原位透射电镜技术在电池领域的研究进展

doi:10.12028/j.issn.2095-4239.2019.0117

储能科学与技术 ›› 2019, Vol. 8 ›› Issue (6): 1050-1061.doi: 10.12028/j.issn.2095-4239.2019.0117

• 锂电池失效分析与测试技术专刊 • 上一篇下一篇

原位透射电镜技术在电池领域的研究进展

张利强¹, 唐永福², 刘秋男¹, 孙海明¹, 杨婷婷¹, 黄建宇^1,3

1 清洁纳米能源中心, 亚稳材料制备技术与科学国家重点实验室, 燕山大学材料科学与工程学院, 河北秦皇岛 066004;
2 燕山大学环境与化学工程学院, 河北秦皇岛 066004;
3 湘潭大学材料科学与工程学院, 湖南湘潭 411105

收稿日期:2019-06-03 修回日期:2019-06-29 出版日期:2019-11-01 发布日期:2019-07-31
通讯作者: 黄建宇,教授,主要研究方向为新能源材料,E-mail:jhuang@ysu.edu.cn。
作者简介:张利强(1985-),男,副研究员,主要研究方向为原位透射电子显微学,E-mail:liqiangzhang85@163.com
基金资助:
国家自然科学基金（51772262），国家重点研发计划（2018YFB0104300，2017YFB0702001）项目。

Review of in situ transmission electron microscopy studies of battery materials

ZHANG Liqiang¹, TANG Yongfu², LIU Qiunan¹, SUN Haiming¹, YANG Tingting¹, HUANG Jianyu^1,3

1 Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, School of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004, Hebei, China;
2 Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, Hebei, China;
3 School of Materials Science and Engineering, Xiangtan University, Xiangtan 411105, Hunan, China

Received:2019-06-03 Revised:2019-06-29 Online:2019-11-01 Published:2019-07-31

摘要/Abstract

摘要： 本文总结了原位透射电镜在电池研究领域的一些重要研究进展。虽然经过多年的研究，但是电极材料以及其与电解质界面（SEI）在充放电过程中结构、形貌、成分的变化过程还不清楚，以上结构演化与电池性能的相关性更是了解甚少，急需要设计一种新的实验技术可以在微观尺度上对其变化进行观察，原位透射电镜技术正是为了满足这样的需求而设计的。原位电镜拥有高时空分辨率和能量分辨率，可实时观察各类纳米电极材料及SEI在充放电过程中的微观变化。本文首先讨论在透射电镜中组装纳米电池的实验方法，然后讨论了应用此技术在研究锂离子电池、金属空气电池等领域的一些重要研究进展，最后对应用原位透射电镜技术研究电池的未来发展方向进行展望。原位透射电镜技术可以直接和实时观察电极材料和SEI在电化学反应中的微观变化行为，这对于深入了解电池失效机理和设计高性能电池具有重要指导意义。

关键词: 原位电镜, 锂离子电池, 金属空气电池, 纳米电池, SEI

Abstract: This review summarizes recent important research progress in the field of in situ transmission electron microscopy (TEM) studies of batteries. Although enormous efforts have been devoted to understanding the fundamental electrochemistry of batteries, the structure, morphology and composition evolution of the electrode materials during charging and discharging are still unclear. Furthermore, how to correlate microstructure evolution with battery performance is still challenging. Thus, it is important to develop advanced in situ TEM techniques to monitor structural evolution of electrode materials during cycling in real time and to correlate the structural information with the batteries performance so as to advance our understanding of batteries. In this review, we firstly summarize the experimental techniques of assembling nano batteries under high vacuum condition in TEM to enable battery studies. Then discuss important research progress in the application of in situ techniques in the research of lithium/sodium ion batteries and metal air batteries. Finally, perspectives on future directions on the application of in situ TEM in battery studies are provided. The in situ TEM technology can directly and in real-time observe the microscopic behavior of battery materials in electrochemical reactions, deepen the understanding of the failure behavior of battery materials in charge and discharge, and provide a scientific basis for the design of high-stability batteries and broaden their application fields.

Key words: in situ TEM, lithium ion batteries, metal air batteries, nano batteries, SEI

中图分类号:

TK911

张利强, 唐永福, 刘秋男, 孙海明, 杨婷婷, 黄建宇. 原位透射电镜技术在电池领域的研究进展[J]. 储能科学与技术, 2019, 8(6): 1050-1061.

ZHANG Liqiang, TANG Yongfu, LIU Qiunan, SUN Haiming, YANG Tingting, HUANG Jianyu. Review of in situ transmission electron microscopy studies of battery materials[J]. Energy Storage Science and Technology, 2019, 8(6): 1050-1061.

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[16] KONG F, KOSTECKI R, NADEAU G, et al. In situ studies of SEI formation[J]. Journal of Power Sources, 2001, 97:58-66.
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[20] YAO L B, XIA W W, ZHANG H T, et al. In situ visualization of sodium transport and conversion reactions of FeS₂ nanotubes made by morphology engineering[J]. Nano Energy, 2019, 60:424-431.
[21] LIU H H, ZHENG H, LI L, et al. Surface-coating-mediated electrochemical performance in CuO nanowires during the sodiation-desodiation cycling[J]. Advanced Materials Interfaces, 2018, 5(4):1701255.
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[23] ZHOU W D, WANG C M, ZHANG Q L, et al. Tailoring pore size of nitrogen-doped hollow carbon nanospheres for confining sulfur in lithium-sulfur batteries[J]. Advanced Energy Materials, 2015, 5(16):1401752.
[24] LIU W R, YANG M H, WU H C, et al. Enhanced cycle life of Si anode for Li-ion batteries by using modified elastomeric binder[J]. Electrochemical and Solid-State Letters, 2005, 8(2):A100-A103.
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[35] KANG B, CEDER G. Battery materials for ultrafast charging and discharging[J]. Nature, 2009, 458(7235):190-193.
[36] CUI L-F, RUFFO R, CHAN C K, et al. Crystalline-amorphous core-shell silicon nanowires for high capacity and high current battery electrodes[J]. Nano Letters, 2008, 9(1):491-495.
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[43] LIU Q N, GENG L, YANG T T, et al. In situ imaging electrocatalysis in a Na-O₂ battery with Au-coated MnO₂ nanowires air cathode[J]. Energy Storage Materials, 2019,19:48-55.
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[46] ZHANG L Q, TANG Y S, LIU Q N, et al. Probing the charging and discharging behavior of K-CO₂ nanobatteries in an aberration corrected environmental transmission electron microscope[J]. Nano Energy, 2018, 53:544-549.
[47] LI Y Z, LI Y B, PEI A, et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy[J]. Science, 2017, 358(6362):506-510.
[48] ZACHMAN M J, TU Z Y, CHOUDHURY S, et al. Cryo-STEM mapping of solid-liquid interfaces and dendrites in lithium-metal batteries[J]. Nature, 2018, 560(7718):345-349.
[49] GAO P, ISHIKAWA R, TOCHIGI E, et al. Atomic-scale tracking of a phase transition from spinel to rocksalt in Lithium Manganese Oxide[J]. Chemistry of Materials, 2017, 29(3):1006-1013.
[50] YAN P F, ZHENG J M, TANG Z-K, et al. Injection of oxygen vacancies in the bulk lattice of layered cathodes[J]. Nature Nanotechnology, 2019, 14:602-608.
[51] GONG Y, ZHANG J N, JIANG L W, et al. In situ atomic-scale observation of electrochemical delithiation induced structure evolution of LiCoO₂ cathode in a working all-solid-state battery[J]. Journal of the American Chemical Society, 2017, 139(12):4274-4277.

原位透射电镜技术在电池领域的研究进展

Review of in situ transmission electron microscopy studies of battery materials

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