La3掺杂尖晶石LiMn2O4的第一性原理研究.DOCVIP

La3+掺杂尖晶石LiMn204的第一性原理 研究 Ott梁兴华tw王玉江 广西科技大学广西大学广东工业大学 采用第一性原理，研究丫 La3+掺杂尖晶石LiMn/),的电子态密度、原子布局、电 荷密度等。结果表明，La3掺杂后体系结构稳定，带隙降低、费米附近能带数增 加，费米能由_1.50eV增加到-0.86eV，平均电压提高，充放电速率提高;总态 密度中0、Mn、La提供的能量高，其形成的化学键强度大，空间构架稳固，晶体 塌陷的几率低;形成能为负值，La-0, Mn—0键长较短，共价性强，键稳定不易 断裂，循环稳定性提高;LiLa^Mn^A理论容量比LiMn204高。 关键词： 第一性原理;掺杂;尖晶石LiMn204;电荷密度; 基金：广西汽车零部件与整车技术重点实验室自主研宂课题(15-A-03-01、 2015KFZD02) First-principle study on La-doped spinel LiMn204 Huang Meihong Liang Xinghua Zeng Shuaibo Wang Yujiang Chen Haiyan Guangxi University ofScience and Technology; Guangxi University; Guangdong University of Technology; Abstract： The electron density of states, atomic population and electric charge density of La-doped spinel LiMn20i were investigated by first-principles theory. The results showed that the structure of La-doped spinel LiMn20, was stable, the band gap decreased and the number of bands near the Fermi energy increased. The Fermi energy was increased from -1. 50 eV to~0. 86 eV, the average voltage and the charge-discharge rate were increased simultaneously. 0, Mn and La provided high energy for the total density of states and form strong chemical bonds, indicated that the space frame was stable and the probability of crystal collapse was low. The formation energy of LiLaoLnuA was negative and La—0，Mn—0 bond was short, thus the covalent was strong and the bond was stable, therefore the cycle stability was improved. The theoretical capacity of LiLao.^sMni.^sOj was higher than LiMn20b Keyword： first-principles; doping; spinel LiMn204; electric charge density; 尖晶石锰酸锂（IJMnA）正极材料因为其成本低廉、环境友好、资源丰富而成为 锂离子（Li）动力电池材料之一[1-2]。LiMr^O,材料的应用集屮在消费类电池市 场（如手机、笔记本电脑和平板电脑等）UL作为动力电池主要用于电动工具、 电动自行车和电动汽车等领域包1。相对于其它正极材料，LiMn20,具有原料丰富、 价格低廉及无毒性等优点，因此LiMn204正极材料成为Li电池首选材料之一 [5-6] o自上世纪90年代日本索尼公司将18650电池商品化以来，由于其高比功 率密度和能量密度特性[7-8],使其在激烈的市场竞争屮仍具有较好应用前景 [9-10]。然而，由于在高温下充放电性能较差的弱点大大限制了 Li电池的发展。 通常改进LiMn20,正极材料的性能有掺杂和包覆两种方法IU1。本研宄釆用第一 性原理对La掺杂LiMn20,进行研究，分析了几何优化、能带、原子布局、电子密 度等，并与实验数据进行对比，揭示La摻杂对LiMn20,材料性能的影响。 1实验部分 1.1模型的构