A critical size of silicon nano-anodes for lithium rechargeable batteries.

Due to the high theoretical capacity (ca. 4200 mAhg ) of Si when Li4.4Si is formed, it has been extensively investigated for use as a high-capacity anode material that can replace graphite, which is currently used (372 mAhg ). However, Si exhibits significant volume changes (> 360%) during Li alloying and dealloying. These changes cause cracking and crumbling of the electrode material and a consequent loss of electrical contact between individual particles and hence severe capacity drop. However, such mechanical strain induced by volume change can be reduced by employing smaller particles. To this end, synthetic methods such as spark ablation, aerogel techniques, and sputtering have been employed. Formation of crystalline Si nanoparticles requires higher temperatures due to the more covalent nature of these particles compared to Ge particles, and at low temperature amorphous phases become more common. The first commonly recognized successful production of Si nanoclusters was reported byHeath et al. They showed that Si nanocrystals capped with alkyl groups can be produced by reduction of SiCl4 and RSiCl3 (R=H, C8H17) according to the reaction SiCl4+RSiCl3+Na!Si+NaCl. This process was carried out at high temperature (385 8C) and high pressure (>100 atm) in a steel bomb fitted into a heating mantle. A process that utilizes SiCl4 reduction at room temperature under an inert atmosphere was initially reported by Kauzlarich et al. However, the drawback of their method was that the product obtained at room temperature was not fully crystallized and was severely capped with alkyl terminators. Moreover, an annealing process above 900 8C is required to obtain the crystalline phase. Similar solution syntheses have been reported at low or high temperature after reducing Si salts with LiAlH4 [13,14] or alkyl silanes. However, all of these methods produce a broad particle size distribution or involve aggregation of the nanoparticles. Furthermore, they all yield amounts of material too small for use in anode production for lithium secondary batteries. We now report a synthetic method using reverse micelles at high pressure and temperature in a bomb that produces Si nanoparticles (n-Si) with various particle sizes without aggregation and thus enables the optimal nanoparticle size for use in anode materials to be chosen. Figure 1 shows the XRD pattern and TEM images of n-Si prepared with trimethyloctadecylammonium bromide (OTAB) surfactant. The XRD pattern clearly shows forma-