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An atom-economy route for the fabrication of α-MnS@C microball with ultrahigh supercapacitance: The significance of in-situ vulcanization

https://doi.org/10.1016/j.jcis.2021.02.130Get rights and content

Highlights

  • One composite α-MnS@C was prepared by an atom-economy route of in-situ vulcanization.

  • α-MnS@C exhibits core–shell nanostructure, high porosity and good conductivity.

  • The α-MnS@C electrode owns remarkable specific capacitance and power density.

Abstract

In this study, we have introduced a facile, effective and low-cost process of in-situ vulcanization for preparing α-MnS@C composite via simple calcination-thermolysis of one manganese coordination polymer (CP-1-ZX). In this procedure, the 1D chain [-Mn-SO4-] in CP-1-ZX is completely reduced into α-MnS by the as-synthesized carbon. So the in-situ vulcanization provides an atom-economy route to fabricate sulfides by using least synthetic steps and sulfur sources. The α-MnS@C composite maintains the microball morphology of CP-1-ZX precursor, which is composed of many core–shell nanoparticles. Due to high porosity, hierarchical pores and good conductivity, the specific capacitance of α-MnS@C is up to 856F g−1 at 0.5 A g−1, and keeps 82% retention after 5000 cycles. Meanwhile, one asymmetric supercapacitor cell (ASC) is assembled by combining α-MnS@C with commercial active carbon (AC). The α-MnS@C//AC device delivers prominent energy density of 28.4 Wh kg−1 at power density of 395 W kg−1, and still retains 17.8 Wh kg−1 at 8020 W kg−1. Furthmore, four tandem ASC devices can brightly glow a lamp bulb for 30 s. Therefore, the α-MnS@C composite shows great applications in supercapacitors.

Graphical abstract

One core–shell composite α-MnS@C was prepared by a facile and atom-economy route of in-situ vulcanization, i.e. straightforward calcination-thermolysis of CP-1-ZX. The specific capacitance of α-MnS@C is up to 856F g−1, and corresponding ASC α-MnS@C//AC delivers prominent energy density of 28.4 Wh kg−1, which imply broad applications of α-MnS@C in supercapacitors.

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Introduction

With the rising of fossil fuel prices and the increasing environmental problems caused by fossil fuel combustion, the global community is looking for eco-friendly energy resources. Sustainable and renewable power, such as the wind, solar and tide, are considered as potential substitutes of future energy because of their negligible impacts on environment [1], [2]. However, the supplies of clean energy sources are intermittent, and it is better to store the power for convenient exploit. Among those fast-developing energy storage systems, supercapacitors (SCs) possess superior characteristics of high power density, fast charge and discharge speed, and long cycle life, which have attracted tremendous attention [3]. For example, Zhao et al. have reported that sheet-like birnessite δ-MnO2 coupling with carbon exhibits good electrochemical capacitive performance in terms of specific capacitance, rate capability and cycling stability [4]. One most important application of SCs is running electric vehicles, which could provide ultrahigh power density during the acceleration.

Transition-metal sulfides, as one kind of p-type semiconductors with wide gaps, have been widely studied in SCs, because of their impressive theoretical capacitance and low expenditure [5], [6], [7]. However, the syntheses of sulfides in most literatures are complex, poisonous and problematic. To our knowledge, vulcanization is a very common protocal in the mainstream production of sulfides, and too much hazardous chemical reagents (e.g. sulfur powder, Na2S and thiourea) are depleted during the sulfurization process, which brights about serious environmental pollution [8], [9], [10]. Therefore, it is imperative to develop novel manufacturing technology for the fabrication of sulfides.

Coordination polymers (CPs) are assembled from metal ions (clusters) and organic ligands in turn to form multi-dimensional long-term ordered architectures [11]. Except for completely ordered structures, ingredients and topologies can be ingeniously adjusted, and CPs also exhibit many intriguing morphologies. Moreover, CPs contain abundant metal and carbon sources, which would be transformed into metallic and carbon materials through the calcination-thermolysis procedure, respectively [12], [13]. Therefore, CPs are appropriate sacrificial precursors, and we bear in mind that sulfide@carbon composites may be successfully synthesized by the solid-state thermolysis. The integrated carbon compensates for the weakness of pure sulfide in porosity and conductivity, and the combination will improve the capacitance, rate capability and recycling of hybrid SCs [14], [15]. Herein, we demonstrate a facile and affordable atom-economy route of in-situ vulcanization to fabricate α-MnS@C composite. Miscellaneous analyses and electrochemical investigations are carried out on α-MnS@C, and its potential application towards supercapacitors is extensively explored.

Section snippets

Crystal structure of CP-1-ZX

Single-crystal X-ray diffraction analysis reveals that CP-1-ZX crystallizes in the triclinic space group P-1. In the asymmetric unit, there are two crystallographically independent MnII ions (Mn1 and Mn2). As shown in Fig. 1a, the Mn1 ion is equatorially surrounded by three oxygen atoms form three sulfate ions and one water molecule, and axially coordinated by two imidazole groups from individual bibp ligands, forming an octahedral coordination environment. The Mn2 ion also lies in an

Conclusion

In this paper, one core–shell α-MnS@C composite was prepared by the simple calcination-thermolysis of CP-1-ZX microball sample. The CP-1-ZX precursor shows a 1D chain [-Mn-SO4-], which is directly transformed into α-MnS during the calcination. So the facile and efficient synthesis of α-MnS@C is coded as in-situ vulcanization, which is proved to be an atom-economy route. The α-MnS@C composite exhibits unique microball morphology, core–shell nanostructure, high porosity, hierarchical pores and

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgement

This work was supported by the National Natural Science Foundation of China (21673177).

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