MoS2/RGO复合材料的电化学性能和第一性原理研究

doi:10.19799/j.cnki.2095-4239.2022.0669

摘要/Abstract

摘要：

利用MoS₂高的理论储锂容量和石墨烯良好的导电性能，采用一步水热法成功制备出卷曲片层状的MoS₂/RGO复合材料，通过X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱(EDS)、Raman光谱等手段对其进行了结构、形貌、和成分的表征，并通过第一性原理计算了MoS₂和MoS₂/RGO模型的最稳定锂离子吸附位置、电荷密度、差分电荷密度、态密度和扩散能垒。实验结果表明，MoS₂/RGO复合材料在前70次充放电循环中，保持着800 mAh/g以上的高放电比容量，经过100次循环后，放电比容量为515.3 mAh/g，明显高于单一MoS₂(170.8 mAh/g)，同时，该复合材料具有优于单一MoS₂的倍率性能，经过1000 mA/g的大电流密度循环后重新回到100 mA/g时，MoS₂/RGO复合材料仍保持在高的放电比容量(941.2 mAh/g)。第一性原理计算结果表明，在石墨烯的作用下，MoS₂层的Mo原子附近的电荷呈减少趋势，MoS₂/RGO整体态密度增强，使价带中的电子更容易跃迁到导带，同时，MoS₂/RGO较单一MoS₂低的扩散能垒(0.25 eV)使锂离子更容易扩散，这解释了在石墨烯的作用下，MoS₂/RGO复合材料拥有优于单一MoS₂的电化学性能。

关键词: 水热法制备, MoS₂/RGO复合材料, 电化学性能, 第一性原理计算

Abstract:

Based on the high theoretical lithium storage capacity of molybdenum disulfide (MoS₂) and the good conductivity of graphene, a curly lamellar MoS₂/reduced graphene oxide (RGO) composite was successfully prepared by a one-step hydrothermal method. The structure, morphology, and composition of the MoS₂/RGO composite were characterized using an X-ray diffractometer, scanning electron microscope, X-ray energy spectrometer, and Raman spectrometer. The most stable adsorption position of lithium-ion, charge density, charge density difference, density of states, and diffusion energy barrier of MoS₂ and MoS₂/RGO models were calculated by first-principles. Results show that the MoS₂/RGO composite maintains a high discharge specific capacity of more than 800 mAh/g in the first 70 charge and discharge cycles. After 100 cycles, the discharge specific capacity of the MoS₂/RGO composite is 515.3 mAh/g, which is significantly higher than that of MoS₂(170.8 mAh/g). Simultaneously, the composite material shows a better rate of performance than MoS₂. When the current density is back to 100 mA/g after the 1000 mA/g high current density cycle, the MoS₂/RGO composite still maintains a high discharge specific capacity (941.2 mAh/g). The first-principles calculation results show that the charge near the Mo atom of MoS₂ decreases, and the whole density of states of the MoS₂/RGO composite is enhanced due to the action of graphene, making it easier for electrons in the valence band to migrate to the conduction band. Furthermore, compared with MoS₂, the low diffusion energy barrier (0.25 eV) of MoS₂/RGO makes it easier for lithium ions to diffuse. Therefore, it explains why the MoS₂/RGO composite has a better electrochemical performance than MoS₂ with the effect of graphene.

Key words: hydrothermal preparation, MoS₂/RGO composite, electrochemical performance, first-principles calculation

中图分类号:

O 469

祝玉婷, 闫共芹, 林羽芊. MoS₂/RGO复合材料的电化学性能和第一性原理研究[J]. 储能科学与技术, 2023, 12(3): 698-709.

Yuting ZHU, Gongqin YAN, Yuqian LIN. Electrochemical properties and First-principles study of MoS₂/rGO composite[J]. Energy Storage Science and Technology, 2023, 12(3): 698-709.

图/表 17

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模型	K点	截断能/eV	能量收敛值 /(eV/atom)	原子间相互作用力 /(eV/Å)	内应力/GPa
Li	2×2×2	310	2.0×10^-5	0.05	0.1
MoS₂	3×3×2	450	2.0×10^-5	0.05	0.1
Gr	2×2×1	450	2.0×10^-5	0.05	0.1
MoS₂/Gr	2×2×1	450	2.0×10^-5	0.05	0.1

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MoS₂/RGO复合材料的电化学性能和第一性原理研究

Electrochemical properties and First-principles study of MoS₂/rGO composite

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