Regular ArticleAn atom-economy route for the fabrication of α-MnS@C microball with ultrahigh supercapacitance: The significance of in-situ vulcanization
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.
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).
References (40)
- et al.
Electrodeposited MnS on Graphene wrapped Ni-Foam for Enhanced Supercapacitor Applications
Electrochim. Acta
(2018) - et al.
All-solid-state flexible asymmetric supercapacitors with high energy and power densities based on NiCo2S4@MnS and active carbon
J. Energy Chemistry
(2017) - et al.
Novel fabrication of Ni3S2/MnS composite as high performance supercapacitor electrode
J. Alloy. Compounds
(2017) - et al.
Nanoporous carbon spheres derived from metal-phenolic coordination polymers for supercapacitor and biosensor
J. Colloid Interf. Sci.
(2019) - et al.
3D urchin-like architectures assembled by MnS nanorods encapsulated in N-doped carbon tubes for superior lithium storage capability
Chem. Eng. J.
(2019) - et al.
Novel porous carbon nanosheet derived from a 2D Cu-MOF: Ultrahigh porosity and excellent performances in the supercapacitor cell
Carbon
(2019) - et al.
g-C3N4 doped MnS as high performance electrode material for supercapacitor application
Mater. Lett.
(2019) - et al.
Ultrasonication-assisted ultrafast reduction of graphene oxide by zinc powder at room temperature
Carbon
(2011) - et al.
Low-temperature synthesis of pure rock-salt structure manganese sulfide using a single-source molecular precursor
Chem. Eng. J.
(2008) - et al.
CoS2 engulfed ultra-thin S-doped g-C3N4 and its enhanced electrochemical performance in hybrid asymmetric supercapacitor
J Colloid Interf Sci
(2021)
Facile synthesis of microsized MnO/C composites with high tap density as high performance anodes for Li-ion batteries
Chem. Eng. J.
3D CNTs/graphene network conductive substrate supported MOFs-derived CoZnNiS nanosheet arrays for ultra-high volumetric/gravimetric energy density hybrid supercapacitor
J Colloid Interf Sci
A MXene-based EDA-Ti3C2Tx intercalation compound with expanded interlayer spacing as high performance supercapacitor electrode material
Carbon
Synthesis of MnS microfibers for high performance flexible supercapacitors
Mater. design
Nanohoneycomb-like manganese cobalt sulfide/three dimensional graphene-nickel foamhybid electrodes for high-rate capability supercapacitors
Appl. Surf. Sci.
A mini-microplasma-based synthesis reactor for growing highly crystalline carbon nanotubes
Carbon
Ordered Self-supporting NiV LDHs@P-Nickel foam Nano-array as High-Performance supercapacitor electrode
J Colloid Interf Sci
Ultrathin metal-organic framework nanosheets for electrocatalytic oxygen evolution
Nat. Energy
Nanostructured materials for advanced energy conversion and storage devices
Nat. Mater.
A review of electrode materials for electrochemical supercapacitors
Chem. Soc. Rev.
Cited by (7)
Mn-MOF derived manganese sulfide as peroxymonosulfate activator for levofloxacin degradation: An electron-transfer dominated and radical/nonradical coupling process
2023, Journal of Environmental Sciences (China)Citation Excerpt :The crystalline structures of the as-obtained catalysts were confirmed by XRD. The XRD pattern of the α-MnS prepared in this study exhibits the pure α-MnS phase with the diffraction peaks at 29.6°, 34.3°, 49.3°, 58.3°, 61.5°and 72.3°, corresponding to the (111), (200), (220), (311), (222) and (400) lattice planes (JCPDS: 06-0518) (Zhang et al., 2021a). Meanwhile, the XRD pattern of the as-prepared γ-MnS fits well with the γ-MnS phase with the lattice constant 2θ peaks and the corresponding lattice at 25.8° (100), 27.7° (002), 29.6° (101), 38.5° (102), 45.6° (110), 50.1° (103), 54.3° (112) (JCPDS: 40-1289) (Gui et al., 2011).
Manganese-based coordination framework derived manganese sulfide nanoparticles integrated with carbon sheets for application in supercapacitor
2023, Advanced Powder TechnologyCitation Excerpt :The MnS nanoparticles with size of 200 nm were embedded in polymer derived carbon network, which effectively inhibited aggregation and volume change and improved conductivity. As a result, MnS@C microballs demonstrated a remarkably enhanced pseudocapacitance (856F/g, 0.5 A/g, 2.0 M KOH) [35]. Despite above advances, the eletrochemical performance of MnS still needs to be further improved to meet the demand of large-scale energy storage.
Ball-milling fabrication of n-p heterojunctions Bi<inf>4</inf>O<inf>5</inf>Br<inf>2</inf>/α-MnS with strengthened photocatalytic removal of bisphenol A in a Z-Scheme model
2023, Separation and Purification TechnologyCitation Excerpt :In Fig. 3b, the Bi 4f spectrum of Bi4O5Br2 consists of two signal peaks with binding energies at around 164.9 and 159.6 eV, ascribed to Bi 4f5/2 and Bi 4f7/2 orbitals with a difference of 5.3 eV, revealing the presence of Bi3+ species in lattices [41]. In Fig. 3c, Mn 2p spectrum of α-MnS includes two peaks at 653.2 and 641.6 eV with a distinction of 11.6 eV, corresponding to Mn 2p1/2 and Mn 2p3/2 orbitals of Mn2+ cations in lattices, respectively [42]. Signals of Bi 4f and Mn 2p in composite BMS0.05 move downfield compared those in bare Bi4O5Br2 and α-MnS, confirming the presence of strong interaction between both phases [43], as also stated by the DFT calculations.
Efficient activation of peroxymonosulfate by MnS/Fe-MOF hybrid catalyst for sulfadiazine degradation: Synergistic effects and mechanism
2022, Separation and Purification TechnologyCitation Excerpt :The 2θ peaks and the corresponding lattice of MIL-100(Fe) are observed at 5.3° (3 3 3), 11° (4 2 8), 14.2° (0 8 8), 18.2° (7911), 20.1° (4814), and 27.7° (9321) [17]. Additionally, there also are the weak diffraction peaks of MnS at 29.6°, 34.3°, 49.3°, 61.5°and 72.3°, corresponding to the (1 1 1), (2 0 0), (2 2 0), (2 2 2) and (4 0 0) lattice planes of α-MnS (JCPDS: 06–0518) [18]. It indicated that MnS was successfully bounded to the as-prepared composite.
Nanostructure and phase engineering integration of amorphous Ni-Co sulfide/crystalline MnS/rGO cathode and ultra-small Fe<inf>2</inf>O<inf>3</inf> nanodots/rGO anode for all-solid-state asymmetric supercapacitors
2022, Journal of Energy StorageCitation Excerpt :Even at high specific power of 7524.9 W kg−1, the specific energy can maintain 26.1 Wh kg−1. These values are higher than those of reported of ASC devices in the literature, such as Ni-Mn-S//AC [53], α-MnS@C//AC [54], r-CoNi2S4//AC [14], NiCo2S4/PRGO//AC [55], NiCoS@SBA-C//SBA-C [56], α-Fe2O3 NDs/RGO//Co3O4 NDs/RGO [27], NCM-S@HCNS//3D-rGO [17], GRHNiCo2S4//AC [57]. Fig. 8h shows the capacity retention of the ASC device during consecutive charge-discharge cycling for 10,000 cycles at 10 A g−1.