In this paper, a nanostructured SnSb anode for Li-ion battery has been prepared by a two-step electrode design consisting of the electrochemically assisted template growth of Cu nanopillars onto a current collector followed by electrochemical plating of SnSb, there among, Cu nanopillars current collector was obtained by P. Simon's method. We try to take advantage of the nanostructuration of our electrodes to buffer the mechanical strains occurring during the cycling of tin and antimony with Li+, thanks to larger free space available for alloy–dealloying reactions, delivers a high cycle life and good power performance.
Firstly, Cu nanopillars current collectors were obtained using previously reported procedure. Briefly, arrays of copper nanorods on copper disk substrate were prepared by pulsed cathodic electrodeposition through an alumina oxide membrane. The electrolytic cell assembly has been described in P. Simon's work. Secondly, Copper nanopillars were covered with SnSb by means of an electro-co-deposition process from an aqueous solution consisting of SnSO4, KSbOC4H4O6∙1/2H2O, K4P207∙l0H2O and gelatin. The SnSb coating was produced at a constant cathode current density using a two-electrode glass cell at room temperature. Cu substrate containing copper nanopillars acted as the working electrode, whereas a Pt foil served as the counter electrode. The electrodeposits were carried out for a certain deposition time in a galvanostatic mode. After SnSb electro-co-deposition, the obtained SnSb nanostructured anodes were washed with distilled water and acetone successively and then placed under argon atmosphere to avoid oxidation. The morphology, structure and composition of these anode materials were characterized by XRD, SEM and EDS, respectively. The electrochemical reaction mechanism, charge/discharge capacity and cycle performance were analyzed by various electrochemical measurements. And on this basis, we investigated the correlations between material properties and electrochemical performance of the electrode.
The scanning electron microscopy (SEM) image clearly shows SnSb nanoparticles are uniformly deposited on the surface of the Cu nanopillars without any coalescence between them. This particular nanostructure is expected to be able to accommodate volume variations occurring during cycling in a lithium cell and thus result in excellent capacity retention. EDS analysis of the deposits of SnSb on Cu nanopillars current collectors gave a Sn:Sb atomic ratio of about 1: 1. The peaks of X-ray diffraction (XRD) pattern are attributed to the SnSb phase and show a rather amorphous feature. Electrochemical measurements showed that the SnSb nanostructured anodes show a relatively smooth voltage curve and a high initial coulombic efficiency of 95.7%,Quite different the curves with distinct voltage plateaus of the SnSb film electrode which SnSb deposited on a flat surface. And more importantly, the SnSb nanostructured electrode exhibited a high initial reversible storage capacity of about 738.9mAh/g and excellent capacity retention with only 10.6% decay over 30 cycles. The reversible capacity and capacity retention is high compared with the similar materials reported by other literatures.
Obviously, the SnSb alloy deposited on the Cu nanopillars experiences the same internal stress as that of the SnSb alloy deposited on a flat Cu surface. In the case of the nanostructured electrode, however, the volume variations upon cycling are effectively buffered by the large free volume between the pillars, thus giving to the electrode the observed excellent capacity retention. It is anticipated that the AAO template-assisted method could also be applied to synthesize other promising nanostructured electrode materials by electrodeposition.