微孔碳材料修饰的隔膜用于高性能锂硫电池

doi:10.16085/j.issn.1000-6613.2021-2007

摘要/Abstract

摘要：

锂硫电池具有较高的能量密度，是有发展前景的能量存储体系之一。但“穿梭效应”严重制约了锂硫电池的实际应用，为解决该问题，本文通过简单的一步热解法合成了孔径均匀的微孔碳材料，探究了微孔碳材料修饰隔膜后对锂硫电池性能的影响。结果表明，制备的微孔碳材料孔径集中在0.56nm左右，修饰隔膜后不仅能够有效抑制“穿梭效应”的产生，还有利于加快锂离子的传输，确保正极一侧溶解的多硫化物的再次利用。在0.1C的电流密度下，采用微孔碳材料修饰隔膜的电池首次放电比容量为1359mAh/g，循环100次之后容量能保持在966mAh/g，而修饰之前的传统聚丙烯隔膜，循环100次之后的比容量仅为409mAh/g；在1C的电流密度下循环500圈后，采用微孔碳材料修饰隔膜的电池容量保持率为88%，表现出优异的循环稳定性。

关键词: 微孔碳材料, 隔膜, 穿梭效应, 锂硫电池, 电化学, 纳米结构, 制备

Abstract:

Owing to the higher energy density, lithium-sulfur batteries have become one of the most promising energy storage systems. However, the shuttle effect derived from polysulfide hiders its large-scale commercial application. To solve this problem, a unique microporous carbon (UMC) via facile pyrolysis to modify separator in lithium sulfur battery was synthesized. The UMC with a uniform pore size of 0.56nm had abundant nanopores, facilitating lithium ion transportation and ensuring the re-used of polysulfides on the cathode side. With a current density of 0.1C, the initial discharge specific capacity of the battery was 1359mAh/g and the capacity retained 966mAh/g after 100 cycles. It also delivered good capacitance retention of 88% after 500 cycles, indicating excellent cycling stability. On the contrary, the specific capacity of commercial PP was only 409mAh/g after 100 times.

Key words: microporous carbon, modified separator, shuttle effect, lithium sulfur battery, electrochemistry, nanostructure, preparation

中图分类号:

TM912.9

金玮. 微孔碳材料修饰的隔膜用于高性能锂硫电池[J]. 化工进展, 2022, 41(8): 4386-4396.

JIN Wei. Microporous carbon modified separator for high performance lithium sulfur batteries[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4386-4396.

图/表 12

图1 UMC的制备极其修饰的隔膜在锂硫电池中的应用

图2 PVDF和Super P/S的TGA图

图3 UMC的TEM图

图4 UMC、PP和UMC/PP的表面SEM图

图5 UMC/PP的力学性能测试

图6 UMC的N2吸附-脱附曲线、孔径分布图、XRD图和Raman光谱图

图7 多硫化物在PP和UMC/PP的H型电解池中的扩散示意图

图8 PP和UMC/PP在不同扫描速率下的CV曲线，C1、C2和A1处的峰值电流Ip与扫描速率的0.5次方拟合曲线，锂离子扩散系数

图9 基于PP和UMC/PP的锂硫电池在循环前和循环后的EIS曲线（内插图为等效电路图）

表1 基于PP和UMC/PP的锂硫电池在循环前后的阻抗

隔膜	循环前		循环100次后
隔膜	R_s/Ω	R_ct/Ω	R_s/Ω	R_t/Ω	R_ct/Ω
PP	7.54	44.01	3.42	11.61	28.52
UMC/PP	7.43	18.99	3.28	6.78	14.56

图10 基于PP和UMC/PP的锂硫电池在0.1C时不同圈数的充放电曲线

图11 基于PP和UMC/PP的锂硫电池的电化学性能

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