Hierarchically nanoporous carbons derived from empty fruit bunches for high performance supercapacitors

  • Choi, Min Sung (School of Chemical Engineering, College of Engineering, Sungkyunkwan University) ;
  • Park, Sulki (School of Chemical Engineering, College of Engineering, Sungkyunkwan University) ;
  • Lee, Hyunjoo (Clean Energy Center, Korea Institute of Science and Technology) ;
  • Park, Ho Seok (School of Chemical Engineering, College of Engineering, Sungkyunkwan University)
  • Received : 2016.11.04
  • Accepted : 2017.08.12
  • Published : 2018.01.31


Hierarchically porous, chemically activated carbon materials are readily derived from biomass using hydrothermal carbonization (HTC) and chemical activation processes. In this study, empty fruit bunches (EFB) were chosen as the carbon source due to their sustainability, high lignin-content, abundance, and low cost. The lignin content in the EFB was condensed and carbonized into a bulk non-porous solid via the HTC process, and then transformed into a hierarchical porous structure consisting of macro- and micropores by chemical activation. As confirmed by various characterization results, the optimum activation temperature for supercapacitor applications was determined to be $700^{\circ}C$. The enhanced capacitive performance is attributed to the textural property of the extremely high specific surface area of $2861.4m^2\;g^{-1}$. The prepared material exhibited hierarchical porosity and surface features with oxygen functionalities, such as carboxyl and hydroxyl groups, suitable for pseudocapacitance. Finally, the as-optimized nanoporous carbons exhibited remarkable capacitive performance, with a specific capacitance of $402.3F\;g^{-1}$ at $0.5A\;g^{-1}$, a good rate capability of 79.8% at current densities from $0.5A\;g^{-1}$ to $10A\;g^{-1}$, and excellent life cycle behavior of 10,000 cycles with 96.5% capacitance retention at $20A\;g^{-1}$.


Supported by : National Research Foundation (NRF)


  1. Simon P, Gogotsi Y. Materials for electrochemical capacitors. Nat Mater, 7, 845 (2008).
  2. Zhang LL, Zhao XS. Carbon-based materials as supercapacitor electrodes. Chem Soc Rev, 38, 2520 (2009).
  3. Huang Y, Liang J, Chen Y. An overview of the applications of graphene- based materials in supercapacitors. Small, 8, 1805 (2010).
  4. Winter M, Brodd RJ. What are batteries, fuel cells, and supercapacitors? Chem Rev, 104, 4245 (2004). cr020730k.
  5. Wang Y, Shi Z, Huang Y, Ma Y, Wang C, Chen M, Chen Y. Supercapacitor devices based on graphene materials. J Phys Chem C, 113, 13103 (2009).
  6. Frackowiak E, Beguin F. Carbon materials for the electrochemical storage of energy in capacitors. Carbon, 39, 937 (2001).
  7. Pandolfo AG, Hollenkamp AF. Carbon properties and their role in supercapacitors. J Power Sources, 157, 11 (2006).
  8. Emmenegger C, Mauron P, Sudan P, Wenger P, Hermann V, Gallay R, Zuttel A. Investigation of electrochemical double-layer (ECDL) capacitors electrodes based on carbon nanotubes and activated carbon materials. J Power Sources, 124, 321 (2003).
  9. Xu B, Wu F, Chen R, Cao G, Chen S, Yang Y. Mesoporous activated carbon fiber as electrode material for high-performance electrochemical double layer capacitors with ionic liquid electrolyte. J Power Sources, 195, 2118 (2010). 2009.09.077.
  10. Ruiz V, Blanco C, Santamaria R, Ramos-Fernandez JM, Martinez- Escandell M, Sepúlveda-Escribano A, Rodriguez-Reinoso F. An activated carbon monolith as an electrode material for supercapacitors. Carbon, 47, 195 (2009). 2008.09.048.
  11. Wang G, Zhang L, Zhang J. A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev, 41, 797 (2012).
  12. Chen SM, Ramachandran R, Mani V, Saraswathi R. Recent advancements in electrode materials for the highperformance electrochemical supercapacitors: a review. Int J Electrochem Sci, 9, 4072 (2014).
  13. Wei L, Sevila M, Fuertes AB, Mokaya R, Yushin G. Hydrothermal carbonization of abundant renewable natural organic chemicals for high-performance supercapacitor electrodes. Adv Energy Mater, 1, 356 (2011).
  14. Crini G. Non-conventional low-cost adsorbents for dye removal: a review. Bioresour Technol, 97, 1061 (2006).
  15. Ioannidou O, Zabaniotou A. Agricultural residues as precursors for activated carbon production: a review. Renewable Sustainable Energy Rev, 11, 1966 (2007). rser.2006.03.013.
  16. Nor NM, Chung LL, Teong LK, Mohamed AR. Synthesis of activated carbon from lignocellulosic biomass and its applications in air pollution control: a review. J Environ Chem Eng, 1, 658 (2013).
  17. Tay T, Ucar S, Karagoz S. Preparation and characterization of activated carbon from waste biomass. J Hazard Mater, 165, 481 (2009).
  18. Titirici MM, White RJ, Falco C, Sevilla M. Black perspectives for a green future: hydrothermal carbons for environment protection and energy storage. Energy Environ Sci, 5, 6796 (2101).
  19. Hayashi J, Kazehaya A, Muroyama K, Watkinson AP. Preparation of activated carbon from lignin by chemical activation. Carbon, 38, 1873 (2000).
  20. Gao Y, Yue Q, Gao B, Sun Y, Wang W, Li Q, Wang Y. Preparation of high surface area-activated carbon from lignin of papermaking black liquor by KOH activation for Ni(II) adsorption. Chem Eng J, 217, 345 (2013).
  21. Roman S, Gonzalez JF, Gonzalez-Garcia CM, Zamora F. Control of pore development during $CO_2$ and steam activation of olive stones. Fuel Process Technol, 89, 715 (2008). 2007.12.015.
  22. Fan M, Marshall W, Daugaard D, Brown RC. Steam activation of chars produced from oat hulls and corn stover. Bioresour Technol, 93, 103 (2004).
  23. Nabais JMV, Nunes P, Carrott PJM, Ribeiro Carrott MML, Garcia AM, Diaz-Diez MA. Production of activated carbons from coffee endocarp by $CO_2$ and steam activation. Fuel Process Technol, 89, 262 (2008).
  24. Amaya A, Medero N, Tancredi N, Silva H, Deiana C. Activated carbon briquettes from biomass materials. Bioresour Technol, 98, 1635 (2007).
  25. Stavropoulos GG, Zabaniotou AA. Production and characterization of activated carbons from olive-seed waste residue. Microporous Mesoporous Mater, 82, 79 (2005). micromeso.2005.03.009.
  26. Ahmadpour A, Do DD. The preparation of activated carbon from macadamia nutshell by chemical activation. Carbon, 35, 1723 (1997).
  27. Oh GH, Park CR. Preparation and characteristics of rice-strawbased porous carbons with high adsorption capacity. Fuel, 81, 327 (2002).
  28. Adinata D, Wan Daud WMA, Aroua MK. Preparation and characterization of activated carbon from palm shell by chemical activation with $K_2CO_3$. Bioresour Technol, 98, 145 (2007).
  29. Tsai WT, Chang CY, Lee SL. A low cost adsorbent from agricultural waste corn cob by zinc chloride activation. Bioresour Technol, 64, 211 (1998).
  30. Sudaryanto Y, Hartono SB, Irawaty W, Hindarso H, Ismadji S. High surface area activated carbon prepared from cassava peel by chemical activation. Bioresour Technol, 97, 734 (2006). https://doi. org/10.1016/j.biortech.2005.04.029.
  31. Chang J, Gao Z, Wang X, Wu D, Xu F, Wang X, Guo Y, Jiang K. Activated porous carbon prepared from paulownia flower for high performance supercapacitor electrodes. Electrochim Acta, 157, 290 (2015).
  32. Li Z, Lv W, Zhang C, Li B, Kang F, Yang QH. A sheet-like porous carbon for high-rate supercapacitors produced by the carbonization of an eggplant. Carbon, 92, 11 (2015). carbon.2015.02.054.
  33. Nabais JMV, Teixeira JG, Almeida I. Development of easy made low cost bindless monolithic electrodes from biomass with controlled properties to be used as electrochemical capacitors. Bioresour Technol, 102, 2781 (2011). biortech.2010.11.083.
  34. Omar R, Idris A, Yunus R, Khalid K, Aida Isma MI. Characterization of empty fruit bunch for microwave-assisted pyrolysis. Fuel, 90, 1536 (2009).
  35. Misson M, Haron R, Kamaroddin MFA, Amin NAS. Pretreatment of empty palm fruit bunch for production of chemicals via catalytic pyrolysis. Bioresour Technol, 100, 2867 (2009).
  36. Farma R, Deraman M, Awitdrus A, Talib IA, Taer E, Basri NH, Manjunatha JG, Ishak MM, Dollah BNM, Hashmi SA. Preparation of highly porous binderless activated carbon electrodes from fibres of oil palm empty fruit bunches for application in supercapacitors. Bioresour Technol, 132, 254 (2013).
  37. Kang S, Li X, Fan J, Chang J. Hydrothermal conversion of lignin: a review. Renewable Sustainable Energy Rev, 27, 546 (2013).
  38. Sevilla M, Macia-Agullo JA, Fuertes AB. Hydrothermal carbonization of biomass as a route for the sequestration of $CO_2$: chemical and structural properties of the carbonized products. Biomass Bioenergy, 35, 3152 (2011). 2011.04.032.
  39. Jain A, Xu C, Jayaraman S, Balasubramanian R, Lee JY, Srinivasan MP. Mesoporous activated carbons with enhanced porosity by optimal hydrothermal pre-treatment of biomass for supercapacitor applications. Microporous Mesoporous Mater, 218, 55 (2015).
  40. Kota M, Yu X, Yeon SH, Cheong HW, Park HS. Ice-templated three dimensional nitrogen doped graphene for enhanced supercapacitor performance. J Power Sources, 303, 372 (2016).
  41. Gogotsi Y, Simon P. True performance metrics in electrochemical energy storage. Science, 334, 917 (2011). science.1213003.
  42. Pandey MP, Kim CS. Lignin depolymerization and conversion: a review of thermochemical methods. Chem Eng Technol, 34, 29 (2011).
  43. Roman R, Valente Nabais JM, Ledesma B, Gonzalez JF, Laginhas C, Titirici MM. Production of low-cost adsorbents with tunable surface chemistry by conjunction of hydrothermal carbonization and activation processes. Microporous Mesoporous Mater, 165, 127 (2013).
  44. Sevilla M, Fuertes AB. The production of carbon materials by hy drothermal carbonization of cellulose. Carbon, 47, 2281 (2009).
  45. Kruse A, Funke A, Titirici MM. Hydrothermal conversion of biomass to fuels and energetic materials. Curr Opin Chem Biol, 17, 515 (2013).
  46. Babel K, Jurewicz K. KOH activated lignin based nanostructured carbon exhibiting high hydrogen electrosorption. Carbon, 46, 1948 (2008).
  47. Yang X, Li M, Guo N, Yan M, Yang R, Wang F. Functionalized porous carbon with appropriate pore size distribution and open hole texture prepared by $H_2O_2$ and EDTA-2Na treatment of loofa sponge and its excellent performance for supercapacitors. RSC Adv, 6, 4365 (2016).
  48. Peng C, Lang J, Xu S, Wang X. Oxygen-enriched activated carbons from pomelo peel in high energy density supercapacitors. RSC Adv, 4, 54662 (2014).
  49. Wickramaratne NP, Jaroniec M. Importance of small micropores in $CO_2$ capture by phenolic resin-based activated carbon spheres. J Mater Chem A, 1, 112 (2013). C2TA00388K.
  50. Wei L, Yushin G. Nanostructured activated carbons from natural precursors for electrical double layer capacitors. Nano Energy, 1, 552 (2012).
  51. Nishihara H, Itoi H, Kogure T, Hou PX, Touhara H, Okino F, Kyotani T. Investigation of the ion storage/transfer behavior in an electrical double-layer capacitor by using ordered microporous carbons as model materials. Chemistry, 15, 5355 (2009). https://
  52. Palmre V, Lust E, Janes A, Koel M, Peikolainen AL, Torop J, Johanson U, Aabloo A. Electroactive polymer actuators with carbon aerogel electrodes. J Mater Chem, 21, 2577 (2011). https://doi. org/10.1039/C0JM01729A.
  53. Sevilla M, Foulston R, Mokaya R. Superactivated carbide-derived carbons with high hydrogen storage capacity. Energy Environ Sci, 3, 223 (2010).
  54. Hashaikeh R, Fang Z, Butler IS, Hawari J, Kozinski JA. Hydrothermal dissolution of willow in hot compressed water as a model for biomass conversion. Fuel, 86, 1614 (2007). https://doi. org/10.1016/j.fuel.2006.11.005.
  55. Suhas, Carrott PJM, Ribeiro Carrott MML. Lignin-from natural adsorbent to activated carbon: a review. Bioresour Technol, 98, 2301 (2007).
  56. Wang H, Gao Q, Hu J. High hydrogen storage capacity of porous carbons prepared by using activated carbon. J Am Chem Soc, 131, 7016 (2009).
  57. Huber L, Ruch P, Hauert R, Saucke G, Matam SK, Michel B, Koebel MM. Monolithic nitrogen-doped carbon as a water sorbent for high-performance adsorption cooling. RSC Adv, 6, 25267 (2016).
  58. Ma F, Wan J, Wu G, Zhao H. Highly porous carbon microflakes derived from catkins for high-performance supercapacitors. RSC Adv, 5, 44416 (2015).
  59. Sobon G, Sotor J, Jagiello J, Kozinski R, Zdrojek M, Holdyski M, Paletko P, Boguslawski J, Lipinska L, Abramski KM. Graphene oxide vs. reduced graphene oxide as saturable absorbers for Erdoped passively mode-locked fiber laser. Opt Express, 20, 19463 (2012).
  60. Chingombe P, Saha B, Wakeman RJ. Surface modification and characterisation of a coal-based activated carbon. Carbon, 43, 3132 (2005).
  61. Ma X, Yang H, Yu L, Chen Y, Li Y. Preparation, surface and pore structure of high surface area activated carbon fibers from bamboo by steam activation. Materials, 7, 4431 (2014). https://doi. org/10.3390/ma7064431.
  62. Feng W, He P, Ding S, Zhang G, He M, Dong F, Wen J, Du L, Liu M. Oxygen-doped activated carbons derived from three kinds of biomass: preparation, characterization and performance as electrode materials for supercapacitors. RSC Adv, 6, 5949 (2016).
  63. Zhang LL, Zhao X, Stoller MD, Zhu Y, Ji H, Murali S, Wu Y, Perales S, Clevenger B, Ruoff RS. Highly conductive and porous activated reduced graphene oxide films for high-power supercapacitors. Nano Lett, 12, 1806 (2012). nl203903z.
  64. Genovese M, Jiang J, Lian K, Holm N. High capacitive performance of exfoliated biochar nanosheets from biomass waste corn cob. J Mater Chem A, 3, 2903 (2015). C4TA06110A.
  65. Peng H, Ma G, Sun K, Mu J, Zhou X, Lei Z. A novel fabrication of nitrogen-containing carbon nanospheres with high rate capability as electrode materials for supercapacitors. RSC Adv, 5, 12034 (2015).
  66. Jana M, Khanra P, Murmu NC, Samanta P, Lee JH, Kuila T. Covalent surface modification of chemically derived graphene and its application as supercapacitor electrode material. Phys Chem Chem Phys, 16, 7618 (2014).
  67. Peng C, Yan XB, Wang RT, Lang JW, Ou YJ, Xue QJ. Promising activated carbons derived from waste tea-leaves and their application in high performance supercapacitors electrodes. Electrochim Acta, 87, 401 (2013).
  68. Cheng Q, Tang J, Ma J, Zhang H, Shinya N, Qin LC. Graphene and carbon nanotube composite electrodes for supercapacitors with ultra- high energy density. Phys Chem Chem Phys, 13, 17615 (2011).
  69. Zhang J, Xu J, Zhang D. A structural supercapacitor based on graphene and hardened cement paste. J Electrochem Soc, 163, E83 (2016).
  70. Liu HJ, Cui WJ, Jin LH, Wang CX, Xia YY. Preparation of threedimensional ordered mesoporous carbon sphere arrays by a twostep templating route and their application for supercapacitors. J Mater Chem, 19, 3661 (2009).
  71. Xiong W, Liu M, Gan L, Lv Y, Li Y, Li Y, Yang L, Xu Z, Hao Z, Liu H, Chen L. A novel synthesis of mesoporous carbon microspheres for supercapacitor electrodes. J Power Sources, 196, 10461 (2011).