Balcı Fadime Mert, Kudu Ömer Ulaş, Yılmaz Eda, Dag Ömer
Department of Chemistry, Bilkent University, 06800, Ankara, Turkey.
Institute of Materials Science and Nanotechnology, National Nanotechnology Research Center (UNAM), Bilkent University, 06800, Ankara, Turkey.
Chemistry. 2016 Dec 23;22(52):18873-18880. doi: 10.1002/chem.201604253. Epub 2016 Nov 18.
Mesoporous Li Ti O (LTO) thin film is an important anode material for lithium-ion batteries (LIBs). Mesoporous films could be prepared by self-assembly processes. A molten-salt-assisted self-assembly (MASA) process is used to prepare mesoporous thin films of LTOs. Clear solutions of CTAB, P123, LiNO , HNO , and Ti(OC H ) in ethanol form gel-like meso-ordered films upon either spin or spray coating. In the assembly process, the CTAB/P123 molar ratio of 14 is required to accommodate enough salt species in the mesophase, in which the Li /P123 ratio can be varied between molar ratios of 28 and 72. Calcination of the meso-ordered films produces transparent mesoporous spinel LTO films that are abbreviated as Cxx-yyy-zzz or CAxx-yyy-zzz (C=calcined, CA=calcined-annealed, xx=Li /P123 molar ratio, and yyy=calcination and zzz=annealing temperatures in Celsius) herein. All samples were characterized by using XRD, TEM, N -sorption, and Raman techniques and it was found that, at all compositions, the LTO spinel phase formed with or without an anatase phase as an impurity. Electrochemical characterization of the films shows excellent performance at different current rates. The CA40-350-450 sample performs best among all samples tested, yielding an average discharge capacity of (176±1) mA h g at C/2 and (139±4) mA h g at 50 C and keeping 92 % of its initial discharge capacity upon 50 cycles at C/2.
介孔钛酸锂(LTO)薄膜是锂离子电池(LIBs)的一种重要负极材料。介孔薄膜可通过自组装工艺制备。采用熔盐辅助自组装(MASA)工艺制备LTO的介孔薄膜。十六烷基三甲基溴化铵(CTAB)、聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)、硝酸锂、硝酸和钛酸四异丙酯(Ti(OC₃H₇)₄)在乙醇中的澄清溶液经旋涂或喷涂后形成凝胶状介观有序薄膜。在组装过程中,需要CTAB/P123摩尔比为14,以便在中间相中容纳足够的盐类物质,其中Li⁺/P123的比例可在28至72的摩尔比之间变化。对介观有序薄膜进行煅烧可得到透明的介孔尖晶石LTO薄膜,在此处简称为Cxx-yyy-zzz或CAxx-yyy-zzz(C =煅烧,CA =煅烧-退火,xx = Li⁺/P123摩尔比,yyy =煅烧温度,zzz =退火温度,单位为摄氏度)。所有样品均采用X射线衍射(XRD)、透射电子显微镜(TEM)、氮气吸附和拉曼技术进行表征,结果发现,在所有组成中,LTO尖晶石相均有形成,且可能含有或不含有作为杂质的锐钛矿相。薄膜的电化学表征显示在不同电流倍率下具有优异的性能。在所有测试样品中,CA40-350-450样品表现最佳,在C/2倍率下平均放电容量为(176±1) mA h g⁻¹,在50 C倍率下为(139±4) mA h g⁻¹,在C/2倍率下进行50次循环后仍保持其初始放电容量的92%。