Effect of binders on performances of ceramic coated separators for lithium-ion batteries

doi:10.12028/j.issn.2095-4239.2018.0113

Abstract

Abstract: In order to optimize the thermal stability of the ceramic coated separators and improve the safety and electrochemical performance of lithium ion batteries, polyimide (PI) with good thermal stability and poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) with excellent electrochemical stability are used as binder to coat the aluminum oxide (Al₂O₃) particles onto both sides of commercial PE separator in this work. According to the test results of ceramic coated separators prepared by different binder components, the PI binder can obviously improve the thermal stability of the ceramic coated separator, however the cell performance is not satisfying. In addition, the poor electrochemical properties of the PI binder can reduce the electrochemical stability and compatibilities with electrodes. PVDF-HFP has been widely used in lithium-ion batteries because of its excellent electrochemical properties. PVDF-HFP can swell in the electrolyte, the swollen PVDF-HFP can adhere electrode so that lithium ions can pass across the separator. Adding an appropriate amount of PVDF-HFP in the binder can improve the ionic conductivity, electrochemical stability, lithium metal-electrode compatibility and other properties of the ceramic coated separator while maintaining its good thermal stability because of the presence of PI binder. Therefore, the using of appropriate components of PI and PVDF-HFP binders can synergistically improve the performance of the using of ceramic coated separator. Finally, the cell performances of the Li|LiCoO₂ cells with the optimized inorganic composite separator are enhanced obviously. The capacity and the capacity retention of the cell using the optimized ceramic coated separator at 8 C is 109.3 mA·h·g^-1 and 66.1%, which are much better than those (88.7 mA·h·g^-1 and 54.7%) of the cell using the PE separator.

Key words: ceramic coated separator, binders, polyimide, poly (vinylidene fluoride-co-hexafluoropro-pylene), lithium-ion batteries

CLC Number:

O631
O646

ZHONG Guobin, WANG Zhonghui, LIANG Xin, XIANG Hongfa. Effect of binders on performances of ceramic coated separators for lithium-ion batteries[J]. Energy Storage Science and Technology, 2018, 7(6): 1139-1145.

References

[1] ETACHERI V, MAROM R, ELAZARI R, et al. Challenges in the development of advanced Li-ion batteries:A review[J]. Energy Environ. Sci., 2011, 4 (9):3243-3262.
[2] GOODENOUGH J B, KIM Y. Challenges for rechargeable Li batteries[J]. Chem. Mater., 2010, 22 (3):587-603.
[3] 夏永高, 刘兆平. 锂离子电池高容量富锂锰基正极材料研究进展[J]. 储能科学与技术, 2016, 5 (3):384-387. XIA Y G, LIU Z P. Research progress on the Li-excess Mn-based cathode materials with high capacity for lithium-ion battery[J]. Energy Storage Science and Technology, 2016, 5 (3):384-387.
[4] 李泓. 锂离子电池基础科学问题 (XV)——总结和展望[J]. 储能科学与技术, 2015, 4 (3):306-318. LI H. Fundamental scientific aspects of lithium ion batteries (XV)-Summary and outlook[J]. Energy Storage Science and Technology, 2015, 4 (3):306-318.
[5] 肖伟, 巩亚群, 王红, 等. 锂离子电池隔膜技术进展[J]. 储能科学与技术, 2016, 5 (2):188-196. XIAO W, GONG Y Q, WANG H, et al. Research progress of separators for lithium-ion batteries[J]. Energy Storage Science and Technology, 2016, 5 (2):188-196.
[6] DAI M, SHEN J X, ZHANG J Y, et al. A novel separator material consisting of ZeoliticImidazolate Framework-4 (ZIF-4) and its electrochemical performance for lithium-ions battery[J]. J. Power Sources, 2017, 369:27-34.
[7] ARORA P, ZHANG Z M. Battery separators[J]. Chem. Rev., 2004, 104 (10):4419-4462.
[8] 王畅, 吴大勇. 锂离子电池隔膜及技术进展[J]. 储能科学与技术, 2016, 5 (2):120-128. WANG C, WU D. LIB separators and the recent technical progress[J]. Energy Storage Science and Technology, 2016, 5 (2):120-128.
[9] LEE H, YANILMAZ M, TOPRAKCI O, et al. A review of recent developments in membrane separators for rechargeable lithium-ion batteries[J]. Energy Environ. Sci., 2014, 7 (12):3857-3886.
[10] ZHU X M, JIANG X Y, AI X P, et al. TiO₂ ceramic-grafted polyethylene separators for enhanced thermostability and electrochemical performance of lithium-ion batteries[J]. J. Membr. Sci., 2016, 504:97-103.
[11] ZHANG Y C, WANG Z H, XIANG H F, et al. A thin inorganic composite separator for lithium-ion batteries[J]. J. Membr. Sci., 2016, 509:19-26.
[12] XIE Y, ZOU H L, XIANG H F, et al. Enhancement on the wettability of lithium battery separator toward nonaqueous electrolytes[J]. J. Membr. Sci., 2016, 503:25-30.
[13] WANG Y, WANG S Q, FANG J Q, et al. A nano-silica modified polyimide nanofiber separator with enhanced thermal and wetting properties for high safety lithium-ion batteries[J]. J. Membr. Sci., 2017, 537:248-254.
[14] XIANG H F, CHEN J J, LI Z, et al. An inorganic membrane as a separator for lithium-ion battery[J]. J. Power Sources, 2011, 196:8651-8655.
[15] YANILMAZ M, LU Y, ZHU J D, et al. Silica/polyacrylonitrile hybrid nanofiber membrane separators via sol-gel and electrospinning techniques for lithium-ion batteries[J]. J. Power Sources, 2016, 313:205-212.
[16] LIANG X X, YANG Y, JIN X, et al. The high performances of SiO₂/Al₂O₃-coated electrospun polyimide fibrous separator for lithium-ion battery[J]. J. Membr. Sci., 2015, 493:1-7.
[17] FASCIANI C, PANERO S, HASSOUN J, et al. Novel configuration of poly (vinylidenedifluoride)-based gel polymer electrolyte for application in lithium-ion batteries[J]. J. Power Sources, 2015, 294:180-186.
[18] LUO X Y, LIAO Y H, ZHU Y M, et al. Investigation of nano-CeO₂ contents on the properties of polymer ceramic separator for high voltage lithium ion batteries[J]. J. Power Sources, 2017, 348:229-238.
[19] SHI C, ZHANG P, CHEN L X, et al. Effect of a thin ceramic-coating layer on thermal and electrochemical properties of polyethylene separator for lithium-ion batteries[J]. J. Power Sources, 2014, 270:547-553.
[20] MIAO R Y, LIU B W, ZHU Z Z, et al. PVDF-HFP-based porous polymer electrolyte membranes for lithium-ion batteries[J]. J. Power Sources, 2008, 184 (2):420-426.
[21] DENG Y M, SONG X N, MA Z, et al. Al₂O₃/PVdF-HFP-CMC/PE separator prepared using aqueous slurry and post-hot-pressing method for polymer lithium-ion batteries with enhanced safety[J]. Electrochim. Acta, 2016, 212:416-425.
[22] KIM K J, KWON H K, PARK M S, et al. Ceramic composite separators coated with moisturized ZrO₂ nanoparticles for improving the electrochemical performance and thermal stability of lithium ion batteries[J]. Phys. Chem.Chem. Phys., 2014, 16 (20):9337-9343.
[23] DONG F, BEN L, STEVE A, et al. Nano SiO₂ particle formation and deposition on polypropylene separators for lithium-ion batteries[J]. J. Power Sources, 2012, 206 (1):325-333.
[24] CHO J, JUNG Y C, LEE Y S, et al. High performance separator coated with amino-functionalized SiO₂ particles for safety enhanced lithium-ion batteries[J]. J. Membr. Sci., 2017, 535:151-157.
[25] ZHANG S S, XU K, FOSTER D L, et al. Microporous gel electrolyte Li-ion battery[J]. J. Power. Sources., 2004, 125 (1):114-118.
[26] LEE Y, LEE H, LEE T, et al. Synergistic thermal stabilization of ceramic/co-polyimide coated polypropylene separators for lithium-ion batteries[J]. J. Power Sources, 2015, 294:537-544.
[27] YU L H, JIN Y, LIN Y S. Ceramic coated polypropylene separators for lithium-ion batteries with improved safety:Effects of high melting point organic binder[J]. RSC Adv., 2016, 6 (46):40002-40009.
[28] SHI C, DAI J H, SHEN X, et al. A high-temperature stable ceramic-coated separator prepared with polyimide binder/Al₂O₃ particles for lithium-ion batteries[J]. J. Membr. Sci., 2016, 517:91-99.
[29] YANG P T, ZHANG P, SHI C, et al. The functional separator coated with core-shell structured silica-poly (methyl methacrylate) sub-microspheres for lithium-ion batteries[J]. J. Membr. Sci., 2015, 474:148-155.