Cathodic exfoliation of graphite into graphene nanoplatelets in aqueous solution of alkali metal salts
Source abstract
Abstract
Electrochemical exfoliation has emerged as a green, effective and scalable route for mass production of graphene. Cathodic exfoliation of graphite, offers a direct production of high quality and low defect graphene. However, the protocols for cathodic exfoliation reported to date, use mostly non-aqueous electrolytes which require extended period of intercalation, and post-treatment to further exfoliate the intercalated graphene layers. In contrast, the employment of environment friendly aqueous-based electrolytes, coupling with a shorter exfoliation period would be attractive features of any new protocol. Here, we demonstrate efficient cathodic electrochemical exfoliation of graphite to graphene nanoplatelets in aqueous electrolytes using common and inexpensive alkali-metal salts such as KCl. The key driving force to exfoliate graphite successfully in aqueous electrolyte is applying a sufficiently high voltage, and a high salt concentration which facilitate cation intercalation, and promotes hydrogen evolution to exfoliate the graphene. The cathodic exfoliated graphene nanoplatelets using KCl aqueous electrolyte exhibits a low defect density (ID/IG of 0.06, a C/O ratio of 57.8), high graphite exfoliation yields (> 80%) in short times (< 10 min for a graphite foil of 1 cm × 1 cm × 0.0254 cm, 30.0 mg). The highly conductive structure consists mainly of 10–13 layers graphene sheets that serve as an excellent support material for electrocatalytic reactions. This environment-benign aqueous-based cathodic electrochemical exfoliation of graphite opens a new opportunity in large-scale and low-cost production of high-quality graphene nanoplatelets.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Graphene research and applications · Advancements in Battery Materials · 2D Materials and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (59)
Show source-provided references
1. Novoselov KS, Geim AK, Morozov SV et al (2004) Electric field effect in atomically thin carbon films. Science 306:666–669. https://doi.org/10.1126/science.110289610.1126/science.1102896 ↗
2. Ferrari AC, Bonaccorso F, Fal’Ko V et al (2015) Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems. Nanoscale 7:4598–4810. https://doi.org/10.1039/c4nr01600a10.1039/c4nr01600a ↗
3. Dreyer DR, Ruoff RS, Bielawski CW (2010) From conception to realization: an historial account of graphene and some perspectives for its future. Angew Chem Int Ed 49(49):9336–9344. https://doi.org/10.1002/anie.20100302410.1002/anie.201003024 ↗
4. Novoselov KS, Fal′ko VI, Colombo L, Gellert PR, Schwab MG, Kim K (2012) A roadmap for graphene. Nature 490:192–200. https://doi.org/10.1038/nature1145810.1038/nature11458 ↗
5. Li X, Cai W, An J et al (2009) Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324:1312–1314. https://doi.org/10.1126/science.117124510.1126/science.1171245 ↗
6. Subrahmanyam KS, Panchakarla LS, Govindaraj A, Rao CNR (2009) Simple method of preparing graphene flakes by an Arc-discharge method. J Phys Chem C 113:4257–4259. https://doi.org/10.1021/jp900791y10.1021/jp900791y ↗
7. Varrla E, Paton KR, Backes C et al (2014) Turbulence-assisted shear exfoliation of graphene using household detergent and a kitchen blender. Nanoscale 6:11810–11819. https://doi.org/10.1039/C4NR03560G10.1039/C4NR03560G ↗
8. Rasuli H, Rasuli R, Alizadeh M, BoonTong G (2020) Microwave-assisted exfoliation and tearing of graphene oxide in the presence of TiO2 nanoparticles. Results Phys 18:103200. https://doi.org/10.1016/j.rinp.2020.10320010.1016/j.rinp.2020.103200 ↗
9. Morales GM, Schifani P, Ellis G et al (2011) High-quality few layer graphene produced by electrochemical intercalation and microwave-assisted expansion of graphite. Carbon 49:2809–2816. https://doi.org/10.1016/j.carbon.2011.03.00810.1016/j.carbon.2011.03.008 ↗
10. Chua CK, Pumera M (2014) Chemical reduction of graphene oxide: a synthetic chemistry viewpoint. Chem Soc Rev 43:291–312. https://doi.org/10.1039/C3CS60303B10.1039/C3CS60303B ↗
11. Hernandez Y, Nicolosi V, Lotya M et al (2008) High-yield production of graphene by liquid-phase exfoliation of graphite. Nat Nanotechnol 3:563–568. https://doi.org/10.1038/nnano.2008.21510.1038/nnano.2008.215 ↗
12. Low CTJ, Walsh FC, Chakrabarti MH, Hashim MA, Hussain MA (2013) Electrochemical approaches to the production of graphene flakes and their potential applications. Carbon 54:1–21. https://doi.org/10.1016/j.carbon.2012.11.03010.1016/j.carbon.2012.11.030 ↗
13. Yang S, Lohe MR, Müllen K, Feng X (2016) New-generation graphene from electrochemical approaches: production and applications. Adv Mater 28:6213–6221. https://doi.org/10.1002/adma.20150532610.1002/adma.201505326 ↗
14. Ambrosi A, Chua CK, Bonanni A, Pumera M (2014) Electrochemistry of graphene and related materials. Chem Rev 114:7150–7188. https://doi.org/10.1021/cr500023c10.1021/cr500023c ↗
15. Liu F, Wang C, Sui X et al (2019) Synthesis of graphene materials by electrochemical exfoliation: Recent progress and future potential. Carbon Energy 1:173–199. https://doi.org/10.1002/cey2.1410.1002/cey2.14 ↗
16. Li L, Zhang D, Deng J, Fang J, Gou Y (2020) Review—preparation and application of graphene-based hybrid materials through electrochemical exfoliation. J Electrochem Soc 167:086511. https://doi.org/10.1149/1945-7111/ab933b10.1149/1945-7111/ab933b ↗
17. Yang S, Zhang P, Nia AS, Feng X (2020) Emerging 2D Materials Produced via Electrochemistry. Adv Mat 32:1907857. https://doi.org/10.1002/adma.20190785710.1002/adma.201907857 ↗
18. Ambrosi A, Chua CK, Latiff NM et al (2016) Graphene and its electrochemistry—an update. Chem Soc Rev 45:2458–2493. https://doi.org/10.1039/C6CS00136J10.1039/C6CS00136J ↗
19. Chuang C-H, Su C-Y, Hsu K-T et al (2015) A green, simple and cost-effective approach to synthesize high quality graphene by electrochemical exfoliation via process optimization. RSC Adv 5:54762–54768. https://doi.org/10.1039/C5RA07710A10.1039/C5RA07710A ↗
20. Zhong YL, Tian Z, Simon GP, Li D (2015) Scalable production of graphene via wet chemistry: progress and challenges. Mater Today 18:73–78. https://doi.org/10.1016/j.mattod.2014.08.01910.1016/j.mattod.2014.08.019 ↗
21. Berger C, Song Z, Li X et al (2006) electronic confinement and coherence in patterned epitaxial graphene. Science 312:1191–1196. https://doi.org/10.1126/science.112592510.1126/science.1125925 ↗
22. Marcano DC, Kosynkin DV, Berlin JM et al (2010) improved synthesis of graphene oxide. ACS Nano 4:4806–4814. https://doi.org/10.1021/nn100636810.1021/nn1006368 ↗
23. Liu J, Poh CK, Zhan D et al (2013) Improved synthesis of graphene flakes from the multiple electrochemical exfoliation of graphite rod. Nano Energy 2:377–386. https://doi.org/10.1016/j.nanoen.2012.11.00310.1016/j.nanoen.2012.11.003 ↗
24. Parvez K, Wu Z-S, Li R et al (2014) Exfoliation of graphite into graphene in aqueous solutions of inorganic salts. J Am Ceram Soc 136:6083–6091. https://doi.org/10.1021/ja501715610.1021/ja5017156 ↗
25. Nguyen V-T, Le PA, Hsu Y-C, Wei K-H (2020) Plasma-induced exfoliation provides onion-like graphene-surrounded MoS2 nanosheets for a highly efficient hydrogen evolution reaction. ACS Appl Mater Interfaces 12:11533–11542. https://doi.org/10.1021/acsami.9b2090210.1021/acsami.9b20902 ↗
26. El Garah M, Bertolazzi S, Ippolito S et al (2018) MoS2 nanosheets via electrochemical lithium-ion intercalation under ambient conditions. FlatChem 9:33–39. https://doi.org/10.1016/j.flatc.2018.06.00110.1016/j.flatc.2018.06.001 ↗
27. Ambrosi A, Sofer Z, Pumera M (2017) Electrochemical exfoliation of layered black phosphorus into phosphorene. Angew Chem Int Ed 56:10443–10445. https://doi.org/10.1002/anie.20170507110.1002/anie.201705071 ↗
28. Li J, Chen C, Liu S et al (2018) Ultrafast Electrochemical expansion of black phosphorus toward high-yield synthesis of few-layer phosphorene. Chem Mater 30:2742–2749. https://doi.org/10.1021/acs.chemmater.8b0052110.1021/acs.chemmater.8b00521 ↗
29. Abdelkader AM, Cooper AJ, Dryfe RAW, Kinloch IA (2015) How to get between the sheets: a review of recent works on the electrochemical exfoliation of graphene materials from bulk graphite. Nanoscale 7:6944–6956. https://doi.org/10.1039/C4NR06942K10.1039/C4NR06942K ↗
30. Su C-Y, Lu A-Y, Xu Y, Chen F-R, Khlobystov AN, Li L-J (2011) High-quality thin graphene films from fast electrochemical exfoliation. ACS Nano 5:2332–2339. https://doi.org/10.1021/nn200025p10.1021/nn200025p ↗
31. Parvez K, Li R, Puniredd SR et al (2013) Electrochemically exfoliated graphene as solution-processable, highly conductive electrodes for organic electronics. ACS Nano 7:3598–3606. https://doi.org/10.1021/nn400576v10.1021/nn400576v ↗
32. Pei S, Wei Q, Huang K, Cheng H-M, Ren W (2018) Green synthesis of graphene oxide by seconds timescale water electrolytic oxidation. Nat Commun 9:145. https://doi.org/10.1038/s41467-017-02479-z10.1038/s41467-017-02479-z ↗
33. Cao J, He P, Mohammed MA et al (2017) Two-step electrochemical intercalation and oxidation of graphite for the mass production of graphene oxide. J Am Chem Soc 139:17446–17456. https://doi.org/10.1021/jacs.7b0851510.1021/jacs.7b08515 ↗
34. Munuera JM, Paredes JI, Villar-Rodil S, Ayan-Varela M, Martinez-Alonso A, Tascon JMD (2016) Electrolytic exfoliation of graphite in water with multifunctional electrolytes: en route towards high quality, oxide-free graphene flakes. Nanoscale 8:2982–2998. https://doi.org/10.1039/C5NR06882G10.1039/C5NR06882G ↗
35. Chen C-H, Yang S-W, Chuang M-C, Woon W-Y, Su C-Y (2015) Towards the continuous production of high crystallinity graphene via electrochemical exfoliation with molecular in situ encapsulation. Nanoscale 7:15362–15373. https://doi.org/10.1039/C5NR03669K10.1039/C5NR03669K ↗
36. Munuera JM, Paredes JI, Enterría M et al (2017) Electrochemical exfoliation of graphite in aqueous sodium halide electrolytes toward low oxygen content graphene for energy and environmental applications. ACS Appl Mater Interfaces 9:24085–24099. https://doi.org/10.1021/acsami.7b0480210.1021/acsami.7b04802 ↗
37. Wang H, Wei C, Zhu K et al (2017) Preparation of graphene sheets by electrochemical exfoliation of graphite in confined space and their application in transparent conductive films. ACS Appl Mater Interfaces 9:34456–34466. https://doi.org/10.1021/acsami.7b0989110.1021/acsami.7b09891 ↗
38. Lee C-Y, Mitchell DRG, Molino P, Fahy A, Wallace GG (2019) Tunable solution-processable anodic exfoliated graphene. Appl Mater Today 15:290–296. https://doi.org/10.1016/j.apmt.2019.02.00810.1016/j.apmt.2019.02.008 ↗
39. Raccichini R, Varzi A, Passerini S, Scrosati B (2014) The role of graphene for electrochemical energy storage. Nat Mater 14:271–279. https://doi.org/10.1038/nmat417010.1038/nmat4170 ↗
40. Zhou M, Tang J, Cheng Q, Xu G, Cui P, Qin L-C (2013) Few-layer graphene obtained by electrochemical exfoliation of graphite cathode. Chem Phys Lett 572:61–65. https://doi.org/10.1016/j.cplett.2013.04.01310.1016/j.cplett.2013.04.013 ↗
41. Cooper AJ, Wilson NR, Kinloch IA, Dryfe RAW (2014) Single stage electrochemical exfoliation method for the production of few-layer graphene via intercalation of tetraalkylammonium cations. Carbon 66:340–350. https://doi.org/10.1016/j.carbon.2013.09.00910.1016/j.carbon.2013.09.009 ↗
42. Abdelkader AM, Kinloch IA, Dryfe RAW (2014) Continuous electrochemical exfoliation of micrometer-sized graphene using synergistic ion intercalations and organic solvents. ACS Appl Mater Interfaces 6:1632–1639. https://doi.org/10.1021/am404497n10.1021/am404497n ↗
43. Zhong YL, Swager TM (2012) Enhanced electrochemical expansion of graphite for in situ electrochemical functionalization. J Am Chem Soc 134:17896–17899. https://doi.org/10.1021/ja309023f10.1021/ja309023f ↗
44. Kamali AR, Fray DJ (2015) Large-scale preparation of graphene by high temperature insertion of hydrogen into graphite. Nanoscale 7:11310–11320. https://doi.org/10.1039/C5NR01132A10.1039/C5NR01132A ↗
45. Kim H-K, Kamali AR, Roh KC, Kim K-B, Fray DJ (2016) Dual coexisting interconnected graphene nanostructures for high performance supercapacitor applications. Energy Environ Sci 9:2249–2256. https://doi.org/10.1039/C6EE00815A10.1039/C6EE00815A ↗
46. Yang Y, Lu F, Zhou Z, Song W, Chen Q, Ji X (2013) Electrochemically cathodic exfoliation of graphene sheets in room temperature ionic liquids N-butyl, methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and their electrochemical properties. Electrochim Acta 113:9–16. https://doi.org/10.1016/j.electacta.2013.09.03110.1016/j.electacta.2013.09.031 ↗
47. Wei D, Grande L, Chundi V et al (2012) Graphene from electrochemical exfoliation and its direct applications in enhanced energy storage devices. Chem Commun 48:1239–1241. https://doi.org/10.1039/C2CC16859F10.1039/C2CC16859F ↗
48. Huang S-Y, Le P-A, Yen P-J et al (2020) Cathodic plasma–induced syntheses of graphene nanosheet/MnO2/WO3 architectures and their use in supercapacitors. Electrochim Acta 342:136043. https://doi.org/10.1016/j.electacta.2020.13604310.1016/j.electacta.2020.136043 ↗
49. Yen P-J, Sahoo SK, Chiang Y-C et al (2019) Using Different ions to tune graphene stack structures from sheet- to onion-like during plasma exfoliation, with supercapacitor applications. Nanoscale Res Lett 14:1–11. https://doi.org/10.1186/s11671-019-2963-510.1186/s11671-019-2963-5 ↗
50. Yen P-J, Ilango PR, Chiang Y-C et al (2019) Tunable nitrogen-doped graphene sheets produced with in situ electrochemical cathodic plasma at room temperature for lithium-ion batteries. Mater Today Energy 12:336–347. https://doi.org/10.1016/j.mtener.2019.01.00310.1016/j.mtener.2019.01.003 ↗
51. Yen P-J, Ting C-C, Chiu Y-C et al (2017) Facile production of graphene nanosheets comprising nitrogen-doping through in situ cathodic plasma formation during electrochemical exfoliation. J Mater Chem C 5:2597–2602. https://doi.org/10.1039/C6TC03128E10.1039/C6TC03128E ↗
52. Van Thanh D, Li L-J, Chu C-W, Yen P-J, Wei K-H (2014) Plasma-assisted electrochemical exfoliation of graphite for rapid production of graphene sheets. RSC Adv 4:6946–6949. https://doi.org/10.1039/C3RA46807K10.1039/C3RA46807K ↗
53. García-Dalí S, Paredes JI, Munuera JM, Villar-Rodil S, Martínez-Alonso A, Tascón JMD (2019) An aqueous cathodic delamination route towards high quality graphene flakes for oil sorption and electrochemical charge storage applications. Chem Eng J 372:1226–1239. https://doi.org/10.1016/j.cej.2019.04.20110.1016/j.cej.2019.04.201 ↗
54. Zhang Y, Xu Y (2019) Simultaneous electrochemical dual-electrode exfoliation of graphite toward scalable production of high-quality graphene. Adv Funct Mater 29:1902171. https://doi.org/10.1002/adfm.20190217110.1002/adfm.201902171 ↗
55. Ponomarev EA, Neumann-Spallart M, Hodes G, Lévy-Clément C (1996) Electrochemical deposition of MoS2 thin films by reduction of tetrathiomolybdate. Thin Solid Films 280:86–89. https://doi.org/10.1016/0040-6090(95)08204-210.1016/0040-6090(95)08204-2 ↗
56. Dubouis N, Serva A, Salager E, Deschamps M, Salanne M, Grimaud A (2018) The fate of water at the electrochemical interfaces: electrochemical behavior of free water versus coordinating water. J Phys Chem Lett 9:6683–6688. https://doi.org/10.1021/acs.jpclett.8b0306610.1021/acs.jpclett.8b03066 ↗
57. Vatamanu J, Borodin O (2017) Ramifications of water-in-salt interfacial structure at charged electrodes for electrolyte electrochemical stability. J Phys Chem Lett 8:4362–4367. https://doi.org/10.1021/acs.jpclett.7b0187910.1021/acs.jpclett.7b01879 ↗
58. Mähler J, Persson I (2012) A study of the hydration of the alkali metal ions in aqueous solution. Inorg Chem 51:425–438. https://doi.org/10.1021/ic201869310.1021/ic2018693 ↗
59. Shearer CJ, Slattery AD, Stapleton AJ, Shapter JG, Gibson CT (2016) Accurate thickness measurement of graphene. Nanotechnology 27:125704. https://doi.org/10.1088/0957-4484/27/12/12570410.1088/0957-4484/27/12/125704 ↗