Silicon is an attractive alloy-type anode material for lithium ion batteries because of its highest known capacity (4200 mAh/g). However silicon's large volume change upon lithium insertion and extraction, which causes pulverization and capacity fading, has limited its applications. Designing nanoscale hierarchical structures is a novel approach to address the issues associated with the large volume changes. In this letter, we introduce a core-shell design of silicon nanowires for highpower and long-life lithium battery electrodes. Silicon crystalline-amorphous core-shell nanowires were grown directly on stainless steel current collectors by a simple one-step synthesis. Amorphous Si shells instead of crystalline Si cores can be selected to be electrochemically active due to the difference of their lithiation potentials. Therefore, crystalline Si cores function as a stable mechanical support and an efficient electrical conducting pathway while amorphous shells store Li(+) ions. We demonstrate here that these core-shell nanowires have high charge storage capacity ( approximately 1000 mAh/g, 3 times of carbon) with approximately 90% capacity retention over 100 cycles. They also show excellent electrochemical performance at high rate charging and discharging (6.8 A/g, approximately 20 times of carbon at 1 h rate).

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The impedance behavior of silicon nanowire electrodes has been investigated to understand the electrochemical process kinetics that influences the performance when used as a high-capacity anode in a lithium ion battery. The ac response was measured by using impedance spectroscopy in equilibrium conditions at different lithium compositions and during several cycles of charge and discharge in a half cell vs. metallic lithium. The impedance analysis shows the contribution of both surface resistance and solid state diffusion through the bulk of the nanowires. The surface process is dominated by a solid electrolyte layer (SEI) consisting of an inner, inorganic insoluble part and several organic compounds at the outer interface, as seen by XPS analysis. The surface resistivity, which seems to be correlated with the Coulombic efficiency of the electrode, grows at very high lithium contents due to an increase in the inorganic SEI thickness. We estimate the diffusion coefficient of about 2 × 10 -10 cm 2 /s for lithium diffusion in silicon. A large increase in the electrode impedance was observed at very low lithium compositions, probably due to a different mechanism for lithium diffusion inside the wires. Restricting the discharge voltage to 0.7 V prevents this large impedance and improves the electrode lifetime. Cells cycled between 0.07 and 0.70 V vs. metallic lithium at a current density of 0.84 A/g (C/5) showed good Coulombic efficiency (about 99%) and maintained a capacity of about 2000 mAh/g after 80 cycles.

Spinel LiMn2O4 is a low-cost, environmentally friendly, and highly abundant material for Li-ion battery cathodes. Here, we report the hydrothermal synthesis of single-crystalline beta-MnO2 nanorods and their chemical conversion into free-standing single-crystalline LiMn2O4 nanorods using a simple solid-state reaction. The LiMn2O4 nanorods have an average diameter of 130 nm and length of 1.2 microm. Galvanostatic battery testing showed that LiMn2O4 nanorods have a high charge storage capacity at high power rates compared with commercially available powders. More than 85% of the initial charge storage capacity was maintained for over 100 cycles. The structural transformation studies showed that the Li ions intercalated into the cubic phase of the LiMn2O4 with a small change of lattice parameter, followed by the coexistence of two nearly identical cubic phases in the potential range of 3.5 to 4.3 V.