快速电化学剥离天然脉石墨制备石墨烯用于透明导电薄膜的研究
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摘要
目的开发一种基于电化学剥离天然脉石墨的石墨烯量产制备工艺,并研究其剥离石墨烯的品质,最后验证以该量产石墨烯作为原料制备透明导电薄膜的可行性。方法以相同的电化学工艺剥离天然脉石墨、高定向热解石墨以及人工石墨制备石墨烯,然后用共聚焦光学显微镜(OM)、扫描探针显微镜(AFM)、拉曼光谱仪(Raman)和X-射线光电子能谱仪(XPS)考察天然脉石墨剥离的石墨烯尺寸和品质,并将其与另外两种石墨烯及基于文献报道的热/化学还原氧化石墨烯进行对比,最后以天然脉石墨剥离的石墨烯制备成透明导电膜并测量其电导率和透光率。结果以天然脉石墨通过电化学剥离得到的石墨烯主要以1—3层石墨烯为主,平均横向尺寸和厚度分别为5.9μm和2.4 nm。Raman及XPS分析表明,该石墨烯的品质可与电化学剥离高定向热解石墨得到的石墨烯相媲美,并且优于人工石墨烯和基于热/化学还原的氧化石墨烯的品质。最后以天然脉石墨烯为原料,通过界面自组装及后续的转移工艺于石英基板上制备了透明的石墨烯导电薄膜,在83.1%的透光率下,该薄膜的方阻低至13 k?/□,相对于以人工石墨经电化学剥离得到的石墨烯为原料所制备的导电薄膜有较大的提升。结论以天然脉石墨作为原料并通过电化学剥离得到的石墨烯的尺寸较大、缺陷少、官能化程度低,可应用于透明导电膜的制备,这主要归因于天然脉石墨的致密结晶性及高含碳量。
Graphene has been considered as a promising candidate to replace the traditional metallic oxide to prepare transparent conductive film based on its superior electrical conductivity and high visible light transmittance. However, so far no appropriate method is found to prepare high-quality and low-cost graphene in a large quantity. Therefore, the work aims to develop a technology to prepare the graphene based on fast electrochemical exfoliation of natural vein graphite and study the performance to exfoliate natural vein graphite and finally verify the feasibility to prepare the transparent conductive film by the graphene in volume production. The same electrochemical technology was used to exfoliate natural vein graphite and highly oriented pyrolytic graphiteand artificial graphite was used to prepare the graphene. The size and quality of the graphene exfoliated from natural vein graphite were investigated by OM, AFM, Raman and XPS. Then, the graphene exfoliated from natural vein graphite was compared with other two kinds of graphene and the graphene based on thermal/chemical reduction-oxidation reported in the literature. The transparent conductive film was prepared by the graphene exfoliated from natural vein graphite and its conductivity and light transmittance were measured. The graphene based on fast electrochemical exfoliation of natural vein graphite was mainly composed of 1—3 layers and the average horizontal size and thickness were respectively 5.9 μm and 2.4 nm. Through Raman and XPS analysis, the quality of such graphene could be compared favourably with that from highly oriented pyrolytic graphite by electrochemical exfoliation and better than that of artificial graphite and graphene based on thermal/chemical reduction-oxidation. Such graphene was used as raw materials to prepare the transparent graphene conductive film on the quartz by the interface self-assembly andthe subsequent transferring. At the light transmittance of 83.1%, the sheet resistance of the film decreased to 13 k?/□, but improved greatly when compared with that of conductive film prepared by the graphene based on electrochemical exfoliation. The graphene prepared by electrochemical exfoliation with natural vein graphite as raw materials has large size, few defects and low degree of functionalization and can be used to prepare the transparent conductive film due to dense crystallization and high carbon contents of natural vein graphite.
Graphene has been considered as a promising candidate to replace the traditional metallic oxide to prepare transparent conductive film based on its superior electrical conductivity and high visible light transmittance. However, so far no appropriate method is found to prepare high-quality and low-cost graphene in a large quantity. Therefore, the work aims to develop a technology to prepare the graphene based on fast electrochemical exfoliation of natural vein graphite and study the performance to exfoliate natural vein graphite and finally verify the feasibility to prepare the transparent conductive film by the graphene in volume production. The same electrochemical technology was used to exfoliate natural vein graphite and highly oriented pyrolytic graphiteand artificial graphite was used to prepare the graphene. The size and quality of the graphene exfoliated from natural vein graphite were investigated by OM, AFM, Raman and XPS. Then, the graphene exfoliated from natural vein graphite was compared with other two kinds of graphene and the graphene based on thermal/chemical reduction-oxidation reported in the literature. The transparent conductive film was prepared by the graphene exfoliated from natural vein graphite and its conductivity and light transmittance were measured. The graphene based on fast electrochemical exfoliation of natural vein graphite was mainly composed of 1—3 layers and the average horizontal size and thickness were respectively 5.9 μm and 2.4 nm. Through Raman and XPS analysis, the quality of such graphene could be compared favourably with that from highly oriented pyrolytic graphite by electrochemical exfoliation and better than that of artificial graphite and graphene based on thermal/chemical reduction-oxidation. Such graphene was used as raw materials to prepare the transparent graphene conductive film on the quartz by the interface self-assembly andthe subsequent transferring. At the light transmittance of 83.1%, the sheet resistance of the film decreased to 13 k?/□, but improved greatly when compared with that of conductive film prepared by the graphene based on electrochemical exfoliation. The graphene prepared by electrochemical exfoliation with natural vein graphite as raw materials has large size, few defects and low degree of functionalization and can be used to prepare the transparent conductive film due to dense crystallization and high carbon contents of natural vein graphite.
引文
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[2]CHEN J H,JANG C,XIAO S,et al.Intrinsic and extrinsic performance limits of graphene devices on Si O2[J].Nature nanotechnology,2008,3(4):206-209.
[3]LI X,ZHU Y,CAI W,et al.Transfer of large-area graphene films for high-performance transparent conductive electrodes[J].Nano letters,2009,9(12):4359-4363.
[4]LEE C,WEN X,KYSAR J W,et al.Measurement of the elastic properties and intrinsic strength of monolayer graphene[J].Science,2008,321(5887):385-388.
[5]BAE S,KIM H,LEE Y,et al.Roll-to-roll production of 30-inch graphene films for transparent electrodes[J].Nature nanotechnology,2010,5(8):574-578.
[6]HUANG C K,OU Y,BIE Y,et al.Well-aligned graphene arrays for field emission displays[J].Applied physics letters,2011,98(26):263104.
[7]WASSEI J K,KANER R B.Graphene,a promising transparent conductor[J].Materials today,2010,13(3):52-59.
[8]NOVOSELOV K S,GEIM A K,MOROZOV S V,et al.Electric field effect in atomically thin carbon films[J].Science,2004,306(5696):666-669.
[9]NOVOSELOV K S,JIANG D,SCHEDIN F,et al.Two-dimensional atomic crystals[J].Proceedings of the national academy of sciences of the United States of America,2005,102(30):10451-10453.
[10]LI X,CAI W,AN J,et al.Large-area synthesis of high-quality and uniform graphene films on copper foils[J].Science,2009,324(5932):1312-1314.
[11]SU C Y,LU A Y,WU C Y,et al.Direct formation of wafer scale graphene thin layers on insulating substrates by chemical vapor deposition[J].Nano letters,2011,11(9):3612-3616.
[12]BECERRIL H A,MAO J,LIU Z,et al.Evaluation of solution-processed reduced graphene oxide films as transparent conductors[J].ACS nano,2008,2(3):463-470.
[13]EDA G,FANCHINI G,CHHOWALLA M.Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material[J].Nature nanotechnology,2008,3(5):270-274.
[14]SU C Y,XU Y,ZHANG W,et al.Electrical and spectroscopic characterizations of ultra-large reduced graphene oxide monolayers[J].Chemistry of materials,2009,21(23):5674-5680.
[15]SU C Y,LU A Y,XU Y,et al.High-quality thin graphene films from fast electrochemical exfoliation[J].ACS nano,2011,5(3):2332-2339.
[16]RATHNAYAKE R,WIJAYASINGHE H,PITAWALA H,et al.Synthesis of graphene oxide and reduced graphene oxide by needle platy natural vein graphite[J].Applied surface science,2016,393:309-315.
[17]TOUZAIN P,BALASOORIYA N,BANDARANAYAKEK,et al.Vein graphite from the bogala and kahatagaha-kolongaha mines,sri lanka:A possible origin[J].Canadian mineralogist,2010,48(6):1373-1384.
[18]SUN H,LI X,LI Y,et al.High-quality monolithic graphene films via laterally stitched growth and structural repair of isolated flakes for transparent electronics[J].Chemistry of materials,2017,29(18):7808-7815.
[19]KANG F,LENG Y,ZHANG T Y.Influences of H2O2 on synthesis of H2SO4-GICs[J].Journal of physics&chemistry of solids,1996,57(68):889-892.
[20]GEE C M,TSENG C C,WU F Y,et al.Flexible transparent electrodes made of electrochemically exfoliated graphene sheets from low-cost graphite pieces[J].Displays,2013,34(4):315-319.
[21]FERRARI A C,MEYER J C,SCARDACI V,et al.Raman spectrum of graphene and graphene layers[J].Physical review letters,2006,97(18):187401.
[22]GUPTA A,CHEN G,JISHI P,et al.Raman scattering from high-frequency phonons in supported n-graphene layer films[J].Nano letters,2006,6(12):2667-2673.
[23]YAN K,PENG H,ZHOU Y,et al.Formation of bilayer bernal graphene:Layer-by-layer epitaxy via chemical vapor deposition[J].Nano letters,2011,11(3):1106-1110.
[24]TSENG I H,CHANG J C,HUANG S L,et al.Enhanced thermal conductivity and dimensional stability of flexible polyimide nanocomposite film by addition of functionalized graphene oxide[J].Polymer international,2013,62(5):827-835.
[25]ZHANG L B,WANG J Q,WANG H G,et al.Preparation,mechanical and thermal properties of functionalized graphene/polyimide nanocomposites[J].Composites part A:Applied science&manufacturing,2012,43(9):1537-1545.
[26]KIM G Y,CHIO M C,LEE D,et al.2D-aligned graphene sheets in transparent polyimide/graphene nanocomposite films based on noncovalent interactions between poly(amic acid)and graphene carboxylic acid[J].Macromolecular materials&engineering,2012,297(4):303-311.
[27]MARCANO D C,KOSYNIKIN D V,BERLIN J M,et al.Improved synthesis of graphene oxide[J].ACS nano,2010,4(8):4806-4814.