Citation: Tong Zhenkun, Fang Shan, Zheng Hao, Zhang Xiaogang. Zn₂GeO₄ Nanorods@Graphene Composite as Anode Materials for Li-ion Batteries[J]. Acta Chimica Sinica, ;2016, 74(2): 185-190. doi: 10.6023/A15100658 shu

Zn₂GeO₄ Nanorods@Graphene Composite as Anode Materials for Li-ion Batteries

1.
Jiangsu Key Laboratory of Materials and Technology for Energy Conversion, College of Material Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 211106

Corresponding author: Zhang Xiaogang, azhangxg@nuaa.edu.cn
Received Date: 14 October 2015

Fund Project: the National Natural Science Foundation of China Nos. 21173120, 51372116the Fundamental Research Funds for the Central Universities of NUAA NP2014403, NJ20140004the Natural Science Foundation of Jiangsu Province BK2011030the National Basic Research Program of China (973 Program) No. 2014CB239701

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Commercial graphite anode material for lithium-ion batteries (LIB) with a theoretical specific capacity of 372 mAh·g^-1 is unable to satisfy the requirements of increasing mobility and high energy demands. Therefore, it is necessary to develop alternative anode material with high specific capacity. In recent years, a large amount of research has been worked out in the area of high capacity anode materials, for example, silicon (Si) and germanium (Ge). However, the large volume changes of Si and Ge during the charge and discharge process result in the cracking and pulverization of active material and delamination from the current collector, leading to a rapid decay during the cycling. As a semiconductor, Zn₂GeO₄ possesses a high capacity of 1443 mAh·g^-1 which is 90.19% as high as Ge. Nevertheless, the weight rate of germanium element in Zn₂GeO₄ is only 27.15%, which can effectively cut down the cost of anode material. In this work, Zn₂GeO₄ nanorods were synthesized through a hydrothermal method by using GeO₂ and Zn(CH₃COO)2·2H₂O and combined with RGO to form a 3D composite. In a typical synthesis, 1.10 g Zn(CH₃COO)2·2H₂O and 0.52 g GeO₂ was added into 15 mL deionized (DI) water and the pH of the mixture was adjusted to 7~8 by using NaOH aqueous solution. Then, the hydrothermal treatment was performed at 140℃ for 24 h in an oven to obtain Zn₂GeO₄ nanorods. Finally, the Zn₂GeO₄ nanorods were filtrated with GO to form a uniform membrane and reduced by hydrazine hydrate. The Zn₂GeO₄ nanorods and Zn₂GeO₄@RGO composite were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, etc. SEM and TEM testified that Zn₂GeO₄ nanorods were firmly adhered on the surface of graphene sheets, which can effectively avoid the stacking of graphene sheets. The graphene sheets connected with each other to form an electric conductive network, which can improve the electrical conductivity of the composite. Furthermore, the electrodes are fabricated without conductive additive that can improve the weight ratio of the active material in the whole electrodes. The excellent electrochemical performance showed that the 3D architecture electrode which worked as a stable framework to accommodate the volume change of active material during Li+insertion/extraction. It delivers a specific capacity of 1189.5 mAh·g^-1 at 500 mA·g^-1 after 190 discharge/charge cycles. When at different current densities of 0.8, 1.6, 3.2 A·g^-1, the capacities were found to be about 880, 700, 450 mAh·g^-1, respectively. Even at a high current density of 6.4 A·g^-1, the capacity can maintain about 250 mAh·g^-1. These results indicate that the composite possesses outstanding cycling stability and excellent rate performance.
- lithium-ion batteries,
- anode materials,
- zinc germanate nanorod,
- reduced graphene oxide,
- hydrothermal method
1. [1]
  Tarascon, J. M.; Armand, M. Nature 2001, 414, 359.
2. [2]
  Szczech, J. R.; Jin, S. Energy Environ. Sci. 2011, 4, 56.
3. [3]
  Hu, L. B.; Wu, H.; La Mantia, F.; Yang, Y. A.; Cui, Y. ACS Nano 2010, 4, 5843.
4. [4]
  Goodenough, J. B.; Kim, Y. Chem. Mater. 2010, 22, 587.
5. [5]
  Armand, M.; Tarascon, J. M. Nature 2008, 451, 652.
6. [6]
  Cheng, Y. W.; Lin, C. K.; Chu, Y. C.; Abouimrane, A.; Chen, Z. H.; Ren, Y.; Liu, C. P.; Tzeng, Y. H.; Auciello, O. Adv. Mater. 2014, 26, 3724.
7. [7]
  Fang, S.; Shen, L. F.; Tong, Z. K.; Zheng, H.; Zhang, F.; Zhang, X. G. Nanoscale 2015, 7, 7409.
8. [8]
  Fang, S.; Shen, L. F.; Zheng, H.; Zhang, X. G. J. Mater. Chem. A 2015, 3, 149.
9. [9]
10. [10]
  Yoo, H.; Lee, J. I.; Kim, H.; Lee, J. P.; Cho, J.; Park, S. Nano Lett. 2011, 11, 4324.
11. [11]
  Chen, Y.; Yan, C.; Schmidt, O. G. Adv. Energy Mater. 2013, 3, 1269.
12. [12]
13. [13]
  Graetz, J.; Ahn, C. C.; Yazami, R.; Fultz, B. J. Electrochem. Soc. 2004, 151, A698.
14. [14]
  Chan, C. K.; Zhang, X. F.; Cui, Y. Nano Lett. 2008, 8, 307.
15. [15]
  Cui, G. L.; Gu, L.; Zhi, L. J.; Kaskhedikar, N.; van Aken, P. A.; Mullen, K.; Maier, J. Adv. Mater. 2008, 20, 3079.
16. [16]
  Seng, K. H.; Park, M. H.; Guo, Z. P.; Liu, H. K.; Cho, J. Angew. Chem. Int. Ed. 2012, 51, 5657.
17. [17]
  Beaulieu, L. Y.; Eberman, K. W.; Turner, R. L.; Krause, L. J.; Dahn, J. R. Electrochem. Solid-State Lett. 2001, 4, A137.
18. [18]
  Key, B.; Bhattacharyya, R.; Morcrette, M.; Seznec, V.; Tarascon, J. M.; Grey, C. P. J. Am. Chem. Soc. 2009, 131, 9239.
19. [19]
  Liu, X. H.; Liu, Y.; Kushima, A.; Zhang, S. L.; Zhu, T.; Li, J.; Huang, J. Y. Adv. Energy Mater. 2012, 2, 722.
20. [20]
  Yi, R.; Feng, J.; Lv, D.; Gordin, M. L.; Chen, S.; Choi, D.; Wang, D. Nano Energy 2013, 2, 498.
21. [21]
  Feng, Y.; Li, X. D.; Shao, Z. P.; Wang, H. T. J. Mater. Chem. A 2015, 3, 15274.
22. [22]
  Chen, W. M.; Lu, L. Y.; Maloney, S.; Yang, Y.; Wang, W. Y. Phys. Chem. Chem. Phys. 2015, 17, 5109.
23. [23]
  Li, W. W.; Wang, X. F.; Liu, B.; Xu, J.; Liang, B.; Luo, T.; Luo, S. J.; Chen, D.; Shen, G. Z. Nanoscale 2013, 5, 10291.
24. [24]
  Geim, A. K. Angew. Chem. Int. Ed. 2011, 50, 6966.
25. [25]
  Wang, B.; Li, X. L.; Zhang, X. F.; Luo, B.; Jin, M. H.; Liang, M. H.; Dayeh, S. A.; Picraux, S. T.; Zhi, L. J. ACS Nano 2013, 7, 1437.
26. [26]
  Zou, F.; Hu, X. L.; Sun, Y. M.; Luo, W.; Xia, F. F.; Qie, L.; Jiang, Y.; Huang, Y. H. Chem. Eur. J. 2013, 19, 6027.
27. [27]
  Zou, F.; Hu, X. L.; Qie, L.; Jiang, Y.; Xiong, X. Q.; Qiao, Y.; Huang, Y. H. Nanoscale 2014, 6, 924.
28. [28]
  Li, W.; Yin, Y. X.; Xin, S.; Song, W. G.; Guo, Y. G. Energy Environ. Sci. 2012, 5, 8007.
29. [29]
  Rong, A.; Gao, X. P.; Li, G. R.; Yan, T. Y.; Zhu, H. Y.; Qu, J. Q.; Song, D. Y. J. Phys. Chem. B 2006, 110, 14754.
30. [30]
  Chen, Z.; Yan, Y.; Xin, S.; Li, W.; Qu, J.; Guo, Y. G.; Song, W. G. J. Mater. Chem. A 2013, 1, 11404.
31. [31]
  Ge, X.; Wang, X.; Wang, Z.; Yao, S.; Feng, J.; Liu, D. P.; Song, S. Y.; Zhang, H. J. Chem. Eur. J. 2015, 21, 14768.
32. [32]
  Li, W. W.; Wang, X. F.; Liu, B.; Luo, S. J.; Liu, Z.; Hou, X. J.; Xiang, Q. Y.; Chen, D.; Shen, G. Z. Chem. Eur. J. 2013, 19, 8650.
33. [33]
34. [34]
35. [35]
  Sharma, Y.; Sharma, N.; Rao, G. V. S.; Chowdari, B. V. R. Adv. Funct. Mater. 2007, 17, 2855.
36. [36]
  Liu, J. P.; Li, Y. Y.; Ding, R. M.; Jiang, J.; Hu, Y. Y.; Ji, X. X.; Chi, Q. B.; Zhu, Z. H.; Huang, X. T. J. Phys. Chem. C 2009, 113, 5336.
37. [37]
  Wang, R.; Wu, S. P.; Lv, Y. C.; Lin, Z. Q. Langmuir 2014, 30, 8215.
38. [38]
  Wang, X. L.; Han, W. Q.; Chen, H. Y.; Bai, J. M.; Tyson, T. A.; Yu, X. Q.; Wang, X. J.; Yang, X. Q. J. Am. Chem. Soc. 2011, 133, 20692.
39. [39]
  Liu, J. P.; Li, Y. Y.; Huang, X. T.; Li, G. Y.; Li, Z. K. Adv. Funct. Mater. 2008, 18, 1448.
40. [40]
  Feng, J. K.; Xia, H.; Lai, M. O.; Lu, L. J. Phys. Chem. C 2009, 113, 20514.
41. [41]
  Park, M. H.; Cho, Y.; Kim, K.; Kim, J.; Liu, M. L.; Cho, J. Angew. Chem. Int. Ed. 2011, 50, 9647.
42. [42]
  Xue, X. Y.; Chen, Z. H.; Xing, L. L.; Yuan, S.; Chen, Y. J. Chem. Commun. 2011, 47, 5205.
43. [43]
  Seo, M. H.; Park, M.; Lee, K. T.; Kim, K.; Kim, J.; Cho, J. Energy Environ. Sci. 2011, 4, 425.
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沈阳化工大学材料科学与工程学院沈阳 110142

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Zn₂GeO₄ Nanorods@Graphene Composite as Anode Materials for Li-ion Batteries