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化学进展 2021, Vol. 33 Issue (12): 2270-2282 DOI: 10.7536/PC201145 前一篇   后一篇

• 综述 •

锂电池中的凝胶聚合物电解质

杨琪1,2, 邓南平2,*(), 程博闻2, 康卫民1,2,*()   

  1. 1 天津工业大学纺织科学与工程学院 天津 300387
    2 天津工业大学分离膜与膜过程国家重点实验室 天津 300387
  • 收稿日期:2020-12-01 修回日期:2021-01-26 出版日期:2021-03-04 发布日期:2021-03-04
  • 通讯作者: 邓南平, 康卫民
  • 基金资助:
    国家自然科学基金项目(51973157); 国家自然科学基金项目(51673148); 国家自然科学基金项目(51678411); 国家博士后科研基金(2019M651047); 天津市科技计划(19PTSYJC00010)
Richhtml ( 274 ) 引用

Gel Polymer Electrolytes in Lithium Batteries

Qi Yang1,2, Nanping Deng2(), Bowen Cheng2, Weimin Kang1,2()   

  1. 1 School of Textile Science and Engineering, Tiangong University,Tianjin 300387, China
    2 State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University,Tianjin 300387, China
  • Received:2020-12-01 Revised:2021-01-26 Online:2021-03-04 Published:2021-03-04
  • Contact: Nanping Deng, Weimin Kang
  • Supported by:
    the National Natural Science Foundation of China(51973157); the National Natural Science Foundation of China(51673148); the National Natural Science Foundation of China(51678411); the China Postdoctoral Science Foundation(2019M651047); the Science and Technology Plans of Tianjin(19PTSYJC00010)

锂电池目前在人们生活中已经得到广泛应用,但是传统的液体电解质沸点低且易泄漏,容易引起锂枝晶生长和安全问题。凝胶聚合物电解质(GPEs)的状态介于液态电解质和固态电解质之间,不仅可以作为电解质,还可以作为隔膜,这样可以减少液体电解质的泄漏以及改善固体电解质的界面电阻。本文综述了锂电池中制备不同类型的GPEs的方法,如溶液浇铸法、相转化法、原位聚合法、UV(紫外)固化法和静电纺丝法等,重点总结了不同纤维基的GPEs(聚(偏二氟乙烯)(PVDF)、聚(偏二氟乙烯-共六氟丙烯)(PVDF- HFP)、聚甲基丙烯酸甲酯(PMMA)、聚丙烯腈(PAN)和聚间亚苯基间苯二甲酰胺(PMIA))在锂电池中的运用,并通过对不同基质的改性来改善电解质的离子电导率,阻碍锂枝晶的生长。最后,本文对锂电池中GPEs的未来发展前景进行了展望,讨论和提出的策略将为今后高性能锂电池的实际应用提供更多的途径。

关键词： 凝胶聚合物电解质, 锂电池, 界面稳定性, 离子电导率

Lithium batteries have been widely used. However, traditional liquid electrolyte applied in the cell bring about unsatisfactory growth of lithium dendrite and safety problems due to its leak and low boiling point. Gel polymer electrolytes (GPEs) are intermediate substance between liquid electrolyte and solid electrolyte, which can act as not only electrolyte, but also battery separator, which reduce leakage risk of liquid electrolytes and high interface resistance of solid electrolytes. In the review, the preparation methods of different types of GPEs in lithium batteries, such as solution casting, phase conversion, in-situ polymerization, UV(ultraviolet) curing and electrospinning methods are concluded, and the applications of different fibers-based GPEs (poly (vinylidenefluoride, PVDF), poly (vinylidene fluoride-co-hexafluoropropene, PVDF-HFP), polymethyl methacrylate (PMMA), poly acrylonitrile (PAN) and poly-m-phenyleneisophthalamide (PMIA)) in lithium batteries are emphatically summarized. Finally, we conclude with an outlook section to provide some insights on the future prospects of GPEs in lithium batteries. The discussion and proposed strategies in the review will offer more avenues to the practical application of lithium batteries with high electrochemical performance in the future.

Contents

1 Introduction

2 Preparation methods of GPEs

2.1 Solution casting method

2.2 Phase inversion method

2.3 In-situ polymerization technology

2.4 UV curing technology

2.5 Electrospining method

3 GPEs in lithium ion batteries

3.1 GPEs based on PVDF

3.2 GPEs based on PVDF-HFP

3.3 GPEs based on PMMA

3.4 GPEs based on PAN

3.5 GPEs based on PMIA

3.6 Others

4 Conclusion and outlook

Key words: gel polymer electrolytes, lithium batteries, interfacial stability, ionic conductivity
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图1 锂离子电池充放电原理图[1]
Fig.1 The Schematic diagram of charging and discharging of lithium ion battery[1]
图2 PP负载的POSS-(C3H6Cl)8/PVDF GPE膜的制备过程[36]
Fig.2 Preparation of POSS-(C3H6Cl)8/PVDF GPE membrane supported by PP[36]
图3 原始PVDF和PVDF/石墨烯聚合物电解质的SEM图像:(a~c)原始PVDF,(d~f)PVDF/石墨烯,(a、d)俯视图,(b、e)横视图,(c、f)仰视图[39]
Fig.3 SEM images of pristine PVDF and PVDF/graphene polymer electrolyte: (a~c) pristine PVDF, (d~f) PVDF/graphene, (a, d) top view, (b, e) cross-section view, (c, f) bottom view[39]
图4 (a)微球形成的示意图;(b)微球对GPE性能的影响[41]
Fig.4 (a) Schematic representations of the formation of microspheres; (b) the effects of microspheres on the GPE properties[41]
图5 动力学图示演示了(a)0%、(b)30%和(c)50% LiSnOS凝胶电解质混合电池的充电状态[65].
Fig.5 The schematic kinetic presentation to demonstrate the charging state of hybrid batteries with (a) 0%, (b) 30%, and (c) 50% LiSnOS in the gel electrolyte[65]
图6 PVDF-HFP/LLZO复合分离器的微观结构[53]
Fig.6 The proposed microstructure of the PVDF-HFP/LLZO composite separator[53]
图7 PHP@PHL纤维的TEM图[34]
Fig.7 TEM diagram of PHP@PHL fiber[34]
图8 凝胶聚合物电解质的制备程序:(a)在电池组件上原位聚合,用于锂电池;(b)在隔膜上原位聚合,用于LSV测量;(c)用于电导率和LSV测量的自支撑膜[67]
Fig.8 Preparation procedure for gel polymer electrolytes: (a) in situ polymerized on cell components for use in lithium-ion cells;(b) in situ polymerized on separator for use in LSV measurements; (c) self-standing membrane for use in conductivity and LSV measurements[67]
图9 原始PAN膜(a、b、c)和PAN/OMMT(d、e、f)的SEM图像:俯视图(a、d),仰视图(b、e),横截面(c、f)[16]
Fig.9 SEM images of pristine PAN membrane (a, b, c) and PAN/OMMT membrane (d, e, f): upper view (a, d), bottom view (b, e), cross section (c, f)[16]
图10 相转化法的相关机制[26]
Fig.10 The related illustrations of phase inversion method[26]
图11 纤维素/聚乙二醇GPE的锂离子传输机理原理图[27]
Fig.11 The schematic of lithium-ion transporting mechanism of cellulose/PEG GPE[27]
图12 (a)GPE@LFP阴极和GPE@LFP//CGPE//Li电池制备路线示意图;(b)GPE@LFP阴极和(c)GPE@LFP//CGPE//Li电池微观模型;(d)LFP阴极的SEM图像;(e)GPE@LFP阴极;(f)GPE@LFP阴极的TEM图像[88]
Fig.12 (a) Schematic illustration for the preparation route of GPE@LFP cathode and GPE@LFP//CGPE//Li cell; microscopic model of (b) GPE@LFP cathode and (c) GPE@LFP//CGPE//Li cell; SEM images of (d) LFP cathode; (e) GPE@LFP cathode; f) TEM images of GPE@LFP cathode[88]
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