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Remarkable anodic performance of lead titanate 1D nanostructures via in-situ irreversible formation of abundant Ti^3＋ as conduction pathways

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Nano Research 2016年第2期9卷 353-362页

作者： Zhiyong Shi Jin Wang Wenxi Wang Yixiang Zhang Bo Li Zhouguang Lu Yadong Li Division of Energy and Environment in Graduate School at Shenzhen Tsinghua University Shenzhen 518055 China Department of materials Science and Engineering South University of Science and Technology of China Shenzhen 518055 China Department of Chemistry Tsinghua University Beijing 100084 China

PX-phase PbTiO3 （PT） nanowires with open channels running along the length direction have been investigated as an anode material for lithium ion batteries. This material shows a stabilized reversible specific capacity of about 410 mAh·g^-1 up to 200 cycles with a charge/discharge voltage plateau of around 0.3-0.65 V. In addition, it exhibits superior high-rate performance, with 90% and 77% capacity retention observed at 1 and 2 A·g^-1, respectively. At a very high current rate of 10 A·g^-1, a specific capacity of over 170 mAh·g^-1 is retained up to 100 cycles, significantly outperforming the rate capability reported for Pb and Pb oxides. The results of X-ray photoelectron spectroscopy （XPS） and transmission electron microscopy （TEM） analyses along with the cyclic voltammogram results reveal that the PX-phase PT nanowires undergo irreversible structural amorphization and reduction reactions during the initial cycle, which allow them to transform into a composite structure composed of 2-5 nm Pb nanoparticles uniformly dispersed in the 1D amorphous Li2O·TiO2·LiTiO2 matrix. In this composite structure, the presence of abundant amounts of Ti^3＋ in both the charged and discharged states enhances the electrical conductance of the system, whereas the presence of ultrafine Pb nanoparticles imparts high reversible capacity. The structurally stable TiO2-based amorphous matrix can also considerably buffer the volume variation during the charge/discharge process, thereby facilitating extremely stable cycling performance. This compound combines the high specific capacity of Pb-based materials and the good rate capability of Ti^3＋-based wiring. Our results might furnish a possible route for achieving superior cycling and rate performance and contribute towards the search for next-generation anode materials.

关键词： PbTiO3 nanowires lithium ion anode materials amorphous Ti^3+-rich matrix composite structure

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