CeO2纳米晶的添加对锂硫电池电化学性能的影响

doi:10.15541/jim20140671

摘要/Abstract

摘要：

以Ce(OH)₄为原料, 采用热分解法制备得到粒径小于10 nm的CeO₂纳米晶。制备得到的CeO₂纳米晶表面存在丰富的羟基和硝基, 作为硫正极添加剂, 一方面可以有效吸附硫和多硫化锂, 抑制多硫化锂在电解液中的溶解和穿梭效应的发生, 进而提高电池的循环性能。同时, 可以改善电极和电解液之间的接触性, 提高活性物质利用率。其中, 含有5wt%的CeO₂纳米晶的锂硫电池在0.1C和0.5C(1C=1675 mA/g)的充放电倍率下, 100周之后放电比容量分别达750 mAh/g和598 mAh/g, 远高于不含有CeO₂纳米晶的523 mAh/g和395 mAh/g, 同时, 循环前后的电池阻抗也明显降低。

关键词: 锂硫电池, CeO2纳米晶, 电极添加剂, 循环性能

Abstract:

The CeO₂ nano-crystal less than 10 nm was fabricated by using thermal decomposition method with Ce(OH)₄ as the raw material. CeO₂ nano-crystal with abundant -OH and -NO₂ was used as the additive in the sulfur cathode. The additive can adsorb sulfur and lithium polysulfides during charge/discharge process, suppressing the dissloving and migrating of lithium polysulfides in the electrolyte. Thus the “shuttle effect” caused by dissloving of lithium polysulfides can be evidently inhibited, resulting in the enhanced cycle performance and the improved coulombic efficiency of Li-S battery. Furthermore, CeO₂ nano-crystal with abundant -OH and -NO₂ is beneficial to enhance the wettability between electrolyte and sulfur cathode, improving the utilization rate of active material. With 5wt% CeO₂ nano-crystal added in the sulfur cathode, the discharge capacities at 0.1C and 0.5C (1C=1675 mA/g) after 100 cycles are as high as 750 mAh/g and 598 mAh/g, respectively, both much higher than those of the sulfur cathode without CeO₂ nanocrystal. Simultaneously, the resistance of the cell is also reduced evidently before and after cycling owing to the addition of CeO₂ nano-crystal in the cathode.

Key words: lithium-sulfur battery, CeO2 nano-crastal, additive, cycle performance

中图分类号:

TQ174

马国强, 温兆银, 王清松, 靳俊, 吴相伟, 张敬超. CeO₂纳米晶的添加对锂硫电池电化学性能的影响[J]. 无机材料学报, 2015, 30(9): 913-918.

MA Guo-Qiang, WEN Zhao-Yin, WANG Qing-Song, JIN Jun, WU Xiang-Wei, ZHANG Jing-Chao. Effects of CeO₂ Nano-crystal on Electrochemical Properties of Lithium/Sulfur Batteries[J]. Journal of Inorganic Materials, 2015, 30(9): 913-918.

图/表 8

图 1 (a)CeO2纳米晶的TEM图和(b)乙炔黑的SEM照片

Fig. 1 (a) TEM image of CeO2 nano-crystal and (b) SEM image of the acetylene black

图 2 CeO2纳米晶的FTIR图谱

Fig. 2 FTIR spectrum of CeO2 nano-crystal

图 3 S/AB/CeO2复合材料的SEM照片(a),相应区域的高角环形暗场像(b)及相应区域的Ce(c)、C (d)、S (e)元素面扫描结果

Fig. 3 SEM image of S/AB/CeO2 composite (a) and correspoding HAADF image (b), and element Ce (c), C (d) and S (e) maping of the same domain

图4 不同电极材料循环50周前后的SEM形貌

Fig. 4 SEM morphologies of sulfur electrodes (a) before cycling, (b) without CeO2 after 50 cycles, (c) with CeO2 before cycling and (d) with CeO2 after 50 cycles

图5 添加CeO2纳米晶前后硫正极的CV曲线(a)及电池的放电曲线(b)

Fig. 5 CV curves (a) and discharge curves (b) of the sulfur cathode with and without CeO2 nano-crystal

图6 添加CeO2纳米晶前后电池循环性能(a)及电池库伦效率(b)的变化

Fig. 6 Cycling performance (a) and coulombic efficiencies (b) of the sulfur cathode before and after the addition of CeO2 nano-crystal

图7 添加CeO2纳米晶之后硫正极倍率性能的变化

Fig. 7 Rate capabilities of the sulfur cathode with and without CeO2 nanocrystal

图8 添加CeO2纳米晶前后电池电阻的变化及电池循环后电阻变化

Fig. 8 AC impedance spectra of the sulfur cathode with and without CeO2 nano-crystal

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CeO₂纳米晶的添加对锂硫电池电化学性能的影响

Effects of CeO₂ Nano-crystal on Electrochemical Properties of Lithium/Sulfur Batteries

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