Citation: Jian Wang, Bo Yin, Tian Gao, Xingyi Wang, Wang Li, Xingxing Hong, Zhuqing Wang, Haiyong He. Reduced Graphene Oxide Modified Few-Layer Exfoliated Graphite to Enhance the Stability of the Negative Electrode of a Graphite-Based Potassium Ion Battery[J]. Acta Physico-Chimica Sinica, ;2022, 38(2): 201208. doi: 10.3866/PKU.WHXB202012088 shu

Reduced Graphene Oxide Modified Few-Layer Exfoliated Graphite to Enhance the Stability of the Negative Electrode of a Graphite-Based Potassium Ion Battery

Jian Wang ^{1, 2} ,
Bo Yin ² ,
Tian Gao ² ,
Xingyi Wang ² ,
Wang Li ² ,
Xingxing Hong ² ,
Zhuqing Wang ^1,, ,
Haiyong He ^2,,

1.
College of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246002, Anhui Province, China
2.
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Institute of New Energy Technology, Ningbo 315201, Zhejiang Province, China

Corresponding author: Zhuqing Wang, wangzhq@aqnu.edu.cn Haiyong He, hehaiyong@nimte.ac.cn
Received Date: 31 December 2020
Revised Date: 22 January 2021
Accepted Date: 26 January 2021
Available Online: 1 February 2021
Fund Project: the National Natural Science Foundation of China 51872304Ningbo S & T Innovation 2025 Major Special Program 2018B10024

The intercalation of potassium in graphite provides high energy density owing to the low potential of 0.24 V vs. K/K⁺, thereby making it a promising anode material for potassium ion batteries. However, the high volume expansion (60%) of graphite after potassium intercalation induces significant stress and electrode pulverization. Additionally, the sluggish kinetics of potassium insertion undermine the rate capability of electrodes. Using few-layer exfoliated graphite (EG) as a negative electrode material effectively relieves expansion-induced stress. Unfortunately, the close stacking of ultra-thin two-dimensional EG impedes ion transport. Furthermore, EG with smooth surfaces lacks active sites to adsorb K⁺, which is unfavorable for intercalation reactions. To address these problems, in this study, we designed an rGO/EG/rGO sandwich that coats EG with reduced graphene oxide (rGO). This complex material has two main advantages: (1) its 3D network can effectively prevent EG from stacking and buffer the volumetric variation of EG to improve the cyclic stability of the electrode, and (2) the loose structure and rich functional groups of rGO can also enhance the kinetic of potassium intercalation. Through hydrothermal reduction, GO was coated onto the EG surface and cross-linked to form a 3D network, by which EG stacking could be effectively mitigated. The rGO : EG ratio was precisely controlled by modulating the amount of reactant GO and EG. Transmission electron microscopy and scanning electron microscopy images showed that the rGO was uniformly coated on the EG surface to form a sandwich structure. X-ray diffraction patterns and Raman spectra demonstrated that rGO was physically adsorbed on the EG surface without notable chemical interactions. The EG structure was retained to ensure that its characteristic electrochemical properties were unaffected. Cyclic voltammetry and galvanostatic cycling tests were performed on the complex material with various rGO : EG ratios, exhibiting that rGO : EG = 1 : 1 (w/w) was optimal with a specific capacity of 443 mAh·g^-1 at 50 mA·g^-1. Even when operated at a high current density of 800 mA·g^-1, a specific capacity of 190 mAh·g^-1 was achieved, retaining 42.9% of the low-rate capacity, far exceeding those of pristine EG (14.2%) and rGO (27.2%). These results demonstrate that the rGO coating indeed enhanced the kinetics of potassium intercalation and efficiently improved the capacity and rate capability compared to pristine EG. We hope this work sheds light on novel approaches to improving potassium intercalation mechanisms in graphite.
- Potassium ion battery,
- Negative electrode,
- Hydrothermal synthesis,
- Composite material,
- Exfoliated graphite,
- Graphene oxide,
- Synergy
1. [1]
  Pei, Z.; Fan, G.; Qin, X. Energy Storage Sci. Technol. 2020, 9 (5), 1562. doi: 10.19799/j.cnki.2095-4239.2020.0252
2. [2]
  Liu, S. J.; Zhang, C.; Sun, Y. D.; Chen, Q.; He, L. F.; Zhang, K.; Zhang, J.; Liu, B.; Chen, L. F. Coord. Chem. Rev. 2020, 413, 213266. doi: 10.1016/j.ccr.2020.213266 doi: 10.1016/j.ccr.2020.213266
3. [3]
  Fedotov, S. S.; Khasanova, N. R.; Samarin, A. S.; Drozhzhin, O. A.; Batuk, D.; Karakulina, O. M.; Hadermann, J.; Abakumov, A. M.; Antipov, E. V. Chem. Mater. 2016, 28, 411. doi: 10.1021/acs.chemmater.5b04065 doi: 10.1021/acs.chemmater.5b04065
4. [4]
  Eftekhari, A.; Jian, Z.; Ji, X. ACS Appl. Mater. Interfaces 2017, 9, 4404. doi: 10.1021/acsami.6b07989 doi: 10.1021/acsami.6b07989
5. [5]
  Liu, Y. C.; Huang, B.; Shao, Y. J.; Shen, M. Y.; Du, L.; Liao, S. J. Prog. Chem. 2019, 31 (9), 1329. doi: 10.7536/PC190212
6. [6]
  Huang, H.; Wang, J.; Yang, X.; Hu, R.; Liu, J.; Zhang, L.; Zhu, M. Angew. Chem. Int. Ed. 2020, 59 (34), 14504. doi: 10.1002/anie.202004193 doi: 10.1002/anie.202004193
7. [7]
  Wang, S.; Xiong, P.; Guo, X.; Zhang, J.; Gao, X.; Zhang, F.; Tang, X.; Notten, P. H. L.; Wang, G. Adv. Funct. Mater. 2020, 30 (27), 2001588. doi: 10.1002/adfm.202001588 doi: 10.1002/adfm.202001588
8. [8]
  Zhao, R.; Di, H.; Hui, X.; Zhao, D.; Wang, R.; Wang, C.; Yin, L. Energy Environ. Sci. 2020, 13 (1), 246. doi: 10.1039/c9ee03250a doi: 10.1039/c9ee03250a
9. [9]
  Qi, S. H.; Deng, J. W.; Zhang, W. C.; Feng, Y. Z.; Ma, J. M. Rare Met. 2020, 39 (9), 970. doi: 10.1007/s12598-020-01454-w doi: 10.1007/s12598-020-01454-w
10. [10]
  Wei, C.; Tao, Y.; Fei, H.; An, Y.; Tian, Y.; Feng, J.; Qian, Y. Energy Storage Mater. 2020, 30, 206. doi: 10.1016/j.ensm.2020.05.018 doi: 10.1016/j.ensm.2020.05.018
11. [11]
  Wang, W.; Ji, B.; Yao, W.; Zhang, X.; Zheng, Y.; Zhou, X.; Kidkhunthod, P.; He, H.; Tang, Y. Sci. China Mater. 2020, 64, 1047. doi: 10.1007/s40843-020-1512-0 doi: 10.1007/s40843-020-1512-0
12. [12]
  Zhang, H.; Luo, C.; He, H.; Wu, H. H.; Zhang, L.; Zhang, Q.; Wang, H.; Wang, M. S. Nanoscale Horiz. 2020, 5 (5), 895. doi: 10.1039/d0nh00018c doi: 10.1039/d0nh00018c
13. [13]
  Zhang, Z.; Jia, B.; Liu, L.; Zhao, Y.; Wu, H.; Qin, M.; Han, K.; Wang, W. A.; Xi, K.; Zhang, L.; et al. ACS Nano 2019, 13 (10), 11363. doi: 10.1021/acsnano.9b04728 doi: 10.1021/acsnano.9b04728
14. [14]
  Ji, B.; Yao, W.; Zheng, Y.; Kidkhunthod, P.; Zhou, X.; Tunmee, S.; Sattayaporn, S.; Nat. Commun. 2020, 11 (1), 1225. doi: 10.1038/s41467-020-15044-y doi: 10.1038/s41467-020-15044-y
15. [15]
  Yu, A.; Pan, Q.; Zhang, M.; Xie, D.; Tang, Y. Adv. Funct. Mater. 2020, 30 (24), 2001440. doi: 10.1002/adfm.202001440 doi: 10.1002/adfm.202001440
16. [16]
  Kim, C.; Yang, K. S.; Kojima, M.; Yoshida, K.; Kim, Y. J.; Kim, Y. A.; Endo, M. Adv. Funct. Mater. 2006, 16 (18), 2393. doi: 10.1002/adfm.200500911 doi: 10.1002/adfm.200500911
17. [17]
  Chen, J.; Cheng, Y.; Zhang, Q.; Luo, C.; Li, H. Y.; Wu, Y.; Zhang, H.; Wang, X.; Liu, H.; He, X.; et al. Adv. Funct Mater. 2021, 31 (1), 2007158. doi: 10.1002/adfm.202007158 doi: 10.1002/adfm.202007158
18. [18]
  Gabaudan, V.; Monconduit, L.; Stievano, L.; Berthelot, R. Front. Energy Res. 2019, 7, 46. doi: 10.3389/fenrg.2019.00046 doi: 10.3389/fenrg.2019.00046
19. [19]
  Zhang, C.; Zhao, H.; Lei, Y. Energy Environ. Mater. 2020, 3 (2), 105. doi: 10.1002/eem2.12059 doi: 10.1002/eem2.12059
20. [20]
  Wu, Y.; Zhao, H.; Wu, Z.; Yue, L.; Liang, J.; Liu, Q.; Luo, Y.; Gao, S.; Lu, S.; Chen, G.; et al. Energy Storage Mater. 2021, 34, 483. doi: 10.1016/j.ensm.2020.10.015 doi: 10.1016/j.ensm.2020.10.015
21. [21]
  Jian, Z.; Luo, W.; Ji, X. J. Am. Chem. Soc. 2015, 137 (36), 11566. doi: 10.1021/jacs.5b06809 doi: 10.1021/jacs.5b06809
22. [22]
  Qin, L.; Xiao, N.; Zheng, J.; Lei, Y.; Zhai, D.; Wu, Y. Adv. Energy Mater. 2019, 9 (44), 1902618. doi: 10.1002/aenm.201902618 doi: 10.1002/aenm.201902618
23. [23]
  Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Science 2004, 306 (5696), 666. doi: 10.1126/science.1102896 doi: 10.1126/science.1102896
24. [24]
  Liu, X. T.; Zhang, J. C.; Chen, H.; Liu, Z. F. Acta Phys. -Chim. Sin. 2021, 37, 2012047. doi: 10.3866/PKU.WHXB202012047
25. [25]
  Chung, D. D. L. J. Mater. Sci. 2016, 51 (1), 544. doi: 10.1007/s10853-015-9284-6 doi: 10.1007/s10853-015-9284-6
26. [26]
  Doughty, D. H.; Butler, P. C.; Akhil, A. A.; Clark, N. H.; Boyes, J. D. Electrochem. Soc. Interface 2010, 19 (3), 49. doi: 10.1149/2.f05103if doi: 10.1149/2.f05103if
27. [27]
  Hong, W.; Zhang, Y.; Yang, L.; Tian, Y.; Ge, P.; Hu, J.; Wei, W.; Zou, G.; Hou, H.; Ji, X. Nano Energy 2019, 65, 104038. doi: 10.1016/j.nanoen.2019.104038 doi: 10.1016/j.nanoen.2019.104038
28. [28]
  Yang, W.; Zhou, J.; Wang, S.; Zhang, W.; Wang, Z.; Lv, F.; Wang, K.; Sun, Q.; Guo, S. Energy Environ. Sci. 2019, 12 (5), 1605. doi: 10.1039/c9ee00536f doi: 10.1039/c9ee00536f
29. [29]
  Chou, S. L.; Wang, J. Z.; Choucair, M.; Liu, H. K.; Stride, J. A.; Dou, S. X. Electrochem. Commun. 2010, 12 (2), 303. doi: 10.1016/j.elecom.2009.12.024 doi: 10.1016/j.elecom.2009.12.024
30. [30]
  Zhou, X.; Yin, Y. X.; Wan, L. J.; Guo, Y. G. Chem. Commun. 2012, 48 (16), 2198. doi: 10.1039/c2cc17061b doi: 10.1039/c2cc17061b
31. [31]
  Zhang, E.; Jia, X.; Wang, B.; Wang, J.; Yu, X.; Lu, B. Adv. Sci. 2020, 7 (15), 2000470. doi: 10.1002/advs.202000470 doi: 10.1002/advs.202000470
32. [32]
  Wang, Y.; Gao, X.; Li, L.; Wang, M.; Shui, J.; Xu, M. Nano Energy 2020, 67, 104248. doi: 10.1016/j.nanoen.2019.104248 doi: 10.1016/j.nanoen.2019.104248
33. [33]
  Nawar, A. M.; Yahia, I. S.; Al-Kotb, M. S. J. Mater. Sci. -Mater. Electron. 2020, 31 (15), 12127. doi: 10.1007/s10854-020-03759-z doi: 10.1007/s10854-020-03759-z
34. [34]
  Jian, Z.; Hwang, S.; Li, Z.; Hernandez, A. S.; Wang, X.; Xing, Z.; Su, D.; Ji, X. Adv. Funct. Mater. 2017, 27 (26), 1700324. doi: 10.1002/adfm.201700324 doi: 10.1002/adfm.201700324
35. [35]
  Tang, Z. Y.; Xue, J. J.; Liu, C. Y.; Zhuang, X. G. Acta Phys. -Chim. Sin. 2001, 17 (5), 38. doi: 10.3866/PKU.WHXB20010501
36. [36]
  Wan, J.; Chen, Q. Q.; Li, W.; Pan, L. H.; Zhao, Z. H.; Yu, D. D.; Tang, Z. H.; He, H. Y. Electrochim. Acta 2020, 345, 136238. doi: 10.1016/j.electacta.2020.136238 doi: 10.1016/j.electacta.2020.136238
37. [37]
  Chen, L. F.; Hou, C. C.; Zou, L.; Kitta, M.; Xu, Q. Sci. Bull. 2021, 66 (2), 170. doi: 10.1016/j.scib.2020.06.022 doi: 10.1016/j.scib.2020.06.022
38. [38]
  Chen, D. M. Chin. Phys. Soc. 2010, 59 (9), 6399. doi: 10.7498/aps.59.6399 doi: 10.7498/aps.59.6399
39. [39]
  Zhang, K. L; Li, W.; Cai, W. L.; Chen, L. F.; Wang, D.; Chen, Y. H.; Pan, H. L.; Wang, L. B.; Qian, Y. T. Inorg. Chem. Front. 2019, 6 (4), 955. doi: 10.1039/c9qi00052f doi: 10.1039/c9qi00052f
1. [1]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
2. [2]
  Tao Xu , Wei Sun , Tianci Kong , Jie Zhou , Yitai Qian . Stable Graphite Interface for Potassium Ion Battery Achieving Ultralong Cycling Performance. Acta Physico-Chimica Sinica, 2024, 40(2): 2303021-0. doi: 10.3866/PKU.WHXB202303021
3. [3]
  Fan Yang , Zheng Liu , Da Wang , KwunNam Hui , Yelong Zhang , Zhangquan Peng . Preparation and Properties of P-Bi₂Te₃/MXene Superstructure-based Anode for Potassium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2303006-0. doi: 10.3866/PKU.WHXB202303006
4. [4]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
5. [5]
  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
6. [6]
  Yinjie Xu , Suiqin Li , Lihao Liu , Jiahui He , Kai Li , Mengxin Wang , Shuying Zhao , Chun Li , Zhengbin Zhang , Xing Zhong , Jianguo Wang . Enhanced Electrocatalytic Oxidation of Sterols using the Synergistic Effect of NiFe-MOF and Aminoxyl Radicals. Acta Physico-Chimica Sinica, 2024, 40(3): 2305012-0. doi: 10.3866/PKU.WHXB202305012
7. [7]
  Xuechen Hu , Qiuying Xia , Fan Yue , Xinyi He , Zhenghao Mei , Jinshi Wang , Hui Xia , Xiaodong Huang . Electrochemical Characteristics of LiNbO₃ Anode Film and Its Applications in All-Solid-State Thin-Film Lithium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2309046-0. doi: 10.3866/PKU.WHXB202309046
8. [8]
  Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270
9. [9]
  Han ZHANG , Jianfeng SUN , Jinsheng LIANG . Hydrothermal synthesis and luminescent properties of broadband near-infrared Na₃CrF₆ phosphor. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 349-356. doi: 10.11862/CJIC.20240098
10. [10]
  Xue Xiao , Jiachun Li , Xiangtong Meng , Jieshan Qiu . Sulfur-Doped Carbon-Coated Fe_0.95S_1.05 Nanospheres as Anodes for High-Performance Sodium Storage. Acta Physico-Chimica Sinica, 2024, 40(6): 2307006-0. doi: 10.3866/PKU.WHXB202307006
11. [11]
  Yihan Xue , Xue Han , Jie Zhang , Xiaoru Wen . NCQDs修饰FeOOH基复合材料的制备及其电容脱盐性能. Acta Physico-Chimica Sinica, 2025, 41(7): 100072-0. doi: 10.1016/j.actphy.2025.100072
12. [12]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
13. [13]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Research on Cu-Based and Pt-Based Catalysts for Hydrogen Production through Methanol Steam Reforming. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-0. doi: 10.1016/j.actphy.2025.100049
14. [14]
  Yue Zhang , Bao Li , Lixin Wu . GO-Assisted Supramolecular Framework Membrane for High-Performance Separation of Nanosized Oil-in-Water Emulsions. Acta Physico-Chimica Sinica, 2024, 40(5): 2305038-0. doi: 10.3866/PKU.WHXB202305038
15. [15]
  Lisha LEI , Wei YONG , Yiting CHENG , Yibo WANG , Wenchao HUANG , Junhuan ZHAO , Zhongjie ZHAI , Yangbin DING . Application of regenerated cellulose and reduced graphene oxide film in synergistic power generation from moisture electricity generation and Mg-air batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1151-1161. doi: 10.11862/CJIC.20240202
16. [16]
  Yunting Shang , Yue Dai , Jianxin Zhang , Nan Zhu , Yan Su . Something about RGO (Reduced Graphene Oxide). University Chemistry, 2024, 39(9): 273-278. doi: 10.3866/PKU.DXHX202306050
17. [17]
  Jiatong Hu , Qiyi Wang , Ruiwen Tang , Jiajing Feng . Photocatalytic Journey of Perylene Diimides in a Competitive Arena. University Chemistry, 2025, 40(5): 328-333. doi: 10.12461/PKU.DXHX202407015
18. [18]
  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
19. [19]
  Yu Guo , Zhiwei Huang , Yuqing Hu , Junzhe Li , Jie Xu . Recent Advances in Iron-based Heterostructure Anode Materials for Sodium Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(3): 2311015-0. doi: 10.3866/PKU.WHXB202311015
20. [20]
  Chaolin Mi , Yuying Qin , Xinli Huang , Yijie Luo , Zhiwei Zhang , Chengxiang Wang , Yuanchang Shi , Longwei Yin , Rutao Wang . Galvanic Replacement Synthesis of Graphene Coupled Amorphous Antimony Nanoparticles for High-Performance Sodium-Ion Capacitor. Acta Physico-Chimica Sinica, 2024, 40(5): 2306011-0. doi: 10.3866/PKU.WHXB202306011

Get Citation

PDF

XML

Metrics

PDF Downloads(43)
Abstract views(1825)
HTML views(305)

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