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

Abstract

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

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

Figures/Tables 8

Fig 1

Fig 2

Table 1

Fig 3

Fig 4

Fig 5

Fig 6

Fig 7

References 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]	Yong Zhang, Haojie Lu, Xiaoping Liang, Mingchao Zhang, Huarun Liang, Yingying Zhang. Silk Materials for Intelligent Fibers and Textiles: Potential, Progress and Future Perspective [J]. Acta Phys. -Chim. Sin., 2022, 38(9): 2103034-.
[2]	Kunjie Wu, Yongyi Zhang, Zhenzhong Yong, Qingwen Li. Continuous Preparation and Performance Enhancement Techniques of Carbon Nanotube Fibers [J]. Acta Phys. -Chim. Sin., 2022, 38(9): 2106034-.
[3]	Meihui Jiang, Lizhi Sheng, Chao Wang, Lili Jiang, Zhuangjun Fan. Graphene Film for Supercapacitors: Preparation, Foundational Unit Structure and Surface Regulation [J]. Acta Phys. -Chim. Sin., 2022, 38(2): 2012085-.
[4]	Tao Liang, Bin Wang. Interlayer Covalently Enhanced Graphene Materials: Construction, Properties, and Applications [J]. Acta Phys. -Chim. Sin., 2022, 38(1): 2011059-.
[5]	Jing Miao,Ruifeng Guo,Zhihong Liu. Preparation of BaO·4B₂O₃·5H₂O Nanomaterial and Evaluation of Its Flame Retardant Performance to PP by Thermal Decomposition Kinetics Method [J]. Acta Physico-Chimica Sinica, 2020, 36(6): 1905052-.
[6]	Hongyao YIN,Yue YU,Zongcheng LI,Ganghong ZHANG,Yujun FENG. Smart Honeycomb-Patterned Porous Films: Fabrications, Responsive Properties, and Applications [J]. Acta Physico-Chimica Sinica, 2019, 35(12): 1341-1356.
[7]	Wei-Shi DU,Yao-Kang LÜ,Zhi-Wei CAI,Cheng ZHANG. Flexible All-Solid-State Supercapacitor Based on Three-Dimensional Porous Graphene/Titanium-Containing Copolymer Composite Film [J]. Acta Phys. -Chim. Sin., 2017, 33(9): 1828-1837.
[8]	Ying-Jie ZHANG,Zi-Yi ZHU,Peng DONG,Zhen-Ping QIU,Hui-Xin LIANG,Xue LI. New Research Progress of the Electrochemical Reaction Mechanism, Preparation and Modification for LiFePO₄ [J]. Acta Phys. -Chim. Sin., 2017, 33(6): 1085-1107.
[9]	Qian WU,Wei-Zheng WENG,Chun-Li LIU,Chuan-Jing HUANG,Wen-Sheng XIA,Hui-Lin WAN. Effect of Preparation Methods on Photo-Induced Formation of Peroxide Species on Nd₂O₃ [J]. Acta Phys. -Chim. Sin., 2017, 33(10): 2064-2071.
[10]	Xue ZHANG,Yang HAN,Shuang-Zhi CHAI,Nan-Tao HU,Zhi YANG,Hui-Juan GENG,Hao WEI. Advances in Cu₂ZnSn(S,Se)₄ Thin Film Solar Cells [J]. Acta Phys. -Chim. Sin., 2016, 32(6): 1330-1346.
[11]	LIANG Yi, LU Yun, YAO Wei-Shang, ZHANG Xue-Tong. Polyimide Aerogels Crosslinked with Chemically Modified Graphene Oxide [J]. Acta Phys. -Chim. Sin., 2015, 31(6): 1179-1185.
[12]	LI Zhi-Guang, MA Xiao-Yan, HONG Qing, GUAN Xing-Hua. Functional Applications of Ordered Honeycomb-Patterned Porous Films Based on the Breath Figure Technique [J]. Acta Phys. -Chim. Sin., 2015, 31(3): 393-411.
[13]	Jin-Hua. GONG,Chen-Hui. WANG,Zi-Jun. BIAN,Li. YANG,Jun. HU,Hong-Lai. LIU. Asymmetric Polyimide Mixed Matrix Membranes with Porous Materials-Modified Surfaces for CO₂/N₂ and CO₂/CH₄ Separations [J]. Acta Phys. -Chim. Sin., 2015, 31(10): 1963-1970.
[14]	DENG Tao-Li, YAN Shi-Run, HU Jian-Guo. Preparation and Up-Conversion Photoluminescence Properties of GdAlO₃：Er³⁺, Yb³⁺ Phosphors [J]. Acta Phys. -Chim. Sin., 2014, 30(4): 773-780.
[15]	YU Hui-Mei, PAN Xiu-Hong, ZHANG Ming-Hui, LIU Yan, YU Jian-Ding. Thermal and Mechanical Properties of Nd³⁺/Yb³⁺ Co-Doped Titanate Glass with Upconversion Emissions [J]. Acta Phys. -Chim. Sin., 2014, 30(2): 227-231.

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

RichHTML

Full text @ ScienceDirect

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 25

Related Articles 15

Metrics

Recommended 0