There is great interest in developing rechargeable lithium batteries with higher energy capacity and longer cycle life for applications in portable electronic devices, electric vehicles and implantable medical devices. Silicon is an attractive anode material for lithium batteries because it has a low discharge potential and the highest known theoretical charge capacity (4,200 mAh g(-1); ref. 2). Although this is more than ten times higher than existing graphite anodes and much larger than various nitride and oxide materials, silicon anodes have limited applications because silicon's volume changes by 400% upon insertion and extraction of lithium which results in pulverization and capacity fading. Here, we show that silicon nanowire battery electrodes circumvent these issues as they can accommodate large strain without pulverization, provide good electronic contact and conduction, and display short lithium insertion distances. We achieved the theoretical charge capacity for silicon anodes and maintained a discharge capacity close to 75% of this maximum, with little fading during cycling.
Ge nanowire electrodes fabricated by using vapor-liquid-solid growth on metallic current collector substrates were found to have good performance during cycling with Li. An initial discharge capacity of 1141 mA.h/g was found to be stable over 20 cycles at the C/20 rate. High power rates were also observed up to 2C with Coulombic efficiency > 99%. Structural characterization revealed that the Ge nanowires remain intact and connected to the current collector after cycling. Nanowires connected directly to the current collector have facile strain relaxation and material durability, short Li diffusion distances, and good electronic conduction. Thus, Ge nanowire anodes are promising candidates for the development of high-energy-density lithium batteries.
Layered-structure nanoribbons with efficient electron transport and short lithium ion insertion lengths are promising candidates for Li battery applications. Here we studied at the single nanostructure level the chemical, structural, and electrical transformations of V2O5 nanoribbons. We found that transformation of V2O5 into the omega-Li3V2O5 phase depends not only on the width but also the thickness of the nanoribbons. Transformation can take place within 10 s in thin nanoribbons, suggesting a Li diffusion constant 3 orders of magnitude faster than in bulk materials, resulting in a significant increase in battery power density (360 C power rate). For the first time, complete delithiation of omega-Li3V2O5 back to the single-crystalline, pristine V2O5 nanoribbon was observed, indicating a 30% higher energy density. These new observations are attributed to the ability of facile strain relaxation and phase transformation at the nanoscale. In addition, efficient electronic transport can be maintained to charge a Li3V2O5 nanoribbon within less than 5 s. These exciting nanosize effects can be exploited to fabricate high-performance Li batteries for applications in electric and hybrid electric vehicles.
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