Nitrogen-doped porous carbon/Sn composites as high capacity and long life anode materials for lithium-ion batteries

doi:10.1016/j.matlet.2015.04.104

Materials Letters

Volume 155, 15 September 2015, Pages 18-22

https://doi.org/10.1016/j.matlet.2015.04.104 Get rights and content

Highlights

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Nitrogen-doped porous carbon/Sn composites are successfully prepared for the first time.
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The novel composites are prepared by the combined carbonization and activation process.
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The nitrogen-doped porous carbon is an effective and versatile matrix.
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The nitrogen-doped porous carbon/Sn composites show high capacity and long life.

Abstract

Novel nitrogen-doped porous carbon/Sn composites (NCSs) are successfully prepared by the carbonization-activation process. As a result, the NCSs show good electrochemical performance as anode materials for LIBs, including high reversible capacity of 1117.1 mA h g⁻¹, long life over 250 cycles, and good rate capability (218 mA h g⁻¹ at 5 A g⁻¹). The effective synthesis strategy might open new avenues for the design of high-performance carbon/metal composite materials.

Introduction

High energy lithium-ion batteries (LIBs) are now actively developed as a prime candidate for energy storage system [1], [2], [3], [4], [5], [6]; however graphite, the most commonly used anode material in commercial LIBs, has limited theoretical capacity (372 mA h g⁻¹), which is far from adequate to meet the ever-growing demand of various consumer electronic devices. In comparison, metallic Sn has much high theoretical specific capacity (992 mA h g⁻¹) and high reversible capacity compared to Sn-oxides [7], [8]. Nevertheless, their remarkable lithium-storage capabilities are usually accompanied by the serious volume change (about 300%) upon cycling, resulting in the pulverization of the electrodes and then poor cycling life.

Recent reports have demonstrated that the combination of nanosized Sn particles with various carbon materials (such as graphene, nanofibers, and pyrolytic carbon) can lead to the improved electrochemical performance than that of bare nanosized Sn particles [9], [10], [11], [12], [13]. In this case, if the carbon matrix itself also has high capacity, the Sn/carbon composites could show better electrochemical performance by the synergistic effect. It is well known that nitrogen-doped porous carbon materials have attracted great attention in providing lithiation capability and cycling stability [14], [15], [16]. Very recently, we have demonstrated that the nitrogen-doped porous carbon sheets could show the exceptional electrochemical performance [17]. However, to the best of our knowledge, the preparation of nitrogen-doped porous carbon/Sn composites is rarely reported and remains a big challenge.

Herein, we report a facile strategy to synthesize nitrogen-doped porous carbon/Sn composites (NCSs) via the carbonization-activation process. SnO₂ nanoparticles were reduced to Sn nanoparticles, PPy was used as the carbon and nitrogen source, and KOH served as an activating agent to form porous structure during the carbonization process. Benefiting from the presence of N and porous nanostructure, the NCSs exhibit good electrochemical performance.

Section snippets

Experimental

Synthesis of NCSs: The SnO₂ nanoparticles [18] (0.15 g) were dispersed in water (100 mL). Then, cetrimonium bromide (0.5 g) and ammonium persulfate (1.37 g) were successively added. After stirring 30 min, 0.83 mL pyrrole was added to the mixture and the mixture was kept at 0–5 °C for 24 h. The black precipitate was collected, washed for several times, and finally dried overnight at 80 °C. Then, the above samples (400 mg) were dispersed in KOH solution (20 mL, 7 M). After stirring for 24 h, the product was

Results and discussion

SEM image (Fig. 1a) shows the formation of composite with a broad size distribution from hundreds of nanometers to a few micrometers. Obviously, the carbonization-activation process destroys the morphology of composite precursor composed of SnO₂ nanoparicles coated by PPy. It is well known that Sn has low melting point, which aggravates liquid coalescence during extended carbonization. High temperature carbonization results in the reduction from SnO₂ to Sn nanoparticles, in the meantime

Conclusion

Nitrogen-doped porous carbon/Sn composites are successfully fabricated via the carbonization-activation process for the first time. The synergistic effect of nitrogen-doped porous carbon with Sn plays pivotal roles in improving the lithium storage performance. As a result, the enhanced reversible capacity, rate and cycle performance are achieved when the composites are evaluated as anode materials for LIBs. The method presented here could also be explored to controllably fabricate other metal

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant no. 21404014, 51202018) and Jilin Science & Technology Department (the development plan project of science and technology No. 201201120, 20150520002JH) and Training Programs of Innovation and Entrepreneurship for Undergraduates (No. 2014S034).

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Nitrogen-doped porous carbon/Sn composites as high capacity and long life anode materials for lithium-ion batteries

Highlights

Abstract

Introduction

Section snippets

Experimental

Results and discussion

Conclusion

Acknowledgments

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