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Controllably fabricating carbon microspheres with hierarchical porous structure for supercapacitors

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Abstract

The porous carbon microspheres (PCS) with hierarchical pore structure were fabricated by annealing the mixtures of aluminum potassium sulfate, calcium carbonate, and corn starch in a tube furnace in N2 atmospheres. The mechanisms of forming carbon microspheres and producing the hierarchical pore structures were explored. The result shows that formation of carbon spheres depends on the pretreated starch by KAl (SO4)2, and CaCO3 can promote more mesoporous structure produced. The resulting PCS-Ca1 electrode exhibits a high capacitance of 300 F g−1 at a current density of 0.5 A g−1, a superior rate capability of 228 F g−1 at 20 A g−1, and almost no capacitance fading (only 0.6% loss after 10,000 cycles) in 6 mol L−1 KOH electrolyte. The symmetric supercapacitor fabricated with PCS-Ca1 electrodes displays a high energy density of 8.54 Wh kg−1 at a power density of 125 W kg−1 in 6 mol L−1 KOH electrolyte.

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References

  1. Oh T, Kim M, Choi J, Kim J (2018) Design of graphitic carbon nitride nanowires with captured mesoporous carbon spheres for EDLC electrode materials. Ionics 24:3957–3965

    Article  CAS  Google Scholar 

  2. Wang D, Chen Y, Wang H, Zhao P, Liu W, Wang Y, Yang J (2018) N-doped porous carbon anchoring on carbon nanotubes derived from ZIF-8/polypyrrole nanotubes for superior supercapacitor electrodes. Appl Surf Sci 457:1018–1024

    Article  CAS  Google Scholar 

  3. Wang J, Chang J, Wang L, Hao J (2018) One-step and low-temperature synthesis of CoMoO4 nanowire arrays on Ni foam for asymmetric supercapacitors. Ionics 24:3967–3973

    Article  CAS  Google Scholar 

  4. Jiang L, Yuan X, Liang J, Zhang J, Wang H, Zeng G (2016) Nanostructured core-shell electrode materials for electrochemical capacitors. J Power Sources 331:408–425

    Article  CAS  Google Scholar 

  5. Kim C, Ngoc BTN, Yang KS, Kojima M, Kim YA, Kim YJ, Endo M, Yang SC (2007) Self-sustained thin webs consisting of porous carbon nanofibers for supercapacitors via the electrospinning of polyacrylonitrile solutions containing zinc chloride. Adv Mater 19:2341–2346

    Article  CAS  Google Scholar 

  6. Atchudan R, Edison TNJI, Perumal S, Lee YR (2017) Green synthesis of nitrogen-doped graphitic carbon sheets with use of Prunus persica for supercapacitor applications. Appl Surf Sci 393:276–286

    Article  CAS  Google Scholar 

  7. Xu X, Liu Y, Wang M, Zhu C, Lu T, Zhao R, Pan L (2016) Hierarchical hybrids with microporous carbon spheres decorated three-dimensional graphene frameworks for capacitive applications in supercapacitor and deionization. Electrochim Acta 193:88–95

    Article  CAS  Google Scholar 

  8. Pang J, Zhang W, Zhang H, Zhang J, Zhang H, Cao G, Han M, Yang Y (2018) Sustainable nitrogen-containing hierarchical porous carbon spheres derived from sodium lignosulfonate for high-performance supercapacitors. Carbon 132:280–293

    Article  CAS  Google Scholar 

  9. Wang H, Zhou H, Gao M, Zhu Y-a, Liu H, Gao L, Wu M (2019) Hollow carbon spheres with artificial surface openings as highly effective supercapacitor electrodes. Electrochim Acta 298:552–560

  10. Liu S, Cai Y, Zhao X, Liang Y, Zheng M, Hu H, Dong H, Jiang S, Liu Y, Xiao Y (2017) Sulfur-doped nanoporous carbon spheres with ultrahigh specific surface area and high electrochemical activity for supercapacitor. J Power Sources 360:373–382

    Article  CAS  Google Scholar 

  11. Zhu D, Wang Y, Gan L, Liu M, Cheng K, Zhao Y, Deng X, Sun D (2015) Nitrogen-containing carbon microspheres for supercapacitor electrodes. Electrochim Acta 158:166–174

    Article  CAS  Google Scholar 

  12. Liu M, Qian J, Zhao Y, Zhu D, Gan L, Chen L (2015) Core–shell ultramicroporous@microporous carbon nanospheres as advanced supercapacitor electrodes. J Mater Chem 3:11517–11526

    Article  CAS  Google Scholar 

  13. Wang G, Zhang J, Kuang S, Zhou J, Xing W, Zhuo S (2015) Nitrogen-doped hierarchical porous carbon as an efficient electrode material for supercapacitors. Electrochim Acta 153:273–279

    Article  CAS  Google Scholar 

  14. Zhang X, Li Y, Cao C (2012) Facile one-pot synthesis of mesoporous hierarchically structured silica/carbon nanomaterials. J Mater Chem 22:13918–13921

    Article  CAS  Google Scholar 

  15. Falco C, Sieben JM, Brun N, Sevilla M, Morallón E, Cazorla-Amorós D, Titirici MM (2013) Hydrothermal carbons from hemicellulose-derived aqueous hydrolysis products as electrode materials for supercapacitors. ChemSusChem 6:374–382

    Article  CAS  PubMed  Google Scholar 

  16. Yu X, Lu J, Zhan C, Lv R, Liang Q, Huang ZH, Shen W, Kang F (2015) Synthesis of activated carbon nanospheres with hierarchical porous structure for high volumetric performance supercapacitors. Electrochim Acta 182:908–916

    Article  CAS  Google Scholar 

  17. Chen X, Kierzek K, Jiang Z, Chen H, Tang T, Wojtoniszak M, Kalenczuk RJ, Chu PK, Borowiakpalen E (2011) Synthesis, growth mechanism, and electrochemical properties of hollow mesoporous carbon spheres with controlled diameter. J Phys Chem C 115:17717–17724

    Article  CAS  Google Scholar 

  18. Liu R, Mahurin SM, Li C, Unocic RR, Idrobo JC, Gao H, Pennycook SJ, Dai S (2011) Dopamine as a carbon source: the controlled synthesis of hollow carbon spheres and yolk-structured carbon nanocomposites. Angew Chem Int Ed 123:6931–6934

    Article  Google Scholar 

  19. Lu AH, Sun T, Li WC, Sun Q, Han F, Liu DH, Guo Y (2011) Synthesis of discrete and dispersible hollow carbon nanospheres with high uniformity by using confined nanospace pyrolysis. Angew Chem Int Ed 50:11765–11768

    Article  CAS  Google Scholar 

  20. Min L, Wei L, Shouxin L (2011) Hydrothermal synthesis, characterization, and KOH activation of carbon spheres from glucose. Carbohydr Res 346:999–1004

    Article  CAS  Google Scholar 

  21. Zhao S, Wang CY, Chen MM, Wang J, Shi ZQ (2009) Potato starch-based activated carbon spheres as electrode material for electrochemical capacitor. J Phys Chem Solids 70:1256–1260

    Article  CAS  Google Scholar 

  22. 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 184:32–39

    Article  CAS  Google Scholar 

  23. Wang Y, Chen Y, Liu Y, Liu W, Zhao P, Li Y, Dong Y, Wang H, Yang J (2019) Urchin-like Ni1/3Co2/3(CO3)0.5OH·0.11H2O anchoring on polypyrrole nanotubes for supercapacitor electrodes. Electrochim Acta 295:989–996

    Article  CAS  Google Scholar 

  24. Li Z, Mi H, Liu L, Bai Z, Zhang J, Zhang Q, Qiu J (2018) Nano-sized ZIF-8 anchored polyelectrolyte-decorated silica for nitrogen-rich hollow carbon shell frameworks toward alkaline and neutral supercapacitors. Carbon 136:176–186

    Article  CAS  Google Scholar 

  25. Zhao S, Li XY, Wang CY, Chen MM (2012) Preparation of bowl-like and eggshell-like hollow carbon microspheres from potato starch. Mater Lett 70:54–56

    Article  CAS  Google Scholar 

  26. Zhao S, Wang C-Y, Chen M-M, Sun J-H (2009) Mechanism for the preparation of carbon spheres from potato starch treated by NH4Cl. Carbon 47:331–333

    Article  CAS  Google Scholar 

  27. Shi N, Liu Q, Ma L, Wang T, Zhang Q, Zhang Q, Liao Y (2014) Direct degradation of cellulose to 5-hydroxymethylfurfural in hot compressed steam with inorganic acidic salts. RSC Adv 4:4978

    Article  CAS  Google Scholar 

  28. Chang J, Gao Z, Wang X, Wu D, Xu F, Wang X, Guo Y, Jiang K (2015) Activated porous carbon prepared from paulownia flower for high performance supercapacitor electrodes. Electrochim Acta 157:290–298

    Article  CAS  Google Scholar 

  29. Fan X, Yu C, Ling Z, Yang J, Qiu J (2013) Hydrothermal synthesis of phosphate-functionalized carbon nanotube-containing carbon composites for supercapacitors with highly stable performance. Appl Mater Interfaces 5:2104–2110

    Article  CAS  Google Scholar 

  30. Huang C, Puziy AM, Sun T, Poddubnaya OI, Suárez-García F, Tascón J, Hulicova-Jurcakova D (2014) Capacitive behaviors of phosphorus-rich carbons derived from lignocelluloses. Electrochim Acta 137:219–227

    Article  CAS  Google Scholar 

  31. Yang W, Yang W, Kong L, Song A, Qin X, Shao G (2018) Phosphorus-doped 3D hierarchical porous carbon for high-performance supercapacitors: a balanced strategy for pore structure and chemical composition. Carbon 127:557–567

    Article  CAS  Google Scholar 

  32. Zhu D, Wang Y, Lu W, Zhang H, Song Z, Luo D, Gan L, Liu M, Sun D (2017) A novel synthesis of hierarchical porous carbons from interpenetrating polymer networks for high performance supercapacitor electrodes. Carbon 111:667–674

    Article  CAS  Google Scholar 

  33. Gao Z, Chen C, Chang J, Chen L, Wu D, Xu F, Jiang K (2018) Balanced energy density and power density: asymmetric supercapacitor based on activated fullerene carbon soot anode and graphene-Co3O4 composite cathode. Electrochim Acta 260:932–943

    Article  CAS  Google Scholar 

  34. Zhang Y, Jia M, Yu J, Fan J, Wang L, Zou Y, Zhao Y (2016) A tunable hierarchical porous carbon from starch pretreated by calcium acetate for high performance supercapacitors. J Solid State Electrochem 20:733–741

    Article  CAS  Google Scholar 

  35. Wang L, Wang Y, Wu M, Wei Z, Cui C, Mao M, Zhang J, Han X, Liu Q, Ma J (2018) Nitrogen, fluorine, and boron ternary doped carbon fibers as cathode electrocatalysts for zinc-air batteries. Small 14(20):1800737

    Article  CAS  Google Scholar 

  36. Wu M, Wang Y, Wei Z, Wang L, Zhuo M, Zhang J, Han X, Ma J (2018) Ternary doped porous carbon nanofibers with excellent ORR and OER performance for zinc–air batteries. J Mater Chem 6(23):10918–10925

    Article  CAS  Google Scholar 

  37. Fang Q, Zhou X, Deng W, Liu Y, Zheng Z, Liu Z (2017) Nitrogen-doped graphene nanoscroll foam with high diffusion rate and binding affinity for removal of organic pollutants. Small 13:1603779

    Article  CAS  Google Scholar 

  38. Lee SW, Yabuuchi N, Gallant BM, Chen S, Kim BS, Hammond PT, Shao-Horn Y (2010) High-power lithium batteries from functionalized carbon-nanotube electrodes. Nat Nanotechnol 5:531–537

    Article  CAS  PubMed  Google Scholar 

  39. Pan L, Sun S, Zhang A, Jiang K, Zhang L, Dong C, Huang Q, Wu A, Lin H (2015) Truly fluorescent excitation-dependent carbon dots and their applications in multicolor cellular imaging and multidimensional sensing. Adv Mater 27:7782–7787

    Article  CAS  PubMed  Google Scholar 

  40. 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

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  41. Itagaki M, Hatada Y, Shitanda I, Watanabe K (2010) Complex impedance spectra of porous electrode with fractal structure. Electrochim Acta 55:6255–6262

    Article  CAS  Google Scholar 

  42. Wang J, Liu H, Sun H, Hua W, Wang H, Liu X, Wei B (2018) One-pot synthesis of nitrogen-doped ordered mesoporous carbon spheres for high-rate and long-cycle life supercapacitors. Carbon 127:85–92

    Article  CAS  Google Scholar 

  43. Guo H, Ding B, Wang J, Zhang Y, Hao X, Wu L, An Y, Dou H, Zhang X (2018) Template-induced self-activation route for nitrogen-doped hierarchically porous carbon spheres for electric double layer capacitors. Carbon 136:204–210

  44. Zhou C, Chen X, Liu H, Zhou J, Ma Z, Jia M, Song H (2017) Heteroatom-doped multilocular carbon nanospheres with high surface utilization and excellent rate capability as electrode material for supercapacitors. Electrochim Acta 236:53–60

    Article  CAS  Google Scholar 

  45. Hao ZQ, Cao JP, Zhao XY, Wu Y, Zhu JS, Dang YL, Zhuang QQ, Wei XY (2018) Preparation of porous carbon spheres from 2-keto-l-gulonic acid mother liquor by oxidation and activation for electric double-layer capacitor application. J Colloid Interface Sci 513:20–27

    Article  CAS  PubMed  Google Scholar 

  46. Lin G, Ma R, Zhou Y, Hu C, Yang M, Liu Q, Kaskel S, Wang J (2018) Three-dimensional interconnected nitrogen-doped mesoporous carbons as active electrode materials for application in electrocatalytic oxygen reduction and supercapacitors. J Colloid Interface Sci 527:230–240

    Article  CAS  PubMed  Google Scholar 

  47. Fan Y, Yang X, Zhu B, Liu P-F, Lu H-T (2014) Micro-mesoporous carbon spheres derived from carrageenan as electrode material for supercapacitors. J Power Sources 268:584–590

    Article  CAS  Google Scholar 

  48. Chen A, Li Y, Yu Y, Ren S, Wang Y, Xia K, Li S (2016) Nitrogen-doped hollow carbon spheres for supercapacitors application. J Alloys Compd 688:878–884

    Article  CAS  Google Scholar 

  49. Wang G, Liang K, Liu L, Yu Y, Hou S, Chen A (2018) Fabrication of monodisperse hollow mesoporous carbon spheres by using “confined nanospace deposition” method for supercapacitor. J Alloys Compd 736:35–41

    Article  CAS  Google Scholar 

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Funding

This work was financially supported by the Natural Science Foundations of China (no. 21703152), State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of Jilin University (no. 17JCQNJC06100), and Science and Technology Correspondent Project of Tianjin (nos. 17JCTPJC47300 and 18JCTPJC61300).

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Correspondence to Jianguo Yu or Yuning Qu.

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Yu, J., Li, Y., Qu, Y. et al. Controllably fabricating carbon microspheres with hierarchical porous structure for supercapacitors. Ionics 25, 3341–3349 (2019). https://doi.org/10.1007/s11581-019-02885-x

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  • DOI: https://doi.org/10.1007/s11581-019-02885-x

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