Advertisement

The excellent capacitive capability for N,P-doped carbon microsphere/reduced graphene oxide nanocomposites in H2SO4/KI redox electrolyte

  • Qimeng Sun
  • Yueming LiEmail author
  • Tao HeEmail author
Composites

Abstract

In order to ameliorate the capacitance and energy density of supercapacitors in aqueous electrolytes, nitrogen- and phosphorus-codoped carbon microspheres/reduced graphene oxide nanocomposites are obtained by hydrothermal treatment of graphite oxide and N,P-doped carbon microsphere. The as-prepared nanocomposites display a high specific surface area of 604.3 m2 g−1 and hierarchical pore structure composed of micropores, mesopores, and macropores. N,P-codoped carbon microspheres/reduced graphene oxide are used as electrode materials in the redox electrolyte of H2SO4 and KI aqueous solution, exhibiting a excellent capacitance performance of up to ~ 654 F g−1 at 2 A g−1, corresponding to the energy density of 14.53 Wh kg−1 at power density of 402 W kg−1. Even at a high current of 20 A g−1, the electrode can keep a capacitance of 318 F g−1, showing an energy density of 7 Wh kg−1 at power density of 3984 W kg−1. This study indicates the potential of nitrogen- and phosphorus-codoped carbon microspheres/reduced graphene oxide in high energy density supercapacitor.

Notes

Acknowledgements

This work was financially supported by the Natural Science Foundation of Hebei Province (Grant No. E2014203033), the foundation of State Key Laboratory of Metastable Materials Science and Technology, and the open foundation of Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) (111 Project, B12015).

Supplementary material

10853_2019_3414_MOESM1_ESM.docx (2.5 mb)
Supplementary material 1 (DOCX 2581 kb)

References

  1. 1.
    Zhong C, Deng Y, Hu W, Qiao J, Zhang L, Zhang J (2015) A review of electrolyte materials and compositions for electrochemical supercapacitors. Chem Soc Rev 44(21):7484–7539.  https://doi.org/10.1039/c5cs00303b Google Scholar
  2. 2.
    Wang F, Wu X, Yuan X, Liu Z, Zhang Y, Fu L, Zhu Y, Zhou Q, Wu Y, Huang W (2017) Latest advances in supercapacitors: from new electrode materials to novel device designs. Chem Soc Rev 46(22):6816–6854.  https://doi.org/10.1039/c7cs00205j Google Scholar
  3. 3.
    Lu P, Müller L, Hoffmann M, Chen X (2017) Taper silicon nano-scaffold regulated compact integration of 1D nanocarbons for improved on-chip supercapacitor. Nano Energy 41:618–625.  https://doi.org/10.1016/j.nanoen.2017.10.019 Google Scholar
  4. 4.
    Sheng L, Jiang L, Wei T, Liu Z, Fan Z (2017) Spatial charge storage within honeycomb-carbon frameworks for ultrafast supercapacitors with high energy and power densities. Adv Energy Mater 7(19):1700668.  https://doi.org/10.1002/aenm.201700668 Google Scholar
  5. 5.
    Cakici M, Kakarla RR, Alonso-Marroquin F (2017) Advanced electrochemical energy storage supercapacitors based on the flexible carbon fiber fabric-coated with uniform coral-like MnO2 structured electrodes. Chem Eng J 309:151–158.  https://doi.org/10.1016/j.cej.2016.10.012 Google Scholar
  6. 6.
    Xu Z, Zhuang X, Yang C, Cao J, Yao Z, Tang Y, Jiang J, Wu D, Feng X (2016) Nitrogen-doped porous carbon superstructures derived from hierarchical assembly of polyimide nanosheets. Adv Mater 28(10):1981–1987.  https://doi.org/10.1002/adma.201505131 Google Scholar
  7. 7.
    Kim HT, Shin H, Jeon IY, Yousaf M, Baik J, Cheong HW, Park N, Baek JB, Kwon TH (2017) Carbon-heteroatom bond formation by an ultrasonic chemical reaction for energy storage systems. Adv Mater.  https://doi.org/10.1002/adma.201702747 Google Scholar
  8. 8.
    Dong X, Jin H, Wang R, Zhang J, Feng X, Yan C, Chen S, Wang S, Wang J, Lu J (2018) High volumetric capacitance, ultralong life supercapacitors enabled by waxberry-derived hierarchical porous carbon materials. Adv Energy Mater 8(11):1702695.  https://doi.org/10.1002/aenm.201702695 Google Scholar
  9. 9.
    Gao Y, Li L, Jin Y, Wang Y, Yuan C, Wei Y, Chen G, Ge J, Lu H (2015) Porous carbon made from rice husk as electrode material for electrochemical double layer capacitor. Appl Energy 153:41–47.  https://doi.org/10.1016/j.apenergy.2014.12.070 Google Scholar
  10. 10.
    Chen J, Wei H, Fu N, Chen H, Lan G, Lin H, Han S (2017) Facile synthesis of nitrogen-containing porous carbon as electrode materials for superior-performance electrical double-layer capacitors. J Mater Sci 53(3):2137–2148.  https://doi.org/10.1007/s10853-017-1664-7 Google Scholar
  11. 11.
    Lei D, Song K-H, Li X-D, Kim H-Y, Kim B-S (2016) Nanostructured polyaniline/kenaf-derived 3D porous carbon materials with high cycle stability for supercapacitor electrodes. J Mater Sci 52(4):2158–2168.  https://doi.org/10.1007/s10853-016-0504-5 Google Scholar
  12. 12.
    Sheng L, Chang J, Jiang L, Jiang Z, Liu Z, Wei T, Fan Z (2018) Multilayer-folded graphene ribbon film with ultrahigh areal capacitance and high rate performance for compressible supercapacitors. Adv Func Mater 28(21):1800597.  https://doi.org/10.1002/adfm.201800597 Google Scholar
  13. 13.
    Peng Z, Lin J, Ye R, Samuel EL, Tour JM (2015) Flexible and stackable laser-induced graphene supercapacitors. ACS Appl Mater Interfaces 7(5):3414–3419.  https://doi.org/10.1021/am509065d Google Scholar
  14. 14.
    Wang X, Wan F, Zhang L, Zhao Z, Niu Z, Chen J (2018) Large-area reduced graphene oxide composite films for flexible asymmetric sandwich and microsized supercapacitors. Adv Func Mater 28(18):1707247.  https://doi.org/10.1002/adfm.201707247 Google Scholar
  15. 15.
    Jose SP, Tiwary CS, Kosolwattana S, Raghavan P, Machado LD, Gautam C, Prasankumar T, Joyner J, Ozden S, Galvao DS, Ajayan PM (2016) Enhanced supercapacitor performance of a 3D architecture tailored using atomically thin rGO–MoS2 2D sheets. RSC Adv 6(96):93384–93393.  https://doi.org/10.1039/c6ra20960b Google Scholar
  16. 16.
    Wu K, Liu D, Tang Y (2018) In-situ single-step chemical synthesis of graphene-decorated CoFe2O4 composite with enhanced Li ion storage behaviors. Electrochim Acta 263:515–523.  https://doi.org/10.1016/j.electacta.2018.01.047 Google Scholar
  17. 17.
    Wu K, Du K, Hu G (2018) A novel design concept for fabricating 3D graphene with the assistant of anti-solvent precipitated sulphates and its Li-ion storage properties. J Mater Chem A 6(8):3444–3453.  https://doi.org/10.1039/c7ta10850h Google Scholar
  18. 18.
    Kim B, Chung H, Kim W (2012) High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes. Nanotechnology 23(15):155401.  https://doi.org/10.1088/0957-4484/23/15/155401 Google Scholar
  19. 19.
    Tran C, Kalra V (2013) Fabrication of porous carbon nanofibers with adjustable pore sizes as electrodes for supercapacitors. J Power Sources 235:289–296.  https://doi.org/10.1016/j.jpowsour.2013.01.080 Google Scholar
  20. 20.
    Hou S, Wang M, Xu X, Li Y, Li Y, Lu T, Pan L (2017) Nitrogen-doped carbon spheres: a new high-energy-density and long-life pseudo-capacitive electrode material for electrochemical flow capacitor. J Colloid Interface Sci 491:161–166.  https://doi.org/10.1016/j.jcis.2016.12.033 Google Scholar
  21. 21.
    Yan J, Liu J, Fan Z, Wei T, Zhang L (2012) High-performance supercapacitor electrodes based on highly corrugated graphene sheets. Carbon 50(6):2179–2188.  https://doi.org/10.1016/j.carbon.2012.01.028 Google Scholar
  22. 22.
    Liu B, Yang M, Chen H, Liu Y, Yang D, Li H (2018) Graphene-like porous carbon nanosheets derived from salvia splendens for high-rate performance supercapacitors. J Power Sources 397:1–10.  https://doi.org/10.1016/j.jpowsour.2018.06.100 Google Scholar
  23. 23.
    Li Y, Wang Z, Li L, Peng S, Zhang L, Srinivasan M, Ramakrishna S (2016) Preparation of nitrogen- and phosphorous co-doped carbon microspheres and their superior performance as anode in sodium-ion batteries. Carbon 99:556–563.  https://doi.org/10.1016/j.carbon.2015.12.066 Google Scholar
  24. 24.
    Senthilkumar ST, Selvan RK, Melo JS (2013) Redox additive/active electrolytes: a novel approach to enhance the performance of supercapacitors. J Mater Chem A 1(40):12386.  https://doi.org/10.1039/c3ta11959a Google Scholar
  25. 25.
    Senthilkumar ST, Selvan RK, Ponpandian N, Melo JS, Lee YS (2013) Improved performance of electric double layer capacitor using redox additive (VO2+/VO2 +) aqueous electrolyte. J Mater Chem A 1(27):7913.  https://doi.org/10.1039/c3ta10998d Google Scholar
  26. 26.
    Roldán S, Granda M, Menéndez R, Santamaría R, Blanco C (2011) Mechanisms of energy storage in carbon-based supercapacitors modified with a quinoid redox-active electrolyte. J Phys Chem C 115(35):17606–17611.  https://doi.org/10.1021/jp205100v Google Scholar
  27. 27.
    Wang L, Mu G, Tian C, Sun L, Zhou W, Yu P, Yin J, Fu H (2013) Porous graphitic carbon nanosheets derived from cornstalk biomass for advanced supercapacitors. Chemsuschem 6(5):880–889.  https://doi.org/10.1002/cssc.201200990 Google Scholar
  28. 28.
    Senthilkumar ST, Selvan RK, Lee YS, Melo JS (2013) Electric double layer capacitor and its improved specific capacitance using redox additive electrolyte. J Mater Chem A 1(4):1086–1095.  https://doi.org/10.1039/c2ta00210h Google Scholar
  29. 29.
    Lota G, Frackowiak E (2009) Striking capacitance of carbon/iodide interface. Electrochem Commun 11(1):87–90.  https://doi.org/10.1016/j.elecom.2008.10.026 Google Scholar
  30. 30.
    Jayaramulu K, Dubal DP, Nagar B, Ranc V, Tomanec O, Petr M, Datta KKR, Zboril R, Gómez-Romero P, Fischer RA (2018) Ultrathin hierarchical porous carbon nanosheets for high-performance supercapacitors and redox electrolyte energy storage. Adv Mater 30(15):1705789.  https://doi.org/10.1002/adma.201705789 Google Scholar
  31. 31.
    Ye S, Feng J, Wu P (2013) Deposition of three-dimensional graphene aerogel on nickel foam as a binder-free supercapacitor electrode. ACS Appl Mater Interfaces 5(15):7122–7129.  https://doi.org/10.1021/am401458x Google Scholar
  32. 32.
    Sankar KV, Kalai Selvan R (2015) Improved electrochemical performances of reduced graphene oxide based supercapacitor using redox additive electrolyte. Carbon 90:260–273.  https://doi.org/10.1016/j.carbon.2015.04.023 Google Scholar
  33. 33.
    Gao P, Liu ZH, Xue G, Han B, Zhou MH (2011) Preparation and characterization of activated carbon produced from rice straw by (NH4)2HPO4 activation. Bioresour Technol 102(3):3645–3648.  https://doi.org/10.1016/j.biortech.2010.11.080 Google Scholar
  34. 34.
    Huang W, Zhang H, Huang Y, Wang W, Wei S (2011) Hierarchical porous carbon obtained from animal bone and evaluation in electric double-layer capacitors. Carbon 49(3):838–843.  https://doi.org/10.1016/j.carbon.2010.10.025 Google Scholar
  35. 35.
    Wei J, Zhou D, Sun Z, Deng Y, Xia Y, Zhao D (2013) A controllable synthesis of rich nitrogen-doped ordered mesoporous carbon for CO2 capture and supercapacitors. Adv Func Mater 23(18):2322–2328.  https://doi.org/10.1002/adfm.201202764 Google Scholar
  36. 36.
    Ma C, Song Y, Shi J, Zhang D, Zhai X, Zhong M, Guo Q, Liu L (2013) Preparation and one-step activation of microporous carbon nanofibers for use as supercapacitor electrodes. Carbon 51:290–300.  https://doi.org/10.1016/j.carbon.2012.08.056 Google Scholar
  37. 37.
    Xu D, Tong Y, Yan T, Shi L, Zhang D (2017) N,P-codoped meso-/microporous carbon derived from biomass materials via a dual-activation strategy as high-performance electrodes for deionization capacitors. ACS Sustain Chem Eng 5(7):5810–5819.  https://doi.org/10.1021/acssuschemeng.7b00551 Google Scholar
  38. 38.
    Hameed BH, Din AT, Ahmad AL (2007) Adsorption of methylene blue onto bamboo-based activated carbon: kinetics and equilibrium studies. J Hazard Mater 141(3):819–825.  https://doi.org/10.1016/j.jhazmat.2006.07.049 Google Scholar
  39. 39.
    Li Y, Zhao D (2015) Preparation of reduced graphite oxide with high volumetric capacitance in supercapacitors. Chem Commun 51(26):5598–5601.  https://doi.org/10.1039/c4cc08038f Google Scholar
  40. 40.
    Han J, Xu G, Ding B, Pan J, Dou H, MacFarlane DR (2014) Porous nitrogen-doped hollow carbon spheres derived from polyaniline for high performance supercapacitors. J Mater Chem A 2(15):5352–5357.  https://doi.org/10.1039/c3ta15271e Google Scholar
  41. 41.
    Zhao X, Wang S, Wu Q (2017) Nitrogen and phosphorus dual-doped hierarchical porous carbon with excellent supercapacitance performance. Electrochim Acta 247:1140–1146.  https://doi.org/10.1016/j.electacta.2017.07.077 Google Scholar
  42. 42.
    Yu S, Li Y, Pan N (2014) KOH activated carbon/graphene nanosheets composites as high performance electrode materials in supercapacitors. RSC Adv 4(90):48758–48764.  https://doi.org/10.1039/c4ra06710j Google Scholar
  43. 43.
    Gao Z, Zhang L, Chang J, Wang Z, Wu D, Xu F, Guo Y, Jiang K (2018) Catalytic electrode-redox electrolyte supercapacitor system with enhanced capacitive performance. Chem Eng J 335:590–599.  https://doi.org/10.1016/j.cej.2017.11.037 Google Scholar
  44. 44.
    Lee KH, Oh J, Son JG, Kim H, Lee SS (2014) Nitrogen-doped graphene nanosheets from bulk graphite using microwave irradiation. ACS Appl Mater Interfaces 6(9):6361–6368.  https://doi.org/10.1021/am405735c Google Scholar
  45. 45.
    Yang J, Gunasekaran S (2013) Electrochemically reduced graphene oxide sheets for use in high performance supercapacitors. Carbon 51:36–44.  https://doi.org/10.1016/j.carbon.2012.08.003 Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and EngineeringYan Shan UniversityQinhuangdaoChina
  2. 2.Shanghai Advanced Research InstituteChinese Academy of SciencesShanghaiChina
  3. 3.Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education)Nankai UniversityTianjinChina

Personalised recommendations