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Structure and electrochemical performance of BaLi2−x Na x Ti6O14 (0≤x≤2) as anode materials for lithium-ion battery

锂离子电池BaLi2−x Na x Ti6O14 (0≤x≤2)负极材料的结构与电化学性能

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Abstract

A series of BaLi2−x Na x Ti6O14(0≤x≤2) compounds as lithium storage materials were synthesized by a facile solid-state method. X-ray diffraction Rietveld refinement shows that the Bragg positions correspond to the BaLi2Ti6O14, indicating a successful preparation. The Na+ ions doped BaLi2-Ti6O14 compounds have larger unit-cell volume than the pristine one because ionic radius of Na+ ion is 55% larger than that of Li+ ion. SEM shows that the BaLi2−x Na x Ti6O14 (x=0, 0.5 and 1) powders show similar irregular shaped particles between 500 and 1000 nm. However, BaLi2−x Na x Ti6O14 (x=1.5 and 2) powders show similar rod-like shape. CV reveals that the passivating film is mainly formed during the first insertion process, and the solid electrolyte interface film on the surface of BaLi2−x Na x Ti6O14 (0≤x≤2) is formed below 0.7 V in the first cycle. Compared with other samples, BaLi0.5Na1.5Ti6O14 exhibits higher reversible capacity, better rate capability and superior cyclability. BaLi0.5Na1.5Ti6O14 delivers the delithiation capacities of 162.1 mA h g−1 at 50 mA g−1, 158.1 mA h g−1 at 100 mA g−1, 156.7 mA h g−1 at 150 mA g−1, 152.2 mA h g−1 at 200 mA g−1, 147.3 mA h g−1 at 250 mA g−1 and 142 mA h g−1 at 300 mA g−1, respectively. An interesting thing is that BaNa2Ti6O14 as anode also shows an acceptable electrochemical performance. All these improved electrochemical performances of BaLi0.5Na1.5Ti6O14 are attributed to the lowest polarization and the highest lithium ion diffusion coefficient among all samples. Hence, BaLi0.5Na1.5Ti6O14 with excellent cycling performance, simple synthesis route and wide discharge voltage range can be a possible anode candidate for lithium-ion batteries.

摘要

本文采用简单的高温固相法制备了BaLi2−x Na x Ti6O14 (0≤x≤2)系列化合物作为储锂材料. XRD Rietveld精确表明Bragg点与BaLi2Ti6O14相对应, 由于Na+的半径比Li+的半径大55%, 因此Na+掺杂的BaLi2Ti6O14化合物具有比纯BaLi2Ti6O14更大的晶胞体积. SEM测试结果表明,BaLi2−x Na x Ti6O14 (x=0, 0.5, 1)粉末呈相似的不规则的颗粒状, 粒径大约在500到1000 nm之间. 但是, BaLi2−x Na x Ti6O14 (x=1.5, 2)展示了棒状的形貌. 循环伏安结果表明, 钝化膜主要在第一次嵌锂过程时形成, BaLi2−x Na x Ti6O14 (0≤x≤2)表面的SEI膜主要在第一次循环且电位在0.7 V以下时形成. 相对于其他样品, BaLi0.5Na1.5Ti6O14具有较高的可逆容量, 较好的倍率性能和优异的循环性能. 电流密度为50、100、150、200、250和300mA g−1时, BaLi0.5Na1.5Ti6O14的脱锂容量分别为162.1、158.1、156.7、152.2、147.3和142 mA h g−1. 有趣的是, BaNa2Ti6O14作为阳极也展示了可接受的电化学性能. BaLi0.5Na1.5Ti6O14所提高的电化学性能可以归因于其最小的极化和最高的锂离子扩散系数. 因具有优异的循环性能、简单的合成路线和宽的放电区间, BaLi0.5Na1.5Ti6O14可作为锂离子电池负极候选材料.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51404002), Anhui Provincial Natural Science Foundation (1508085MB25), the Natural Science Foundation of Guangdong Province (2016A030310127) and Anhui Provincial Science Fund for Excellent Young Scholars (gxyqZD2016066).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan, 243002, China

    Wei Tao  (陶伟), Mao-Lian Xu  (徐茂莲), Yan-Rong Zhu  (朱彦荣) & Ting-Feng Yi  (伊廷锋)

  2. School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan, 523808, China

    Qianyu Zhang  (张千玉)

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  1. Wei Tao  (陶伟)
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  2. Mao-Lian Xu  (徐茂莲)
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  5. Ting-Feng Yi  (伊廷锋)
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Corresponding authors

Correspondence to Yan-Rong Zhu  (朱彦荣), Qianyu Zhang  (张千玉) or Ting-Feng Yi  (伊廷锋).

Additional information

Author contributions Tao W, Xu ML performed the materials synthesis, characterization and electrochemical measurements. Zhang Q was involved in data analysis and discussion. Yi TF and Zhu YR conceived the strategy, supervised the design of experiments, and wrote the manuscript, and all authors participated in the general discussion.

Conflict of interset The authors declare that they have no conflict of interest.

Supplementary information The charge/discharge specific capacities of BaLi2−x Na x Ti6O14 (x=0.0, 0.5, 1.0, 1.5, 2.0) samples at different cycle numbers are available in the online version of the paper.

Wei Tao received his BE degree from Anhui University of Technology in 2015. He is now a second year Master student in Prof. Ting-Feng Yi's group at Anhui University of Technology. His research focuses on the application of functional materials in lithium-ion batteries.

Qianyu Zhang received his PhD degree from Fudan University, China. He was a visiting scholar at the University of California, San Diego from 2013 to 2014. He worked as an assistant researcher at Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences from 2015 to 2017. Currently, he is an associate professor at Dongguan University of Technology, China. His research involves exploring high-performance electrode materials for Li-ion battery.

Ting-Feng Yi received his BE degree in chemical engineering and technology from Liaocheng University in 2001. He then obtained his MSc degree in applied chemistry in 2004 and PhD degree in chemical engineering and technology from Harbin Institute of Technology in 2007. He joined Anhui University of Technology as an assistant professor of chemistry in 2007. He is currently a professor of Anhui University of Technology, China. His research interests include the synthesis of electrochemical functional materials and their application in lithium-ion battery, supercapacitor and lead-acid battery. For detail please see his research ID: http://www.researcherid.com/rid/F-4594-2012.

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Tao, W., Xu, ML., Zhu, YR. et al. Structure and electrochemical performance of BaLi2−x Na x Ti6O14 (0≤x≤2) as anode materials for lithium-ion battery. Sci. China Mater. 60, 728–738 (2017). https://doi.org/10.1007/s40843-017-9065-8

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