LiNi1/3Co1/3Mn1/3O2@C复合材料的制备及电化学性能

doi:10.7503/cjcu20170215

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (1): 141.doi: 10.7503/cjcu20170215

LiNi_1/3Co_1/3Mn_1/3O₂@C复合材料的制备及电化学性能

王坤², 黄梦怡¹, 张小颂¹, 黄俊杰¹(), 邓祥², 刘长路²

1. 绍兴文理学院化学化工学院, 绍兴 312000
2. 四川文理学院化学化工学院, 达州 635000

收稿日期:2017-04-11 出版日期:2018-01-10 发布日期:2017-12-21
作者简介:联系人简介: 黄俊杰, 男, 博士, 副教授, 主要从事高能材料电化学性能研究. E-mail:hjj@usx.edu.cn
基金资助:
浙江省重点研发计划项目(批准号: 2015C01002)、绍兴市科技局项目(批准号: 2014B70016)和四川文理学院科研项目(批准号: 2016KZ002Y)资助

Preparation and Electrochemical Performance of LiNi_1/3Co_1/3Mn_1/3O₂@C Composite^†

WANG Kun², HUANG Mengyi¹, ZHANG Xiaosong¹, HUANG Junjie^1,^*(), DENG Xiang², LIU Changlu²

1. College of Chemistry & Chemical Engineering, Shaoxing University, Shaoxing 312000, China
2. College of Chemistry & Chemical Engineering, Sichuan University of Art and Science, Dazhou 635000, China

Received:2017-04-11 Online:2018-01-10 Published:2017-12-21
Contact: HUANG Junjie E-mail:hjj@usx.edu.cn
Supported by:
† Supported by the Zhejiang Provincial Key Research Project, China(No.2015C01002), the Foundation of the Science Technology Bureau of Shaoxing, China(No.2014B70016) and the Research Project of Sichuan University of Art and Science, China(No.2016KZ002Y)

摘要/Abstract

摘要：

采用活性炭吸附含Co²⁺, Mn²⁺, Ni²⁺和Li⁺的乙酸盐混合溶液, 辅以高温热处理制备了碳包覆LiNi_1/3Co_1/3Mn_1/3O₂(NCM@C). 透射电子显微镜(TEM)观测结果表明, 碳包覆层的厚度约为10 nm. 电化学性能测试结果表明, 在0.2C下首次放电比容量为181 mA·h/g, 首次充放电效率为90.7%; 在20C倍率下, NCM@C仍具有78 mA·h/g的放电比容量, 而采用溶胶凝胶法制备的LiNi_1/3Co_1/3Mn_1/3O₂(NCM) 的比容量仅为39 mA·h/g; NCM@C还表现出良好的循环稳定性, 在0.2C倍率下循环50周容量保持率为88.1%, 而NCM容量保持率仅为66.4%.

关键词: LiNi1/3Co1/3Mn1/3O2, 碳包覆, 正极材料, 锂离子电池, 电化学性能

Abstract:

Carbon coated LiNi_1/3Co_1/3Mn_1/3O₂(NCM@C) was prepared by active carbon to adsorb the mixed solution of acetate salts of Co²⁺, Mn²⁺, Ni²⁺ and Li⁺. Transmission electron microscopy(TEM) image shows that the surfaces of LiNi_1/3Co_1/3Mn_1/3O₂ particles are homogeneously coated by carbon with a thickness about 10 nm. The initial discharge capacity of NCM@C is 181 mA·h/g at 0.2C, and its initial Columbic efficiency is 90.7%. Meanwhile, the discharge capacity of NCM@C is 78 mA·h/g at 20C, while it is only 39 mA·h/g for LiNi_1/3Co_1/3Mn_1/3O₂(NCM) that prepared by a co-precipitation method. NCM@C also shows good cycling stability, the capacity retention is 88.1% after 50 cycles at 0.2C, while it is only 66.4% for NCM.

Key words: LiNi1/3Co1/3Mn1/3O2, Carbon coating, Cathode material, Lithium ion battery, Electrochemical performance

中图分类号:

O646

TrendMD:

王坤, 黄梦怡, 张小颂, 黄俊杰, 邓祥, 刘长路. LiNi_1/3Co_1/3Mn_1/3O₂@C复合材料的制备及电化学性能. 高等学校化学学报, 2018, 39(1): 141.

WANG Kun, HUANG Mengyi, ZHANG Xiaosong, HUANG Junjie, DENG Xiang, LIU Changlu. Preparation and Electrochemical Performance of LiNi_1/3Co_1/3Mn_1/3O₂@C Composite^†. Chem. J. Chinese Universities, 2018, 39(1): 141.

图/表 11

Fig.1 SEM(A—C) and TEM(D—F) images of NCM(A, D), NCM@C(B, E) and LiNi1/3Co1/3Mn1/3O2(C, F)

Fig.2 XRD patterns of NCM(a) and NCM@C(b)(A) and rievelt refinement XRD patterns of NCM(B) and NCM@C(C)

Table 1 Crystal parameters of NCM and NCM@C

Sample	a/nm	c/nm	c/a	I₍₀₀₃₎/I₍₁₀₄₎
NCM	0.28672	1.42703	4.9771	1.5104
NCM@C	0.28625	1.42811	4.9891	1.6635

Fig.3 EDS images of NCM(A) and NCM@C(B)

Table 2 Atom ratios of NCM and NCM@C

Sample	Expected Li/Ni/Co/Mn	Measured Li/Ni/Co/Mn
NCM	1.0/0.33/0.33/0.33	1.01/0.34/0.36/0.31
NCM@C	1.0/0.33/0.33/0.33	1.03/0.33/0.34/0.32

Fig.4 Initial charge-discharge curves of NCM(a) and NCM@C(b) at 0.2C

Fig.5 Rate capability of NCM(■) and NCM@C(●)

Fig.6 Fitted Nyquist plots(A) and relationships between Zre and ω-1/2(B) at low frequency region of NCM and NCM@C

Fig.7 Fitted equivalent circuits of NCM(A) and NCM@C(B)

Table 3 EIS parameters of NCM and NCM@C after the 1st cycle

Sample	R_e/Ω	R_s1/Ω	R_s2/Ω	R_ct/Ω	σ/(Ω·cm²)	10¹⁴ $D L i +$ /(cm²·s^-1)
NCM	12.9	49.7		52.3	440.3	1.286
NCM@C	8.6	30.5	6.3	34.6	302.5	2.728

Table 3 EIS parameters of NCM and NCM@C after the 1st cycle

Sample	R_e/Ω	R_s1/Ω	R_s2/Ω	R_ct/Ω	σ/(Ω·cm²)	10¹⁴ $D L i +$ /(cm²·s^-1)
NCM	12.9	49.7		52.3	440.3	1.286
NCM@C	8.6	30.5	6.3	34.6	302.5	2.728

Fig.8 Cycling performance of NCM(a) and NCM@C(b) at 0.2C

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LiNi_1/3Co_1/3Mn_1/3O₂@C复合材料的制备及电化学性能

Preparation and Electrochemical Performance of LiNi_1/3Co_1/3Mn_1/3O₂@C Composite^†

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