English

Ultra-Low-Temperature Supercapacitor Based on Holey Graphene and Mixed-Solvent Organic Electrolyte

• Zheng Bo ^{1, 2,} ,
• Jing Kong ^1, ,
• Huachao Yang ^{1, 2, ,} ,
• Zhouwei Zheng ^1, ,
• Pengpeng Chen ^1, ,
• Jianhua Yan ^1, ,
• Kefa Cen ^1,

• 1.

  State Key Laboratory of Clean Energy Utilization, College of Energy Engineering, Zhejiang University, Hangzhou 310027, China

• 2.

  Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou 311215, China

Corresponding author: Huachao Yang, Email: huachao@zju.edu.cn; Tel.: +86-571-87951369

• Received Date: 21 May 2020
  Accepted Date: 01 July 2020
  Revised Date: 16 June 2020
  Available Online: 15 April 2022
• Fund Project:

  the National Natural Science Foundation of China 

  the Zhejiang Provincial Natural Science Foundation of China 

  the Key R & D Program of Zhejiang Province, China 

  the China Postdoctoral Science Foundation 

Abstract: Supercapacitors that can withstand extremely low temperatures have become desirable in applications including portable electronic devices, hybrid electric vehicles, and renewable energy conversion systems. Graphene is considered as a promising electrode material for supercapacitors owing to its high specific surface area (up to 2675 m²·g^-1) and electrical conductivity (approximately 2 × 10² S·m^-1). However, the restacking of graphene sheets decreases the accessible surface area, reduces the ion diffusion rate and prolongs the ion transport pathways, thereby limiting the energy storage performance at low temperatures (typically < 100 F·g^-1 at sub-zero temperatures). Herein, we fabricate a supercapacitor based on holey graphene and mixed-solvent organic electrolyte for ultra-low-temperature applications (e.g., -60 ℃). Reduced holey graphene oxide (rHGO) was synthesized as the electrode material via an oxidative-etching process with H₂O₂. Methyl formate was mixed with propylene carbonate to improve the electrolyte conductivity at temperatures ranging from -60 to 25 ℃. The as-fabricated supercapacitor showed a high room-temperature capacitance of 150.5 F·g^-1 at 1 A·g^-1, which was almost 1.5 times greater than that of the supercapacitor using untreated reduced graphene oxide (rGO; 101.4 F·g^-1). The improved capacitance could be attributed to the increased accessible surface rendered by the abundant mesopores and macropores on the holey surface. As the temperature decreased to -60 ℃, the rHGO supercapacitor still delivered a high capacitance of 106.2 F·g^-1 with a retention of 70.6%, which was superior to other state-of-the-art graphene-based supercapacitors. Electrochemical impedance spectra tests revealed that the ion diffusion resistance in rHGO was significantly smaller than that in rGO and less influenced by temperature with a lower activation energy. This was because the holey morphology can provide transport pathways for ions and reduce the ion diffusion length during charging/discharging, consequently diminishing the diffusion resistance at low temperatures. Specifically, at -60 ℃, the energy density of supercapacitor reached up to 26.9 Wh·kg^-1 at 1 A·g^-1 with a maximum power density of 18.7 kW·kg^-1 at 20 A·g^-1, surpassing the low-temperature performance of conventional carbon-based supercapacitors. Moreover, after 10000 cycles at -60 ℃ with a current density of 5 A·g^-1, 89.1% of capacitance was retained, suggesting the stable and reliable power output of the current supercapacitor at extremely low temperatures.

Key words:
• Supercapacitor
•  /  Ultra-low temperature
•  /  Holey graphene
•  /  Mixed-solvent organic electrolyte
•  /  Electrochemical performance

• 1. [1]

     Zhang, L. L.; Zhao, X. S. Chem. Soc. Rev. 2009, 38, 2520. doi: 10.1039/B813846J

  2. [2]

     Simon, P.; Gogotsi, Y. Nat. Mater. 2008, 7, 845. doi: 10.1038/nmat2297

  3. [3]

     Simon, P.; Gogotsi, Y. Acc. Chem. Res. 2013, 46, 1094. doi: 10.1021/ar200306b

  4. [4]

     Huang, P.; Pech, D.; Lin, R.; Mcdonough, J. K.; Brunet, M.; Taberna, P.; Gogotsi, Y.; Simon, P. Electrochem. Commun. 2013, 36, 53. doi: 10.1016/j.elecom.2013.09.003

  5. [5]

     Li, X.; Wei, B. Nano Energy 2013, 2, 159. doi: 10.1016/j.nanoen.2012.09.008

  6. [6]

     Brandon, E. J.; West, W. C.; Smart, M. C.; Whitcanack, L. D.; Plett, G. A. J. Power Sources 2007, 170, 225. doi: 10.1016/j.jpowsour.2007.04.001

  7. [7]

     Shi, Z.; Yu, X.; Wang, J.; Hu, H.; Wu, C. Electrochim. Acta 2015, 174, 215. doi: 10.1016/j.electacta.2015.05.133

  8. [8]

     Jänes, A.; Lust, E. J. Electroanal. Chem. 2006, 588, 285. doi: 10.1016/j.jelechem.2006.01.003

  9. [9]

     Cheng, F.; Yu, X.; Wang, J.; Shi, Z.; Wu, C. Electrochim. Acta 2016, 200, 106. doi: 10.1016/j.electacta.2016.03.113

  10. [10]

      Orita, A.; Kamijima, K.; Yoshida, M. J. Power Sources 2010, 195, 7471. doi: 10.1016/j.jpowsour.2010.05.066

  11. [11]

      Anouti, M.; Timperman, L. Phys. Chem. Chem. Phys. 2013, 15, 6539. doi: 10.1039/C3CP44680H

  12. [12]

      Ruiz, V.; Huynh, T.; Sivakkumar, S. R.; Pandolfo, A. RSC Adv. 2012, 2, 5591. doi: 10.1039/C2RA20177A

  13. [13]

      Lang, J.; Zhang, X.; Liu, L.; Yang, B.; Yang, J.; Yan, X. J. Power Sources 2019, 423, 271. doi: 10.1016/j.jpowsour.2019.03.096

  14. [14]

      Kang, J.; Jayaram, S. H.; Rawlins, J.; Wen, J. Electrochim. Acta 2014, 144, 200. doi: 10.1016/j.electacta.2014.07.158

  15. [15]

      Korenblit, Y.; Kajdos, A.; West, W. C.; Smart, M. C.; Brandon, E. J.; Kvit, A.; Jagiello, J.; Yushin, G. Adv. Funct. Mater. 2012, 22, 1655. doi: 10.1002/adfm.201102573

  16. [16]

      Xu, J.; Yuan, N.; Razal, J. M.; Zheng, Y.; Zhou, X.; Ding, J.; Cho, K.; Ge, S.; Zhang, R.; Gogotsi, Y.; Baughman, R. H. Energy Storage Mater. 2019, 22, 323. doi: 10.1016/j.ensm.2019.02.016

  17. [17]

      Ye, L.; Liang, Q.; Huang, Z. H.; Lei, Y.; Zhan, C.; Bai, Y.; Li, H.; Kang, F.; Yang, Q. H. J. Mater. Chem. A 2015, 3, 18860. doi: 10.1039/C5TA04581A

  18. [18]

      Liu, C.; Yu, Z.; Neff, D.; Zhamu, A.; Jang, B. Z. Nano Lett. 2010, 10, 4863. doi: 10.1021/nl102661q

  19. [19]

      Raccichini, R.; Varzi, A.; Passerini, S.; Scrosati, B. Nat. Mater. 2015, 14, 271. doi: 10.1038/nmat4170

  20. [20]

      Stankovich, S.; Dikin, D. A.; Piner, R. D.; Kohlhaas, K. A.; Kleinhammes, A.; Jia, Y.; Wu, Y.; Nguyen, S. T.; Ruoff, R. S. Carbon 2007, 45, 1558. doi: 10.1016/j.carbon.2007.02.034

  21. [21]

      Xu, Y.; Lin, Z.; Zhong, X.; Huang, X.; Weiss, N. O.; Huang, Y.; Duan, X. Nat. Commun. 2014, 5, 4554. doi: 10.1038/ncomms5554

  22. [22]

      Lin, Z.; Taberna, P. L.; Simon, P. Electrochim. Acta 2016, 206, 446. doi: 10.1016/j.electacta.2015.12.097

  23. [23]

      Kang, J.; Atashin, S.; Jayaram, S. H.; Wen, J. Z. Carbon 2017, 111, 338. doi: 10.1016/j.carbon.2016.10.017

  24. [24]

      Hummers, W. S.; Offeman, R. E. J. Am. Chem. Soc. 1958, 80, 1339. doi: 10.1021/ja01539a017

  25. [25]

      杜惟实, 吕耀康, 蔡志威, 张诚. 物理化学学报, 2017, 33, 1828 doi: 10.3866/PKU.WHXB201705089Du, W. S.; Lü, Y. K.; Cai, Z. W.; Zhang, C. Acta Phys. -Chim. Sin. 2017, 33, 1828. doi: 10.3866/PKU.WHXB201705089

  26. [26]

      杨康, 帅骁睿, 杨化超, 严建华, 岑可法. 物理化学学报, 2019, 35, 755. doi: 10.3866/PKU.WHXB201810009Yang, K.; Shuai, X. R.; Yang, H. C.; Yan, J. H.; Cen, K. F. Acta Phys. -Chim. Sin. 2019, 35, 755. doi: 10.3866/PKU.WHXB201810009

  27. [27]

      Xu, Y.; Chen, C. Y.; Zhao, Z.; Lin, Z.; Lee, C.; Xu, X.; Wang, C.; Huang, Y.; Shakir, M. I.; Duan, X. Nano Lett. 2015, 15, 4605. doi: 10.1021/acs.nanolett.5b01212

  28. [28]

      Peng, L.; Fang, Z.; Zhu, Y.; Yan, C.; Yu, G. Adv. Energy Mater. 2018, 8, 1702179. doi: 10.1002/aenm.201702179

  29. [29]

      Thomsen, C.; Reich, S. Phys. Rev. Lett. 2000, 85, 5214. doi: 10.1103/PhysRevLett.85.5214

  30. [30]

      Haynes, W. M. CRC Handbook of Chemistry and Physics. 95th ed.; CRC Press: Boca Raton, 2014.

  31. [31]

      Zhong, C.; Deng, Y.; Hu, W.; Qiao, J.; Zhang, L.; Zhang, J. Chem. Soc. Rev. 2015, 44, 7484. doi: 10.1039/C5CS00303B

  32. [32]

      Muench, S.; Wild, A.; Friebe, C.; Häupler, B.; Janoschka, T.; Schubert, U. S. Chem. Rev. 2016, 116, 9438. doi: 10.1021/acs.chemrev.6b00070

  33. [33]

      Izadi-Najafabadi, A.; Yamada, T.; Futaba, D. N.; Hatori, H.; Iijima, S.; Hata, K. Electrochem. Commun. 2010, 12, 1678. doi: 10.1016/j.elecom.2010.09.020

  34. [34]

      Tsai, W. Y.; Lin, R.; Murali, S.; Li, Zhang, L.; McDonough, J. K.; Ruoff, R. S.; Taberna, P. L.; Gogotsi, Y.; Simon, P. Nano Energy 2013, 2, 403. doi: 10.1016/j.nanoen.2012.11.006

  35. [35]

      Vellacheri, R.; Al-Haddad, A.; Zhao, H.; Wang, W.; Wang, C.; Lei, Y. Nano Energy 2014, 8, 231. doi: 10.1016/j.nanoen.2014.06.015

  36. [36]

      Zhang, S.; Pan, N. Adv. Energy Mater. 2015, 5, 1401401. doi: 10.1002/aenm.201401401

  37. [37]

      Mathis, T. S.; Kurra, N.; Wang, X.; Pinto, D.; Simon, P.; Gogotsi, Y. Adv. Energy Mater. 2019, 9, 1902007. doi: 10.1002/aenm.201902007

  38. [38]

      Bo, Z.; Zhu, W.; Ma, W.; Wen, Z.; Shuai, X.; Chen, J.; Yan, J.; Wang, Z.; Cen, K.; Feng, X. Adv. Mater. 2013, 25, 5799. doi: 10.1002/adma.201301794

  39. [39]

      Chen, L.; Li, H.; Yoshitake, H.; Qi, L.; Gu, N.; Wang, H. Electrochim. Acta 2015, 157, 333. doi: 10.1016/j.electacta.2014.09.161

  40. [40]

      Hung, K.; Masarapu, C.; Ko, T.; Wei, B. J. Power Sources 2009, 193, 944. doi: 10.1016/j.jpowsour.2009.01.083

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