage
Applied Energy
(2016) - et al.
Monodisperse SnO2 anchored reduced graphene oxide nanocomposites as negative electrode with high rate capability and long cyclability for lithium-ion batteries
J. Power Sources
(2014) - et al.
A SnO2/graphene composite as a high stability electrode for lithium ion batteries
Carbon
(2011) - et al.
High rate SnO2-graphene dual aerogel anodes and their kinetics of lithiation and sodiation
Nano Energy
(2015) - et al.
Tin oxide/graphene aerogel nanocomposites building superior rate capability for lithium ion batteries
Electrochim. Acta
(2015) - et al.
High-performance tin oxide-nitrogen doped graphene aerogel hybrids as anode materials for lithium-ion batteries
J. Power Sources
(2014) - et al.
Novel synthesis of tin oxide/graphene aerogel nanocomposites as anode materials for lithium ion batteries
J. Alloys Compd.
(2015)
Porous SnO2@C/graphene nanocomposite with 3D carbon conductive network as a superior anode material for lithium-ion batteries
Electrochim. Acta
Carbon and graphene double protection strategy to improve the SnO(x) electrode performance anodes for lithium-ion batteries
Nanoscale
Scalable preparation of porous micron-SnO2/C composites as high performance anode material for lithium ion battery
J. Power Sources
Facile synthesis of tin dioxide-based high performance anodes for lithium ion batteries assisted by graphene gel
J. Power Sources
Building better batteries
Nature
A 3.6 V lithium-based fluorosulphate insertion positive electrode for lithium-ion batteries
Nature Mater.
Nanostructured materials for advanced energy conversion and storage devices
Nat. Mater.
Tin-based amorphous oxide: a high-capacity lithium-ion-storage material
Science
Preparation and electrochemical properties of SnO2 nanowires for application in lithium on batteries
Angew. Chem Int. Ed.
Ultrafast and scalable laser liquid synthesis of tin oxide nanotubes and its application in lithium ion batteries
Nanoscale
Nanowire-templated formation of SnO2/carbon nanotubes with enhanced lithium storage properties
Nanoscale
Ultrathin SnO2 nanosheets: oriented attachment mechanism, nonstoichiometric defects, and enhanced lithium-ion battery performances
J. Phys. Chem. C
Formation of uniform N-doped carbon-coated SnO2 submicroboxes with enhanced lithium storage properties
Adv. Energy. Mater.
A robust composite of SnO2 hollow nanospheres enwrapped by graphene as a high-capacity anode material for lithium-ion batteries
J. Mater. Chem.
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