Lithium Storage Performance of Hollow and Core/Shell TiO2 Microspheres Containing Carbon

doi:10.1016/j.cjche.2014.09.005

Abstract

Abstract: TiO₂ microspheres containing carbon have been synthesized viaa one-pot hydrothermal process using CTAB as the mesoporous template and nanoparticle stabilizer and Ti(SO₄)₂ and sucrose as titanium and carbon precursors, respectively. Through well designed calcinations, TiO₂ microspheres with various amounts of carbon-residue, such as core/shell C@TiO₂, hollow neat H-TiO₂, and hollow C/TiO₂ composites, are obtained.When these microspheres are used as anode materials for lithium ion batteries, the lithium storage performance is significantly influenced by the structure and carbon-residue. With a thin shell of TiO₂ nanoparticles and carbon-residue, the capacity of hollow C/TiO₂ composites maintains at 143.3 mA·h·g^-1 at 0.5 C (83.5 mA·g^-1) after 100 cycles. Moreover, after high rate charge/discharge cycles from 0.2 C to 20 C and back to 0.2 C again, the reversible capacity recovers atas high as 195.1 mA·h·g^-1 with respect to its initial value of 205.0 mA·h·g^-1. The results of cycle voltammograms and electrochemical impedance spectroscopy further reveal that Li⁺ insertion/extraction processes are reversible, and the diffusion coefficient of Li⁺ in the hollow C/TiO₂ composites is much higher than those of others, because the hollow structure can act as the ion-buffering reservoir and facilitate Li⁺ transfer from both sides of the shell, and the carbon-residue in the shell improves the conductivity as well.

Key words: Lithium ion battery, Titanium dioxide microsphere, Hollow, Core/shell, Electrochemical properties

摘要： TiO₂ microspheres containing carbon have been synthesized viaa one-pot hydrothermal process using CTAB as the mesoporous template and nanoparticle stabilizer and Ti(SO₄)₂ and sucrose as titanium and carbon precursors, respectively. Through well designed calcinations, TiO₂ microspheres with various amounts of carbon-residue, such as core/shell C@TiO₂, hollow neat H-TiO₂, and hollow C/TiO₂ composites, are obtained.When these microspheres are used as anode materials for lithium ion batteries, the lithium storage performance is significantly influenced by the structure and carbon-residue. With a thin shell of TiO₂ nanoparticles and carbon-residue, the capacity of hollow C/TiO₂ composites maintains at 143.3 mA·h·g^-1 at 0.5 C (83.5 mA·g^-1) after 100 cycles. Moreover, after high rate charge/discharge cycles from 0.2 C to 20 C and back to 0.2 C again, the reversible capacity recovers atas high as 195.1 mA·h·g^-1 with respect to its initial value of 205.0 mA·h·g^-1. The results of cycle voltammograms and electrochemical impedance spectroscopy further reveal that Li⁺ insertion/extraction processes are reversible, and the diffusion coefficient of Li⁺ in the hollow C/TiO₂ composites is much higher than those of others, because the hollow structure can act as the ion-buffering reservoir and facilitate Li⁺ transfer from both sides of the shell, and the carbon-residue in the shell improves the conductivity as well.

关键词: Lithium ion battery, Titanium dioxide microsphere, Hollow, Core/shell, Electrochemical properties

Songgyun Ri, Honggui Deng, Lihui Zhou, Jun Hu, Honglai Liu, Ying Hu. Lithium Storage Performance of Hollow and Core/Shell TiO₂ Microspheres Containing Carbon[J]. , 2014, 22(10): 1153-1161.

References

[1] I.Moriguchi, R. Hidaka, H. Yamada, T. Kudo, H. Murakami, N. Nakashima, A mesoporous nanocomposite of TiO₂ and carbon nanotubes as a high-rate Li-intercalation electrode material, Adv. Mater. 18 (1) (2006) 69-73.
[2] S.K. Yoon, A. Manthiram, Hollow core-shell mesoporous TiO₂ spheres for lithium ion storage, J. Phys. Chem. C 115 (19) (2011) 9410-9416.
[3] Z. Yang, D. Choi, S. Kerisit, K.M. Rosso, D. Wang, J. Zhang, G. Graff, J. Liu, Nanostructures and lithiumelectrochemical reactivity of lithiumtitanites and titaniumoxides: a review, J. Power Sources 192 (2) (2009) 588-598.
[4] G. Sudant, E. Baudrin, D. Larcher, J.M. Tarascon, Electrochemical lithium reactivity with nanotextured anatase-type TiO₂, J. Mater. Chem. 15 (2005) 1263-1269.
[5] P. Balaya, A.J. Bhattacharyya, J. Jamnik, Y.F. Zhukovskii, E.A. Kotomin, J. Maier, Nanoionics in the context of lithium batteries, J. Power Sources 159 (1) (2006) 171-178.
[6] H. Li, L.H. Shi, Q. Wang, L.Q. Chen, X.J. Huang, Nano-alloy anode for lithium ion batteries, Solid State Ionics 148 (3-4) (2002) 247-258.
[7] Y.G. Guo, J.S. Hu, L.J. Wan, Nanostructured materials for electrochemical energy conversion and storage devices, Adv. Mater. 20 (15) (2008) 2878-2887.
[8] J. Tang, Y.Y. Wu, E.W. McFarland, G.D. Stucky, Synthesis and photocatalytic properties of highly crystalline and ordered mesoporous TiO₂ thin films, Chem. Commun. (2004) 1670-1671.
[9] R.L. Liu, Y.J. Ren, Y.F. Shi, F. Zhang, L.J. Zhang, B. Tu, D.Y. Zhao, Controlled synthesis of ordered mesoporous C-TiO₂ nanocomposites with crystalline titania frameworks from organic-inorganic-amphiphilic coassembly, Chem. Mater. 20 (3) (2008) 1140-1146.
[10] J.W. Lee, M.C. Orilall, S.C. Warren, M. Kamperman, F.J. Disalvo, U. Wiesner, Direct access to thermally stable and highly crystalline mesoporous transition-metal oxides with uniform pores, Nat. Mater. 7 (2008) 222-228.
[11] J. Chen, Z. Hua, Y. Yan, A.A. Zakhidov, R.H. Baughman, L. Xu, Template synthesis of ordered arrays of mesoporous titania spheres, Chem. Commun. 46 (2010) 1872-1874.
[12] Y.G. Guo, Y.S. Hu, J. Maier, Synthesis of hierarchically mesoporous anatase spheres and their application in lithium batteries, Chem. Commun. 26 (2006) 2783-2785.
[13] J.M. Szeifert, J.M. Feckl, D.F. Rohlfing, Y.J. Liu, V. Kalousek, J. Rathousky, T. Bein, Ultrasmall titania nanocrystals and their direct assembly into mesoporous structures showing fast lithium insertion, J. Am. Chem. Soc. 132 (36) (2010) 12605-12611.
[14] W. Yue, C. Randorn, P.S. Attidekou, Z.X. Su, J.T.S. Irvine, W.Z. Zhou, Syntheses, Li insertion, and photoactivity of mesoporous crystalline TiO₂, Adv. Funct. Mater. 19 (17) (2009) 2826-2833.
[15] Z. Wang, L. Zhou, X.W. Lou(David), Metal oxide hollow nanostructures for lithiumion batteries, Adv. Mater. 24 (14) (2012) 1903-1911.
[16] Z.Wang, X.W. Lou (David), TiO₂ nanocages: fast synthesis, interior functionalization and improved lithium storage properties, Adv. Mater. 24 (30) (2012) 4124-4129.
[17] X. Sun, J. Liu, Y. Li, Use of carbonaceous polysaccharide microspheres as templates for fabricating metal oxide hollow spheres, Chem. Eur. J. 12 (7) (2006) 2039-2047.
[18] H.Wang, Z.Wu, Y. Liu, A simple two-step template approach for preparing carbondoped mesoporous TiO₂ hollow microspheres, J. Phys. Chem. C 113 (30) (2009) 13317-13324.
[19] M.M. Titirici,M. Antonietti, A. Thomas, A generalized synthesis ofmetal oxide hollow spheres using a hydrothermal approach, Chem. Mater. 18 (16) (2006) 3808-3812.
[20] K. Yang, F. Tan, F.Wang, Y. Long, Y.Wen, Response surface optimization for process parameters of LiFePO₄/C preparation by carbothermal reduction technology, Chin. J. Chem. Eng. 20 (4) (2012) 793-802.
[21] S.K. Das, S. Darmakolla, A.J. Bhattacharyya, High lithium storage inmicrometre sized mesoporous spherical self-assembly of anatase titania nanospheres and carbon, J. Mater. Chem. 20 (2010) 1600-1606.
[22] S.B. Bothara, S. Singh, Thermal studies on natural polysaccharide, Asian Pac. J. Trop. Biomed. 2 (2) (2012) S1031-S1035.
[23] X.W. Lou, Y. Wang, C. Yuan, J.Y. Lee, L.A. Archer, Template-free synthesis of SnO₂ hollow nanostructures with high lithium storage capacity, Adv. Mater. 18 (17) (2006) 2325-2329.
[24] T. Ohno, K. Sarukawa, K. Tokieda, M. Matsumura, Morphology of a TiO₂ photocatalyst (Degussa, P-25) consisting of anatase and rutile crystalline phases, J. Catal. 203 (1) (2001) 82-86.
[25] G.F. Ortiz, I. Hanzu, T. Djenizian, P. Lavela, J.L. Tirado, P. Knauth, Alternative Li-ion battery electrode based on self-organized titania nanotubes, Chem. Mater. 21 (1) (2009) 63-67.
[26] G.Q. Liu, L. Wen, G.Y. Liu, Q.Y. Wu, H.Z. Luo, B.Y. Ma, Y.W. Tian, Synthesis and electrochemical properties of Li₄Ti₅O₁₂, J. Alloys Compd. 509 (22) (2011) 6427-6432.
[27] M. Wagemaker, R. van de Krol, A.P.M. Kentgens, A.A. van Well, F.M. Mulder, Two phase morphology limits lithium diffusion in TiO₂ (anatase): a 7Li MAS NMR study, J. Am. Chem. Soc. 123 (46) (2001) 11454-11461.

Lithium Storage Performance of Hollow and Core/Shell TiO₂ Microspheres Containing Carbon

Lithium Storage Performance of Hollow and Core/Shell TiO₂ Microspheres Containing Carbon

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