锂离子电池石墨负极材料的边缘碳原子计算模型

摘要

Based on the hexagonal crystallite model of graphite,the electrochemical characteristics of carbon atoms on the edge and basal plane were proposed by analyzing graphite crystal structure and bonds of carbon atoms in different sites.A spherical close-packed model for graphite particle was developed.The fractions of surface carbon atoms (SCA) and edge carbon atoms (ECA) were derived in the expression of crystallographic parameters and particle size,and the effects of ECA on the initial irreversible capacity and the mechanisms of action were analyzed and verified.The results show that the atoms on the edge are more active for electrochemical reactions,such as electrolyte decomposition and tendency to form stable bond with other atoms and groups.For the practical graphite particle,corresponding modifying factors were introduced to revise the difference in calculating results.The revised expression is suitable for the calculation of the fractions of SCA and ECA for carbon materials such as graphite,disordered carbon and modified graphite.%基于石墨的六角层片模型,通过分析石墨晶体结构及不同位置碳原子的成键特性,提出石墨晶体中的边缘碳原子和基面碳原子具有不同的电化学特性,建立球形石墨颗粒的紧密堆积模型,推导石墨颗粒中表面碳原子(SCA)及边缘碳原子(ECA)分数与石墨的晶体结构参数和颗粒尺寸之间的计算公式,讨论ECA对首次不可逆容量的影响机理并进行验证.结果表明,边缘碳原子的电化学活性较高,易于发生电解液分解并与其它碳原子或基团形成稳固的联接.对于实际石墨颗粒,通过引入相应的修正因子可以修正计算结果,修正后的计算公式可以适用于多种碳材料,如石墨,乱层碳及改性石墨的SCA及ECA分数的计算.