Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2, rue de la Houssinière BP32229, F44322 Nantes Cedex, France.
Inorg Chem. 2010 Sep 20;49(18):8457-64. doi: 10.1021/ic1010192.
Nanosized TiO(2)(B) has been investigated as a possible candidate to replace Li(4)Ti(5)O(12) or graphite as the negative electrode for a Li-ion battery. Nanoribbon precursors, classically synthesized in autogenous conditions at temperatures higher than 170 °C in alkaline medium, have been obtained, under reflux (T ∼ 120 °C, P = 1 bar). After ionic exchange, these nanoribbons exhibit a surface area of 140 m(2) g(-1), larger than those obtained under autogenous conditions or by solid state chemistry. These nanoparticles transform after annealing to isomorphic titanium dioxide. They mainly crystallize as the TiO(2)(B) variety with only 5% of anatase. This quantification of the anatase/TiO(2)(B) ratio was deduced from Raman spectroscopy measurement. TEM analysis highlights the excellent crystallinity of the nanosized TiO(2)(B), crystallizing as 6 nm thin nanoribbons. These characteristics are essential in lithium batteries for a fast lithium ion solid state diffusion into the active material. In lithium batteries, the TiO(2)(B) nanoribbons exhibit a good capacity and an excellent rate capability (reversible capacity of 200 mA h g(-1) at C/3 rate (111 mA g(-1)), 100 mA h g(-1) at 15C rate (5030 mA g(-1)) for a 50% carbon black loaded electrode). The electrode formulation study highlights the importance of the electronic and ionic connection around the active particles. The cycleability of the nano-TiO(2)(B) is another interesting point with a capacity loss of 5% only, over 500 cycles at 3C.
纳米 TiO(2)(B) 已被研究作为锂离子电池负极的可能候选材料,以替代 Li(4)Ti(5)O(12) 或石墨。纳米带前体在碱性介质中于回流条件下(T ∼ 120°C,P = 1 巴)在 170°C 以上的温度下自发生成,得到纳米带。经过离子交换后,这些纳米带的比表面积为 140 m(2) g(-1),大于在自发生成条件下或通过固态化学方法获得的纳米带。这些纳米颗粒在退火后转化为同构的二氧化钛。它们主要结晶为 TiO(2)(B) 变体,只有 5%的锐钛矿。这种锐钛矿/TiO(2)(B) 比值的定量推断来自拉曼光谱测量。TEM 分析突出了纳米 TiO(2)(B) 的优异结晶度,结晶为 6nm 厚的纳米带。这些特性对于锂离子电池中锂离子在活性材料中的快速固态扩散至关重要。在锂离子电池中,TiO(2)(B) 纳米带表现出良好的容量和优异的倍率性能(在 C/3 速率(111 mA g(-1))下具有 200 mA h g(-1)的可逆容量,在 15C 速率(5030 mA g(-1))下具有 100 mA h g(-1)的可逆容量,对于负载 50%炭黑的电极)。电极配方研究突出了活性颗粒周围电子和离子连接的重要性。纳米 TiO(2)(B) 的循环性能也是另一个有趣的方面,在 3C 下经过 500 次循环后,容量损失仅为 5%。