黏结剂对锂离子电池陶瓷涂敷隔膜的性能影响

doi:10.12028/j.issn.2095-4239.2018.0113

储能科学与技术 ›› 2018, Vol. 7 ›› Issue (6): 1139-1145.doi: 10.12028/j.issn.2095-4239.2018.0113

黏结剂对锂离子电池陶瓷涂敷隔膜的性能影响

钟国彬¹, 王中会², 梁鑫², 项宏发²

1. 广东电网有限责任公司电力科学研究院, 广东广州 510080;
2. 合肥工业大学材料科学与工程学院, 安徽合肥 230009

收稿日期:2018-07-02 修回日期:2018-07-30 出版日期:2018-11-01 发布日期:2018-08-21
通讯作者: 项宏发,教授,博士生导师,主要从事锂离子电池研究,E-mail:hfxiang@hfut.edu.cn。
作者简介:钟国彬(1984-),男,博士,高级工程师,主要从事锂离子电池研究,E-mail:zhongguobin@gddky.csg.cn
基金资助:
南方电网公司科技项目（GDKJQQ20152008）。

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

ZHONG Guobin¹, WANG Zhonghui², LIANG Xin², XIANG Hongfa²

1. Electric Power Research Institute of Guangdong Power Grid Company Limited, Guangzhou 510080, Guangdong, China;
2. School of Material Science and Engineering, Hefei University of Technology, Hefei 230009, Anhui, China

Received:2018-07-02 Revised:2018-07-30 Online:2018-11-01 Published:2018-08-21
Contact: 10.12028/j.issn.2095-4239.2018.0113

摘要/Abstract

摘要： 为优化陶瓷涂敷隔膜热稳定性，提高锂离子电池的安全性和电化学性能，本工作选用热稳定性优异的聚酰亚胺和电化学稳定的聚偏氟乙烯六氟丙烯作为复合黏结剂，将Al₂O₃无机颗粒涂敷于商品级聚烯烃隔膜两侧。通过调控两种黏结剂组分含量，测试隔膜性能发现，增加聚酰亚胺的含量可以明显提高涂覆隔膜的热稳定性，但隔膜的电化学性能不理想；在黏结剂中引入适量的聚偏氟乙烯六氟丙烯组分，涂覆隔膜可在保持其热稳定性的同时，获得良好的离子电导率、电化学稳定性和金属锂电极兼容性等性能。最后选用电化学性能表现最为优异且热稳定性良好的黏结剂组分制备陶瓷涂敷隔膜，在Li|LiCoO₂电池中，比聚烯烃隔膜表现出更优异的电化学性能，在8 C倍率下的放电比容量为109.3 mA/g，容量保持率为66.1%，而使用PE隔膜的电池的放电比容量和容量保持率仅为88.7 mA/g和54.7%。

关键词: 陶瓷涂敷隔膜, 黏结剂, 聚酰亚胺, 聚偏氟乙烯六氟丙烯, 锂离子电池

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

中图分类号:

O631
O646

钟国彬, 王中会, 梁鑫, 项宏发. 黏结剂对锂离子电池陶瓷涂敷隔膜的性能影响[J]. 储能科学与技术, 2018, 7(6): 1139-1145.

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.

参考文献

[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.

黏结剂对锂离子电池陶瓷涂敷隔膜的性能影响

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

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