Effect of K-Doping on the Sodium-storage Performance of Sodium Vanadate Nanoplates

doi:10.6023/A19010040

Acta Chim. Sinica ›› 2019, Vol. 77 ›› Issue (7): 625-633.DOI: 10.6023/A19010040 Previous Articles Next Articles

Article

钾掺杂对钒酸钠纳米片储钠性能的影响

宋学霞^a,b, 李继成^a, 李朝晖^a, 李喜飞^b, 丁燕怀^c, 肖启振^a, 雷钢铁^a

a 湘潭大学化学学院教育部环境友好化学和应用重点实验室湘潭 411105;
b 西安理工大学先进电化学能源研究院西安 710048;
c 湘潭大学土木与力学工程学院湘潭 411105

投稿日期:2019-01-23 发布日期:2019-07-02
通讯作者: 李朝晖, 李喜飞 E-mail:lzh69@xtu.edu.cn;xfli2011@hotmail.com
基金资助:
项目受国家自然科学基金（Nos.51572194，51672189）和湖南省自然科学基金（Nos.2018JJ2386，2018JJ2393）资助.

Effect of K-Doping on the Sodium-storage Performance of Sodium Vanadate Nanoplates

Song Xuexi^a,b, Li Jicheng^a, Li Zhaohui^a, Li Xifei^b, Ding Yanhuai^c, Xiao Qizhen^a, Lei Gangtie^a

a Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105;
b Institute of Advanced Electrochemical Energy, Xi'an University of Technology, Xi'an 710048;
c College of Civil Engineering and Mechanics, Xiangtan University, Xiangtan 411105

Received:2019-01-23 Published:2019-07-02
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 51572194, 51672189), and the Hunan Provincial Natural Science Foundation (Nos. 2018JJ2386, 2018JJ2393).

1. Effect of K-Doping on the Sodium-storage Performance of Sodium Vanadate Nanoplates.PDF(982KB)

Abstract

Na-ion batteries with lower cost than Li-ion batteries would be developed to large-scale energy-storage device to store solar and wind energies. However, large radius renders Na⁺ ions to insert into/extract out the layered transition metal oxides (LTMOs) sluggishly. To improve the intercalation dynamics of Na⁺ ions, the interlayer spacing of crystals has to be expanded for those LTMOs that are capable of fast lithiation and delithiation. Herein, a LTMO based on vanadium is firstly doped with larger K⁺ ions to expand the interlayer spacing to yield K⁺-doped sodium vanadate (Na₅K_xV₁₂O₃₂) cathode material by a hydrothermal method at 200℃ for 24 h followed by calcination at 500℃ for 3 h. The samples were characterized by scanning electron microscope (SEM)/transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) technologies. Effect of the doping amount of K⁺ on the structure and sodium-storage performance of the sample was studied in detail. The synthesized materials display nanoplate morphology viewing from the TEM images. K⁺ ions are doped into the interlayer of the sodium vanadate crystallites, which is proved by analysis of the XRD patterns and XPS spectra. Expanded interlayer spacing favors Na⁺ ions' intercalation and deintercalation between the[V₃O₈]^- layers, which is testified by the chemical diffusion coefficient of cathodes, thus enhancing the rate capability. On the other hand, the chemically pre-intercalated K⁺ ions are pinned in the crystallites during insertion and extraction of Na⁺ ions and act as pillars to stabilize the layered structure, improving the cycliability of the cathode. However, excessive doping of K⁺ leads to a discounted rate capability of the cathode, suggesting an optimized amount of K⁺ doping into the crystal. The results from galvanostatic charge-discharge tests indicate that the obtained NVO(3K) sample, in which 0.118 mol of K⁺ ions are doped into per mol of Na₅V₁₂O₃₂, presents the best electrochemical performance among the various samples. It can deliver the maximum capacities of 169, 160, 148, 132, 98 and 69 mAh·g^-1 at the rates of 0.1C, 0.2C, 0.5C, 1C, 3C and 10C after activated for several times over the voltage window of 4.0~1.5 V (vs. Na⁺/Na), respectively. Even run at 3C rate, it can retain 93.0% of the maximum capacity after 1000 cycles, exhibiting excellent rate capability and stable cycliability. The results suggest that doping of K⁺ ions into the interlayer of crystallites can significantly improving the rate capability as well as cycling performance of the obtained Na₅V₁₂O₃₂. Our investigation demonstrates that design of K⁺-doped sodium vanadate cathode materials is beneficial for harvesting superior performance, of which the Na₅K_0.118V₁₂O₃₂ nanoplates can be developed into a novel cathode material for sodium-ion batteries in the future.

Key words: sodium-ion battery, Na₅V₁₂O₃₂, cation doping, cathode material, electrochemical performance

Cite this article

Song Xuexi, Li Jicheng, Li Zhaohui, Li Xifei, Ding Yanhuai, Xiao Qizhen, Lei Gangtie. Effect of K-Doping on the Sodium-storage Performance of Sodium Vanadate Nanoplates[J]. Acta Chim. Sinica, 2019, 77(7): 625-633.

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钾掺杂对钒酸钠纳米片储钠性能的影响

Effect of K-Doping on the Sodium-storage Performance of Sodium Vanadate Nanoplates

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