水热法制备富锂型Li2+4xMn0.6+2xNi0.6-6xCr0.8O4及其结构与电化学特性

doi:10.7503/cjcu20130599

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (2): 362.doi: 10.7503/cjcu20130599

水热法制备富锂型Li₂₊₄_xMn_0.6+2_xNi_0.6-6_xCr_0.8O₄及其结构与电化学特性

赵利芳¹, 张茜², 贺诗词³, 刘伟伟², 杨裕生⁴, 郑军伟², 潘勤敏¹, 李德成²()

1. 苏州大学材料与化学化工学部, 苏州 215123
2. 苏州大学江苏省锂离子电池材料重点实验室, 化学电源研究所, 苏州 215006
3. 安徽省阜阳市产品质量监督检验所, 阜阳 236000
4. 北京防化研究院, 北京 100083

收稿日期:2013-06-27 出版日期:2014-02-10 发布日期:2013-09-02
作者简介:联系人简介: 李德成, 男, 博士, 教授, 主要从事锂离子电池材料研究. E-mail:lidecheng@suda.edu.cn
基金资助:
国家自然科学基金(批准号: 20973200)资助

Structure and Electrochemical Properties of Li-rich Li₂₊₄_xMn_0.6+2_xNi_0.6-6_xCr_0.8O₄ Spinel Prepared by Hydrothermal Method^†

ZHAO Lifang¹, ZHANG Qian², HE Shici³, LIU Weiwei², YANG Yusheng⁴, ZHENG Junwei², PAN Qinmin¹, LI Decheng^2,^*()

1. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
2. Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of Chemical Power Sources,Soochow University, Suzhou 215006, China
3. Fuyang Product Quality Supervision and Inspection Institution, Fuyang 236000, China
4. Research Institute of Chemical Defense, Beijing 100083, China

Received:2013-06-27 Online:2014-02-10 Published:2013-09-02
Contact: LI Decheng E-mail:lidecheng@suda.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.20973200)

摘要/Abstract

摘要：

采用水热法制备了系列富锂尖晶石型正极材料L $i 2 + 4 x$ M $n 0.6 + 2 x$ N $i 0.6 - 6 x$ Cr_0.8O₄(x=1/30, 1/20, 1/15, 1/12), 通过X射线衍射(XRD)、电感耦合等离子体-原子发射光谱(ICP-AES)、扫描电子显微镜(SEM)、 X射线光电子能谱 (XPS)、傅里叶变换红外光谱(FTIR)、拉曼光谱、循环伏安(CV)和充放电测试等手段对其结构及电化学性能进行表征. 结果表明, 所制备的系列材料为富锂型高电压尖晶石结构正极材料, 该系列样品在4.7 V左右有放电平台. x=1/15和x=1/12时, 样品中的Cr为+3价, 没有观测到Cr⁶⁺. 随着x值的增大, 样品中Li离子与过渡金属离子的混排减小, 样品的充放电比容量逐渐增大, 且2.7 V处的放电平台容量也增加. 当x=1/12时, 样品具有较好的充放电比容量和倍率特性, 首次放电比容量为107.3 mA·h/g, 20次循环后容量保持率为84.9%.

关键词: 锂离子电池, 正极材料, 富锂尖晶石结构, 水热法, 高电压

Abstract:

A series of cathode materials, L $i 2 + 4 x$ M $n 0.6 + 2 x$ N $i 0.6 - 6 x$ Cr_0.8O₄(x=1/30, 1/20, 1/15, 1/12), was prepared via hydrothermal method, and their composition, structure and electrochemical properties were investigated using X-ray diffraction(XRD), inductively coupled plasma-atomic emission spectrometry(ICP-AES), scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS), Fourier transform infrared spectrometry(FTIR), Raman spectrometry and charge-discharge tests. XRD measurements combining with ICP results reveal that the obtained samples are Li-rich type spinel structure. Moreover, XPS results suggest that the valence for Cr is +3 for x=1/15 and 1/12 and no Cr⁶⁺ exist. As to their electrochemical properties, it is found that these materials have a high-voltage plateau near 4.7 V and a low-voltage near 2.7 V. With the increase of x value, both charge and discharge capacities of the samples increase. The sample with x=1/12 shows a good cyclic performance as well as good rate capability.

Key words: Lithium ion battery, Cathode material, Li-rich spinel structure, Hydrothermal method, High-voltage

中图分类号:

TrendMD:

赵利芳, 张茜, 贺诗词, 刘伟伟, 杨裕生, 郑军伟, 潘勤敏, 李德成. 水热法制备富锂型Li₂₊₄_xMn_0.6+2_xNi_0.6-6_xCr_0.8O₄及其结构与电化学特性. 高等学校化学学报, 2014, 35(2): 362.

ZHAO Lifang, ZHANG Qian, HE Shici, LIU Weiwei, YANG Yusheng, ZHENG Junwei, PAN Qinmin, LI Decheng. Structure and Electrochemical Properties of Li-rich Li₂₊₄_xMn_0.6+2_xNi_0.6-6_xCr_0.8O₄ Spinel Prepared by Hydrothermal Method^†. Chem. J. Chinese Universities, 2014, 35(2): 362.

图/表 9

Fig.1 XRD patterns of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: a. 1/30; b. 1/20; c. 1/15; d. 1/12.

Fig.2 FTIR spectra of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: a. 1/30; b. 1/20; c. 1/15; d. 1/12.

Fig.3 Raman spectra of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: a. 1/30; b. 1/20; c. 1/15; d. 1/12.

Table 1 Results of the composition analysis for the Li2+4xMn0.6+2xNi0.6-6xCr0.8O4(x=1/30, 1/20, 1/15, 1/12)

Aimed product	Obtained product
LMn_0.667NCr_0.8O₄	Li_1.077Mn_0.617Ni_0.399Cr_0.82O₄
LMn_0.700NCr_0.8O₄	Li_1.149Mn_0.675Ni_0.293Cr_0.896O₄
LMn_0.733NCr_0.8O₄	Li_1.241Mn_0.751Ni_0.211Cr_0.899O₄
LMn_0.767Ni_0.1Cr_0.8O₄	Li_1.925Mn_0.697Ni_0.129Cr_0.880O₄

Fig.4 XPS spectra of Mn2p(A), Li1s(B), Ni2p(C) and Cr2p(D) of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: a. 1/12; b. 1/15.

Fig.5 SEM images of as-prepared Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: (A) 1/30; (B) 1/20; (C) 1/15; (D) 1/12.

Fig.6 Initial charge(a—d) and discharge(a'—d') curves of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4 at a current density of 20 mA/g in 2.0—5.0 V voltage rangex: a, a'. 1/30; b, b'. 1/20; c, c'. 1/15;d, d'. 1/12.

Fig.7 Cyclic voltammograms of Li2.3333Mn0.7667Ni0.1Cr0.8O4(x=1/12) at a sweep rate of 0.05 mV/s between 2.0 and 5.0 V

Fig.8 Cyclic performance of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4 at a current density of 20 mA/g in 2.0—5.0 V voltage range(A) and rate capabilities of as-prepared Li2+4xMn0.6+2xNi0.6-6xCr0.8O4(B)x: a. 1/12; b. 1/15; c. 1/20; d. 1/30.

参考文献 28

[1]	Yang M. C., Xu B., Cheng J. H., Pan C. J., Hwang B. J., Meng Y. S., Chem. Mater., 2011, 23, 2832—2841
[2]	Benedek R., Johnson C. S., Thackeray M. M., Electrochemical and Solid-State Letters, 2006, 9(6), A289—A291
[3]	Lu H. Q., Wu F., Su Y. F., Li N., Chen S., Bao L. Y., Chem. J. Chinese Universities, 2011, 32(4), 946—951
	(卢华权, 吴锋, 苏岳锋, 李宁, 陈实, 包丽颖.高等学校化学学报,2011, 32(4), 946—951)
[4]	Fang H. S., Wang Z. X., Zhang B., Li X. H., Li G. S., Electrochem. Commun., 2007, 9, 1077—1082
[5]	Hagh N. M., Amatucci G. G., J. Power Sources, 2010, 195, 5005—5012
[6]	He S. C., Zhang Q., Liu W. W., Fang G. Q., Sato Y., Zheng J. W., Li D. C., Chem. Res. Chinese Universities, 2013, 29(2), 329—332
[7]	Wang S. J., Zhao Y. J., Zhao C. S., Xia D. G., Chem. J. Chinese Universities, 2009, 30(12), 2358—2362
	(王绥军, 赵煜娟, 赵春松, 夏定国.高等学校化学学报,2009, 30(12), 2358—2362)
[8]	Ohzuku T., Makimura Y., Chem. Lett., 2001, 30, 744—745
[9]	Ohzuku T., Ueda A., Nagayama M., Iwakoshi Y., Komori H., Electrochimica Acta, 1993, 38, 1159—1167
[10]	Kim H. S., Kong M., Kim K., Kim I. J., Gu H. B., J. Power Sources, 2007, 171, 917—921
[11]	Ito A., Li D., Ohsawa Y., Sato Y., J. Power Sources, 2008, 183, 344—346
[12]	Feng C. Q., Zhang K. L., Sun J. T., Spectroscopy and Spectral Analysis, 2003, 23(2), 279—281
	(冯传启, 张克立, 孙聚堂.光谱学与光谱分析,2003, 23(2), 279—281)
[13]	Aitchison P., Ammundsen B., Jones D. J., Burns G., Rozière J., J. Mater. Chem., 1999, 9, 3125—3130
[14]	Ammundsen B., Burns G. R., Islam M. S., Kanoh H., Rozière J., J. Phys. Chem. B, 1999, 103, 5175—5180
[15]	Wei Y., Nam K. W., Kim K. B., Chen G., Solid State Ionics, 2006, 177, 29—35
[16]	Liu D., Han J., Dontigny M., Charest P., Guerfi A., Zaghib K., Goodenough J. B., J. Electrochem. Soc., 2010, 157, A770—A775
[17]	Ohzuku T., Tatsumi K., Matoba N., Sawai K., J. Electrochem. Soc., 2000, 147, 3592—3597
[18]	Zhang Q., Liu W. W., Fang G. Q., Xia B. B., Sun H. D., Kaneko S., Yang Y. S., Zheng J. W., Li D. C., J. Ionrg. Mater., 2013, 28, 616—622
	(张茜, 刘伟伟, 方国清, 夏丙波, 孙洪丹, 金子信悟, 杨裕生, 郑军伟, 李德成.无机材料学报, 2013, 28, 616—622)
[19]	Bardi U., Atrei A., Rovida G., Surf. Sci., 1992, 268, 87—97
[20]	Yu D. C., Cao W. J., Wu H. Y., Zhao J. F., Acta Physico-Chimica Sinica, 2007, 23, 683—687
	(余德才, 曹文娟, 吴海玉, 赵剑锋.物理化学学报, 2007, 23, 683—687)
[21]	Stranick M. A., Surf. Sci. Spec., 1999, 6, 39—46
[22]	Jang S. H., Kang T., Kim H. J., Kim K.Y., Appl. Phys. Lett., 2002, 81, 105—107
[23]	Zhang Q., He S. C., Liu W. W., Fang G. Q., Sato Y., Yang Y. S., Zheng J. W., Li D. C., Chin. J. Inorg. Chem., 2012, 28(12), 2501—2507
	(张茜, 贺诗词, 刘伟伟, 方国清, 金子信悟, 杨裕生, 郑军伟, 李德成.无机化学学报,2012, 28(12), 2501—2507)
[24]	Yoon W. S., Iannopollo S., Grey C. P., Carlier D., Gorman J., Reed J., Ceder G., Electrochem. Solid-State Lett., 2004, 7, A167—A171
[25]	Komaba S., Takei C., Nakayama T., Ogata A., Yabuuchi N., Electrochem. Commun., 2010, 12, 355—358
[26]	Park Y. J., Hong Y. S., Wu X., Ryu K. S., Chang S. H., J. Power Sources, 2004, 129, 288—295
[27]	Lu C. H., Lee W. C., Liou S. J., Ting-Kuo F. G., J. Power Sources, 1999, 81, 696—699
[28]	Myung S. T., Komaba S., Hirosaki N., Kumagai N., Electrochem. Commun., 2002, 4, 397—401

水热法制备富锂型Li₂₊₄_xMn_0.6+2_xNi_0.6-6_xCr_0.8O₄及其结构与电化学特性

Structure and Electrochemical Properties of Li-rich Li₂₊₄_xMn_0.6+2_xNi_0.6-6_xCr_0.8O₄ Spinel Prepared by Hydrothermal Method^†

RichHTML

PDF (PC)