- Nano Express
- Open Access
l-Cysteine-Assisted Synthesis of Urchin-Like γ-MnS and Its Lithium Storage Properties
© The Author(s). 2016
- Received: 30 July 2016
- Accepted: 26 September 2016
- Published: 3 October 2016
MnS has been attracting more and more attentions in the fields of lithium ion batteries (LIBs) because of its high energy density and low voltage potential. In this paper, we present a simple method for the preparation of urchin-like γ-MnS microstructures using l-cysteine and MnCl2 · 4H2O as the starting materials. The urchin-like γ-MnS microstructures exhibit excellent cycling stability (823.4 mA h g−1 at a current density of 500 mA g−1, after 1000 cycles). And the discharge voltage is about 0.75 V, making it a good candidate for the application as the anode material in LIBs. SEM, TEM, and XRD were employed to inspect the changes of the active materials during the electrochemical process, which clearly indicate that the structural pulverization and reformation of the γ-MnS microstructures play important roles for the maintenance of the electrochemical performance during the charge/discharge process.
- Lithium ion battery
- Urchin-like γ-MnS microstructures
Nowadays, lithium ion batteries (LIBs) have been widely used in our daily lives, such as cellphones, laptops, electric vehicles, and other portable electrical devices [1–4]. Though graphite has been widely used in the commercial LIBs, the relatively low theoretical capacity (372 mA h g−1) and poor rate performance severely limits its application in various fields . Thus, many efforts are devoted to developing electrode materials with high capacity, cycling stability, and low cost.
Recently, transitional metal sulfides such as cobalt sulfides [6–8], nickel sulfides [9, 10], copper sulfides [11, 12], ferric sulfides [13, 14], and manganese sulfides [15–20] have attracted much attention as an alternative for anode material in LIBs. As an important member of transitional metal sulfides, MnS is considered to be a good candidate for the next generation of anode material because of its high energy density (~616 mA h g−1) and low voltage potential (average discharge voltage at ~0.65 V and charge voltage at ~1.25 V) [16, 17, 20, 21]. For this reason, a great number of MnS micro-/nanostructures with different morphologies have been successfully prepared, all of which show excellent electrochemical performance when used as the anode materials in LIBs. For instance, Robinson and co-workers have successfully prepared MnS nanoparticles using the electrophoretic deposition (EDP) method, which can deliver a reversible capacity of 470 mA h g−1 at a current density of C/5 after 100 cycles . Zhang’s group has also succeeded in the preparation of coral-like α-MnS using a facile two-step method. Because of the unique structures, the as-synthesized coral-like α-MnS exhibits excellent electrochemical performance. Under a current density of 500 mA g−1, the as-synthesized coral-like α-MnS can still deliver a reversible capacity of 699 mA h g−1 after 400 cycles . Kang’s group have also reported the synthesis of MnS-C using the spray drying process, which exhibits a discharge capacity of 786 mA h g−1 at a current density of 500 mA g−1 after 100 cycles . Despite these remarkable progresses, the electrochemical performance of MnS-based anode material is still far from satisfying when considering its practical use in LIBs. According to the previous reports, the relatively poor cycling stability and low discharge capacity are still the main problems that prevent them from large-scale application.
It is well known that the electrochemical performance of the electrode material is highly dependent on its morphology and crystalline texture [5, 6]. Thus, a MnS nanostructure with proper morphological design would be expected to greatly enhance the electrochemical performance of the anode material. Herein, we reported the synthesis of urchin-like γ-MnS via a simple solvothermal method using l-cysteine and MnCl2 · 4H2O as the raw materials. Thanks to the unique 3D structure, the as-synthesized urchin-like γ-MnS exhibits excellent cycling stability. The discharge capacity can still reach 823.4 mA h g−1 after discharging for 1000 cycles at the current density of 500 mA g−1. Besides the cycling stability, the as-prepared urchin-like γ-MnS structures also exhibit satisfying rate performance. SEM, TEM, and XRD were employed to inspect the changes of the active materials during the electrochemical process, which clearly indicate that the structural pulverization and reformation of the γ-MnS structures play importance roles for the maintenance of the electrochemical performance during the charge/discharge process.
Preparation of the Urchin-Like γ-MnS Nanostructures
The urchin-like γ-MnS nanostructures were synthesized via a facile solvothermal method. In a typical experiment, 1 mmol MnCl2 · 4H2O was firstly dissolved in the mixed solvent composing of 10 mL double-distilled water and 20 mL diethylene glycol (DEG). The mixed solution was then heated to 70 °C under constant stirring. In the next step, 2 mmol l-cysteine was added to the above solution. After heating at 70 °C for 2 h, the white turbid liquid was transferred into a 50-mL Teflon-lined stainless steel autoclave and heated to 180 °C for 18 h. After cooling down to room temperature, the ochre product was collected by centrifugation and washed three times with water and ethanol. The as-obtained product was finally dried in vacuum at 60 °C for 12 h.
Phase purities of the as-prepared samples were characterized using X-ray powder diffraction (XRD, Bruker D8 advanced diffractometer with Cu-Kα radiation, λ = 1.5406 Å). The sizes and morphologies of the samples were investigated using the field emission scanning electron microscopy (FESEM, Hitachi S-4800) and transmission electron microscope (TEM, Hitachi H7700, 120 kV). The high-resolution transmission electron microscopy (HRTEM) images were taken using a transmission electron microscopy (TEM, JEOL-2010) with an accelerating voltage of 200 kV. The surface information as well as chemical composition of the samples were examined using the X-ray photoelectron spectrum (XPS, ESCALAB250). The specific surface area and pore size distribution were determined by the Brunauer-Emmett-Teller (BET) nitrogen adsorption and desorption apparatus (Quantachrome autosorb IQ-C).
The working electrodes were prepared by mixing γ-MnS, carbon black (Super-P) and carboxyl methyl cellulose binders (CMC) with a weight ratio of 5:3:2. The slurry was coated on copper foil and then dried in vacuum at 100 °C for 12 h. And the active material on each copper foil was weighted to be ~1.46 mg cm−2. The CR2032 coin cells were assembled in an argon-filled glove box (Mikrouna, Super (1220/750)) with moisture and oxygen concentrations below 0.1 ppm. The electrolyte was a solution of 1 M LiPF6 in a mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) at volume ratio of 4:2:4. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were measured by electrochemical workstation (CHI760E). The galvanostatic charged and discharged characteristics were tested in a voltage range from 0.01 to 3.0 V with LAND CT2001A battery tester.
In our synthesis, l-cysteine is excessive. The free thiol groups of the excessive cysteine molecule will bind to the surfaces of the initial formed γ-MnS nanoparticles. Meanwhile, the hydrogen bonds and S-S bonds will form between the cysteine molecules. Driven by the interactions of hydrogen bonds among tiny particles, H2O and DEG, the as-formed γ-MnS tiny nanoparticles will cross-link together, leading to the formation of irregular microparticles when the solvothermal reaction has been conducted for 1 h . As the solvothermal reaction has been conducted at 180 °C for 5 h, these irregular aggregates will gradually transform to γ-MnS microspheres via the Ostwald ripening process [8, 24, 33–36]. Because of the strong interactions between cysteine and Mn2+, the growth rate of γ-MnS can be effectively controlled. The growth rate in all the direction is nearly the same under the influence of l-cysteine, leading to the formation of γ-MnS microspheres in this step. As the reaction went on, the influence of l-cysteine gradually weakens because of the thermal decomposition process during the solvothermal process. Driven by the intrinsic anisotropic growth habit of γ-MnS, the 1D γ-MnS nanorods will gradually form on the surfaces of the γ-MnS microspheres. As the solvothermal reaction went on, the as-formed nanorods grow longer and longer. When the reaction has been conducted for 18 h, the urchin-like microstructures finally form.
Figure 6b shows the discharge/charge voltage profiles of the γ-MnS of different cycles at the current of 500 mA g−1 between 0.01 and 3.0 V. According to the discharge/charge profiles, the initial discharge capacity is 825.5 mA h g−1 and the corresponding columbic efficiency is about 69.06 %. The loss in initial columbic efficiency can be attributed to be the formation of the SEI layer and decomposition of the electrolyte, which have been widely reported for many anode materials [42–45]. The discharge and charge plateaus of the as-prepared γ-MnS electrode are ~0.65 and ~1.25 V, respectively, which are in well agreement with the CV results. The discharging voltage plateau in the second cycle is much higher than the corresponding value in the first cycle, indicating the irreversible reactions of γ-MnS and formation of unstable SEI layer [17, 38, 46, 47]. More interesting, in the third cycle, the discharge and charge plateaus became stable, which is in accord with the cycling performance as shown in Fig. 6c.
Comparison of electrochemical performance with previously reported structure
In summary, urchin-like γ-MnS structures were successfully synthesized by a facile solvothermal method using l-cysteine and MnCl2 · 4H2O as the raw materials. A two-step growth mechanism has been proposed for the formation of the urchin-like γ-MnS structures. The product exhibits excellent cycling stability (823.4 mA h g−1 at the current density of 500 mA g−1 after 1000 cycles) and the discharge voltage is ~0.75 V. SEM, TEM, and XRD were employed to investigate the transformation of the active materials during the charge/discharge process, which clearly indicate that the structural degradation and reformation of the active material play the key roles for the maintenance of the cycling stability. Considering the simple preparation process, excellent cycling stability, and low voltage potential of the as-prepared sample, the product is considered to be a potential candidate anode material in LIBs.
The authors thank the National Basic Research Program of China (Grant No. 2011CBA00701), National Natural Science Foundation of China (Grant Nos. 21171084 and 21373106), and the Program for Scientific Research Innovation Team in Colleges and Universities of Shandong Province for financial support.
DX prepared the manuscript and carried out the experiment. DZS, XXZ, SYZ, and YYD helped in the technical support for the characterizations. SYZ designed the experiment. RRJ and YWS participated in the experiment. All the authors discussed the results and approved the final manuscript.
The authors declare that they have no competing interests.
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