物理化学学报 >> 2022, Vol. 38 >> Issue (3): 2001007.doi: 10.3866/PKU.WHXB202001007

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石墨烯嵌锂的拉曼成像

唐诗怡1,2, 鹿高甜3, 苏毅3, 王广3, 李炫璋3, 张广琦3, 魏洋3,*(), 张跃钢2,3,*()   

  1. 1 上海大学材料科学与工程学院,上海 200444
    2 中国科学院苏州纳米技术与纳米仿生研究所,江苏 苏州 215123
    3 清华大学物理系,清华-富士康纳米科技研究中心,北京 100084
  • 收稿日期:2020-01-02 录用日期:2020-03-06 发布日期:2020-03-16
  • 通讯作者: 魏洋,张跃钢 E-mail:weiyang@tsinghua.edu.cn;yuegang.zhang@tsinghua.edu.cn
  • 基金资助:
    国家重点研发计划(2016YFB0100100);国家重点研发计划(2018YFA0208401);国家自然科学基金(21433013);国家自然科学基金(61774090);国家自然科学基金(51472142);中国科学院国际合作局对外合作重点项目(121E32KYSB20150004)

Raman Mapping of Lithiation Process on Graphene

Shiyi Tang1,2, Gaotian Lu3, Yi Su3, Guang Wang3, Xuanzhang Li3, Guangqi Zhang3, Yang Wei3,*(), Yuegang Zhang2,3,*()   

  1. 1 School of Materials Science and Engineering, Shanghai University, Shanghai 20044, China
    2 Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, Jiangsu Province, China
    3 Department of Physics & Tsinghua-Foxconn Nanotechnology Research Center, Tsinghua University, Beijing 100084, China
  • Received:2020-01-02 Accepted:2020-03-06 Published:2020-03-16
  • Contact: Yang Wei,Yuegang Zhang E-mail:weiyang@tsinghua.edu.cn;yuegang.zhang@tsinghua.edu.cn
  • About author:Email: yuegang.zhang@tsinghua.edu.cn; Tel.: +86-10-62788965 (Y.Z.)
    Email: weiyang@tsinghua.edu.cn; +86-10-62794280 (Y.W.)
  • Supported by:
    the National Key R & D Program of China(2016YFB0100100);the National Key R & D Program of China(2018YFA0208401);the National Natural Science Foundation of China(21433013);the National Natural Science Foundation of China(61774090);the National Natural Science Foundation of China(51472142);the CAS-DOE Joint Research Program(121E32KYSB20150004)

摘要:

锂离子电池由于具有高能量密度,高循环寿命,低自放电率的优势,成为当前使用最为广泛的储能器件。层状材料是极为常用的负极材料,其微观嵌锂行为的研究对提高电池的能量密度和循环寿命有重要意义。本工作发展了一种新的平板微电池结构,可用于研究锂离子在各类二维层状纳米材料中的嵌锂行为。我们用机械剥离的单片少层石墨烯为正极,热蒸镀的锂金属为负极,构成石墨烯电池,用恒电压放电的方法进行嵌锂测试。采用拉曼成像技术收集石墨烯G峰信号的空间分布,实现对锂的嵌入过程的显微观测。发现了锂在石墨烯中沿层间扩散迁移,以及石墨烯断层对锂扩散的阻碍作用。这些结果有助于理解放电时锂在石墨烯电极中扩散过程,并且这项研究开发的平板微电池结构可用于多种材料的电化学过程中的微观过程表征,同时可实现与光学、电学、电子显微学等多种表征手段的兼容,具有较好的应用前景。

关键词: 平板微电池, 石墨烯, 嵌锂, 拉曼成像, 断层

Abstract:

Lithium-ion batteries are the most widely used energy storage device owing to their advantages such as high energy density, high cycle life, and low self-discharge rate. Because two-dimensional (2D) materials are commonly used as anode materials, the study of their lithiation behaviors is significant for improving the energy density and cycle life of batteries. Although some spectroscopic methods have been developed for studying the intercalation/deintercalation process of lithium in graphene, a new characterization technique that can directly investigate ion diffusion pathways at a microscale level would be beneficial to provide more detailed information on the mechanism of electrochemical reactions. It is an efficient solution to utilize the high spatial resolution of microscopic characterization to study the microscale electrochemical process. For this purpose, it becomes necessary to develop special specimens and setups that can undergo electrochemical experiments and are also compatible with microscopic characterization techniques. Herein, we developed a new planar micro-battery architecture on a SiO2-coated silicon substrate that can be used to study the lithiation behaviors of various 2D materials using the micro-Raman mapping technique. In this planar micro-battery, the mechanically exfoliated few-layer graphene was used as the positive electrode, the thermal-evaporated lithium metal was employed as the negative electrode, and the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide with lithium bis(trifluoromethane)sulfonimide was used as the electrolyte. The micro-battery was tested using the galvanostatic discharge method on a probe station in an argon glove box. The selected lab-on-chip solution makes the lithiation of graphene observable under the micro-Raman spectroscope with a high spatial resolution. Raman mapping was successfully performed and graphene G-band signals were observed. Based on the facts that a small amount of lithium intercalation in graphene induces a blueshift of its G-band, and a large amount of lithium intercalation induces the splitting of the G-band into G- and G+, we can correlate the degree of lithiation in graphene with its G-band signals and thus monitor the lithium intercalation process on graphene in the planar micro-battery. The time-dependent lithium distribution in graphene at different discharge stages could be obtained by comparing the G-band Raman mapping images to the corresponding optical micrographs. On the basis of these analyses, it was found that lithium ions diffuse between the layers in graphene and terminate at the graphene fault. These results help us understand the diffusion process of lithium in the graphene electrode during discharge. Moreover, the as-developed micro-battery is compatible with more characterization methodologies, such as optical microscopy, electrical transport, and electron microscopy, providing a broad application platform.

Key words: Planar micro-battery, Graphene, Lithiation, Raman mapping, Fault

MSC2000: 

  • O646