WO2020187332A1 - 一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用 - Google Patents

一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用 Download PDF

Info

Publication number
WO2020187332A1
WO2020187332A1 PCT/CN2020/083030 CN2020083030W WO2020187332A1 WO 2020187332 A1 WO2020187332 A1 WO 2020187332A1 CN 2020083030 W CN2020083030 W CN 2020083030W WO 2020187332 A1 WO2020187332 A1 WO 2020187332A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
graphene
graphene film
substrate
solid transfer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2020/083030
Other languages
English (en)
French (fr)
Inventor
彭蠡
高超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University
Hangzhou Gaoxi Technology Co Ltd
Original Assignee
Zhejiang University
Hangzhou Gaoxi Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University, Hangzhou Gaoxi Technology Co Ltd filed Critical Zhejiang University
Publication of WO2020187332A1 publication Critical patent/WO2020187332A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment

Definitions

  • the invention relates to a high-performance nano material and a preparation method thereof, in particular to a method and application for electrocatalytic preparation of a defect-free random-layer stacked graphene nano-film.
  • a defect-free random-layer stacked graphene nano film with nano-level thickness can be obtained membrane.
  • the graphene film of macroscopically assembled graphene oxide or graphene nanosheets is the main application form of nano-scale graphene.
  • the commonly used preparation methods are suction filtration, scraping, spin coating, spray coating, and dip coating. Through further high temperature treatment, the defects of graphene can be repaired, and the conductivity and thermal conductivity of graphene film can be effectively improved. It can be widely used in smart phones, smart portable hardware, tablet computers, notebook computers and other portable electronic devices. .
  • the thickness of the graphene film sintered at high temperature is generally more than 1um, and a lot of gas is enclosed inside.
  • the closed pores remain in the form of folds, resulting in poor orientation and density of the graphene film. It becomes smaller, and the degree of AB stacking between layers is poor, which seriously affects the further improvement of graphene film performance.
  • nano-scale graphene films generally refer to polycrystalline graphene films prepared by chemical vapor deposition methods, which are fixed on a certain substrate after being transferred by wet or dry methods, and cannot be independent in the air. support.
  • the graphene film itself has a polycrystalline structure, and its performance is greatly affected by grain boundaries.
  • AB-stacked graphene requires higher preparation (higher temperature and maintenance time), and non-AB structure in optoelectronic applications is more conducive to the migration of photoelectrons, and there is currently no graphene dominated by a chaotic layer stack structure membrane.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, and provide a method and application for preparing a defect-free disordered layer stacking graphene nano-film.
  • the solid transfer method includes the following steps:
  • the graphene oxide is formulated into a graphene oxide aqueous solution with a concentration of 0.5-10ug/mL, and the mixed cellulose ester (MCE) is used as a substrate to suction and filter to form a film.
  • MCE mixed cellulose ester
  • the molten solid transfer agent is uniformly coated on the surface of the reduced graphene oxide film, and cooled at room temperature.
  • the solid transfer agent is selected from the following substances, such as paraffin, aluminum chloride, iodine, naphthalene, arsenic trioxide, phosphorus pentachloride, acrylamide, ferric chloride, sulfur, red phosphorus, ammonium chloride, Ammonium bicarbonate, potassium iodide, norbornene, caffeine, melamine, water, rosin, tert-butanol, sulfur trioxide and other small molecular solid substances that can be sublimated or volatilized under certain conditions.
  • substances such as paraffin, aluminum chloride, iodine, naphthalene, arsenic trioxide, phosphorus pentachloride, acrylamide, ferric chloride, sulfur, red phosphorus, ammonium chloride, Ammonium bicarbonate, potassium iodide, norbornene, caffeine, melamine, water, rosin, tert-butanol, sulfur trioxide and other small molecular solid
  • the good solvent of the MCE film is selected from one or more of acetone, n-butanol, ethanol, and isopropanol.
  • the independent self-supporting graphene film is prepared by the water stripping method, and the preparation method is as follows:
  • the graphene film is peeled from the AAO base film, specifically: the AAO base film with the graphene film attached to the surface is placed on the water surface with the graphene film facing up; pressing the AAO base film to make The AAO basement membrane sinks, and the graphene membrane floats on the water surface.
  • a substrate is used to lift the graphene film floating on the water surface from bottom to top, so that the graphene film is spread on the surface of the substrate, and there is a layer of water medium between the graphene film and the substrate.
  • the substrate with the graphene film loaded on the surface is freeze-dried.
  • the graphene film is self-supporting and separated from the substrate.
  • the porosity of the surface of the AAO base film is not less than 40%.
  • the substrate described in step 2 is a hydrophobic substrate.
  • the upper surface of the substrate described in step 2 has a recessed area.
  • the pressing position is the edge of the AAO base film.
  • the thickness of the graphene film can reach 4 nm.
  • the graphene film may be a graphene oxide film or a reduced graphene oxide film.
  • the application of defect-free random layer stacking graphene nano-film is: applied to nano-level acoustic wave generators.
  • the said nano-level acoustic wave generator includes a substrate with a thermal conductivity of less than 200W/mK, a defect-free random-layer stacked graphene nano-membrane flat on the substrate, an electrical signal input unit and two silver glues for audio current input.
  • the two silver glue electrodes are respectively arranged on both ends of the sound wave generating film, the sound wave generating film, the two silver glue electrodes and the electrical signal input unit are connected in series to form a loop; in the defect-free disordered layer stacking graphene nano film, graphene
  • the lamellae have a conjugated structure and are free of defects; the interlayer stacking method is disorderly stacking.
  • the present invention gradually raises the temperature of the independently self-supporting graphene film to 2000 degrees, (1-60 degrees per minute), maintains it for 1-2 hours, repairs most of the defective structure, while maintaining the graphite The state of chaotic stacking of vinyl sheets. Then energize the film to activate carbon atoms and promote the flow of carbon atoms, thereby further repairing atomic structural defects. The two work together to greatly reduce the defect structure repair temperature of the graphene film.
  • the non-ab structure weakens the interlayer force and reduces the conduction of phonons in the vertical direction, thereby increasing the horizontal transmission and increasing the thermal conductivity in the horizontal direction.
  • the defect-free structure facilitates the transmission of electrons and phonons, and does not form electrical resistance and thermal resistance.
  • the fast heating and cooling rate determines that this film has excellent sound quality and high sound clarity. While ensuring transparency, the invention guarantees great electrical conductivity and mechanical load-bearing performance, and can withstand the tension of the battery during the discharge process and the flexible bending process of the battery.
  • the film is used as a photoanode, counter electrode, etc.; in comparison, graphene has a higher electron mobility, and there is no heavy metal pollution problem, which reduces costs and improves light conversion efficiency.
  • FIG. 1 is a schematic diagram of the structure of an independently self-supporting graphene film prepared in Example 1;
  • Figure 2 is a Raman diagram of the film prepared in Example 1;
  • Figure 3 is a TEM image of the film prepared in Example 1;
  • Fig. 4 is a schematic diagram of the process of peeling off the graphene film from the AAO base film.
  • Fig. 5 is an experimental process diagram of Example 4 AAO base film exfoliating graphene film.
  • Example 6 is a photograph of the self-supporting graphene film prepared in Example 4.
  • Example 7 is an atomic force microscope image of the self-supporting graphene film prepared in Example 4.
  • Fig. 8 is a schematic diagram of the substrate of Example 5.
  • 1 is a substrate with a depressed center
  • 2 is a graphene film
  • 3 is water.
  • the graphene oxide is formulated into a graphene oxide aqueous solution with a concentration of 0.5ug/mL, and the mixed cellulose ester (MCE) is used as a substrate to suction and filter to form a film.
  • MCE mixed cellulose ester
  • the graphene film supported by the solid transfer agent obtained above is slowly volatilized off the solid transfer agent at 120 degrees to obtain an independent self-supporting graphene film, the thickness of the graphene film is about 30 atomic layers, and the transparency is 95 %.
  • graphene has a few wrinkles. It can be seen in Figure 2 that the defect peak in Raman is basically absent, which proves the defect-free structure of the graphene film.
  • Figure 3 TEM electron diffraction pattern shows that the stacking of graphene sheets is chaotic stacking. Its horizontal thermal conductivity reaches 2500W/mK, electrical conductivity reaches 1.5MS/m, and the wavelength range of photoelectric detection reaches terahertz.
  • the determined air thermal vibration amplitude namely the pitch
  • the input signal can adjust the air thermal vibration frequency, and then the frequency of the sound can be changed to produce different sounds.
  • the graphene oxide is formulated into a graphene oxide aqueous solution with a concentration of 10ug/mL, and the mixed cellulose ester (MCE) is used as a substrate to suction and filter to form a film.
  • MCE mixed cellulose ester
  • the TEM electron diffraction pattern shows that the stacking of graphene sheets is chaotic stacking. Its horizontal thermal conductivity reaches 2100W/mK, electrical conductivity reaches 1.3MS/m, and the wavelength range of photoelectric detection reaches terahertz.
  • the determined air thermal vibration amplitude namely the pitch
  • the input signal can adjust the air thermal vibration frequency, and then the frequency of the sound can be changed to produce different sounds.
  • the graphene oxide is formulated into a graphene oxide aqueous solution with a concentration of 8ug/mL, and the mixed cellulose ester (MCE) is used as a substrate to suction and filter to form a film.
  • MCE mixed cellulose ester
  • the TEM electron diffraction pattern shows that the stacking of graphene sheets is chaotic stacking. Its horizontal thermal conductivity reaches 1800W/mK, electrical conductivity reaches 1.1MS/m, and the wavelength range of photoelectric detection reaches terahertz.
  • the TEM electron diffraction pattern shows that the stacking of graphene sheets is chaotic stacking. Its horizontal thermal conductivity reaches 1800W/mK, electrical conductivity reaches 1.1MS/m, and the wavelength range of photoelectric detection reaches terahertz.
  • the determined air thermal vibration amplitude namely the pitch
  • the input signal can adjust the air thermal vibration frequency, and then the frequency of the sound can be changed to produce different sounds.
  • the graphene film is peeled from the AAO base film, specifically: the AAO base film with a reduced graphene oxide film attached to the surface (with a porosity of 40%), with the graphene film facing upward, On the water surface, as shown in Figures 4 and 5a; press the edge of the AAO basement membrane, as shown in Figure 5b, the AAO basement membrane begins to sink, as shown in Figure 5c. Finally, the AAO basement membrane sinks to the bottom of the cup and the graphene membrane floats on the water surface (dashed circle) Inside), as shown in Figures 5b and 5d.
  • the TEM electron diffraction pattern shows that the stacking of graphene sheets is chaotic stacking. Its horizontal thermal conductivity reaches 2700W/mK (self-heating test), and its electrical conductivity reaches 1.7MS/m. The wavelength range of photoelectric detection reaches terahertz.
  • the determined air thermal vibration amplitude namely the pitch
  • the input signal can adjust the air thermal vibration frequency, and then the frequency of the sound can be changed to produce different sounds.
  • the ultra-thin graphene oxide film is obtained by suction filtration on the AAO basement membrane;
  • the TEM electron diffraction pattern shows that the stacking of graphene sheets is chaotic stacking. Its horizontal thermal conductivity reaches 2600W/mK, electrical conductivity reaches 1.5MS/m; the wavelength range of photoelectric detection reaches terahertz.
  • the suction filtration method is currently recognized as the most uniform method for preparing graphene membranes.
  • the concentration can be adjusted to control the thickness of the graphene membrane, and the minimum thickness can be a layer of graphene.
  • the concentration of graphene increases, under pressure, the newly added graphene gradually fills the gaps of the first layer of graphene, so that the first layer of graphene is gradually filled completely, and then develops into the second layer, repeating the above
  • a graphene nano film with a thickness spanning from 2 to tens of thousands of graphene layers can be prepared. Therefore, those skilled in the art can obtain a graphene film with a thickness of 4 nm through simple adjustment of experimental parameters.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法，石墨烯膜由独立自支撑的石墨烯膜经过热处理、电处理得到。步骤如下：（1）制备独立自支撑的石墨烯膜；厚度方向，石墨烯膜的层数不大于200；（2）将石墨烯膜逐步升温到2000℃，升温速度不大于60℃/min，维持1-2小时，然后给薄膜通电，电流大小为1-20A，维持1-4h。

Description

一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用 技术领域
本发明涉及高性能纳米材料及其制备方法，尤其涉及一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用，通过该方法可以获得纳米级厚度的无缺陷乱层堆叠石墨烯纳米膜。
背景技术
2010年，英国曼彻斯特大学的两位教授Andre GeiM和Konstantin Novoselov因为首次成功分离出稳定的石墨烯获得诺贝尔物理学奖，掀起了全世界对石墨烯研究的热潮。石墨烯有优异的电学性能(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，同时石墨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。
宏观组装氧化石墨烯或者石墨烯纳米片的石墨烯膜是纳米级石墨烯的主要应用形式，常用的制备方法是抽滤法、刮膜法、旋涂法、喷涂法和浸涂法等。通过进一步的高温处理，能够修补石墨烯的缺陷，能够有效的提高石墨烯膜的导电性和热导性，可以广泛应用于智能手机、智能随身硬件、平板电脑、笔记本电脑等随身电子设备中去。
但是目前，高温烧结过的石墨烯膜厚度一般在1um以上，里面封闭了很多的气体，在高压压制的过程中，封闭的气孔以褶皱的形式保留下来，导致石墨烯膜取向度变差，密度变小，并且层间AB堆叠度差，严重影响了石墨烯膜性能的进一步提高。另外，目前还没有工作报道基于氧化石墨烯的纳米级石墨烯膜的制备。通常情况下，纳米级石墨烯膜一般指的是化学气相沉积方法制备的多晶石墨烯膜，其应用湿法或者干法转移后被固定在某个基底上，不能实现在空气中独立的自支撑。这种石墨烯膜本身是多晶结构，其性能受晶界影响很大。
最重要的是，AB堆积的石墨烯制备要求较高(较高的温度以及维持时间)，而光电应用中非AB结构更有利于光电子的迁移，而目前还没有乱层堆叠结构主导的石墨烯膜。
发明内容
本发明的目的是克服现有技术的不足，提供一种无缺陷乱层堆叠石墨烯纳米膜的制备方法与应用。
本发明的目的是通过以下技术方案实现的：一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法，步骤如下：
(1)制备独立自支撑的石墨烯膜；厚度方向，石墨烯膜的层数不大于200；
(2)将石墨烯膜逐步升温到2000℃，升温速度不大于60℃/min，维持1-2小时，然后给薄膜通电，电流大小为1-20A，维持1-4h。
进一步地，采用固体转移法制备独立自支撑的石墨烯膜。
进一步地，所述固体转移法包括如下步骤：
(1.1)将氧化石墨烯配制成浓度为0.5-10ug/mL氧化石墨烯水溶液，以混和纤维素酯(MCE)为基底抽滤成膜。
(1.2)将贴附于MCE膜的氧化石墨烯膜置于密闭容器中，60-100度HI高温熏蒸1-10h。
(1.3)将融化的固体转移剂均匀涂敷在还原氧化石墨烯膜表面，并于室温下冷却。
(1.4)将涂敷有固体转移剂的石墨烯膜放置于MCE膜的良溶剂中，刻蚀掉MCE膜。
(1.5)将上述得到的固体转移剂支撑的石墨烯膜在固体转移剂挥发的温度下挥发掉固体转移剂，得到独立自支撑的石墨烯膜。
进一步地，所述的固体转移剂，选自如下物质，例如石蜡、氯化铝、碘、萘、三氧化二砷、五氯化磷、丙烯酰胺、三氯化铁、硫、红磷、氯化铵、碳酸氢铵、碘化钾、降冰片烯、咖啡因、三聚氰胺、水、松香、叔丁醇、三氧化硫等可在某种条件下升华或者挥发的小分子固态物质。
进一步地，所述MCE膜的良溶剂选自丙酮、正丁醇、乙醇、异丙醇中的一种或多种。
进一步地，采用水剥离方法制备独立自支撑的石墨烯膜，制备方法如下：
(1.1)将石墨烯膜从AAO基底膜上剥离，具体为：将表面贴合有石墨烯膜的AAO基底膜以石墨烯膜所在的面朝上，置于水面上；按压AAO基底膜，使得AAO基底膜下沉，石墨烯膜漂浮于水面。
(1.2)利用一基底将漂浮于水面的石墨烯膜从下往上捞起，使得石墨烯膜平铺于基底表面，且石墨烯膜与基底之间具有一层水介质。
(1.3)将表面载有石墨烯膜的基底进行冷冻干燥，石墨烯膜自支撑，且与基底分离。
进一步地，所述AAO基底膜的表面的孔隙率不小于40％。
进一步地，步骤2中所述的基底为疏水基底。
进一步地，步骤2中所述的基底的上表面具有凹陷区域。
上述步骤1中，按压位置为AAO基底膜的边缘。所述石墨烯膜的厚度可以达到4nm。石墨烯膜可以为氧化石墨烯膜或还原后的氧化石墨烯膜。
无缺陷乱层堆叠石墨烯纳米膜的应用为：应用于纳米级声波发生器等。所述的纳米级声波发生器包括热导率低于200W/mK的基底、平铺于基底上的无缺陷乱层堆叠石墨烯纳米膜，以及电信号输入单元和两个音频电流输入用银胶电极，两个银胶电极分别设置在声波发生薄膜的两端，声波发生薄膜、两个银胶电极和电信号输入单元串联形成回路；所述无缺陷乱层堆叠石墨烯纳米膜中，石墨烯片层为共轭结构，无缺陷；层间堆叠方式为乱层无序堆叠。
本发明的有益效果在于：本发明将独立自支撑的石墨烯膜逐步升温到2000度，(1-60度每分钟)，维持1-2小时，修复了大部分的缺陷结构，同时保持了石墨烯片层乱层堆叠的状态。然后给薄膜通电，活化碳原子，促进碳原子流动，从而进一步修复原子结构缺陷。两者共同作用，大大降低了石墨烯膜的缺陷结构修复温度。非ab结构使得层间作用力减弱，降低声子在垂直方向的传导，从而增加水平传输，增加水平方向的热导率。无缺陷结构有利于电子和声子的传输，不会形成电阻和热阻。升降温速率快，决定此薄膜具有极好的音质，声音清晰度高。本发明在在保证透明的同时，保证了极大的导电率和力学承载性能，可承受电池在放电过程以及电池柔性弯折过程中的张力作用。使用时，该薄膜作为光阳极、对电极等；相比而言，石墨烯具有更高的电子迁移率，而且没有重金属污染问题存在，降低了成本，提高光转化效率。
附图说明
图1为实施例1制备的独立自支撑的石墨烯膜的结构示意图；
图2为实施例1制备的薄膜的拉曼图；
图3为实施例1制备的薄膜的TEM图；
图4为AAO基底膜剥离石墨烯膜的流程示意图。
图5为实施例4AAO基底膜剥离石墨烯膜的实验过程图。
图6为实施例4制备得到的自支撑石墨烯膜的照片。
图7为实施例4制备得到的自支撑石墨烯膜的原子力显微镜图。
图8为实施例5的基底示意图，图中，1为中心凹陷的基底，2为石墨烯膜，3为水。
具体实施方式
实施例1：
(1)将氧化石墨烯配制成浓度为0.5ug/mL氧化石墨烯水溶液，以混和纤维素酯(MCE)为基底抽滤成膜。
(2)将贴附于MCE膜的氧化石墨烯膜置于密闭容器中，60度HI高温熏蒸1h。
(3)用蒸镀、流延等方法将融化的石蜡均匀涂敷在还原氧化石墨烯膜表面，并于室温下缓慢冷却。
(4)将涂敷有固体转移剂的石墨烯膜用乙醇缓慢洗涤，溶解MCE膜。
(5)将上述得到的固体转移剂支撑的石墨烯膜在120度下缓慢挥发掉固体转移剂，得到独立自支撑的石墨烯膜，该石墨烯膜的厚度为30原子层左右，透明度为95％。
(6)将石墨烯膜逐步升温到2000℃，升温速度60℃/min，维持2小时，然后给薄膜通电，电流大小为1A，维持4h。
如图1所示，石墨烯具有少量褶皱。图2中可以看出，拉曼中缺陷峰基本不存在，证明了石墨烯膜的无缺陷结构。图3TEM电子衍射图谱表明，石墨烯片层之间堆叠方式为乱层堆叠。其水平方向的热导率达到2500W/mK，电导率达到1.5MS/m，光电探测的波长范围达到太赫兹。
在石墨烯膜的左右两侧连接两个电极，并用控温传感器测量石墨烯电热膜的温度变化，这种石墨烯膜在大气环境下，在10V的直流电压下，只需要1.2秒就达到了稳定温度270℃，而断电后，由于石墨烯膜优异的热传导性，膜的温度在1秒内就降到接近室温。对T＝1s时刻，利用红外探测仪获得薄膜表面温度分布图，该石墨烯膜沿两个电极所在直线方向上，温度稳定，均在270℃左右。
将上述石墨烯膜2×2cm 2平铺于聚酰亚胺基底(热导率0.35W/mK)上，在石墨烯薄膜两端涂覆银胶电极，将两个银胶电极分别与电信号输入单元的正负极相连，构成本发明所述的纳米级声波发生器。由于该薄膜电导率高，在外加电压情况下会剧烈放热升温，撤离外加电压，薄膜热逸散速度极高，两者共同作用，使得薄膜可以快速的升降温，从而引起薄膜处空气的热震动，从而发声。因此，通过8V的直流电压的辅助加载，另外通过电信号输入单元输入指定的音频信号，以调节整体输入的电压和变化频率，便可以获得确定的空气热震动幅度，即音高；调节输入信号频率便可以调节空气热震动频率，进而发声的频率改变，发出不同的声音。
实施例2：
(1)将氧化石墨烯配制成浓度为10ug/mL氧化石墨烯水溶液，以混和纤维素酯(MCE)为基底抽滤成膜。
(2)将贴附于MCE膜的氧化石墨烯膜置于密闭容器中，100度HI高温熏蒸10h。
(3)用蒸镀、流延等方法将融化的松香均匀涂敷在还原氧化石墨烯膜表面，并于室温下缓慢冷却。
(4)将涂敷有固体转移剂的石墨烯膜放置于丙酮中，去除MCE膜。
(5)将上述得到的固体转移剂支撑的石墨烯膜在300度下缓慢挥发掉松香，得到独立自支撑的石墨烯膜，其厚度为60原子层左右，透明的为10％。
(6)将石墨烯膜逐步升温到2000℃，升温速度45℃/min，维持1小时，然后给薄膜通电，电流大小为20A，维持1h。
经测试，拉曼中缺陷峰基本不存在，证明了石墨烯膜的无缺陷结构。TEM电子衍射图谱表明，石墨烯片层之间堆叠方式为乱层堆叠。其水平方向的热导率达到2100W/mK，电导率达到1.3MS/m，光电探测的波长范围达到太赫兹。
在石墨烯膜的左右两侧连接两个电极，并用控温传感器测量石墨烯电热膜的温度变化，这种石墨烯膜在大气环境下，在8V的直流电压下，只需要0.9秒就达到了稳定温度280℃，而断电后，由于石墨烯膜优异的热传导性，膜的温度在1.2秒内就降到接近室温。该石墨烯膜沿两个电极所在直线方向上，温度稳定，均在280℃左右。
将上述石墨烯膜2×2cm 2平铺于聚酰亚胺基底(热导率0.35W/mK)上，在石墨烯薄膜两端涂覆银胶电极，将两个银胶电极分别与电信号输入单元的正负极相连，构成本发明所述的纳米级声波发生器。由于该薄膜电导率高，在外加电压情况下会剧烈放热升温，撤离外加电压，薄膜热逸散速度极高，两者共同作用，使得薄膜可以快速的升降温，从而引起薄膜处空气的热震动，从而发声。因此，通过8V的直流电压的辅助加载，另外通过电信号输入单元输入指定的音频信号，以调节整体输入的电压和变化频率，便可以获得确定的空气热震动幅度，即音高；调节输入信号频率便可以调节空气热震动频率，进而发声的频率改变，发出不同的声音。
实施例3：
(1)将氧化石墨烯配制成浓度为8ug/mL氧化石墨烯水溶液，以混和纤维素酯(MCE)为基底抽滤成膜。
(2)将贴附于MCE膜的氧化石墨烯膜置于密闭容器中，80度HI高温熏 蒸8h。
(3)用蒸镀、流延等方法将融化的降冰片烯均匀涂敷在还原氧化石墨烯膜表面，并于室温下缓慢冷却。
(4)将涂敷有固体转移剂的石墨烯膜放置于异丙醇中，去除MCE膜。
(5)将上述得到的固体转移剂支撑的石墨烯膜在100度下缓慢挥发掉固体转移剂，得到独立自支撑的石墨烯膜，其厚度为200原子层左右。
(6)将石墨烯膜逐步升温到2000℃，升温速度20℃/min，维持1小时，然后给薄膜通电，电流大小为10A，维持1h。
经测试，拉曼中缺陷峰基本不存在，证明了石墨烯膜的无缺陷结构。TEM电子衍射图谱表明，石墨烯片层之间堆叠方式为乱层堆叠。其水平方向的热导率达到1800W/mK，电导率达到1.1MS/m，光电探测的波长范围达到太赫兹。
经测试，拉曼中缺陷峰基本不存在，证明了石墨烯膜的无缺陷结构。TEM电子衍射图谱表明，石墨烯片层之间堆叠方式为乱层堆叠。其水平方向的热导率达到1800W/mK，电导率达到1.1MS/m，光电探测的波长范围达到太赫兹。
在石墨烯膜的左右两侧连接两个电极，并用控温传感器测量石墨烯电热膜的温度变化，这种石墨烯膜在大气环境下，在8V的直流电压下，只需要0.6秒就达到了稳定温度300℃，而断电后，由于石墨烯膜优异的热传导性，膜的温度在1.3秒内就降到接近室温。该石墨烯膜沿两个电极所在直线方向上，温度稳定，均在300℃左右。
将上述石墨烯膜2×2cm 2平铺于聚酰亚胺基底(热导率0.35W/mK)上，在石墨烯薄膜两端涂覆银胶电极，将两个银胶电极分别与电信号输入单元的正负极相连，构成本发明所述的纳米级声波发生器。由于该薄膜电导率高，在外加电压情况下会剧烈放热升温，撤离外加电压，薄膜热逸散速度极高，两者共同作用，使得薄膜可以快速的升降温，从而引起薄膜处空气的热震动，从而发声。因此，通过8V的直流电压的辅助加载，另外通过电信号输入单元输入指定的音频信号，以调节整体输入的电压和变化频率，便可以获得确定的空气热震动幅度，即音高；调节输入信号频率便可以调节空气热震动频率，进而发声的频率改变，发出不同的声音。
实施例4：
(1)通过控制石墨烯溶液的浓度，通过抽滤方法在AAO基底膜抽滤得到超薄的还原氧化石墨烯膜；
(2)将石墨烯膜从AAO基底膜上剥离，具体为：将表面贴合有还原氧化 石墨烯膜的AAO基底膜(孔隙率为40％)，以石墨烯膜所在的面朝上，置于水面上，如图4和5a；按压AAO基底膜边缘，如图5b，AAO基底膜开始下沉，如图5c，最后，AAO基底膜沉于杯底，石墨烯膜漂浮于水面(虚线圈内)，如图5b和5d。
(3)利用一表面印有“浙江大学”的玻璃基底将漂浮于水面的石墨烯膜从下往上捞起，使得石墨烯膜平铺于基底表面，且石墨烯膜与基底之间具有一层水介质。
(4)将表面载有石墨烯膜的基底进行冷冻干燥，石墨烯膜自支撑，如图6所示，且与基底分离。经原子力显微镜测试，其厚度为4nm，如图7所示。
(5)将石墨烯膜逐步升温到2000℃，升温速度60℃/min，维持2小时，然后给薄膜通电，电流大小为20A，维持1h。
经测试，拉曼中缺陷峰基本不存在，证明了石墨烯膜的无缺陷结构。TEM电子衍射图谱表明，石墨烯片层之间堆叠方式为乱层堆叠。其水平方向的热导率达到2700W/mK(自加热发测试)，电导率达到1.7MS/m。光电探测的波长范围达到太赫兹。
在石墨烯膜的左右两侧连接两个电极，并用控温传感器测量石墨烯电热膜的温度变化，这种石墨烯膜在大气环境下，在12V的直流电压下，只需要2秒就达到了稳定温度230℃，而断电后，由于石墨烯膜优异的热传导性，膜的温度在0.5秒内就降到接近室温。该石墨烯膜沿两个电极所在直线方向上，温度稳定，均在230℃左右。
将上述石墨烯膜2×2cm 2平铺于聚酰亚胺基底(热导率0.35W/mK)上，在石墨烯薄膜两端涂覆银胶电极，将两个银胶电极分别与电信号输入单元的正负极相连，构成本发明所述的纳米级声波发生器。由于该薄膜电导率高，在外加电压情况下会剧烈放热升温，撤离外加电压，薄膜热逸散速度极高，两者共同作用，使得薄膜可以快速的升降温，从而引起薄膜处空气的热震动，从而发声。因此，通过12V的直流电压的辅助加载，另外通过电信号输入单元输入指定的音频信号，以调节整体输入的电压和变化频率，便可以获得确定的空气热震动幅度，即音高；调节输入信号频率便可以调节空气热震动频率，进而发声的频率改变，发出不同的声音。
实施例5
(1)通过控制石墨烯溶液的浓度，通过抽滤方法在AAO基底膜抽滤得到超薄的氧化石墨烯膜；
(2)将石墨烯膜从AAO基底膜上剥离，具体为：将表面贴合有氧化石墨烯膜的AAO基底膜(孔隙率为60％)，以石墨烯膜所在的面朝上，置于水面上，按压AAO基底膜边缘，AAO基底膜开始下沉，最后，AAO基底膜沉于杯底，石墨烯膜漂浮于水面，石墨烯膜成功剥离。
(3)利用一表面印有“浙江大学”的亲水硅基底(硅表面亲水处理，中心凹陷，如图8所示)将漂浮于水面的石墨烯膜从下往上捞起，使得石墨烯膜平铺于基底中心位置，石墨烯膜与凹陷的中心处具有水介质。
(4)将表面载有石墨烯膜的基底进行冷冻干燥，石墨烯膜自支撑，且与基底分离。经原子力显微镜测试，其厚度为14nm。
(5)将石墨烯膜逐步升温到2000℃，升温速度4℃/min，维持2小时，然后给薄膜通电，电流大小为1A，维持4h。
经测试，拉曼中缺陷峰基本不存在，证明了石墨烯膜的无缺陷结构。TEM电子衍射图谱表明，石墨烯片层之间堆叠方式为乱层堆叠。其水平方向的热导率达到2600W/mK，电导率达到1.5MS/m；光电探测的波长范围达到太赫兹。
需要说明的是，抽滤法是目前公认的最均匀制备石墨烯膜的方法，在一定的抽滤液量下，可以调控浓度来对石墨烯膜的厚度进行控制，厚度最低可以是一层石墨烯，随着石墨烯浓度的增加，在压力作用下，新增的石墨烯逐步填充到第一层石墨烯的间隙，使得第一层石墨烯逐步完全填充，进而发展成第二层，不断重复以上步骤，可以制备厚度跨越2层到上万层石墨烯的石墨烯纳米膜。因此，本领域技术人员可通过简单的实验参数调整即可获得厚度为4nm的石墨烯膜。
在石墨烯膜的左右两侧连接两个电极，并用控温传感器测量石墨烯电热膜的温度变化，这种石墨烯膜在大气环境下，在10V的直流电压下，只需要0.8秒就达到了稳定温度260℃，而断电后，由于石墨烯膜优异的热传导性，膜的温度在1.1秒内就降到接近室温。该石墨烯膜沿两个电极所在直线方向上，温度稳定，均在270℃左右。
将上述石墨烯膜2×2cm 2平铺于聚酰亚胺基底(热导率0.35W/mK)上，在石墨烯薄膜两端涂覆银胶电极，将两个银胶电极分别与电信号输入单元的正负极相连，构成本发明所述的纳米级声波发生器。由于该薄膜电导率高，在外加电压情况下会剧烈放热升温，撤离外加电压，薄膜热逸散速度极高，两者共同作用，使得薄膜可以快速的升降温，从而引起薄膜处空气的热震动，从而发声。因此，通过10V的直流电压的辅助加载，另外通过电信号输入单元输入指定的音频信号，以调节整体输入的电压和变化频率，便可以获得确定的空气热震动 幅度，即音高；调节输入信号频率便可以调节空气热震动频率，进而发声的频率改变，发出不同的声音。

Claims (9)

  1. 一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法，其特征在于，步骤如下：
    (1)制备独立自支撑的石墨烯膜；厚度方向，石墨烯膜的层数不大于200；
    (2)将石墨烯膜逐步升温到2000℃，升温速度不大于60℃/min，维持1-2小时，然后给薄膜通电，电流大小为1-20A，维持1-4h。
  2. 根据权利要求1所述的制备方法，其特征在于，采用固体转移法制备独立自支撑的石墨烯膜。
  3. 根据权利要求2所述的方法，其特征在于，所述固体转移法包括如下步骤：
    (1.1)将氧化石墨烯配制成浓度为0.5-10ug/mL氧化石墨烯水溶液，以混和纤维素酯(MCE)为基底抽滤成膜；
    (1.2)将贴附于MCE膜的氧化石墨烯膜置于密闭容器中，60-100度HI高温熏蒸1-10h；
    (1.3)将融化的固体转移剂均匀涂敷在还原氧化石墨烯膜表面，并于室温下冷却；
    (1.4)将涂敷有固体转移剂的石墨烯膜放置于MCE膜的良溶剂中，刻蚀掉MCE膜；
    (1.5)将上述得到的固体转移剂支撑的石墨烯膜在固体转移剂挥发的温度下挥发掉固体转移剂，得到独立自支撑的石墨烯膜。
  4. 如权利要求3所述的方法，其特征在于，所述的固体转移剂，选自如下物质:石蜡、氯化铝、碘、萘、三氧化二砷、五氯化磷、丙烯酰胺、三氯化铁、硫、红磷、氯化铵、碳酸氢铵、碘化钾、降冰片烯、咖啡因、三聚氰胺、水、松香、叔丁醇、三氧化硫等可在某种条件下升华或者挥发的小分子固态物质；所述MCE膜的良溶剂选自丙酮、正丁醇、乙醇、异丙醇中的一种或多种。
  5. 根据权利要求1所述的方法，其特征在于，采用水剥离方法制备独立自支撑的石墨烯膜，制备方法如下：
    (1.1)将石墨烯膜从AAO基底膜上剥离，具体为：将表面贴合有石墨烯膜的AAO基底膜以石墨烯膜所在的面朝上，置于水面上；按压AAO基底膜，使得AAO基底膜下沉，石墨烯膜漂浮于水面；
    (1.2)利用一基底将漂浮于水面的石墨烯膜从下往上捞起，使得石墨烯膜平铺于基底表面，且石墨烯膜与基底之间具有一层水介质；
    (1.3)将表面载有石墨烯膜的基底进行冷冻干燥，石墨烯膜自支撑，且与基底分离。
  6. 根据权利要求5所述的方法，其特征在于，所述AAO基底膜的表面的孔隙率不小于40％。
  7. 根据权利要求5所述的方法，其特征在于，步骤2中所述的基底为疏水基底。
  8. 根据权利要求5所述的方法，其特征在于，步骤2中所述的基底的上表面具有凹陷区域。
  9. 如权利要求1所述方法制备得到的石墨烯纳米膜的应用，其特征在于，所述应用为：应用于纳米级声波发生器；所述的纳米级声波发生器包括热导率低于200W/mK的基底、平铺于基底上的无缺陷乱层堆叠石墨烯纳米膜，以及电信号输入单元和两个音频电流输入用银胶电极，两个银胶电极分别设置在声波发生薄膜的两端，声波发生薄膜、两个银胶电极和电信号输入单元串联形成回路。
PCT/CN2020/083030 2019-03-17 2020-04-02 一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用 Ceased WO2020187332A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910200722.4 2019-03-17
CN201910200722.4A CN109928387A (zh) 2019-03-17 2019-03-17 一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用

Publications (1)

Publication Number Publication Date
WO2020187332A1 true WO2020187332A1 (zh) 2020-09-24

Family

ID=66987417

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/083030 Ceased WO2020187332A1 (zh) 2019-03-17 2020-04-02 一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用

Country Status (2)

Country Link
CN (1) CN109928387A (zh)
WO (1) WO2020187332A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118183724A (zh) * 2024-03-21 2024-06-14 松山湖材料实验室 一种调控悬空石墨烯薄膜张力的方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109928387A (zh) * 2019-03-17 2019-06-25 杭州高烯科技有限公司 一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用
CN111359449B (zh) * 2020-03-03 2021-05-18 清华大学 电活性膜及其制备方法
CN112071978B (zh) * 2020-09-14 2022-08-09 杭州高烯科技有限公司 一种大面积石墨烯基磁阻器件的制备方法
CN112179868B (zh) * 2020-09-25 2022-05-13 杭州高烯科技有限公司 一种光调制太赫兹分子检测器件的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844760A (zh) * 2010-04-29 2010-09-29 中国科学院化学研究所 一种还原氧化石墨烯的制备方法与应用
CN107857252A (zh) * 2017-10-13 2018-03-30 浙江大学 一种独立自支撑石墨烯膜的制备方法
CN108892133A (zh) * 2018-07-10 2018-11-27 浙江大学 一种纳米级声波发生薄膜及纳米级声波发生器
CN109928387A (zh) * 2019-03-17 2019-06-25 杭州高烯科技有限公司 一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用
CN109950048A (zh) * 2019-03-17 2019-06-28 杭州高烯科技有限公司 一种石墨烯基薄膜太阳能电池

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10343916B2 (en) * 2010-06-16 2019-07-09 The Research Foundation For The State University Of New York Graphene films and methods of making thereof
TWI523077B (zh) * 2013-10-29 2016-02-21 財團法人金屬工業研究發展中心 石墨烯特性調整方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844760A (zh) * 2010-04-29 2010-09-29 中国科学院化学研究所 一种还原氧化石墨烯的制备方法与应用
CN107857252A (zh) * 2017-10-13 2018-03-30 浙江大学 一种独立自支撑石墨烯膜的制备方法
CN108892133A (zh) * 2018-07-10 2018-11-27 浙江大学 一种纳米级声波发生薄膜及纳米级声波发生器
CN109928387A (zh) * 2019-03-17 2019-06-25 杭州高烯科技有限公司 一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用
CN109950048A (zh) * 2019-03-17 2019-06-28 杭州高烯科技有限公司 一种石墨烯基薄膜太阳能电池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QI, Z.J. ET AL.: "Electronic Transport of Recrystallized Freestanding Graphene Nanoribbons", ACS NANO, vol. 9, no. 4, 4 March 2015 (2015-03-04), XP055645286, ISSN: 1936-086X, DOI: 20200518154944A *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118183724A (zh) * 2024-03-21 2024-06-14 松山湖材料实验室 一种调控悬空石墨烯薄膜张力的方法和应用

Also Published As

Publication number Publication date
CN109928387A (zh) 2019-06-25

Similar Documents

Publication Publication Date Title
Ma et al. Recent advances in preparation and application of laser-induced graphene in energy storage devices
CN109928387A (zh) 一种电催化制备无缺陷乱层堆叠石墨烯纳米膜的方法与应用
CN107857252B (zh) 一种独立自支撑石墨烯膜的制备方法
CN107651673B (zh) 一种纳米级厚度独立自支撑褶皱石墨烯膜及其制备方法
CN107857251B (zh) 一种纳米级厚度独立自支撑发泡石墨烯膜及其制备方法
CN109911888B (zh) 一种无缺陷乱层堆叠石墨烯纳米膜的制备方法与应用
CN110564087B (zh) 一种直立型石墨烯-高分子聚合物复合材料及其制备方法
CN108892133B (zh) 一种纳米级声波发生薄膜及纳米级声波发生器
CN106629834A (zh) 一种再结晶法制备铅卤钙钛矿纳米线的方法
CN105399139B (zh) 一种诱导二氧化钛纳米颗粒自组装形成珍珠链结构的方法
Li et al. Flexible Ti3C2Tx MXene Film Coupled with Defect‐Rich MoO3 Spacer‐Contributor Toward High‐Performance Wearable Energy Storage
WO2019071943A1 (zh) 独立自支撑石墨烯膜及其制备方法
CN108217627B (zh) 一种独立自支撑石墨烯碳管复合膜的制备方法
WO2019169456A1 (en) A method of forming porous graphene-based structures
WO2022218088A1 (zh) 用于制备多孔石墨烯膜的方法、多孔石墨烯膜和电极
CN108862263B (zh) 基于电化学氧化还原制备类生物三维微纳米多孔石墨烯的方法
CN108955860B (zh) 一种高强石墨烯膜基声波探测器
CN108821264B (zh) 一种纳米级声波发生器
CN109928385A (zh) 一种无缺陷密堆积石墨烯亚微米薄膜的制备方法与应用
CN109821721A (zh) 一种基于无缺陷乱层堆叠石墨烯纳米膜的纳米级声波发生器
CN108962628A (zh) 一种利用半导体激光器直写制备柔性电容器的方法
CN108793129B (zh) 一种异质石墨烯膜及其制备方法
CN109950048A (zh) 一种石墨烯基薄膜太阳能电池
CN112071978A (zh) 一种大面积石墨烯基磁阻器件的制备方法
CN108862246B (zh) 一种音色可调的纳米级声波发生器

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20773164

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20773164

Country of ref document: EP

Kind code of ref document: A1