锂离子电池用离子塑性晶体-离子液体聚合物全固态电解质

doi:10.12028/j.issn.2095-4239.2018.0151

储能科学与技术 ›› 2018, Vol. 7 ›› Issue (6): 1113-1119.doi: 10.12028/j.issn.2095-4239.2018.0151

锂离子电池用离子塑性晶体-离子液体聚合物全固态电解质

杨凯华, 廖柱, 黎雪松, 章正熙, 杨立

上海交通大学化学化工学院, 上海 200240

收稿日期:2018-08-14 修回日期:2018-08-29 出版日期:2018-11-01 发布日期:2018-08-18
通讯作者: 章正熙,助理研究员,主要研究方向为高性能高安全电解质及电极材料,E-mail:zhengxizhang@sjtu.edu.cn;杨立,教授,主要研究方向为高性能二次电池,E-mail:liyangce@sjtu.edu.cn。
作者简介:杨凯华(1994-),男,硕士研究生,主要研究方向为高性能高安全电解质,E-mail:yangkaihua@sjtu.edu.cn
基金资助:
国家自然科学基金项目（51772188）。

Novel ionic plastic crystal-polymeric ionic liquid all-solid-state electrolytes for lithium ion batteries

YANG Kaihua, LIAO Zhu, LI Xuesong, ZHANG Zhengxi, YANG Li

School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2018-08-14 Revised:2018-08-29 Online:2018-11-01 Published:2018-08-18
Contact: 10.12028/j.issn.2095-4239.2018.0151

摘要/Abstract

摘要： 离子塑性晶体作为一类新型的固态电解质材料，近年来受到研究人员的极大关注。本文合成了一种新型离子塑性晶体：N，N-二甲基吡咯双氟磺酰亚胺（P₁₁FSI），并将其与吡咯阳离子离子液体聚合物-聚二甲基二烯丙基铵双氟磺酰亚胺（PILFSI）和锂盐（LiFSI）复合制备了P₁₁FSI-PILFSI-LiFSI全固态电解质。采用差示扫描量热法、热重分析、阻抗测试、线性扫描伏安法及对称锂电池测试等一系列表征技术对全固态电解质的热性能和电化学性能进行了系统研究。所制备的电解质膜具有好的柔韧性和热稳定性，高的离子电导率和电化学稳定性，以及与金属锂良好的界面相容性。将全固态电解质应用于Li/LiFePO₄电池中，在50℃、0.2 C充放电倍率时，电池放电比容量在60次循环后仍可达151.1 mA·h/g，容量保持率为96.8%；且在0.5 C、1.0 C倍率下放电比容量仍然高达138.1 mA·h/g和128.1 mA·h/g，展现出高的放电比容量，好的循环性能和倍率性能，有望应用于全固态锂离子电池中。

关键词: 离子塑性晶体, 离子液体聚合物, 全固态电解质, 锂离子电池

Abstract: As a kind of new solid electrolyte materials, ionic plastic crystals have received much attention in recent years. In this paper, a novel ionic plastic crystal N, N-dimethylpyrrolidinium bis (fluorosulfonyl)imide (P₁₁FSI) was firstly synthesized, and blended with pyrrolidinium-based polymeric ionic liquid (PILFSI) and lithium salt (LiFSI) to obtain a series of new solid electrolytes.The thermal and electrochemical properties of as-prepared solid electrolytes are investigated by differential scanning calorimeter, thermogravimetric analysis, impedance spectroscopy measurements, linear sweep voltammetry and symmetrical lithium cell test. The as-prepared solid electrolytes exhibit good flexibility and thermal stability, high ionic conductivity and electrochemical stability, as well as good compatibility with the lithium metal. Particularly, Li/LiFePO₄ cells assembled with as-obtained solid electrolytes present high discharge capacity (151.1 mA·h·g^-1), good cycle life and rate performance. This finding indicates that the solid electrolyte system obtained in our work has great potential for use in all-solid-state lithium ion batteries.

Key words: ionic plastic crystal, polymeric ionic liquid, all-solid-state electrolyte, lithium batteries

中图分类号:

TM911

杨凯华, 廖柱, 黎雪松, 章正熙, 杨立. 锂离子电池用离子塑性晶体-离子液体聚合物全固态电解质[J]. 储能科学与技术, 2018, 7(6): 1113-1119.

YANG Kaihua, LIAO Zhu, LI Xuesong, ZHANG Zhengxi, YANG Li. Novel ionic plastic crystal-polymeric ionic liquid all-solid-state electrolytes for lithium ion batteries[J]. Energy Storage Science and Technology, 2018, 7(6): 1113-1119.

参考文献

[1] XU K. Electrolytes and interphases in Li-ion batteries and beyond[J]. Chemical Reviews, 2014, 114 (23):11503-11618.
[2] GOODENOUGH J B, KIM Y. Challenges for rechargeable Li batteries[J]. Chemistry of Materials, 2010, 22 (3):587-603.
[3] 李泓. 全固态锂电池:梦想照进现实[J]. 储能科学与技术, 2018, 7 (2):188-193.
[4] MOTAVALLI J. A solid future[J]. Nature, 2015, 526 (7575):S96.
[5] TARASCON J M, ARMAND M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001, 414:359.
[6] 杜奥冰, 柴敬超, 张建军, 等. 锂电池用全固态聚合物电解质的研究进展[J]. 储能科学与技术, 2016, 5 (5):627-648. DU Aobing, CHAI Jingchao, ZHANG Jianjun, et al. All-solid-state lithium-ion batteries based on polymer electrolytes:State of the art, challenges and future trends[J]. Energy Storage Science and Technology, 2016, 5 (5):627-648.
[7] 何向明, 蒲薇华, 王莉, 等. 锂离子塑性晶体常温固体电解质[J]. 化学进展, 2006 (1):24-29. HE Xiangming, PU Weihua, WANG Li, et al. Plastic crystals:An effective ambient temperature all-solid-state electrolyte for lithium batteries[J]. Progress in Chemistry, 2006 (1):24-29.
[8] JIN L, NAIRN K M, FORSYTH C M, et al. Structure and transport properties of a plastic crystal ion conductor:Diethyl (methyl) (isobutyl) phosphonium hexafluorophosphate[J]. Journal of the American Chemical Society, 2012, 134 (23):9688-9697.
[9] MACFARLANE D R, MEAKIN P, SUN J, et al. Pyrrolidinium imides:A new family of molten salts and conductive plastic crystal phases[J]. The Journal of Physical Chemistry B, 1999, 103 (20):4164-4170.
[10] ADEBAHR J, GROZEMA F C, DELEEUW S W, et al. Structure and dynamics of the plastic crystal tetramethylammonium dicyanamide-A molecular dynamics study[J]. Solid State Ionics, 2006, 177 (33):2845-2850.
[11] ABU-LEBDEH Y, ALARCO P J, ARMAND M. Conductive organic plastic crystals based on pyrazolium imides[J]. Angewandte Chemie International Edition, 2003, 42 (37):4499-4501.
[12] HAN H-B, NIE J, LIU K, et al. Ionic liquids and plastic crystals based on tertiary sulfonium and bis (fluorosulfonyl)imide[J]. Electrochimica Acta, 2010, 55 (3):1221-1226.
[13] IRANIPOUR N, GUNZELMANN D J, SEEBER A, et al. Ionic transport through a composite structure of N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystals reinforced with polymer nanofibres[J]. Journal of Materials Chemistry A, 2015, 3 (11):6038-6052.
[14] YOSHIZAWA-FUJITA M, KISHI E, SUEMATSU M, et al. A plastic electrolyte material in a highly desirable temperature range:N-ethyl-N-methylpyrrolidinium bis (fluorosulfonyl)amide[J]. Chemistry Letters, 2014, 43 (12):1909-1911.
[15] FORSYTH M, HUANG J, MACFARLANE D R. Lithium doped-methyl-ethylpyrrolidinium bis (trifluoromethanesulfonyl) amide fast-ion conducting plastic crystals[J]. Journal of Materials Chemistry, 2000, 10 (10):2259-2265.
[16] SUNARSO J, SHEKIBI Y, EFTHIMIADIS J, et al. Optimising organic ionic plastic crystal electrolyte for all solid-state and higher than ambient temperature lithium batteries[J]. Journal of Solid State Electrochemistry, 2012, 16 (5):1841-1848.
[17] PRINGLE J M. Recent progress in the development and use of organic ionic plastic crystal electrolytes[J]. Physical Chemistry Chemical Physics, 2013, 15 (5):1339-1351.
[18] JIN L, HOWLETT P C, PRINGLE J M, et al. An organic ionic plastic crystal electrolyte for rate capability and stability of ambient temperature lithium batteries[J]. Energy & Environmental Science, 2014, 7 (10):3352-3361.
[19] WANG X, ZHU H, GREENE G W, et al. Enhancement of ion dynamics in organic ionic plastic crystal/PVDF composite electrolytes prepared by co-electrospinning[J]. Journal of Materials Chemistry A, 2016, 4 (25):9873-9880.
[20] HOWLETT P C, PONZIO F, FANG J, et al. Thin and flexible solid-state organic ionic plastic crystal-polymer nanofibre composite electrolytes for device applications[J]. Physical Chemistry Chemical Physics, 2013, 15 (33):13784-13789.
[21] ZHOU Y, WANG X, ZHU H, et al. Solid-state lithium conductors for lithium metal batteries based on electrospun nanofiber/plastic crystal composites[J]. ChemSusChem, 2017, 10 (15):3135-3145.
[22] PONT A L, MARCILLA R, DE MEATZA I, et al. Pyrrolidinium-based polymeric ionic liquids as mechanically and electrochemically stable polymer electrolytes[J]. Journal of Power Sources, 2009, 188 (2):558-563.
[23] SHAPLOV A S, MARCILLA R, MECERREYES D. Recent advances in innovative polymer electrolytes based on poly (ionic liquid)s[J]. Electrochimica Acta, 2015, 175:18-34.
[24] LI X, ZHANG Z, LI S, et al. Polymeric ionic liquid-ionic plastic crystal all-solid-state electrolytes for wide operating temperature range lithium metal batteries[J]. Journal of Materials Chemistry A, 2017, 5 (40):21362-21369.
[25] YIN K, ZHANG Z, YANG L, et al. An imidazolium-based polymerized ionic liquid via novel synthetic strategy as polymer electrolytes for lithium ion batteries[J]. Journal of Power Sources, 2014, 258:150-154.
[26] CUI Z Y, XU Y Y, ZHU L P, et al. Preparation of PVDF/PEO-PPO-PEO blend microporous membranes for lithium ion batteries via thermally induced phase separation process[J]. Journal of Membrane Science, 2008, 325 (2):957-963.
[27] FERGUS J W. Ceramic and polymeric solid electrolytes for lithium-ion batteries[J]. J. Power Sources, 2010, 195 (15):4554-4569.
[28] MEYER W H. Polymer electrolytes for lithium-ion batteries[J]. Advanced Materials, 1998, 10 (6):439-448.
[29] XU K. Electrolytes and interphases in Li-ion batteries and beyond[J]. Chem. Rev., 2014, 114 (23):11503-11618.
[30] YIN K, ZHANG Z, LI X, et al. Polymer electrolytes based on dicationic polymeric ionic liquids:Application in lithium metal batteries[J]. Journal of Materials Chemistry A, 2015, 3 (1):170-178.
[31] LU Y, KORF K, KAMBE Y, et al. Ionic-liquid-nanoparticle hybrid electrolytes:applications in lithium metal batteries[J]. Angewandte Chemie International Edition, 2014, 53 (2):488-492.
[32] ZHANG J, BAI Y, SUN X G, et al. Superior conductive solid-like electrolytes:Nanoconfining liquids within the hollow structures[J]. Nano Letters, 2015, 15 (5):3398-3402.
[33] PADHI A K, NANJUNDASWAMY K S, GOODENOUGH J B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries[J]. Journal of the Electrochemical Society, 1997, 144 (4):1188-1194.
[34] LI X, ZHANG Z, LI S, et al. Polymeric ionic liquid-plastic crystal composite electrolytes for lithium ion batteries[J]. Journal of Power Sources, 2016, 307:678-683.
[35] WU F, TAN G, CHEN R, et al. Novel solid-state Li/LiFePO₄ battery configuration with a ternary nanocomposite electrolyte for practical applications[J]. Advanced Materials, 2011, 23 (43):5081-5085.

锂离子电池用离子塑性晶体-离子液体聚合物全固态电解质

Novel ionic plastic crystal-polymeric ionic liquid all-solid-state electrolytes for lithium ion batteries

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	李海涛, 孔令丽, 张欣, 余传军, 王纪威, 徐琳. N/P设计对高镍NCM/Gr电芯性能的影响[J]. 储能科学与技术, 2022, 11(7): 2040-2045.
[2]	刘显茜, 孙安梁, 田川. 基于仿生翅脉流道冷板的锂离子电池组液冷散热[J]. 储能科学与技术, 2022, 11(7): 2266-2273.
[3]	陈龙, 夏权, 任羿, 曹高萍, 邱景义, 张浩. 多物理场耦合下锂离子电池组可靠性研究现状与展望[J]. 储能科学与技术, 2022, 11(7): 2316-2323.
[4]	易顺民, 谢林柏, 彭力. 基于VF-DW-DFN的锂离子电池剩余寿命预测[J]. 储能科学与技术, 2022, 11(7): 2305-2315.
[5]	祝庆伟, 俞小莉, 吴启超, 徐一丹, 陈芬放, 黄瑞. 高能量密度锂离子电池老化半经验模型[J]. 储能科学与技术, 2022, 11(7): 2324-2331.
[6]	王宇作, 王瑨, 卢颖莉, 阮殿波. 孔结构对软碳负极储锂性能的影响[J]. 储能科学与技术, 2022, 11(7): 2023-2029.
[7]	孔为, 金劲涛, 陆西坡, 孙洋. 对称蛇形流道锂离子电池冷却性能[J]. 储能科学与技术, 2022, 11(7): 2258-2265.
[8]	霍思达, 薛文东, 李新丽, 李勇. 基于CiteSpace知识图谱的锂电池复合电解质可视化分析[J]. 储能科学与技术, 2022, 11(7): 2103-2113.
[9]	邓健想, 赵金良, 黄成德. 高能量锂离子电池硅基负极黏结剂研究进展[J]. 储能科学与技术, 2022, 11(7): 2092-2102.
[10]	欧宇, 侯文会, 刘凯. 锂离子电池中的智能安全电解液研究进展[J]. 储能科学与技术, 2022, 11(6): 1772-1787.
[11]	韩俊伟, 肖菁, 陶莹, 孔德斌, 吕伟, 杨全红. 致密储能：基于石墨烯的方法学和应用实例[J]. 储能科学与技术, 2022, 11(6): 1865-1873.
[12]	辛耀达, 李娜, 杨乐, 宋维力, 孙磊, 陈浩森, 方岱宁. 锂离子电池植入传感技术[J]. 储能科学与技术, 2022, 11(6): 1834-1846.
[13]	燕乔一, 吴锋, 陈人杰, 李丽. 锂离子电池负极石墨回收处理及资源循环[J]. 储能科学与技术, 2022, 11(6): 1760-1771.
[14]	沈秀, 曾月劲, 李睿洋, 李佳霖, 李伟, 张鹏, 赵金保. γ射线辐照交联原位固态化阻燃锂离子电池[J]. 储能科学与技术, 2022, 11(6): 1816-1821.
[15]	丁奕, 杨艳, 陈锴, 曾涛, 黄云辉. 锂离子电池智能消防及其研究方法[J]. 储能科学与技术, 2022, 11(6): 1822-1833.