Science China Materials

, Volume 62, Issue 7, pp 947–954 | Cite as

Temperature-resistant and flexible supercapacitors based on 10-inch wafer-scale nanocarbon films

  • Xiaobei Zang (臧晓蓓)Email author
  • Yi Hou (后羿)
  • Teng Wang (王腾)
  • Rujing Zhang (张儒静)
  • Feiyu Kang (康飞宇)Email author
  • Hongwei Zhu (朱宏伟)Email author


Most of the supercapacitors reported in literatures showed little or no flexibility in the working temperature around 150°C. However, the supercapacitors are generally exposed under complex system or extreme temperature, such as electric vehicles and extremely cold area. Herein, we successfully fabricated a large-scale robust nanocarbon hybrid film consisting of reduced graphene oxide (rGO), carbon nanotubes (CNTs) and MnOx nano-flowers with the size up to 550 cm2. The mechanical properties of the hybrid films depend on the ratio of CNTs. The supercapacitors prepared with the hybrid films exhibit high flexibility and keep their performances in a temperature range from −20 to 200°C. In addition, the devices display remarkable electrochemical and deformation stability at extreme temperature. This strategy has a potential for the more efficient preparation of flexible electrode materials.


temperature-resistant 10-inch nanocarbon film flexible supercapacitor 



现有超级电容器的工作温度区间约为150°C, 但柔性较差. 在实际工作环境中, 存在一些极端的温度环境, 比如, 极寒地区. 本文制备 了面积高达550 cm2 (常规尺寸的29倍)的石墨烯/碳纳米管/锰氧化物复合薄膜, 并将其用于耐温柔性超级电容器. 该电极材料的性能取决 于复合薄膜中石墨烯、碳纳米管和锰氧化物的比例. 此柔性超级电容器可在−20–200°C温度区间内保持良好的电化学性能和柔性, 表现出 优异的稳定性. 本文为复合纳米材料薄膜的大批量制备和适用于宽温度区间的柔性超级电容器的发展奠定了基础.



This work was supported by the Key Research and Development Program of Shandong Province (2017GGX20123) and the Fundamental Research Funds for the Central Universities of China (17CX02063 and 18CX02158A).

Supplementary material

40843_2018_9399_MOESM1_ESM.pdf (588 kb)
Temperature-resistant and flexible supercapacitors based on 10-inch wafer-scale nanocarbon films


  1. 1.
    El-Kady MF, Strong V, Dubin S, et al. Laser scribing of highperformance and flexible graphene-based electrochemical capacitors. Science, 2011, 335: 1326–1330CrossRefGoogle Scholar
  2. 2.
    Zhang L, DeArmond D, Alvarez NT, et al. Flexible micro-supercapacitor based on graphene with 3D structure. Small, 2017, 13: 1603114CrossRefGoogle Scholar
  3. 3.
    Zhu Y, Cao T, Li Z, et al. Two-dimensional SnO2/graphene heterostructures for highly reversible electrochemical lithium storage. Sci China Mater, 2018, 61: 1527–1535CrossRefGoogle Scholar
  4. 4.
    Masarapu C, Zeng HF, Hung KH, et al. Effect of temperature on the capacitance of carbon nanotube supercapacitors. ACS Nano, 2009, 3: 2199–2206CrossRefGoogle Scholar
  5. 5.
    Brachet M, Gaboriau D, Gentile P, et al. Solder-reflow resistant solid-state micro-supercapacitors based on ionogels. J Mater Chem A, 2016, 4: 11835–11843CrossRefGoogle Scholar
  6. 6.
    Zhao G, Li X, Huang M, et al. The physics and chemistry of graphene-on-surfaces. Chem Soc Rev, 2017, 46: 4417–4449CrossRefGoogle Scholar
  7. 7.
    Nair RR, Blake P, Grigorenko AN, et al. Fine structure constant defines visual transparency of graphene. Science, 2008, 320: 1308CrossRefGoogle Scholar
  8. 8.
    Yoo JJ, Balakrishnan K, Huang J, et al. Ultrathin planar graphene supercapacitors. Nano Lett, 2011, 11: 1423–1427CrossRefGoogle Scholar
  9. 9.
    Lei Z, Lu L, Zhao XS. The electrocapacitive properties of graphene oxide reduced by urea. Energy Environ Sci, 2012, 5: 6391–6399CrossRefGoogle Scholar
  10. 10.
    Das S, Sudhagar P, Ito E, et al. Effect of HNO3 functionalization on large scale graphene for enhanced tri-iodide reduction in dyesensitized solar cells. J Mater Chem, 2012, 22: 20490–20497CrossRefGoogle Scholar
  11. 11.
    Lee Y, Bae S, Jang H, et al. Wafer-scale synthesis and transfer of graphene films. Nano Lett, 2010, 10: 490–493CrossRefGoogle Scholar
  12. 12.
    Bae S, Kim H, Lee Y, et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat Nanotech, 2010, 5: 574–578CrossRefGoogle Scholar
  13. 13.
    Stoller MD, Magnuson CW, Zhu Y, et al. Interfacial capacitance of single layer graphene. Energy Environ Sci, 2011, 4: 4685CrossRefGoogle Scholar
  14. 14.
    Zang X, Li X, Zhu M, et al. Graphene/polyaniline woven fabric composite films as flexible supercapacitor electrodes. Nanoscale, 2015, 7: 7318–7322CrossRefGoogle Scholar
  15. 15.
    Wu ZS, Ren W, Wang DW, et al. High-energy MnO2 nanowire/graphene and graphene asymmetric electrochemical capacitors. ACS Nano, 2010, 4: 5835–5842CrossRefGoogle Scholar
  16. 16.
    Cao N, Zhang Y. Study of reduced graphene oxide preparation by hummers’ method and related characterization. J Nanomaterials, 2015, 2015: 168125Google Scholar
  17. 17.
    Maiti UN, Lim J, Lee KE, et al. Three-dimensional shape engineered, interfacial gelation of reduced graphene oxide for high rate, large capacity supercapacitors. Adv Mater, 2014, 26: 615–619CrossRefGoogle Scholar
  18. 18.
    Wang J, Liang M, Fang Y, et al. Rod-coating: towards large-area fabrication of uniform reduced graphene oxide films for flexible touch screens. Adv Mater, 2012, 24: 2874–2878CrossRefGoogle Scholar
  19. 19.
    Liu S, Wu X, Zhang D, et al. Ultrafast dynamic pressure sensors based on graphene hybrid structure. ACS Appl Mater Interfaces, 2017, 9: 24148–24154CrossRefGoogle Scholar
  20. 20.
    Su CY, Lu AY, Xu Y, et al. High-quality thin graphene films from fast electrochemical exfoliation. ACS Nano, 2011, 5: 2332–2339CrossRefGoogle Scholar
  21. 21.
    Pan N, Guan D, Yang Y, et al. A rapid low-temperature synthetic method leading to large-scale carboxyl graphene. Chem Eng J, 2014, 236: 471–479CrossRefGoogle Scholar
  22. 22.
    Robinson JT, Zalalutdinov M, Baldwin JW, et al. Wafer-scale reduced graphene oxide films for nanomechanical devices. Nano Lett, 2008, 8: 3441–3445CrossRefGoogle Scholar
  23. 23.
    Shi J, Li X, Cheng H, et al. Graphene reinforced carbon nanotube networks for wearable strain sensors. Adv Funct Mater, 2016, 26: 2078–2084CrossRefGoogle Scholar
  24. 24.
    Zhang R, Li X, Zhang L, et al. A flexible platform containing graphene mesoporous structure and carbon nanotube for hydrogen evolution. Adv Sci, 2016, 3: 1600208CrossRefGoogle Scholar
  25. 25.
    Zang X, Zhang R, Zhen Z, et al. Flexible, temperature-tolerant supercapacitor based on hybrid carbon film electrodes. Nano Energy, 2017, 40: 224–232CrossRefGoogle Scholar
  26. 26.
    Zhou Y, Hu X, Shang Y, et al. Highly flexible all-solid-state supercapacitors based on carbon nanotube/polypyrrole composite films and fibers. RSC Adv, 2016, 6: 62062–62070CrossRefGoogle Scholar
  27. 27.
    Shang Y, Wang C, He X, et al. Self-stretchable, helical carbon nanotube yarn supercapacitors with stable performance under extreme deformation conditions. Nano Energy, 2015, 12: 401–409CrossRefGoogle Scholar
  28. 28.
    Wu S, Chen G, Kim NY, et al. Creating pores on graphene platelets by low-temperature KOH activation for enhanced electrochemical performance. Small, 2016, 12: 2376–2384CrossRefGoogle Scholar
  29. 29.
    Cheng T, Xu J, Tan Z, et al. A spray-freezing approach to reduced graphene oxide/MoS2 hybrids for superior energy storage. Energy Storage Mater, 2015, 10: 282–290CrossRefGoogle Scholar
  30. 30.
    Kim M, Hwang Y, Kim J. Graphene/MnO2-based composites reduced via different chemical agents for supercapacitors. J Power Sources, 2013, 239: 225–233CrossRefGoogle Scholar
  31. 31.
    Fan Z, Yan J, Wei T, et al. Asymmetric supercapacitors based on graphene/MnO2 and activated carbon nanofiber electrodes with high power and energy density. Adv Funct Mater, 2011, 21: 2366–2375CrossRefGoogle Scholar
  32. 32.
    Reddy ALM, Shaijumon MM, Gowda SR, et al. Coaxial MnO2/ carbon nanotube array electrodes for high-performance lithium batteries. Nano Lett, 2009, 9: 1002–1006CrossRefGoogle Scholar
  33. 33.
    He Y, Chen W, Li X, et al. Freestanding three-dimensional graphene/ MnO2 composite networks as ultralight and flexible supercapacitor electrodes. ACS Nano, 2013, 7: 174–182CrossRefGoogle Scholar
  34. 34.
    Guo FM, Xu RQ, Cui X, et al. Highly flexible, tailorable and allsolid-state supercapacitors from carbon nanotube–MnOx composite films. RSC Adv, 2015, 5: 89188–89194CrossRefGoogle Scholar
  35. 35.
    Patel MN, Wang X, Slanac DA, et al. High pseudocapacitance of MnO2 nanoparticles in graphitic disordered mesoporous carbon at high scan rates. J Mater Chem, 2012, 22: 3160–3169CrossRefGoogle Scholar
  36. 36.
    Peng L, Peng X, Liu B, et al. Ultrathin two-dimensional MnO2/ graphene hybrid nanostructures for high-performance, flexible planar supercapacitors. Nano Lett, 2013, 13: 2151–2157CrossRefGoogle Scholar
  37. 37.
    Augustyn V, Simon P, Dunn B. Pseudocapacitive oxide materials for high-rate electrochemical energy storage. Energy Environ Sci, 2014, 7: 1597–1614CrossRefGoogle Scholar
  38. 38.
    Wei W, Cui X, Chen W, et al. Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chem Soc Rev, 2011, 40: 1697–1721CrossRefGoogle Scholar
  39. 39.
    Xu K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem Rev, 2004, 104: 4303–4418CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Materials Science and EngineeringChina University of Petroleum (East China)QingdaoChina
  2. 2.State Key Laboratory of New Ceramics and Fine Processing, Center for Nano and Micro Mechanics (CNMM), School of Materials Science and EngineeringTsinghua UniversityBeijingChina
  3. 3.Division of Energy and Environment, Graduate School of ShenzhenTsinghua UniversityShenzhenChina

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