Journal of Materials Science

, Volume 54, Issue 19, pp 12747–12757 | Cite as

A facile synthesis of nitrogen-doped hierarchical porous carbon with hollow sphere structure for high-performance supercapacitors

  • Yunpeng Shang
  • Xudong Hu
  • Xin Li
  • Shu Cai
  • Guangchuan Liang
  • Junmei Zhao
  • Chunming ZhengEmail author
  • Xiaohong SunEmail author
Energy materials


In this work, nitrogen-doped carbon with hierarchical porous and hollow sphere structure has been synthesized through a simple and facile route of spray drying using glycine as the nitrogen-containing carbon source. After KOH activation, the prepared material (NHPCA) shows a large specific surface area of 962 m2 g−1 with moderate N-doping of 5.74% and exhibits a high specific capacitance of 271 F g−1 in 6 M KOH electrolyte at 1.0 A g−1, remarkable rate capability and particularly stable cycling performance with no significant specific capacitance drop after 10000 cycles at 1.0 A g−1. The excellent electrochemical properties come from the unique structure and the doping of nitrogen. The hierarchical pore structure improves the efficiency of electrolyte ions transport, and diffusion and the hollow sphere structure further facilitates mass transport. The doping of nitrogen increases the total capacitance by providing redox pseudo-capacitance. The results indicate the as-prepared nitrogen-doped carbon with hierarchical porous and hollow sphere structure can be used as a hopeful candidate for an efficient electrode of commercial supercapacitors devices.



This work was supported by the National Natural Science Foundation of China, NSFC (51772205, 51572192, 51772208, 51472179), and the General Program of Municipal Natural Science Foundation of Tianjin (17JCYBJC17000, 17JCYBJC22700).

Compliance with ethical standards

Conflict of interest

All authors listed have declared that they have no conflict of interest.

Supplementary material

10853_2019_3744_MOESM1_ESM.docx (533 kb)
Supplementary material 1 (DOCX 532 kb)


  1. 1.
    Sun J, Niu J, Liu M et al (2018) Biomass-derived nitrogen-doped porous carbons with tailored hierarchical porosity and high specific surface area for high energy and power density supercapacitors. Appl Surf Sci 427:807–813. CrossRefGoogle Scholar
  2. 2.
    Li X, Sun X, Gao Z et al (2018) Highly reversible and fast sodium storage boosted by improved interfacial and surface charge transfer derived from the synergistic effect of heterostructures and pseudocapacitance in SnO2-based anodes. Nanoscale 10:2301–2309. CrossRefGoogle Scholar
  3. 3.
    Chu S, Majumdar A (2012) Opportunities and challenges for a sustainable energy future. Nature 488:294–303. CrossRefGoogle Scholar
  4. 4.
    Zhong C, Deng Y, Hu W et al (2015) A review of electrolyte materials and compositions for electrochemical supercapacitors. Chem Soc Rev 44:7484–7539. CrossRefGoogle Scholar
  5. 5.
    Choudhary N, Li C, Moore J et al (2017) Asymmetric supercapacitor electrodes and devices. Adv Mater 29:1605336. CrossRefGoogle Scholar
  6. 6.
    Zhang S, Pan N (2015) Supercapacitors performance evaluation. Adv Energy Mater 5:1401401. CrossRefGoogle Scholar
  7. 7.
    Lim E, Jo C, Lee J (2016) A mini review of designed mesoporous materials for energy-storage applications: from electric double-layer capacitors to hybrid supercapacitors. Nanoscale 8:7827–7833. CrossRefGoogle Scholar
  8. 8.
    Lei C, Amini N, Markoulidis F et al (2013) Activated carbon from phenolic resin with controlled mesoporosity for an electric double-layer capacitor (EDLC). J Mater Chem A 1:6037–6042. CrossRefGoogle Scholar
  9. 9.
    Zhang X, Ma L, Gan M et al (2017) Fabrication of 3D lawn-shaped N-doped porous carbon matrix/polyaniline nanocomposite as the electrode material for supercapacitors. J Power Sources 340:22–31. CrossRefGoogle Scholar
  10. 10.
    Chen Y, Wang B, Hou T et al (2018) Enhanced electrochemical performance of SnS nanoparticles/CNTs composite as anode material for sodium-ion battery. Chin Chem Lett 29:187–190. CrossRefGoogle Scholar
  11. 11.
    Wei H, Qian W, Fu N et al (2017) Facile synthesis of nitrogen-doped porous carbons for CO2 capture and supercapacitors. J Mater Sci 52:10308–10320. CrossRefGoogle Scholar
  12. 12.
    Chen Y, Hu X, Evanko B et al (2018) High-rate FeS2/CNT neural network nanostructure composite anodes for stable, high-capacity sodium-ion batteries. Nano Energy 46:117–127. CrossRefGoogle Scholar
  13. 13.
    Wang Z, Xiong Y, Guan S (2016) A simple CaCO3-assisted template carbonization method for producing nitrogen doped porous carbons as electrode materials for supercapacitors. Electrochim Acta 188:757–766. CrossRefGoogle Scholar
  14. 14.
    Kang D, Liu Q, Gu J et al (2015) “Egg-Box”-assisted fabrication of porous carbon with small mesopores for high-rate electric double layer capacitors. ACS Nano 9:11225–11233. CrossRefGoogle Scholar
  15. 15.
    Yu P, Zhang Z, Zheng L et al (2016) A novel sustainable flour derived hierarchical nitrogen-doped porous carbon/polyaniline electrode for advanced asymmetric supercapacitors. Adv Energy Mater 6:1601111. CrossRefGoogle Scholar
  16. 16.
    Xie Q, Huang X, Zhang Y et al (2018) High performance aqueous symmetric supercapacitors based on advanced carbon electrodes and hydrophilic poly(vinylidene fluoride) porous separator. Appl Surf Sci 443:412–420. CrossRefGoogle Scholar
  17. 17.
    Kan K, Wang L, Yu P et al (2016) 2D quasi-ordered nitrogen-enriched porous carbon nanohybrids for high energy density supercapacitors. Nanoscale 8:10166–10176. CrossRefGoogle Scholar
  18. 18.
    Wang W, Quan H, Gao W et al (2017) N-doped hierarchical porous carbon from waste boat-fruited sterculia seed for high performance supercapacitors. RSC Adv 7:16678–16687. CrossRefGoogle Scholar
  19. 19.
    Ba Y, Pan W, Pi S et al (2018) Nitrogen-doped hierarchical porous carbon derived from a chitosan/polyethylene glycol blend for high performance supercapacitors. RSC Adv 8:7072–7079. CrossRefGoogle Scholar
  20. 20.
    Zou K, Deng Y, Chen J et al (2018) Hierarchically porous nitrogen-doped carbon derived from the activation of agriculture waste by potassium hydroxide and urea for high-performance supercapacitors. J Power Sources 378:579–588. CrossRefGoogle Scholar
  21. 21.
    Xin L, Li R, Lu Z et al (2018) Hierarchical metal-organic framework derived nitrogen-doped porous carbon by controllable synthesis for high performance supercapacitors. J Electroanal Chem 813:200–207. CrossRefGoogle Scholar
  22. 22.
    Zhao Z, Liu S, Zhu J et al (2018) Hierarchical nanostructures of nitrogen-doped porous carbon polyhedrons confined in carbon nanosheets for high-performance supercapacitors. ACS Appl Mater Interfaces 10:19871–19880. CrossRefGoogle Scholar
  23. 23.
    Hou J, Cao C, Idrees F, Ma X (2015) Hierarchical porous nitrogen-doped carbon nanosheets derived from silk for ultrahigh-capacity battery anodes and supercapacitors. ACS Nano 9:2556–2564. CrossRefGoogle Scholar
  24. 24.
    Ma F, Zhao H, Sun L et al (2012) A facile route for nitrogen-doped hollow graphitic carbon spheres with superior performance in supercapacitors. J Mater Chem 22:13464. CrossRefGoogle Scholar
  25. 25.
    Yuan C, Liu X, Jia M et al (2015) Facile preparation of N- and O-doped hollow carbon spheres derived from poly(o-phenylenediamine) for supercapacitors. J Mater Chem A 3:3409–3415. CrossRefGoogle Scholar
  26. 26.
    Liu L, Xu S-D, Yu Q et al (2016) Nitrogen-doped hollow carbon spheres with a wrinkled surface: their one-pot carbonization synthesis and supercapacitor properties. Chem Commun 52:11693–11696. CrossRefGoogle Scholar
  27. 27.
    Han J, Xu G, Ding B et al (2014) Porous nitrogen-doped hollow carbon spheres derived from polyaniline for high performance supercapacitors. J Mater Chem A 2:5352–5357. CrossRefGoogle Scholar
  28. 28.
    Chen A, Li Y, Liu L et al (2017) Controllable synthesis of nitrogen-doped hollow mesoporous carbon spheres using ionic liquids as template for supercapacitors. Appl Surf Sci 393:151–158. CrossRefGoogle Scholar
  29. 29.
    He D, Niu J, Dou M et al (2017) Nitrogen and oxygen co-doped carbon networks with a mesopore-dominant hierarchical porosity for high energy and power density supercapacitors. Electrochim Acta 238:310–318. CrossRefGoogle Scholar
  30. 30.
    Zhang L, Xu L, Zhang Y et al (2018) Facile synthesis of bio-based nitrogen- and oxygen-doped porous carbon derived from cotton for supercapacitors. RSC Adv 8:3869–3877. CrossRefGoogle Scholar
  31. 31.
    Zhang X, Niu Q, Guo Y et al (2018) Heteroatom-doped porous carbons derived from moxa floss of different storage years for supercapacitors. RSC Adv 8:16433–16443. CrossRefGoogle Scholar
  32. 32.
    Jeong HM, Lee JW, Shin WH et al (2011) Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogen-doped sites at basal planes. Nano Lett 11:2472–2477. CrossRefGoogle Scholar
  33. 33.
    Wei L, Sevilla M, Fuertes AB et al (2011) Hydrothermal carbonization of abundant renewable natural organic chemicals for high-performance supercapacitor electrodes. Adv Energy Mater 1:356–361. CrossRefGoogle Scholar
  34. 34.
    Okuyama K, Wuled Lenggoro I (2003) Preparation of nanoparticles via spray route. Chem Eng Sci 58:537–547. CrossRefGoogle Scholar
  35. 35.
    Abdullah M, Iskandar F, Shibamoto S et al (2004) Preparation of oxide particles with ordered macropores by colloidal templating and spray pyrolysis. Acta Mater 52:5151–5156. CrossRefGoogle Scholar
  36. 36.
    Okuyama K, Abdullah M, Lenggoro IW, Iskandar F (2006) Preparation of functional nanostructured particles by spray drying. Adv Powder Technol 17:587–611. CrossRefGoogle Scholar
  37. 37.
    Vehring R (2008) Pharmaceutical particle engineering via spray drying. Pharm Res 25:999–1022. CrossRefGoogle Scholar
  38. 38.
    Ma L, Sun G, Ran J et al (2018) One-pot template-free strategy toward 3D hierarchical porous nitrogen-doped carbon framework in situ armored homogeneous NiO nanoparticles for high-performance asymmetric supercapacitors. ACS Appl Mater Interfaces 10:22278–22290. CrossRefGoogle Scholar
  39. 39.
    Ma Z, Shao G, Fan Y et al (2017) Fabrication of high-performance all-solid-state asymmetric supercapacitors based on stable α-MnO2@NiCo2O4 core–shell heterostructure and 3D-nanocage N-doped porous carbon. ACS Sustain Chem Eng 5:4856–4868. CrossRefGoogle Scholar
  40. 40.
    Widiyastuti W, Wang W-N, Lenggoro IW et al (2007) Simulation and experimental study of spray pyrolysis of polydispersed droplets. J Mater Res 22:1888–1898. CrossRefGoogle Scholar
  41. 41.
    Chen XY, Chen C, Zhang ZJ et al (2013) Nitrogen-doped porous carbon prepared from urea formaldehyde resins by template carbonization method for supercapacitors. Ind Eng Chem Res 52:10181–10188. CrossRefGoogle Scholar
  42. 42.
    Peng H, Ma G, Sun K et al (2014) Facile synthesis of poly(p-phenylenediamine)-derived three-dimensional porous nitrogen-doped carbon networks for high performance supercapacitors. J Phys Chem C 118:29507–29516. CrossRefGoogle Scholar
  43. 43.
    Mao Z, Zhao S, Wang J et al (2018) Facile synthesis of nitrogen-doped porous carbon as robust electrode for supercapacitors. Mater Res Bull 101:140–145. CrossRefGoogle Scholar
  44. 44.
    Choi I-A, Kwak D-H, Han S-B, Park K-W (2018) Nitrogen-doped bi-modal porous carbon nanostructure derived from glycine for supercapacitors. J Ind Eng Chem 63:112–116. CrossRefGoogle Scholar
  45. 45.
    Sha Y, Lou J, Bai S et al (2015) Facile preparation of nitrogen-doped porous carbon from waste tobacco by a simple pre-treatment process and their application in electrochemical capacitor and CO2 capture. Mater Res Bull 64:327–332. CrossRefGoogle Scholar
  46. 46.
    Yang W, Du Z, Ma Z et al (2016) Facile synthesis of nitrogen-doped hierarchical porous lamellar carbon for high-performance supercapacitors. RSC Adv 6:3942–3950. CrossRefGoogle Scholar
  47. 47.
    Jiang L, Sheng L, Chen X et al (2016) Construction of nitrogen-doped porous carbon buildings using interconnected ultra-small carbon nanosheets for ultra-high rate supercapacitors. J Mater Chem A 4:11388–11396. CrossRefGoogle Scholar
  48. 48.
    Zhou J, Bao L, Wu S et al (2017) Chitin based heteroatom-doped porous carbon as electrode materials for supercapacitors. Carbohydr Polym 173:321–329. CrossRefGoogle Scholar
  49. 49.
    Li X, Sun X, Gao Z et al (2018) A simple one-pot strategy for synthesizing ultrafine SnS2 nanoparticle/graphene composites as anodes for lithium/sodium-ion batteries. Chemsuschem 11:1549–1557. CrossRefGoogle Scholar
  50. 50.
    Li B, Cheng Y, Dong L et al (2017) Nitrogen doped and hierarchically porous carbons derived from chitosan hydrogel via rapid microwave carbonization for high-performance supercapacitors. Carbon NY 122:592–603. CrossRefGoogle Scholar
  51. 51.
    Selvamani V, Ravikumar R, Suryanarayanan V et al (2016) Garlic peel derived high capacity hierarchical N-doped porous carbon anode for sodium/lithium ion cell. Electrochim Acta 190:337–345. CrossRefGoogle Scholar
  52. 52.
    Hu X, Sun X, Yoo SJ et al (2018) Nitrogen-rich hierarchically porous carbon as a high-rate anode material with ultra-stable cyclability and high capacity for capacitive sodium-ion batteries. Nano Energy 56:828–839. CrossRefGoogle Scholar
  53. 53.
    Mondal AK, Kretschmer K, Zhao Y et al (2017) Nitrogen-doped porous carbon nanosheets from eco-friendly eucalyptus leaves as high performance electrode materials for supercapacitors and lithium ion batteries. Chem A Eur J 23:3683–3690. CrossRefGoogle Scholar
  54. 54.
    Mondal AK, Kretschmer K, Zhao Y et al (2017) Naturally nitrogen doped porous carbon derived from waste shrimp shells for high-performance lithium ion batteries and supercapacitors. Microporous Mesoporous Mater 246:72–80. CrossRefGoogle Scholar
  55. 55.
    Wang Y, Fugetsu B, Wang Z et al (2017) Nitrogen-doped porous carbon monoliths from polyacrylonitrile (PAN) and carbon nanotubes as electrodes for supercapacitors. Sci Rep 7:40259. CrossRefGoogle Scholar
  56. 56.
    Wang C, Wu D, Wang H et al (2018) Biomass derived nitrogen-doped hierarchical porous carbon sheets for supercapacitors with high performance. J Colloid Interface Sci 523:133–143. CrossRefGoogle Scholar
  57. 57.
    Kang X, Zhu H, Wang C et al (2018) Biomass derived hierarchically porous and heteroatom-doped carbons for supercapacitors. J Colloid Interface Sci 509:369–383. CrossRefGoogle Scholar
  58. 58.
    Xin L, Liu Q, Liu J et al (2017) Hierarchical metal-organic framework derived nitrogen-doped porous carbon/graphene composite for high performance supercapacitors. Electrochim Acta 248:215–224. CrossRefGoogle Scholar
  59. 59.
    Li X, Zhao Y, Bai Y et al (2017) A non-woven network of porous nitrogen-doping carbon nanofibers as a binder-free electrode for supercapacitors. Electrochim Acta 230:445–453. CrossRefGoogle Scholar
  60. 60.
    Li Q, Xu D, Guo J et al (2017) Protonated g-C3N4@polypyrrole derived N-doped porous carbon for supercapacitors and oxygen electrocatalysis. Carbon NY 124:599–610. CrossRefGoogle Scholar
  61. 61.
    Niu Q, Gao K, Tang Q et al (2017) Large-size graphene-like porous carbon nanosheets with controllable N-doped surface derived from sugarcane bagasse pith/chitosan for high performance supercapacitors. Carbon NY 123:290–298. CrossRefGoogle Scholar
  62. 62.
    Liu Z, Xiao K, Guo H et al (2017) Nitrogen-doped worm-like graphitized hierarchical porous carbon designed for enhancing area-normalized capacitance of electrical double layer supercapacitors. Carbon NY 117:163–173. CrossRefGoogle Scholar
  63. 63.
    Zhao J, Li Y, Wang G et al (2017) Enabling high-volumetric-energy-density supercapacitors: designing open, low-tortuosity heteroatom-doped porous carbon-tube bundle electrodes. J Mater Chem A 5:23085–23093. CrossRefGoogle Scholar
  64. 64.
    Wang C, Wu D, Wang H et al (2017) Nitrogen-doped two-dimensional porous carbon sheets derived from clover biomass for high performance supercapacitors. J Power Sources 363:375–383. CrossRefGoogle Scholar
  65. 65.
    Lei Y, Gan M, Ma L et al (2017) Synthesis of nitrogen-doped porous carbon from zeolitic imidazolate framework-67 and phenolic resin for high performance supercapacitors. Ceram Int 43:6502–6510. CrossRefGoogle Scholar

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

Authors and Affiliations

  1. 1.School of Materials Science and Engineering, Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of EducationTianjin UniversityTianjinPeople’s Republic of China
  2. 2.State Key Laboratory of Hollow-Fiber Membrane Materials and Membrane Processes, School of Environmental and Chemical EngineeringTianjin Polytechnic UniversityTianjinPeople’s Republic of China
  3. 3.Department of Chemistry and BiochemistryUniversity of California, Santa BarbaraSanta BarbaraUSA
  4. 4.Institute of Power Source and Ecomaterials ScienceHebei University of TechnologyTianjinPeople’s Republic of China
  5. 5.CAS Key Laboratory of Green Process and Engineering, Institute of Process EngineeringChinese Academy of SciencesBeijingPeople’s Republic of China

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