采用原位成孔法制备热闭孔特性的高强度聚酰亚胺多孔薄膜

doi:10.3866/PKU.WHXB202306010

物理化学学报 >> 2024, Vol. 40 >> Issue (9): 2306010.doi: 10.3866/PKU.WHXB202306010

采用原位成孔法制备热闭孔特性的高强度聚酰亚胺多孔薄膜

柏雨婷¹, 严岑琪¹, 李祯²^,*(), 秦家强¹^,*(), 程沛¹^,*()

¹ 四川大学高分子科学与工程学院, 成都 610065
² 中国海关科学技术研究中心, 北京 100026

收稿日期:2023-06-05 修回日期:2023-07-26 录用日期:2023-07-27 发布日期:2023-08-08
通讯作者: Email: 729431051@qq.com (李祯)jqqin@scu.edu.cn (秦家强)chengpei@scu.edu.cn; Tel.: +86-28-85405401 (程沛)
基金资助:
国家自然科学基金(51873127)

Preparation of High-Strength Polyimide Porous Films with Thermally Closed Pore Property by In Situ Pore Formation Method

Yuting Bai¹, Cenqi Yan¹, Zhen Li²^,*(), Jiaqiang Qin¹^,*(), Pei Cheng¹^,*()

¹ College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, China
² Science and Technology Research Center of China Customs, Beijing 100026, China

Received:2023-06-05 Revised:2023-07-26 Accepted:2023-07-27 Published:2023-08-08
Contact: Email: 729431051@qq.com (Zhen Li)jqqin@scu.edu.cn (Jiaqiang Qin)chengpei@scu.edu.cn; Tel.: +86-28-85405401 (Pei Cheng)
Supported by:
the National Natural Science Foundation of China(51873127)

摘要/Abstract

摘要：

提高电池隔膜的热稳定性、化学稳定性和力学强度，可以避免电池发生热失控等安全事故，对于提高电池的安全性能具有至关重要的作用。聚酰亚胺(Polyimide，PI)热稳定性优异、化学稳定性好、力学强度高，是电池隔膜材料的理想选择之一。本文研究了一种具有高温自闭孔性质的热塑性PI多孔薄膜的制备方法，通过将聚酰胺酸与有机碱三乙胺(Triethylamine，TEA)成盐，经热酰亚胺化后释放出TEA，原位成孔制备出具有高强度的PI多孔薄膜。通过红外，扫描电镜，力学性能表征等手段研究了PI多孔薄膜的成孔机理，微观形貌及影响因素，受热自闭孔历程，构效关系。研究结果表明：PI薄膜在热酰亚胺化过程中TEA脱除原位形成孔洞结构，孔洞的尺寸可以通过TEA的含量进行调控。该PI多孔薄膜具有热闭孔特性，且在闭孔前、后均呈现出优异的力学强度(~120 MPa)。本文采用原位成孔法构筑了具有优异热稳定性、高力学强度的PI多孔薄膜，该PI多孔薄膜在高温时可自闭孔，隔绝物质、热量的传输，有望为电池提供更有力的安全保障。

关键词: 多孔薄膜, 聚酰亚胺, 高温自闭孔, 制备方法, 力学性能

Abstract:

Improving the thermal stability, chemical stability, and mechanical strength of battery separators is crucial to prevent safety incidents like thermal runaway in batteries. This significantly enhances the overall safety performance of batteries. Among various options, polyimide (PI) stands out as an ideal choice due to its outstanding thermal stability, excellent chemical stability, and high mechanical strength. However, existing preparation methods of PI separators, such as non-solvent induced phase separation (NIPS), template method, and electrospinning, often suffer from issues like inadequate mechanical strength. Therefore, this study focused on investigating a novel method to prepare thermoplastic PI porous films with thermally closed pores and enhanced mechanical strength. Several characterization techniques, including scanning electron microscopy (SEM), in situ Fourier transform infrared spectroscopy (FTIR), and thermal gravimetric analyzer (TGA)-FTIR coupling, were employed to understand the pore-forming mechanism of PI porous films. The findings revealed that the temperature range of triethylamine (TEA) removal was consistent with the main stage of the imidization reaction and pore formation. This indicated that the pore structure was formed in situ during the thermal imidization process when TEA was stripped out of the PI film. PI films with varying TEA contents were prepared to investigate the impact on pore structure, showing that pore size could be regulated by TEA content. A more regular reticulated small pore structure on the macroporous pore wall was observed when TEA content was ≥ 100%. SEM analysis showed that the films were thermally self-closed at a heat treatment temperature of 300 ℃. Additionally, TGA indicated that the thermal decomposition temperature of PI porous film reached 580 ℃. The mechanical strength of the PI films before and after pore closure was investigated, demonstrating excellent mechanical strength of approximately 120 MPa. The novel in situ pore formation method for PI porous films through the salt-formation method of poly (amic acid) (PAA) with the organic base TEA, followed by TEA release during thermal imidization, resulted in PI porous films with outstanding thermal stability and high mechanical strength. The self-closure of the PI porous film at high temperatures effectively isolates material and heat transport, providing robust safety assurance for batteries. This advancement has the potential to significantly improve battery safety and performance.

Key words: Porous film, Polyimide, Thermally closed pore property, Preparation method, Mechanical property

柏雨婷, 严岑琪, 李祯, 秦家强, 程沛. 采用原位成孔法制备热闭孔特性的高强度聚酰亚胺多孔薄膜[J]. 物理化学学报, 2024, 40(9), 2306010. doi: 10.3866/PKU.WHXB202306010

Yuting Bai, Cenqi Yan, Zhen Li, Jiaqiang Qin, Pei Cheng. Preparation of High-Strength Polyimide Porous Films with Thermally Closed Pore Property by In Situ Pore Formation Method[J]. Acta Phys. -Chim. Sin. 2024, 40(9), 2306010. doi: 10.3866/PKU.WHXB202306010

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202306010

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I9/2306010

图/表 8

图1

图2

表1

图3

图4

图5

图6

图7

参考文献 25

1	Zhang X.; Sun Q.; Zhen C.; Niu Y.; Han Y.; Zeng G.; Chen D.; Feng C.; Chen N.; Lv W.; et al Energy Storage Mater. 2021, 37, 628. doi: 10.1016/j.ensm.2021.02.042
2	Waqas M.; Ali S.; Feng C.; Chen D.; Han J.; He W. Small 2019, 15(33), 1901689. doi: 10.1002/smll.201901689
3	Costa C. M.; Lee Y.-H.; Kim J.-H.; Lee S.-Y.; Lanceros-Méndez S. Energy Storage Mater. 2019, 22, 346. doi: 10.1016/j.ensm.2019.07.024
4	Lu L.; Han X.; Li J.; Hua J.; Ouyang M. J. Power Sources 2013, 226, 272. doi: 10.1016/j.jpowsour.2012.10.060
5	Sun Y.; Liu N.; Cui Y. Nat. Energy 2016, 1(7), 16071. doi: 10.1038/nenergy.2016.71
6	Liu X.; Ren D.; Hsu H.; Feng X.; Xu G.-L.; Zhuang M.; Gao H.; Lu L.; Han X.; Chu Z.; et al Joule 2018, 2(10), 2047. doi: 10.1016/j.joule.2018.06.015
7	Zhang J.; Liu Z.; Kong Q.; Zhang C.; Pang S.; Yue L.; Wang X.; Yao J.; Cui G. ACS Appl. Mater. Interfaces 2013, 5(1), 128. doi: 10.1021/am302290n
8	Costa C. M.; Rodrigues L. C.; Sencadas V.; Silva M. M.; Rocha J. G.; Lanceros-Méndez S. J. Membr. Sci. 2012, 07–408, 193. doi: 10.1016/j.memsci.2012.03.044
9	Liu X.; Song K.; Lu C.; Huang Y.; Duan X.; Li S.; Ding Y. J. Membr. Sci. 2018, 555, 1. doi: 10.1016/j.memsci.2018.03.027
10	Hu S.; Lin S.; Tu Y.; Hu J.; Wu Y.; Liu G.; Li F.; Yu F.; Jiang T. J. Mater. Chem. A 2016, 4(9), 3513. doi: 10.1039/C5TA08694A
11	Ding Y.; Hou H.; Zhao Y.; Zhu Z.; Fong H. Prog. Polym. Sci. 2016, 61, 67. doi: 10.1016/j.progpolymsci.2016.06.006
12	Liaw D.-J.; Wang K.-L.; Huang Y.-C.; Lee K.-R.; Lai J.-Y.; Ha C.-S. Prog. Polym. Sci. 2012, 37(7), 907. doi: 10.1016/j.progpolymsci.2012.02.005
13	Ma P.; Dai C.; Wang H.; Li Z.; Liu H.; Li W.; Yang C. Compos. Commun. 2019, 16, 84. doi: 10.1016/j.coco.2019.08.011
14	Maeyoshi Y.; Ding D.; Kubota M.; Ueda H.; Abe K.; Kanamura K.; Abe H. ACS Appl. Mater. Interfaces 2019, 11(29), 25833. doi: 10.1021/acsami.9b05257
15	Lin D.; Zhuo D.; Liu Y.; Cui Y. J. Am. Chem. Soc. 2016, 138(34), 11044. doi: 10.1021/jacs.6b06324
16	Maeyoshi Y.; Miyamoto S.; Munakata H.; Kanamura K. J. Power Sources 2017, 350, 103. doi: 10.1016/j.jpowsour.2017.03.053
17	Li M. N.; Zhang Z. J.; Yin Y. T.; Guo W. C.; Bai Y. G.; Zhang F.; Zhao B.; Shen F.; Han X. G. ACS Appl. Mater. Interfaces 2020, 12(3), 3610. doi: 10.1021/acsami.9b19049
18	Lin C. E.; Zhang H.; Song Y. Z.; Zhang Y.; Yuan J. J.; Zhu B. K. J. Mater. Chem. A 2018, 6(3), 991. doi: 10.1039/c7ta08702k
19	Zhang H.; Lin C.-E.; Zhou M.-Y.; John A. E.; Zhu B.-K. Electrochim. Acta 2016, 187, 125. doi: 10.1016/j.electacta.2015.11.028
20	Kong L.; Yan Y.; Qiu Z.; Zhou Z.; Hu J. J. Membr. Sci. 2018, 549, 321. doi: 10.1016/j.memsci.2017.12.028
21	Wang L. L.; Liu F.; Shao W. L.; Cui S. Z.; Zhao Y. M.; Zhou Y. M.; He J. X. Compos. Commun. 2019, 16, 150. doi: 10.1016/j.coco.2019.09.004
22	Miao Y. E.; Zhu G. N.; Hou H. Q.; Xia Y. Y.; Liu T. X. J. Power Sources 2013, 226, 82. doi: 10.1016/j.jpowsour.2012.10.027
23	Wang Y.; Wang S.; Fang J.; Ding L.-X.; Wang H. J. Membr. Sci. 2017, 537, 248. doi: 10.1016/j.memsci.2017.05.023
24	Kim J.-H.; Kim J.-H.; Choi K.-H.; Yu H. K.; Kim J. H.; Lee J. S.; Lee S.-Y. Nano Lett. 2014, 14(8), 4438. doi: 10.1021/nl5014037
25	Seo Y.; Lee S. M.; Kim D. Y.; Kim K. U. Macromolecules 1997, 30(13), 3747. doi: 10.1021/ma961482v

Temperature (℃)	Imidization (%)
80 ^a	2.82
80 ^b	46.72
100 ^b	62.90
140 ^b	91.84
220 ^b	98.35
300 ^b	100.00

[1]	于冉, 胡晨, 郭锐利, 刘若男, 夏力行, 杨岑玉, 水江澜. 杂多酸H₃PW₁₂O₄₀高效催化MgH₂储氢[J]. 物理化学学报, 2025, 41(1): 100001 - .
[2]	张勇, 陆浩杰, 梁晓平, 张明超, 梁华润, 张莹莹. 蚕丝基智能纤维及织物：潜力、现状与未来展望[J]. 物理化学学报, 2022, 38(9): 2103034 - .
[3]	吴昆杰, 张永毅, 勇振中, 李清文. 碳纳米管纤维的连续制备及高性能化[J]. 物理化学学报, 2022, 38(9): 2106034 - .
[4]	姜美慧, 盛利志, 王超, 江丽丽, 范壮军. 超级电容器用石墨烯薄膜：制备、基元结构及表面调控[J]. 物理化学学报, 2022, 38(2): 2012085 - .
[5]	刘晓婷, 张金灿, 陈恒, 刘忠范. 超洁净石墨烯薄膜的制备方法[J]. 物理化学学报, 2022, 38(1): 2012047 - .
[6]	苗静,郭睿凤,刘志宏. BaO∙4B₂O₃∙5H₂O纳米材料的制备及其对聚丙烯阻燃性能的热分解动力学方法评价[J]. 物理化学学报, 2020, 36(6): 1905052 - .
[7]	殷鸿尧,于跃,李宗诚,张港鸿,冯玉军. 智能蜂窝状有序多孔薄膜：体系构建、响应性能及应用探索[J]. 物理化学学报, 2019, 35(12): 1341 -1356 .
[8]	杜惟实,吕耀康,蔡志威,张诚. 基于三维多孔石墨烯/含钛共轭聚合物复合多孔薄膜的柔性全固态超级电容器[J]. 物理化学学报, 2017, 33(9): 1828 -1837 .
[9]	张英杰,朱子翼,董鹏,邱振平,梁慧新,李雪. LiFePO₄电化学反应机理、制备及改性研究新进展[J]. 物理化学学报, 2017, 33(6): 1085 -1107 .
[10]	吴倩,翁维正,刘春丽,黄传敬,夏文生,万惠霖. 制备方法对Nd₂O₃上过氧物种光诱导生成的影响[J]. 物理化学学报, 2017, 33(10): 2064 -2071 .
[11]	张雪,韩洋,柴双志,胡南滔,杨志,耿会娟,魏浩. Cu₂ZnSn(S,Se)₄薄膜太阳电池研究进展[J]. 物理化学学报, 2016, 32(6): 1330 -1346 .
[12]	梁祎, 卢赟, 姚维尚, 张学同. 化学改性氧化石墨烯交联的聚酰亚胺气凝胶[J]. 物理化学学报, 2015, 31(6): 1179 -1185 .
[13]	栗志广, 马晓燕, 洪清, 管兴华. 呼吸图案法制备蜂窝状有序多孔薄膜及其功能化应用[J]. 物理化学学报, 2015, 31(3): 393 -411 .
[14]	龚金华,王臣辉,卞子君,阳立,胡军,刘洪来. 多孔材料表面修饰聚酰亚胺非对称混合基质膜对CO₂/N₂和CO₂/CH₄的气体分离[J]. 物理化学学报, 2015, 31(10): 1963 -1970 .
[15]	邓陶丽, 闫世润, 胡建国. GdAlO₃：Er³⁺，Yb³⁺荧光粉的制备与上转换发光性能[J]. 物理化学学报, 2014, 30(4): 773 -780 .

采用原位成孔法制备热闭孔特性的高强度聚酰亚胺多孔薄膜

Preparation of High-Strength Polyimide Porous Films with Thermally Closed Pore Property by In Situ Pore Formation Method

RichHTML

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 25

相关文章 15

Metrics

推荐阅读 0