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化学进展 2021, Vol. 33 Issue (1): 124-135 DOI: 10.7536/PC200684 前一篇   后一篇

• 综述 •

高陶瓷含量复合固态电解质

刘秋艳1,2, 王雪锋1,*(), 王兆翔1,2,*(), 陈立泉1   

  1. 1 中国科学院物理研究所 北京 100190
    2 中国科学院大学材料与光电技术学院 北京 100049
  • 收稿日期:2020-06-28 修回日期:2020-08-16 出版日期:2021-01-24 发布日期:2020-09-10
  • 通讯作者: 王雪锋, 王兆翔
  • 作者简介:
    * Corresponding author e-mail: (Xuefeng Wang); (Zhaoxiang Wang)
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Composite Solid Electrolytes with High Contents of Ceramics

Qiuyan Liu1,2, Xuefeng Wang1,*(), Zhaoxiang Wang1,2,*(), Liquan Chen1   

  1. 1 Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
    2 College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2020-06-28 Revised:2020-08-16 Online:2021-01-24 Published:2020-09-10
  • Contact: Xuefeng Wang, Zhaoxiang Wang

全固态锂二次电池兼具高能量密度和高安全性特点。高陶瓷含量的陶瓷-聚合物复合固态电解质综合了聚合物电解质的柔韧性和陶瓷电解质的高机械强度与高锂离子迁移数等优点,有望优先其他形式固态电解质应用于全固态锂二次电池。本文在简要介绍固态复合电解质后,重点从复合电解质膜的性能特点与制备方法、陶瓷-聚合物界面相互作用以及由此导致的新的离子传导机制等方面介绍高陶瓷含量陶瓷-聚合物复合固态电解质的研究进展。最后,展望了复合固态电解质所面临的一些基础科学与应用问题,并从陶瓷-聚合物界面相互作用角度提出未来复合固态电解质的研究方向和可能的解决方案。我们希望本文对于其他传导离子的复合电解质也有借鉴和启发意义。

关键词： 复合固态电解质, 离子电导率, 离子传输机制, 固态锂电池, 金属锂

The all-solid secondary lithium batteries are characteristic of high energy density and high safety. Combining the high flexibility of the polymer electrolytes and the high mechanical strength and high Li-ion transference number of the ceramic electrolytes, the ceramic-polymer composite solid electrolytes with high ceramic contents(HCC) are expected to find applications prior to the other solid electrolytes in the all-solid secondary lithium batteries. Following a brief introduction on the composite solid electrolytes, the recent advances of the HCC ceramic-polymer composite electrolyte are reviewed in the general performances of the composite electrolytes, the fabrications of their membranes, the ceramic-polymer interfacial interactions and the resultant new ionic transport mechanisms. At the end of this review, we prospect the fundamental and applicable issues that the HCC composite electrolytes have to meet and propose the future research directions and possible solutions to these questions. We wish that this review could be of help for the R&D of the composite solid electrolytes of other ions as well.

Contents

1 Introduction

2 Composite solid electrolytes with high ceramic contents

2.1 Characteristics of high ceramic-contents composite electrolytes

2.2 Fabrication of high ceramic-content composite membranes

3 Ceramic-polymer interactions and extra Li-ion transport passage

3.1 Ceramic-polymer interfacial interactions

3.2 Optimization of ceramic-polymer composite electrolytes

4 Conclusion and perspectives

Key words: composite solid electrolyte, ionic conductivity, mechanism of ion transport, solid lithium battery, lithium metal
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表1 一些高陶瓷含量复合固态电解质及其性质[30,32,33,38,40,43,44,54,58 ?~60,103,106 ? ?~109]
Table 1 Some composite solid electrolytes with high contents of ceramics[30,32,33,38,40,43,44,54,58 ?~60,103,106 ? ?~109]
Composition Conductivity t Li E.C.W ref
3 g PEC, 0.5 g P(VDF-HFP), 6 g LiFSI / 7 g LLZO nano particles 52.4 at 55 ℃ 0.82 4.8 30
PEO+BPEG+LiTFSI(EO/Li +=20∶1 m/m) / 70%(w/w) LATP micron particles 250 at 60 ℃ 0.49 / 32
PEO+LiTFSI(EO/Li +=10∶1 m/m) / 62%(w/w) 3D LLZO framework 85 at 25 ℃,1000 at 60 ℃ / 5 33
PEO+LiTFSI(EO/Li +=5/4 w/w) / 95%(w/w) LPS 531 at RT / / 38
PEO+LiTFSI(EO/Li +=2∶1 w/w) / 50%(w/w) 3D LLZO 89 at RT 0.27 5.5 40
PEO+LiTFSI(EO/Li +=12∶1 m/m) / 70%(w/w) LLZO 85 at 60 ℃ 0.29 5 43
PEO+LiClO 4(EO/Li +=15∶1 m/m) / 70%(w/w) Al-LLZO 7.59 at 25 ℃, 1930 at 70 ℃ / 5 44
PEGDA+LiTFSI(EO/Li +=12∶1 m/m) / 50%(w/w) Silane-modified
LLAZO nanofibers 		470 at RT 0.41 5.3 54
PEO+LiTFSI(EO/Li +=8∶1 m/m) / 50%(w/w) LAGP 30.9 at 25 ℃ / / 58
PPC+LiFSI(PC/Li +=1/4 w/w) / 80%(w/w) LAGP 210 at 25 ℃ / / 59
PEO+PEG+LiTFSI(EO/Li +=2∶3 w/w) / 80%(w/w) LLZTO micron particles 62.4 at 25 ℃, 524 at 80 ℃ / 5.2 60
PEO+LiTFSI(EO/Li +=10∶1 m/m) / 80%(w/w) LLZTO micron particles 55 at RT 0.4 5 103
PEO+LiTFSI(EO/Li +=8∶1 m/m) / 80%(w/w) PDA modified LLZTO nano particles 110 at 30 ℃ / 4.8 106
PEO+LiTFSI(EO/Li +=12∶1 m/m) / 56%(w/w) 3D LLZAO framework 251 at RT 0.53 5.58 107
PEO+PEG+LiClO 4(EO/Li +=8∶1 m/m) / 40%(v/v) Aligned LATP nano particles 52 at RT / / 108
PEO+PEG+LiTFSI(EO/Li +=8∶1 m/m) / 40%(v/v) Aligned LAGP nano particles 167 at RT 0.56 4.5 109
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摘要

高陶瓷含量复合固态电解质