CuF2/MoO3/C复合正极的电化学阻抗谱研究

doi:10.61558/2993-074X.2108

电化学（中英文） ›› 2013, Vol. 19 ›› Issue (2): 155-163. doi: 10.61558/2993-074X.2108

CuF₂/MoO₃/C复合正极的电化学阻抗谱研究

史月丽，吴楠，沈明芳，董佳群，庄全超^*，江利

中国矿业大学材料科学与工程学院锂离子电池实验室，江苏徐州 221116

收稿日期:2012-07-16 修回日期:2012-08-30 出版日期:2013-04-28 发布日期:2012-09-10
通讯作者: 庄全超 E-mail:zqc209@126.com
基金资助:
2012年中国矿业大学高水平论文专项基金（No. 2012LWB13）资助

An Electrochemical Impedance Spectroscopic Study of CuF₂/MoO₃/C Cathode Composites

SHI Yue-li, WU Nan, SHEN Ming-fang, DONG Jia-qun, ZHUANG Quang-chao^*, JIANG Li

School of Materials Science and Engineering, China University of Mining & Technology, Xuzhou 221166, Jiangsu, China

Received:2012-07-16 Revised:2012-08-30 Published:2013-04-28 Online:2012-09-10
Contact: ZHUANG Quang-chao E-mail:zqc209@126.com

摘要/Abstract

摘要： 采用球磨方法制备了CuF₂/MoO₃/C复合材料电极，利用X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、恒流充放电、循环伏安（CV）和电化学阻抗谱（EIS）等方法表征与观察复合材料的结构与形貌，测试了电极的电化学性能. 结果表明，球磨CuF₂和MoO₃晶粒的尺寸为200 ～ 300 nm. CuF₂/MoO₃/C复合电极10 mA?g-1电流密度首次放电容量为647 mAh.g^-1，但随之复合材料循环寿命迅速衰减.循环伏安曲线首次放电，2.2 V左右出现了一个还原峰，第2、3周期该还原峰电位升至3.2 V左右. CuF₂/MoO₃/C复合电极的Nyquist图由高、中频区两个半圆串接和一条斜线组成. 放电过程，高频区半圆相应于锂离子扩散多层SEI膜，还与电极材料与集流体的接触有关. 中频区半圆与CuF₂和MoO₃及C的肖特基接触有关. 低频区斜线反映扩散传递过程. CuF₂/MoO₃/C电极电荷传递阻力较大，这可能也是CuF₂/MoO₃/C电极容量较快衰减的原因.

关键词: CuF₂/MoO₃/C复合材料, 转化反应, 电化学阻抗谱, 肖特基接触阻抗

Abstract: Composite electrode of CuF₂/MoO₃/C was fabricated through high energy mechanical milling. The properties of CuF₂/MoO₃/C were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (TEM), galvanostatic charge-discharge measurements, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the grain sizes of CuF₂ and MoO₃ after milling were 200 ~ 300 nm, and the initial discharge capacity of CuF₂/MoO₃/C was 647 mAh?g-1 at room temperature and at a current density of 10 mA.g^-1. However, the capacity decayed rapidly in the next cycles. CV curves showed one reduction peak at 2.2 V in the first cycle and another one at 3.2 V in the following cycles. The Nyquist diagram of CuF₂/MoO₃/C electrode consisted of two semicircles and one line. During the discharge process, the high frequency semicircle (HFS) may be associated with not only the Li⁺ migration through the SEI film, but also contact resistance between the CuF₂/MoO₃/C composites and the current collector. The middle frequency semicircle (MFS) should be related to the Schottky contact between CuF₂ and conductive agents, which may be the important feature of such composites materials with big band gap. Besides the low frequency line may be related to the diffusion step. A very large value of charge transfer resistance for the CuF₂/MoO₃/C electrode may induce the rapid decay in capacity.

Key words: CuF2/MoO3/C composite electrode, conversion reactions, electrochemical impedance spectra, Schottky contact impedance

中图分类号:

TM912.9

史月丽, 吴楠, 沈明芳, 董佳群, 庄全超, 江利. CuF₂/MoO₃/C复合正极的电化学阻抗谱研究[J]. 电化学（中英文）, 2013, 19(2): 155-163.

SHI Yue-li, WU Nan, SHEN Ming-fang, DONG Jia-qun, ZHUANG Quang-chao, JIANG Li. An Electrochemical Impedance Spectroscopic Study of CuF₂/MoO₃/C Cathode Composites[J]. Journal of Electrochemistry, 2013, 19(2): 155-163.

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https://electrochem.xmu.edu.cn/CN/Y2013/V19/I2/155

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CuF₂/MoO₃/C复合正极的电化学阻抗谱研究

An Electrochemical Impedance Spectroscopic Study of CuF₂/MoO₃/C Cathode Composites

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