Preparation and Performance of Hollow Spherical Li₄Ti₅O₁₂ Doped by Mg²⁺

Abstract

The microstructure and performance of Li₄Ti₅O₁₂ doped by Mg prepared by hydrothermal method and solid phase method were investigated. Lithium dihydrate, magnesium acetate and tetrabutyl titanate were used as the main raw materials. This study reveals that Mg²⁺ has influences on the spherical structure, crystal development of Li₄Ti₅O₁₂ and the electrochemical performances. The hollow spherical structure is composed of nano-sheet structure and the nano-sheet structure can be affected by the Mg²⁺ content. For Li4-xMgxTi₅O₁₂, the sheet structure can be refined with the increment of Mg²⁺ content when x value is 0-0.1 and coarsen with the increment of Mg²⁺ content when x value is 0.1-0.2. The hollow spherical Li₄Ti₅O₁₂ powders prepared by hydrothermal method have better performance. The optimal Mgdoped amount of hydrothermal method is 0.1. At 0.1C, the first discharge capacity of Li3.9Mg0.1Ti₅O₁₂ prepared through hydrothermal method at 0.1C and 10 cycles is 182 and 178 mA h g⁻¹, respectively.

Keywords

hydrothermal method / hollow spherical Li₄Ti₅O₁₂ / nano-particles / Mg-doped / cycle Performance

References

[1] Jamiati M, Khoshnevisan B, Mohammadi M. Effect of Se Dopping on the Structural and Electronic Properties, Charge Redistribution and Efficiency of the Cu₂ZnSnS₄ Solar Cells[J]. Energy Source Part A, 2017, 39(23): 2181-2186.

[2] He J, Long F, Peng D, et al. Ribbon-like Cu Doped V6O13 as Cathode Material for High-performance Lithium Ion Batteries[J]. J. Wuhan University of Technology-Mater. Sci. Ed., 2017, 32(6): 1397-1401.

[3] Kavan L, Procházka J, Spitler TM, et al. Li Insertion into Li₄Ti₅O₁₂ (Spinel) Charge Capability vs Particle Size in Thin-film Electrodes[J]. J. Electrochem. Soc., 2003, 150(7): A1000-A1007.

[4] Wen Z, Huang S, Yang X, et al. High Rate Electrode Materials for Lithium Ion Batteries[J]. Solid State Ionics, 2008, 179(27): 1800-1805.

[5] Guerfi A, Charest P, Kinoshita K, et al. Nano Electronically Conductive Titanium-spinel as Lithium Ion Storage Negative Electrode[J]. J. Power Sources, 2004, 126(1-2): 163-168.

[6] Wei Y, Zhang S, Niu H, et al. Hydrothermal Synthesis and Capacitance Property of Cobalt Sulfide/Graphene Oxide Nanocomposite[J]. J. Wuhan University of Technology-Mater. Sci. Ed., 2017, 32(1): 80-84.

[7] Xin WH, Dan Z, Chang J C. Mass Transfer Phenomena at Nation Coated Electrodes: Limits of the Membrane Model[J]. J. Mater. Sci., 2005, 40(16): 2577-2583.

[8] Molenda J, Palubiak D. Transport and Electrochemical Properties of the LiyCr_xMn2-xO4 Cathode Material[J]. J. Power Sources, 2005, 144(1): 176-182.

[9] Zhao L H Y S, Li H, et al. Porous Li₄Ti₅O₁₂ Coated with N-Doped Carbon from Ionic Liquids for Li-Ion Batteries[J]. Adv. Mater., 2011, 23(11): 1385-1388.

[10] Yang Z, Choi D, Kerisit S, et al. Nanostructures and Lithium Electrochemical Reactivity of Lithium Titanites and Titanium Oxides: A Review[J]. J. Power Sources, 2009, 192(2): 588-598.

[11] Yi TF, Jiang L J, Shu J, et al. Recent Development and Application of Li₄Ti₅O₁₂ as Anode Material of Lithium Ion Battery[J]. J. Phys. Chem. Solids, 2010, 71(9): 1236-1242.

[12] Li S, Wang J P, Jiang K L. Mesoporous Li₄Ti₅O₁₂ Nanoclusters as High Performance Negative Electrodes for Lithium Ion Batteries[J]. J. Power Sources., 2014, 12(5): 265-272.

[13] Yin YH, Xu J J, Cao Z X. Synthesis and Electrochemical Performance of Li₄Ti₅O₁₂ Hollow Microspheres Assembled by Nanoparticles[J]. Mater. Lett., 2013, 10(7): 12-57.

[14] Huang S, Wen Z, Zhu X, et al. Preparation and Cycling Performance of A13+ and F-Co-substituted Compounds Li₄A1_xT_i5-xFyO₁₂-y[J]. Electrochim. Acta, 2005, 50(20): 4057-4062.

[15] Huang H, Yin S C, Nazar L F. Approaching Theoretical Capacity of LiFePO4 at Room Temperature at High Rates[J]. Electrochem. Solid ST., 2001, 4(10): A170-A172.

[16] Wolfenstine J, Allen J L. Electrical Conductivity and Charge Compensation in Ta Doped Li₄Ti₅O₁₂[J]. J. Power Sources., 2008, 180(1): 582-585.

[17] Stenina IA, Sobolev A N, Yaroslavtsev S A, et al. Influence of Iron Doping on Structure and Electrochemical Properties of Li₄Ti₅O₁₂[J]. Electrochim. Acta, 2016, 219: 524-530.

[18] Guerfi A, Charest P, Kinoshita K, et al. Nano Electronically Conductive Titanium-spinel as Lithium Ion Storage Negative Electrode[J]. J. Power Sources, 2004, 126(1-2): 163-168.

[19] Guan X, Chen X, Li G, et al. Direct Synthesis of Carbon-coated Li₄Ti₅O₁₂ Mesoporous Nanoparticles for High-rate Lithium-ion Batteries[J]. RSC Adv., 2013, 3(9): 3088-3094.

[20] Zhang Z, Cao L, Huang J, et al. Hydrothermal Synthesis of Zn-doped Li₄Ti₅O₁₂ with Improved High Rate Properties for Lithium Ion Batteries[J]. Ceramics Int., 2013, 39(6): 6139-6143.

[21] Lai C, Wu Z Z, Zhu Y X, et al. Ball-milling Assisted Solid-state Reaction Synthesis of Mesoporous Li₄Ti₅O₁₂ for Lithium-ion Batteries Anode[J]. J. Power Sources., 2013, 226: 71-74.

[22] Xu D, Jiang H, Li M, et al. Facile Preparation of Al₂O₃ Hollow Microspheres Via a Urea-mediated Precipitation Process[J]. J. Wuhan University of Technology-Mater. Sci. Ed., 2019, 34(3): 579-586.

[23] Xu T, Wang M, Wang T. Effects of N Doping on the Microstructures and Optical Properties of TiO2[J]. J. Wuhan University of Technology-Mater. Sci. Ed., 2019, 34(1): 55-63.