石墨烯及其复合材料的制备、性质及应用研究
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摘要
石墨烯是一种二维纳米材料,仅由一个原子层厚的单层石墨片构成。这种材料潜力巨大,集多种优异特性于一身,具有超强的导电、导热性能及机械强度,超高的载流子迁移率、透光性及巨大的比表面积。在很多方面,比如透明导电薄膜、电子器件、能源存储、催化、生物医药等展现出巨大的应用前景。本论文从合成、性质、应用等出发,开展了还原石墨烯及其薄膜的低温制备、非氧化直接剥离石墨、制备石墨烯复合凝胶及纤维等工作,具体研究内容和结果如下：
采用钠-氨溶液低温还原方式,实现了氧化石墨烯及其薄膜的高效还原。金属钠在液氨中产生高活性的溶剂电子可以有效消除含氧基团、恢复π共轭结构,石墨烯含氧量只有5.6wt%,单层石墨烯的迁移率高达123cm2V/s。利用红外光谱考察了氧化石墨烯的含氧官能团在不同还原时间的演变,并推测了电子还原的反应机制。通过直接溶液浸泡的方式,制备了石墨烯透明导电薄膜,过程只要几分钟,在80%透光率下,其平面膜阻只有350Ω/平方。还制备了石墨烯-碳纳米管复合薄膜。制备了基于还原石墨烯的超电容,比电容达263F/g。利用还原石墨烯负载铂作为甲醇催化的催化剂,发现其催化效果明显增强。
借助研磨过程,金属钠“引爆”插入石墨层间的硫酸分子,产生迅速而猛烈的化学能释放,可以实现石墨的直接剥离。它不经过氧化-还原过程从而保证其高质量。原子力显微镜和高分辨电镜可以证明成功制备出了单层石墨烯,通过衍射斑点可以证明石墨烯的结晶性很好,晶格完美。红外、拉曼、电子能谱显示石墨烯的氧化程度很低、缺陷少,具有高品质。利用剥离石墨烯制备了透明导电薄膜,其透光率85%,膜阻～760Ω/square。还制备了石墨烯基超电容,其比电容值为120F/g。利用高品质的石墨烯作为负载贵金属Pt纳米颗粒的载体,进行催化甲醇氧化的实验,显示了很好的催化活性和抗碳质残余物的沉积的能力。此外,还实现了利用金属钠的气氛对石墨的直接剥离。
通过对氧化石墨烯和聚乙烯醇混合物的直接化学还原,制备了石墨烯-聚乙烯醇复合凝胶,改进了石墨烯的分散性,提高了其载荷的传输性能。通过热拉伸或直接拉伸的方式,制备了石墨烯-聚乙烯醇复合纤维,并且应用微装配的音叉器件评估了复合纤维的力学性能。发现仅添加0.68vol%的石墨烯,聚合物复合材料的杨氏模量提高200%。通过对石墨烯复合物的热性质研究,发现添加石墨烯可以极大提高复合物的热稳定性。复合材料中石墨烯拉曼光谱振动频带的位移表明石墨烯和聚合物之间存在相互作用。
Graphene is a two-dimensional nanomaterial, consisted of only one atom thick layer of graphite. This material has great potential in various applications, due to its excellent features in a high electrical and thermal conductivity, high mechanical strength, high carrier mobility, high transparency and huge specific surface area. Graphene shows a great prospect in many ways, such as transparent conductive film, electronic devices, energy storage, catalysis, bio-medicine, etc.. In this dissertation, we focus on the synthesis, properties, applications of graphene, including low temperature reduction of graphene, direct exfoliation of graphite, and preparation of graphene composite material. The main innovative work and specific research results are summarized as follows:
Highly reduced graphene oxide (RGO) and RGO film were prepared by Na-NH3solution. The solvated electrons in Na-NH3solution can effectively facilitate the de-oxygenation of GO and the restoration of π-conjugation to produce RGO samples with an oxygen content of5.6wt%at low temperature. Electrical characterization of single RGO flakes demonstrates a high hole-mobility of123cm2/Vs. To probe the fundamental mechanism for the reduction of GO with solvated electrons, we have carried out detailed Fourier transform infrared spectroscopy (FTIR) study to monitor the evolution of the functional groups in GO during the reduction process. Additionally, we show that the pre-formed GO thin film can be directly reduced to form RGO film with a combined low sheet resistance (～350Ω/square with～80%transmittance) in few minutes. We also have fabricated the graphene-carbon nanotube composite films using this method. We have prepared the RGO-based ultracapacitors with specific capacitance of263F/g and produced the Pt/RGO composites as high-efficient catalyst for methanol oxidation.
High quality graphene was prepared by direct exfoliation of the graphite without oxidizing and damaging the graphene sheets through a grinding-assisted chemical bursting-process when the pre-intercalated oleum was ignited by sodium. The definitive evidence that the as-made graphene sheets are only a single atomic layer thickness was observed with atomic force microscopy (AFM) and high-resolution TEM (HRTEM). The high quality of the graphene sheets were supported by selected area electron diffraction (SAED), Raman, FTIR, and X-ray photoelectron spectroscopy (XPS), which also demonstrate our graphene samples with less defects or oxides. Using the exfoliated graphene, we are able to fabricate high performance graphene-based ultracapacitors (120F/g), transparent conductive film (～760Ω/square with～85%transmittance) and Pt/graphene nanocomposites as high-efficient catalyst for methanol oxidation. In addition, we slao use the vapor of the metallic sodium to directly exfoliate the oleum pre-intercalated graphite.
By in situ chemical reduction of the graphite oxide (GO) mixed with poly(vinyl alcohol)(PVA), we successfully fabricated reduced graphene oxide (rGO)-PVA composite hydrogels with improved dispersion and load transfer in their composites. The rGO-PVA composite wires were made by thermal-drawing or by directly drawing from rGO-PVA dispersion and their mechanical properties were rapidly evaluated using a microfabricated tuning fork device. It was found that the Young's modulus of the polymer composites increase by ca.200%with only0.68vol%addition of the rGO. The thermal properties of the composites were studied by differential scanning calorimetry (DSC), and it was observed that the addition of graphene to PVA highly improves the thermal stability of the composites. Raman spectroscopy revealed the existence of an interaction between the graphene and the polymer via the shift in the vibration bands of the graphene in the composites.
采用钠-氨溶液低温还原方式,实现了氧化石墨烯及其薄膜的高效还原。金属钠在液氨中产生高活性的溶剂电子可以有效消除含氧基团、恢复π共轭结构,石墨烯含氧量只有5.6wt%,单层石墨烯的迁移率高达123cm2V/s。利用红外光谱考察了氧化石墨烯的含氧官能团在不同还原时间的演变,并推测了电子还原的反应机制。通过直接溶液浸泡的方式,制备了石墨烯透明导电薄膜,过程只要几分钟,在80%透光率下,其平面膜阻只有350Ω/平方。还制备了石墨烯-碳纳米管复合薄膜。制备了基于还原石墨烯的超电容,比电容达263F/g。利用还原石墨烯负载铂作为甲醇催化的催化剂,发现其催化效果明显增强。
借助研磨过程,金属钠“引爆”插入石墨层间的硫酸分子,产生迅速而猛烈的化学能释放,可以实现石墨的直接剥离。它不经过氧化-还原过程从而保证其高质量。原子力显微镜和高分辨电镜可以证明成功制备出了单层石墨烯,通过衍射斑点可以证明石墨烯的结晶性很好,晶格完美。红外、拉曼、电子能谱显示石墨烯的氧化程度很低、缺陷少,具有高品质。利用剥离石墨烯制备了透明导电薄膜,其透光率85%,膜阻～760Ω/square。还制备了石墨烯基超电容,其比电容值为120F/g。利用高品质的石墨烯作为负载贵金属Pt纳米颗粒的载体,进行催化甲醇氧化的实验,显示了很好的催化活性和抗碳质残余物的沉积的能力。此外,还实现了利用金属钠的气氛对石墨的直接剥离。
通过对氧化石墨烯和聚乙烯醇混合物的直接化学还原,制备了石墨烯-聚乙烯醇复合凝胶,改进了石墨烯的分散性,提高了其载荷的传输性能。通过热拉伸或直接拉伸的方式,制备了石墨烯-聚乙烯醇复合纤维,并且应用微装配的音叉器件评估了复合纤维的力学性能。发现仅添加0.68vol%的石墨烯,聚合物复合材料的杨氏模量提高200%。通过对石墨烯复合物的热性质研究,发现添加石墨烯可以极大提高复合物的热稳定性。复合材料中石墨烯拉曼光谱振动频带的位移表明石墨烯和聚合物之间存在相互作用。
Graphene is a two-dimensional nanomaterial, consisted of only one atom thick layer of graphite. This material has great potential in various applications, due to its excellent features in a high electrical and thermal conductivity, high mechanical strength, high carrier mobility, high transparency and huge specific surface area. Graphene shows a great prospect in many ways, such as transparent conductive film, electronic devices, energy storage, catalysis, bio-medicine, etc.. In this dissertation, we focus on the synthesis, properties, applications of graphene, including low temperature reduction of graphene, direct exfoliation of graphite, and preparation of graphene composite material. The main innovative work and specific research results are summarized as follows:
Highly reduced graphene oxide (RGO) and RGO film were prepared by Na-NH3solution. The solvated electrons in Na-NH3solution can effectively facilitate the de-oxygenation of GO and the restoration of π-conjugation to produce RGO samples with an oxygen content of5.6wt%at low temperature. Electrical characterization of single RGO flakes demonstrates a high hole-mobility of123cm2/Vs. To probe the fundamental mechanism for the reduction of GO with solvated electrons, we have carried out detailed Fourier transform infrared spectroscopy (FTIR) study to monitor the evolution of the functional groups in GO during the reduction process. Additionally, we show that the pre-formed GO thin film can be directly reduced to form RGO film with a combined low sheet resistance (～350Ω/square with～80%transmittance) in few minutes. We also have fabricated the graphene-carbon nanotube composite films using this method. We have prepared the RGO-based ultracapacitors with specific capacitance of263F/g and produced the Pt/RGO composites as high-efficient catalyst for methanol oxidation.
High quality graphene was prepared by direct exfoliation of the graphite without oxidizing and damaging the graphene sheets through a grinding-assisted chemical bursting-process when the pre-intercalated oleum was ignited by sodium. The definitive evidence that the as-made graphene sheets are only a single atomic layer thickness was observed with atomic force microscopy (AFM) and high-resolution TEM (HRTEM). The high quality of the graphene sheets were supported by selected area electron diffraction (SAED), Raman, FTIR, and X-ray photoelectron spectroscopy (XPS), which also demonstrate our graphene samples with less defects or oxides. Using the exfoliated graphene, we are able to fabricate high performance graphene-based ultracapacitors (120F/g), transparent conductive film (～760Ω/square with～85%transmittance) and Pt/graphene nanocomposites as high-efficient catalyst for methanol oxidation. In addition, we slao use the vapor of the metallic sodium to directly exfoliate the oleum pre-intercalated graphite.
By in situ chemical reduction of the graphite oxide (GO) mixed with poly(vinyl alcohol)(PVA), we successfully fabricated reduced graphene oxide (rGO)-PVA composite hydrogels with improved dispersion and load transfer in their composites. The rGO-PVA composite wires were made by thermal-drawing or by directly drawing from rGO-PVA dispersion and their mechanical properties were rapidly evaluated using a microfabricated tuning fork device. It was found that the Young's modulus of the polymer composites increase by ca.200%with only0.68vol%addition of the rGO. The thermal properties of the composites were studied by differential scanning calorimetry (DSC), and it was observed that the addition of graphene to PVA highly improves the thermal stability of the composites. Raman spectroscopy revealed the existence of an interaction between the graphene and the polymer via the shift in the vibration bands of the graphene in the composites.
引文
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