纳米纤维素/Al2O3胶体/PE锂离子电池隔膜的制备及其成膜机理

doi:10.16085/j.issn.1000-6613.2020-1928

化工进展 ›› 2021, Vol. 40 ›› Issue (10): 5624-5633.DOI: 10.16085/j.issn.1000-6613.2020-1928

纳米纤维素/Al₂O₃胶体/PE锂离子电池隔膜的制备及其成膜机理

时培东¹(), 胡春蕊², 郑苗苗², 赵娟³, 刘锐¹, 贾原媛²()

^1.天津科技大学食品科学与工程学院，天津 300457
^2.天津市卤水化工与资源生态化利用重点实验室，天津科技大学化工与材料学院，天津 300457
^3.天津科技大学现代分析技术研究中心，天津 300457

收稿日期:2020-09-21 修回日期:2021-04-24 出版日期:2021-10-10 发布日期:2021-10-25
通讯作者: 贾原媛
作者简介:时培东（1997—），男，硕士研究生，研究方向为生物质材料。E-mail：shipeidong@mail.tust.edu.cn。
基金资助:
天津市教委科研计划项目（自然科学）一般项目(2018KJ089)

Preparation of nanocellulose/Al₂O₃ sol/PE lithium-ion battery separation membrane and it’s film-forming mechanism

SHI Peidong¹(), HU Chunrui², ZHENG Miaomiao², ZHAO Juan³, LIU Rui¹, JIA Yuanyuan²()

^1.College of Food Science and Engineering, Tianjin University of Science and Technology, Tianjin 300457, China
^2.Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco-utilization, College of Chemical Engineering and Materials, Tianjin University of Science and Technology, Tianjin 300457, China
^3.Research Centre of Modern Analysis Technology, Tianjin University of Science and Technology, Tianjin 300457, China

Received:2020-09-21 Revised:2021-04-24 Online:2021-10-10 Published:2021-10-25
Contact: JIA Yuanyuan

摘要/Abstract

摘要：

当前商业上常用聚烯烃薄膜作为锂离子电池隔膜，但是其热收缩性差和力学性能弱的缺点限制了锂离子电池的应用，因此研究具备高热稳定性和对电解液具有良好润湿性的电池隔膜显得尤为重要。本文利用层层自组装技术制备纳米纤维素/Al₂O₃胶体/PE锂离子电池隔膜，探究出了制备NC/A-PE膜的适宜条件：Al₂O₃溶胶的固含量为2%（质量分数），麦麸纳米纤维素悬浮液的固含量为0.2%（质量分数），浸润时间为5min，组装层数为20层。结果表明，组装后的电池隔膜的热稳定性和电解液润湿性均得到了显著改善；其杨氏模量最高可提高至原来的235.2%，在电池隔膜组装的过程中能有效抵抗形变；经过扫描电子显微镜（SEM）、原子力显微镜（AFM）、场发射扫描电镜（FEM）、傅里叶变换红外光谱（FTIR）表征，证实氧化铝及纤维素成功地组装于PE基膜上，呈现出层次分明、厚度均一的多层膜结构，以此方法制备的电池隔膜安全无毒，热稳定性、力学性能和电解液润湿性得到了显著改善，有潜在的应用前景。

关键词: 电池隔膜, 层层自组装, 纳米纤维素, 氧化铝

Abstract:

Currently, polyolefin films are commonly used as commercial battery’s separation membranes, but their poor thermal shrinkage and weak mechanical properties limit the application of lithium-ion batteries. Therefore, it is particularly important to develop the membranes with high thermal stability and excellent wettability in organic liquid electrolytes. The nanocellulose/Al₂O₃ colloid /PE separation membrane for lithium-ion battery was prepared by layer-by-layer self-assembly technology, and the optimal preparation conditions for the NC/A-PE membrane were determined as the solid content of Al₂O₃ sol 2%(mass fraction), the solid content of wheat bran nanocellulose suspension 0.2%(mass fraction), the infiltration time 5min, and the number of assembly layers 20. The thermal stability and the wettability of the electrolyte were improved with a 235.2% increase in the maximum Young’s modulus, which can effectively resist deformation during the membrane assembly. Scanning electron microscope (SEM), atomic force microscope (AFM) and field emission electron microscope (FEM) characterizations confirmed that aluminum oxide and nanocellulose were successfully assembled on the PE membrane, showing a stratified structure with distinct layers and uniform thickness. The battery separation membrane prepared by this method was green, safe, and non-toxic, and its thermal stability, mechanical properties and wettability to electrolyte have been significantly improved, showing a potential application prospect.

Key words: battery separator membrane, layer-by-layer assembly, nanocellulose, aluminium oxide（Al₂O₃）

中图分类号:

O341

时培东, 胡春蕊, 郑苗苗, 赵娟, 刘锐, 贾原媛. 纳米纤维素/Al₂O₃胶体/PE锂离子电池隔膜的制备及其成膜机理[J]. 化工进展, 2021, 40(10): 5624-5633.

SHI Peidong, HU Chunrui, ZHENG Miaomiao, ZHAO Juan, LIU Rui, JIA Yuanyuan. Preparation of nanocellulose/Al₂O₃ sol/PE lithium-ion battery separation membrane and it’s film-forming mechanism[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5624-5633.

图/表 11

图1 纳米纤维素/Al2O3胶体/PE锂离子电池膜组装工艺流程

图2 不同等离子体处理条件下PE膜接触角随时间的变化

图3 不同条件下温度对NC/A-PE膜热收缩率的影响

图4 不同组装层数NC/A-PE膜对吸液率的影响

图5 NC/A-PE膜的拉伸强度及杨氏模量随浸润时间、Al2O3固含量及麦麸纤维素固含量（质量分数）的变化规律

图6 各样品的SEM图

图7 20-NC/A-PE膜FEM图

图8 不同隔膜层数的AFM表面形貌图和3D立体图

图9 NC/A-PE膜厚度和粗糙度随组装层数的变化

图10 NC/A-PE膜负载涂层后质量随组装层数的变化

图11 各样品的红外图谱a—麦麸纳米纤维素；b—PE膜；c—等离子体处理后的PE膜；d—NC/A-PE膜

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纳米纤维素/Al₂O₃胶体/PE锂离子电池隔膜的制备及其成膜机理

Preparation of nanocellulose/Al₂O₃ sol/PE lithium-ion battery separation membrane and it’s film-forming mechanism

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