Controllable Fabrication of Multi-tiered Nanoporous Anodic TiO 2 –TiN Composite Films as High-Performance Anode Materials for Lithium-Ion Batteries
Controllable Fabrication of Multi-tiered Nanoporous Anodic TiO 2 –TiN Composite Films as High-Performance Anode Materials for Lithium-Ion Batteries
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DOI：
10.1016/j.electacta.2016.05.210
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发表时间：
2016-09
影响因子：
6.6
通讯作者：
Song-Zhu Kure-Chu;Haruki Sakuyama;S. Saito;S. Miura;H. Yashiro;Hidetoshi Hirahara;H. Segawa;K. Wada;S. Inoue
中科院分区：
文献类型：
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作者：
Song-Zhu Kure-Chu;Haruki Sakuyama;S. Saito;S. Miura;H. Yashiro;Hidetoshi Hirahara;H. Segawa;K. Wada;S. Inoue
本研究提出了一种新的方法来制备多层纳米多孔TiO2-TiN复合膜（NTTC）钛箔在电解液中含有NH4NO3的简易阳极氧化。NTTC膜具有层厚度为250 - 600 nm的独特层压纳米结构，其中每层包括直径为30 - 60 nm的圆柱形孔。NTTC膜的含量为2.2 - 6.0at. %氮以TiN和吸附的NH4+离子的形式存在，这归因于在NH4NO3电解液中阳极氧化期间的电化学/化学反应。此外，新的双层次NTTC薄膜与大（约250 - 300 nm）和小（约80 nm）的孔隙上的顶部和底部层，分别通过连续的阳极氧化在硫酸盐和硝酸盐为基础的电解质系统。具体而言，在（NH4）2SO4·NH4NO3溶液中形成的双层次NTTC膜提供约2504 mAh cm-3的高比容量，并在锂离子电池测试期间表现出优异的循环稳定性，容量保持率接近100%。NTTC膜的高容量主要归因于在TiO 2基质中包含高导电性TiN（改善阳极TiO 2膜导电性）及其高度纳米多孔结构（由于高表面积和存在快速离子扩散路径而促进Li+插入/脱嵌）。
The present study proposed a novel approach to fabricate multi-tiered nanoporous TiO2–TiN composite (NTTC) films on Ti foils by facile anodization in an aqueous electrolyte containing NH4NO3. The NTTC films possess a unique laminated nanostructure with a tier thickness of 250–600 nm, where each tier comprises cylindrical pores of ϕ30–60-nm diameters. The NTTC films contained 2.2–6.0 at.% nitrogen in the forms of TiN and adsorbed NH4+ions, which is attributed to the electrochemical/chemical reactions during anodization in NH4NO3electrolytes. Moreover, novel dual-hierarchical NTTC films with large (ϕ250–300 nm) and small (ϕ80 nm) pores on the top and bottom layers, respectively, are fabricated by a successive anodization in sulfate- and nitrate-based electrolyte systems. Specifically, the dual-hierarchical NTTC film formed in (NH4)2SO4⇒ NH4NO3solutions delivers a high-specific capacity of around 2504 mAh cm−3, and exhibit excellent cycling stability with nearly 100% capacity retention during lithium-ion battery tests. The high capacities of the NTTC films can be attributed primarily to the inclusion of highly conductive TiN in the TiO2matrix (improving the anodic TiO2film conductivity) and their highly nanoporous structure (facilitating Li+insertion/de-insertion because of the high surface area and presence of fast ion diffusion paths.)