One-Step Scalable Fabrication of Nitrogen and Chlorine Co-doped Graphene by Electrochemical Exfoliation for High-Performance Supercapacitors

Abstract

The stacking and aggregation of graphene nanosheets have been obstacles to their application as electrode materials for microelectronic devices. This study deploys a one-step, scalable, facile electrochemical exfoliation technique to fabricate nitrogen (N) and chlorine (Cl) co-doped graphene nanosheets (i.e., N–Cl–G) via the application of constant voltage on graphite in a mixture of 0.1 mol/L H₂SO₄ and 0.1 mol/L NH₄Cl without using dangerous and exhaustive operation. The introduction of Cl (with its large radius) and N, both with high electrical negativity, facilitates the modulation of the electronic structure of graphene and creation of rich structural defects in it. Consequently, in the as-constructed supercapacitors, N–Cl–G exhibits a high specific capacitance of 77 F/g at 0.2 A/g and remarkable cycling stability with 91.7% retention of initial capacitance after 20,000 cycles at 10 A/g. Furthermore, a symmetrical supercapacitor assembled with N–Cl–G as the positive and negative electrodes (denoted as N–Cl–G//N–Cl–G) exhibits an energy density of 3.38 Wh/kg at a power density of 600 W/kg and superior cycling stability with almost no capacitance loss after 5000 cycles at 5 A/g. This study provides a scalable protocol for the facile fabrication of high-performance co-doped graphene as an electrode material candidate for supercapacitors.

Graphical Abstract

N, Cl co-doped graphene (i.e., N–Cl–G) is fabricated in situ via a one-step, scalable, facile electrochemical exfoliation process. Benefiting from the ultrathin nanosheet structure of N–Cl–G with large margin size and rich functional groups, the as-prepared N–Cl–G-based supercapacitor exhibits high specific capacitance and remarkable cycling stability. Precisely, the symmetrical N–Cl–G//N–Cl–G supercapacitor (N–Cl–G as both the positive and negative electrodes) exhibits high-energy density and superior cycling stability, highlighting its considerable potential for industrial application.

References

[1.] Nithya VD. A review on holey graphene electrode for supercapacitor. J Energy Storage, 2021, 44,

[2.] Jin XG, Shan YY, Sun FC, et al. . Applications of transition metal (Fe Co, Ni)-based metal–organic frameworks and their derivatives in batteries and supercapacitors. Trans Tianjin Univ, 2022, 28(6): 446-468.

[3.] Xu YK, Liu ZY, Cong WH, et al. . Application and progress of confinement synthesis strategy in electrochemical energy storage. Trans Tianjin Univ, 2023, 29(2): 151-187.

[4.] Wu ZS, Winter A, Chen L, et al. . Three-dimensional nitrogen and boron Co-doped graphene for high-performance all-solid-state supercapacitors. Adv Mater, 2012, 24(37): 5130-5135.

[5.] Cao LH, Li HL, Liu XL, et al. . Nitrogen, sulfur co-doped hierarchical carbon encapsulated in graphene with “sphere-in-layer” interconnection for high-performance supercapacitor. J Colloid Interface Sci, 2021, 599: 443-452.

[6.] Cheng J, Jiao RZ, Sun QW. Free-standing N, S co-doped graphene aerogels coupled with Eucalyptus wood tar-based activated carbon and cellulose nanofibers for high-performance supercapacitor and removal of Cr(VI). Int J Biol Macromol, 2024, 254(Pt 1,

[7.] Wang Z, Yang L, Yang YZ, et al. . Research of PVDF dielectric materials based on graphene surface brush. J Liaocheng Univ (Nat Sci Ed), 2023, 36(4): 67-73

[8.] Worsley EA, Margadonna S, Bertoncello P. Application of graphene nanoplatelets in supercapacitor devices: a review of recent developments. Nanomaterials, 2022, 12(20): 3600.

[9.] Lin Z, Goikolea E, Balducci A, et al. . Materials for supercapacitors: when Li-ion battery power is not enough. Mater Today, 2018, 21(4): 419-436.

[10.] Banda H, Périé S, Daffos B, et al. . Sparsely pillared graphene materials for high-performance supercapacitors: improving ion transport and storage capacity. ACS Nano, 2019, 13(2): 1443-1453.

[11.] Sun ZX, Fang SY, Hu YH. 3D graphene materials: from understanding to design and synthesis control. Chem Rev, 2020, 120(18): 10336-10453.

[12.] Qiu CJ, Jiang LL, Gao YG, et al. . Effects of oxygen-containing functional groups on carbon materials in supercapacitors: a review. Mater Des, 2023, 230,

[13.] Li YF, Ye SY, Lin J, et al. . A pore-forming strategy toward porous carbon-based substrates for high performance flexible lithium metal full batteries. Energy Environ Mater, 2023, 6(3,

[14.] Ding Y, Li YC, Dai YJ, et al. . A novel approach for preparing in situ nitrogen doped carbon via pyrolysis of bean pulp for supercapacitors. Energy, 2021, 216,

[15.] Khalafallah D, Quan XY, Ouyang C, et al. . Heteroatoms doped porous carbon derived from waste potato peel for supercapacitors. Renew Energy, 2021, 170: 60-71.

[16.] Xu YS, Xiao MJ, Liu TT, et al. . Nitrogen, boron and fluorine tri-doped carbon nanotubes on carbon cloth as the electrode materials for supercapacitors. J Electroanal Chem, 2023, 948,

[17.] Li YJ, Zhu G, Huang HL, et al. . A N, S dual doping strategy via electrospinning to prepare hierarchically porous carbon polyhedra embedded carbon nanofibers for flexible supercapacitors. J Mater Chem A, 2019, 7(15): 9040-9050.

[18.] Wang ZY, Xiao JR, Li XY. Effects of heteroatom (boron or nitrogen) substitutional doping on the electronic properties of graphene nanoribbons. Solid State Commun, 2012, 152(2): 64-67.

[19.] Khandelwal M, Tran CV, Lee J, et al. . Nitrogen and boron co-doped densified laser-induced graphene for supercapacitor applications. Chem Eng J, 2022, 428,

[20.] Rotte NK, Naresh V, Muduli S, et al. . Microwave aided scalable synthesis of sulfur, nitrogen co-doped few-layered graphene material for high-performance supercapacitors. Electrochim Acta, 2020, 363,

[21.] Liu BB, Zhang QH, Zhang LN, et al. . Electrochemically exfoliated chlorine-doped graphene for flexible all-solid-state micro-supercapacitors with high volumetric energy density. Adv Mater, 2022, 34(19,

[22.] Deng B, Liu ZF, Peng HL. Toward mass production of CVD graphene films. Adv Mater, 2019, 31(9,

[23.] De Fazio D, Purdie DG, Ott AK, et al. . High-mobility, wet-transferred graphene grown by chemical vapor deposition. ACS Nano, 2019, 13(8): 8926-8935.

[24.] Eigler S, Hirsch A. Chemistry with graphene and graphene oxide-challenges for synthetic chemists. Angew Chem Int Ed Engl, 2014, 53(30): 7720-7738.

[25.] Yang W, Chen GR, Shi ZW, et al. . Epitaxial growth of single-domain graphene on hexagonal boron nitride. Nat Mater, 2013, 12(9): 792-797.

[26.] Muñoz-Batista M, Rodriguez-Padron D, Puente-Santiago AR, et al. . Mechanochemistry: toward sustainable design of advanced nanomaterials for electrochemical energy storage and catalytic applications. ACS Sustain Chem Eng, 2018, 6(8): 9530-9544.

[27.] Lu AK, Li HY, Yu Y. Holey graphene synthesized by electrochemical exfoliation for high-performance flexible microsupercapacitors. J Mater Chem A, 2019, 7(13): 7852-7858.

[28.] Nagyte V, Kelly DJ, Felten A, et al. . Raman fingerprints of graphene produced by anodic electrochemical exfoliation. Nano Lett, 2020, 20(5): 3411-3419.

[29.] Yang S, Lohe MR, Müllen K, et al. . New-generation graphene from electrochemical approaches: production and applications. Adv Mater, 2016, 28(29): 6213-6221.

[30.] Pei SF, Wei QW, Huang K, et al. . Green synthesis of graphene oxide by seconds timescale water electrolytic oxidation. Nat Commun, 2018, 9(1): 145.

[31.] Zhang Y, Xu YL. Simultaneous electrochemical dual-electrode exfoliation of graphite toward scalable production of high-quality graphene. Adv Funct Mater, 2019, 29(37): 1902171,

[32.] Zhou J, Liu BB, Zheng H, et al. . One-step construction of strongly coupled Co₃V₂O₈/Co₃O₄/MXene heterostructure via in situ Co–F bonds for high performance all-solid-state asymmetric supercapacitors. Rare Met, 2024, 43(2): 682-691.

[33.] Cao JY, He P, Mohammed MA, et al. . Two-step electrochemical intercalation and oxidation of graphite for the mass production of graphene oxide. J Am Chem Soc, 2017, 139(48): 17446-17456.

[34.] Feng J, Pu FZ, Li ZX, et al. . Interfacial interactions and synergistic effect of CoNi nanocrystals and nitrogen-doped graphene in a composite microwave absorber. Carbon, 2016, 104: 214-225.

[35.] Yang YC, Shi W, Zhang RH, et al. . Electrochemical exfoliation of graphite into nitrogen-doped graphene in glycine solution and its energy storage properties. Electrochim Acta, 2016, 204: 100-107.

[36.] Wang PS, Xiao JY, Guo MM, et al. . Preparation of graphite nanoflakes and supported noble metal/alloy nanoparticles by paired electrolysis with graphite electrodes. J Electrochem Soc, 2014, 161(10): H606-H611.

[37.] Gu Y, Fan LQ, Huang JL, et al. . N-doped reduced graphene oxide decorated NiSe₂ nanoparticles for high-performance asymmetric supercapacitors. J Power Sources, 2019, 425: 60-68.

[38.] Edison TNJI, Atchudan R, Karthik N, et al. . Electrochemically exfoliated graphene sheets as electrode material for aqueous symmetric supercapacitors. Surf Coat Technol, 2021, 416,

[39.] Hong WW, Zhang Y, Yang L, et al. . Carbon quantum dot micelles tailored hollow carbon anode for fast potassium and sodium storage. Nano Energy, 2019, 65,

[40.] Sharif F, Zeraati AS, Ganjeh-Anzabi P, et al. . Synthesis of a high-temperature stable electrochemically exfoliated graphene. Carbon, 2020, 157: 681-692.

[41.] Rivera-Gavidia LM, Fernández de la Puente I, Hernández-Rodríguez MA, et al. . Bi-functional carbon-based catalysts for unitized regenerative fuel cells. J Catal, 2020, 387: 138-144.

[42.] Zhang YQ, Rawat RS, Fan HJ. Plasma for rapid conversion reactions and surface modification of electrode materials. Small Meth, 2017, 1(9): 1700164.

[43.] Sun HM, Wang Q, Wu T, et al. . Plasma-assisted synthesis of pyrrolic-nitrogen doped reduced graphene oxide to enhance supercapacitor performance. Appl Surf Sci, 2020, 527,

[44.] Xu CA, Hu Y, Yang ZH. Influence of oxidation temperature on the structure of graphene oxide. J Liaocheng Univ (Nat Sci Ed), 2024, 37(4): 57-63

[45.] Zhang Y, Zhu JY, Ren HB, et al. . Facile synthesis of nitrogen-doped graphene aerogels for electrode materials in supercapacitors. Chin J Chem, 2017, 35(7): 1069-1078.

[46.] Chulliyote R, Hareendrakrishnakumar H, Joseph MG. Template free one pot synthesis of heteroatom doped porous carbon electrodes for high performance symmetric supercapacitor. Electrochim Acta, 2020, 337,

[47.] Ji LL, Wang B, Yu YL, et al. . N, S Co-doped biomass derived carbon with sheet-like microstructures for supercapacitors. Electrochim Acta, 2020, 331,

[48.] Wang TR, Su YP, Xiao M, et al. . One-step hydrothermal synthesis of a CoTe@rGO electrode material for supercapacitors. Trans Tianjin Univ, 2022, 28(2): 112-122.

[49.] Ren ZD, Luo HW, Mao HC, et al. . Hybrid supercapacitor based on graphene and Ni/Ni(OH)₂ nanoparticles formed by a modified electrochemical exfoliation method. Chem Phys Lett, 2020, 760,

[50.] Hamra AAB, Lim HN, Chee WK, et al. . Electro-exfoliating graphene from graphite for direct fabrication of supercapacitor. Appl Surf Sci, 2016, 360: 213-223.

[51.] Chen KF, Xue DF. Preparation of colloidal graphene in quantity by electrochemical exfoliation. J Colloid Interface Sci, 2014, 436: 41-46.

[52.] Chen X, Li Y, Li C, et al. . A novel strategy of multi-element nanocomposite synthesis for high performance ZnO-CoSe₂ supercapacitor material development. Chin J Chem, 2021, 39(9): 2441-2450.

[53.] Xiao M, Zhao ML, Wang TR, et al. . Construction of desirable NiCoTe₂ nanosheet arrays on a carbon cloth substrate as a positive electrode material for a high-performance asymmetric supercapacitor. Trans Tianjin Univ, 2022, 28(2): 153-161.

[54.] Zeng YX, Lin ZQ, Wang ZF, et al. . In situ activation of 3D porous Bi/carbon architectures: toward high-energy and stable nickel-bismuth batteries. Adv Mater, 2018, 30(18,

[55.] Zhou M, Li XW, Cui JJ, et al. . Synthesis and capacitive performances of graphene/N-doping porous carbon composite with high nitrogen content and two-dimensional nanoarchitecture. Int J Electrochem Sci, 2012, 7(10): 9984-9996.

[56.] Sadak O, Sundramoorthy AK, Gunasekaran S. Facile and green synthesis of highly conducting graphene paper. Carbon, 2018, 138: 108-117.

[57.] Kumar R, Sahoo S, Joanni E, et al. . Heteroatom doped graphene engineering for energy storage and conversion. Mater Today, 2020, 39: 47-65.