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SCIENCE CHINA Materials, Volume 60, Issue 5: 427-437(2017) https://doi.org/10.1007/s40843-017-9033-5

Hollow and hierarchical Na2Li2Ti6O14 microspheres with high electrochemical performance as anode material for lithium-ion battery

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  • ReceivedJan 4, 2017
  • AcceptedApr 10, 2017
  • PublishedApr 26, 2017

Abstract

Relying on a solvent thermal method, spherical Na2Li2Ti6O14 was synthesized. All samples prepared by this method are hollow and hierarchical structures with the size of about 2–3 μm, which are assembled by many primary nanoparticles (~300 nm). Particle morphology analysis shows that with the increase of temperature, the porosity increases and the hollow structure becomes more obvious. Na2Li2Ti6O14 obtained at 800°C exhibits the best electrochemical performance among all samples. Charge-discharge results show that Na2Li2Ti6O14 prepared at 800°C can delivers a reversible capacity of 220.1, 181.7, 161.6, 144.2, 118.1 and 97.2 mA h g−1 at 50, 140, 280, 560, 1400, 2800 mA g−1. However, Na2Li2Ti6O14-bulk only delivers a reversible capacity of 187, 125.3, 108.3, 88.7, 69.2 and 54.8 mA h g−1 at the same current densities. The high electrochemical performances of the as-prepared materials can be attributed to the distinctive hollow and hierarchical spheres, which could effectively reduce the diffusion distance of Li ions, increase the contact area between electrodes and electrolyte, and buffer the volume changes during Li ion intercalation/deintercalation processes.


Funded by

National Natural Science Foundation of China(21301052,51404002)

Natural Science Foundation of Heilongjiang Province(E2016056)

Specialized Research Fund for the Doctoral Program of Higher Education(20132301120001)

Postdoctoral Science-Research Developmental Foundation of Heilongjiang Province(LBH-Q13138)

Applied Technology Research and Development Program of Harbin(2015RAQXJ032)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21301052 and 51404002), Natural Science Foundation of Heilongjiang Province (E2016056), Specialized Research Fund for the Doctoral Program of Higher Education (20132301120001), Postdoctoral Science-Research Developmental Foundation of Heilongjiang Province (LBH-Q13138), and Applied Technology Research and Development Program of Harbin (2015RAQXJ032).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Xie Y and Zhu YR conceived the strategy and supervised the design of experiments. Fan SS, Zhong H and Lou M performed the experiments on the materials synthesis, characterization, and electrochemical measurements. Fan SS wrote the manuscript, and all authors participated in the revision of the manuscript. Yu HT was involved in data analysis and discussion.


Author information

Shan-Shan Fan received her BSc degree in applied chemistry from Luoyang Normal University in 2015. She entered Heilongjiang University to pursue her master's degree in science in 2015. She is interested in the application of quantum chemistry and the synthesis and electrochemical performance of anode materials for lithium ion battery applications.


Ying Xie received his BE degree in fine chemical engineering from Harbin University of Science and Technology in 2002. He then obtained MSc degree in chemical engineering in 2004 and PhD degree in chemical engineering and technology from Harbin Institute of Technology in 2008. He joined Heilongjiang University in 2008, and then became a member of the Key Laboratory of Functional Inorganic Material Chemistry. He is currently a professor of Heilongjiang University. His research interests include theoretical predictions on the structures and properties of inorganic compounds and the synthesis of electrode materials and their applications in lithium-ion battery.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


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  • Figure 1

    XRD patterns of Na2Li2Ti6O14 power prepared at different temperatures. (a) Standard PDF#52-0690, (b) NLTO-bulk, NLTO obtained at (c) 500°C, (d) 600°C, (e) 700°C, (f) 800°C and (g) 900°C.

  • Figure 2

    Crystal structure of Na2Li2Ti6O14 compounds.

  • Figure 3

    SEM images of Na2Li2Ti6O14 powder prepared at different temperatures. (a, b) 600°C, (c, d) 700°C, (e, f) 800°C, (g, h) 900°C and (i, j) NLTO-bulk.

  • Figure 4

    HRTEM images of NLTO-800 sample.

  • Figure 5

    (a, b) EDS images and mapping for (c) Na, (d) Ti, and (e) O elements in NLTO-800 sample.

  • Figure 6

    CVs for (a) NLTO-700, (b) NLTO-800 and (c) NLTO-bulk samples.

  • Figure 7

    Charge-discharge curves at the 1st, 10th, 30th and 50th cycles for (a) NLTO-700, (b) NLTO-800, and (c) NLTO-bulk samples. (d) Cyclic performance and Coulombic efficiency (at 50 mA g−1) for different samples.

  • Figure 8

    Charge-discharge curves for (a) NLTO-700, (b) NLTO-800 and (c) NLTO-bulk samples and (d) rate capabilities for NLTO-700, NLTO-800 and NLTO-bulk.

  • Figure 9

    (a) Nyquist plot and (b) Zre as a function of ω−0.5 at low-frequency region for NLTO-700, NLTO-800 and NLTO-bulk samples.

  • Table 1   Lattice constants calculated from XRD Rietveld refinement for different samples

    NLTO-bulk

    NLTO-600

    NLTO-700

    NLTO-800

    a (Å)

    16.5024

    16.4896

    16.4736

    16.4906

    b (Å)

    5.7516

    5.7431

    5.7383

    5.7434

    c (Å)

    11.2309

    11.2268

    11.2172

    11.2258

  • Table 2   EIS for different NaLiTiO samples

    Samples

    NLTO-700

    NLTO-800

    NLTO-bulk

    σ (Ω s−0.5)

    1,177.62

    378.51

    896.52

    DLi (cm2 s−1)

    5.51×10−17

    5.33×10−16

    3.21×10−17

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