Department of Materials Science and Engineering and ‡Department of Chemical Engineering, Stanford University , Stanford, California 94305, United States.
ACS Nano. 2014 May 27;8(5):5249-56. doi: 10.1021/nn501308m. Epub 2014 May 5.
Sulfur is a cathode material for lithium-ion batteries with a high specific capacity of 1675 mAh/g. The rapid capacity fading, however, presents a significant challenge for the practical application of sulfur cathodes. Two major approaches that have been developed to improve the sulfur cathode performance include (a) fabricating nanostructured conductive matrix to physically encapsulate sulfur and (b) engineering chemical modification to enhance binding with polysulfides and, thus, to reduce their dissolution. Here, we report a three-dimensional (3D) electrode structure to achieve both sulfur physical encapsulation and polysulfides binding simultaneously. The electrode is based on hydrogen reduced TiO2 with an inverse opal structure that is highly conductive and robust toward electrochemical cycling. The relatively enclosed 3D structure provides an ideal architecture for sulfur and polysulfides confinement. The openings at the top surface allow sulfur infusion into the inverse opal structure. In addition, chemical tuning of the TiO2 composition through hydrogen reduction was shown to enhance the specific capacity and cyclability of the cathode. With such TiO2 encapsulated sulfur structure, the sulfur cathode could deliver a high specific capacity of ∼1100 mAh/g in the beginning, with a reversible capacity of ∼890 mAh/g after 200 cycles of charge/discharge at a C/5 rate. The Coulombic efficiency was also maintained at around 99.5% during cycling. The results showed that inverse opal structure of hydrogen reduced TiO2 represents an effective strategy in improving lithium sulfur batteries performance.
硫是一种具有 1675 mAh/g 高比容量的锂离子电池阴极材料。然而,其快速的容量衰减对硫阴极的实际应用提出了重大挑战。为了提高硫阴极的性能,已经开发了两种主要的方法,包括(a)构建纳米结构的导电基质来物理封装硫,以及(b)通过工程化学修饰来增强与多硫化物的结合,从而减少其溶解。在这里,我们报告了一种同时实现硫物理封装和多硫化物结合的三维(3D)电极结构。该电极基于具有反蛋白石结构的氢还原 TiO2,具有高导电性和对电化学循环的强稳定性。相对封闭的 3D 结构为硫和多硫化物的限制提供了理想的架构。顶部表面的开口允许硫注入反蛋白石结构。此外,通过氢还原对 TiO2 组成进行化学调谐被证明可以提高阴极的比容量和循环稳定性。采用这种 TiO2 封装的硫结构,硫阴极在开始时可以提供约 1100 mAh/g 的高比容量,在 C/5 倍率下经过 200 次充放电循环后,可逆容量约为 890 mAh/g。在循环过程中,库仑效率也保持在 99.5%左右。结果表明,氢还原 TiO2 的反蛋白石结构代表了提高锂硫电池性能的有效策略。