Elsevier

Chemical Engineering Journal

Volume 308, 15 January 2017, Pages 340-346
Chemical Engineering Journal

Preparation of porous ZnO/ZnFe2O4 composite from metal organic frameworks and its applications for lithium ion batteries

https://doi.org/10.1016/j.cej.2016.09.071Get rights and content

Highlights

  • Porous ZnO/ZnFe2O4 composite was prepared by microwave reactions.

  • The ZnO/ZnFe2O4 composite exhibits superior electrochemical cycling performance.

  • This work provides a simple approach for preparing porous metal oxide composites.

Abstract

Metal organic frameworks (MOFs) are convenient precursors for preparing porous structures. In this work, the Prussian Blue (one kind of MOFs) is reacted with Zn acetate under microwave irradiation, forming hydroxides and carbonates nanosheets on the surface of Prussian Blue. After pyrolysis, a composite of ZnO/ZnFe2O4 porous nanoparticles was obtained and applied as anode material for lithium ion batteries. The composite shows a good capacity of 804 mAh g−1 for 500 cycles at a current density of 1000 mA g−1.

Introduction

Porous materials with well-defined structural, compositional and morphological properties have been intensively investigated for electrochemical energy storage because of their porosity, providing extra space for volume change, which are beneficial for lithium ions insertion and extraction [1], [2]. There is a rapid growth in exploring approaches to fabricate porous structures, such as templates methods [3], [4], [5], freezing technology [6] etc. Among them, the templates strategy contributes a lot for preparing porous networks. Recently, metal organic frameworks (MOFs) are one novel potential template to fabricate porous structures with well-controlled morphologies [7]. Park et al. have prepared porous carbon-coated ZnO quantum dots through pyrolysis of IRMOF-1 [8]; Low’s group have employed the Prussian Blue MOF to obtain hollow and porous Fe2O3 or Fe2O3/SnO2 composites [9], [10]. Our group has obtained porous Fe2O3/MOx microcubes (M = Cu, Ni, Co, etc.) through ion exchange approach [11]. Porous carbon-coated CuCo2O4 concave polyhedrons were formed through pyrolysis of a zeoliticimidazolate framework (ZIF) [12]. However, there are relatively little reports on the preparation of bimetallic oxides composites by employing MOFs.

In this work, porous nanoparticles of ZnO/ZnFe2O4 composite are obtained for high cycling and good rate performance lithium ion batteries. Firstly, Prussian Blue is reacted with Zn acetate in aqueous solutions under microwave irradiation in a hydrothermal condition. The product is then annealed in air to remove the organic components and leave behind porous ZnO/ZnFe2O4 composite. The composite is utilized as lithium anode, which exhibit 804 mAh g−1 for 500 cycles at the current density of 1000 mA g−1. This performance is superior to the reported ZnO or ZnFe2O4 based composites. The good performance may result from the porous structures of the composite nanoparticles, which not only supply more transportation channels for lithium ions, but also provide buffer for accommodating volume extension in the discharge/charge process. This work may provide a general approach for preparing porous bimetallic oxide composites.

Section snippets

Synthesis of porous ZnO/ZnFe2O4 composite

Prussian Blue (PB) was firstly synthesized according to the Ref. [11]. 0.3 g of PB nanoparticles were then dispersed into three beakers each with 5 mL of distilled water. 0.1, 0.15 and 0.6 g of Zn(CH3COO)2·2H2O were respectively added to the dispersions under sonication (weight ratios of PB:Zn(CH3COO)2·2H2O are 3:1, 2:1, 1:2). The three mixtures were nextly transferred to a microwave reactor, and then each was kept at 150 °C with a microwave flexible power for 30 min. Finally, the precipitant were

Results and discussions

Fig. 2a and b show SEM images of the intermediate products obtained by using PB and Zn(CH3COO)2·2H2O ratio of 1:2 after microwave-assisted reaction. It can be seen that surface of the PB cubes are covered with a high density of flakes with a thickness about tens of nanometers. With PB:Zn(CH3COO)2·2H2O ratios of 2:1 (Fig. 2c) and 3:1 (Fig. 2d), nanoparticles of much lower densities are decorated on the original PB cubes instead. The precursor obtained with a PB: Zn(CH3COO)2·2H2O ratio of 1:2 was

Conclusions

We have designed a porous ZnO/ZnFe2O4 composite structure constructed with small nanoparticles by employing microwave reactions of Prussian blue and Zn acetate. This ZnO/ZnFe2O4 composite exhibits superior electrochemical cycling performance due to the porous structure which supplies ion channels for fast transportation of lithium ions. Moreover, the porous structure may provide extra space for accommodating volume change during cycling. This method provides a general approach for preparing

Acknowledgements

This project has been financially supported by National Natural Science Foundation of China (No. 51602263), Fundamental Research Funds for the Central Universities (XDJK2015C099, SWU114079), China Postdoctoral Science Foundation (2015M572427, 2016T90827) and Chongqing Postdoctoral Research Project (xm2015019).

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