Elsevier

Journal of Power Sources

Volume 426, 30 June 2019, Pages 33-39
Journal of Power Sources

Facile preparation of MnO/nitrogen-doped porous carbon nanotubes composites and their application in energy storage

https://doi.org/10.1016/j.jpowsour.2019.04.026Get rights and content

Highlights

  • A facile strategy is developed to prepare MnO/N-PCNTs composite.

  • The MnO/N-PCNTs shows a high electrochemical performance for Li+ storage.

  • The MnO/N-PCNTs delivers a reversible capacity of 652 mAh g−1 at 100 mA g−1.

  • The MnO/N-PCNTs exhibits an excellent cycling stability.

Abstract

We report a novel approach to prepare MnO/nitrogen-doped porous carbon nanotubes composites by using a hypercrosslinked tubular porous polymer precursor, which is obtained by a facile strategy of Friedel-Crafts reaction of triphenylamine and formaldehyde dimethyl acetal promoted by ferric trichloride. Owing to the high redox activity of the loaded MnO with uniform distribution on the nitrogen-doped porous carbon nanotubes surface, the enhanced surface area, and the plentiful porous structures of the one dimensional nitrogen-doped porous carbon nanotubes, the lithium-ion batteries fabricated from the MnO/nitrogen-doped porous carbon nanotubes composites exhibit a high electrochemical performance, including a reversible capacity of 652 mAh g−1 at 100 mA g−1 and an excellent cycling stability with a capacity retention of 512 mAh g−1 at 500 mA g−1 after 250 charge−discharge cycles. The result demonstrates that this kind of MnO/nitrogen-doped porous carbon nanotubes composites are promising candidates for high performance energy storage devices.

Introduction

Rechargeable lithium-ion batteries (LIBs) have been widely used for portable electronics, tools and electric vehicles [[1], [2], [3]]. The key point in LIBs is the nature of electrode material, which affects significantly the performance of LIBs. However, the commercial graphite anode cannot meet the ever-increasing demand for LIBs with high electrochemical performance due to its low capacity [4]. To this end, considerable attention has been paid to developing alternative electrode materials for high electrochemical performance LIBs [5,6]. To date, significant achievements have been made on transition metal oxides (e.g. NiO [7], SnO2 [8], Fe3O4 [9], RuO2 [10], MnO2 [11], MnOOH [12,13], and MnO [14]) for LIBs. In particular, MnO has received tremendous recent interest because of its high capacity (theoretically 756 mAh g−1) [15], low potential plateau, and the plentiful Mn source [16,17]. Nevertheless, the MnO-based electrode commonly suffers from low electrical conductivity, large volume expansion, poor rate performance and cycling stability [18,19]. Therefore, a range of strategies have been developed to enhance the electrochemical performance of MnO-based LIBs. These mainly include nano-sized MnO and carbon-based nano-composites, such as the combination of activated carbon and MnO [20], MnO@C composites [21], core-shell MnO/C [22], MnO/C nanotubes [23], and MnO/carbon nanopeapods [24]. Among them, one dimensional (1D) porous carbon nanotubes show some advantages to obtain MnO/C nanotubes composite electrode for high performance LIBs. The 1D tubular nature can endow the composite electrode high electrical conductivity, and the high surface area of porous carbon nanotubes can provide the composite electrode with plentiful active sites for Li storage and promote the charge transfer and Li ions transportation [25]. In addition, the N-doped carbonaceous electrode materials can provide some defects and enhance the electrochemical activity [26,27]. Therefore, high-performance LIBs could be expected by using MnO/N-doped porous carbon nanotubes composite electrode materials.

We recently demonstrated that porous carbon nanotubes with high surface area could be easily obtained by pyrolysis of a 1D tubular hypercrosslinked polymer [28], which could be facilely prepared via Friedel-Crafts alkylation of aromatic hydrocarbon and formaldehyde dimethyl acetal (FDA) promoted by FeCl3 at mild reaction conditions. Herein, we synthesized a novel N-containing porous hypercrosslinked tubular polymer using triphenylamine (TPA) as the building block. MnO/N-doped porous carbon nanotubes (MnO/N-PCNTs) composite was further obtained by pyrolysis of the N-containing hypercrosslinked tubular polymer precursor loaded with Mn(CH3COO)2·4H2O. The obtained composite material as anode for LIBs exhibits excellent electrochemical performances.

Section snippets

Synthesis of the N-HCPTs precursor

A flask was charged with triphenylamine (1.0 mmol, 245 mg), FeCl3 (3.0 mmol, 486 mg), formaldehyde dimethyl acetal (3.0 mmol, 228 mg) and 1,2-dichloroethane (50 mL). The reaction mixture was ultrasonicated for 3 h at room temperature. The obtained solid from filtration was washed by water, methanol, dichloromethane and acetone, respectively. After Soxhlet extraction with tetrahydrofuran for 24 h, the N-HCPTs product was dried in vacuum and obtained as a tawny powder (yield: 80.9%). Elemental

Results and discussion

Fig. 1 displays the preparation strategy of the MnO/N-PCNTs composite. Initially, the nitrogen-containing tubular hypercrosslinked polymer (N-HCPTs) precursor was prepared by a Friedel-Crafts reaction of TPA and FDA without any template and surfactant under ultrasonic condition according to our previous report [28]. Then, the obtained N-HCPTs precursor was immersed in the ethanol solution containing Mn(CH3COO)2·4H2O to get the mixture of N-HCPTs and Mn(CH3COO)2·4H2O. The MnO/N-PCNTs composite

Conclusion

In conclusion, we report a facile approach to prepare MnO and N-doped porous carbon nanotubes composite by pyrolysis of a nitrogen-containing hypercrosslinked tubular polymer loaded with manganese acetate. The N-HCPTs precursor could be facilely prepared via Friedel-Crafts reaction of triphenylamine and formaldehyde dimethyl acetal promoted by FeCl3. The resultant MnO/N-PCNTs shows outstanding electrochemical performances as anode for LIBs because of the high redox activity of the MnO, the

Acknowledgment

This work was supported by the National Natural Science Foundation of China (21574077, 21574087 & 21304055), the Fundamental Research Funds for the Central Universities (GK201801001 & GK201701007).

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