Carbon nanotubes branched on three-dimensional, nitrogen-incorporated reduced graphene oxide/iron oxide hybrid architectures for lithium ion battery anode

doi:10.1016/j.jallcom.2017.07.264

Journal of Alloys and Compounds

Volume 726, 5 December 2017, Pages 88-94

https://doi.org/10.1016/j.jallcom.2017.07.264 Get rights and content

Highlights

•
Unique hybrid hierarchical architectures are created.
•
Dense CNTs are branched on 3D macroporous NG-Fe hybrid.
•
A high purity of α-Fe₂O₃ phase is formed for the 3D CNT@NG-Fe.
•
Anode performances are enhanced by N configuration and hierarchical structure.

Abstract

The carbon nanotubes (CNTs) branched on three-dimensional (3D) macroporous, nitrogen-incorporated reduced graphene oxide (NG)/iron oxide (CNT/NG-Fe) hybrid architectures have been prepared via an ice templating and microwave synthesis. Compared with the pristine RGO, the CNTs can be more readily and uniformly grown on the 3D NG surfaces due to the good electronic conductivity by N-type configurations. As demonstrated by the electrochemical performances, the discharge capacity of the 3D CNT/NG-Fe is 1208 mAh g⁻¹ at 50 mA g⁻¹ which is greater than 890 and 820 mAh g⁻¹ of the CNT/G-Fe and NG. When the rate increases from 100 to 1000 mAh g⁻¹, the capacity retention reaches 52% of initial capacity corresponding to the discharge capacity of 947 mAh g⁻¹. After 130 cycles at 100 mA g⁻¹, the capacity gradually increases to 1020 mAh g⁻¹ with the Coulombic efficiency of >98.5%. The enhanced capacity, rate capability and cyclic stability of the CNT/NG-Fe are associated with the doping effect of N-configuration and unique hierarchical structure consisting of the dense CNT branches on 3D macroporous continuity.

Graphical abstract

Introduction

Graphene is two-dimensional (2D) arrays of carbon atoms arranged in a hexagonal pattern [1], whereas carbon nanotube (CNT) forms tubular one-dimensional (1D) structure [2]. Both of CNT and graphene have received significant attention due to their outstanding properties such as high electrical conductivity, large surface area, good mechanical property, and electrochemical and thermal stabilities for energy-related applications. For instance, they were applied for a broad range of applicative fields, such as supercapacitors [3], battery [4], solar cells [5], electrocatalyst [6], sensors [7], etc. Moreover, hybrid materials which take advantages of integrating CNT and graphene into multi-dimensional hierarchical architecture are considered as a promising candidate for lithium ion battery (LIB) [8].

Recently, the three-dimensional (3D) hierarchical architecture of carbon nanomaterials has been investigated to achieve prominent structural features such as large available area, fast ion and mass transport, percolated electron transfer and structural integrity [9]. Accordingly, the poor rate and cyclic capabilities of transition metal oxides, which are a critical challenge of conversion-based material [10], could be improved by depositing on such 3D macroporous internetworked reduced graphene oxide (RGO) [11]. For instance, 3D RGO/TiO₂, RGO/SnO₂ [12], RGO/MnO₂ [13], RGO/Fe₂O₃ [14], RGO/NiO [15], RGO/WO₃ [16], RGO/CuO [17], and RGO/CoO [18] hybrid architectures were developed for LIB applications.

Another important strategy to improve electrochemical properties of carbon nanomaterials is the incorporation of heteroatoms such as nitrogen (N) [19], oxygen (O) [20], phosphorus (P) [3], sulfur (S) [11] and fluorine (F) [21] into the graphitic lattice. Such heteroatom chemistry leads to modify electronic structure and electrochemical reactivity depending on the chemical identity, bonding configuration and composition [22]. Motivated by these findings, N-RGO, O-RGO, P-RGO, S-RGO and F-RGO were synthesized to achieve enhanced performances of LIB [23].

Taking full advantages of the afore-mentioned chemistries, for the first time, we demonstrate the unique hierarchical architecture, where a bunch of CNTs are branched on the 3D macroporous, N-incorporated RGO/iron oxide (CNT/NG-Fe) hybrids, constructed via an ice templating and microwave synthesis. The features of this complex hybrid architecture can be described along the following lines. (1) The 3D N-incorporated RGOs act as conductive networking substrate to provide large surface area for the deposition of iron oxide nanoparticles, to facilitate Li ion transport and to delocalize stress created by volume expansion during charge/discharging process. (2) The CNT branches offer 1D conducting pathway between intra- or interparticles and inhibiting restacking of RGO nanosheets. (3) The iron oxide nanoparticles are high capacity materials for enhancing charge storage capacity of carbon nanomaterials.

Section snippets

Synthesis of 3D NG

The graphene oxide (GO) was synthesized by modified Hummers method [24]. Firstly, 100 mg of as-obtained GOs was dispersed into 10 mL of deionized (DI) water, and ultrasonicated for 1 h to make the homogenous dispersion. Secondly, 500 mg of melamine was added into 20 mL of DI water, and then the mixture was stirred and heated at 80 °C for 1 h. Finally, two dispersions were mixed together and stirred to make the homogenous solution. The final solution was frozen by liquid nitrogen and

Results and discussion

As shown in Fig. 1, the 3D CNT/NG-Fe was synthesized through an ice templating and microwave irradiation synthesis. First, the 3D macroporous NG was synthesized via a simple and facile ice-templating method using GO and melamine precursor. The resulting material was used as the internetworked substrate for the growth of CNT branches. The homogeneous mixture of NG and ferrocene catalysts was treated under microwave irradiation to deposit CNT branches onto the surface of NG. During the microwave

Conclusion

In summary, we have successful synthesized a novel CNT growth on hierarchical NG by microwave-assisted method and applied as high-capacity anode materials in to LIBs. 3D macroporous architecture of NG was very crucial for depositing the iron oxide nanoparticles during the microwave irradiation, which assisted the uniform growth of CNT onto the NG skeleton. This hierarchical structure consisting of 1D CNT branches, iron oxide nanoparticles and 3D NG was beneficial for facilitating lithium ion

Acknowledgment

This work was supported by both the financial support from the R&D Convergence Program (CAP-15-02-KBSI) of NST (National Research Council of Science & Technology) and the Energy Efficiency & Resources program of the Korea of Energy Technology Evaluation and Planning (KETEP), and was granted financial resources from the Ministry of Trade, Industry & Energy, Republic of Korea (No. 20152020105770).

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Carbon nanotubes branched on three-dimensional, nitrogen-incorporated reduced graphene oxide/iron oxide hybrid architectures for lithium ion battery anode

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis of 3D NG

Results and discussion

Conclusion

Acknowledgment

Nano Energy

Carbon

Carbon

J. Power Sources

J. Alloys Compd.

Appl. Surf. Sci.

J. Power Sources

Carbon

J. Alloys Compd.

Electric field effect in atomically thin carbon Films

Science

Helical microtubules of graphitic carbon

Nature

Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells

J. Phys. Chem. C

Graphene based electrochemical sensors and biosensors: a Review

Electroanalysis

Graphene–nanotube–iron hierarchical nanostructure as lithium ion battery anode

ACS Nano

Chemical modification of graphene aerogels for electrochemical capacitor applications

Phys. Chem. Chem. Phys.

Graphene-mimicking 2D porous Co3O4 nanofoils for lithium battery applications

Adv. Funct. Mater.

Microwave synthesis of SnO2 nanocrystals decorated on the layer-by-layer reduced graphene oxide for an application into lithium ion battery anode

J. Alloys Compd.

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Sci. Rep.

Graphene-mimicking 2D porous Co₃O₄ nanofoils for lithium battery applications