English

Preparation of Carbon Coated Ti₂Nb₂O₉ Nanosheets and Its Sodium Ion Storage Properties

• Lu Xiaoxia ,
• Dong Shengyang ,
• Chen Zhijie ,
• Wu Langyuan ,
• Zhang Xiaogang ^,

• Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Materials Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, P. R. China

Corresponding author: Xiaogang Zhang, Email: azhangxg@nuaa.edu.cn

• Received Date: 05 June 2019
  Accepted Date: 21 July 2019
  Revised Date: 04 July 2019
  Available Online: 15 May 2020
• Fund Project:

  The project was supported by the National Natural Science Foundation of China (U1802256, 51672128, 21773118, 21875107), the Prospective Joint Research Project of Cooperative Innovation Fund of Jiangsu Province, China (BE2018122), the Foundation of Graduation Innovation Center in NUAA, China (kfjj20180613) and the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions, China (PAPD)

Abstract: In the past few decades, new energy industries have developed rapidly due to the threat of the depletion of non-renewable resources. Among them, the lithium-ion battery has attracted significant attention of various researchers. However, lithium-ion batteries are limited by the uneven distribution of lithium resources and high cost. Sodium, which is in the same periodic group as Lithium, can help alleviate the problems related to the limited development of lithium ion batteries owing to the shortage of lithium resources. Sodium ion batteries are cheap, with varying choice of electrolytes, and have relatively stable electrochemical performances. However, the radius of a sodium ion is larger than that of a lithium ion, leading to slow ion transportation as well as changes in the volume of the host material during the charging and discharging processes. Therefore, compared with existing lithium ion batteries, sodium ion battery anode materials are very limited. Moreover, most sodium ion battery electrode materials have low specific capacities and poor cycle retention rates. Among these, ternary metal oxides, which have two different cations and can reversibly react with sodium ions are promising high-capacity anode materials for sodium ion batteries. In this study, Ti₂Nb₂O₉ nanosheets are obtained by ion-exchange and chemical-delaminate methods. The carbon-coated Ti₂Nb₂O₉ nanosheets are obtained after hydrothermal coating with sucrose and calcination. From the thermogravimetric analysis (TG) curve, the carbon content in the composites is calculated to be approximately 8.0%. Owing to the rich reactive sites and a short ion transport pathway, the Ti₂Nb₂O₉/C electrode delivers a high reversible capacity of 265.2 mAh·g^-1 at a current density of 50 mA·g^-1. Even at a high current density of 500 mA·g^-1, the electrode exhibits an excellent electrochemical performance with a reversible capacity of 160.9 mAh·g^-1 after 200 cycles (capacity retention of 75.3%). Additionally, the Ti₂Nb₂O₉/C nanosheets exhibit high reversible capacities of 251.3, 224.6, 197.4, 176.3, and 156.5 mAh·g^-1 at the current densities of 100, 200, 500, 1000, and 2000 mA·g^-1, respectively. It is demonstrated through the use X-ray photoelectron spectroscopy (XPS) that the following process involving the transfer of four electrons occurs: Ti⁴⁺/Ti³⁺, Nb⁵⁺/Nb⁴⁺, during the charging and discharging process of the Ti₂Nb₂O₉ electrode in the voltage range of 0.01–3.0 V. The theoretical specific capacity of Ti₂Nb₂O₉ in this process is calculated to be 252 mAh·g^-1, corresponding to the electrochemical data. Overall, this study demonstrates that the Ti₂Nb₂O₉/C anode nanosheets have an excellent charge-discharge performance, cycle stability, and rate performance in sodium ion batteries, thereby providing a feasible choice for sodium ion battery anode materials.

Key words:
• Sodium ion battery
•  /  Delaminate
•  /  Ti₂Nb₂O₉ nanosheet
•  /  Carbon coating
•  /  Anode material

• 1. [1]

     Pan, H.; Hu, Y. S.; Chen, L. Energy Environ. Sci. 2013, 6, 2338. doi: 10.1039/C3EE40847G

  2. [2]

     Slater, M. D.; Kim, D.; Lee, E.; Johnson, C. S. Adv. Funct. Mater. 2013, 23, 947. doi: 10.1002/adfm.201200691

  3. [3]

     Ge, Y.; Jiang, H.; Fu, K.; Zhang, C. H.; Zhu, J. D.; Chen, C.; Lu, Y.; Qiu, Y. P.; Zhang, X. W. J. Power Sources 2014, 272, 860. doi: 10.1016/j.jpowsour.2014.08.131

  4. [4]

     Xiong, H.; Slater, M. D.; Balasubramanian, M.; Johnson, C. S.; Rajh, T. J. Phys. Chem. Lett. 2011, 2, 2560. doi: 10.1021/jz2012066

  5. [5]

     Sun, Q.; Ren, Q. Q.; Li, H.; Fu, Z. W. Electrochem. Commun. 2011, 13, 1462. doi: 10.1016/j.elecom.2011.09.020

  6. [6]

     Alcántara, R.; Jaraba, M.; Lavela, P.; Tirado, J. L. Chem. Mater. 2002, 14, 2847. doi: 10.1021/cm025556v

  7. [7]

     Osada, M.; Sasaki, T. J. Mater. Chem. 2009, 19, 2503. doi: 10.1039/B820160A

  8. [8]

     Yabuuchi, N.; Kubota, K.; Dahbi, M.; Komaba, S. Chem. Rev. 2014, 114, 11636. doi: 10.1021/cr500192f

  9. [9]

     Ge, P.; Fouletier, M. Solid State Ionics 1988, 28, 1172. doi: 10.1016/0167-2738(88)90351-7

  10. [10]

      Luo, X. F.; Yang, C. H.; Peng, Y. Y.; Pu, N. W.; Ger, M. D.; Hsieh, C. T.; Chang, J. K. J. Mater. Chem. A 2015, 3, 10320. doi: 10.1039/C5TA00727E

  11. [11]

      Wen, Y.; He, K.; Zhu, Y. J.; Han, F. D.; Xu, Y. H.; Matsuda, I.; Ishii, Y.; Cumings, J.; Wang, C. S. Nat. Commun. 2014, 5, 4033. doi: 10.1038/ncomms5033

  12. [12]

      Chen, C. J.; Wen, Y. W.; Hu, X. L.; Ji, X, L.; Yan, M. Y.; Mai, L. Q.; Hu, P.; Shan, B.; Huang, Y. H. Nat. Commun. 2015, 6, 6929. doi: 10.1038/ncomms7929

  13. [13]

      Sun, Y.; Zhao, L.; Pan, H. L.; Lu, X.; Gu, L.; Hu, Y. S.; Li, H.; Armand, M.; Ikuhara, Y.; Chen, L. Q.; et al. Nat. Commun. 2013, 4, 1870. doi: 10.1038/ncomms2878

  14. [14]

      Yu, H. J.; Ren, Y.; Xiao, D. D.; Guo, S. H.; Zhu, Y. B.; Qian, Y. M.; Gu, L; Zhou, H. S. Angew. Chem. Int. Ed. 2014, 53, 8963. doi: 10.1002/anie.201404549

  15. [15]

      Dong, S. Y.; Shen, L. F.; Li, H. S.; Pang, G.; Dou, H. Zhang, X. G. Adv. Funct. Mater. 2016, 26, 3703. doi: 10.1002/adfm.201600264

  16. [16]

      Rudola, A.; Saravanan, K.; Mason, C. W.; Balaya, P. J. Mater. Chem. A 2013, 1, 2653. doi: 10.1039/C2TA01057G

  17. [17]

      Li, H. S.; Zhu, Y.; Dong, S.Y.; Shen, L. F.; Chen, Z. J.; Zhang, X. G.; Yu, G. H. Chem. Mater. 2016, 28, 5753. doi: 10.1021/acs.chemmater.6b01988

  18. [18]

      Lim, E.; Jo, C.; Kim, M. S.; Kim, M.; Chun, J.; Kim, H.; Park, J.; Roh, K. C.; Kang, K.; Yoon, S.; et al. Adv. Funct. Mater. 2016, 26, 3711. doi: 10.1002/adfm.201505548

  19. [19]

      Wu, L. M.; Bresser, D.; Buchholz, D.; Giffin, G. A.; Castro, C. R.; Ochel, A.; Passerini, S. Adv. Energy Mater. 2015, 5, 1401142. doi: 10.1002/aenm.201401142

  20. [20]

      陈程成, 张宁, 刘永畅, 王一菁, 陈军.物理化学学报, 2016, 32, 349. doi: 10.3866/PKU.WHXB201512073Chen, C. C.; Zhang, N.; Liu, Y. C.; Wang, Y. J.; Chen, J. Acta Phys. -Chim. Sin. 2016, 32, 349. doi: 10.3866/PKU.WHXB201512073

  21. [21]

      Shen, L. F.; Yu, L.; Yu, X. Y.; Zhang, X. G.; Lou, X. W. Angew. Chem. Int. Ed. 2015, 54, 1868. doi: 10.1002/anie.201409776

  22. [22]

      赵明宇, 朱琳, 付博文, 江素华, 周永宁, 宋云.物理化学学报, 2019, 35, 193 doi: 10.3866/PKU.WHXB201801241Zhao, M. Y.; Zhu, L.; Fu, B. W.; Jiang, S. H.; Zhou, Y. N.; Song, Y. Acta Phys. -Chim. Sin. 2019, 35, 193. doi: 10.3866/PKU.WHXB201801241

  23. [23]

      Hasegawa, G.; Kanamori, K.; Kiyomura, T.; Kurata, H.; Nakaishi, K.; Abe, T. Adv. Energy Mater. 2015, 5, 1400730. doi: 10.1002/aenm.201400730

  24. [24]

      Han, J. T.; Goodenough, J. B. Chem. Mater. 2011, 23, 3404. doi: 10.1021/cm201515g

  25. [25]

      Tang, K.; Mu, X. K.; Aken, P. A. V.; Yu, Y.; Maier, J. Adv. Energy Mater. 2013, 3, 49. doi: 10.1002/aenm.201200396

  26. [26]

      Shang, B.; Peng, Q. M.; Jiao, X.; Xi, G. C.; Hu, X. B. Ionics 2018, 1, 10. doi: 10.1007/s11581-018-2784-z

  27. [27]

      Li, S.; Cao, X.; Schmidt, C. N.; Xu, Q.; Uchaker, E.; Pei, Y.; Cao, G. Z. J. Mater. Chem. A2016, 4, 4242. doi: 10.1039/c5ta10510b

  28. [28]

      Colin, J. F.; Pralong, V.; Hervieu, M.; Caignaert, V.; Raveau, B. Chem. Mater. 2008, 20, 1534. doi: 10.1021/cm702978g

  29. [29]

      Shen, L. F.; Wang, Y.; Lv, H. F.; Chen, S. Q.; Aken, P. A.; Wu, X. J.; Maier, J.; Yu, Y. Adv. Mater. 2018, 30, 1804378. doi: 10.1002/adma.201804378

  30. [30]

      Xing, L. D.; Yu, Q. Y.; Jiang, B.; Chu, J. H.; Lao, C. Y.; Wang, M.; Han, K.; Liu, Z. W.; Bao, Y. P.; Wang, W. J. Mater. Chem. A 2019, 7, 5760. doi: 10.1039/C8TA12497C

  31. [31]

      Park, H.; Song, T.; Paik, U. J. Mater. Chem. A 2015, 3, 8590. doi: 10.1039/C5TA00467E

  32. [32]

      Rebbah, H.; Desgardin, G.; Raveau, B. Mater. Research Bulletin 1979, 14, 1125. doi: 10.1016/0025-5408(79)90206-X

•