碳酸乙烯酯在ZnO（1010）表面吸附和分解的第一性原理研究
Ethylene Carbonate Adsorption and Decomposition on Pristine and Defective ZnO (1010) Surface: A First-Principles Study
摘要：
为了获得合适的涂层候选物，对锂离子电池阴极的涂层材料与电解质之间的反应性的基本理解是重要的。本文采用第一性原理密度泛函理论（DFT）方法研究了碳酸亚乙酯（EC）在ZnO（10-10）、O空位和Zn空位缺陷ZnO（10-10）上的吸附和分解反应.从热力学和动力学两方面研究了脱氢和EC开环反应生成CO2和C2 H4气体的可能分解途径。首先，我们发现分子EC通过其羰基氧（OC）与表面Zn之间的键合优先吸附在原始和缺陷ZnO（1010）上。其次，随后的分解反应显示EC在原始和有缺陷的ZnO上都有很大的分解趋势（10-10）。这种趋势由在原始和有缺陷的ZnO（10-10）（相对于EC气相计算）上分解EC的范围从-1.5eV到-2.5eV的大的热力学驱动力指示。然而，EC分解的大趋势受到EC分解的高活化能垒的阻碍，在Zn空位缺陷的ZnO（10-10）上的最低活化能垒为0.96 eV。因此，我们的研究结果表明，EC在ZnO（10-10）上的分解主要是由于其分解速度慢，而不是热力学因素受到阻碍。
英文摘要：
Fundamental understanding of the reactivity between coating material of Li-ion battery cathode and electrolyte is important in order to obtain suitable coating candidates. Herein, we study ethylene carbonate (EC) adsorption and decomposition reactions on pristine, O vacancy- and Zn vacancy-defected ZnO (10-10) by means of first-principles density functional theory (DFT) calculations. Possible decomposition pathways via H-abstraction and EC ring-opening reaction that leads to the generation of CO2 and C2H4 gases are studied from the thermodynamic and kinetic aspects. Firstly, we find that molecular EC preferably adsorbs on both pristine and defective ZnO (1010) via the bonding between its carbonyl oxygen (OC) and surface Zn. Secondly, subsequent decomposition reactions show large tendency of EC to decompose on both pristine and defective ZnO (10-10). This tendency is indicated by the large thermodynamic driving forces to decompose EC that range from -1.5 eV to -2.5 eV on both pristine and defective ZnO (10-10) (calculated with respect to EC gas phase). The large tendency of EC to decompose, however, is hindered by the high activation barriers of the EC decomposition, shown by the lowest activation barrier of 0.96 eV on Zn vacancy defected ZnO (10-10). Our results thus indicate that EC decomposition on ZnO (10-10) is mainly hindered due to its slow rate of decomposition instead of the thermodynamic factors.
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