Citation: 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 Physico-Chimica Sinica, ;2024, 40(9): 230601. doi: 10.3866/PKU.WHXB202306010 shu

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

Yuting Bai ¹ ,
Cenqi Yan ¹ ,
Zhen Li ^2,, ,
Jiaqiang Qin ^1,, ,
Pei Cheng ^1,,

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

Corresponding author: Zhen Li, 729431051@qq.com Jiaqiang Qin, jqqin@scu.edu.cn Pei Cheng, chengpei@scu.edu.cn
Received Date: 5 June 2023
Revised Date: 26 July 2023
Accepted Date: 27 July 2023
Available Online: 8 August 2023
Fund Project: the National Natural Science Foundation of China 51873127

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.
- Porous film,
- Polyimide,
- Thermally closed pore property,
- Preparation method,
- Mechanical property
1. [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 doi: 10.1016/j.ensm.2021.02.042
2. [2]
  Waqas, M.; Ali, S.; Feng, C.; Chen, D.; Han, J.; He, W. Small 2019, 15 (33), 1901689. doi: 10.1002/smll.201901689 doi: 10.1002/smll.201901689
3. [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 doi: 10.1016/j.ensm.2019.07.024
4. [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 doi: 10.1016/j.jpowsour.2012.10.060
5. [5]
  Sun, Y.; Liu, N.; Cui, Y. Nat. Energy 2016, 1 (7), 16071. doi: 10.1038/nenergy.2016.71 doi: 10.1038/nenergy.2016.71
6. [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 doi: 10.1016/j.joule.2018.06.015
7. [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 doi: 10.1021/am302290n
8. [8]
  Costa, C. M.; Rodrigues, L. C.; Sencadas, V.; Silva, M. M.; Rocha, J. G.; Lanceros-Méndez, S. J. Membr. Sci. 2012, 407–408, 193. doi: 10.1016/j.memsci.2012.03.044 doi: 10.1016/j.memsci.2012.03.044
9. [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 doi: 10.1016/j.memsci.2018.03.027
10. [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 doi: 10.1039/C5TA08694A
11. [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 doi: 10.1016/j.progpolymsci.2016.06.006
12. [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 doi: 10.1016/j.progpolymsci.2012.02.005
13. [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 doi: 10.1016/j.coco.2019.08.011
14. [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 doi: 10.1021/acsami.9b05257
15. [15]
  Lin, D.; Zhuo, D.; Liu, Y.; Cui, Y. J. Am. Chem. Soc. 2016, 138 (34), 11044. doi: 10.1021/jacs.6b06324 doi: 10.1021/jacs.6b06324
16. [16]
  Maeyoshi, Y.; Miyamoto, S.; Munakata, H.; Kanamura, K. J. Power Sources 2017, 350, 103. doi: 10.1016/j.jpowsour.2017.03.053 doi: 10.1016/j.jpowsour.2017.03.053
17. [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 doi: 10.1021/acsami.9b19049
18. [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 doi: 10.1039/c7ta08702k
19. [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 doi: 10.1016/j.electacta.2015.11.028
20. [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 doi: 10.1016/j.memsci.2017.12.028
21. [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 doi: 10.1016/j.coco.2019.09.004
22. [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 doi: 10.1016/j.jpowsour.2012.10.027
23. [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 doi: 10.1016/j.memsci.2017.05.023
24. [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 doi: 10.1021/nl5014037
25. [25]
  Seo, Y.; Lee, S. M.; Kim, D. Y.; Kim, K. U. Macromolecules 1997, 30 (13), 3747. doi: 10.1021/ma961482v doi: 10.1021/ma961482v
1. [1]
  Feng Zheng , Ruxun Yuan , Xiaogang Wang . “Research-Oriented” Comprehensive Experimental Design in Polymer Chemistry: the Case of Polyimide Aerogels. University Chemistry, 2024, 39(10): 210-218. doi: 10.12461/PKU.DXHX202404027
2. [2]
  Jiaxin Su , Jiaqi Zhang , Shuming Chai , Yankun Wang , Sibo Wang , Yuanxing Fang . Optimizing Poly(heptazine imide) Photoanodes Using Binary Molten Salt Synthesis for Water Oxidation Reaction. Acta Physico-Chimica Sinica, 2024, 40(12): 2408012-0. doi: 10.3866/PKU.WHXB202408012
3. [3]
  Xinyuan Shi , Chenyangjiang , Changyu Zhai , Xuemei Lu , Jia Li , Zhu Mao . Preparation and Photoelectric Performance Characterization of Perovskite CsPbBr₃ Thin Films. University Chemistry, 2024, 39(6): 383-389. doi: 10.3866/PKU.DXHX202312019
4. [4]
  Zhuo WANG , Xiaotong LI , Zhipeng HU , Junqiao PAN . Three-dimensional porous carbon decorated with nano bismuth particles: Preparation and sodium storage properties. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 267-274. doi: 10.11862/CJIC.20240223
5. [5]
  Qianqian ZHU , Lihui XU , Hong PAN , Chengjian YAO , Hong ZHAO , Nan MA , Xiaolin SHI , Zihan SHEN , Weijun ZHANG , Zhongjian WANG . Waste cotton fabric-ased porous carbon materials: Preparation and wave-absorbing properties. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1555-1564. doi: 10.11862/CJIC.20250040
6. [6]
  Wendian XIE , Yuehua LONG , Jianyang XIE , Liqun XING , Shixiong SHE , Yan YANG , Zhihao HUANG . Preparation and ion separation performance of oligoether chains enriched covalent organic framework membrane. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1528-1536. doi: 10.11862/CJIC.20240050
7. [7]
  Ronghui LI . Photocatalysis performance of nitrogen-doped CeO₂ thin films via ion beam-assisted deposition. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1123-1130. doi: 10.11862/CJIC.20240440
8. [8]
  Zhaomei LIU , Wenshi ZHONG , Jiaxin LI , Gengshen HU . Preparation of nitrogen-doped porous carbons with ultra-high surface areas for high-performance supercapacitors. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 677-685. doi: 10.11862/CJIC.20230404
9. [9]
  Peiyu Zhang , Aixin Song , Jingcheng Hao , Jiwei Cui . 高频超声法制备聚多巴胺薄膜综合实验. University Chemistry, 2025, 40(6): 210-214. doi: 10.12461/PKU.DXHX202407081
10. [10]
  Xuechen Hu , Qiuying Xia , Fan Yue , Xinyi He , Zhenghao Mei , Jinshi Wang , Hui Xia , Xiaodong Huang . Electrochemical Characteristics of LiNbO₃ Anode Film and Its Applications in All-Solid-State Thin-Film Lithium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2309046-0. doi: 10.3866/PKU.WHXB202309046
11. [11]
  Bao Jia , Yunzhe Ke , Shiyue Sun , Dongxue Yu , Ying Liu , Shuaishuai Ding . Innovative Experimental Teaching for the Preparation and Modification of Conductive Organic Polymer Thin Films in Undergraduate Courses. University Chemistry, 2024, 39(10): 271-282. doi: 10.12461/PKU.DXHX202404121
12. [12]
  Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270
13. [13]
  Yongwei ZHANG , Chuang ZHU , Wenbin WU , Yongyong MA , Heng YANG . Efficient hydrogen evolution reaction activity induced by ZnSe@nitrogen doped porous carbon heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 650-660. doi: 10.11862/CJIC.20240386
14. [14]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, 2024, 39(3): 327-335. doi: 10.3866/PKU.DXHX202309074
15. [15]
  Yuanpei ZHANG , Jiahong WANG , Jinming HUANG , Zhi HU . Preparation of magnetic mesoporous carbon loaded nano zero-valent iron for removal of Cr(Ⅲ) organic complexes from high-salt wastewater. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1731-1742. doi: 10.11862/CJIC.20240077
16. [16]
  Zehao Zhang , Zheng Wang , Haibo Li . Preparation of 2D V₂O₃@Pourous Carbon Nanosheets Derived from V₂CF_x MXene for Capacitive Desalination. Acta Physico-Chimica Sinica, 2024, 40(8): 2308020-0. doi: 10.3866/PKU.WHXB202308020
17. [17]
  Dongdong Yao , JunweiGu , Yi Yan , Junliang Zhang , Yaping Zheng . Teaching Phase Separation Mechanism in Polymer Blends Using Process Representation Teaching Method: A Teaching Design for Challenging Theoretical Concepts in “Polymer Structure and Properties” Course. University Chemistry, 2025, 40(4): 131-137. doi: 10.12461/PKU.DXHX202408125
18. [18]
  Jiatong Hu , Qiyi Wang , Ruiwen Tang , Jiajing Feng . Photocatalytic Journey of Perylene Diimides in a Competitive Arena. University Chemistry, 2025, 40(5): 328-333. doi: 10.12461/PKU.DXHX202407015
19. [19]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
20. [20]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(844)
HTML views(78)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142