二氧化锰纳米片改性隔膜在锂硫电池中的应用

doi:10.11949/0438-1157.20191319

摘要/Abstract

摘要：

锂硫电池具有较高的理论能量密度，被认为是最有发展潜力的下一代高能量密度储能器件之一。然而多硫化物穿过隔膜形成的穿梭效应导致电池容量衰减过快、使用寿命降低，严重阻碍了锂硫电池商业化。以层状氧化石墨烯为模板，采用氧化还原法合成了二氧化锰纳米片，通过低压抽滤获得二氧化锰改性隔膜。利用TEM、XRD、FTIR、SEM、AFM等对该二氧化锰纳米片及改性隔膜的微观结构、形貌等进行表征；采用恒电流充放电、循环伏安法、电化学阻抗法对二氧化锰改性隔膜电化学性能进行测试。研究结果表明，二氧化锰纳米片能均匀覆盖聚丙烯隔膜表面的微孔，通过物理阻隔和催化作用，有效抑制了多硫化物的穿梭，提高了锂硫电池的比容量和循环稳定性。

关键词: 纳米材料, 膜, 催化作用, 锂硫电池, 二氧化锰纳米片, 抑制穿梭效应, 循环稳定性

Abstract:

Lithium-sulfur batteries have a higher theoretical energy density and are considered to be one of the most promising next-generation high-energy-density energy storage devices. However, the commercialization of lithium-sulfur batteries is seriously hindered by capacity decay and poor cyclic life caused by polysulfide shuttle. Manganese dioxide nanosheets were prepared by redox method using graphene oxide nanosheets as template. TEM, XRD, FTIR, SEM, AFM were used to characterize the microstructure and morphology of the manganese dioxide nanosheets and the modified separator. The electrochemical properties of the manganese dioxide modified separator were tested by using constant current charge and discharge, cyclic voltammetry and electrochemical impedance method. The results show that the manganese dioxide nanosheets can cover the micropores on separator surface of polypropylene uniformly, thus effectively inhibiting the shuttle of polysulfide through physical barrier and catalysis, and improving the specific capacity and cycle stability of lithium-sulfur battery.

Key words: nanomaterials, membranes, catalysis, lithium-sulfur batteries, manganese dioxide nanosheets, inhibition of shuttle effect, cyclic stability

中图分类号:

O 646.21

彭娜, 翟鹏飞, 王景涛, 王俊晓, 刘咏. 二氧化锰纳米片改性隔膜在锂硫电池中的应用[J]. 化工学报, 2020, 71(5): 2389-2400.

Na PENG, Pengfei ZHAI, Jingtao WANG, Junxiao WANG, Yong LIU. Application of manganese dioxide nanosheets modified separator for lithium-sulfur batteries[J]. CIESC Journal, 2020, 71(5): 2389-2400.

图/表 14

图1 GO和MnO2的XRD谱图和拉曼光谱图

Fig.1 XRD patterns and Raman spectra of GO and MnO2

图2 GO和MnO2的红外光谱图

Fig.2 FT-IR spectra of GO and MnO2

图3 GO、MnO2 的TG曲线和电导率

Fig.3 TG curves and conductivity test of GO and MnO2

图4 GO和MnO2的TEM图和MnO2的AFM图

Fig.4 TEM images of GO and MnO2, and AFM image of MnO2

图5 PP、GO/PP、MnO2/PP隔膜的AFM图及高度分布和MnO2/PP隔膜的SEM图

Fig.5 AFM images and corresponding height profiles of PP, GO/PP and MnO2/PP separators, and SEM images of MnO2/PP separator

图6 PP、GO/PP、MnO2/PP隔膜的接触角

Fig.6 Images of contact angles of PP, GO/PP and MnO2/PP separators

图7 Li2S6的吸附实验及渗透实验

Fig.7 Adsorption measurements and permeation test of Li2S6

图8 S 2p和Mn 2p的XPS谱图

Fig.8 XPS spectrum of S 2p and Mn 2p

图9 Super-P、GO、MnO2的极化曲线和PP和MnO2/PP隔膜的红外光谱图

Fig.9 Polarization curves of Super-P,GO,MnO2 and FT-IR spectra of PP and MnO2/PP separators

图10 充放电曲线及循环性能图

Fig.10 Charge/discharge curves and cycling performance

图11 PP、GO/PP、MnO2/PP隔膜的阻抗图

Fig.11 EIS spectra of PP, GO/PP and MnO2/PP separators

图12 PP、GO/PP、MnO2/PP隔膜电池的循环伏安曲线

Fig.12 CV curves of PP, GO/PP and MnO2/PP separators

图13 不同隔膜电池的倍率性能图

Fig.13 Rate performance of cells with different separators

图14 1 C下的循环性能图

Fig.14 Cycling performance of MnO2/PP at 1 C

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