Elsevier

Journal of Power Sources

Volume 426, 30 June 2019, Pages 250-258
Journal of Power Sources

Controlled formation of BNb3O9 nanobelts as superior host material for high performance electrochemical energy storage

https://doi.org/10.1016/j.jpowsour.2019.04.051Get rights and content

Highlights

  • BNb3O9 hollowed-out nanobelts are formed by an adjustable-voltage electrospinning.

  • BNb3O9 hollowed-out nanobelts show superior performance to the microparticles.

  • LiFePO4/BNb3O9 cell presents 66% capacity retention after 200 cycles at 700 mA g−1.

  • Structural evolution of BNb3O9 upon lithiation is analyzed by in situ XRD.

Abstract

Ultra-stable anode materials for lithium-ion batteries are increasing in demand as highly sustainable energy storage system with excellent charge transport becomes unprecedentedly important. Here, a novel Li-ion full cell, utilizing BNb3O9 hollowed-out nanobelts as the typical intercalation anode and commercial LiFePO4 as the cathode in organic electrolyte, is reported. Moreover, the hollowed-out framework of BNb3O9 nanobelts, prepared by an adjustable-voltage electrospinning method, exhibits prominent cyclic stability (116.1 mAh g−1 at 700 mA g−1 (12C) over 1000 cycles) and outstanding rate capability (126.8 mAh g−1 at 900 mA g−1) in half cell. The key finding is that the formation mechanism of BNb3O9 hollowed-out nanobelts can be thoroughly discussed by scanning electron microscope. The contribution of the external pseudocapacitance largely affects the rate capability, which is determined via kinetic analysis. Furthermore, the lithium storage mechanism and structural evolution of BNb3O9 are investigated through in-situ X-ray diffraction. Such preeminent electrochemical performance and distinctive morphology endow BNb3O9 hollowed-out nanobelts with potentials as anode materials for lithium-ion batteries.

Introduction

Rechargeable lithium-ion batteries (LIBs) are extensively considered as one of the most advanced and vital energy storage devices owing to their high power density and low impact to environment [[1], [2], [3], [4], [5], [6], [7]]. Graphite as a commercialized anode material is successful for LIBs because of its low cost and relatively large theoretical capacity (372 mAh g−1). However, lithium intercalation at low operating voltage (about 0.1–0.2 V vs. Li+/Li) may lead to the formation of lithium dendrites during high-rate charge and discharge [[8], [9], [10]]. Therefore, it is necessary to explore alternative anode materials which are able to react with lithium at voltages above 0.5 V in the organic electrolytes.

In this aspect, titanium-based oxides have attracted widespread attention because of their suitable lithium ion insertion/extraction voltage window of 1.0–2.0 V. Particularly, the zero-strain Li4Ti5O12 with spinel structure is reported to be a dominant candidate for high-performance LIBs [[11], [12], [13], [14], [15], [16], [17]]. However, its low theoretical capacity cannot satisfy the demand of current market, which is the main drawback of Li4Ti5O12 [18,19]. Additionally, the other titanium-based oxides such as TiO2, LiCrTiO4 and LiTi2(PO4)3, also show the low theoretical capacity (<200 mAh g−1) with a Ti4+/Ti3+ redox couple [[20], [21], [22], [23], [24], [25]]. Recent research trends in exploring anode materials for LIBs have been devoted to niobium-based oxides because of their relatively high theoretical capacity (389 mAh g−1, supposing 2e transfer formula unit). Besides, Nb5+/Nb4+ and Nb4+/Nb3+, as two pairs of redox couples, are located within the voltage range of 1–3 V, which may avoid the formation of the solid electrolyte interface (SEI) film during charge and discharge cycles [[26], [27], [28], [29], [30], [31]].

Herein, we report a facile and efficient approach to synthesize BNb3O9 hollowed-out nanobelts (denoted as BNO-H) by electrostatic spinning technology for the first time. The resulting hollowed-out banded structure is characterized by interconnected nanocrystallines with an average diameter of 100 nm and macropores separated by these nanocrystallines. Excitingly, the BNO-H shows enhanced electrochemical performances. Moreover, we find that in the voltage window of 1.0–3.0 V, five lithium ions can be stored in BNO-H structure per formula unit during discharge process, leading to a discharge capacity of 309 mAh g−1. In order to further insight into the lithium storage mechanism, we investigated the structural change of the BNO-H electrodes based on in-situ X-ray diffraction technique. The results display that BNO-H suffers a complicated two-phase reaction and three solid solution processes. The BNO-H shows not only ultrahigh reversibility, but also a high capacity, indicating it is a pretty hopeful anode material for LIBs.

Section snippets

Synthesis of BNb3O9 nanomaterials

The raw materials of poly (vinylpyrrolidone) (PVP) (MW ≈ 1300000, Macklin), H3BO3 (AR, Macklin) and C10H5NbO20 (AR, Macklin) were commercially available. The distilled water and absolute ethanol at a volume ratio of 1:4 were used as the solvent. After that, 1.116 g of C10H5NbO20 and 0.043 g of H3BO3 were added into the above solvent to form a mixed solution. Then, 1.6 g PVP was dissolved in the above mixed solution (16 mL). After magnetic stirring for 12 h, the obtained precursor solution was

Results and discussion

The general formation procedure of complex one-dimensional (1D) nanostructures is studied via electrospinning. Firstly, the cross-section of the initial liquid jet is often in circular shape due to the applied static voltage. Secondly, the ejected circular precursor undergoes a transient movement towards the grounded collector driven by electrostatic field force. Thirdly, the spun precursor fibers are solidified and collected over the grounded collector. Based on the mentioned analysis, the

Conclusions

The designed concept for synthesizing the BNO-H presents in this work is easily reproducible and facile. The growth of 1D hollowed-out banded structure is controlled by a simple electrospinning technique with different applied voltages. This provides an alternative approach for fabricating valuable hollowed-out banded materials by varying applied voltages.

By right of the distinctive hollowed-out banded structure, the BNO-H shows ascendant electrochemical performance as the anode for lithium ion

Acknowledgments

This work is sponsored by National Natural Science Foundation of China (U1632114), Ningbo Key Innovation Team (2014B81005), and K.C. Wong Magna Fund in Ningbo University.

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