Effect of Size Regulation of Natural Molybdenite on Electrochemical Performance for Lithium-ion Batteries
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摘要:
负极材料的尺寸对锂离子电池性能有着重要影响，设计研磨时间制备不同尺寸的天然辉钼矿，探究尺寸与锂离子电池的电化学性能之间的联系。粒度分布仪得出分别研磨30（M30）、60（M60）和90 min（M90）的样品其平均尺寸分别为19.45、13.14和11.23 μm；XRD和SEM表明尺寸越小，晶粒尺寸越小，边缘破碎越严重；电化学性能测试表明，三者首圈容量分别为851、797和649 mAh·g-1，100圈后容量保持率分别为30%、38%和85%。M90具有最大的锂离子扩散系数为3.29×10-10，以0.1~0.8 mV·s-1的不同CV扫描速率计算得出赝电容为主要的容量贡献，可实现电子和离子的快速穿梭。天然辉钼矿的尺寸越小，首圈容量越小，但循环和倍率性能更好和反应动力学更快，并提出类似天然辉钼矿层状储锂模型来阐明天然辉钼矿尺寸与锂离子电池性能关系。
Abstract:The size of anode materials has an essential effect on the performance of lithium-ion batteries. The grinding time was designed to prepare different sizes of natural molybdenite, and the relationship between the size and the electrochemical performance of lithium-ion batteries was explored. The average sizes of the samples abraded for 30 (M30), 60 (M60), and 90 min (M90) were 19.45, 13.14, and 11.23 μm, respectively. XRD and SEM show that the smaller the particle size, the smaller the grain size, and the more serious the edge crushing is. Electrochemical performance tests showed that the first cycle capacities of the three groups were 851, 797, and 649 mAh·g-1, respectively, and the capacity retention rates after 100 cycles were 30%, 38%, and 85%, respectively. M90 had the maximum lithium-ion diffusion coefficient of 3.29×10-10, and the pseudocapacitance was the main contribution to the capacity calculated at different CV scanning rates of 0.1~0.8 mV·s-1, which could realize rapid electron and ion shuttle. The smaller the size of natural molybdenite, the smaller the first cycle capacity, but better cycle and rate performance and faster reaction kinetics, and similar to the natural molybdenite layered lithium storage model were proposed to clarify the relationship between the size of natural molybdenite and the performance of the lithium-ion battery.
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图 9 M90电化学动力学分析图: (a) 0.1 ~ 0.2 mV·s-1的扫描速率CV曲线; (b) 氧化态和还原态的log i vs log V曲线; (c) 0.2 mV·s-1时的CV曲线由电容和扩散控制贡献; (d)柱状图显示了不同扫描速率下天然辉钼矿电极的赝电容和扩散控制贡献的比值
Figure 9.
表 1 不同尺寸天然辉钼矿的交流阻抗谱的拟合值
Table 1. Fitting values of alternating current impedance spectra of natural molybdenite with different particle sizes
Electrode M30 M60 M90 Re 2.79 2.59 2.51 Rct 51.44 44.25 38.77 
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表 2 不同尺寸天然辉钼矿的因子和DLi+值
Table 2. Different granularity of natural molybdenite factor and DLi+ values
Electrode M30 M60 M90 σ 14.02 11.18 7.04 DLi+ 8.31×10-11 1.30×10-10 3.29×10-10
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