Facile Synthesis of Mn-Doped ZnO Porous Nanosheets as Anode Materials for Lithium Ion Batteries with a Better Cycle Durability
© Wang et al. 2015
Received: 26 April 2015
Accepted: 16 June 2015
Published: 3 July 2015
Porous Zn1 − x Mn x O (x = 0.1, 0.2, 0.44) nanosheets were prepared by a low-cost, large-scale production and simple approach, and the applications of these nanosheets as an anode material for Li-ion batteries (LIBs) were explored. Electrochemical measurements showed that the porous Zn0.8Mn0.2O nanosheets still delivered a stable reversible capacity of 210 mA h g−1 at a current rate of 120 mA g−1 up to 300 cycles. These results suggest that the facile synthetic method of producing porous Zn0.8Mn0.2O nanostructure can realize a better cycle durability with stable reversible capacity.
ZnO, as 3d a transition-metal oxide, has been considered as an anode material for Li-ion batteries (LIBs) due to the following characteristics: high specific capacity (978 mA h g−1), abundance, low cost, non-toxic, easily produced, and chemically stable [1–5]. However, it often suffers the loss of capacity upon the cycling due to drastic volume changes during the formation of lithium zinc alloys [6–8]. Therefore, a lot of effort has been devoted to overcome these problems; correspondingly, many methods have been developed, such as (i) preparing ordered nanostructured materials [2, 9]; (ii) incorporating with Ni3ZnC0.7 ; (iii) coating with Ni, C, and CoO-C layers [6, 11, 12]; and (iv) doping with Mg . These techniques enhance the conductivity, facilitate the lithiation/delithiation process, or buffer the volume changes. For example, Ping et al. reported Zn1 − x Mg x O (x = 0, 0.18) thin films showed an improved cycling stability compared to that of ZnO thin films. The doped Mg ions may only act as a buffer in a form of MgO to alleviate the stress caused by the volume changes during the formation of lithium–zinc alloys .
Mn-doped ZnO has been widely investigated for their optical properties, magnetic properties, and sensing properties [14–18]. However, it has rarely been used as anode materials in LIBs. In this work, we successfully synthesized porous Zn1 − x Mn x O (x = 0.1, 0.2, 0.44) nanosheets in high yield using a facile method. The electrode performance of the samples was electrochemically investigated, and the representative as-synthesized Zn1 − x Mn x O (x = 0.2) exhibited a better cycle durability with stable reversible capacity of 210 mA h g−1 for up to 300 cycles at 120 mA g−1.
ZnO precursor synthesis
Synthesis of Zn1 − x Mn x O
The as-prepared particles were characterized by powder X-ray diffraction (XRD) on a Philips X’pert X-ray diffractometer equipped with Cu Kα radiation (λ = 1.5418 Å). The morphologies of the samples were examined on a field-emission scanning electron microscopy (FESEM; JEOL JSM-6700 F) and a transmission electron microscopy (TEM; JEOL-2010). The HRTEM images were taken on an aberration-corrected analytical transmission electron microscopy (ARM200F). N2 adsorption–desorption isotherms were measured on a Micromeritics ASAP-2000 nitrogen adsorption apparatus at 150 K.
The electrodes for electrochemical testing consisted of 70 wt% active materials, 15 wt% conductive material (acetylene black), and 15 wt% binder (polyvinylidene fluoride (PVDF)). Test cells (2016) were assembled in glove box using lithium metal as the anode, Celgard 2600 as the separator, and 1 M LiPF6 in ethylene carbonate and dimethyl carbonate solution (v/v, 1:1). The galvanostatical charge/discharge measurement was carried out by a LAND-CT2001 battery cycler (Wuhan, China) testing system in the voltage range of 0.01–3.0 V (vs. Li/Li+).
Results and Discussion
In conclusion, the Mn-doped ZnO porous nanosheets were successfully synthesized by a simple approach and their electrochemical performance were evaluated. The obtained Zn0.8Mn0.2O porous nanosheets exhibit better cycle durability with good reversible capacity. The cavities among nanosheets maybe could effectively suppress the volume expansion during cycling and enhances the electric conductivity of electrodes, etc., giving rise to better electrochemical performance and cycling stability. In addition, our results provide a simple, effective strategy to fabricate the Zn0.8Mn0.2O nanostructure.
This work was supported by the Yang Fan project of Science and Technology Commission of Shanghai Municipality (No.14YF1409700) and the Young Teacher Training Scheme of Shanghai (No. ZZgcd14008) and the National Natural Science Foundation of China (No. 21171158, No. 50903018, No 21305086).
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