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


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.


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.


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.


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  • 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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