Journal of Materials Science

, Volume 54, Issue 7, pp 5625–5640 | Cite as

Nitrogen- and oxygen-rich dual-decorated carbon materials with porosity for high-performance supercapacitors

  • Haijun Chen
  • Jing Chen
  • Daming Chen
  • Huanming Wei
  • Ping Liu
  • Wei Wei
  • Hualin LinEmail author
  • Sheng HanEmail author
Energy materials


A series of N/O co-doping porous carbon materials are fabricated from benzotriazole as nitrogen-containing precursor through simple chemical activation (phosphoric acid as activator) and thermolysis process under nitrogen atmosphere. Abundant heteroatoms or functional groups (O: 11.4 at.%; N: 6.5 at.%) in the N/O-3-700 sample can improve the overall electrochemical performance of the material, which is because they can enhance physicochemical properties and induce the pronounced pseudocapacitance. In three-electrode system, the resultant product (N/O-3-700) has a highest specific capacitance value of 357.8 F g−1 at 0.1 A g−1 and good cycle stability (remains more than 94% after 10000 at 1 A g−1), which are attributed to large specific area (1337.7 m2 g−1) and proper functional groups (the sum of N-5 and N-6 content: 42.2 at.%; quinone: 14.3 at.%, C=O and/or COOH: 16.0 at.%). And in symmetric two-electrode cell, the N/O-3-700//N/O-3-700 cell possesses highest energy density of 17.80 Wh kg−1 at 1 A g−1 and still has a high energy density (12.51 Wh kg−1) at 10 A g−1. Thus, the N/O-doped porous carbon can be used for supercapacitors.



This work was supported from the National Natural Science Foundation of China (Project Numbers 21606151, 21504057 and 21707092), Shanghai Excellent Technology Leaders Program (Project Number 17XD1424900), Shanghai Leading Talent Program (Project Number 017), Science and Technology Commission of Shanghai Municipality Project (Project Number 18090503800), Shanghai Natural Science Foundation of Shanghai (Project Numbers 17ZR1441700 and 14ZR1440500), Collaborative Innovation Fund of SIT (Project Number XTCX2015-9), Professor of Special Appointment at Shanghai Institutions of Higher Learning (Eastern Scholar), Shanghai Association for Science and Technology Achievements Transformation Alliance Program (Project Number LM201680).

Compliance with ethical standards

Conflict of interest

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

Supplementary material

10853_2018_2993_MOESM1_ESM.doc (1.6 mb)
Supplementary material 1 (DOC 1624 kb)


  1. 1.
    You PY, Kamarudin SK (2017) Recent progress of carbonaceous materials in fuel cell applications: an overview. Chem Eng J 309:489–502Google Scholar
  2. 2.
    Kim YJ, Yang CM, Park KC, Kaneko K, Kim YA, Noguchi M, Fujino T, Oyama S, Endo M (2012) Edge-enriched, porous carbon-based, high energy density supercapacitors for hybrid electric vehicles. Chemsuschem 5(3):535–541Google Scholar
  3. 3.
    Li J, Liu W, Xiao D, Wang X (2017) Oxygen-rich hierarchical porous carbon made from pomelo peel fiber as electrode material for supercapacitor. Appl Surf Sci. Google Scholar
  4. 4.
    Xiong D, Li X, Bai Z, Li J, Shan H, Fan L, Long C, Li D, Lu X (2018) Rational design of hybrid Co3O4/graphene films: free-standing flexible electrodes for high performance supercapacitors. Electrochim Acta 259:338–347Google Scholar
  5. 5.
    Xin Z, Li W, Fang W, He X, Zhao L, Chen H, Zhang W, Sun Z (2017) Enhanced specific surface area by hierarchical porous graphene aerogel/carbon foam for supercapacitor. J Nanopart Res 19(12):373–382Google Scholar
  6. 6.
    Hu S, Hsieh YL (2017) Lignin derived activated carbon particulates as an electric supercapacitor: carbonization and activation on porous structures and microstructures. RSC Adv 7(48):30459–30468Google Scholar
  7. 7.
    Kim KO, Song KH, Kang CY, Lee JS, Gopiraman M, Kim IS (2017) Nitrogen- and oxygen-containing porous ultrafine carbon nanofiber: a highly flexible electrode material for supercapacitor. J Mater Sci Technol 33(5):424–431Google Scholar
  8. 8.
    Xiao PW, Meng Q, Zhao L, Li JJ, Wei Z, Han BH (2017) Biomass-derived flexible porous carbon materials and their applications in supercapacitor and gas adsorption. Mater Des 129:164–172Google Scholar
  9. 9.
    Kim ND, Kim W, Ji BJ, Oh S, Kim P, Kim Y, Yi J (2008) Electrochemical capacitor performance of N-doped mesoporous carbons prepared by ammoxidation. J Power Sources 180(1):671–675Google Scholar
  10. 10.
    Tang C, Liu Y, Yang D, Yang M, Li H (2017) Oxygen and nitrogen co-doped porous carbons with finely-layered schistose structure for high-rate-performance supercapacitors. Carbon 122:538–546Google Scholar
  11. 11.
    Xu Y, Lin Z, Huang X, Wang Y, Huang Y, Duan X (2013) Functionalized graphene hydrogel-based high-performance supercapacitors. Adv Mater 25(40):5779–5784Google Scholar
  12. 12.
    Wu ZS, Sun Y, Tan YZ, Yang S, Feng X, Mullen K (2012) Three-dimensional graphene-based macro- and mesoporous frameworks for high-performance electrochemical capacitive energy storage. J Am Chem Soc 134(48):19532–19535Google Scholar
  13. 13.
    To JWF, Zheng C, Yao H, He J, Kim K, Chou HH, Pan L, Wilcox J, Yi C, Bao Z (2015) Ultrahigh surface area three-dimensional porous graphitic carbon from conjugated polymeric molecular framework. ACS Cent Sci 1(2):68–76Google Scholar
  14. 14.
    Mondal AK, Kretschmer K, Zhao Y, Liu H, Wang C, Sun B, Wang G (2016) Nitrogen-doped porous carbon nanosheets from eco-friendly eucalyptus leaves as high performance electrode materials for supercapacitors and lithium ion batteries. Chem Eur J 23(15):3683–3690Google Scholar
  15. 15.
    Chmiola J, Yushin G, Gogotsi Y, Portet C, Simon P, Taberna PL (2006) Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer. Science 313(5794):1760–1763Google Scholar
  16. 16.
    Hulicova-Jurcakova D, Kodama M, Shiraishi S, Hatori H, Zhu ZH, Lu GQ (2009) Nitrogen-enriched nonporous carbon electrodes with extraordinary supercapacitance. Adv Funct Mater 19(11):1800–1809Google Scholar
  17. 17.
    Carriazo D, Gutiérrez MC, Picó F, Rojo JM, Fierro JLG, Ferrer ML, Monte Fd (2012) Phosphate-functionalized carbon monoliths from deep eutectic solvents and their use as monolithic electrodes in supercapacitors. Chemsuschem 5(8):1405–1409Google Scholar
  18. 18.
    Wang Y, Xia Y (2013) Recent progress in supercapacitors: from materials design to system construction. Adv Mater 25(37):5336–5342Google Scholar
  19. 19.
    Wang DW, Li F, Liu M, Lu GQ, Cheng HM (2008) 3D aperiodic hierarchical porous graphitic carbon material for high-rate electrochemical capacitive energy storage. Angew Chem 47(2):373–382Google Scholar
  20. 20.
    Xiong D, Li X, Bai Z, Lu S (2018) Recent advances in layered Ti3C2Tx MXene for electrochemical energy storage. Small 14(17):1703419Google Scholar
  21. 21.
    You B, Jiang J, Fan S (2014) Three-dimensional hierarchically porous all-carbon foams for supercapacitor. ACS Appl Mater Interfaces 6(17):15302–15308Google Scholar
  22. 22.
    Wang DW, Li F, Lu GQ, Cheng HM (2008) Synthesis and dye separation performance of ferromagnetic hierarchical porous carbon. Carbon 46(12):1593–1599Google Scholar
  23. 23.
    Chen Z, Ren W, Gao L, Liu B, Pei S, Cheng HM (2011) Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition. Nat Mater 10(6):424–428Google Scholar
  24. 24.
    Lv Y, Gan L, Liu M, Xiong W, Xu Z, Zhu D, Wright DS (2012) A self-template synthesis of hierarchical porous carbon foams based on banana peel for supercapacitor electrodes. J Power Sources 209(209):152–157Google Scholar
  25. 25.
    Zhao Y, Ran W, He J, Song Y, Zhang C, Xiong DB, Gao F, Wu J, Xia Y (2015) Oxygen-rich hierarchical porous carbon derived from artemia cyst shells with superior electrochemical performance. ACS Appl Mater Interfaces 7(2):1132–1139Google Scholar
  26. 26.
    Zhou J, Lian J, Hou L, Zhang J, Gou H, Xia M, Zhao Y, Strobel TA, Tao L, Gao F (2015) Ultrahigh volumetric capacitance and cyclic stability of fluorine and nitrogen co-doped carbon microspheres. Nat Commun 6:8503–8510Google Scholar
  27. 27.
    Nasini UB, Bairi VG, Ramasahayam SK, Bourdo SE, Viswanathan T, Shaikh AU (2014) Phosphorous and nitrogen dual heteroatom doped mesoporous carbon synthesized via microwave method for supercapacitor application. J Power Sources 250(3):257–265Google Scholar
  28. 28.
    Montes-Morán MA, Suárez D, Menéndez JA, Fuente E (2004) On the nature of basic sites on carbon surfaces: an overview. Carbon 42(7):1219–1225Google Scholar
  29. 29.
    Liu Z, Mi J, Yang Y, Tan X, Lv C (2014) Easy synthesis of phosphorus-incorporated three-dimensionally ordered macroporous carbons with hierarchical pores and their use as electrodes for supercapacitors. Electrochim Acta 115(3):206–215Google Scholar
  30. 30.
    Lee YH, Lee YF, Chang KH, Hu CC (2011) Synthesis of N-doped carbon nanosheets from collagen for electrochemical energy storage/conversion systems. Electrochem Commun 13(1):50–53Google Scholar
  31. 31.
    Wang S, Ren Z, Li J, Ren Y, Zhao L, Yu J (2014) Cotton-based hollow carbon fibers with high specific surface area prepared by ammonia etching for supercapacitor application. RSC Adv 4(59):31300–31307Google Scholar
  32. 32.
    Jurewicz K, Pietrzak R, Nowicki P, Wachowska H (2008) Capacitance behaviour of brown coal based active carbon modified through chemical reaction with urea. Electrochim Acta 53(16):5469–5475Google Scholar
  33. 33.
    Sharma RK, Rastogi AC, Desu SB (2008) Pulse polymerized polypyrrole electrodes for high energy density electrochemical supercapacitor. Electrochem Commun 10(2):268–272Google Scholar
  34. 34.
    Gupta V, Miura N (2006) High performance electrochemical supercapacitor from electrochemically synthesized nanostructured polyaniline. Mater Lett 60(12):1466–1469Google Scholar
  35. 35.
    Zhang J, Chen G, Zhang Q, Kang F, You B (2015) Self-assembly synthesis of N-doped carbon aerogels for supercapacitor and electrocatalytic oxygen reduction. ACS Appl Mater Interfaces 7(23):12760–12766Google Scholar
  36. 36.
    Wang L, Gao Z, Chang J, Liu X, Wu D, Xu F, Guo Y, Jiang K (2015) Nitrogen-doped porous carbons as electrode materials for high-performance supercapacitor and dye-sensitized solar cell. ACS Appl Mater Interfaces 7(36):20234–20244Google Scholar
  37. 37.
    Hui Z, Jiao Y, Wang X, Wang H, Yang X (2013) Microorganism-derived heteroatom-doped carbon materials for oxygen reduction and supercapacitors. Adv Funct Mater 23(10):1305–1312Google Scholar
  38. 38.
    Zhang Z, Zhou Z, Peng H, Qin Y, Li G (2014) Nitrogen- and oxygen-containing hierarchical porous carbon frameworks for high-performance supercapacitors. Electrochim Acta 134:471–477Google Scholar
  39. 39.
    Shang TX, Ren RQ, Zhu YM, Jin XJ (2015) Oxygen- and nitrogen-co-doped activated carbon from waste particleboard for potential application in high-performance capacitance. Electrochim Acta 163:32–40Google Scholar
  40. 40.
    Seredych M, Hulicova-Jurcakova D, Gao QL, Bandosz TJ (2008) Surface functional groups of carbons and the effects of their chemical character, density and accessibility to ions on electrochemical performance. Carbon 46(11):1475–1488Google Scholar
  41. 41.
    Xiong D, Li X, Fan L, Bai Z (2018) Three-dimensional heteroatom-doped nanocarbon for metal-free oxygen reduction electrocatalysis: a review. Catalysts 8(8):301. Google Scholar
  42. 42.
    Sing KSW (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (recommendations 1984). Pure Appl Chem 57(4):603–619Google Scholar
  43. 43.
    Li W, Wu J, Higgins DC, Choi J-Y, Chen Z (2012) Determination of iron active sites in pyrolyzed iron-based catalysts for the oxygen reduction reaction. ACS Catal 2(12):2761–2768Google Scholar
  44. 44.
    Ma Z, Zhang H, Yang Z, Ji G, Yu B, Liu X, Liu Z (2016) Mesoporous nitrogen-doped carbons with high nitrogen contents and ultrahigh surface areas: synthesis and applications in catalysis. Green Chem 18(7):1976–1982Google Scholar
  45. 45.
    Hellgren N, Haasch RT, Schmidt S, Hultman L, Petrov I (2016) Interpretation of X-ray photoelectron spectra of carbon-nitride thin films: new insights from in situ XPS. Carbon 108:242–252Google Scholar
  46. 46.
    Weidenthaler Claudia, Lu An-Hui, Schmidt Wolfgang, Schüth Ferdi (2006) X-ray photoelectron spectroscopic studies of PAN-based ordered mesoporous carbons (OMC). Microporous Mesoporous Mater 88(1):238–243Google Scholar
  47. 47.
    Hulicova-Jurcakova D, Seredych M, Gao QL, Bandosz TJ (2009) Combined effect of nitrogen- and oxygen-containing functional groups of microporous activated carbon on its electrochemical performance in supercapacitors. Adv Funct Mater 19(3):438–447Google Scholar
  48. 48.
    Su F, Poh CK, Chen JS, Xu G, Wang D, Li Q, Lin J, Lou XW (2011) Nitrogen-containing microporous carbon nanospheres with improved capacitive properties. Energy Environ Sci 4(3):717–724Google Scholar
  49. 49.
    Puziy AM, Poddubnaya OI, Socha RP, Gurgul J, Wisniewski M (2008) XPS and NMR studies of phosphoric acid activated carbons. Carbon 46(15):2113–2123Google Scholar
  50. 50.
    Zhou Z, Zhang Z, Peng H, Qin Y, Li G, Chen K (2014) Nitrogen- and oxygen-containing activated carbon nanotubes with improved capacitive properties. RSC Adv 4(11):5524–5530Google Scholar
  51. 51.
    Siggel MRF, Thomas TD (1989) Linear correlation of oxygen core-ionization energies of alcohols and acids with those of the corresponding methyl and ethyl ethers and esters. J Electron Spectrosc Relat Phenom 48(1):101–116Google Scholar
  52. 52.
    Dharmalingam P, Ramanan V, Karthikeyan GG, Palani NS, Ilangovan R, Ramamurthy P (2017) A study on the electrochemical performance of nitrogen and oxygen co-doped carbon dots derived from a green precursor for supercapacitor applications. J Mater Sci Mater Electron 28(24):18489–18496Google Scholar
  53. 53.
    Tan Z, Ni K, Chen G, Zeng W, Tao Z, Ikram M, Zhang Q, Wang H, Sun L, Zhu X, Wu X, Ji H, Ruoff RS, Zhu Y (2017) Incorporating pyrrolic and pyridinic nitrogen into a porous carbon made from C60 molecules to obtain superior energy storage. Adv Mater 29(8):1603414–1603421Google Scholar
  54. 54.
    Fu N, Wei HM, Lin HL, Li L, Ji CH, Yu NB, Chen HJ, Han S, Xiao GY (2017) Iron nanoclusters as template/activator for the synthesis of nitrogen doped porous carbon and its CO2 adsorption application. ACS Appl Mater Interfaces 9(11):9955–9963Google Scholar
  55. 55.
    Zhu L, Gao Q, Tan Y, Tian W, Xu J, Yang K, Yang C (2015) Nitrogen and oxygen co-doped microporous carbons derived from the leaves of Euonymus japonicas as high performance supercapacitor electrode material. Microporous Mesoporous Mater 210:1–9Google Scholar
  56. 56.
    Chen C, Xu G, Wei X, Yang L (2016) A macroscopic three-dimensional tetrapod-separated graphene-like oxygenated N-doped carbon nanosheet architecture for use in supercapacitors. J Mater Chem A 4(25):9900–9909Google Scholar
  57. 57.
    Liu R, Zhang H, Liu S, Zhang X, Wu T, Ge X, Zang Y, Zhao H, Wang G (2016) Shrimp-shell derived carbon nanodots as carbon and nitrogen sources to fabricate three-dimensional N-doped porous carbon electrocatalysts for the oxygen reduction reaction. Phys Chem Chem Phys 18(5):4095–4101Google Scholar
  58. 58.
    Yuan C, Liu X, Jia M, Luo Z, Yao J (2015) Facile preparation of N- and O-doped hollow carbon spheres derived from poly(o-phenylenediamine) for supercapacitors. J Mater Chem A 3(7):3409–3415Google Scholar
  59. 59.
    Chaudhari NK, Song MY, Yu JS (2014) Heteroatom-doped highly porous carbon from human urine. Sci Rep 4:5221–5230Google Scholar
  60. 60.
    Ferrari AC (2007) Raman spectroscopy of graphene and graphite: disorder, electron–phonon coupling, doping and nonadiabatic effects. Solid State Commun 143(1–2):47–57Google Scholar
  61. 61.
    Perazzolo V, Durante C, Pilot R, Paduano A, Zheng J, Rizzi GA, Martucci A, Granozzi G, Gennaro A (2015) Nitrogen and sulfur doped mesoporous carbon as metal-free electrocatalysts for the in situ production of hydrogen peroxide. Carbon 95:949–963Google Scholar
  62. 62.
    Brandiele R, Picelli L, Pilot R, Causin V, Martucci A, Rizzi GA, Isse AA, Durante C, Gennaro A (2017) Nitrogen and sulfur doped mesoporous carbons, prepared from templating silica, as interesting material for supercapacitors. ChemistrySelect 2(24):7082–7090Google Scholar
  63. 63.
    Perazzolo V, Grądzka E, Durante C, Pilot R, Vicentini N, Rizzi GA, Granozzi G, Gennaro A (2016) Chemical and electrochemical stability of nitrogen and sulphur doped mesoporous carbons. Electrochim Acta 197:251–262Google Scholar
  64. 64.
    Chen CM, Zhang Q, Zhao XC, Zhang B, Kong QQ, Yang MG, Yang QH, Wang MZ, Yang YG, Schlögl R (2012) Hierarchically aminated graphene honeycombs for electrochemical capacitive energy storage. J Mater Chem 22(28):14076–14084Google Scholar
  65. 65.
    Li Q, Jiang R, Dou Y, Wu Z, Huang T, Feng D, Yang J, Yu A, Zhao D (2011) Synthesis of mesoporous carbon spheres with a hierarchical pore structure for the electrochemical double-layer capacitor. Carbon 49(4):1248–1257Google Scholar
  66. 66.
    Béguin F, Szostak K, Lota G, Frackowiak E (2005) A self-supporting electrode for supercapacitors prepared by one-step pyrolysis of carbon nanotube/polyacrylonitrile blends. Adv Mater 17(19):2380–2384Google Scholar
  67. 67.
    Zhao X, Wang S, Wu Q (2017) Nitrogen and phosphorus dual-doped hierarchical porous carbon with excellent supercapacitance performance. Electrochim Acta 247:1140–1146Google Scholar
  68. 68.
    Zhang Y, Jia M, Gao H, Yu J, Wang L, Zou Y, Qin F, Zhao Y (2015) Porous hollow carbon spheres: facile fabrication and excellent supercapacitive properties. Electrochim Acta 184:32–39Google Scholar
  69. 69.
    Xia K, Huang Z, Zheng L, Han B, Gao Q, Zhou C, Wang H, Wu J (2017) Facile and controllable synthesis of N/P co-doped graphene for high-performance supercapacitors. J Power Sources 365:380–388Google Scholar
  70. 70.
    Wang X, Lou M, Yuan X, Dong W, Dong C, Bi H, Huang F (2017) Nitrogen and oxygen dual-doped carbon nanohorn for electrochemical capacitors. Carbon 118:511–516Google Scholar
  71. 71.
    Teo EYL, Muniandy L, Ng EP, Adam F, Mohamed AR, Jose R, Chong KF (2016) High surface area activated carbon from rice husk as a high performance supercapacitor electrode. Electrochim Acta 192:110–119Google Scholar
  72. 72.
    Zhou J, Zhang Z, Xing W, Yu J, Han G, Si W, Zhuo S (2015) Nitrogen-doped hierarchical porous carbon materials prepared from meta-aminophenol formaldehyde resin for supercapacitor with high rate performance. Electrochim Acta 153:68–75Google Scholar
  73. 73.
    Yang C, Li CYV, Li F, Chan KY (2013) Complex impedance with transmission line model and complex capacitance analysis of ion transport and accumulation in hierarchical core–shell porous carbons. J Electrochem Soc 160(4):H271–H278Google Scholar
  74. 74.
    Yi J, Qing Y, Wu C, Zeng Y, Wu Y, Lu X, Tong Y (2017) Lignocellulose-derived porous phosphorus-doped carbon as advanced electrode for supercapacitors. J Power Sources 351:130–137Google Scholar
  75. 75.
    Liu Y, Li G, Guo Y, Ying Y, Peng X (2017) Flexible and binder-free hierarchical porous carbon film for supercapacitor electrodes derived from MOFs/CNT. ACS Appl Mater Interfaces 9(16):14043–14050Google Scholar
  76. 76.
    Han X, Jiang H, Zhou Y, Hong W, Zhou Y, Gao P, Ding R, Liu E (2018) A high performance nitrogen-doped porous activated carbon for supercapacitor derived from pueraria. J Alloys Compd 744:544–551Google Scholar

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Authors and Affiliations

  1. 1.School of Chemical and Environmental EngineeringShanghai Institute of TechnologyShanghaiPeople’s Republic of China

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