Hydrothermal synthesis of core-shell Mn3O4@C microspheres as superior anode materials for high-performance lithium-ion storage
Graphical abstract
The core-shell Mn3O4@C microspheres with ultra-long cycling life and outstanding rate performance are synthesized successfully through a facile hydrothermal process.
Introduction
The rational design and development of high capacity and long lifespan electrode materials for rechargeable lithium-ion batteries (LIBs) are of great importance to meet the surging demands of energy devices [[1], [2], [3]]. Mn3O4 has exhibited promising applications for advanced LIBs in virtue of its high theoretical capacity (937 mAh/g), abundant resources, low cost and excellent safety performance [4,5]. However, Mn3O4 displays an extremely low electronic conductivity (10−7 to 10−8 S/cm) and drastic volume change during the charge/discharge processes, which severely hinders its practical applications [6,7].
Up to now, a large number of practical measures have been taken to improve these problems, such as morphology control [8,9], metal ion doping [10], and carbon composites [[11], [12], [13]]. Among them, carbon composite materials are a robust strategy to improve the electronic conductivity, effectively release the stress from the volume change during Li+ insertion/extraction and reduce unwanted side reactions between the electrode and the electrolyte [14,15]. Park et al. have synthesized carbon nanofiber/Mn3O4 by an electrophoretic deposition method, which exhibits a discharge capacity of 760 mAh/g after 50 cycles at 0.1 A/g [12]. Wang et al. have developed a solvothermal method for the synthesis of graphene/Mn3O4 nanocomposite membrane that delivers a high capacity of 308 mAh/g at 2 A/g [13]. Recently, RF has been employed as carbon source, which possesses high yield, low cost, stable chemical properties, good adsorption and catalytic performance of the prepared carbon spheres [[16], [17], [18]]. Zhang et al. have synthesized Fe3O4@C nanospheres by a Stöber method with RF as carbon sources, which exhibits a high adsorption capacity of 31.5 mg/g in water and 2 mg/g in cyclohexane solution [17]. Yang et al. have developed noble metal@RF core-shell nanostructures to promote research into catalytic applications [18]. Nonetheless, seldom research has been explored utilizing RF carbonization to improve the electrochemical properties of Mn3O4 for LIBs.
In this paper, we successfully designed the Mn3O4@C microspheres by a facile solvothermal synthesis method to take advantage of RF as carbon sources. Comparing to traditional strategies, our strategy can more easily implement and synthesize the Mn3O4@C microspheres with a homogeneous thin carbon layer, which can effectively raise the electrical conductivity and alleviate the volume change during Li+ insertion/extraction process. Furthermore, the Mn3O4@C microspheres exhibit superior electrochemical performance compared with Mn3O4.
Section snippets
Preparation of MnO2 microspheres
The MnO2 microspheres were synthesized by precipitation reaction. MnSO4 (0.012 mol) and NH4HCO3 (0.12 mol) were dissolved in distilled water (840 mL), respectively, to obtain A and B solutions. Then, the alcohol solution (168 mL) as dispersants were added to A solution under magnetic stirring for 20 min to gain C solution. The B solution was added to C solution under stirring for 2 h. The obtained precipitates were washed with distilled water and alcohol several times, subsequently dried at
Results and discussion
Based on extensive literature review, with the increase of temperature, hexagonal phase of MnO2 (PDF no. 30-0820) (Fig. S1) can be transformed into Mn2O3 and Mn3O4 gradually, and it is beneficial to form the oxide of low valence states at high temperature environment. In this experiment, because of the inert atmosphere and the presence of carbon, it is more conducive to the transformation of manganese to the low valence states [[19], [20], [21]]. For pure Mn3O4, all of the diffraction peaks can
Conclusions
In this paper, we strategically constructed Mn3O4@C microspheres via a low-temperature hydrothermal method and subsequently annealing treatment. The Mn3O4@C microsphere delivers a superior high-rate capacity of 372.3 mAh/g at 3.2 A/g and a stable long-term life span remaining a reversible capacity of 992 mAh/g after 800 cycles at 1 A/g. The RF plays an essential role in forming the core-shell structure and heightening the electronic conductivity of Mn3O4. This method provides a straightforward
Acknowledgments
This work is supported by the National Natural Science Foundation of China (Nos. 51479019 and 21476035) and Fundamental Research Funds for the Central Universities (3132016341).
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