Facilely self-assembled MnS/S-doped reduced graphene oxide network with enhanced performance for potassium-ion battery
Introduction
Potassium-ion batteries (KIBs) have been considered as promising alternatives to lithium-ion batteries (LIBs) owing to the high abundance of potassium mines, similar electrochemical behavior to LIBs and low reaction potential of K+/K (−2.92 V vs standard hydrogen electrode) [1]. Nevertheless, the much larger radius (1.38 Å) of K-ion than that of Li-ion (0.76 Å) results in difficult potassiation/depotassiation processes, and the huge distortion toward host material and sluggish diffusion kinetics make the search and design of suitable electrode materials very challengeable [2].
Based on the mature experiences in high-performance anodes of LIBs, transition metal sulfides (TMSs) with weak metal-sulfur bonds have received growing attention for KIB applications recently due to the attractive specific capacity and the advantages in conductivity and reaction activity compared to metal oxides [3]. It is noted that the effective exploitation of TMS-dominated anode materials is highly depended on the rational nanostructure design and the hybridization with high-conductive carbon matrices. These strategies have been widely confirmed for overcoming the spiny issues like enormous volume fluctuation, poor intrinsic electrical conductivity and polysulfide shuttling effect of the bare TMS electrodes. Up to now, only several successful cases, such as CoS nanoclusters/graphene [4], ReS2 nanosheets/carbon nanofibers [5] and Yolk-shell NiSx@C nanosheets [6], are demonstrated for receiving high reversible capacity and enhanced cycling/rate performances. Therefore, more efforts should be done to explore diversiform TMS anode materials for enriching the potential candidates of practical KIBs.
As the typical member of TMS group, MnS with high theoretical capacity of ~616 mAh g−1, low reaction potential and cost advantage is a suitable choice for energy storage [7], which however is still not employed for KIB applications up to now. In this study, we develop a MnS/S-doped reduced graphene oxide (MnS@S-rGO) hybrid material through a facile self-assembly method. A special 3D network configuration in which the MnS nanoparticles are firmly confined in the graphene wrinkles is constructed. It is well known that rGO has been widely employed as superior matrix benefiting from the high conductivity, large specific surface area, as well as the robust mechanical strength and flexibility [8]. And the heteroatom (e.g. N, S, P, F) doping in the carbon matrices can further contribute to the increased reversible active sites, enhanced electronic conductivity and improved surface wettability of electrode materials [9], [10]. As a result, the MnS@S-rGO composite electrode exhibits greatly enhanced K-storage performances, such as stable reversible capacity of 215 mAh g−1 and excellent rate capability (capacity retention of 41.6% at 1000 mA g−1).
Section snippets
The preparation process of the MnS@S-rGO composite.
Firstly, 0.075 g of KMnO4 was added into a mixed solvent of dimethylformamide and H2O (1:1, v/v) and stirred for 12 h to obtain uniform MnOOH NPs. After centrifugation, the sediment and 6.8 mL of GO suspension (7.7 mg mL−1) were ultrasonically dispersed in 60 mL distilled water for 1 h. Subsequently, the homogenous suspension was poured into plenty of liquid nitrogen and vacuumly freeze-dried. Finally, 0.1 g of the flocculent product was mixed with 0.3 g of sulfur powder and heat-treated at
Results and discussion
The phase composition of the MnS@S-rGO composite is determined by XRD measurement (Fig. 1a). All the diffraction peaks are indexed to α-MnS phase with cubic configuration (JCPDS No. 06-0518), suggesting the high purity of the MnS component. It is noted that the (3 1 1) peak is much weaker than that in the JCPDS card, which could be due to the depressed growth of (3 1 1) crystal plane during the sulfuration process [11]. The XPS survey spectrum (Fig. 1b) manifests the coexistence of Mn, S, C and
Conclusions
We fabricate a MnS nanoparticles/S-doped reduced graphene oxide composite with 3D network structure through a self-assembly strategy. The graphene nanosheets wrap the MnS nanoparticles firmly, and meanwhile interconnect with each other to form a perforative configuration. Benefiting to the robust 3D graphene skeleton and the confinement of graphene wrinkles to MnS, the composite electrode exhibits stable cycling performance and high rate capacity retention. The bifunctional strategy sheds light
CRediT authorship contribution statement
Pengyu Han: Data curation, Writing - original draft, Software. Yun Zhao: Writing - review & editing, Supervision.
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 financially supported by National Natural Science Foundation of China [No. 51702191] and the Shanxi “1331 Project” Key Innovative Research Team.
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