Abstract
In lithium-ion batteries (LIBs), separators play a vital role in lithium-ion (Li+) transport, and thus affect rate performance, battery life, and safety. Here, a new kind of multifunctional copolymer poly(acrylonitrile-co-lithium acrylate-co-butyl acrylate) (PAAB-Li) is synthesized through soap-free emulsion polymerization, and is used to form homogeneous-covered separator based on PP matrix by a simple dip-annealing process. Compared to the bare PP separator, the modified separators with PAAB-Li enable higher ionic conductivity, higher lithium ion transference number (increased from 0.360 to 0.525), and lower interface impedance (reduced from 155 Ω to 34 Ω). It has been indicated that PAAB-Li functional layer significantly promotes the fast transport of Li+ and improves the compatibility of the separator/electrolyte-electrode interface. The LiCoO2/graphite cells with the PAAB-Li-assisted separator demonstrate excellent cycle stability and rate performance. In addition, the Li symmetric cells with the modified separator stably cycle over 800 h, indicating the functional layer effectively suppresses the lithium dendrite growth. This facile strategy can be easily applied to LIBs requiring high safety and even be scalable to Li metal batteries. Moreover, the possible mechanism of the PAAB-Li functional layer promoting fast and uniform Li+ transport is discussed in this paper.
Similar content being viewed by others
References
Johnson, B. A.; White, R. E. Characterization of commercially available lithiumion batteries. J. Power Sources 1998, 70, 48–54.
Scrosati, B.; Hassoun, J.; Sun, Y. K. Lithium-ion batteries. A look into the future. Energy Environ. Sci. 2011, 4, 3287–3295.
Tarascon, J. M.; Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 2001, 414, 359–367.
Bieker, G.; Winter, M.; Bieker, P. Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode. Phys. Chem. Chem. Phys. 2015, 17, 8670–8679.
Kuo, P. L.; Wu, C. A.; Lu, C. Y.; Tsao, C. H.; Hou, C. H.; Hou, S. S. High performance of transferring lithium ion for polyacrylonitrile-interpenetrating crosslinked polyoxyethylene network as gel polymer electrolyte. ACS Appl. Mater. Interfaces 0014, 6, 3156–3162.
Wang, F. M.; Lee, J. T.; Cheng, J. H.; Cheng, C. S.; Yang, C. R. The network gel polymer electrolyte based on poly(acrylate-co-imide) and its transport properties in lithium ion batteries. J. Solid State Electrochem. 2009, 13, 1425–1431.
Zuo, T. T.; Wu, X. W.; Yang, C. P.; Yin, Y. X.; Ye, H.; Li, N. W.; Guo, Y. G. Graphitized carbon fibers as multifunctional 3D current collectors for high areal capacity Li anodes. Adv. Mater. 2017, 29, 1700389.
Wang, Q. S.; Mao, B. B.; Stoliarov, S. I.; Sun, J. H. A review of lithium ion battery failure mechanisms and fire prevention strategies. Prog. Energy Combust. Sci. 2019, 73, 95–131.
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.
Zahn, R.; Lagadec, M. F.; Hess, M.; Wood, V. Improving ionic conductivity and lithium-ion transference number in lithium-ion battery separators. ACS Appl. Mater. Interfaces 2016, 8, 32637–32642.
Lagadec, M. F.; Zahn, R.; Wood, V. Characterization and performance evaluation of lithium-ion battery separators. Nat. Energy 2019, 4, 16–25.
Lin, C. E.; Zhang, H.; Song, Y. Z.; Zhang, Y.; Yuan, J. J.; Zhu, B. K. Carboxylated polyimide separator with excellent lithium ion transport properties for a high-power density lithium-ion battery. J. Mater. Chem. A 2018, 6, 991.
Park, J. H.; Park, W.; Kim, J. H.; Ryoo, D.; Kim, H. S.; Jeong, Y. U.; Kim, D. W.; Lee, S. Y. Close-packed poly(methyl methacrylate) nanoparticle arrays-coated polyethylene separators for high-power lithium-ion polymer batteries. J. Power Sources 2011, 196, 7035.
Kim, D. W.; Ko, J. M.; Chun, J. H.; Kim, S. H.; Park, J. K. Electrochemical performances of lithium-ion cells prepared with polyethylene oxide-coated separators. Electrochem. Commun. 2001, 3, 535.
Wan, J. Y.; **e, J.; Kong, X.; Liu, Z.; Liu, K.; Shi, F. F.; Pei, A.; Chen, H.; Chen, W.; Chen, J.; Zhang, X. K.; Zong, L. Q.; Wang, J. Y.; Chen, L. Q.; Qin, J.; Cui, Y. Ultrathin, flexible, solid polymer composite electrolyte enabled with aligned nanoporous host for lithium batteries. Nat. Nanotechnol. 2019, 14, 705.
Zhang, Y.; Yuan, J. J.; Song, Y. Z.; Yin, X.; Sun, C. C.; Zhu, L. P.; Zhu, B. K. Tannic acid/polyethyleneimine-decorated polypropylene separators for Li-ion batteries and the role of the interfaces between separator and electrolyte. Electrochim. Acta 2018, 275, 25–31.
Zhang, C.; Liang, H. Q.; Pi, J. K.; Wu, G. P.; Xu, Z. K. Polypropylene separators with robust mussel-inspired coatings for high lithiumion battery performances. Chinese J. Polym. Sci. 0019, 37, 1015–1022.
Meng, Z. T.; Huang, Y. D.; Li, J.; Yang, R. N.; Wang, X. C.; Guo, Y.; Liu, Z. J.; **, M. R.; Su, W. Q.; Wang, L. Deposition of cross-linked dopamine and polyethylenimine on polypropylene separators via one-step soaking method for Li-S batteries. J. Electrochem. Soc. 2019, 166, A546–A550.
Gao, K.; Hu, X.; Yi, T.; Dai, C. PE-g-MMA polymer electrolyte membrane for lithium polymer battery. Electrochim. Acta 2006, 52, 443.
Liao, Y. H.; Zhou, D. Y.; Rao, M. M.; Li, W. S.; Cai, Z. P.; Liang, Y. Self-supported poly(methyl methacrylate-acrylonitrile-vinyl acetate)-based gel electrolyte for lithium ion battery. J. Power Sources 2009, 189, 139–144.
Zheng, T.; He, X.; Pu, W.; Wan, C.; Jiang, C. Preparation of poly(acrylonitrile-butyl acrylate) gel electrolyte for lithium-ion batteries. Electrochim. Acta 2006, 52, 688–693.
Arora, P.; Zhang, Z. M. Battery separators. Chem. Rev. 2004, 104, 4419–4462.
Stephan, A. M. Review on gel polymer electrolytes for lithium batteries. Eur. Polym. J. 2006, 42, 21–42.
Kim, J. Y.; Kim, S. K.; Lee, S. J.; Lee, S. Y.; Lee, H. M.; Ahn, S. Preparation of micro-porous gel polymer for lithium ion polymer battery. Electrochim. Acta 2004, 50, 363–366.
Lu, W.; Yuan, Z.; Zhao, Y.; Zhang, H.; Zhang, H.; Li, X. Porous membranes in secondary battery technologies. Chem. Soc. Rev. 2017, 46, 2199–2236.
Tsutsumi, H.; Matsuo, A.; Takase, K.; Doi, S.; Hisanaga, A.; Onimura, K.; Oishi, T. Conductivity enhancement of polyacrylonitrile-based electrolytes by addition of cascade nitrile compounds. J. Power Sources 2000, 90, 33–38.
Liao, Y.; Rao, M.; Li, W.; Tan, C.; Yi, J.; Chen, L. Improvement in ionic conductivity of self-supported P(MMA-AN-VAc) gel electrolyte by fumed silica for lithium ion batteries. Electrochim. Acta 2009, 54, 6396–6402.
Luo, S.; Liu, Z.; Liu, B.; Liu, Q. Preparation of semi-IPN(BA-VAc-VAE) by emulsion polymerization and its properties investigation. Bull. Mat. Sci. 2011, 34, 1531–1536.
Choi, Y. S. Poly(n -butyl acrylate-co-methyl methacrylate) and poly(n-butyl acrylate-co-styrene) silicate nanocomposites prepared by emulsion polymerization. Macromol. Res. 2003, 11, 425–430.
Pieczonka, N. P. W.; Borgel, V.; Ziv, B.; Leifer, N.; Dargel, V.; Aurbach, D.; Kim, J. H.; Liu, Z. Y.; Huang, X. S.; Krachkovskiy, S. A.; Goward, G. R.; Halalay, I.; Powell, B. R.; Manthiram, A. Lithium polyacrylate (LiPAA) as an advanced binder and a passivating agent for high-voltage li-ion batteries. Adv. Energy Mater. 2015, 51501008, 1501008.
Zuo, T. T.; Wu, X. W.; Yang, C. P.; Yin, Y. X.; Ye, H.; Li, N. W.; Guo, Y. G. Graphitized carbon fibers as multifunctional 3D current collectors for high areal capacity Li anodes. Adv. Mater. 2017, 29.
Fan, L.; Zhuang, H. L.; Gao, L.; Lu, Y.; Archer, L. A. Regulating Li deposition at artificial solid electrolyte interphases. J. Mater. Chem. A 2017, 5, 3483–3492.
Xu, K. Toward reliable values of electrochemical stability limits for electrolytes. Chem. Rev. 2004, 104, 4303.
Xu, K.; Ding, S. P.; Jow, T. R. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. J. Electrochem. Soc. 1999, 146, 4172.
Zhang, H.; Lin, C. E.; Zhou, M. Y.; John, A. E.; Zhu, B. K. High thermal resistance polyimide separators prepared via soluble precusor and non-solvent induced phase separation process for lithium ion batteries. Electrochim. Acta 2016, 187, 125–133.
Zhang, H.; Zhang, Y.; Yao, Z.; John, A. E.; Li, Y.; Li, W.; Zhu, B. Novel configuration of polyimide matrix-enhanced cross-linked gel separator for high performance lithium ion batteries. Electrochim. Acta 2016, 204, 176–182.
Song, Y. Z.; Yuan, J. J.; Yin, X.; Zhang, Y.; Lin, C. E.; Sun, C. C.; Fang, L. F.; Zhu, B.; Zhu, L. P. Effect of polyphenol-polyamine treated polyethylene separator on the ionic conduction and interface properties for lithium-metal anode batteries. J. Electroanal. Chem. 2018, 816, 68–74.
Sun, X. G.; Kerr, J. B. Synthesis and characterization of network single ion conductors (NSIC) based on comb-branched polyepoxide ethers and lithium bis(allylmalonato)borate. Macromolecules 2006, 39, 362–372.
Doyle, M.; Fuller, T. F.; Newman, J. Modeling of galvanostatic charge and discharge of the lithium polymer insertion cell. J. Electrochem. Soc. 1993, 140, 1526–1533.
**ang, Y.; Li, J.; Lei, J.; Liu, D.; **e, Z.; Qu, D.; Li, K.; Deng, T.; Tang, H. Advanced separators for lithium-ion and lithium-sulfur batteries: a review of recent progress. ChemSusChem 2016, 9, 3023–3039.
Zhang, Y.; Song, Y. Z.; Yuan, J. J.; Yin, X.; Sun, C. C.; Zhu, B. K. Polypropylene separator coated with a thin layer of poly(lithium acrylate-co-butyl acrylate) for high-performance lithium-ion batteries. J. Appl. Polym. Sci. 2018, 135.
Wang, Z. Y.; Guo, F. L.; Chen, C.; Shi, L. Y.; Yuan, S.; Sun, L. N.; Zhu, J. F. Self-assembly of PEI/SiO2 on polyethylene separators for Liion batteries with enhanced rate capability. ACS Appl. Mater. Interfaces 2015, 7, 3314–3322.
Doyle, R. P.; Chen, X.; Macrae, M.; Srungavarapu, A.; Smith, L. J.; Gopinadhan, M.; Osuji, C. O.; Granados-Focil, S. Poly(ethylenimine)-based polymer blends as single-ion lithium conductors. Macromolecules 2014, 47, 3401–3408.
Huo, H. Y.; Wu, B.; Zhang, T.; Zheng, X. S.; Ge, L.; Xu, T. W.; Guo, X. X.; Sun, X. L. Anion-immobilized polymer electrolyte achieved by cationic metal-organic framework filler for dendrite-free solidstate batteries. Energy Storage Mater. 2019, 18, 59–67.
Li, Q.; Zhu, S.; Lu, Y. 3D porous Cu current collector/Li-metal composite anode for stable lithium-metal batteries. Adv. Funct. Mater. 2017, 27, 11606422.
Acknowledgments
This work was financially supported by the National 863 Program of China (No. 2012AA03A602), National Key R&D Program of China (No. 2017YFE0114100), Science and Technology Project of Guangdong Province of China (No. 2019 ST115), and the National Natural Science Foundation of China (No. 21805240).
Author information
Authors and Affiliations
Corresponding authors
Electronic Supplementary Information
Rights and permissions
About this article
Cite this article
Yan, Y., Kong, QR., Sun, CC. et al. Copolymer-assisted Polypropylene Separator for Fast and Uniform Lithium Ion Transport in Lithium-ion Batteries. Chin J Polym Sci 38, 1313–1324 (2020). https://doi.org/10.1007/s10118-020-2455-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10118-020-2455-1