Robust Composite Separator Randomly Interwoven by PI and Pre-oxidized PAN Nanofibers for High Performance Lithium-ion Batteries

Ying Li; Chen Pan; Feng Gan; Zhi-Xun Lin; Jin-Chao Yu; Zhen-Zhen Wei; Yan Zhao

doi:10.1007/s10118-024-3180-y

Your Location：

Home >

Browse articles >

Robust Composite Separator Randomly Interwoven by PI and Pre-oxidized PAN Nanofibers for High Performance Lithium-ion Batteries

RESEARCH ARTICLE | Updated：2024-11-04

- Robust Composite Separator Randomly Interwoven by PI and Pre-oxidized PAN Nanofibers for High Performance Lithium-ion Batteries
- Chinese Journal of Polymer Science Vol. 42, Issue 11, Pages: 1768-1779(2024)
- Affiliations：
  
  a.College of Textile and Clothing Engineering, National Engineering Laboratory for Modern Silk, Soochow University, Suzhou 215123, China
  b.College of Textile Science and Engineering, Wuyi University, Jiangmen 529020, China
- Author bio：
  
  gf@dhu.edu.cn (F.G.)
  zzwei@suda.edu.cn (Z.Z.W.)
- Funds：
- DOI：10.1007/s10118-024-3180-y
  CLC：
- Received：12 April 2024，
  
  Revised：2024-05-28，
  
  Accepted：03 June 2024，
  
  Online First：13 September 2024，
  
  Published：30 November 2024
- Accepted：
Scan QR Code
Li, Y.; Pan, C.; Gan, F.; Lin, Z. X.; Yu, J. C.; Wei, Z. Z.; Zhao, Y. Robust composite separator randomly interwoven by PI and pre-oxidized PAN nanofibers for high performance lithium-ion batteries. Chinese J. Polym. Sci. 2024, 42, 1768–1779

Ying Li, Chen Pan, Feng Gan, et al. Robust Composite Separator Randomly Interwoven by PI and Pre-oxidized PAN Nanofibers for High Performance Lithium-ion Batteries[J]. Chinese Journal of Polymer Science, 2024, 42(11): 1768-1779.
Li, Y.; Pan, C.; Gan, F.; Lin, Z. X.; Yu, J. C.; Wei, Z. Z.; Zhao, Y. Robust composite separator randomly interwoven by PI and pre-oxidized PAN nanofibers for high performance lithium-ion batteries. Chinese J. Polym. Sci. 2024, 42, 1768–1779 DOI： 10.1007/s10118-024-3180-y.

Ying Li, Chen Pan, Feng Gan, et al. Robust Composite Separator Randomly Interwoven by PI and Pre-oxidized PAN Nanofibers for High Performance Lithium-ion Batteries[J]. Chinese Journal of Polymer Science, 2024, 42(11): 1768-1779. DOI： 10.1007/s10118-024-3180-y.

摘要

In this work

a cross-electrospinning with heat treatment strategy to obtain a composite separator (PI/oPAN) randomly interwoven by PI and pre-oxidized PAN (oPAN) nanofibers was proposed. PI/oPAN separator reconcile high porosity wi

th superior mechanical strength because of the formation of a PI fibrous network adhered by the oPAN component. Moreover

obtained PI/oPAN separator presented high ionic conductivity and Li

transference number

resulting in a desirable and stable cell cycling performance.

Abstract

Electrospun nanofibrous separators

despite lacking superior mechanical strength

have gained widespread attention with high porosity and facile processing. Herein

utilizing the fact that thermal imidization temperature of poly(amic acid) (PAA) into polyimide (PI) coincides with the pre-oxidation temperature of polyacrylonitrile (PAN) into carbon fiber

we proposed a new cross-electrospinning strategy to obtain a composite nanofibrous separator (PI/oPAN) randomly interwoven by PI and pre-oxidized PAN (oPAN) nanofibers

via

synchronously electrospinning the PAA and PAN onto the same collector and then heat-treating for 2 h at 300 °C. The resultant PI/oPAN separator was able to preserve high porosity (71.7%)

electrolyte wettability and thermal stability of PI nanofibrous membrane

and surprisingly exhibited high mechanical strength

being 3 times of PI

which mainly because of the numerous adhesion points generated by the melting of PAN in the pre-oxidation process. Meanwhile

the polar groups of oPAN and 3D fibrous network enhanced the PI/oPAN separator’s ionic conductivity and Li

transference number

rendering the corresponding cell with more stable cycling performance than cells assembled with pure PI

PAN or commercial PP separator. Therefore

this work might provide a new avenue for the ongoing design and further development of LIB separators capable of high safety and high performance.

关键词

Keywords

references

Sasaki, T.; Ukyo, Y.; Novak, P. Memory effect in a lithium-ion battery. Nat. Mater. 2013 , 12 , 569−575..

Notter, D. A.; Gauch, M.; Widmer, R.; Wäger, P.; Stamp, A.; Zah, R.; Althaus, H. J. Contribution of Li-ion batteries to the environmental impact of electric vehicles. Environ. Sci. Technol. 2010 , 44 , 6550−6556..

Zeng, X. Q.; Li, M.; Abd El-Hady, D.; Alshitari, W.; Al-Bogami, A. S.; Lu, J.; Amine, K. Commercialization of lithium battery technologies for electric vehicles. Adv. Energy Mater. 2019 , 9 , 1900161..

Jang, J.; Oh, J.; Jeong, H.; Kang, W.; Jo, C. A review of functional separators for lithium metal battery applications. Materials 2020 , 13 , 4625..

Yang, Y.; Chen, Z.; Lv, T.; Dong, K.; Liu, Y.; Qi, Y.; Cao, S.; Chen, T. Ultrafast self-assembly of supramolecular hydrogels toward novel flame-retardant separator for safe lithium ion battery. J. Colloid Interface Sci. 2023 , 649 , 591−600..

Francis, C. F. J.; Kyratzis, I. L.; Best, A. S. Lithium-ion battery separators for ionic-liquid electrolytes: a review. Adv. Mater. 2020 , 32 , 1904205..

Yu, J.; Dong, N.; Liu, B.; Tian, G.; Qi, S.; Wu, D. A newly-developed heat-resistance polyimide microsphere coating to enhance the thermal stability of commercial polyolefin separators for advanced lithium-ion battery. Chem. Eng. J. 2022 , 442 , 136314..

Lee, H.; Yanilmaz, M.; Toprakci, O.; Fu, K.; Zhang, X. W. A review of recent developments in membrane separators for rechargeable lithium-ion batteries. Energy Environ. Sci. 2014 , 7 , 3857− 3886..

Ding, L.; Zhang, C.; Wu, T.; Yang, F.; Lan, F.; Cao, Y.; Xiang, M. Effect of temperature on compression behavior of polypropylene separator used for Lithium-ion battery. J. Power Sources 2020 , 466 , 228300..

Yu, Y.; Liu, M.; Chen, Z. Y.; Zhang, Z. H.; Qiu, T.; Hu, Z. X.; Xiang, H. X.; Zhu, L. P.; Xu, G. Y.; Zhu, M. F. Advances in Nonwoven-based separators for lithium-ion batteries. Adv. Fiber Mater. 2023 , 5 , 1827−1851..

Wang, L.; Liu, F.; Shao, W.; Cui, S.; Zhao, Y.; Zhou, Y.; He, J. Graphite oxide dopping polyimide nanofiber membrane via electrospinning for high performance lithium-ion batteries. Compos. Commun. 2019 , 16 , 150−157..

Gao, X.; Sheng, L.; Yang, L.; Xie, X.; Li, D.; Gong, Y.; Cao, M.; Bai, Y.; Dong, H.; Liu, G.; Wang, T.; Huang, X.; He, J. High-stability core-shell structured PAN/PVDF nanofiber separator with excellent lithium-ion transport property for lithium-based battery. J. Colloid Interface Sci. 2023 , 636 , 317−327..

Miao, Y. E.; Zhu, G. N.; Hou, H. Q.; Xia, Y. Y.; Liu, T. X. Electrospun po lyimide nanofiber-based nonwoven separators for lithium-ion batteries. J. Power Sources 2013 , 226 , 82−86..

Shayapat, J.; Chung, O. H.; Park, J. S. Electrospun polyimide-composite separator for lithium-ion batteries. Electrochim. Acta 2015 , 170 , 110−121..

Lee, J. H.; Manuel, J.; Choi, H.; Park, W. H.; Ahn, J. H. Partially oxidized polyacrylonitrile nanofibrous membrane as a thermally stable separator for lithium ion batteries. Polymer 2015 , 68 , 335−343..

Woo, J. C.; Youk, J. H.; Kim, D. S.; Ahn, J. H. Heating effect on physical and electrochemical properties of nanofibrous polyacrylonitrile separator for lithium batteries. J. Nanosci. Nanotechnol. 2014 , 14 , 9232−9236..

Hwang, K.; Kwon, B.; Byun, H. Preparation of PVdF nanofiber membranes by electrospinning and their use as secondary battery separators. J. Membrane Sci. 2011 , 378 , 111−116..

Bicy, K.; Gueye, A. B.; Rouxel, D.; Kalarikkal, N.; Thomas, S. Lithium-ion battery separators based on electrospun PVDF: a review. Surf. Interfaces 2022 , 31 , 101977..

Yanilmaz, M. Evaluation of electrospun PVA/SiO 2 nanofiber separator membranes for lithium-ion batteries. J. Text. I. 2020 , 111 , 447−452..

Hao, J. L.; Lei, G. T.; Li, Z. H.; Wu, L. J.; Xiao, Q. Z.; Wang, L. A novel polyethylene terephthalate nonwoven separator based on electrospinning technique for lithium ion battery. J. Membrane Sci. 2013 , 428 , 11−16..

Yu, H.; Shi, Y.; Yuan, B.; He, Y.; Qiao, L.; Wang, J.; Lin, Q.; Chen, Z.; Han, E. Recent developments of polyimide materials for lithium-ion battery separators. Ionics 2021 , 27 , 907−923..

Ding, Y.; Hou, H.; Zhao, Y.; Zhu, Z.; Fong, H. Electrospun polyimide nanofibers and their applications. Prog. Polym. Sci. 2016 , 61 , 67−103..

Lu, Z. H.; Sui, F.; Miao, Y. E.; Liu, G. H.; Li, C.; Dong, W.; Cui, J.; Liu, T. X.; Wu, J. X.; Yang, C. L. Polyimide separators for rechargeable batteries. J. Energy Chem. 2021 , 58 , 170−197..

Li, L.; Liu, P.; Fu, Q. S.; Gong, Y.; Zhang, S. R.; He, H. J.; Chen, J. Study on preparation of polyacrylonitrile/polyimide composite lithium-ion battery separator by electrospinning. J. Mater. Res. 2019 , 34 , 642−651..

Ul Arifeen, W.; Kim, M.; Ting, D.; Kurniawan, R.; Choi, J.; Yoo, K.; Ko, T. J. Hybrid thermal resistant electrospun polymer membrane as the separator of lithium ion batteries. Mater. Chem. Phys. 2020 , 245 , 122780..

Arifeen, W. U.; Choi, J.; Yoo, K.; Shim, J.; Ko, T. J. A nano-silica/polyacrylonitrile/polyimide composite separator for advanced fast charging lithium-ion batteries. Chem. Eng. J. 2021 , 417 , 128075..

Chen, S. L.; Han, D. H.; Hou, H. Q. High strength electrospun fibers. Polym. Adv. Technol. 2011 , 22 , 295−303..

Rahaman, M. S. A.; Ismail, A. F.; Mustafa, A. A review of heat treatment on polyacrylonitrile fiber. Polym. Degrad. Stabil. 2007 , 92 , 1421−1432..

Qin, X.-H. Structure and property of electrospinning PAN nanofibers by different preoxidation temperature. J. Therm. Anal. Calorim. 2010 , 99 , 571−575..

Zou, Y.; Jiang, S.; Hu, X.; Xu, W.; Chen, Z.; Liu, K.; Hou, H. Influence of pre-oxidation on mechanical properties of single electrospun polyacrylonitrile nanofiber. Mater. Today Commun. 2021 , 26 , 102069..

Cao, D.; Deng, J.; Jiang, L.; Li, X.; Zhang, G. Designing polyimide/polyacrylonitrile/polyimide sandwich composite separator for rechargeable lithium-ion batteries. J. Energy Storage 2022 , 55 , 105496..

Li, M. L.; Sheng, L.; Zhang, H.; Yang, Y.; Xu, R.; Bai, Y. Z.; Song, S. J.; Liu, G. J.; Wang, T.; Huang, X. L.; He, J. P. Effect of the heat treatment temperature on mechanical and electrochemical properties of polyimide separator for lithium ion batteries. J. Mater. Sci. 2020 , 55 , 16158−16170..

Morita, K.; Murata, Y.; Ishitani, A.; Murayama, K.; Ono, T.; Nakajima, A. Characterization of commercially available PAN (Polyacrylonitrile)-based carbon-fibers. Pure Appl. Chem. 1986 , 58 , 455−468..

Liu, Y.; Liu, Y.; Shang, L.; Ao, Y. H. Study on the structural evolution of polyacrylonitrile fibers in stepwise heat treatment process and its relationship with properties. J. Appl. Polym. Sci. 2022 , 139 , e52077..

Huang, H.; Yu, B.; Wang, X. A high thermal stable pre-oxidized polyacrylonitrile nanofiber separator for lithium-ion battery. J. Appl. Polym. Sci. 2023 , 140 , e54410..

Liu, J. H.; Wang, P.; Gao, Z.; Li, X.; Cui, W.; Li, R.; Ramakrishna, S.; Zhang, J.; Long, Y. Z. Review on electrospinning anode and separators for lithium ion batteries. Renew. Sust. Energ. Rev. 2024 , 189 , 113939..

Zhai, Y. Y.; Wang, N.; Mao, X.; Si, Y.; Yu, J. Y.; Al-Deyab, S. S.; El-Newehy, M.; Ding, B. Sandwich-structured PVdF/PMIA/PVdF nanofibrous separators with robust mechanical strength and thermal stability for lithium ion batteries. J. Mater. Chem. A 2014 , 2 , 14511−14518..

Zhang, H.; Zhang, Y.; Yao, Z. K.; John, A. E.; Li, Y.; Li, W. S.; Zhu, B. K. Novel configuration of polyimide matrix-enhanced cross-linked gel separator for high performance li thium ion batteries. Electrochim. Acta 2016 , 204 , 176−182..

Xing, J.; Fan, W.; Li, J.; Wang, Z.; Wei, Z.; Zhao, Y. Orientation gradient architecture of nanofibrous separator towards mechanical enhancement and ion transport acceleration for lithium-ion batteries. Electrochim. Acta 2023 , 441 , 141794..

Pozyczka, K.; Marzantowicz, M.; Dygas, J. R.; Krok, F. Ionic conductivity and lithium transference number of poly(ethylene oxide): LiTFSI system. Electrochim. Acta 2017 , 227 , 127−135..

Wang, Y.; Guo, M.; Fu, H.; Wu, Z.; Zhang, Y.; Chao, G.; Chen, S.; Zhang, L.; Liu, T. Thermotolerant separator of cross-linked polyimide fibers with narrowed pore size for lithium-ion batteries. J. Membr. Sci. 2022 , 662 , 121004..

Liu, Y.; Li, C.; Li, C. X.; Xu, L. H.; Zhou, S.; Zhang, Z.; Zhang, J. X.; Soham, D.; Fan, R.; Liu, H.; Chen, G.; Li, Y. Y.; Ling, T.; Li, Z. P.; Tao, J. S.; Wan, J. Y. Porous, robust, thermally stable, and flame retardant nanocellulose/polyimide separators for safe lithium-ion batteries. J. Mater. Chem. A 2023 , 11 , 23360−23369..

Leng, X.; Yang, M.; Li, C.; Arifeen, W. U.; Ko, T. J. High-performance separator for lithium-ion battery based on dual-hybridizing of materials and processes. Chem. Eng. J. 2022 , 433 , 133773..

Chen, Z.; Guan, M. D.; Cheng, Y. W.; Li, H.; Ji, G. J.; Chen, H.; Fu, X. G.; Awuye, D. E.; Zhu, Y. B.; Yin, X. C.; Man, Z. M.; Wu, C. Boehmite-enhanced poly(vinylidene fluoride- co -hexafluoropropylene)/polyacrylonitrile (PVDF-HFP/PAN) coaxial electrospun nanofiber hybrid membrane: a superior separator for lithium-ion batteries. Adv. Compos. Hybrid Mater. 2023 , 6 , 219..

Views

240

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Molecularly Engineered Polyimide Films with Switchable Cavitation for Bidirectional Passive Thermal Regulation

Hydrogen Bonding in Gel Polymer Electrolyte Enables High Performance High-mass-loading Silicon Anode

High-performance Polyimide Cuff Tube with Tunable Mechanics and Long-term Biocompatibility for Microvascular Anastomosis

Boehmite/Polyacrylonitrile Composite Nanofiber Separator with Enhanced Ionic Conductivity and Thermal Stability for Lithium-Ion Batteries

Molecular Segregation and Melt Memory in Dilute Polycaprolactone with Reduced Entanglements

Related Author

Qiao-Ran Zhang

Xin-Fei Wang

Ya-Nan Chen

Bo-Yuan Zhou

Hong-Liang Wei

Xiao-Yu Cao

Jin Wang

Xin-Ran Bi

Related Institution

Key Laboratory of Multifunctional Nanomaterials and Smart Systems, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences

School of Chemistry and Chemical Engineering, Henan University of Technology

School of Energy (National Industry-Education Platform for Energy Storage), Tianjin University

School of Materials Science and Engineering, State Key Laboratory of Advanced Materials for Intelligent Sensing, Tianjin University

State Key Laboratory of Advanced Fiber Materials, College of Materials Science and Engineering, Donghua University

⁰