Co掺杂改性尖晶石型Li1.035Mn1.965O4的合成及其电化学性能

doi:10.3724/SP.J.1077.2014.14031

摘要/Abstract

摘要：

采用湿化学-后续热处理技术, 合成了掺钴尖晶石锰酸锂材料。X射线衍射(XRD)分析结果表明, 钴的掺入没有改变材料的Fd3m结构。扫描电子显微镜(SEM)分析表明, 所合成的材料颗粒均匀, 形貌规整, 粒径分布较窄。透射电子显微镜(TEM)结果表明, Li_1.035Co_0.035Mn_1.930O₄具有完好的结晶态。充放电测试结果表明, 在室温下钴掺杂能够提高材料的电性能。当产物为Li_1.035Co_0.035Mn_1.930O₄时, 其电性能达到最优: 以0.5C充放电,首次放电容量为113 mAh/g, 经过100次循环后容量保持率为93.8%, 经过4C放电后仍然能够保持0.5C放电容量的76.1%; 而未掺钴的Li_1.035Mn_1.965O₄经过4C放电容量仅保持0.5C放电容量的64.8%。电化学阻抗测试结果表明, 钴离子的掺杂能够提高锰酸锂材料的锂离子扩散速率。

关键词: 锂离子电池, 钴掺杂, 水热法, 尖晶石锰酸锂

Abstract:

Spinel powders of Li_1.035Co_xMn_1.965-_xO₄(x=0-0.100) systems were synthesized by a simple wet chemical process with post heat-treatment. X-ray diffraction (XRD) patterns reveal that the Co doping does not affect the Fd3m space group of the cathode materials. Scanning electron microscope (SEM) images show that the Li_1.035Co_xMn_1.965-_xO₄ cathode materials have a uniform and nearly cubic morphology with a narrow size distribution. Transmission electron microscope (TEM) results demonstrate that the Li_1.035Co_0.035Mn_1.930O₄powder has a good crystalline state. The electrochemical testing results indicate that the prepared Co-doped Li_1.035Co_xMn_1.965-_xO₄ samples show a better cycling ability and rate capability at room temperature than that of Co-free Li_1.035Mn_1.965O₄. In particular, the Li_1.035Co_0.035Mn_1.930O₄ sample delivers a reversible specific capacity of 113 mAh/g in 1^st cycle and retains 93.8% of its initial capacity after 100 cycles at 0.5C rate. When discharging at 4C rate, the Li_1.035Co_0.035Mn_1.930O₄ powder maintains 86 mAh/g, which is 76.1% of the reversible capacity at 0.5C. Comparatively, the Li_1.035Mn_1.965O₄ powder maintains only 64.8% of its reversible capacity at 0.5C discharge rate. The electrochemical impedance spectroscopy results show that Co ion doping can enhance the electrical conductivity and the Li-ion diffusion coefficient. These results indicate a superior cycling and rate performance compared with the pristine one.

Key words: lithium ion batteries, Co doping, hydrothermal method, spinel lithium manganese oxide

中图分类号:

TM912

李运姣, 许虎, 孔龙, 李华成, 李春霞, 章贤臻, 韩强. Co掺杂改性尖晶石型Li_1.035Mn_1.965O₄的合成及其电化学性能[J]. 无机材料学报, 2014, 29(6): 661-666.

LI Yun-Jiao, XU Hu, KONG Long, LI Hua-Cheng, LI Chun-Xia, ZHANG Xian-Zhen, HAN Qiang. Synthesis and Electrochemical Characterizations of Co-doped Lithium
Manganese Oxide Spinel Li_1.035Mn_1.965O₄[J]. Journal of Inorganic Materials, 2014, 29(6): 661-666.

图/表 7

Fig. 1 XRD patterns of Li1.035CoxMn1.965-xO4 samples

Fig. 2 The lattice constant of Li1.035CoxMn1.965-xO4 samples as a function of the Co doping content

Fig. 3 SEM images of the Li1.035CoxMn1.965-xO4 spinel as a function of the Co doping content

Fig. 4 TEM (a), HRTEM (b) and SAED (c) images of the as- prepared Li1.035Co0.035Mn1.930O4 powder

Fig. 5 Discharge curves at 0.1C rate (a), discharge capacity with cycling number at different current rates (b) and cycling <br/>performance at 0.5C (c) of Li1.035CoxMn1.965-x

Fig. 6 Electrochemical impedance spectra (EIS) of the samples in the discharged state (about 3.0 V, vs Li+/Li) after 3 cycles with an equivalent circuit diagram inserted

Table 1 The impedance parameters of Li1.035CoxMn1.965-xO4 samples

Samples	R_s/Ω	R_ct/Ω	W_o-T	L/nm	D_Li⁺/(cm²•s^-1)
x = 0	4.32	129.40	1.976	596	1.81×10^-9
x = 0.035	3.28	79.12	0.121	621	3.19×10^-8
x = 0.065	3.39	91.20	0.286	618	1.37×10^-8
x = 0.100	3.85	102.00	0.547	609	6.85×10^-9

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Co掺杂改性尖晶石型Li_1.035Mn_1.965O₄的合成及其电化学性能

Synthesis and Electrochemical Characterizations of Co-doped Lithium
Manganese Oxide Spinel Li_1.035Mn_1.965O₄

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