中空碳双面修饰的隔膜在高性能锂硫电池中的应用
Application of double-side modified separator with hollow carbon material in high-performance Li-S battery
作者单位E-mail
张渝 嘉兴南湖学院新材料工程学院, 嘉兴 314001
上海交通大学电子信息与电气工程学院微纳电子系, 上海 200240 
 
赵芳芳 上海交通大学电子信息与电气工程学院微纳电子系, 上海 200240  
潘聪 嘉兴大学数据科学学院, 嘉兴 314001 pancong@zjxu.edu.cn 
王鹏 嘉兴大学生物与化学工程学院, 嘉兴 314001 pengwang@zjxu.edu.cn 
魏良明 上海交通大学电子信息与电气工程学院微纳电子系, 上海 200240 lmwei@sjtu.edu.cn 
摘要: 为减少多硫化锂(LIPs)“穿梭效应”及锂枝晶对锂硫电池的影响,采用刮涂法制备中空碳材料修饰隔膜。接触角测试表明修饰隔膜对LIPs具有更强的吸引力,其对LIPs“穿梭”的有效抑制也可以通过渗透性实验进一步得到印证。在隔膜的正极对称电池测试中,电流响应显示中空碳材料的催化使LIPs快速转化为Li2S。通过隔膜的负极对称电池测试发现修饰隔膜呈现出更稳定的电压-时间曲线。为证明隔膜修饰对锂硫电池性能改进的效果,分别采用聚丙烯(PP)隔膜、单面改性和双面改性的PP隔膜组装成纽扣电池并进行电化学测试,其中电极材料的硫负载量为1.8~2.0 mg·cm-2。GITT(恒电流间歇滴定法)测试和锂离子扩散系数计算表明,改性隔膜的离子传输更快且阻抗较小。通过分析第1、5、10、50及100次的充放电循环阻抗谱图发现,中空碳材料的多通道能够为锂离子的传输提供更多的通道,因此能够使锂离子具有更加稳定的扩散行为。在电流密度为0.2C时,由双面改性隔膜组装的锂硫电池在首次充放电时有1 035 mAh·g-1的可逆比容量,700圈后仍有500 mAh·g-1的高比容量,并在高硫负载时表现出500 mAh·g-1的可逆比容量。双面修饰隔膜赋予了锂硫电池优异的电化学性能,这是由于中空碳材料的修饰加速了LIPs的转化和吸附,有效缓解了LIPs的穿梭效应,且对锂枝晶有很好的抑制作用,提高了锂硫电池的安全性。
关键词: 锂硫电池  多孔碳  多硫化物  隔膜修饰
基金项目: 国家自然科学基金(No.51272155,21875061,21975066)和浙江省教育厅科研基金(No.Y202249253)资助。
Abstract: To reduce the “shuttle effects” of lithium polysulfides (LIPs) and the lithium dendrites in Li-S batteries, the separator modified by hollow carbon material was prepared by the simple scraping method. It can be found from the contact angle tests that the layers formed by the porous carbon of uniform width exhibited both stronger attractions to LIPs and better permeability of electrolytes than the bare polypropylene (PP) separator. Permeation tests further showed an effective block over LIPs by the modification layers. Cathode symmetrical batteries with Celgard 3501 separator were assembled and the current response tests implied a conversion of LIPs to Li2S catalyzed by hollow carbon materials. Lithium symmetrical batteries with modified separators were assembled and the voltage-time profile of charge-discharge processes showed better stability owing to the prevention of lithium dendrites. The Li-S batteries were assembled with sulfur loading of 1.8-2.0 mg·cm-2 and with the bare PP, single-side modified, and double-side modified separators. Calculations of the diffusion coefficient of lithium-ion from galvanostatic intermittent titration technique (GITT) tests and Nyquist plots both indicated the faster ion transportation for the modified separators. Smaller semicircles for impedance were also found in the plots. Nyquist plots after the 1st, 5th, 10th, 50th, and 100th cycles were analyzed to show a stable diffusion behavior of lithium ions, which should be caused by the multichannel from hollow carbon material to provide more paths for Li+ ion transportation. Li-S batteries with double-side modified separators presented a high specific capacity of 1 035 mAh·g-1 in the first cycle and 500 mAh·g-1 after 700 cycles at the current density of 0.2C, 630 mAh·g-1 after 100 cycles at 1C, and 505 mAh·g-1 after 100 cycles at 2C. The rate performance also behaved superior to the cells with bare PP as the separator. The cell assembled with higher sulfur content (3.2 mg·cm-2) also presented the reverse specific capacity of 500 mAh·g-1 at 0.2C. These battery performances could be ascribed to the porous hollow carbon materials for their adsorption and conversion of LIPs and their prevention of dendrites. Thus, the physicochemical interaction between hollow carbon and LIPs effectively alleviates the shuttle effect and the bifunctional modification of the separator could prevent the growth of lithium dendrites to improve the safety of the Li-S batteries.
Keywords: Li-S battery  porous carbon  polysulfide  separator modification
投稿时间:2023-10-30 修订日期:2024-03-31
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张渝,赵芳芳,潘聪,王鹏,魏良明.中空碳双面修饰的隔膜在高性能锂硫电池中的应用[J].无机化学学报,2024,40(6):1218-1232.
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