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一步固相法合成 Li4Ti5O12/C 的动力学分析。

Kinetic analysis of one-step solid-state reaction for Li4Ti5O12/C.

机构信息

College of Chemistry and Materials Science, Sichuan Normal University, Chengdu, Sichuan, China.

出版信息

J Phys Chem A. 2011 Nov 24;115(46):13413-9. doi: 10.1021/jp2075644. Epub 2011 Oct 21.

Abstract

The kinetics of one-step solid-state reaction of Li(4)Ti(5)O(12)/C in a dynamic nitrogen atmosphere was first studied by means of thermogravimetric-differential thermal analysis technique at five different heating rates. According to the double equal-double steps method, the Li(4)Ti(5)O(12)/C solid-state reaction mechanism could be properly described as the Jander equation, which was a three-dimensional diffusion with spherical symmetry, and the reaction mechanism functions were listed as follows: f(α) = (3)/(2)(1 - α)(2/3)1 - (1 - α)(1/3), G(α) = 1 - (1 - α)(1/3). In FWO method, average activation energy, frequency factor, and reaction order were 284.40 kJ mol(-1), 2.51 × 10(18) min(-1), and 1.01, respectively. However, the corresponding values in FRL method were 271.70 kJ mol(-1), 1.00 × 10(17) min(-1), and 0.96, respectively. Moreover, the values of enthalpy of activation, Gibbs free energy of activation, and entropy of activation at the peak temperature were 272.06 kJ mol(-1), 240.16 kJ mol(-1), and 44.24 J mol(-1) K(-1), respectively.

摘要

在动态氮气气氛中,通过热重-差热分析技术,首次在五个不同的加热速率下研究了 Li(4)Ti(5)O(12)/C 一步固相反应的动力学。根据双等双步法,Li(4)Ti(5)O(12)/C 固相反应机理可以恰当地描述为 Jander 方程,这是一个具有球对称性的三维扩散,反应机理函数列如下:f(α) = (3)/(2)(1 - α)(2/3)1 - (1 - α)(1/3),G(α) = 1 - (1 - α)(1/3)。在 FWO 方法中,平均活化能、频率因子和反应级数分别为 284.40 kJ mol(-1)、2.51 × 10(18) min(-1)和 1.01。然而,在 FRL 方法中,相应的值分别为 271.70 kJ mol(-1)、1.00 × 10(17) min(-1)和 0.96。此外,在峰值温度下,活化焓、活化自由能和活化熵的值分别为 272.06 kJ mol(-1)、240.16 kJ mol(-1)和 44.24 J mol(-1) K(-1)。

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