WO2018188420A1 - 一种柔性石墨烯膜及其制备方法 - Google Patents

一种柔性石墨烯膜及其制备方法 Download PDF

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WO2018188420A1
WO2018188420A1 PCT/CN2018/077171 CN2018077171W WO2018188420A1 WO 2018188420 A1 WO2018188420 A1 WO 2018188420A1 CN 2018077171 W CN2018077171 W CN 2018077171W WO 2018188420 A1 WO2018188420 A1 WO 2018188420A1
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film
graphene oxide
graphene
flexible
liquid
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PCT/CN2018/077171
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French (fr)
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高超
许震
肖友华
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杭州高烯科技有限公司
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Priority claimed from CN201710232708.3A external-priority patent/CN106986335B/zh
Priority claimed from CN201710232564.1A external-priority patent/CN107055517B/zh
Application filed by 杭州高烯科技有限公司 filed Critical 杭州高烯科技有限公司
Priority to JP2019517978A priority Critical patent/JP6746782B2/ja
Priority to US16/469,145 priority patent/US20200095128A1/en
Priority to RU2019135900A priority patent/RU2742409C1/ru
Priority to EP18784925.2A priority patent/EP3611130B1/en
Priority to KR1020197033247A priority patent/KR102284825B1/ko
Publication of WO2018188420A1 publication Critical patent/WO2018188420A1/zh

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    • C01B32/198—Graphene oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B1/002—Devices comprising flexible or deformable elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
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    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B32/184—Preparation
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    • C01B32/182—Graphene
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    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/62605—Treating the starting powders individually or as mixtures
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the invention relates to the field of nanomaterial preparation, and in particular to a method for preparing a flexible graphene film.
  • Graphene is a two-dimensional single-atom layer honeycomb periodic lattice structure crystal composed of carbon atoms and sp 2 hybrid orbitals. It has excellent electrical properties (electron mobility at room temperature can reach 2 ⁇ 10 5 cm 2 /Vs) , outstanding thermal conductivity 5000W / (MK), extraordinary specific surface area (2630M 2 / g), its Young's modulus (1100GPa) and breaking strength (125GPa). Graphene has excellent electrical and thermal conductivity superior to that of metal. At the same time, it has the advantages of high temperature and corrosion resistance, and its good mechanical properties and low density make it have the potential to replace metals in the field of electrothermal materials.
  • Graphene film is a macroscopic application form of graphene.
  • most of the current flexible graphene films are based on the shrinkage of the stretched polymer substrate to control the macroscopic undulation wrinkles of the graphene film or to prepare the corresponding structure of the graphene film based on the surface structure of the substrate. It does not assemble the macroscopic graphene film by controlling the state of the graphene monolith, which is not spontaneously generated.
  • the object of the present invention is to provide a flexible graphene film and a preparation method thereof in view of the deficiencies of the prior art.
  • the object of the present invention is achieved by the following technical solution: a flexible graphene film formed by lapped graphene oxide sheets overlapping each other, or by pleated graphene sheets overlapping each other, the film has low crystallinity At 60%.
  • a method for preparing a flexible graphene oxide film comprising the steps of:
  • a method for preparing a flexible graphene film comprising the steps of:
  • the good solvent is selected from the group consisting of: N,N-dimethylformamide, water, N-methylpyrrolidone, acetone, dimethyl sulfoxide, pyridine, dioxane, N, N- One or more of dimethylacetamide, tetrahydrofuran, and ethylene glycol are mixed in any ratio.
  • the thickness of the wiper film is 0.5-30 mm, and the wiper speed is 1-20 mm/s.
  • the poor solvent is selected from the group consisting of ethyl acetate, dichloromethane, alkanes, methanol, ethanol, n-butanol, ethylene glycol, propylene glycol, glycerol, isobutanol, methyl acetate, acetic acid.
  • the poor solvent is selected from the group consisting of ethyl acetate, dichloromethane, alkanes, methanol, ethanol, n-butanol, ethylene glycol, propylene glycol, glycerol, isobutanol, methyl acetate, acetic acid.
  • butyl ester and acetic acid are mixed in any ratio.
  • the reduction mode is selected from the group consisting of chemical reduction, thermal reduction, and electroreduction.
  • the present invention utilizes the interaction of a good solvent and a poor solvent to construct a graphene film having microscopic and macroscopic multi-stage wrinkles, which has excellent flexibility and resistance to certain stretching and bending. It has been tested to have a crystallinity of less than 60% or even less than 30%; the film has excellent flexibility, the elongation at break of the graphene oxide film is 20 to 50%, and the elongation at break of the graphene film after reduction 15 to 50%, and the graphene film after reduction has a conductivity of 10,000 to 80,000 s/m, which has great applications in the fields of flexible graphene films and flexible electronic devices.
  • Figure 1 is an analog diagram of crystalline and amorphous graphene oxide films and crystalline and amorphous polymers
  • FIG. 2 is a comparison diagram of XRD diffraction of a flexible graphene oxide film and a crystalline graphene oxide film;
  • Figure 3 is a mechanical tensile curve of a flexible graphene oxide film
  • FIG. 4 is a surface scanning electron micrograph (A) and a cross-sectional scanning electron micrograph (B) of a graphene film.
  • Figure 5 is a comparison chart of XRD diffraction of a flexible graphene film and a crystalline graphene film
  • Figure 6 is a mechanical tensile curve (A) of the flexible film and a resistance change curve (B) under bending of the flexible film.
  • a liquid GO film composed of a high concentration of monolithic graphene oxide is placed in a poor solvent to be immersed, and a good solvent of the liquid GO film is replaced by a poor solvent, resulting in shrinkage collapse of the graphene oxide sheet and wrinkling of the GO sheet.
  • Bonding to each other, similar to cross-linking polymer to form a cross-linked network, to construct an amorphous (amorphous) GO film (as shown in Figure 1) further in the drying process, poor solvent volatilization, under capillary action Refolding occurs in macroscopic form; this microscopic and macroscopic multi-stage pleats give the graphene film excellent flexibility and resistance to certain stretching and bending. It has been tested to have a crystallinity of less than 60%, or even less than 30%, and an elongation at break of 20 to 50%, and further, by reduction, a super-flexible graphene film is obtained.
  • the graphene oxide DMF solution having a concentration of 5 mg/mL was scraped through a doctor blade to a thickness of 30 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film obtained in the step 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after soaking for 6 hours.
  • the graphene oxide gel film in step 2 was suspended in an oven at 70 ° C for 10 h to obtain a flexible graphene oxide film.
  • the XRD diffraction comparison chart of Fig. 2 clearly shows that the graphene oxide film treated by the poor solvent soaking treatment has a low crystallinity.
  • the graphene oxide film which is not deposited by the poor solvent soaking treatment has a high crystallization peak, similar to a crystalline polymer.
  • a graphene oxide DMF solution having a concentration of 10 mg/mL was scraped through a doctor blade to a thickness of 1 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film obtained in 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after soaking for 24 hours.
  • the graphene gel film of 2 was suspended in an oven at 70 ° C for 10 h to obtain a flexible graphene oxide film with a crystallinity of 21% and an elongation at break of 35% in the mechanical tensile test. As shown in Fig. 3, creases are not left after repeated folding for more than 100,000 times.
  • 4 is a surface scanning electron micrograph of a graphene oxide film, in which the surface of the graphene oxide film has a rich wrinkle structure, and the curved undulation of the cross-sectional view also indicates that the graphene oxide sheet is not regularly deposited, thereby knowing the graphite oxide.
  • the olefin film is a full pleat from the inside out.
  • a graphene oxide (N-methylpyrrolidone) solution having a concentration of 15 mg/mL was scraped through a doctor blade to a thickness of 2 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film obtained in the step 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after soaking for 6 hours.
  • step 2 graphene oxide gel film was suspended in an oven at 80 ° C for 15 h to obtain a flexible graphene oxide film having a crystallinity of 15% and an elongation at break of 40% in a mechanical tensile test. There are no creases left in more than 100,000 folds.
  • a graphene oxide (N,N-dimethylacetamide) solution having a concentration of 20 mg/mL was scraped through a doctor blade to a thickness of 3 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film obtained in the step 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after the immersion time for 15 hours.
  • the step 2 graphene oxide gel film is suspended in an oven at 90 ° C for 10 h to obtain a flexible graphene oxide film having a crystallinity of 16% and an elongation at break of 50% in a mechanical tensile test. There are no creases left in more than 100,000 folds.
  • the graphene oxide DMF solution having a concentration of 8 mg/mL was scraped through a doctor blade to a thickness of 0.5 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film obtained in the step 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after soaking for 2 hours.
  • the graphene oxide gel film in step 2 is suspended in an oven at 65 ° C for 5 h to obtain a flexible graphene oxide film having a crystallinity of 14% and an elongation at break of 27% in a mechanical tensile test. Repeatedly folded more than 100,000 times without leaving creases.
  • a graphene oxide pyridine solution having a concentration of 14 mg/mL was scraped through a doctor blade to a thickness of 1 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film is immersed in methanol for 2 hours to carry out gelation to obtain a graphene oxide gel film;
  • the graphene oxide gel film was suspended in an oven at 65 ° C for 5 h to obtain a flexible graphene oxide film with a crystallinity of 59.7% and an elongation at break of 20% in the mechanical tensile test. More than 10,000 times did not leave creases.
  • the graphene oxide DMF solution having a concentration of 8 mg/mL was scraped through a doctor blade to a thickness of 2 mm to obtain a liquid graphene film.
  • the liquid graphene oxide film obtained in the step 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after soaking for 6 hours.
  • step 2 graphene gel film was suspended in an oven at 70 ° C for 10 h to obtain a flexible graphene oxide film.
  • the flexible graphene oxide film obtained in the step 3 was placed in an aqueous hydroiodic acid solution at 85 ° C for 6 h.
  • the graphene film after the reduction in step 4 is placed in ethanol at 60 ° C for 30 min, the residual hydroiodic acid in the graphene film is washed away, and then naturally dried to obtain a flexible graphene film.
  • the XRD diffraction comparison chart of Fig. 5 clearly shows that the graphene film treated by the poor solvent soaking has a low crystallinity.
  • the graphene film which is not deposited by the poor solvent soaking treatment has a high crystallization peak, similar to a crystalline polymer.
  • a graphene oxide DMF solution having a concentration of 5 mg/mL was scraped through a doctor blade to a thickness of 1 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film obtained in the step 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after soaking for 4 hours.
  • step 2 graphene gel film was suspended in an oven at 70 ° C for 10 h to obtain a flexible graphene oxide film.
  • the flexible graphene oxide film obtained in the step 3 was placed in an aqueous hydroiodic acid solution at 85 ° C for 6 h.
  • the graphene film after reduction is placed in ethanol at 60 ° C for 30 min, the residual hydroiodic acid in the graphene film is washed away, and then naturally dried to obtain a flexible graphene film.
  • the surface of the graphene film has a rich pleat structure, and the curved undulation of the cross-sectional view also indicates that the graphene sheet is not regularly deposited, and thus the graphene film is a full wrinkle from the inside to the outside.
  • the film had a crystallinity of 23% and an elongation at break of 18% (as shown in Fig. 6A), and creases were not left after repeated folding for more than 100,000 times.
  • the graphene film has a small change in electrical resistance during the bending process, as shown in Fig. 6B, and its conductivity is 41,000 s/m.
  • a graphene oxide (N-methylpyrrolidone) solution having a concentration of 15 mg/mL was scraped through a doctor blade to a thickness of 2 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film obtained in the step 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after soaking for 6 hours.
  • step 2 graphene oxide gel film was suspended in an oven at 80 ° C for 15 h to obtain a flexible graphene oxide film.
  • the flexible graphene oxide film obtained in the step 3 was placed in an aqueous hydroiodic acid solution at 80 ° C for 7 h.
  • the graphene film after reduction is placed in ethanol at 60 ° C for 30 min, the residual hydroiodic acid in the graphene film is washed away, and then naturally dried to obtain a flexible graphene film.
  • the crystallinity was 17%, the elongation at break was 31%, and creases were not left after repeated folding for more than 100,000 times.
  • the graphene film has little change in electrical resistance during the bending process, and its conductivity is 35,000 s/m.
  • a graphene oxide (N,N-dimethylacetamide) solution having a concentration of 40 mg/mL was scraped through a doctor blade to a thickness of 30 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film obtained in the step 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after soaking for 24 hours.
  • step 2 graphene oxide gel film was suspended in an oven at 90 ° C for 10 h to obtain a flexible graphene oxide film.
  • the flexible graphene oxide film obtained in the step 3 was placed in an aqueous hydroiodic acid solution at 85 ° C for 8 h.
  • the graphene film after reduction is placed in ethanol at 60 ° C for 30 min, the residual hydroiodic acid in the graphene film is washed away, and then naturally dried to obtain a flexible graphene film.
  • the crystallinity was 18%, the elongation at break was 50%, and creases were not left after repeated folding for more than 100,000 times.
  • the graphene film has little change in electrical resistance during the bending process, and the flexibility, crystallinity, and electrical conductivity thereof are 30,000 s/m.
  • a graphene oxide DMF solution having a concentration of 8 mg/mL was scraped through a doctor blade to a thickness of 0.5 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film obtained in the step 1 was immersed in a poor solvent ethyl acetate, and a self-supporting graphene oxide gel film was formed after 1 hour of soaking.
  • the graphene oxide gel film in step 2 was suspended in an oven at 65 ° C for 5 h to obtain a flexible graphene oxide film.
  • the flexible graphene oxide film obtained in the step 3 was heated in an aqueous solution of hydroiodic acid at 75 ° C for 4 h.
  • the graphene film after reduction is placed in ethanol at 60 ° C for 30 min, the residual hydroiodic acid in the graphene film is washed away, and then naturally dried to obtain a flexible graphene film.
  • the crystallinity was 15%, the elongation at break was 26%, and creases were not left after repeated folding for more than 100,000 times.
  • the graphene film has a small change in electrical resistance during the bending process, and its conductivity is 540,000 s/m.
  • a graphene oxide pyridine solution having a concentration of 14 mg/mL was scraped through a doctor blade to a thickness of 1 mm to obtain a liquid graphene oxide film.
  • the liquid graphene oxide film is immersed in methanol for 2 hours to carry out gelation to obtain a graphene oxide gel film;
  • the graphene oxide gel film is suspended in an oven at 65 ° C for 5 h to obtain a flexible graphene oxide film;
  • the flexible graphene oxide film obtained in the step 3 is subjected to electroreduction.
  • the crystallinity was 59.7%, and the elongation at break in the mechanical tensile test was 15%, and creases were not left after repeated folding for more than 100,000 times.

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Abstract

一种柔性石墨烯膜及其制备方法，包括以下步骤：将氧化石墨烯液态膜放在不良溶剂中的凝胶化；氧化石墨烯凝胶膜的干燥。石墨烯膜具有极好的柔性，其结晶度低于60％，断裂伸长率为15-50％，反复对折10万次以上不留下折痕。所述的石墨烯膜制备方法从微观调控石墨烯单片的形貌来控制石墨烯膜的宏观性质，能够显著提高石墨烯膜的柔性，其工艺简单，易于推广，其在柔性石墨烯薄膜，柔性电子器件等中具有潜在应用。

Description

一种柔性石墨烯膜及其制备方法 技术领域
本发明涉及纳米材料制备领域，特别是一种制备柔性石墨烯膜的方法。
背景技术
2010年，Andre GeiM和Konstantin Novoselov因为首次证实了二维石墨烯的存在，并研究了其优异的性质而获得诺贝尔物理学奖。
石墨烯是由碳原子以sp 2杂化轨道组成的二维单原子层蜂窝状周期点阵结构晶体，其有优异的电学性能(室温下电子迁移率可达2×10 5cm 2/Vs)，突出的导热性能5000W/(MK)，超常的比表面积(2630M 2/g)，其杨氏模量(1100GPa)和断裂强度(125GPa)。石墨烯优异的导电导热性能完全超过金属，同时石烯具有耐高温耐腐蚀的优点，而其良好的机械性能和较低的密度更让其具备了在电热材料领域取代金属的潜力。
石墨烯膜是石墨烯的一个宏观应用形式。然而，目前的柔性石墨烯膜大都基于拉伸的高分子基底的收缩来控制石墨烯膜的宏观起伏褶皱或者基于基底的表面结构来制备相应结构的石墨烯膜。其不是通过控制石墨烯单片的状态来组装宏观石墨烯膜，这种褶皱不是自发产生的。
发明内容
本发明的目的在于针对现有技术的不足，提供一种柔性石墨烯膜及其制备方法。
本发明的目的是通过以下技术方案实现的：一种柔性石墨烯膜，由褶皱的氧化石墨烯片相互搭接而成，或由褶皱的石墨烯片相互搭接而成，膜的结晶度低于60％。
一种柔性氧化石墨烯膜的制备方法，包括以下步骤：
(1)将氧化石墨烯分散于良溶剂中，得到浓度为5-20mg/mL氧化石墨烯溶液，刮膜后，得到液态氧化石墨烯膜；
(2)将液态氧化石墨烯膜浸泡到不良溶剂中2-24小时，进行凝胶化。得到氧化石墨烯凝胶膜；
(3)将氧化石墨烯凝胶膜干燥得到柔性氧化石墨烯膜
一种柔性石墨烯膜的制备方法，包括以下步骤：
(1)将氧化石墨烯分散于良溶剂中，得到浓度为5-40mg/mL氧化石墨烯溶液，刮膜后，得到氧化石墨烯液膜；
(2)将液态氧化石墨烯膜浸泡到不良溶剂中1-24小时，进行凝胶化，得到氧化石墨烯凝胶膜。
(3)将氧化石墨烯凝胶膜干燥得到柔性氧化石墨烯膜
(4)将柔性氧化石墨烯膜进行还原，得到柔性石墨烯膜。
进一步地，步骤1中，所述良溶剂选自：N,N-二甲基甲酰胺，水，N-甲基吡咯烷酮，丙酮，二甲亚砜，吡啶，二氧六环，N,N-二甲基乙酰胺，四氢呋喃，乙二醇中的一种或者多种按任意配比混合而成。
进一步地，刮膜的厚度为0.5-30mm，刮膜速度1-20mm/s。
进一步地，步骤2中，不良溶剂选自：乙酸乙酯，二氯甲烷，烷烃类，甲醇，乙醇，正丁醇，乙二醇，丙二醇，丙三醇，异丁醇，乙酸甲酯，乙酸丁酯，乙酸中的一种或者多种按照任意比例混合而成。
进一步地，可在烘箱中50-100℃直接烘干，或者悬挂烘干，5-24h。
进一步地，步骤(4)中，还原方式选自化学还原、热还原、电还原。
本发明的有益效果：本发明利用良溶剂和不良溶剂的相互作用，构建了具有微观、宏观多级褶皱的石墨烯膜，具有极好的柔性，耐一定的拉伸和弯折。经测试，其结晶度低于60％，甚至达到30％以下；该膜具有极好的柔性，氧化石墨烯膜的断裂伸长率20～50％，还原后的石墨烯膜的断裂伸长率15～50％，且还原后的石墨烯膜的导电率10000-80000s/m，其在柔性石墨烯薄膜和柔性电子器件等领域具有很大应用
附图说明
图1结晶和非晶氧化石墨烯膜与结晶和非晶高分子的类比图；
图2柔性氧化石墨烯膜与结晶性氧化石墨烯膜的XRD衍射对比图；
图3柔性氧化石墨烯膜的机械拉伸曲线；
图4为石墨烯膜的表面扫面电镜图(A)和截面扫面电镜图(B)。
图5柔性石墨烯膜与结晶性石墨烯膜的XRD衍射对比图；
图6柔性膜的机械拉伸曲线(A)和柔性膜弯折下的电阻变化曲线图(B)。
具体实施方式
本发明将由高浓度的单片氧化石墨烯组成的液态GO膜置于不良溶剂中进浸泡处理，液态GO膜的良溶剂被不良溶剂置换，导致氧化石墨烯片发生收缩 坍塌，GO片发生褶皱，相互搭接，类似交联高分子形成交联网络，从而构建出不定形态(非晶态)的GO膜(如图1所示)，进一步地在干燥过程中，不良溶剂挥发，在毛细管作用下，宏观形态上发生再褶皱；这种微观和宏观的多级褶皱赋予了石墨烯膜具有极好的柔性，耐一定的拉伸和弯折。经测试，其结晶度低于60％，甚至达到30％以下，，断裂伸长率20～50％，进一步通过还原，得到超柔性石墨烯膜。
下面结合附图及实施例对本发明作进一步的描述，本实施例只用于对本发明作进一步的说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据上述发明的内容作出一些非本质的改变和调整，均属于本发明的保护范围。
实施例1：
1、将浓度为5mg/mL的氧化石墨烯DMF溶液经由刮刀刮膜，厚度为30mm，得到液态的氧化石墨烯膜。
2、将步骤1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间6h后生成自支撑的氧化石墨烯凝胶膜。
3、将步骤2中氧化石墨烯凝胶膜悬挂置于烘箱中70℃干燥10h，得到柔性氧化石墨烯膜。
对比：其中将步骤1中得到的液态氧化石墨烯直接放入70℃干燥10h，得到结晶性氧化石墨烯膜。
图2的XRD衍射对比图很明显说明了经由不良溶剂浸泡处理的氧化石墨烯膜的结晶性很低。因为氧化石墨烯片在不良溶剂中的收缩褶皱和凝胶膜在干燥过程中溶剂挥发而引起的收缩均会导致氧化石墨烯膜的宏观收缩。而未经不良溶剂浸泡处理堆积规整的氧化石墨烯膜具有较高的结晶峰，类似于结晶性高分子。
实施例2：
1、将浓度为10mg/mL的氧化石墨烯DMF溶液经由刮刀刮膜，厚度为1mm，得到液态的氧化石墨烯膜。
2、将1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间24h后生成自支撑的氧化石墨烯凝胶膜。
3、将2中石墨烯凝胶膜悬挂置于烘箱中70℃干燥10h，得到柔性氧化石墨烯膜，其结晶度为21％，机械拉伸试验中的断裂伸长率为35％，如图3所示，反复对折10万次以上未留下折痕。图4为氧化石墨烯膜的表面扫面电镜图，其 中氧化石墨烯膜表面具有很丰富的褶皱结构，同时截面图的弯曲起伏也说明了氧化石墨烯片不是规整堆积的，由此可知氧化石墨烯膜是由内而外的全面褶皱。
实施例3：
1、将浓度为15mg/mL的氧化石墨烯(N-甲基吡咯烷酮)溶液经由刮刀刮膜，厚度为2mm，得到液态的氧化石墨烯膜。
2、将步骤1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间6h后生成自支撑的氧化石墨烯凝胶膜。
3、将步骤2氧化石墨烯凝胶膜悬挂置于烘箱中80℃干燥15h，得到柔性氧化石墨烯膜，其结晶度为15％，机械拉伸试验中的断裂伸长率为40％，反复对折10万次以上未留下折痕。
实施例4：
1、将浓度为20mg/mL的氧化石墨烯(N,N-二甲基乙酰胺)溶液经由刮刀刮膜，厚度为3mm，得到液态氧化石墨烯膜。
2、将步骤1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间15h后生成自支撑的氧化石墨烯凝胶膜。
3、将步骤2氧化石墨烯凝胶膜悬挂置于烘箱中90℃干燥10h，得到柔性氧化石墨烯膜，其结晶度为16％，机械拉伸试验中的断裂伸长率为50％，反复对折10万次以上未留下折痕。
实施例5：
1、将浓度为8mg/mL的氧化石墨烯DMF溶液经由刮刀刮膜，厚度为0.5mm，得到液态的氧化石墨烯膜。
2、将步骤1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间2h后生成自支撑的氧化石墨烯凝胶膜。
3、将步骤2中氧化石墨烯凝胶膜悬挂置于烘箱中65℃干燥5h，得到柔性氧化石墨烯膜，其结晶度为14％，机械拉伸试验中的断裂伸长率为27％，反复对折10万次以上未留下折痕。
实施例6：
1.将浓度为14mg/mL的氧化石墨烯吡啶溶液经由刮刀刮膜，厚度为1mm，得到液态的氧化石墨烯膜。
2.将液态氧化石墨烯膜浸泡到甲醇中2小时，进行凝胶化，得到氧化石墨烯凝胶膜；
3.将氧化石墨烯凝胶膜悬挂置于烘箱中65℃干燥5h，得到柔性氧化石墨烯膜，其结晶度为59.7％，机械拉伸试验中的断裂伸长率为20％，反复对折10万次以上未留下折痕。
实施例7：
1、将浓度为8mg/mL的氧化石墨烯DMF溶液经由刮刀刮膜，厚度为2mm，得到液态的石墨烯膜。
2、将步骤1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间6h后生成自支撑的氧化石墨烯凝胶膜。
3、将步骤2石墨烯凝胶膜悬挂置于烘箱中70℃干燥10h，得到柔性氧化石墨烯膜。
4、将步骤3中得到的柔性氧化石墨烯膜置于氢碘酸水溶液中85℃加热6h。
5、将步骤4中还原后的石墨烯膜置于60℃乙醇中30min，洗去石墨烯膜中残留的氢碘酸，然后自然晾干，得到柔性的石墨烯膜。
对比：其中将步骤1中得到的液态氧化石墨烯直接放入70℃干燥10h，得到氧化石墨烯膜。其还原过程与步骤4,5中一样。
图5的XRD衍射对比图很明显说明了经由不良溶剂浸泡处理的石墨烯膜的结晶性很低。因为石墨烯片在不良溶剂中的收缩褶皱和凝胶膜在干燥过程中溶剂挥发而引起的收缩均会导致石墨烯膜的宏观收缩。而未经不良溶剂浸泡处理堆积规整的石墨烯膜具有较高的结晶峰，类似于结晶性高分子。
实施例8：
1、将浓度为5mg/mL的氧化石墨烯DMF溶液经由刮刀刮膜，厚度为1mm，得到液态的氧化石墨烯膜。
2、将步骤1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间4h后生成自支撑的氧化石墨烯凝胶膜。
3、将步骤2石墨烯凝胶膜悬挂置于烘箱中70℃干燥10h，得到柔性氧化石墨烯膜。
4、将步骤3中得到的柔性氧化石墨烯膜置于氢碘酸水溶液中85℃加热6h。
5、还原后的石墨烯膜置于60℃乙醇中30min，洗去石墨烯膜中残留的氢碘酸，然后自然晾干，得到柔性的石墨烯膜。石墨烯膜表面具有很丰富的褶皱结 构，同时截面图的弯曲起伏也说明了石墨烯片不是规整堆积的，由此可知石墨烯膜是由内而外的全面褶皱。其膜的结晶度为23％，断裂伸长率为18％(如图6A所示)，反复对折10万次以上未留下折痕。该石墨烯膜在弯折过程中，其电阻变化很小，如图6B所示，其导电率为41000s/m。
实施例9：
1、将浓度为15mg/mL的氧化石墨烯(N-甲基吡咯烷酮)溶液经由刮刀刮膜，厚度为2mm，得到液态的氧化石墨烯膜。
2、将步骤1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间6h后生成自支撑的氧化石墨烯凝胶膜。
3、将步骤2氧化石墨烯凝胶膜悬挂置于烘箱中80℃干燥15h，得到柔性氧化石墨烯膜。
4、将步骤3中得到的柔性氧化石墨烯膜置于氢碘酸水溶液中80℃加热7h。
5、还原后的石墨烯膜置于60℃乙醇中30min，洗去石墨烯膜中残留的氢碘酸，然后自然晾干，得到柔性的石墨烯膜。其结晶度为17％，断裂伸长率为31％，反复对折10万次以上未留下折痕。该石墨烯膜在弯折过程中，其电阻变化很小，其导电率为35000s/m。
实施例10：
1、将浓度为40mg/mL的氧化石墨烯(N,N-二甲基乙酰胺)溶液经由刮刀刮膜，厚度为30mm，得到液态氧化石墨烯膜。
2、将步骤1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间24h后生成自支撑的氧化石墨烯凝胶膜。
3、将步骤2氧化石墨烯凝胶膜悬挂置于烘箱中90℃干燥10h，得到柔性氧化石墨烯膜。
4、将步骤3中得到的柔性氧化石墨烯膜置于氢碘酸水溶液中85℃加热8h。
5、还原后的石墨烯膜置于60℃乙醇中30min，洗去石墨烯膜中残留的氢碘酸，然后自然晾干，得到柔性的石墨烯膜。其结晶度为18％，断裂伸长率为50％，反复对折10万次以上未留下折痕。该石墨烯膜在弯折过程中，其电阻变化很小，柔性、结晶度、其导电率为30000s/m。
实施例11：
1、将浓度为8mg/mL的氧化石墨烯DMF溶液经由刮刀刮膜，厚度为0.5mm， 得到液态的氧化石墨烯膜。
2、将步骤1中得到的液态氧化石墨烯膜浸泡到不良溶剂乙酸乙酯中，浸泡时间1h后生成自支撑的氧化石墨烯凝胶膜。
3、将步骤2中氧化石墨烯凝胶膜悬挂置于烘箱中65℃干燥5h，得到柔性氧化石墨烯膜。
4、将步骤3中得到的柔性氧化石墨烯膜置于氢碘酸水溶液中75℃加热4h。
5、还原后的石墨烯膜置于60℃乙醇中30min，洗去石墨烯膜中残留的氢碘酸，然后自然晾干，得到柔性的石墨烯膜。其结晶度为15％，断裂伸长率为26％，反复对折10万次以上未留下折痕。该石墨烯膜在弯折过程中，其电阻变化很小，其导电率为540000s/m。
实施例12：
1.将浓度为14mg/mL的氧化石墨烯吡啶溶液经由刮刀刮膜，厚度为1mm，得到液态的氧化石墨烯膜。
2.将液态氧化石墨烯膜浸泡到甲醇中2小时，进行凝胶化，得到氧化石墨烯凝胶膜；
3.将氧化石墨烯凝胶膜悬挂置于烘箱中65℃干燥5h，得到柔性氧化石墨烯膜；
4.将步骤3中得到的柔性氧化石墨烯膜进行电还原。其结晶度为59.7％，机械拉伸试验中的断裂伸长率为15％，反复对折10万次以上未留下折痕。

Claims (8)

  1. 一种柔性石墨烯膜，其特征在于，由褶皱的氧化石墨烯片相互搭接而成，或由褶皱的石墨烯片相互搭接而成，膜的结晶度低于60％。
  2. 一种柔性氧化石墨烯膜的制备方法，其特征在于，包括以下步骤：
    (1)将氧化石墨烯分散于良溶剂中，得到浓度为5-20mg/mL氧化石墨烯溶液，刮膜后，得到液态氧化石墨烯膜；
    (2)将液态氧化石墨烯膜浸泡到不良溶剂中2-24小时，进行凝胶化。得到氧化石墨烯凝胶膜；
    (3)将氧化石墨烯凝胶膜干燥得到柔性氧化石墨烯膜
  3. 一种柔性石墨烯膜的制备方法，其特征在于，包括以下步骤：
    (1)将氧化石墨烯分散于良溶剂中，得到浓度为5-40mg/mL氧化石墨烯溶液，刮膜后，得到氧化石墨烯液膜；
    (2)将液态氧化石墨烯膜浸泡到不良溶剂中1-24小时，进行凝胶化，得到氧化石墨烯凝胶膜。
    (3)将氧化石墨烯凝胶膜干燥得到柔性氧化石墨烯膜
    (4)将柔性氧化石墨烯膜进行还原，得到柔性石墨烯膜。
  4. 如权利要求2或3所述柔性石墨烯膜的制备方法，其特征在于：步骤1中，所述良溶剂选自：N,N-二甲基甲酰胺，水，N-甲基吡咯烷酮，丙酮，二甲亚砜，吡啶，二氧六环，N,N-二甲基乙酰胺，四氢呋喃，乙二醇中的一种或者多种按任意配比混合而成。
  5. 如权利要求2或3所述柔性石墨烯膜的制备方法，其特征在于：刮膜的厚度为0.5-30mm，刮膜速度1-20mm/s。
  6. 如权利要求2或3所述柔性石墨烯膜的制备方法，其特征在于：步骤2中，不良溶剂选自：乙酸乙酯，二氯甲烷，烷烃类，甲醇，乙醇，正丁醇，乙二醇，丙二醇，丙三醇，异丁醇，乙酸甲酯，乙酸丁酯，乙酸中的一种或者多种按照任意比例混合而成。
  7. 如权利要求2或3所述柔性石墨烯膜的制备方法，其特征在于：可在烘箱中50-100℃直接烘干，或者悬挂烘干，5-24h。
  8. 如权利要求3中所述柔性石墨烯膜的制备方法，其特征在于：步骤(4)中，还原方式选自化学还原、热还原、电还原。
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