微氧化处理对球形石墨结构及电化学行为的影响

doi:10.3724/SP.J.1077.2012.00151

无机材料学报 ›› 2012, Vol. 27 ›› Issue (2): 151-156.DOI: 10.3724/SP.J.1077.2012.00151 CSTR: 32189.14.SP.J.1077.2012.00151

微氧化处理对球形石墨结构及电化学行为的影响

简志敏¹, 刘洪波¹, 石磊¹, 何月德¹, 肖海河¹, 匡加才²

(1．湖南大学材料科学与工程学院, 长沙 410082; 2. 长沙理工大学材料科学与工程研究所, 长沙 410114)

收稿日期:2011-06-10 修回日期:2011-09-06 出版日期:2012-02-10 网络出版日期:2012-01-05
作者简介:简志敏(1987-), 男, 硕士研究生. E-mail: jianzhimin-001@163.com
基金资助:
国土资源部公益性行业科研专项经费(201011031);湖南省国土资源厅科技项目(2010-08)

Influences of Mild Oxidation Treatment on the Structure and Electrochemical Behavior of Spherical Graphite

JIAN Zhi-Min¹, LIU Hong-Bo¹, SHI Lei¹, HE Yue-De¹, XIAO Hai-He¹, KUANG Jia-Cai²

(1. College of Materials Science and Engineering, Hunan University, Changsha 410082, China; 2. Research institute of Materials Science and Engineering, Changsha University of Science and Technology, Changsha 410114, China)

Received:2011-06-10 Revised:2011-09-06 Published:2012-02-10 Online:2012-01-05
About author:JIAN Zhi-Min. E-mail: jianzhimin-001@163.com

摘要/Abstract

摘要：

研究了微氧化处理对球形石墨的晶体结构、表面形貌和电化学行为的影响. 采用XRD、Raman光谱和SEM等手段分析了样品的结构和形貌, 并采用恒电流充放电测试、粉末微电极技术和慢速扫描循环伏安法(SSCV)研究了微氧化前后石墨负极的电化学行为. 结果表明, 微氧化后石墨颗粒中的结构缺陷增多, 近表面区域的无序度增大, 面内平均晶粒尺寸L_a减小, 且菱形相含量降低, 石墨呈不规则的鳞片状, 部分层面的边缘有卷曲与刻蚀现象. 微氧化后石墨负极的第三次脱锂容量从345.5 mAh/g增加至381.4 mAh/g, 且其循环性能得到有效改善. 同时, 微氧化后锂离子较容易从石墨中脱出, 脱锂过程中一阶Li-GICs(lithium-graphite intercalation compounds, 简称Li-GICs)向二阶Li-GICs的阶转变可在较低的电位下发生.

关键词: 锂离子电池, 负极材料, 球形石墨, 氧化处理, 电化学行为

Abstract:

The effects of mild oxidation treatment on the crystal structure, morphology and electrochemical behavior of spherical graphite were investigated. The structure and morphology of the samples were characterized by XRD, Raman spectra and SEM analysis, respectively. The electrochemical behavior of the samples was studied using galvanostatic charge/discharge test, powder cavity microelectrode technique and slow scan rate cyclic voltammograms. The results indicate that structural defects in graphite particles and disordered degree of near surface region of graphite increase after modification, while the average in-plane crystallite domain size L_aand content of rhombohedral phase decrease. The graphite particles present irregular flake shape and some graphene sheets show flexual and sculptural margin. Electrochemical measures show that reversible capacity of modified graphite increases from 345.5 mAh/g to 381.4 mAh/g, and cycling performance is improved. During deintercalation process of the modified graphite, stage transformation from stage 1 Li-GICs (lithium-graphite intercalation compounds) to stage 2 Li-GICs begins to happen at lower voltage, compared with that of the raw graphite.

Key words: lithium-ion batteries, anode material, spherical graphite, oxidation treatment, electrochemical behavior

中图分类号:

TM912

简志敏, 刘洪波, 石磊, 何月德, 肖海河, 匡加才. 微氧化处理对球形石墨结构及电化学行为的影响[J]. 无机材料学报, 2012, 27(2): 151-156.

JIAN Zhi-Min, LIU Hong-Bo, SHI Lei, HE Yue-De, XIAO Hai-He, KUANG Jia-Cai. Influences of Mild Oxidation Treatment on the Structure and Electrochemical Behavior of Spherical Graphite[J]. Journal of Inorganic Materials, 2012, 27(2): 151-156.

图/表 8

图1 球形石墨(SG)与微氧化石墨(MSGO)的XRD图谱表1 球形石墨与微氧化石墨的结构参数

Fig. 1 XRD patterns of spherical graphite before (SG) and after (MSGO) mild oxidation treatment

Table 1 The structural properties of spherical graphite before (SG) and after (MSGO) mild oxidation treatment

Sample	d₀₀₂/nm	Content of 3R phase/wt%	R value	L_a/nm	D₅₀/μm
SG	0.33553	21.3	0.15	30.35	28.2
MSGO	0.33554	9.9	0.21	20.85	27.6

图2 球形石墨(SG)与微氧化石墨(MSGO)的Raman图谱

Fig. 2 Raman spectra of spherical graphite before (SG) and after (MSGO) mild oxidation treatment

图3 球形石墨(a)、(b)与微氧化石墨(c)、(d)的SEM照片

Fig. 3 SEM images of spherical graphite before (a) and (b) and after (c) and (d) mild oxidation treatment

图4 微氧化处理前后石墨的DFT孔径分布图

Fig. 4 DFT pore size distributions of spherical graphite anode before (SG) and after (MSGO) mild oxidation treatment

图5 微氧化处理前后石墨负极前三次循环的充放电曲线

Fig. 5 First three charge-discharge curves of spherical graphite anode before (SG) and after (MSGO) mild oxidation treatment

图6 球形石墨(a)与微氧化石墨(b)负极的多周期循环伏安图谱

Fig. 6 Repeated CVs profile of spherical graphite anode before (a) and after (b) mild oxidation treatment

图7 微氧化前后石墨负极的慢速扫描循环伏安曲线

Fig. 7 Slow scan rate cyclic voltammograms of spherical graphite anode before (SG) and after (MSGO)mild oxidation treatment

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微氧化处理对球形石墨结构及电化学行为的影响

Influences of Mild Oxidation Treatment on the Structure and Electrochemical Behavior of Spherical Graphite

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