WO2020006942A1 - Method for preparing heterostructured porous graphene oxide film, graphene film and electric generator - Google Patents

Method for preparing heterostructured porous graphene oxide film, graphene film and electric generator Download PDF

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WO2020006942A1
WO2020006942A1 PCT/CN2018/112587 CN2018112587W WO2020006942A1 WO 2020006942 A1 WO2020006942 A1 WO 2020006942A1 CN 2018112587 W CN2018112587 W CN 2018112587W WO 2020006942 A1 WO2020006942 A1 WO 2020006942A1
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graphene oxide
film
porous
oxide film
aerogel
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PCT/CN2018/112587
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Chinese (zh)
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曲良体
程虎虎
黄亚鑫
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清华大学
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    • 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
    • C01B32/198—Graphene oxide
    • 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

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  • the invention relates to the technical field of functional materials, in particular to a method for preparing a porous graphene oxide film with a heterostructure, a graphene film, and a generator.
  • Graphene is a two-dimensional planar structure material with a single atomic layer. It has a large specific surface area, excellent mechanical and electrical properties, and has been widely used in the research of energy conversion and storage, gas sensing, and bionic smart devices.
  • Graphene oxide is graphene rich in oxygen functional groups, and its surface is rich in carbonyl, hydroxyl, and carboxyl groups. Assembling graphene oxide into fibrous, thin film and three-dimensional structural materials will greatly expand the application field of graphene materials.
  • graphene oxide can adsorb moisture in the air, interact with its oxygen-containing functional groups, and generate freely moving hydronium ions, thereby changing the internal dielectric properties. If a heterogeneous structure can be built inside the graphene oxide assembly material, a heterogeneous distribution of internal hydrogen ions will be achieved. The heterogeneous distribution can cause the hydronium ions to spontaneously migrate from a high concentration direction to a low concentration direction, but an oversized graphene oxide sheet cannot move freely. With the migration of hydrated hydrogen ions, positive and negative charges will be separated inside the material, a potential difference will be formed inside the material, and external electricity will be generated.
  • Graphene oxide can spontaneously adsorb water molecules in the air. Therefore, if a heterogeneous structure inside the graphene oxide assembly can be constructed, it is possible to realize a device that spontaneously generates electricity in the air. Related research is still blank.
  • the present invention aims to solve at least one of the technical problems in the related technology to a certain extent.
  • a first object of the present invention is to propose a method for preparing a porous graphene oxide film with a heterostructure, which can effectively improve the practicability, economy, and efficiency of the preparation, and is simple and easy to implement.
  • a second object of the present invention is to provide a graphene film.
  • a third object of the present invention is to provide a generator.
  • an embodiment of the present invention provides a method for preparing a porous graphene oxide film with a heterostructure, including the following steps: freeze-drying and preparing a graphene oxide solution to obtain a graphene oxide aerogel; The bottom of the graphene oxide aerogel is heated and reduced to obtain a reduced graphene oxide aerogel at the bottom portion; pressure is applied to the reduced graphene oxide aerogel at the bottom portion in a vertical direction to obtain a porous graphite oxide with a heterostructure. Olefin film.
  • the method for preparing a heterostructured porous graphene oxide film obtains a heterostructured porous graphene oxide film by freeze-drying a graphene oxide solution, heating and reducing the bottom, and applying a vertical pressure.
  • the required raw material synthesis technology is mature. , Wide range of sources, cheap and easy to obtain, can be produced in large quantities, thereby effectively improving the practicability, economy and efficiency of preparation, simple and easy to achieve.
  • the method for preparing a heterostructured porous graphene oxide film according to the above embodiment of the present invention may also have the following additional technical features:
  • the graphene oxide solution preparation process includes: stirring and mixing 9g of graphite powder, 240mL of concentrated sulfuric acid, and 4.5g of sodium nitrate in an ice bath state; adding 27g of high manganese Acid potassium, and continue to stir for 1 hour; stir for two hours after heating to 30 ° C, and add 450 mL of deionized water after stirring; stir for 20 minutes after heating to 90 ° C, and add 1500 mL of deionized water after stirring; continue to stir and Cool naturally to room temperature, and add 60 mL of hydrogen peroxide after cooling to room temperature; wash with centrifugation to obtain the graphene oxide solution.
  • the freeze-drying time is 24 to 72 hours.
  • the heating and reducing the bottom of the graphene oxide aerogel to obtain a partially reduced graphene oxide aerogel at the bottom further includes: The gel is placed on the surface of a heat source and heated from the bottom of the graphene oxide aerogel, and the oxygen-containing functional group of the graphene oxide aerogel is partially decomposed to obtain a partially reduced graphene oxide aerogel at the bottom.
  • the heating temperature is 250 to 450 ° C.
  • the heating time is 5 to 60 minutes.
  • the thickness of the heterostructured porous graphene oxide film is 50-150 ⁇ m.
  • an embodiment of the second aspect of the present invention proposes a graphene film, which is prepared by using the above-mentioned method for preparing a porous graphene oxide film with a heterostructure.
  • the graphene film has a porous structure and includes an upper part.
  • the lower half wherein the upper half is graphene oxide, and the graphene oxide includes a uniformly distributed oxygen-containing functional group inside; the lower half is partially reduced graphene oxide, and the partially reduced oxide
  • the inside of graphene includes oxygen-containing functional groups distributed in a gradient along the film normal direction, and the distribution direction increases from bottom to top.
  • the graphene film according to the embodiment of the present invention is composed of two integrated parts, the oxygen-containing functional groups of the graphene film are heterogeneously distributed along the film normal direction, and can absorb water molecules in the ambient air, spontaneously form an internal electric field, generate electric energy, and output Observable voltage; the heterostructured porous graphene oxide film has a special structure, high quality, strong electricity generation capacity, and good stability.
  • an embodiment of the third aspect of the present invention provides a generator, which adopts the graphene film described above, and connects the upper and lower surfaces of the graphene film with a metal electrode, and the generator is a metal -Heterostructure porous graphene oxide film-metal sandwich structure, and generates voltage spontaneously in the air.
  • the generator of the embodiment of the present invention is obtained by connecting the upper and lower surfaces of the heterostructured porous graphene oxide film with metal electrodes, respectively.
  • the sandwich-structure generator can spontaneously generate an internal potential in the air, and the electrical energy generation process does not require specific stimulation. Environmental protection, no pollution.
  • the generator according to the above embodiment of the present invention may also have the following additional technical features:
  • the voltage of the spontaneously generated voltage is 20 to 500 mV.
  • the relative humidity of the air is 5 to 100%.
  • FIG. 1 is a flowchart of a method for preparing a heterostructured porous graphene oxide film according to an embodiment of the present invention
  • FIG. 2 is a picture of a graphene oxide aerogel according to an embodiment of the present invention.
  • FIG. 3 is a picture of a partially reduced graphene oxide gel at the bottom according to an embodiment of the present invention.
  • FIG. 4 is a scanning electron microscope photograph of a cross-section of a heterostructured porous graphene oxide film according to an embodiment of the present invention.
  • FIG. 5 is a schematic diagram of the atomic ratio of the O / C element in the electron spectrum data of the normal structure porous graphene oxide film along the normal direction according to an embodiment of the present invention
  • FIG. 6 is a schematic diagram of a metal / heterostructure porous graphene oxide film / metal sandwich structure generator according to an embodiment of the present invention
  • FIG. 7 is a voltage curve diagram of a sandwich-structure generator according to an embodiment of the present invention, which can spontaneously absorb moisture in the air and generate a relative humidity of 5% in an atmospheric environment;
  • FIG. 8 is a voltage curve diagram of a sandwich-structure generator according to an embodiment of the present invention, which can spontaneously absorb moisture in the air and generate an atmospheric environment with a relative humidity of 5%;
  • FIG. 9 is a voltage curve diagram of a sandwich-structured generator according to an embodiment of the present invention, which can spontaneously absorb moisture in the air, and generate a relative humidity of 100% in an atmospheric environment;
  • FIG. 10 is a schematic diagram of 60 generator stacking and series assembly devices according to an embodiment of the present invention.
  • FIG. 11 is a photo of a linear structure connected in series and packaged according to an embodiment of the present invention.
  • FIG. 12 is a photograph of a device connected in series and packaged in a planar structure according to an embodiment of the present invention.
  • FIG. 1 is a flowchart of a method for preparing a heterostructured porous graphene oxide film according to an embodiment of the present invention.
  • the method for preparing the heterostructured porous graphene oxide film includes the following steps:
  • step S101 the graphene oxide solution is prepared by freeze-drying to obtain a graphene oxide aerogel.
  • a graphene oxide solution (3-15 mg / mL) is freeze-dried by using a freeze-drying method to prepare a graphene oxide aerogel (3-15 mg / cm 3 ).
  • the freeze-drying time is 24 to 72 hours.
  • the graphene oxide solution preparation process includes: stirring and mixing 9g of graphite powder, 240mL of concentrated sulfuric acid, and 4.5g of sodium nitrate in an ice bath state; adding 27g of potassium permanganate And continue stirring for 1 hour; after heating to 30 ° C, stir for two hours, and add 450mL of deionized water after stirring; after heating to 90 ° C, stir for 20 minutes, and add 1500mL of deionized water after stirring; continue to stir and naturally cool After reaching room temperature, 60 mL of hydrogen peroxide was added after cooling to room temperature; washing with centrifugation was performed to obtain a graphene oxide solution. It should be noted that in the process of adding potassium permanganate, it should be added slowly to avoid being too fast.
  • step S102 the bottom of the graphene oxide aerogel is heated and reduced to obtain a partially reduced graphene oxide aerogel at the bottom.
  • the graphene oxide aerogel is heated and reduced from the bottom to obtain a partially reduced graphene oxide aerogel at the bottom, further comprising: placing the graphene oxide aerogel on a heat source.
  • the surface is heated from the bottom of the graphene oxide aerogel, and the oxygen-containing functional group at the bottom of the graphene oxide aerogel is partially decomposed to obtain a partially reduced graphene oxide aerogel at the bottom.
  • the heating temperature is 250-450 ° C, and the heating time is 5-60 minutes.
  • the graphene oxide aerogel is placed on the surface of the heat source, and is heated and reduced from the bottom direction, the heating temperature is 250-450 ° C, and the heating time is 5-60 minutes; the bottom of the graphene oxide aerogel First it is heated, the oxygen-containing functional groups are decomposed, and a partially reduced graphene oxide is obtained at the bottom. The upper part has no obvious change due to being away from the heat source; a reduced graphene oxide aerogel is obtained at the bottom.
  • step S103 pressure is applied to the reduced graphene oxide aerogel in the bottom portion in a vertical direction to obtain a porous graphene oxide film with a heterostructure.
  • the thickness of the heterostructured porous graphene oxide film is 50-150 ⁇ m.
  • the graphene oxide aerogel that is partially reduced at the bottom is pressed with a vertical direction to compress the sample into a film having a thickness of 50 to 150 ⁇ m, and finally a porous graphene oxide film with a heterostructure is obtained.
  • a heterostructured porous graphene oxide film is obtained by freeze-drying a graphene oxide solution, heating and reducing at the bottom, and applying pressure vertically, and preparing the required raw material synthesis
  • the technology is mature, with a wide range of sources, cheap and readily available, and can be produced in large quantities, thereby effectively improving the practicability, economy and efficiency of the preparation, and simple and easy to achieve.
  • a graphene film is also provided in an embodiment of the present invention.
  • the graphene film will be described in detail below.
  • the graphene film is prepared by using the above-mentioned heterostructure porous graphene oxide film preparation method.
  • the graphene film has a porous structure and includes an upper half and a lower half, wherein the upper half is graphene oxide and graphite oxide.
  • the inside of the ene includes uniformly distributed oxygen-containing functional groups; the lower part is partially reduced graphene oxide, and the partially-reduced inside of the graphene oxide includes oxygen-containing functional groups that are distributed in a gradient along the film normal direction, and the distribution direction increases from bottom to top.
  • the heterostructured porous graphene oxide film has a porous structure with a total thickness of 50-150 ⁇ m.
  • the film is composed of two integrated parts: the lower part is reduced graphene oxide, and the internal oxygen-containing functional groups The oxygen-containing functions are distributed in a gradient along the normal direction of the film, increasing from bottom to top; the upper part is graphene oxide, and the oxygen-containing functional groups are uniformly distributed inside.
  • the heterogeneous structure of the membrane makes its internal chemical composition and oxygen-containing functional groups in a regular distribution.
  • heterostructured porous graphene oxide film the graphene oxide film is placed in the atmosphere, can spontaneously absorb moisture in the air and interact with oxygen-containing functional groups, induce charge separation in its heterostructure, and then generate electric energy.
  • the graphene film according to the embodiment of the present invention is composed of two integrated parts, the oxygen-containing functional groups of the graphene film are heterogeneously distributed along the film normal direction, and can absorb water molecules in ambient air, spontaneously form an internal electric field, and generate electrical energy. , The output of considerable voltage; the heterostructured porous graphene oxide film has a special structure, high quality, strong electricity generation capacity, and good stability.
  • the embodiment of the present invention also proposes the application of a heterostructured porous graphene oxide film.
  • the graphene film can be applied to a spontaneous electricity generating generator.
  • the generator provided by the embodiment of the present invention will be described in detail below.
  • the generator is obtained by connecting the upper and lower surfaces of the graphene film to a metal electrode, respectively.
  • the generator has a metal-heterostructure porous graphene oxide film-metal sandwich structure and is in the air. Spontaneous voltage generation.
  • the voltage of generating the voltage spontaneously is 20 to 500 mV.
  • the relative humidity of the air is 5 to 100%.
  • a heterostructured porous graphene oxide film which is used in a spontaneous power generator, is specifically: connecting the upper and lower surfaces of the heterostructured porous graphene oxide film with a metal electrode, respectively, to form a metal / Heterostructure porous graphene oxide film / metal sandwich structure generator; sandwich structure generator can generate voltage spontaneously in the air, and the voltage range is 20 ⁇ 500mV.
  • Multiple power generation devices are stacked and assembled in series, and placed in the air, it can generate a voltage of 15V spontaneously, which can charge commercial capacitors, and then power electronic components.
  • the generator can be connected in series and packaged in a linear or planar structure to obtain a bendable, wearable, and rollable self-generating device.
  • the relative humidity of the air ranges from 5 to 100%.
  • the generator according to the embodiment of the present invention is obtained by connecting the upper and lower surfaces of the heterostructured porous graphene oxide film with metal electrodes, respectively.
  • the sandwich structure generator can generate an internal potential spontaneously in the air, and the electrical energy generation process does not require specific stimulation. , Environmental protection, no pollution.
  • Humidity (20% humidity) can generate a voltage of 15V spontaneously in the environment; the above series device can charge the capacitor to 3V, and can charge a single commercial LED lamp (red) after charging.
  • Eight generators were connected in series and packaged in a linear structure ( Figure 11) to obtain a self-generating device that can be bent and worn.
  • Twenty generators were connected in series and packaged in a planar structure (Fig. 12) to obtain a rollable self-generating device.
  • the upper and lower surfaces of the heterostructured porous graphene oxide film are respectively connected with the metal electrodes to form a metal / heterostructured porous graphene oxide film / metal sandwich structure generator; the sandwich structure generator may be in the air. Spontaneously absorb moisture, generate internal potential, and output voltage externally; in an atmospheric environment with a relative humidity of 25%, the generated voltage is 150mV.
  • the upper and lower surfaces of the heterostructured porous graphene oxide film are respectively connected with the metal electrodes to form a metal / heterostructured porous graphene oxide film / metal sandwich structure generator; the sandwich structure generator may be in the air. Spontaneously absorb moisture, generate internal potential, and output voltage externally; in an atmospheric environment with a relative humidity of 25%, the generated voltage is 25mV.
  • the preparation method described in the embodiment of the present invention is simple, the raw material synthesis technology used is mature, the source is wide, cheap and readily available, and it can be produced in large quantities.
  • the heterostructured porous graphene oxide film of the embodiment of the present invention is internally composed of two integrated parts, and its oxygen-containing functional groups are heterogeneously distributed along the film normal direction.
  • the film can absorb water molecules in the ambient air and spontaneously form an intrinsic The electric field generates electric energy and outputs considerable voltage.
  • the heterostructured porous graphene oxide film has a special structure, high quality, strong power generation capacity, and good stability.
  • the upper and lower surfaces of the heterostructured porous graphene oxide film of the embodiment of the present invention are respectively connected with a metal electrode to form a metal / heterostructured porous graphene oxide film / metal sandwich structure generator; the sandwich structure generator can be in air
  • the spontaneous potential is generated in the medium, and a voltage of 20 to 500 mV is output.
  • Multiple devices can be easily connected in series and output a voltage of 15V to power commercial electronic components. Its electrical energy generation process does not require specific stimulation, is green and environmentally friendly, and has no pollution.
  • first and second are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as “first” and “second” may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "a plurality” is at least two, for example, two, three, etc., unless it is specifically and specifically defined otherwise.

Abstract

Disclosed are a method for preparing a heterostructured porous graphene oxide film, a graphene film and an electric generator, wherein the method includes the following steps: freeze-drying a graphene oxide solution to obtain a graphene oxide aerogel; heating the graphene oxide aerogel from the bottom to reduce same in order to obtain a bottom partially-reduced graphene oxide aerogel; and applying pressure to the bottom partially-reduced graphene oxide aerogel in the vertical direction to obtain the heterostructured porous graphene oxide film. The method provides the heterostructured porous graphene oxide film by carrying out freeze drying, bottom heating reduction and vertical pressure application. The raw materials required for the preparation are mature in synthesis technology, widely available in terms f source, inexpensive, are easily obtained, and can be mass-produced, thereby effectively improving the practicability, economy and efficiency of preparation, and being simple and easily implemented.

Description

异质结构多孔氧化石墨烯膜制备方法、石墨烯膜及发电机Method for preparing porous graphene oxide film with heterostructure, graphene film and generator
相关申请的交叉引用Cross-reference to related applications
本申请要求清华大学于2018年07月03日提交的、发明名称为“异质结构多孔氧化石墨烯膜制备方法、石墨烯膜及发电机”的、中国专利申请号“201810715882.8”的优先权。This application claims the priority of Chinese Patent Application No. “201810715882.8” filed by Tsinghua University on July 3, 2018, with the invention name “Heterostructure porous graphene oxide film preparation method, graphene film and generator”.
技术领域Technical field
本发明涉及功能材料技术领域，特别涉及一种异质结构多孔氧化石墨烯膜制备方法、石墨烯膜及发电机。The invention relates to the technical field of functional materials, in particular to a method for preparing a porous graphene oxide film with a heterostructure, a graphene film, and a generator.
背景技术Background technique
石墨烯是一种单原子层二维平面结构材料，其具有巨大的比表面积，优异的力学和电学性能，已经被广泛应用于能量转换和储存、气体传感、仿生智能器件等的研究中。氧化石墨烯是富含有氧官能团的石墨烯，其表面含有丰富的羰基、羟基和羧基等。将氧化石墨烯组装成纤维状、薄膜状和三维结构材料，会极大的拓展石墨烯材料的应用领域。Graphene is a two-dimensional planar structure material with a single atomic layer. It has a large specific surface area, excellent mechanical and electrical properties, and has been widely used in the research of energy conversion and storage, gas sensing, and bionic smart devices. Graphene oxide is graphene rich in oxygen functional groups, and its surface is rich in carbonyl, hydroxyl, and carboxyl groups. Assembling graphene oxide into fibrous, thin film and three-dimensional structural materials will greatly expand the application field of graphene materials.
研究已经证明，氧化石墨烯能够吸附空气中的水分，与其含氧官能团作用，产生可自由移动的水合氢离子，从而改变内部介电性质。如果能够在氧化石墨烯组装材料内部构建异质结构，将会实现内部水合氢离子的异质分布。该异质分布能够使水合氢离子自发的从高浓度方向向低浓度方向迁移，而体积过大的氧化石墨烯片却无法自由移动。随着水合氢离子的迁移，正负电荷会在材料内部分离，在材料内部形成电势差，对外产生电能。Studies have shown that graphene oxide can adsorb moisture in the air, interact with its oxygen-containing functional groups, and generate freely moving hydronium ions, thereby changing the internal dielectric properties. If a heterogeneous structure can be built inside the graphene oxide assembly material, a heterogeneous distribution of internal hydrogen ions will be achieved. The heterogeneous distribution can cause the hydronium ions to spontaneously migrate from a high concentration direction to a low concentration direction, but an oversized graphene oxide sheet cannot move freely. With the migration of hydrated hydrogen ions, positive and negative charges will be separated inside the material, a potential difference will be formed inside the material, and external electricity will be generated.
氧化石墨烯在空气中能够自发的吸附水分子，因此，若能够构建氧化石墨烯组装体内部异质结构，有可能会实现在空气中自发产生电能的器件。目前相关研究还处于空白。Graphene oxide can spontaneously adsorb water molecules in the air. Therefore, if a heterogeneous structure inside the graphene oxide assembly can be constructed, it is possible to realize a device that spontaneously generates electricity in the air. Related research is still blank.
发明内容Summary of the invention
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。The present invention aims to solve at least one of the technical problems in the related technology to a certain extent.
为此，本发明的第一个目的在于提出一种异质结构多孔氧化石墨烯膜制备方法，该方法可以有效提高制备的实用性、经济性和效率，简单易实现。For this reason, a first object of the present invention is to propose a method for preparing a porous graphene oxide film with a heterostructure, which can effectively improve the practicability, economy, and efficiency of the preparation, and is simple and easy to implement.
本发明的第二个目的在于提出一种石墨烯膜。A second object of the present invention is to provide a graphene film.
本发明的第三个目的在于提出一种发电机。A third object of the present invention is to provide a generator.
为达到上述目的，本发明一方面实施例提出了一种异质结构多孔氧化石墨烯膜制备方法，包括以下步骤：对氧化石墨烯溶液冷冻干燥制备，以得到氧化石墨烯气凝胶；将所述 氧化石墨烯气凝胶底部加热还原，以得到底部部分还原的氧化石墨烯气凝胶；对所述底部部分还原的氧化石墨烯气凝胶垂直方向施加压力，以得到异质结构多孔氧化石墨烯膜。In order to achieve the above object, an embodiment of the present invention provides a method for preparing a porous graphene oxide film with a heterostructure, including the following steps: freeze-drying and preparing a graphene oxide solution to obtain a graphene oxide aerogel; The bottom of the graphene oxide aerogel is heated and reduced to obtain a reduced graphene oxide aerogel at the bottom portion; pressure is applied to the reduced graphene oxide aerogel at the bottom portion in a vertical direction to obtain a porous graphite oxide with a heterostructure. Olefin film.
本发明实施例的异质结构多孔氧化石墨烯膜制备方法，通过对氧化石墨烯溶液冷冻干燥、底部加热还原、垂直施加压力得到异质结构多孔氧化石墨烯膜，制备所需的原材料合成技术成熟，来源广泛，廉价易得，可以大批量生产，从而有效提高制备的实用性、经济性和效率，简单易实现。The method for preparing a heterostructured porous graphene oxide film according to the embodiment of the present invention obtains a heterostructured porous graphene oxide film by freeze-drying a graphene oxide solution, heating and reducing the bottom, and applying a vertical pressure. The required raw material synthesis technology is mature. , Wide range of sources, cheap and easy to obtain, can be produced in large quantities, thereby effectively improving the practicability, economy and efficiency of preparation, simple and easy to achieve.
另外，根据本发明上述实施例的异质结构多孔氧化石墨烯膜制备方法还可以具有以下附加的技术特征：In addition, the method for preparing a heterostructured porous graphene oxide film according to the above embodiment of the present invention may also have the following additional technical features:
进一步地，在本发明的一个实施例中，所述氧化石墨烯溶液制备过程包括：将9g石墨粉、240mL浓硫酸、4.5g的硝酸钠在并冰浴状态下搅拌混合均匀；加入27g高锰酸钾，并继续搅拌1小时；升温至30℃之后搅拌两小时，并在搅拌之后加入450mL去离子水；升温至90℃之后搅拌20分钟，并在搅拌之后加入1500mL去离子水；继续搅拌并自然冷却至室温，并在冷却至室温之后加入60mL的过氧化氢；使用离心洗涤得到所述氧化石墨烯溶液。Further, in an embodiment of the present invention, the graphene oxide solution preparation process includes: stirring and mixing 9g of graphite powder, 240mL of concentrated sulfuric acid, and 4.5g of sodium nitrate in an ice bath state; adding 27g of high manganese Acid potassium, and continue to stir for 1 hour; stir for two hours after heating to 30 ° C, and add 450 mL of deionized water after stirring; stir for 20 minutes after heating to 90 ° C, and add 1500 mL of deionized water after stirring; continue to stir and Cool naturally to room temperature, and add 60 mL of hydrogen peroxide after cooling to room temperature; wash with centrifugation to obtain the graphene oxide solution.
进一步地，在本发明的一个实施例中，所述冷冻干燥时间为24～72h。Further, in an embodiment of the present invention, the freeze-drying time is 24 to 72 hours.
进一步地，在本发明的一个实施例中，所述将所述氧化石墨烯气凝胶底部加热还原，以得到底部部分还原的氧化石墨烯气凝胶，进一步包括：将所述氧化石墨烯气凝胶放置在热源表面，从所述氧化石墨烯气凝胶底部加热，氧化石墨烯气凝胶含氧官能团部分分解，以得到底部部分还原的氧化石墨烯气凝胶。Further, in an embodiment of the present invention, the heating and reducing the bottom of the graphene oxide aerogel to obtain a partially reduced graphene oxide aerogel at the bottom further includes: The gel is placed on the surface of a heat source and heated from the bottom of the graphene oxide aerogel, and the oxygen-containing functional group of the graphene oxide aerogel is partially decomposed to obtain a partially reduced graphene oxide aerogel at the bottom.
进一步地，在本发明的一个实施例中，所述加热温度为250～450℃，加热时间为5～60分钟。Further, in an embodiment of the present invention, the heating temperature is 250 to 450 ° C., and the heating time is 5 to 60 minutes.
进一步地，在本发明的一个实施例中，所述异质结构多孔氧化石墨烯膜厚度为50～150μm。Further, in an embodiment of the present invention, the thickness of the heterostructured porous graphene oxide film is 50-150 μm.
为达到上述目的，本发明第二方面实施例提出了一种石墨烯膜，采用上述的异质结构多孔氧化石墨烯膜的制备方法制备得到，所述石墨烯膜为多孔结构，包括上半部分和下半部分，其中，所述上半部分为氧化石墨烯，所述氧化石墨烯内部包括均匀分布的含氧官能团；所述下半部分为部分还原的氧化石墨烯，所述部分还原的氧化石墨烯内部包括沿膜法线方向呈梯度分布的含氧官能团，且所述分布方向由下向上递增。In order to achieve the above object, an embodiment of the second aspect of the present invention proposes a graphene film, which is prepared by using the above-mentioned method for preparing a porous graphene oxide film with a heterostructure. The graphene film has a porous structure and includes an upper part. And the lower half, wherein the upper half is graphene oxide, and the graphene oxide includes a uniformly distributed oxygen-containing functional group inside; the lower half is partially reduced graphene oxide, and the partially reduced oxide The inside of graphene includes oxygen-containing functional groups distributed in a gradient along the film normal direction, and the distribution direction increases from bottom to top.
本发明实施例的石墨烯膜，由一体化的两部分组成，其含氧官能团沿膜法线方向呈异质分布，且可以吸收环境空气中的水分子，自发形成内在电场，产生电能，输出可观电压；该异质结构多孔氧化石墨烯膜结构特殊，质量高、产电能力强、稳定性好。The graphene film according to the embodiment of the present invention is composed of two integrated parts, the oxygen-containing functional groups of the graphene film are heterogeneously distributed along the film normal direction, and can absorb water molecules in the ambient air, spontaneously form an internal electric field, generate electric energy, and output Observable voltage; the heterostructured porous graphene oxide film has a special structure, high quality, strong electricity generation capacity, and good stability.
为达到上述目的，本发明第三方面实施例提出了一种发电机，采用上述的石墨烯膜， 将所述石墨烯膜的上、下表面分别与金属电极连接得到，所述发电机为金属-异质结构多孔氧化石墨烯膜-金属的三明治结构，并在空气中自发产生电压。In order to achieve the above object, an embodiment of the third aspect of the present invention provides a generator, which adopts the graphene film described above, and connects the upper and lower surfaces of the graphene film with a metal electrode, and the generator is a metal -Heterostructure porous graphene oxide film-metal sandwich structure, and generates voltage spontaneously in the air.
本发明实施例的发电机，通过异质结构多孔氧化石墨烯膜的上、下表面分别与金属电极连接得到，三明治结构发电机可以在空气中自发产生内在电势，且电能产生过程无需特定刺激，绿色环保，无污染。The generator of the embodiment of the present invention is obtained by connecting the upper and lower surfaces of the heterostructured porous graphene oxide film with metal electrodes, respectively. The sandwich-structure generator can spontaneously generate an internal potential in the air, and the electrical energy generation process does not require specific stimulation. Environmental protection, no pollution.
另外，根据本发明上述实施例的发电机还可以具有以下附加的技术特征：In addition, the generator according to the above embodiment of the present invention may also have the following additional technical features:
进一步地，在本发明的一个实施例中，所述自发产生电压的电压为20～500mV。Further, in an embodiment of the present invention, the voltage of the spontaneously generated voltage is 20 to 500 mV.
进一步地，在本发明的一个实施例中，所述空气相对湿度为5～100％。Further, in an embodiment of the present invention, the relative humidity of the air is 5 to 100%.
本发明附加的方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。Additional aspects and advantages of the present invention will be given in part in the following description, part of which will become apparent from the following description, or be learned through the practice of the present invention.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
本发明上述的和/或附加的方面和优点从下面结合附图对实施例的描述中将变得明显和容易理解，其中：The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the following description of the embodiments with reference to the accompanying drawings, in which:
图1为根据本发明一个实施例的异质结构多孔氧化石墨烯膜制备方法的流程图；FIG. 1 is a flowchart of a method for preparing a heterostructured porous graphene oxide film according to an embodiment of the present invention; FIG.
图2为根据本发明一个实施例的氧化石墨烯气凝胶图片；2 is a picture of a graphene oxide aerogel according to an embodiment of the present invention;
图3为根据本发明一个实施例的底部部分还原的氧化石墨烯凝胶图片；FIG. 3 is a picture of a partially reduced graphene oxide gel at the bottom according to an embodiment of the present invention; FIG.
图4为根据本发明一个实施例的异质结构多孔氧化石墨烯膜横截面扫描电子显微镜照片；4 is a scanning electron microscope photograph of a cross-section of a heterostructured porous graphene oxide film according to an embodiment of the present invention;
图5为根据本发明一个实施例的异质结构多孔氧化石墨烯膜沿法线方向电子能谱数据中O/C元素原子比示意图；5 is a schematic diagram of the atomic ratio of the O / C element in the electron spectrum data of the normal structure porous graphene oxide film along the normal direction according to an embodiment of the present invention;
图6为根据本发明一个实施例的金属/异质结构多孔氧化石墨烯膜/金属的三明治结构发电机示意图；6 is a schematic diagram of a metal / heterostructure porous graphene oxide film / metal sandwich structure generator according to an embodiment of the present invention;
图7为根据本发明一个实施例的三明治结构发电机在空气中可自发吸收水分，在相对湿度湿度为5％的大气环境中产生的电压曲线图；FIG. 7 is a voltage curve diagram of a sandwich-structure generator according to an embodiment of the present invention, which can spontaneously absorb moisture in the air and generate a relative humidity of 5% in an atmospheric environment;
图8为根据本发明一个实施例的三明治结构发电机在空气中可自发吸收水分，在相对湿度湿度为5％的大气环境中，产生的电压曲线图；FIG. 8 is a voltage curve diagram of a sandwich-structure generator according to an embodiment of the present invention, which can spontaneously absorb moisture in the air and generate an atmospheric environment with a relative humidity of 5%;
图9为根据本发明一个实施例的三明治结构发电机在空气中可自发吸收水分，在相对湿度湿度为100％的大气环境中，产生的电压曲线图；FIG. 9 is a voltage curve diagram of a sandwich-structured generator according to an embodiment of the present invention, which can spontaneously absorb moisture in the air, and generate a relative humidity of 100% in an atmospheric environment;
图10为根据本发明一个实施例的60个所述发电机堆叠串联组装器件示意图；FIG. 10 is a schematic diagram of 60 generator stacking and series assembly devices according to an embodiment of the present invention; FIG.
图11为根据本发明一个实施例的线性结构串联并封装器件照片；FIG. 11 is a photo of a linear structure connected in series and packaged according to an embodiment of the present invention; FIG.
图12为根据本发明一个实施例的以平面结构串联并封装器件照片。FIG. 12 is a photograph of a device connected in series and packaged in a planar structure according to an embodiment of the present invention.
具体实施方式detailed description
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。Hereinafter, embodiments of the present invention will be described in detail. Examples of the embodiments are shown in the drawings, wherein the same or similar reference numerals indicate the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the drawings are exemplary and are intended to explain the present invention, but should not be construed as limiting the present invention.
下面参照附图描述根据本发明实施例提出的异质结构多孔氧化石墨烯膜制备方法、石墨烯膜及发电机，首先将参照附图描述根据本发明实施例提出的。Hereinafter, a method for preparing a porous graphene oxide film with a heterostructure according to an embodiment of the present invention, a graphene film, and a generator will be described with reference to the accompanying drawings.
图1是本发明一个实施例的异质结构多孔氧化石墨烯膜制备方法的流程图。FIG. 1 is a flowchart of a method for preparing a heterostructured porous graphene oxide film according to an embodiment of the present invention.
如图1所示，该异质结构多孔氧化石墨烯膜制备方法包括以下步骤：As shown in FIG. 1, the method for preparing the heterostructured porous graphene oxide film includes the following steps:
在步骤S101中，对氧化石墨烯溶液冷冻干燥制备，以得到氧化石墨烯气凝胶。In step S101, the graphene oxide solution is prepared by freeze-drying to obtain a graphene oxide aerogel.
可以理解的是，本发明实施例采用冷冻干燥法将氧化石墨烯溶液(3～15mg/mL)进行冷冻干燥，制备得到氧化石墨烯气凝胶(3～15mg/cm 3)。其中，冷冻干燥时间为24～72h。 It can be understood that, in the embodiment of the present invention, a graphene oxide solution (3-15 mg / mL) is freeze-dried by using a freeze-drying method to prepare a graphene oxide aerogel (3-15 mg / cm 3 ). The freeze-drying time is 24 to 72 hours.
进一步地，在本发明的一个实施例中，氧化石墨烯溶液制备过程包括：将9g石墨粉、240mL浓硫酸、4.5g的硝酸钠在并冰浴状态下搅拌混合均匀；加入27g高锰酸钾，并继续搅拌1小时；升温至30℃之后搅拌两小时，并在搅拌之后加入450mL去离子水；升温至90℃之后搅拌20分钟，并在搅拌之后加入1500mL去离子水；继续搅拌并自然冷却至室温，并在冷却至室温之后加入60mL的过氧化氢；使用离心洗涤得到氧化石墨烯溶液。需要说明的是，在加入高锰酸钾的过程中，要缓慢的加入，避免过快。Further, in one embodiment of the present invention, the graphene oxide solution preparation process includes: stirring and mixing 9g of graphite powder, 240mL of concentrated sulfuric acid, and 4.5g of sodium nitrate in an ice bath state; adding 27g of potassium permanganate And continue stirring for 1 hour; after heating to 30 ° C, stir for two hours, and add 450mL of deionized water after stirring; after heating to 90 ° C, stir for 20 minutes, and add 1500mL of deionized water after stirring; continue to stir and naturally cool After reaching room temperature, 60 mL of hydrogen peroxide was added after cooling to room temperature; washing with centrifugation was performed to obtain a graphene oxide solution. It should be noted that in the process of adding potassium permanganate, it should be added slowly to avoid being too fast.
在步骤S102中，将氧化石墨烯气凝胶底部加热还原，以得到底部部分还原的氧化石墨烯气凝胶。In step S102, the bottom of the graphene oxide aerogel is heated and reduced to obtain a partially reduced graphene oxide aerogel at the bottom.
进一步地，在本发明的一个实施例中，将氧化石墨烯气凝胶从底部加热还原，以得到底部部分还原的氧化石墨烯气凝胶，进一步包括：将氧化石墨烯气凝胶放置在热源表面，从氧化石墨烯气凝胶底部加热，氧化石墨烯气凝胶底部含氧官能团部分分解，以得到底部部分还原的氧化石墨烯气凝胶。Further, in one embodiment of the present invention, the graphene oxide aerogel is heated and reduced from the bottom to obtain a partially reduced graphene oxide aerogel at the bottom, further comprising: placing the graphene oxide aerogel on a heat source. The surface is heated from the bottom of the graphene oxide aerogel, and the oxygen-containing functional group at the bottom of the graphene oxide aerogel is partially decomposed to obtain a partially reduced graphene oxide aerogel at the bottom.
在本发明的一个实施例中，加热温度为250～450℃，加热时间为5～60分钟。In one embodiment of the present invention, the heating temperature is 250-450 ° C, and the heating time is 5-60 minutes.
可以理解的是，本发明实施例将氧化石墨烯气凝胶放置在热源表面，从底部方向加热还原，加热温度为250～450℃，加热时间为5～60分钟；氧化石墨烯气凝胶底部首先受热，含氧官能团分解，在底部得到部分还原的氧化石墨烯，上半部分由于远离热源无明显变化；得到底部部分还原的氧化石墨烯气凝胶。It can be understood that, in the embodiment of the present invention, the graphene oxide aerogel is placed on the surface of the heat source, and is heated and reduced from the bottom direction, the heating temperature is 250-450 ° C, and the heating time is 5-60 minutes; the bottom of the graphene oxide aerogel First it is heated, the oxygen-containing functional groups are decomposed, and a partially reduced graphene oxide is obtained at the bottom. The upper part has no obvious change due to being away from the heat source; a reduced graphene oxide aerogel is obtained at the bottom.
在步骤S103中，对底部部分还原的氧化石墨烯气凝胶垂直方向施加压力，以得到异质结构多孔氧化石墨烯膜。In step S103, pressure is applied to the reduced graphene oxide aerogel in the bottom portion in a vertical direction to obtain a porous graphene oxide film with a heterostructure.
在本发明的一个实施例中，异质结构多孔氧化石墨烯膜厚度为50～150μm。In one embodiment of the present invention, the thickness of the heterostructured porous graphene oxide film is 50-150 μm.
可以理解的是，在底部部分还原的氧化石墨烯气凝胶，垂直方向施加压力，将样品压制为厚度50～150μm膜，最终得到异质结构多孔氧化石墨烯膜。It can be understood that the graphene oxide aerogel that is partially reduced at the bottom is pressed with a vertical direction to compress the sample into a film having a thickness of 50 to 150 μm, and finally a porous graphene oxide film with a heterostructure is obtained.
根据本发明实施例提出的异质结构多孔氧化石墨烯膜制备方法，通过对氧化石墨烯溶液冷冻干燥、底部加热还原、垂直施加压力得到异质结构多孔氧化石墨烯膜，制备所需的原材料合成技术成熟，来源广泛，廉价易得，可以大批量生产，从而有效提高制备的实用性、经济性和效率，简单易实现。According to the method for preparing a heterostructured porous graphene oxide film according to the embodiment of the present invention, a heterostructured porous graphene oxide film is obtained by freeze-drying a graphene oxide solution, heating and reducing at the bottom, and applying pressure vertically, and preparing the required raw material synthesis The technology is mature, with a wide range of sources, cheap and readily available, and can be produced in large quantities, thereby effectively improving the practicability, economy and efficiency of the preparation, and simple and easy to achieve.
另外，本发明实施例还提出了一种石墨烯膜，下面将对石墨烯膜进行详细阐述。In addition, a graphene film is also provided in an embodiment of the present invention. The graphene film will be described in detail below.
该石墨烯膜，采用上述的异质结构多孔氧化石墨烯膜的制备方法制备得到，石墨烯膜为多孔结构，包括上半部分和下半部分，其中，上半部分为氧化石墨烯，氧化石墨烯内部包括均匀分布的含氧官能团；下半部分为部分还原的氧化石墨烯，部分还原的氧化石墨烯内部包括沿膜法线方向呈梯度分布的含氧官能团，且分布方向由下向上递增。The graphene film is prepared by using the above-mentioned heterostructure porous graphene oxide film preparation method. The graphene film has a porous structure and includes an upper half and a lower half, wherein the upper half is graphene oxide and graphite oxide. The inside of the ene includes uniformly distributed oxygen-containing functional groups; the lower part is partially reduced graphene oxide, and the partially-reduced inside of the graphene oxide includes oxygen-containing functional groups that are distributed in a gradient along the film normal direction, and the distribution direction increases from bottom to top.
可以理解的是，异质结构多孔氧化石墨烯膜，膜为多孔结构，总厚度为50～150μm，膜由一体化的两部分组成：下半部分为还原的氧化石墨烯，其内部含氧官能团含氧官能沿膜法线方向呈梯度分布，由下向上递增；上半部分为氧化石墨烯，其内部含氧官能团分布均匀。该膜的异质结构使其内部化学组成和含氧官能团呈定向规律分布状态。It can be understood that the heterostructured porous graphene oxide film has a porous structure with a total thickness of 50-150 μm. The film is composed of two integrated parts: the lower part is reduced graphene oxide, and the internal oxygen-containing functional groups The oxygen-containing functions are distributed in a gradient along the normal direction of the film, increasing from bottom to top; the upper part is graphene oxide, and the oxygen-containing functional groups are uniformly distributed inside. The heterogeneous structure of the membrane makes its internal chemical composition and oxygen-containing functional groups in a regular distribution.
进一步地，异质结构多孔氧化石墨烯膜，氧化石墨烯膜放置在大气中，能自发吸收空气中的水分并和含氧官能团作用，在其异质结构诱导产生电荷分离，进而产生电能。Further, the heterostructured porous graphene oxide film, the graphene oxide film is placed in the atmosphere, can spontaneously absorb moisture in the air and interact with oxygen-containing functional groups, induce charge separation in its heterostructure, and then generate electric energy.
根据本发明实施例提出的石墨烯膜，由一体化的两部分组成，其含氧官能团沿膜法线方向呈异质分布，且可以吸收环境空气中的水分子，自发形成内在电场，产生电能，输出可观电压；该异质结构多孔氧化石墨烯膜结构特殊，质量高、产电能力强、稳定性好。The graphene film according to the embodiment of the present invention is composed of two integrated parts, the oxygen-containing functional groups of the graphene film are heterogeneously distributed along the film normal direction, and can absorb water molecules in ambient air, spontaneously form an internal electric field, and generate electrical energy. , The output of considerable voltage; the heterostructured porous graphene oxide film has a special structure, high quality, strong electricity generation capacity, and good stability.
此外，本发明实施例还提出了一种异质结构多孔氧化石墨烯膜的应用，石墨烯膜可应用于自发产电发电机，下面将对本发明实施例提出的发电机进行详细阐述。In addition, the embodiment of the present invention also proposes the application of a heterostructured porous graphene oxide film. The graphene film can be applied to a spontaneous electricity generating generator. The generator provided by the embodiment of the present invention will be described in detail below.
该发电机，采用上述的石墨烯膜，将石墨烯膜的上、下表面分别与金属电极连接得到，发电机为金属-异质结构多孔氧化石墨烯膜-金属的三明治结构，并在空气中自发产生电压。The generator is obtained by connecting the upper and lower surfaces of the graphene film to a metal electrode, respectively. The generator has a metal-heterostructure porous graphene oxide film-metal sandwich structure and is in the air. Spontaneous voltage generation.
进一步地，在本发明的一个实施例中，自发产生电压的电压为20～500mV。Further, in an embodiment of the present invention, the voltage of generating the voltage spontaneously is 20 to 500 mV.
进一步地，在本发明的一个实施例中，空气相对湿度为5～100％。Further, in an embodiment of the present invention, the relative humidity of the air is 5 to 100%.
具体而言，异质结构多孔氧化石墨烯膜的应用，膜应用于自发产电发电机，具体为：将异质结构多孔氧化石墨烯膜的上、下表面分别与金属电极连接，形成金属/异质结构多孔氧化石墨烯膜/金属的三明治结构发电机；三明治结构发电机在空气中可自发产生电压，产生电压范围为20～500mV。将多个发电器件堆叠串联组装，放置在空气中，能够自发产生15V的电压，可以给商用电容器充电，进而为电子元器件供电。本发明实施例可以将发电机以线性或者平面结构串联并封装，得到可弯折、可穿戴、可卷曲的自发电器件。空气相 对湿度的范围为5～100％。Specifically, the application of a heterostructured porous graphene oxide film, which is used in a spontaneous power generator, is specifically: connecting the upper and lower surfaces of the heterostructured porous graphene oxide film with a metal electrode, respectively, to form a metal / Heterostructure porous graphene oxide film / metal sandwich structure generator; sandwich structure generator can generate voltage spontaneously in the air, and the voltage range is 20 ~ 500mV. Multiple power generation devices are stacked and assembled in series, and placed in the air, it can generate a voltage of 15V spontaneously, which can charge commercial capacitors, and then power electronic components. In the embodiment of the present invention, the generator can be connected in series and packaged in a linear or planar structure to obtain a bendable, wearable, and rollable self-generating device. The relative humidity of the air ranges from 5 to 100%.
根据本发明实施例的发电机，通过异质结构多孔氧化石墨烯膜的上、下表面分别与金属电极连接得到，三明治结构发电机可以在空气中自发产生内在电势，且电能产生过程无需特定刺激，绿色环保，无污染。The generator according to the embodiment of the present invention is obtained by connecting the upper and lower surfaces of the heterostructured porous graphene oxide film with metal electrodes, respectively. The sandwich structure generator can generate an internal potential spontaneously in the air, and the electrical energy generation process does not require specific stimulation. , Environmental protection, no pollution.
下面将结合具体实施例对异质结构多孔氧化石墨烯膜制备方法、石墨烯膜及发电机进行进一步阐述。In the following, a method for preparing a porous graphene oxide film with a heterostructure, a graphene film, and a generator will be further described in combination with specific embodiments.
在本发明的第一个具体实施例中，具体包括：In the first specific embodiment of the present invention, it specifically includes:
(1)取5ml 3mg/mL氧化石墨烯溶液，放置于-10℃温度下冷冻成块体，放置于冷冻干燥机中24小时，得到3mg/cm 3的氧化石墨烯凝胶，如图2所示。 (1) Take 5ml of 3mg / mL graphene oxide solution, freeze at -10 ° C to form a block, and place in a freeze dryer for 24 hours to obtain a 3mg / cm 3 graphene oxide gel, as shown in Figure 2 Show.
(2)将3mg/cm 3氧化石墨烯凝胶(高度为1cm)放置在加热台上进行热处理，加热台表面温度250℃；由于加热台表面温度在垂直空间方向上递减，使氧化石墨烯凝胶底部首先受热还原，加热处理时间5分钟；得到底部部分还原的氧化石墨烯凝胶；其底部为部分还原的氧化石墨烯，上部为未被还原的氧化石墨烯，如图3所示。 (2) 3mg / cm 3 graphene oxide gel (1cm in height) is placed on a heating table for heat treatment, and the surface temperature of the heating table is 250 ° C; as the surface temperature of the heating table decreases in the vertical direction, the graphene oxide condenses. The bottom of the gum is first reduced by heat, and the heat treatment time is 5 minutes; a partially reduced graphene oxide gel at the bottom is obtained; the bottom is partially reduced graphene oxide, and the upper portion is unreduced graphene oxide, as shown in FIG. 3.
(3)将上述底部部分还原的氧化石墨烯凝胶两端施加压力，制得厚度为120微米的异质结构多孔氧化石墨烯膜；其内部为紧密多孔结构，如图4所示；其内部氧元素与碳元素原子比(O/C，电子能谱数据)，从底部到顶部呈现异质分布，如图5所示，具体为：底部向上12微米范围内，O/C由0.19逐渐增加为0.5；其上部108微米范围内O/C值一定。说明该膜内部化学组成呈异质分布。(3) Apply pressure to both ends of the reduced graphene oxide gel at the bottom to obtain a porous porous graphene oxide film of heterostructure with a thickness of 120 micrometers; the inside is a dense porous structure, as shown in Figure 4; the inside The atomic ratio of oxygen to carbon (O / C, electron spectrum data) shows a heterogeneous distribution from the bottom to the top, as shown in Figure 5, specifically: within the range of 12 microns from the bottom up, O / C gradually increases from 0.19 Is 0.5; the O / C value in the upper 108 micrometer range is constant. This shows that the chemical composition of the membrane is heterogeneously distributed.
(4)将异质结构多孔氧化石墨烯膜的上、下表面分别与金属电极连接，形成金属/异质结构多孔氧化石墨烯膜/金属的三明治结构发电机，如图6所示；三明治结构发电机在空气中可自发吸收水分，产生内在电势，对外输出电压；在相对湿度湿度为5％的大气环境中，产生的电压为105mV(图7)；在相对湿度湿度为25％的大气环境中，产生的电压为205mV(图8)；在相对湿度湿度为100％的环境中，产生的电压为500mV(图9)；将60个发电机堆叠串联组装(图10)，在大气(相对湿度湿度为20％)环境中能够自发产生15V的电压；上述串联器件可以给电容器充电至3V，充电后能够给单个商用LED灯(红色)供电。将8个发电机以线性结构串联并封装(图11)，得到能够可弯折穿戴自发电器件。将20个发电机以平面结构串联并封装(图12)，得到可卷曲自发电器件。(4) Connect the upper and lower surfaces of the heterostructured porous graphene oxide film with metal electrodes to form a metal / heterostructured porous graphene oxide film / metal sandwich structure generator, as shown in FIG. 6; sandwich structure The generator can absorb moisture spontaneously in the air, generate internal potential, and output voltage externally; in an atmospheric environment with relative humidity and humidity of 5%, the generated voltage is 105mV (Figure 7); in an atmospheric environment with relative humidity and humidity of 25% In the environment, the generated voltage is 205mV (Figure 8); in an environment with a relative humidity of 100%, the generated voltage is 500mV (Figure 9); 60 generators are stacked and assembled in series (Figure 10). Humidity (20% humidity) can generate a voltage of 15V spontaneously in the environment; the above series device can charge the capacitor to 3V, and can charge a single commercial LED lamp (red) after charging. Eight generators were connected in series and packaged in a linear structure (Figure 11) to obtain a self-generating device that can be bent and worn. Twenty generators were connected in series and packaged in a planar structure (Fig. 12) to obtain a rollable self-generating device.
在本发明的第二个具体实施例中，具体包括：In a second specific embodiment of the present invention, it specifically includes:
(1)取5ml15mg/mL氧化石墨烯溶液，放置于-10℃温度下冷冻成块体，放置于冷冻干燥机中24小时，得到15mg/cm 3的氧化石墨烯凝胶。 (1) Take 5 ml of a 15 mg / mL graphene oxide solution, freeze it at -10 ° C to form a block, and place it in a freeze dryer for 24 hours to obtain a 15 mg / cm 3 graphene oxide gel.
(2)将15mg/cm 3氧化石墨烯凝胶(高度为1cm)放置在加热台上进行热处理，加热台表面温度400℃；由于加热台表面温度在垂直空间方向上递减，使氧化石墨烯凝胶底部 首先受热还原，加热处理时间15分钟；得到底部部分还原的氧化石墨烯凝胶；其底部为部分还原的氧化石墨烯，上部为未被还原的氧化石墨烯。 (2) 15mg / cm 3 graphene oxide gel (1cm in height) is placed on a heating table for heat treatment, and the surface temperature of the heating table is 400 ° C; as the surface temperature of the heating table decreases in the vertical direction, the graphene oxide condenses. The bottom of the glue is first reduced by heat, and the heat treatment time is 15 minutes; a partially reduced graphene oxide gel at the bottom is obtained; the bottom is partially reduced graphene oxide, and the upper portion is unreduced graphene oxide.
(3)将上述底部部分还原的氧化石墨烯凝胶两端施加压力，制得厚度为80微米的异质结构多孔氧化石墨烯膜；其内部为紧密多孔结构；其内部氧元素与碳元素原子比(O/C，电子能谱数据)，从底部到顶部呈现异质分布。(3) A pressure of two ends of the graphene oxide gel partially reduced at the bottom is applied to obtain a heterostructured porous graphene oxide film having a thickness of 80 micrometers; the inside thereof is a tightly porous structure; and the internal oxygen and carbon atoms Ratio (O / C, electron spectrum data), showing a heterogeneous distribution from bottom to top.
(4)将异质结构多孔氧化石墨烯膜的上、下表面分别与金属电极连接，形成金属/异质结构多孔氧化石墨烯膜/金属的三明治结构发电机；三明治结构发电机在空气中可自发吸收水分，产生内在电势，对外输出电压；在相对湿度湿度为25％的大气环境中，产生的电压为150mV。(4) The upper and lower surfaces of the heterostructured porous graphene oxide film are respectively connected with the metal electrodes to form a metal / heterostructured porous graphene oxide film / metal sandwich structure generator; the sandwich structure generator may be in the air. Spontaneously absorb moisture, generate internal potential, and output voltage externally; in an atmospheric environment with a relative humidity of 25%, the generated voltage is 150mV.
在本发明的第三个具体实施例中，具体包括：In a third specific embodiment of the present invention, it specifically includes:
(1)取5ml10mg/mL氧化石墨烯溶液，放置于-10℃温度下冷冻成块体，放置于冷冻干燥机中24小时，得到10mg/cm 3的氧化石墨烯凝胶。 (1) Take 5 ml of a 10 mg / mL graphene oxide solution, freeze at a temperature of -10 ° C into a block, and place it in a freeze dryer for 24 hours to obtain a 10 mg / cm 3 graphene oxide gel.
(2)将10mg/cm 3氧化石墨烯凝胶(高度为1cm)放置在加热台上进行热处理，加热台表面温度300℃；由于加热台表面温度在垂直空间方向上递减，使氧化石墨烯凝胶底部首先受热还原，加热处理时间60分钟；得到底部部分还原的氧化石墨烯凝胶；其底部为部分还原的氧化石墨烯，顶部为未被还原的氧化石墨烯。 (2) 10mg / cm 3 graphene oxide gel (1cm in height) is placed on a heating table for heat treatment, and the surface temperature of the heating table is 300 ° C; as the surface temperature of the heating table decreases in the vertical direction, the graphene oxide condenses. The bottom of the glue is first reduced by heat, and the heat treatment time is 60 minutes; a partially reduced graphene oxide gel at the bottom is obtained; the bottom is partially reduced graphene oxide, and the top is unreduced graphene oxide.
(3)将上述底部部分还原的氧化石墨烯凝胶两端施加压力，制得厚度为50微米的异质结构多孔氧化石墨烯膜；其内部为紧密多孔结构；其内部氧元素与碳元素原子比(O/C，电子能谱数据)，从底部到顶部呈现异质分布。(3) Apply pressure to both ends of the reduced graphene oxide gel at the bottom to obtain a porous porous graphene oxide film of heterostructure with a thickness of 50 micrometers; the inside is a tight porous structure; the internal oxygen and carbon atoms Ratio (O / C, electron spectrum data), showing a heterogeneous distribution from bottom to top.
(4)将异质结构多孔氧化石墨烯膜的上、下表面分别与金属电极连接，形成金属/异质结构多孔氧化石墨烯膜/金属的三明治结构发电机；三明治结构发电机在空气中可自发吸收水分，产生内在电势，对外输出电压；在相对湿度湿度为25％的大气环境中，产生的电压为25mV。(4) The upper and lower surfaces of the heterostructured porous graphene oxide film are respectively connected with the metal electrodes to form a metal / heterostructured porous graphene oxide film / metal sandwich structure generator; the sandwich structure generator may be in the air. Spontaneously absorb moisture, generate internal potential, and output voltage externally; in an atmospheric environment with a relative humidity of 25%, the generated voltage is 25mV.
综上，本发明实施例的述制备方法简单，所用原材料合成技术成熟，来源广泛，廉价易得，可以大批量生产。本发明实施例的异质结构多孔氧化石墨烯膜内部由一体化的两部分组成，其含氧官能团沿膜法线方向呈异质分布，该膜可以吸收环境空气中的水分子，自发形成内在电场，产生电能，输出可观电压；该异质结构多孔氧化石墨烯膜结构特殊，质量高、产电能力强、稳定性好。将本发明实施例异质结构多孔氧化石墨烯膜的上、下表面分别与金属电极连接，形成金属/异质结构多孔氧化石墨烯膜/金属的三明治结构发电机；三明治结构发电机可以在空气中自发产生内在电势，并输出20～500mV的电压。多个器件可以轻易串联，输出15V的电压，为商用电子元器件供电。其电能产生过程无需特定刺激，绿色环保，无污染。In summary, the preparation method described in the embodiment of the present invention is simple, the raw material synthesis technology used is mature, the source is wide, cheap and readily available, and it can be produced in large quantities. The heterostructured porous graphene oxide film of the embodiment of the present invention is internally composed of two integrated parts, and its oxygen-containing functional groups are heterogeneously distributed along the film normal direction. The film can absorb water molecules in the ambient air and spontaneously form an intrinsic The electric field generates electric energy and outputs considerable voltage. The heterostructured porous graphene oxide film has a special structure, high quality, strong power generation capacity, and good stability. The upper and lower surfaces of the heterostructured porous graphene oxide film of the embodiment of the present invention are respectively connected with a metal electrode to form a metal / heterostructured porous graphene oxide film / metal sandwich structure generator; the sandwich structure generator can be in air The spontaneous potential is generated in the medium, and a voltage of 20 to 500 mV is output. Multiple devices can be easily connected in series and output a voltage of 15V to power commercial electronic components. Its electrical energy generation process does not require specific stimulation, is green and environmentally friendly, and has no pollution.
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本发明的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。In addition, the terms "first" and "second" are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "a plurality" is at least two, for example, two, three, etc., unless it is specifically and specifically defined otherwise.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of this specification, the description with reference to the terms “one embodiment”, “some embodiments”, “examples”, “specific examples”, or “some examples” and the like means specific features described in conjunction with the embodiments or examples , Structures, materials, or features are included in at least one embodiment or example of the invention. In this specification, the schematic expressions of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. In addition, without any contradiction, those skilled in the art may combine and combine different embodiments or examples and features of the different embodiments or examples described in this specification.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limitations on the present invention. Those skilled in the art can interpret the above within the scope of the present invention. Embodiments are subject to change, modification, substitution, and modification.

Claims (10)

  1. 一种异质结构多孔氧化石墨烯膜制备方法，其特征在于，包括以下步骤：A method for preparing a heterostructured porous graphene oxide film, comprising the following steps:
    对氧化石墨烯溶液冷冻干燥制备，以得到氧化石墨烯气凝胶；The graphene oxide solution is prepared by freeze-drying to obtain a graphene oxide aerogel;
    将所述氧化石墨烯气凝胶底部加热还原，以得到底部部分还原的氧化石墨烯气凝胶；以及对所述底部部分还原的氧化石墨烯气凝胶垂直方向施加压力，以得到异质结构多孔氧化石墨烯膜。Heating and reducing the bottom of the graphene oxide aerogel to obtain a reduced graphene oxide aerogel at the bottom portion; and applying pressure to the reduced graphene oxide aerogel at the bottom portion in a vertical direction to obtain a heterostructure Porous graphene oxide film.
  2. 根据权利要求1所述的异质结构多孔氧化石墨烯膜制备方法，其特征在于，所述氧化石墨烯溶液制备过程包括：The method for preparing a porous graphene oxide film with heterostructure according to claim 1, wherein the process of preparing the graphene oxide solution comprises:
    将9g石墨粉、240mL浓硫酸、4.5g的硝酸钠在并冰浴状态下搅拌混合均匀；9g of graphite powder, 240mL of concentrated sulfuric acid, and 4.5g of sodium nitrate are stirred and mixed in an ice bath state;
    加入27g高锰酸钾，并继续搅拌1小时；Add 27 g of potassium permanganate and continue stirring for 1 hour;
    升温至30℃之后搅拌两小时，并在搅拌之后加入450mL去离子水；After heating to 30 ° C, stir for two hours, and add 450mL of deionized water after stirring;
    升温至90℃之后搅拌20分钟，并在搅拌之后加入1500mL去离子水；After heating to 90 ° C., stir for 20 minutes, and add 1500 mL of deionized water after stirring;
    继续搅拌并自然冷却至室温，并在冷却至室温之后加入60mL的过氧化氢；Continue to stir and naturally cool to room temperature, and add 60 mL of hydrogen peroxide after cooling to room temperature;
    使用离心洗涤得到所述氧化石墨烯溶液。The graphene oxide solution was obtained by centrifugal washing.
  3. 根据权利要求1所述的异质结构多孔氧化石墨烯膜制备方法，其特征在于，所述冷冻干燥时间为24～72h。The method of claim 1, wherein the freeze-drying time is 24 to 72 hours.
  4. 根据权利要求1所述的异质结构多孔氧化石墨烯膜制备方法，其特征在于，所述将所述氧化石墨烯气凝胶底部加热还原，以得到底部部分还原的氧化石墨烯气凝胶，进一步包括：The method for preparing a porous graphene oxide film with heterostructure according to claim 1, wherein the bottom of the graphene oxide aerogel is heated and reduced to obtain a partially reduced graphene oxide aerogel at the bottom, Further includes:
    将所述氧化石墨烯气凝胶放置在热源表面，从所述氧化石墨烯气凝胶底部加热，氧化石墨烯凝胶底部含氧官能团部分分解，以得到底部部分还原的氧化石墨烯气凝胶。The graphene oxide aerogel is placed on the surface of a heat source and heated from the bottom of the graphene oxide aerogel, and the oxygen-containing functional group at the bottom of the graphene oxide gel is partially decomposed to obtain a partially reduced graphene oxide aerogel at the bottom. .
  5. 根据权利要求4所述的异质结构多孔氧化石墨烯膜制备方法，其特征在于，所述加热温度为250～450℃，加热时间为5～60分钟。The method of claim 4, wherein the heating temperature is 250 to 450 ° C. and the heating time is 5 to 60 minutes.
  6. 根据权利要求1所述的异质结构多孔氧化石墨烯膜制备方法，其特征在于，所述异质结构多孔氧化石墨烯膜厚度为50～150μm。The method for preparing a porous graphene oxide film with a heterostructure according to claim 1, wherein the thickness of the porous graphene oxide film with a heterostructure is 50-150 μm.
  7. 一种石墨烯膜，其特征在于，采用如权利要求1-6任一项所述的异质结构多孔氧化石墨烯膜的制备方法制备得到，所述石墨烯膜为多孔结构，包括上半部分和下半部分，其中，所述上半部分为氧化石墨烯，所述氧化石墨烯内部包括均匀分布的含氧官能团；所述下半部分为部分还原的氧化石墨烯，所述部分还原的氧化石墨烯内部包括沿膜法线方向呈梯度分布的含氧官能团，且所述分布方向由下向上递增。A graphene film, which is prepared by using the method for preparing a porous graphene oxide film with heterostructure according to any one of claims 1-6, wherein the graphene film has a porous structure and includes an upper part And the lower half, wherein the upper half is graphene oxide, and the graphene oxide includes a uniformly distributed oxygen-containing functional group inside; the lower half is partially reduced graphene oxide, and the partially reduced oxide The inside of graphene includes oxygen-containing functional groups distributed in a gradient along the film normal direction, and the distribution direction increases from bottom to top.
  8. 一种发电机，其特征在于，采用如权利要求7所述的石墨烯膜，将所述石墨烯膜的 上、下表面分别与金属电极连接得到，所述发电机为金属-异质结构多孔氧化石墨烯膜-金属的三明治结构，并在空气中自发产生电压。A generator characterized in that the graphene film according to claim 7 is used, and the upper and lower surfaces of the graphene film are respectively connected to a metal electrode, and the generator is metal-heterostructure porous Graphene oxide film-metal sandwich structure, and generates voltage spontaneously in the air.
  9. 根据权利要求9所述的发电机，其特征在于，所述自发产生电压的电压为20～500mV。The generator according to claim 9, wherein the voltage of the spontaneously generated voltage is 20 to 500 mV.
  10. 根据权利要求9所述的发电机，其特征在于，所述空气相对湿度为5～100％。The generator according to claim 9, wherein the relative humidity of the air is 5 to 100%.
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