勃姆石纳米片增强锂离子电池隔膜性能研究

doi:10.15541/jim20220050

无机材料学报 ›› 2022, Vol. 37 ›› Issue (9): 1009-1015.DOI: 10.15541/jim20220050

勃姆石纳米片增强锂离子电池隔膜性能研究

冯锟¹^,²(), 朱勇¹, 张凯强¹, 陈长¹, 刘宇²(), 高彦峰¹()

1.上海大学材料科学与工程学院, 上海 200444
2.中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2022-01-27 修回日期:2022-03-22 出版日期:2022-09-20 网络出版日期:2022-04-07
通讯作者: 高彦峰, 教授. E-mail: yfgao@shu.edu.cn;
刘宇, 研究员. E-mail: yuliu@mail.sic.ac.cn
作者简介:冯锟(1998-), 男, 硕士研究生. E-mail: fengkun@shu.edu.cn
基金资助:
国家自然科学基金(51873102);上海市教委创新计划(2019-01-07-00-09-E00020)

Boehmite Nanosheets-coated Separator with Enhanced Performance for Lithium-ion Batteries

FENG Kun¹^,²(), ZHU Yong¹, ZHANG Kaiqiang¹, CHEN Zhang¹, LIU Yu²(), GAO Yanfeng¹()

1. School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2022-01-27 Revised:2022-03-22 Published:2022-09-20 Online:2022-04-07
Contact: GAO Yanfeng, professor. E-mail: yfgao@shu.edu.cn;>
LIU Yu, professor. E-mail: yuliu@mail.sic.ac.cn
About author:FENG Kun, male, Master candidate. E-mail: fengkun@shu.edu.cn
Supported by:
National Natural Science Foundation of China(51873102);Innovation Program of Shanghai Municipal Education Commission(2019-01-07-00-09-E00020)

摘要/Abstract

摘要：

采用勃姆石涂覆改性聚烯烃隔膜可以提升锂离子电池的隔膜热稳定性和电解液润湿性。本工作通过简单的水热法合成了平均粒径约为150 nm的勃姆石纳米片, 并采用刮涂法涂覆在聚乙烯(Polyethylene, PE)隔膜表面。该涂覆隔膜的孔隙率达到46.6%、吸液率为138.9%、离子电导率为0.47 mS/cm和锂离子迁移数为0.42, 使得该隔膜组装的锂离子电池具有较好的循环稳定性, 在1C(1C=150 mA/g)的电流密度下循环100次后仍能保留93.7%的放电比容量。同时, 勃姆石纳米片涂覆的隔膜的孔结构分布均匀, 优化了锂离子传输通量, 抑制了锂枝晶。

关键词: 勃姆石, 锂离子电池, 隔膜, 多孔涂层, 粒径分布

Abstract:

It has received extensive attention to modify polyolefin separator by boehmite coating for the improvement of thermal stability and electrolyte wettability, but how to affect the electrochemical performance of the boehmite- coated separators is unclear. In this work, boehmite nanosheets with a mean particle size of 150 nm were synthesized by a simple hydrothermal method, and these nanosheets were coated on the surface of polyethylene (PE) separator by a scraper. The boehmite nanosheet-coated separator has porosity of 46.6%, electrolyte uptake of 138.9%, ionic conductivity of 0.47 mS/cm, and lithium-ion transference number of 0.42. The battery assembled with this separator exhibits good cycling stability, retaining 93.7% discharge specific capacity after 100 cycles at 1C (1C= 150 mA/g). Meanwhile, the boehmite nanosheet-modified separator has a uniformly distributed pore structure, which optimizes the lithium-ion transport flux and suppresses the formation of lithium dendrites.

Key words: boehmite, lithium-ion battery, separator, porous coating, particle size distribution

中图分类号:

TQ174

冯锟, 朱勇, 张凯强, 陈长, 刘宇, 高彦峰. 勃姆石纳米片增强锂离子电池隔膜性能研究[J]. 无机材料学报, 2022, 37(9): 1009-1015.

FENG Kun, ZHU Yong, ZHANG Kaiqiang, CHEN Zhang, LIU Yu, GAO Yanfeng. Boehmite Nanosheets-coated Separator with Enhanced Performance for Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2022, 37(9): 1009-1015.

图/表 9

图1 勃姆石纳米片的(a)XRD图谱、(b) SEM照片、(c)AFM照片和(d)高度剖面图

Fig. 1 (a) XRD pattern, (b)SEM image, (c)AFM image, and (d) cross-sectional height profile of boehmite nanosheets

图2 PE、PE-AlOOHNP和PE-AlOOHNS的物理性质

Fig. 2 Physical properties of PE, PE-AlOOHNP and PE-AlOOHNS Surface SEM images of (a) PE, (b) PE-AlOOHNP and (c) PE-AlOOHNS; Electrolyte contact angles of (d) PE, (e) PE-AlOOHNP and (f) PE-AlOOHNS with insets showing pictures of the electrolyte-wetted separators; (g) Initial photo of the separators at 25 ℃; Photos of the separators after heat treatment at (h) 130 ℃ and (i) 150 ℃ for 30 min (1: PE, 2: PE-AlOOHNP, 3: PE-AlOOHNS)

图3 (a)不同隔膜组装的 SS/SS电池的Nyquist图谱; (b)Li/PE-AlOOHNS/Li电池的计时电流曲线, 插图为极化前后的阻抗图; (c) 含有不同隔膜的SS/Li电池的LSV曲线; 不同隔膜组装的LFP/Li电池的(d)倍率性能, (e) EIS图谱和(f)循环性能曲线

Fig. 3 (a)Nyquist plots of SS/SS cells assembled with different separators; (b) Chronoamperometry profile of Li/PE-AlOOHNS/Li cell with inset showing EIS plots before and after polarization; (c) LSV curves of SS/Li cells assembled with different separators; (d) Rate capabilities, (e) EIS spectra and (f) cycle performances of LFP/Li cells with different separators Colorful figures are available on website

图4 (a) PE, (b) PE-AlOOHNP, (c) PE-AlOOHNS组装的Li/Li对称电池的电压曲线;(d)抑制锂枝晶机理示意图

Fig. 4 Voltage profiles of Li/Li symmetric cells assembled with (a) PE, (b) PE-AlOOHNP and (c) PE-AlOOHNS, and (d) schematic illustration of suppressing lithium dendrite formation

表S1 不同隔膜的物理参数

Table S1 Physical parameters of different separators

	Thickness/μm	Porosity/%	Electrolyte uptake /%	Bulk resistance /Ω	Ionic conductivity /(mS·cm^-1)	Lithium-ion transference number
PE	9	39.6	84.6	1.06	0.43	0.15
PE-AlOOH_NP	12	42.4	112.5	1.37	0.45	0.39
PE-AlOOH_NS	12	46.6	138.9	1.31	0.47	0.42

图S1 勃姆石纳米片粒径分布图

Fig. S1 Particle size distribution of boehmite nanosheets

图S2 不同隔膜的DSC曲线

Fig. S2 DSC curves of different separators

图S3 Li/PE/Li电池的计时电流曲线, 插图为极化前后的阻抗图

Fig. S3 Chronoamperometry profile of Li/PE/Li cell with inset showing the EIS plots before and after polarization

图S4 Li/PE-AlOOHNP/Li电池的计时电流曲线, 插图为极化前后的阻抗图谱

Fig. S4 Chronoamperometry profile of Li/PE-AlOOHNP/Li cell with inset showing the EIS plots before and after polarization

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勃姆石纳米片增强锂离子电池隔膜性能研究

Boehmite Nanosheets-coated Separator with Enhanced Performance for Lithium-ion Batteries

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