Size-controllable synthesis of monodispersed nitrogen-doped carbon nanospheres from polydopamine for high-rate supercapacitors

Abstract

Monodispersed nitrogen-doped carbon nanospheres with tunable particle size (100–230 nm) were synthesized via self-polymerization of biochemical dopamine in the presence of hexamethylenetetramine as a buffer and F127 as a size controlling agent. Hexamethylenetetramine can mildly release NH_3, which in turn initiates the polymerization reaction of dopamine. The carbon nanospheres obtained exhibited a significant energy storage capability of 265 F·g^–1 at 0.5 A·g^–1 and high-rate performance of 82% in 6 mol·L^–1 KOH (20 A·g^–1), which could be attributed to the presence of abundant micro-mesoporous structure, doped nitrogen functional groups and the small particle size. Moreover, the fabricated symmetric supercapacitor device displayed a high stability of 94% after 5000 cycles, revealing the considerable potential of carbon nanospheres as electrode materials for energy storage.

Key words： carbon nanospheres; size-controlled; nitrogen-doped; high-rate; supercapacitors

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by the Natural Science Foundation of Shandong Province (Grant No. ZR2019QEM005), Project of Shandong Province Higher Educational Young Innovative Talent Introduction and Cultivation Team [Environment Function Material Innovation Team].

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2326-8 and is accessible for authorized users.

References

1 Cao S, Zhang H, Zhao Y, Zhao Y. Pillararene/calixarene-based systems for battery and supercapacitor applications. eScience, 2021, 1: 28–43

2 Jiao Z, Chen Y, Du M, Demir M, Yan F, Xia W, Zhang Y, Wang C, Gu M, Zhang X, Zou J. 3D hollow NiCo LDH nanocages anchored on 3D CoO sea urchin-like microspheres: a novel 3D/3D structure for hybrid supercapacitor electrodes. Journal of Colloid and Interface Science, 2023, 633: 723–736

3 Li C, Jiang G, Demir M, Sun Y, Wang R, Liu T. Preparation of rGO/MXene@NiCo-P and rGO/MXene@Fe₂O₃ positive and negative composite electrodes for high-performance asymmetric supercapacitors. Journal of Energy Storage, 2022, 56: 105986

4 Zhou M, Yan S X, Wang Q, Tan M X, Wang D Y, Yu Z Q, Luo S H, Zhang Y H, Liu X. Walnut septum-derived hierarchical porous carbon for ultra-high-performance supercapacitors. Rare Metals, 2022, 41(7): 2280–2291

5 Yu X H, Yi J L, Zhang R L, Wang F Y, Liu L. Hollow carbon spheres and their noble metal-free hybrids in catalysis. Frontiers of Chemical Science and Engineering, 2021, 15(6): 1380–1407

6 Du J, Chen A, Liu L, Li B, Zhang Y. N-doped hollow mesoporous carbon spheres prepared by polybenzoxazines precursor for energy storage. Carbon, 2020, 160: 265–272

7 Zhou R, Wang X, Zhou R, Weerasinghe J, Zhang T, Xin Y, Wang H, Cullen P, Wang H, Ostrikov K K. Non-thermal plasma enhances performances of biochar in wastewater treatment and energy storage applications. Frontiers of Chemical Science and Engineering, 2022, 16(4): 475–483

8 Yang Y X, Ge K K, ur Rehman S, Bi H. Nanocarbon-based electrode materials applied for supercapacitors. Rare Metals, 2022, 41(12): 3957–3975

9 Zhang X, Wang Y, Du Y, Qing M, Yu F, Tian Z Q, Shen P K. Highly active N, S codoped hierarchical porous carbon nanospheres from green and template-free method for supercapacitors and oxygen reduction reaction. Electrochimica Acta, 2019, 318: 272–280

10 Krüner B, Schreiber A, Tolosa A, Quade A, Badaczewski F, Pfaff T, Smarsly B M, Presser V. Nitrogen-containing novolac-derived carbon beads as electrode material for supercapacitors. Carbon, 2018, 132: 220–231

11 Xiong S, Fan J, Wang Y, Zhu J, Yu J, Hu Z. A facile template approach to nitrogen-doped hierarchical porous carbon nanospheres from polydopamine for high-performance supercapacitors. Journal of Materials Chemistry A, 2017, 5(43): 18242–18252

12 Liu B, Zhang Q, Wang Z, Li L, Jin Z, Wang C, Zhang L, Chen L, Su Z. Nitrogen and sulfur-codoped porous carbon nanospheres with hierarchical micromesoporous structures and an ultralarge pore volume for high-performance supercapacitors. ACS Applied Materials & Interfaces, 2020, 12(7): 8225–8232

13 Liu C, Wang J, Li J, Zeng M, Luo R, Shen J, Sun X, Han W, Wang L. Synthesis of N-doped hollow-structured mesoporous carbon nanospheres for high-performance supercapacitors. ACS Applied Materials & Interfaces, 2016, 8(11): 7194–7204

14 Qiu Y, Hou M, Gao J, Zhai H, Liu H, Jin M, Liu X, Lai L. One-step synthesis of monodispersed mesoporous carbon nanospheres for high-performance flexible quasi-solid state micro-supercapacitors. Small, 2019, 15(45): 1903836

15 Zhang X Q, Lu A H, Sun Q, Yu X F, Chen J Y, Li W C. Unconventional synthesis of large pore ordered mesoporous carbon nanospheres for ionic liquid-based supercapacitors. ACS Applied Energy Materials, 2018, 1(11): 5999–6005

16 Liu J, Yang T Y, Wang D W, Lu G Q, Zhao D, Qiao S Z. A facile soft-template synthesis of mesoporous polymeric and carbonaceous nanospheres. Nature Communications, 2013, 4(1): 2798

17 Li N, Qin B, Kang H, Cai N, Huang S, Xiao Q. Engineering hollow carbon spheres: directly from solid resin spheres to porous hollow carbon spheres via air induced linker cleaving. Nanoscale, 2021, 13(32): 13873–13881

18 Xin G, Wang M, Zhang W, Song J, Zhang B. Preparation of high-capacitance N, S co-doped carbon nanospheres with hierarchical pores as supercapacitors. Electrochimica Acta, 2018, 291: 168–176

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

20 Zhang F, Liu X, Yang M, Cao X, Huang X, Tian Y, Zhang F, Li H. Novel S-doped ordered mesoporous carbon nanospheres toward advanced lithium metal anodes. Nano Energy, 2020, 69: 104443

21 Liu R, Mahurin S M, Li C, Unocic R R, Idrobo J C, Gao H J, Pennycook S J, Dai S. Dopamine as a carbon source: the controlled synthesis of hollow carbon spheres and yolk-structured carbon nanocomposites. Angewandte Chemie International Edition, 2011, 50(30): 6799–6802

22 Tang J, Liu J, Li C, Li Y, Tade M O, Dai S, Yamauchi Y. Synthesis of nitrogen-doped mesoporous carbon spheres with extra-large pores through assembly of diblock copolymer micelles. Angewandte Chemie, 2015, 54(2): 588–593

23 Tang J, Wang J, Shrestha L K, Hossain M S A, Alothman Z A, Yamauchi Y, Ariga K. Activated porous carbon spheres with customized mesopores through assembly of diblock copolymers for electrochemical capacitor. ACS Applied Materials & Interfaces, 2017, 9(22): 18986–18993

24 Song Z, Zhu D, Xue D, Yan J, Chai X, Xiong W, Wang Z, Lv Y, Cao T, Liu M, Gan L. Nitrogen-enriched hollow porous carbon nanospheres with tailored morphology and microstructure for all-solid-state symmetric supercapacitors. ACS Applied Energy Materials, 2018, 8(1): 4293–4303

25 Zhu Y P, Liu Y P, Yuan Z Y. Biochemistry-inspired direct synthesis of nitrogen and phosphorus dual-doped microporous carbon spheres for enhanced electrocatalysis. Chemical Communications, 2016, 52(10): 2118–2121

26 Sing K S W. Reporting phisorption data for gas/solid systems. Pure and Applied Chemistry, 1985, 57(4): 603–619

27 Li J, Wang S, Ren Y, Ren Z, Qiu Y, Yu J. Nitrogen-doped activated carbon with micrometer-scale channels derived from luffa sponge fibers as electrocatalysts for oxygen reduction reaction with high stability in acidic media. Electrochimica Acta, 2014, 149: 56–64

28 Wang Y, Song Y, Xia Y. Electrochemical capacitors: mechanism, materials, systems, characterization and applications. Chemical Society Reviews, 2016, 45(21): 5925–5950

29 Wang M, Liu B, Chen H, Yang D, Li H. N/O codoped porous carbons with layered structure for high-rate performance supercapacitors. ACS Sustainable Chemistry & Engineering, 2019, 7(13): 11219–11227

30 Wei W, Chen Z, Zhang Y, Chen J, Wan L, Du C, Xie M, Guo X. Full-faradaicactive nitrogen species doping enables high-energy-density carbon-based supercapacitor. Journal of Energy Chemistry, 2020, 48: 277–284

31 Orlando J D, Lima R M A P, Li L, Sydlik S A, de Oliveira H P. Electrochemical performance of N-doped carbon-based electrodes for supercapacitors. ACS Applied Electronic Materials, 2022, 4(10): 5040–5054

32 Li J, Han K, Wang D, Teng Z, Cao Y, Qi J, Li M, Wang M. Fabrication of high performance structural N-doped hierarchical porous carbon for supercapacitors. Carbon, 2020, 164: 42–50

33 Mo Y, Du J, Lv H, Zhang Y, Chen A. N-doped mesoporous carbon nanosheets for supercapacitors with high performance. Diamond and Related Materials, 2021, 111: 108206

34 Xue D, Zhu D, Xiong W, Cao T, Wang Z, Lv Y, Li L, Liu M, Gan L. Template-free, self-doped approach to porous carbon spheres with high N/O contents for high-performance supercapacitors. ACS Sustainable Chemistry & Engineering, 2019, 7(7): 7024–7034

35 Huang S, Ma D D, Wang X, Shi Y, Xun R, Chen H, Guan H, Tong Y. A space-sacrificed pyrolysis strategy for boron-doped carbon spheres with high supercapacitor performance. Journal of Colloid and Interface Science, 2022, 608: 334–343

36 Wang Y, Lu C, Cao X, Wang Q, Yang G, Chen J. Porous carbon spheres derived from hemicelluloses for supercapacitor application. International Journal of Molecular Sciences, 2022, 23(13): 7101

37 Du J, Zhang Y, Lv H, Chen A. N/B-co-doped ordered mesoporous carbon spheres by ionothermal strategy for enhancing supercapacitor performance. Journal of Colloid and Interface Science, 2021, 587: 780–788

38 Wang H, Zhou H, Gao M, Zhu Y, Liu H, Gao L, Wu M. Hollow carbon spheres with artificial surface openings as highly effective supercapacitor electrodes. Electrochimica Acta, 2019, 298: 552–560

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

40 Zheng S, Cui Y, Zhang J, Gu Y, Shi X, Peng C, Wang D. Nitrogen doped microporous carbon nanospheres derived from chitin nanogels as attractive materials for supercapacitors. RSC Advances, 2019, 9(19): 10976–10982

41 Wang G, Qin J, Zhao Y, Wei J. Nanoporous carbon spheres derived from metal-phenolic coordination polymers for supercapacitor and biosensor. Journal of Colloid and Interface Science, 2019, 544: 241–248

42 Ke C C, Zhang N, Liu F, Yu Q, Wang F Y, Liu L, Zhang R L, Liu X, Zeng R C. Deflated balloon-like nitrogen-rich sulfur-containing hierarchical porous carbons for high-rate supercapacitors. Applied Surface Science, 2019, 484: 716–725

43 Wang Z, Qiang H, Zhu Z, Liu J, Chen C, Zhang D. Facile synthesis of nitrogen-doped mesoporous hollow carbon nanospheres for high-performance supercapacitors. ChemElectroChem, 2018, 5(16): 2242–2249

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

45 Wang T, Sun Y, Zhang L, Li K, Yi Y, Song S, Li M, Qiao Z A, Dai S. Space-confined polymerization: controlled fabrication of nitrogen-doped polymer and carbon microspheres with refined hierarchical architectures. Advanced Materials, 2019, 31(16): 1807876

46 Yang X, Li Y, Zhang P, Sun L, Ren X, Mi H. Hierarchical hollow carbon spheres: novel synthesis strategy, pore structure engineering and application for micro-supercapacitor. Carbon, 2020, 157: 70–79

47 Zhou H, Zhou Y, Li L, Li Y, Liu X, Zhao P, Gao B. Amino acid protic ionic liquids: multifunctional carbon precursor for N/S codoped hierarchically porous carbon materials toward supercapacitive energy storage. ACS Sustainable Chemistry & Engineering, 2019, 7(10): 9281–9290

48 Liu F, Gao Y, Zhang C, Huang H, Yan C, Chu X, Xu Z, Wang Z, Zhang H, Xiao X, Yang W. Highly microporous carbon with nitrogen-doping derived from natural biowaste for high performance flexible solid-state supercapacitor. Journal of Colloid and Interface Science, 2019, 548: 322–332

49 Qiao Y, Liu G, Xu R, Hu R, Liu L, Jiang G, Demir M, Ma P. SrFe_1–xZrxO_3–δ perovskite oxides as negative electrodes for supercapacitors. Electrochimica Acta, 2023, 437: 14152