Nickel foam supported Sn–Co alloy film as anode for lithium ion batteries
Highlights
► Sn–Co alloy film is used as anode in Li-ion batteries. ► Sn–Co alloy film is deposited electrochemically directly onto nickel foam. ► This Ni foam supported Sn–Co anode can buffer the large volume change during lithium insertion and extraction. ► Heat treatment can furtherly improve the electrochemical properties.
Introduction
Recently, tin-based alloys have drawn considerable attention as promising alternative anodes for lithium ion batteries (LIBs) because of their higher specific capacity than traditional graphite materials and their better cycling ability than pure tin anodes [1], [2]. However, the irreversible capacity in the first charge process and the volume expansion followed by a conductivity degradation during charge and discharge cycling are still obstacles to commercialization [3]. Two strategies have been adopted to overcome the electrode deterioration caused by the volume expansion, designing nanostructured electrode materials [4], [5], [6], [7], [8], [9], [10], [11] and use of intermetallic tin-based compounds [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28], [29]. The reaction of intermetallic SnxMY with lithium involves formation of brittle Li–Sn alloys. The relatively inactive metal, M, plays the role of matrix buffer, which effectively suppresses the large volume expansion during the alloying/dealloying process. Accordingly, the intermetallic tin-based materials exhibit a much greater electrochemical capacity than that of a pure tin or graphite electrode.
Various methods have been used to fabricate tin-based alloy materials, such as high-energy ball milling [6], [9], [10], [11], chemical reduction [4], [12] and solid-state reaction [15], [16]. Obtaining the intermetallic tin-based alloys by electrochemical deposition is relatively simple and inexpensive; it can also provide a stable electrochemical capacity [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28]. Hassoun et al. [18] synthesized Sn–Ni film electrodes on Cu foil that showed a capacity of 550 mAh g−1 after 40 cycles. Tamura et al. [23], [24] fabricated an amorphous Sn–Co alloy film by electrocodeposition on Cu foil with a rough surface; the specific capacity of their electrode retained 600 mAh g−1 after 20 cycles.
In this work, Sn–Co alloy films were electrochemically deposited on nickel foam in aqueous solution. Used as current collectors, the nickel foam with a three-dimensional network structure not only increases the electrical conductivity. It also avoids the macrostructural deformation for the tin based electrodes and buffers the large volume change during lithium insertion and extraction [30]. We report the influence on the electrochemical properties of morphological changes of the Sn–Co alloy films on the nickel foam obtained with different current density and heat treatment.
Section snippets
Electrochemical fabrication of Sn–Co film on nickel foam
Nickel foam was used as the metal substrate. As shown in Fig. 1A and B, foamed nickel has a three-dimensional grid structure and shows a high porosity and specific surface area with considerable and uniform strength.
The Sn–Co alloy samples were deposited electrochemically on the nickel foam in a two-electrode cell at 50 °C; a graphite plate was used as the counter electrode. The electrodeposition solution consisted of SnCl2·2H2O (25 g L−1), CoCl2·6H2O (25 g L−1), K4P2O7·3H2O (300 g L−1) and an
Morphological and structural characterization of the Sn–Co films
In order to investigate the influence of the electrodeposition parameters on the morphology and structure of the Sn–Co alloy films supported on nickel foam, three Sn–Co alloy samples were synthesized under the current density of 10 mA cm−2, 30 mA cm−2 and 50 mA cm−2 and named as SnCo-1, SnCo-2 and SnCo-3, respectively. To obtain Sn–Co films with similar film thickness we varied the electrodeposition time for different current densities. The electrodeposition time was 5 min, 8 min and 10 min,
Conclusions
A series of Sn–Co alloy films supported on nickel foam as anode for Lithium ion batteries were deposited electrochemically on nickel foam in an aqueous solution. The morphology of the electrodeposited films was affected by the electrochemical deposition current density and time. Nevertheless, all formed continuous films after heat-treatment at 200 °C for 30 min in nitrogen atmosphere. The capacity and cycling performances of these macroporous Sn–Co alloy films were significantly enhanced. The
Acknowledgements
Financial support from National Science Foundation of China (grant no. 20703013) and the Robert A. Welch Foundation (grant #F-1066), are gratefully acknowledged. D.Z. also thanks the Postdoctor Science Foundation of China (grant no. 20070410219) and the support from China Scholarship Council.
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