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SCIENCE CHINA Materials, Volume 60, Issue 4: 304-314(2017) https://doi.org/10.1007/s40843-016-9002-y

Fast synthesis of uniform mesoporous titania submicrospheres with high tap densities for high-volumetric performance Li-ion batteries

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  • ReceivedDec 19, 2016
  • AcceptedJan 18, 2017
  • PublishedFeb 6, 2017

Abstract

High-tap density electrode materials are greatly desired for Li-ion batteries with high volumetric capacities to fulfill the growing demands of electric vehicles and portable smart devices. TiO2, which is one of the most attractive anode materials, is limited in their application for Li-ion batteries because of its low tap density (usually <1 g cm−3) and volumetric capacity. Herein, we report uniform mesoporous TiO2 submicrospheres with a tap density as high as 1.62 g cm−3 as a promising anode material. Even with a high mass loading of 24 mg cm−2, the TiO2 submicrospheres have impressive volumetric capacities that are more than double those of their counterparts. Moreover, they can be synthesized with ~100% yield and within a reaction time of ~6 h by optimizing the experimental conditions and formation mechanism, exhibiting potential for large-scale production for industrial applications. Other mesoporous anode materials, i.e., high-tap density mesoporous Li4Ti5O12 submicrospheres, are fabricated using the generalized method. We believe that our work provides a significant reference for the industrial production of mesoporous materials for Li-ion batteries with a high volumetric performance.


Funded by

National High Technology Research and Development Program of China(2013AA050901)

National Basic Research Program of China(2015CB251100)

the Thousand Youth Talents Program

National Natural Science Foundation of China(51602173,51371015,11674023)

China Postdoctoral Science Foundation(2016M591186)

Fei Zhao

and Yufeng Luo for their help with the N adsorption/desorption measurements.


Acknowledgment

This work was supported by the National High Technology Research and Development Program of China (2013AA050901), the National Basic Research Program of China (2015CB251100), the Thousand Youth Talents Program, the National Natural Science Foundation of China (51602173, 51371015 and 11674023), and China Postdoctoral Science Foundation (2016M591186). We thank Prof. Jiaping Wang, Fei Zhao, and Yufeng Luo for their help with the N2 adsorption/desorption measurements.


Interest statement

The authors declare that they have no conflicts of interest.


Contributions statement

Zhu K, Shan Z, and Liu K proposed and designed the project. Zhu K performed the experiments and wrote the paper. Liu K, Sun Y, and Wang R revised and polished the paper. All the authors contributed to the general discussion.


Author information

Kunlei Zhu obtained his PhD degree at Tianjin University in 2015, and is now a postdoctoral research fellow at Tsinghua University. His research interests are focused on the syntheses of mesoporous materials and 2D materials for energy storage.


Zhongqiang Shan was born in 1957. He is a full professor at Tianjin University. His current research interests are focused on the energy storgae devices including Li-ion battries, Li-S batteries and supercapacitors.


Kai Liu obtained his PhD degree at Tsinghua University in 2008. He joined Tsinghua University as an associtate professor in 2015 after a period of postdoctoral research at Lawrence-Berkeley National Lab. His current research focuses on the mechanical and electrical properties of low-dimensinal materials and their applications.


Supplement

Supporting information

Experimental details, N2 adsorption/desorption results, SEM images, XRD patterns, Raman spectra, EELS spectra, EDS spectra, the change curves for the diameter of the intermediate TiO2 samples, TEM images, schematic diagrams, Li-ion battery performance measurements, and references are available in the online version of the paper.


References

[1] Gogotsi Y, Simon P. True performance metrics in electrochemical energy storage. Science, 2011, 334: 917-918 CrossRef ADS Google Scholar

[2] Ghidiu M, Lukatskaya MR, Zhao MQ, et al. Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance. Nature, 2014, 516: 78-81 CrossRef ADS Google Scholar

[3] Zhang C, Yang QH. Packing sulfur into carbon framework for high volumetric performance lithium-sulfur batteries. Sci China Mater, 2015, 58: 349-354 CrossRef Google Scholar

[4] Saravanan K, Ananthanarayanan K, Balaya P. Mesoporous TiO2 with high packing density for superior lithium storage. Energy Environ Sci, 2010, 3: 939-948 CrossRef Google Scholar

[5] Liang J, Yu XY, Zhou H, et al. Bowl-like SnO2@carbon hollow particles as an advanced anode material for lithium-ion batteries. Angew Chem Int Ed, 2014, 53: 12803-12807 CrossRef Google Scholar

[6] Wagemaker M, Mulder FM. Properties and promises of nanosized insertion materials for Li-ion batteries. Acc Chem Res, 2013, 46: 1206-1215 CrossRef Google Scholar

[7] Li W, Wu Z, Wang J, et al. A perspective on mesoporous TiO2 materials. Chem Mater, 2014, 26: 287-298 CrossRef Google Scholar

[8] Qiu B, Xing M, Zhang J. Mesoporous TiO2 nanocrystals grown in situ on graphene aerogels for high photocatalysis and lithium-ion batteries. J Am Chem Soc, 2014, 136: 5852-5855 CrossRef Google Scholar

[9] Liu Y, Che R, Chen G, et al. Radially oriented mesoporous TiO2 microspheres with single-crystal-like anatase walls for high-efficiency optoelectronic devices. Sci Adv, 2015, 1: e1500166 CrossRef ADS Google Scholar

[10] Liu Y, Elzatahry AA, Luo W, et al. Surfactant-templating strategy for ultrathin mesoporous TiO2 coating on flexible graphitized carbon supports for high-performance lithium-ion battery. Nano Energy, 2016, 25: 80-90 CrossRef Google Scholar

[11] Guan BY, Yu L, Li J, et al. A universal cooperative assembly-directed method for coating of mesoporous TiO2 nanoshells with enhanced lithium storage properties. Sci Adv, 2016, 2: e1501554 CrossRef ADS Google Scholar

[12] Yu XY, Wu HB, Yu L, et al. Rutile TiO2 submicroboxes with superior lithium storage properties. Angew Chem Int Ed, 2015, 54: 4001-4004 CrossRef Google Scholar

[13] Saito M, Nakano Y, Takagi M, et al. Improvement of tap density of TiO2(B) powder as high potential negative electrode for lithium ion batteries. J Power Sources, 2013, 244: 50-55 CrossRef Google Scholar

[14] Chen D, Caruso RA. Recent progress in the synthesis of spherical titania nanostructures and their applications. Adv Funct Mater, 2013, 23: 1356-1374 CrossRef Google Scholar

[15] Liu H, Bi Z, Sun XG, et al. Mesoporous TiO2-B microspheres with superior rate performance for lithium ion batteries. Adv Mater, 2011, 23: 3450-3454 CrossRef Google Scholar

[16] Trang NTH, Ali Z, Kang DJ. Mesoporous TiO2 spheres interconnected by multiwalled carbon nanotubes as an anode for high-performance lithium ion batteries. ACS Appl Mater Interfaces, 2015, 7: 3676-3683 CrossRef Google Scholar

[17] Zhu K, Tian J, Liu Y, et al. Submicron-sized mesoporous anatase TiO2 beads with a high specific surface synthesized by controlling reaction conditions for high-performance Li-batteries. RSC Adv, 2013, 3: 13149-13155 CrossRef Google Scholar

[18] Zhao T, Luo W, Deng Y, et al. Monodisperse mesoporous TiO2 microspheres for dye sensitized solar cells. Nano Energy, 2016, 26: 16-25 CrossRef Google Scholar

[19] Zhang Y, Shi Y, Liou YH, et al. High performance separation of aerosol sprayed mesoporous TiO2 sub-microspheres from aggregates via density gradient centrifugation. J Mater Chem, 2010, 20: 4162-4167 CrossRef Google Scholar

[20] Hong MP, Kim JY, Vemula K, et al. Synthesis of monodisperse mesoporous TiO2 spheres with tunable sizes between 0.6 and 3.1 μm and effects of reaction temperature, Ti source purity, and type of alkylamine on size and monodispersity. Chem Commun, 2012, 48: 4250-4252 CrossRef Google Scholar

[21] Chen D, Cao L, Huang F, et al. Synthesis of monodisperse mesoporous titania beads with controllable diameter, high surface areas, and variable pore diameters (14−23 nm). J Am Chem Soc, 2010, 132: 4438-4444 CrossRef Google Scholar

[22] Yan K, Qiu Y, Chen W, et al. A double layered photoanode made of highly crystalline TiO2 nanooctahedra and agglutinated mesoporous TiO2 microspheres for high efficiency dye sensitized solar cells. Energy Environ Sci, 2011, 4: 2168-2176 CrossRef Google Scholar

[23] Roh DK, Seo JA, Chi WS, et al. Facile synthesis of size-tunable mesoporous anatase TiO2 beads using a graft copolymer for quasi-solid and all-solid dye-sensitized solar cells. J Mater Chem, 2012, 22: 11079-11085 CrossRef Google Scholar

[24] Wang L, Tomura S, Maeda M, et al. Synthesis of mesoporous TiO2 spheres under static condition. Chem Lett, 2000, 29: 1414-1415 CrossRef Google Scholar

[25] Duan Y, Fu N, Fang Y, et al. Synthesis and formation mechanism of mesoporous TiO2 microspheres for scattering layer in dye-sensitized solar cells. Electrochim Acta, 2013, 113: 109-116 CrossRef Google Scholar

[26] Wang Y, Tang X, Yin L, et al. Sonochemical synthesis of mesoporous titanium oxide with wormhole-like framework structures. Adv Mater, 2000, 12: 1183-1186 CrossRef Google Scholar

[27] Zhang L, Yu JC. A sonochemical approach to hierarchical porous titania spheres with enhanced photocatalytic activity. Chem Commun, 2003, 9: 2078 CrossRef Google Scholar

[28] Wang HE, Jin J, Cai Y, et al. Facile and fast synthesis of porous TiO2 spheres for use in lithium ion batteries. J Colloid Interface Sci, 2014, 417: 144-151 CrossRef Google Scholar

[29] Widoniak J, Eiden-Assmann S, Maret G. Synthesis and characterisation of porous and non-porous monodisperse TiO2 and ZrO2 particles. Colloids Surfaces A-Physicochem Eng Aspects, 2005, 270-271: 329-334 CrossRef Google Scholar

[30] Tsung CK, Fan J, Zheng N, et al. A general route to diverse mesoporous metal oxide submicrospheres with highly crystalline frameworks. Angew Chem Int Ed, 2008, 47: 8682-8686 CrossRef Google Scholar

[31] Das SK, Darmakolla S, Bhattacharyya AJ. High lithium storage in micrometre sized mesoporous spherical self-assembly of anatase titania nanospheres and carbon. J Mater Chem, 2010, 20: 1600 CrossRef Google Scholar

[32] Tong H, Enomoto N, Inada M, et al. Synthesis of mesoporous TiO2 spheres and aggregates by sol-gel method for dye-sensitized solar cells. Mater Lett, 2015, 141: 259-262 CrossRef Google Scholar

[33] Liu H, Li W, Shen D, et al. Graphitic carbon conformal coating of mesoporous TiO2 hollow spheres for high-performance lithium ion battery anodes. J Am Chem Soc, 2015, 137: 13161-13166 CrossRef Google Scholar

[34] Liu H, Ma H, Joo J, et al. Contribution of multiple reflections to light utilization efficiency of submicron hollow TiO2 photocatalyst. Sci China Mater, 2016, 59: 1017-1026 CrossRef Google Scholar

[35] Jin J, Huang SZ, Liu J, et al. Phases hybriding and hierarchical structuring of mesoporous TiO2 nanowire bundles for high-rate and high-capacity lithium batteries. Adv Sci, 2015, 2: 1500070 CrossRef Google Scholar

[36] Lin C, Fan X, Xin Y, et al. Monodispersed mesoporous Li4Ti5O12 submicrospheres as anode materials for lithium-ion batteries: morphology and electrochemical performances. Nanoscale, 2014, 6: 6651-6660 CrossRef ADS Google Scholar

[37] Shin JY, Samuelis D, Maier J. Sustained lithium-storage performance of hierarchical, nanoporous anatase TiO2 at high rates: emphasis on interfacial storage phenomena. Adv Funct Mater, 2011, 21: 3464-3472 CrossRef Google Scholar

[38] Ali Z, Cha SN, Sohn JI, et al. Design and evaluation of novel Zn doped mesoporous TiO2 based anode material for advanced lithium ion batteries. J Mater Chem, 2012, 22: 17625-17629 CrossRef Google Scholar

[39] Hao R, Jiang B, Li M, et al. Fabrication of mixed-crystalline-phase spindle-like TiO2 for enhanced photocatalytic hydrogen production. Sci China Mater, 2015, 58: 363-369 CrossRef Google Scholar

[40] Liu Y, Lan K, Li S, et al. Constructing three-dimensional mesoporous bouquet-posy-like TiO2 superstructures with radially oriented mesochannels and single-crystal walls. J Am Chem Soc, 2017, 139: 517-526 CrossRef Google Scholar

[41] Han T, Chen Y, Tian G, et al. Hydrogenated TiO2/SrTiO3 porous microspheres with tunable band structure for solar-light photocatalytic H2 and O2 evolution. Sci China Mater, 2016, 59: 1003-1016 CrossRef Google Scholar

  • Figure 1

    Schematic of the synthesis of the UMTSs.

  • Figure 2

    SEM (a, b), STEM (c), and TEM images (d) of anatase UMTSs. The upper and lower insets in d show an HRTEM image and an SAED pattern, respectively.

  • Figure 3

    XRD pattern (a), Raman spectrum (b), N2 adsorption/desorption isotherm (c), and pore-size distribution curve (d) of uniform TiO2 spheres. Chart of the tap density of the UMTSs, meso-TiO2 [4], TiO2(B) [13], TiO2 submicroboxes [12], and commercial TiO2 (e).

  • Figure 4

    Uniform mesoporous Li4Ti5O12 submicrospheres: SEM (a), TEM (b), and STEM (c) images; XRD pattern (d); N2 adsorption/desorption isotherm (e); and pore-size distribution curve (f). The peak marked by the asterisk at ~20.4° is indexed to Li2TiO3.

  • Figure 5

    Galvanostatic charge/discharge curves for the first three cycles at 0.1 C (a) and CV curve obtained at a scan rate of 0.1 mV s−1 for the UMTSs. The cycle-performance curves at 1 C (c), a performance-comparison chart (d), and the EIS (e) of the three samples. Volumetric rate capability curves (e) of the UMTSs and commercial TiO2. The mass loading of all the electrodes was 24 mg cm−2.

  • Figure 6

    Schematic of the transport path of Li ions and electrons within the UMTS-based electrodes.

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