Synthesis and Electrochemical Properties of Highly Dispersed Li4Ti5O12 Nanocrystalline as Anode Material for Lithium Secondary Batteries

doi:10.3724/SP.J.1077.2010.00235

Abstract

Abstract: Nano-sized Li₄Ti₅O₁₂ powder with high dispersivity was prepared by a novel solgel route using lauric acid as surfactant. The crystal structure, microstructure and the electrochemical properties of samples were characterized by XRD, FESEM, TGDSC, laser particle size analysis, A.C. impedance and galvanostatically chargedischarge experiments. The results demonstrated that the crystallization, microstructure and electrochemical properties were influenced significantly by heattreatment temperature. Li₄Ti₅O₁₂ powders calcined at 800℃ for 10h were comprised of crystallites with the particle size in the range of 120-275nm, revealing high dispersivity almost without any agglomerates, and exhibiting an excellent electrochemical performance. Its discharge capacities at 0.5C and 1C rates were 174.7mAh/g and 163.3mAh/g, respectively. After 50 cycles, fairly stable cycling performance was achieved without obvious capacity fading. Electrochemical impedance spectroscopy tests demonstrated that the surface reaction kinetics of Li^₄Ti₅O₁₂ was improved significantly from the state of the complete charge to the state of the complete discharge. The charge and discharge results of samples demonstrated that the route to synthesis highly dispersed nanocrystalline was appropriate for preparing Li₄Ti₅O₁₂with high electrochemical performance.

Key words: Li₄Ti₅O₁₂, nanocrystalline, surfactant, discharge capacity

CLC Number:

TQ174

WANG Jin,CHENG Xue-Lian,WANG Zi-Gang,YANG Hui. Synthesis and Electrochemical Properties of Highly Dispersed Li₄Ti₅O₁₂
Nanocrystalline as Anode Material for Lithium Secondary Batteries[J]. Journal of Inorganic Materials, DOI: 10.3724/SP.J.1077.2010.00235.

References

［1］Ohzuku T, Ueda A, Yamamoto N. Zerostrain insertion materials of Li［Li _1/3 Ti _5/3］O4 for rechargeable lithium cells. J. Electrochem. Soc., 1995,142(5): 1431-1435.

［2］Mukai K, Ariyoshi K, Ohzuku T. Comparative study of Li［CrTi］O4, Li［Li _1/3 Ti _5/3］O4 and Li1/2Fe1/2［Li_1/2 Fe _1/2 Ti］O₄ in nonaqueous lithium cells. J. Power Sources, 2005, 146(1/2): 213-216.

［3］Zaghib K, Simoneau M, Armand M, et al. Electrochemical study of Li₄Ti₅O₁₂ as negative electrode for Li-ion polymer rechargeable batteries. J. Power Sources, 1999, 81-82: 300-305.

［4］Ariyoshi K, Yamato R, Ohzuku T. Zero-strain insertion mechanism of Li［Li _1/3 Ti _5/3］O for advanced lithiumion (shuttlecock) batteries. Electrochim. Acta, 2005, 51(6): 1125-1129.

［5］Ge H, Li N, Li D Y, et al. Study on the effect of Li doping in spinel Li _4+x Ti _5-x O₁₂ (0≤x≤2) materials for lithium-ion batteries. Electrochem. Commun., 2008, 10(7): 1031-1034.

［6］Huang S H, Wen Z Y, Zhu X J, et al. Effects of dopant on the electrochemical performance of Li₄Ti₅O₁₂ as electrode material for lithium ion batteries. J. Power Sources, 2007, 165(1): 408-412.

［7］Wolfenstine J, Allen J L. Electrical conductivity and charge compensation in Ta doped Li₄Ti₅O₁₂.J. Power Sources, 2008, 180(1): 582-585.

［8］Robertson A D, Trevino L, Tukamoto H, et al. New inorganic spinel oxides for use as negative electrode materials in future lithium-ion batteries. J. Power Sources, 1999, 81-82: 352-357.

［9］Sun Y K, Jung D J, Lee Y S, et al. Synthesis and electrochemical characterization of spinel Li［Li _(1-x)/3 Cr_xTi _(5-2x) /3］O4 anode materials. J. Power Sources, 2004, 125(2): 242-245.

［10］苏岳峰, 吴峰, 臧戈, 等(SU YueFeng, et al). 多孔炭模板法制备Li₄Ti₅O₁₂及其嵌锂行为. 物理化学学报(Acta Phys.Chim. Sin.), 2008, 24(6): 1002-1006.

［11］Guefri A, Charest P, Kinoshita K, et al. Nano electronically conductive titaniumspinel as lithium ion storage negative electrode. J. Power Sources, 2004,126(1/2): 163-168.

［12］Cheng L, Li X L, Liu H J, et al. Carboncoated Li₄Ti₅O₁₂ as a high rate electrode material for Li-ion intercalation. J. Electrochem. Soc., 2007, 154(7): A692-A697.

［13］Wang G J, Gao J, Fu L J, et al. Preparation and characteristic of carboncoated Li₄Ti₅O₁₂ anode material. J. Power Sources, 2007, 174(2): 1109-1112.

［14］Huang J J, Jiang Z Y. The preparation and characterization of Li4Ti5O12/carbon nanotubes for lithium ion battery. Electrochim. Acta, 2008, 53(26): 7756-7759.

［15］Liu H, Feng Y, Wang K, et al. Synthesis and electrochemical properties of Li₄Ti₅O₁₂/C composite by the PVB rheological phase method. J. Phys. Chem. Solids, 2008, 69(8): 2037-2040.

［16］Jiang C H, Ichihara M, Honma I, et al. Effect of particle dispersion on high rate performance of nanosized Li₄Ti₅O₁₂ anode. Electrochim. Acta, 2007, 52(23): 6470-6475.

［17］Jiang C H, Hosono E J, Ichihara M, et al. Synthesis of nanocrystalline Li₄Ti₅O₁₂ by chemical lithiation of anatase nanocrystals and postannealing. J. Electrochem. Soc., 2008, 155(8): A553-A556.

［18］Choi D, Kumta P N. Surfactant based sol-gel approach to nanostructured LiFePO4 for high rate Li-ion batteries. J. Power Sources, 2007, 163(1/2): 1064-1069.

［19］Bach S, PereiraRamos J P, Baffier N. Electrochemical properties of solgel Li _4/3 Ti _5/3 O₄. J. Power Sources, 1999, 81-82: 273-276.

［20］Fu L J, Liu H, Li C, et al. Electrode materials for lithium secondary batteries prepared by sol-gel methods. Prog. Mater. Sci., 2005, 50(7): 881928.

［21］Xie D, Pan W. Study on BaBi₄Ti₄O₁₅ nanoscaled powders prepared by sol-gel method. Mater. Lett., 2003, 57(19): 2970-2974.

［22］赵国玺. 表面活性剂物理化学. 北京: 北京大学出版社, 1984: 3663.

［23］Robertson A D, Tukamoto H, Irvine J T S. Li1+xFe13xTi1+2xO4 (0≤x≤0.33) based spinel: possible negative electrode materials for future Liion batteries. J. Electrochem. Soc., 1999, 146(11): 39583962.

［24］苏岳峰, 吴峰, 陈朝峰(SU YueFeng, et al). 纳米微晶TiO2合成Li4Ti5O12及其嵌锂行为. 物理化学学报(Acta PhysChim. Sin.), 2004, 20(7): 707711.

［25］Kim D H, Ahn Y S, Kim J. Polyolmediated synthesis of Li4Ti5O12 nanoparticle and its electrochemical properties. Electrochem. Commun., 2005, 7(12): 13401344.

［26］Yuan T, Cai R, Wang K, et al. Combustion synthesis of highperformance Li4Ti5O12 for secondary Liion battery. Ceram. Int., 2009, 35(5): 17571768.

［27］Plett G L. Extended Kalman filtering for battery management systems of LiPBbased HEV battery packs: Part 2. Modeling and identification. J. Power Sources, 2004, 134(2): 277292.

［28］Wolfenstine J, Lee U, Allen J L. Electrical conductivity and ratecapability of Li4Ti5O12 as a function of heattreatment atmosphere. J. Power Sources, 2006, 154(1): 287289.

[1]	WANG Tianyue, WANG Mengying, HUANG Qingjiao, YANG Jiaming, WANG Shunhua, DIAO Xungang. Preparation of Lithium Titanate Thin Film for Electrochromic Smart Window by Sol-Gel Spin Coating Method [J]. Journal of Inorganic Materials, 2021, 36(5): 471-478.
[2]	LI Xue-Lin, ZHU Jian-Feng, JIAO Yu-Hong, HUANG Jia-Xuan, ZHAO Qian-Nan. Manganese Dioxide Morphology on Electrochemical Performance of Ti₃C₂T_x@MnO₂ Composites [J]. Journal of Inorganic Materials, 2020, 35(1): 119-125.
[3]	LU Chang-Jian, ZHU Fa-Quan, Yin Ji-Guang, ZHANG Jian-Bo, YU Ya-Wei, HU Xiu-Lan. Synthesis of α-MnO₂ Nanowires via Facile Hydrothermal Method and Their Application in Li-O₂ Battery [J]. Journal of Inorganic Materials, 2018, 33(9): 1029-1034.
[4]	TAN Yi, XUE Bing. Research Progress on Lithium Titanate as Anode Material in Lithium-ion Battery [J]. Journal of Inorganic Materials, 2018, 33(5): 475-482.
[5]	ZHANG Guo-Xiong, CHEN Yue-Mei, HE Zhen-Ni, LIN Chuan, CHEN Yi-Gang, GUO Hai-Bo. Surfactant Dependence of Nanostructured NiCo₂S₄ Films on Ni Foam for Superior Electrochemical Performance [J]. Journal of Inorganic Materials, 2018, 33(3): 289-294.
[6]	ZHENG Lei, LI Jin, LIU Hong-Bo. Carbon Aerogels Prepared Based on Sol-Gel Reaction of Cellulose Colloid with AEP and Its Adsorption of Copper Ions in Aqueous Solution [J]. Journal of Inorganic Materials, 2017, 32(11): 1159-1164.
[7]	QI Mei-Li, QI Jia, XIAO Gui-Yong, LV Yu-Peng. Effect of Surfactants on the Morphology of Hydroxyapatite Fibers [J]. Journal of Inorganic Materials, 2016, 31(7): 726-730.
[8]	LIANG Pei, XING Song, SHU Hai-Bo, ZHANG Lin, HU Chen-Li. Analogous Three-dimensional MoS₂/Graphene Composites for Reversible Li Storage [J]. Journal of Inorganic Materials, 2016, 31(6): 575-580.
[9]	GAN Qiong-Zhi, WEN Xiao-Ling, DING Yi-Ming, OUYANG Jian-Ming. Adsorption of Cetyltrimethylammonium Bromide on Different-sized Calcium Oxalate Monohydrate and Dihydrate Crystals [J]. Journal of Inorganic Materials, 2016, 31(2): 159-164.
[10]	XU Jin-Fang, SHAO Meng-Meng, NI Zhe-Ming, XIAO Xue-Chun. Surface Properties of Magnesium-iron Hydrotalcite and Its Modified Products by Inverse Gas Chromatography [J]. Journal of Inorganic Materials, 2015, 30(9): 971-976.
[11]	JU Xiang-Wen, WU Ri-Min, ZHOU Ya-Zhou, MA Shuang-Biao, YANG Juan, CHENG Xiao-Nong. Application of Graphene Oxide in Synthesis of Sc₂W₃O₁₂ Powder [J]. Journal of Inorganic Materials, 2015, 30(4): 374-378.
[12]	ZHAO Jing-Jing, SHEN Jun, ZOU Li-Ping, WANG Wen-Qin, ZU Guo-Qing, ZHANG Zhi-Hua. A Low-cost Preparation of SiO₂ Aerogel Monoliths from Silica Sol [J]. Journal of Inorganic Materials, 2015, 30(10): 1081-1084.
[13]	ZHANG Xiao-Qiang, SUN Yi, SHIMAI Shun-Zo, WANG Shi-Wei. Effect of Water-soluble Epoxy Resin on Microstructure and Properties of Porous Alumina Ceramics by Gel-casting [J]. Journal of Inorganic Materials, 2015, 30(10): 1085-1088.
[14]	QIU Cai-Xia, YUAN Zhong-Zhi, LIU Ling, CHENG Si-Jie, LIU Jin-Cheng. Preparation and Characterization of Ge⁴⁺-doping Li₄Ti₅O₁₂ Anode Material for Li-ion Battery and Its Electrochemical Properties [J]. Journal of Inorganic Materials, 2013, 28(7): 727-732.
[15]	GAO Jian, MU Xin, LI Jian-Jun, HE Xiang-Ming, JIANG Chang-Yin. Preparation and Characterization of Porous Spherical Li₄Ti₅O₁₂/C Anode Material for Lithium Ion Batteries [J]. Journal of Inorganic Materials, 2012, 27(3): 253-257.

Synthesis and Electrochemical Properties of Highly Dispersed Li₄Ti₅O₁₂
Nanocrystalline as Anode Material for Lithium Secondary Batteries

PDF (PC)

Knowledge

Cited

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments