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

Figures(5)

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.
1. [1]
  Xueyu Lin , Ruiqi Wang , Wujie Dong , Fuqiang Huang . Rational Design of Bimetallic Oxide Anodes for Superior Li⁺ Storage. Acta Physico-Chimica Sinica, 2025, 41(3): 100021-0. doi: 10.3866/PKU.WHXB202311005
2. [2]
  Xintong Zhu , Bin Cao , Chong Yan , Cheng Tang , Aibing Chen , Qiang Zhang . Advances in coating strategies for graphite anodes in lithium-ion batteries. Acta Physico-Chimica Sinica, 2025, 41(9): 100096-0. doi: 10.1016/j.actphy.2025.100096
3. [3]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-0. doi: 10.3866/PKU.WHXB202311030
4. [4]
  Jingshuo Zhang , Yue Zhai , Ziyun Zhao , Jiaxing He , Wei Wei , Jing Xiao , Shichao Wu , Quan-Hong Yang . Research Progress of Functional Binders in Silicon-Based Anodes for Lithium-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(6): 2306006-0. doi: 10.3866/PKU.WHXB202306006
5. [5]
  Ying Li , Yushen Zhao , Kai Chen , Xu Liu , Tingfeng Yi , Li-Feng Chen . Rational Design of Cross-Linked N-Doped C-Sn Nanofibers as Free-Standing Electrodes towards High-Performance Li-Ion Battery Anodes. Acta Physico-Chimica Sinica, 2024, 40(3): 2305007-0. doi: 10.3866/PKU.WHXB202305007
6. [6]
  Qingtang ZHANG , Xiaoyu WU , Zheng WANG , Xiaomei WANG . Performance of nano Li₂FeSiO₄/C cathode material co-doped by potassium and chlorine ions. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1689-1696. doi: 10.11862/CJIC.20240115
7. [7]
  Liangliang Song , Haoyan Liang , Shunqing Li , Bao Qiu , Zhaoping Liu . Challenges and strategies on high-manganese Li-rich layered oxide cathodes for ultrahigh-energy-density batteries. Acta Physico-Chimica Sinica, 2025, 41(8): 100085-0. doi: 10.1016/j.actphy.2025.100085
8. [8]
  Yuting ZHANG , Zunyi LIU , Ning LI , Dongqiang ZHANG , Shiling ZHAO , Yu ZHAO . Nickel vanadate anode material with high specific surface area through improved co-precipitation method: Preparation and electrochemical properties. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2163-2174. doi: 10.11862/CJIC.20240204
9. [9]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
10. [10]
  Zhuo WANG , Xiaotong LI , Zhipeng HU , Junqiao PAN . Three-dimensional porous carbon decorated with nano bismuth particles: Preparation and sodium storage properties. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 267-274. doi: 10.11862/CJIC.20240223
11. [11]
  Mengxiu Li , Jiahui Mao , Jiangfeng Ni , Liang Li . Three birds with one stone: modification of Li₅FeO₄ with thermal induction of Lewis acid. Acta Physico-Chimica Sinica, 2026, 42(4): 100189-0. doi: 10.1016/j.actphy.2025.100189
12. [12]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189
13. [13]
  Yifeng Xu , Jiquan Liu , Bin Cui , Yan Li , Gang Xie , Ying Yang . “Xiao Li’s School Adventures: The Working Principles and Safety Risks of Lithium-ion Batteries”. University Chemistry, 2024, 39(9): 259-265. doi: 10.12461/PKU.DXHX202404009
14. [14]
  Wen Tang , Luyu Sui , Qian Chen , Jun Shao , Xinwen Peng , Jianwen Jiang , Shuiliang Chen . Project-based Teaching of “the Condensed State of Polymers”: Unveiling the Lithium-Ion Battery Separator. University Chemistry, 2025, 40(11): 115-126. doi: 10.12461/PKU.DXHX202412108
15. [15]
  Siyu Zhang , Kunhong Gu , Bing'an Lu , Junwei Han , Jiang Zhou . Hydrometallurgical Processes on Recycling of Spent Lithium-lon Battery Cathode: Advances and Applications in Sustainable Technologies. Acta Physico-Chimica Sinica, 2024, 40(10): 2309028-0. doi: 10.3866/PKU.WHXB202309028
16. [16]
  Chenyue Huang , Hongfei Zheng , Ning Qin , Canpei Wang , Liguang Wang , Jun Lu . Single-Crystal Nickel-Rich Cathode Materials: Challenges and Strategies. Acta Physico-Chimica Sinica, 2024, 40(9): 2308051-0. doi: 10.3866/PKU.WHXB202308051
17. [17]
  Aoyu Huang , Jun Xu , Yu Huang , Gui Chu , Mao Wang , Lili Wang , Yongqi Sun , Zhen Jiang , Xiaobo Zhu . Tailoring Electrode-Electrolyte Interfaces via a Simple Slurry Additive for Stable High-Voltage Lithium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100037-0. doi: 10.3866/PKU.WHXB202408007
18. [18]
  Rongrong Wang , Chen Li , Xiang Ren , Keliang Zhang , Yu Sun , Xianzhong Sun , Kai Wang , Xiong Zhang , Yanwei Ma . Recent advances and challenges of eco-friendly Ni-rich cathode slurry systems in lithium-ion batteries. Acta Physico-Chimica Sinica, 2026, 42(4): 100222-0. doi: 10.1016/j.actphy.2025.100222
19. [19]
  Tingliang MAO , Zhong WANG , Wenquan JIANG , Hao WAN , Chaojian XING , Xu WU , Rong ZHANG , Zhimin REN , Yanping YIN , Ning LI , Guohua LI , Xiaohe LIU . Research progress on synthesis technology for lithium-rich manganese-based cathode materials. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 668-692. doi: 10.11862/CJIC.20250319
20. [20]
  Yuanchao LI , Weifeng HUANG , Pengchao LIANG , Zifang ZHAO , Baoyan XING , Dongliang YAN , Li YANG , Songlin WANG . Effect of heterogeneous dual carbon sources on electrochemical properties of LiMn_0.8Fe_0.2PO₄/C composites. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 751-760. doi: 10.11862/CJIC.20230252

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(2980)
HTML views(253)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

Metrics

通讯作者: 陈斌, bchen63@163.com

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