WO2022218088A1

WO2022218088A1 - Method for preparing porous graphene film, porous graphene film, and electrode

Info

Publication number: WO2022218088A1
Application number: PCT/CN2022/081128
Authority: WO
Inventors: 王晓京
Original assignee: 王晓京
Priority date: 2021-04-12
Filing date: 2022-03-16
Publication date: 2022-10-20
Also published as: CN113096973A

Abstract

A method for preparing a porous graphene film, a porous graphene film, an electrode, and a capacitor. Freeze-drying technology is used to build continuously interconnected porous graphene oxide networks, and high-compression technology is used to enhance the strength of graphene oxide mechanical structures. The use of laser and microwave irradiation to reduce the porous graphene oxide film achieves efficient large-area reduction and enables supercapacitors having high performance.

Description

用于制备多孔石墨烯膜的方法、多孔石墨烯膜和电极Method for preparing porous graphene film, porous graphene film and electrode

技术领域technical field

本发明涉及用于制备多孔石墨烯膜的方法、多孔石墨烯膜和电极。本发明还涉及多孔石墨烯膜在能量存储装置，例如电容器，超级电容器，电池和燃料电池中的应用。The present invention relates to a method for preparing a porous graphene film, a porous graphene film and an electrode. The present invention also relates to the use of porous graphene membranes in energy storage devices such as capacitors, supercapacitors, batteries and fuel cells.

技术背景technical background

超级电容器(也称为“双电层电容器”)是电化学电容器，其电容值远高于其他电容器。由于其高能量密度，快速充电/放电能力，超过一百万次充电循环的长寿命以及在-40℃至70℃的宽温度范围内工作的能力，超级电容器被广泛用于储能和能源供应。Supercapacitors (also known as "electric double-layer capacitors") are electrochemical capacitors that have much higher capacitance values than other capacitors. Supercapacitors are widely used in energy storage and energy supply due to their high energy density, fast charge/discharge capability, long life of over one million charge cycles, and ability to operate in a wide temperature range from -40°C to 70°C .

典型的超级电容器包括两个被离子渗透膜(“隔膜层”)隔开的电极，以及分别连接到电极的一对集流器。A typical supercapacitor includes two electrodes separated by an ion-permeable membrane ("separator layer"), and a pair of current collectors connected to the electrodes, respectively.

活性炭是常规超级电容器中使用最广泛的电极材料。虽然从理论上讲活性炭可提供大的比表面积，以容纳大量的离子，但是其中大部分的孔是非相连通的，离子不能有效的利用其表面积，因此导致了低的比电容和最大能量密度大概为5-7Wh kg ^-1。因此，为了进一步提高超级电容器的比电容和能量密度，需要开发具有大的比表面积和高电导率的电极材料。 Activated carbon is the most widely used electrode material in conventional supercapacitors. Although in theory activated carbon can provide a large specific surface area to accommodate a large number of ions, most of the pores are non-connected, and ions cannot effectively utilize its surface area, thus resulting in a low specific capacitance and a maximum energy density of approximately 5-7Wh kg ^-1 . Therefore, in order to further improve the specific capacitance and energy density of supercapacitors, it is necessary to develop electrode materials with large specific surface area and high electrical conductivity.

纯石墨烯材料具有2630m ²/g的超大理论比表面积，并具有出色的电导率(>1000S/m)。更重要的是，作为二维层状材料，材料内部的孔全部互连，因此离子可以完全附着在这种材料的表面。因此，石墨烯一直被认为是最有前途的高性能超级电容器的电极材料。在过去的十年中，石墨烯及其衍生物已被广泛开发为超级电容器电极材料来代替活性炭。已经有一些研究实现高性能石墨烯超级电容器。 The pure graphene material has an ultra-large theoretical specific surface area of 2630 m ² /g and excellent electrical conductivity (>1000 S/m). What's more, as a two-dimensional layered material, the pores inside the material are all interconnected, so ions can fully attach to the surface of this material. Therefore, graphene has been regarded as the most promising electrode material for high-performance supercapacitors. In the past decade, graphene and its derivatives have been widely developed as supercapacitor electrode materials to replace activated carbon. There have been some studies to achieve high-performance graphene supercapacitors.

超级电容器的应用必须大规模生产多孔石墨烯薄膜。因此，目前已经有几种方法用来大规模制造多孔石墨烯薄膜。其中所述氧化还原方法，能够大量低成本生产石墨烯多孔材料。然而，该方法已经显示出相对低的导电性和大量的材料缺陷，这些问题限制了制作超级电容器的性能。因此，现在所需要的是解决或改善与现有技术相关的一个或多个缺点或局限，或者至少提供一种可用的替代方案。The application of supercapacitors requires large-scale production of porous graphene films. Therefore, several methods have been developed for the large-scale fabrication of porous graphene films. The redox method can produce graphene porous materials in large quantities and at low cost. However, this approach has shown relatively low electrical conductivity and a large number of material defects, issues that limit the performance of making supercapacitors. What is needed, therefore, is to address or ameliorate one or more of the disadvantages or limitations associated with the prior art, or to at least provide a usable alternative.

发明内容SUMMARY OF THE INVENTION

本发明的第一方面中提供了一种方法，包括：首先结合冷冻和干燥工艺(冻干法)来制作多孔连续互连的氧化石墨烯(GO)网络结构，其中，GO是多孔GO，孔径及孔隙率可以通过控制氧化石墨烯的浓度进行调节。A first aspect of the present invention provides a method, comprising: firstly combining a freezing and drying process (freeze-drying method) to fabricate a porous continuous interconnected graphene oxide (GO) network structure, wherein the GO is porous GO and the pore size is and porosity can be adjusted by controlling the concentration of graphene oxide.

在上一步的基础上使用高压工艺来增强氧化石墨烯的机械结构强度，降低冻干法制作的氧化石墨烯薄膜的厚度。这个步骤中氧化石墨烯结构的孔隙率及孔径可以通过施加的压力来控制的。On the basis of the previous step, a high-pressure process is used to enhance the mechanical structural strength of graphene oxide and reduce the thickness of the graphene oxide film produced by the freeze-drying method. The porosity and pore size of the graphene oxide structure in this step can be controlled by the applied pressure.

然后，使用光束来照射氧化石墨烯，以形成具有三维(3D)网络的预还原氧化石墨烯(PRGO)，所述预还原氧化石墨烯是多孔的。这个步骤中预还原氧化石墨烯的还原程度可以通过调控光功率及扫描速度控制。Then, the graphene oxide is irradiated with a light beam to form pre-reduced graphene oxide (PRGO) having a three-dimensional (3D) network, which is porous. The reduction degree of the pre-reduced graphene oxide in this step can be controlled by adjusting the optical power and scanning speed.

在此基础上，进一步使用微波(MW)辐射来照射具有3D网络的预还原氧化石墨烯来实现氧化石墨烯的还原。这个步骤中还原氧化石墨烯(RGO)的还原程度可以通过微波辐射的强度及辐射时间控制。On this basis, microwave (MW) radiation was further used to irradiate the pre-reduced graphene oxide with 3D network to achieve the reduction of graphene oxide. The degree of reduction of reduced graphene oxide (RGO) in this step can be controlled by the intensity and duration of microwave radiation.

根据本发明，还提供了一种电极，其包括具有3D网络的还原氧化石墨烯，其中3D网络的孔洞结构是相互连通的。According to the present invention, there is also provided an electrode comprising reduced graphene oxide having a 3D network, wherein the pore structure of the 3D network is interconnected.

本发明还提供了一种用于制作3D多孔还原氧化石墨烯的装置，包括：The present invention also provides a device for making 3D porous reduced graphene oxide, comprising:

用于容纳氧化石墨烯(GO)溶液的容器；Containers for holding graphene oxide (GO) solutions;

用于形成3D多孔氧化石墨烯网络的冷冻干燥设备；Freeze-drying equipment for forming 3D porous graphene oxide networks;

用于施加压力以压缩多孔氧化石墨烯网络的加压设备；A pressurized device for applying pressure to compress the porous graphene oxide network;

用于发出光束的照射设备，用于将氧化石墨烯网络预还原；和an irradiation device for emitting a light beam for prereducing the graphene oxide network; and

用于产生微波辐射的装置，其将预还原氧化石墨烯网络进一步还原，形成3D多孔还原氧化石墨烯网络。A device for generating microwave radiation that further reduces the pre-reduced graphene oxide network to form a 3D porous reduced graphene oxide network.

本发明还提供了一种方法，包括：冷冻干燥氧化石墨烯以形成3D多孔氧化石墨烯网络，其中氧化石墨烯包含单层或者多层的多孔氧化石墨烯膜。The present invention also provides a method comprising: freeze-drying graphene oxide to form a 3D porous graphene oxide network, wherein the graphene oxide comprises a single-layer or multi-layer porous graphene oxide film.

本发明还提供了一种方法，包括：The present invention also provides a method, comprising:

用加压设备压缩3D多孔氧化石墨烯网络，其中氧化石墨烯包含单层或者多层的多孔氧化石墨烯膜。Pressurized equipment is used to compress a 3D porous graphene oxide network, wherein the graphene oxide comprises a single or multi-layer porous graphene oxide film.

本发明进一步提供一种方法，包括：The present invention further provides a method, comprising:

使用光束照射3D多孔氧化石墨烯网络，以形成预还原氧化石墨烯(PRGO)，其中所述3D多孔氧化石墨烯网络包括单层或者多层的多孔氧化石墨烯膜。A 3D porous graphene oxide network is irradiated with a light beam to form pre-reduced graphene oxide (PRGO), wherein the 3D porous graphene oxide network comprises a single or multi-layer porous graphene oxide film.

使用微波辐射照射3D多孔预还原氧化石墨烯网络，以形成还原氧化石墨烯，其中所述3D多孔预还原氧化石墨烯网络包括单层或者多层的多孔氧化石墨烯膜。The 3D porous pre-reduced graphene oxide network is irradiated with microwave radiation to form reduced graphene oxide, wherein the 3D porous pre-reduced graphene oxide network comprises a single or multi-layer porous graphene oxide film.

附图说明Description of drawings

以下仅通过举例的方式，参考附图进一步描述本发明的一些实施例，其中：Some embodiments of the present invention are further described below, by way of example only, with reference to the accompanying drawings, wherein:

图1是根据本申请的一些实施方式的用于形成RGO的方法的流程图。1 is a flowchart of a method for forming an RGO according to some embodiments of the present application.

图2是根据本申请的一些实施方式的GO浆料(浆料浓度为169.9mg/ml)的冷冻干燥样品的照片。2 is a photograph of a freeze-dried sample of GO slurry (slurry concentration of 169.9 mg/ml) according to some embodiments of the present application.

图3是根据本申请的一些实施方式的多孔RGO膜的扫描电子显微镜图像。3 is a scanning electron microscope image of a porous RGO film according to some embodiments of the present application.

图4是根据本申请的一些实施方式的氧化石墨烯、激光还原石墨烯以及激光预还原和微波还原的氧化石墨烯膜的拉曼光谱。4 is a Raman spectrum of graphene oxide, laser-reduced graphene, and laser-pre-reduced and microwave-reduced graphene oxide films according to some embodiments of the present application.

图5是根据本申请的一些实施方式的还原氧化石墨烯膜的元素分析结果。5 is an elemental analysis result of a reduced graphene oxide film according to some embodiments of the present application.

图6是根据本申请的一些实施方式的由GO浆料(浆料浓度为169.9mg/ml)制成的超级电容器以不同速度进行扫描的循环伏安法(CV)曲线。6 is a cyclic voltammetry (CV) curve of a supercapacitor made of GO slurry (slurry concentration of 169.9 mg/ml) scanned at different speeds according to some embodiments of the present application.

图7是根据本申请的一些实施方式的由GO浆料(浆料浓度为169.9mg/ml)制成的超级电容器在不同电流密度下扫描的恒流充放电(CCCD)曲线。7 is a constant current charge-discharge (CCCD) curve scanned at different current densities for a supercapacitor made of GO slurry (slurry concentration of 169.9 mg/ml) according to some embodiments of the present application.

图8是根据本申请的一些实施方式的由GO浆料(浆料浓度为169.9mg/ml)制成的超级电容器在不同的电流密度下扫描的比电容与电流密度的关系曲线。8 is a plot of specific capacitance versus current density swept at different current densities for a supercapacitor made of GO slurry (slurry concentration of 169.9 mg/ml) according to some embodiments of the present application.

图9是根据本申请的一些实施方式的由GO浆料(浆料浓度为169.9mg/ml)制成的超级电容器在不同电流密度下扫描的电阻抗光谱曲线。9 is an electrical impedance spectroscopy curve scanned at different current densities for a supercapacitor made of GO slurry (slurry concentration of 169.9 mg/ml) according to some embodiments of the present application.

图10是根据本申请的一些实施方式的由GO浆料(浆料浓度为169.9mg/ml)制成的超级电容器在不同电流密度下扫描的Ragone图。10 is a Ragone plot of supercapacitors made from GO slurry (slurry concentration of 169.9 mg/ml) scanned at different current densities according to some embodiments of the present application.

图11是根据本申请的一些实施方式的由GO浆料(浆料浓度为169.9mg/ml)制成的超级电容器在不同速度下扫描的循环伏安(CV)曲线。11 is a cyclic voltammetry (CV) curve scanned at different speeds of a supercapacitor made of GO slurry (slurry concentration of 169.9 mg/ml) according to some embodiments of the present application.

图12是根据本申请的一些实施方式的由GO浆料(浆料浓度为72mg/ml)制成的超级电容器在不同电流密度下扫描的恒流充放电(CCCD)曲线。12 is a constant current charge-discharge (CCCD) curve scanned at different current densities for a supercapacitor made of GO slurry (slurry concentration of 72 mg/ml) according to some embodiments of the present application.

图13是根据本申请的一些实施方式的由GO浆料(浆料浓度为72mg/ml)制成的超级电容器在不同电流密度下扫描的比电容与电流密度的关系曲线。13 is a plot of specific capacitance versus current density scanned at different current densities for a supercapacitor made of GO slurry (slurry concentration of 72 mg/ml) according to some embodiments of the present application.

图14是根据本申请的一些实施方式的由GO浆料(浆料浓度为72mg/ml)制成的超级电容器在不同电流密度下扫描的电阻抗光谱曲线。14 is an electrical impedance spectroscopy curve scanned at different current densities for a supercapacitor made of GO slurry (slurry concentration of 72 mg/ml) according to some embodiments of the present application.

图15是根据本申请的一些实施方式的由GO浆料(浆料浓度为72mg/ml)制成的超级电容器在不同的电流密度下扫描的Ragone图。15 is a Ragone plot of supercapacitors made from GO slurry (slurry concentration of 72 mg/ml) scanned at different current densities according to some embodiments of the present application.

具体实施方式Detailed ways

[超级电容器的总体结构][Overall structure of supercapacitor]

总览Overview

常规电容器包括两个常规电极，两个电极之间的隔膜以及一对集流器(每个电极一个)。常规电极没有孔，并且电荷存储在常规电极的表面上。集流器连接到电极以从电极传导电荷。A conventional capacitor includes two conventional electrodes, a separator between the two electrodes, and a pair of current collectors (one for each electrode). Conventional electrodes have no pores, and charge is stored on the surface of conventional electrodes. A current collector is connected to the electrodes to conduct charge from the electrodes.

超级电容器使用多孔电极，并且电荷可以附着到多孔电极的多孔表面，即，在孔中以及在多孔电极的表面上。Supercapacitors use porous electrodes, and charges can attach to the porous surface of the porous electrode, ie, in the pores and on the surface of the porous electrode.

超级电容器理论上的电容C与电极的比表面积A成正比，即The theoretical capacitance C of the supercapacitor is proportional to the specific surface area A of the electrode, namely

C∝A (1)C∝A (1)

比表面积A定义为每单位质量或固体或堆积体积的材料的总表面积。Specific surface area A is defined as the total surface area of a material per unit mass or solid or bulk volume.

因此，可以通过增大比表面积A来增加电容C。Therefore, the capacitance C can be increased by increasing the specific surface area A.

理论上，随着孔径的减小，多孔材料的比表面积显着增加。Theoretically, as the pore size decreases, the specific surface area of the porous material increases significantly.

超级电容器的电极可以由活性炭制成，该活性炭通常具有提供高表面积的复杂的多孔结构。但是，带有活性炭电极的超级电容器的实测电容通常比计算得出的“理论”电容低得多，例如，由于活性炭中的一些孔太小而无法使电解质离子扩散到其中，并且由于很难在很小的空间内形成双电层结构。The electrodes of supercapacitors can be made of activated carbon, which typically has a complex porous structure that provides high surface area. However, the measured capacitance of supercapacitors with activated carbon electrodes is often much lower than the calculated "theoretical" capacitance, for example, because some of the pores in the activated carbon are too small for electrolyte ions to diffuse into them, and because it is difficult to The electric double layer structure is formed in a small space.

石墨烯是碳的同素异形体。石墨烯包括至少一个二维薄片，该二维薄片由以六边形蜂窝结构排列的sp ²键合的单层碳原子组成。石墨烯具有非常稳定的结构，高电导率，高韧性，高强度和大的比表面积，这对于超级电容器中的电极材料而言是理想的性能。 Graphene is an allotrope of carbon. Graphene includes at least one two-dimensional flake consisting of a single layer of sp ^- bonded carbon atoms arranged in a hexagonal honeycomb structure. Graphene has a very stable structure, high electrical conductivity, high toughness, high strength and large specific surface area, which are ideal properties for electrode materials in supercapacitors.

然而，直接由石墨烯制造电极具有挑战性或局限性。尽管表面积很大，但使用单层石墨烯形成的超级电容器可能具有有限的体积电容。尽管石墨烯层的堆叠可实现高体积电容，但由于层之间的小间距，离子可能难以进入表面。此外，生产石墨烯的常规方法经常消耗大量能量并且涉及高成本，因此不适合大规模生产。However, fabricating electrodes directly from graphene is challenging or limiting. Despite the large surface area, supercapacitors formed using single-layer graphene may have limited volumetric capacitance. Although the stacking of graphene layers enables high bulk capacitance, ions may have difficulty accessing the surface due to the small spacing between the layers. In addition, conventional methods of producing graphene often consume a lot of energy and involve high costs, so they are not suitable for large-scale production.

氧化石墨烯(GO)是氧化形式的石墨烯，其中单层连接有含氧基团。可以化学还原氧化石墨烯以将氧化石墨烯转化为还原的氧化石墨烯：还原氧化石墨烯是具有比氧化石墨烯更高的电导率的材料。Graphene oxide (GO) is an oxidized form of graphene in which a monolayer is attached with oxygen-containing groups. Graphene oxide can be chemically reduced to convert graphene oxide to reduced graphene oxide: Reduced graphene oxide is a material with higher electrical conductivity than graphene oxide.

本申请描述的是用于超级电容器多孔电极的还原氧化石墨烯结构的制备或制造方法。Described herein are methods for the preparation or fabrication of reduced graphene oxide structures for use in supercapacitor porous electrodes.

本申请所描述的方法可以允许在氧化石墨烯层之间产生一个或多个选定尺寸的孔(例如，具有在1nm至1000nm之间的直径，称为“纳米多孔结构”)，并允许大量生产还原的氧化石墨烯结构和具有还原氧化石墨烯结构的电极，该电极可用于超级电容器。本申请所描述的方法还可以允许制造具有还原氧化石墨烯电极的超级电容器，该超级电容器具有诸如几何设计和/或设备覆盖区(即，电极或超级电容器所占据的空间量)之类的可选特性，并且允许超级电容器与其他电气设备直接集成。使用本申请所描述的方法，可以以简单、有效和低成本的方式来制造具有还原氧化石墨烯电极的超级电容器。The methods described herein can allow the creation of one or more pores of a selected size (eg, having diameters between 1 nm and 1000 nm, termed "nanoporous structures") between graphene oxide layers, and allow a large number of Production of reduced graphene oxide structures and electrodes with reduced graphene oxide structures that can be used in supercapacitors. The methods described herein may also allow the fabrication of supercapacitors with reduced graphene oxide electrodes with variable properties such as geometric design and/or device footprint (ie, the amount of space occupied by the electrodes or supercapacitors). select features and allow direct integration of supercapacitors with other electrical devices. Using the methods described in this application, supercapacitors with reduced graphene oxide electrodes can be fabricated in a simple, efficient, and low-cost manner.

本申请所描述的用于制备还原氧化石墨烯结构的方法包括以下方面：冷冻干燥氧化石墨烯，以形成具有三维多孔结构的氧化石墨烯膜，压缩具有三维多孔结构的氧化石墨烯膜，用光束照射具有三维多孔结构的氧化石墨烯膜以形成预还原的氧化石墨烯膜，并用微波辐照预还原的氧化石墨烯膜以形成还原氧化石墨烯薄。The method for preparing a reduced graphene oxide structure described in this application includes the following aspects: freeze-drying graphene oxide to form a graphene oxide film with a three-dimensional porous structure, compressing the graphene oxide film with a three-dimensional porous structure, using a light beam A graphene oxide film with a three-dimensional porous structure is irradiated to form a pre-reduced graphene oxide film, and the pre-reduced graphene oxide film is irradiated with microwaves to form a reduced graphene oxide film.

多孔氧化石墨烯膜Porous graphene oxide film

在一些实施方案中，用压力机压缩的氧化石墨烯包括一层或多层多孔氧化石墨烯膜。本申请描述的实施方案的方法中采用的多孔氧化石墨烯膜包括多层阵列，该多层阵列包含氧化石墨烯片。In some embodiments, the press-compressed graphene oxide includes one or more layers of porous graphene oxide films. Porous graphene oxide membranes employed in the methods of embodiments described herein include multilayer arrays comprising graphene oxide sheets.

如本申请所用，术语“多层阵列”通常是指包括多个平面的石墨烯基片，其以重叠的方式彼此堆叠以形成类似于层状结构。多层阵列中的平面片可以彼此部分重叠或完全重叠。多层阵列通常是三维结构。As used herein, the term "multilayer array" generally refers to a graphene substrate comprising multiple planes stacked on top of each other in an overlapping manner to form a layer-like structure. The planar sheets in a multilayer array may partially or completely overlap each other. Multilayer arrays are usually three-dimensional structures.

表述“石墨烯基”在本申请中可以用作对包含石墨烯的材料的总体描述，所述材料包括氧化石墨烯和还原的氧化石墨烯。The expression "graphene-based" may be used in this application as a general description of graphene-containing materials, including graphene oxide and reduced graphene oxide.

多层中的平面片可以由氧化石墨烯构成(例如，在氧化石墨烯膜的情况下)。替代地，片可以由还原的氧化石墨烯或氧化石墨烯和还原的氧化石墨烯的混合物组成(例如，在还原的氧化石墨烯膜的情况下)。The planar sheets in the multilayer may be composed of graphene oxide (eg, in the case of graphene oxide films). Alternatively, the sheet may consist of reduced graphene oxide or a mixture of graphene oxide and reduced graphene oxide (eg, in the case of reduced graphene oxide films).

本申请所用的多孔氧化石墨烯膜包括氧化石墨烯片，其中至少一些氧化石墨烯片包含一个或多个孔。在一些实施例中，多层阵列中的氧化石墨烯片的一部分包括至少一个孔，而另一部分的氧化石墨烯片不包括孔。在其他实施例中，氧化石墨烯膜中的每个氧化石墨烯片均包括至少一个孔。本领域技术人员将理解，氧化石墨烯膜中的单层氧化石墨烯片可包含多个孔。Porous graphene oxide films as used herein include graphene oxide sheets, wherein at least some of the graphene oxide sheets contain one or more pores. In some embodiments, a portion of the graphene oxide sheets in the multilayer array includes at least one hole, while another portion of the graphene oxide sheets includes no holes. In other embodiments, each graphene oxide sheet in the graphene oxide film includes at least one pore. Those skilled in the art will understand that a single-layer graphene oxide sheet in a graphene oxide film may contain multiple pores.

氧化石墨烯片中的孔是板平面中的碳原子空位，这会破坏板的规则六边形碳晶格。这些孔可以在氧化石墨烯片中随机地或以高规则性分布。取决于它们的直径，孔可分类为微孔(直径小于2nm)、中孔(直径在约2nm至约50nm范围内)或大孔(直径大于50nm)。The holes in the graphene oxide sheets are carbon atomic vacancies in the plane of the sheet, which disrupt the regular hexagonal carbon lattice of the sheet. These pores can be distributed randomly or with high regularity in the graphene oxide sheets. Depending on their diameter, pores can be classified as micropores (less than 2 nm in diameter), mesopores (with diameters ranging from about 2 nm to about 50 nm in diameter), or macropores (greater than 50 nm in diameter).

在多层结构中，多孔氧化石墨烯膜中的氧化石墨烯片也彼此分离或间隔开。因此，在氧化石墨烯片之间存在层间空间。当在氧化石墨烯膜中时，氧化石墨烯片彼此分离的程度(即距离)在本申请中可以称为片之间的分离距离或层间间隔。In the multilayer structure, the graphene oxide sheets in the porous graphene oxide film are also separated or spaced from each other. Therefore, there are interlayer spaces between the graphene oxide sheets. When in a graphene oxide film, the degree to which graphene oxide sheets are separated from each other (ie, the distance) may be referred to herein as the separation distance or interlayer spacing between sheets.

在本申请描述的实施方案的方法中使用的多孔氧化石墨烯膜包含至少一个含氧官能团。在一些实施例中，氧化石墨烯膜可以包括多个含氧官能团。这种含氧官能团通常存在于形成多孔氧化石墨烯膜的一部分的至少一个氧化石墨烯片中。The porous graphene oxide membranes used in the methods of the embodiments described herein contain at least one oxygen-containing functional group. In some embodiments, the graphene oxide film may include multiple oxygen-containing functional groups. Such oxygen-containing functional groups are typically present in at least one graphene oxide sheet that forms part of the porous graphene oxide film.

如本申请所用，术语“含氧官能团”通常是指共价结合至氧化石墨烯片的碳原子的官能团，例如环氧基，羟基，羰基，羧基。这样的含氧官能团可以是氧化反应的结果。As used herein, the term "oxygen-containing functional group" generally refers to a functional group covalently bonded to a carbon atom of a graphene oxide sheet, eg, epoxy, hydroxyl, carbonyl, carboxyl. Such oxygen-containing functional groups may be the result of oxidation reactions.

在一些实施方案中，多孔氧化石墨烯膜包含位于选自(i)氧化石墨烯片的孔和(ii)两个或多个氧化石墨烯片之间的至少一个中的含氧官能团。In some embodiments, the porous graphene oxide film comprises oxygen-containing functional groups located in at least one selected from the group consisting of (i) pores of graphene oxide sheets and (ii) between two or more graphene oxide sheets.

在一些实施方案中，多孔氧化石墨烯膜包含位于氧化石墨烯片的孔中和两个或多个氧化石墨烯片之间的含氧官能团。In some embodiments, the porous graphene oxide film comprises oxygen-containing functional groups located in the pores of the graphene oxide sheets and between two or more graphene oxide sheets.

位于氧化石墨烯片的孔中的含氧官能团可以位于孔的边缘。氧化石墨烯片中的孔可包含至少一个含氧官能团，并且可包含多个含氧官能团。当单独的氧化石墨烯片包括多个孔时，每个孔可包含至少一个含氧官能团。The oxygen-containing functional groups located in the pores of the graphene oxide sheet can be located at the edges of the pores. The pores in the graphene oxide sheet may contain at least one oxygen-containing functional group, and may contain multiple oxygen-containing functional groups. When an individual graphene oxide sheet includes a plurality of pores, each pore may contain at least one oxygen-containing functional group.

位于两个或多个氧化石墨烯片之间的含氧官能团可以共价键合到氧化石墨烯片的表面，并从氧化石墨烯片的基面延伸到重叠片之间存在的层间空间中。以这种方式，重叠的氧化石墨烯片可以通过含氧官能团彼此间隔开或分开。多孔氧化石墨烯膜包含至少一个含氧官能团，并且可以包含位于两个或更多个氧化石墨烯片之间的多个含氧官能团。Oxygen-containing functional groups located between two or more graphene oxide sheets can be covalently bonded to the surface of the graphene oxide sheets and extend from the basal plane of the graphene oxide sheets into the interlayer space existing between the overlapping sheets . In this way, overlapping graphene oxide sheets can be spaced or separated from each other by oxygen-containing functional groups. The porous graphene oxide film contains at least one oxygen-containing functional group, and may contain a plurality of oxygen-containing functional groups located between two or more graphene oxide sheets.

在一些实施方案中，可用于本申请描述的实施方案的多孔氧化石墨烯膜具有高氧化度。具有高氧化度的多孔氧化石墨烯膜可包含一定量的含氧官能团，以在氧化石墨烯中提供至少约15％，优选至少约20％，更优选至少约25％的氧含量。In some embodiments, porous graphene oxide films useful in embodiments described herein have a high degree of oxidation. Porous graphene oxide films with a high degree of oxidation may contain an amount of oxygen-containing functional groups to provide an oxygen content in the graphene oxide of at least about 15%, preferably at least about 20%, more preferably at least about 25%.

多孔氧化石墨烯膜的氧含量可以通过适当的技术来确定。例如，氧含量以及因此的氧化度可以通过X射线光电子能谱法(XPS)确定，X射线光电子能谱法测量材料中存在的每种化学元素的类型和百分比。在一种形式中，氧化石墨烯膜中氧化石墨烯薄片可以通过XPS确定的碳氧比(C：O)，为约2：1至约4：1，优选为约2.5：1至3：1。The oxygen content of the porous graphene oxide film can be determined by appropriate techniques. For example, the oxygen content and thus the degree of oxidation can be determined by X-ray photoelectron spectroscopy (XPS), which measures the type and percentage of each chemical element present in the material. In one form, the graphene oxide flakes in the graphene oxide film may have a carbon to oxygen ratio (C:O) determined by XPS of from about 2:1 to about 4:1, preferably from about 2.5:1 to 3:1 .

具有高氧化度的多孔氧化石墨烯膜中氧化石墨烯片中可能具有大量的孔以及片之间的大的层间间隔。例如，具有高氧化度的多孔氧化石墨烯膜可能具有氧化石墨烯片，其层间距可达

(埃)。 Porous graphene oxide films with a high degree of oxidation may have a large number of pores in the graphene oxide sheets and large interlayer spacing between the sheets. For example, a porous graphene oxide film with a high degree of oxidation may have graphene oxide sheets with interlayer spacing of up to

(Egypt).

在本文描述的实施方案的方法中使用的多孔氧化石墨烯膜可以从商业来源获得。或者，多孔石墨烯氧化物膜可以由石墨合成，例如，通过由氧化石墨烯溶液产生氧化石墨烯膜。The porous graphene oxide membranes used in the methods of the embodiments described herein can be obtained from commercial sources. Alternatively, porous graphene oxide films can be synthesized from graphite, for example, by producing graphene oxide films from graphene oxide solutions.

氧化石墨烯浆料Graphene oxide paste

可通过以下方法制备用于形成氧化石墨烯膜的氧化石墨烯浆料：Graphene oxide slurries for forming graphene oxide films can be prepared by the following methods:

通过氧化石墨的方法形成氧化石墨烯；Graphene oxide is formed by the method of graphite oxide;

在溶剂中将氧化石墨剥落以形成氧化石墨烯溶液。The graphite oxide is exfoliated in a solvent to form a graphene oxide solution.

下面描述制备氧化石墨烯溶液的示例性方法。Exemplary methods for preparing graphene oxide solutions are described below.

石墨的氧化Oxidation of graphite

在一些实施方案中，纯化的天然石墨粉末(例如，超高纯度的天然石墨粉末)可以用于氧化石墨。In some embodiments, purified natural graphite powder (eg, ultra-high purity natural graphite powder) can be used for graphite oxide.

可以使用常规方法将石墨氧化以生产氧化石墨。在一些实施方案中，可以采用氧化方法，例如Hammers方法(Journal of the American Chemical Society,1958,80(6), 1339)或改进的Hammers方法(ACS nano,2010,4(8),4806)。Graphite can be oxidized using conventional methods to produce graphite oxide. In some embodiments, oxidation methods such as the Hammers method (Journal of the American Chemical Society, 1958, 80(6), 1339) or a modified Hammers method (ACS nano, 2010, 4(8), 4806) may be employed.

氧化石墨剥落Graphite oxide exfoliation

由石墨的氧化产生的氧化石墨烯包括多个平面的氧化石墨烯片，每个氧化石墨烯片包含至少一个含氧官能团。Graphene oxide produced by oxidation of graphite includes a plurality of planar graphene oxide sheets, each graphene oxide sheet comprising at least one oxygen-containing functional group.

剥落氧化石墨以产生氧化石墨烯片。可以使用本领域已知的剥落技术和条件来进行氧化石墨的剥落。Graphite oxide is exfoliated to produce graphene oxide sheets. The exfoliation of graphite oxide can be performed using exfoliation techniques and conditions known in the art.

在一些实施方案中，可以在足以引起氧化石墨烯片分离的条件下将氧化石墨烯悬浮在溶剂中并在溶剂中剥离，制作氧化石墨烯浆料。氧化石墨烯浆料包括悬浮在溶剂中的分离的氧化石墨烯片。分离的氧化石墨烯片可以是单层或几层形式。In some embodiments, graphene oxide slurries can be made by suspending and exfoliating graphene oxide in a solvent under conditions sufficient to cause separation of the graphene oxide sheets. The graphene oxide slurry includes separated graphene oxide sheets suspended in a solvent. The isolated graphene oxide sheets can be in the form of a single layer or several layers.

氧化石墨烯可以悬浮在任何合适的溶剂中。在一些实施方案中，将氧化石墨悬浮在水性溶剂中。在一些实施方案中，水性溶剂基本上不含有机溶剂。在一些优选方案中，水性溶剂是水。水性溶剂的使用允许以环保的方式制备氧化石墨烯膜。Graphene oxide can be suspended in any suitable solvent. In some embodiments, the graphite oxide is suspended in an aqueous solvent. In some embodiments, the aqueous solvent is substantially free of organic solvents. In some preferred embodiments, the aqueous solvent is water. The use of aqueous solvents allows the preparation of graphene oxide films in an environmentally friendly manner.

可以使用合适的剥离技术在浆料中剥离氧化石墨烯。Graphene oxide can be exfoliated in the slurry using a suitable exfoliation technique.

在一些实施方案中，可以对浆料中的氧化石墨进行机械剥离以产生氧化石墨烯片，然后将其分散在溶剂中。机械剥落可以使用超声处理来实现。In some embodiments, the graphite oxide in the slurry can be mechanically exfoliated to produce graphene oxide sheets, which are then dispersed in a solvent. Mechanical exfoliation can be achieved using sonication.

本领域技术人员将理解，超声处理涉及施加声波能量以搅动氧化石墨，并最终导致石墨材料中的氧化石墨烯晶格层状结构被破坏。晶格层状结构的破坏导致氧化石墨烯片层的分离。可以使用已知可用于剥落氧化石墨的超声处理手段和条件。超声处理可以用超声波处理机或超声处理浴进行。Those skilled in the art will understand that sonication involves the application of sonic energy to agitate the graphite oxide and ultimately result in the destruction of the graphene oxide lattice layered structure in the graphite material. The disruption of the lattice layered structure leads to the separation of graphene oxide sheets. Ultrasonic treatment means and conditions known to be useful for exfoliating graphite oxide can be used. Sonication can be performed with a sonicator or a sonication bath.

在一些实施方案中，超声的频率可以在约20kHz至约400kHz的范围内，优选地在约20kHz的频率下对氧化石墨进行超声处理。In some embodiments, the frequency of the ultrasound can be in the range of about 20 kHz to about 400 kHz, preferably at a frequency of about 20 kHz to sonicate the graphite oxide.

在一些实施方案中，将氧化石墨超声处理以产生氧化石墨烯片。In some embodiments, graphite oxide is sonicated to produce graphene oxide sheets.

超声处理可以进行数秒至数小时的时间。时间可以根据要剥落的氧化石墨的量和超声处理的频率而变化。在一些实施方案中，可将氧化石墨超声处理约5分钟至数小时，优选约20分钟至约1小时，更优选约30分钟。Sonication can be performed for a period of seconds to hours. The time can vary depending on the amount of graphite oxide to be exfoliated and the frequency of sonication. In some embodiments, the graphite oxide can be sonicated for about 5 minutes to several hours, preferably about 20 minutes to about 1 hour, more preferably about 30 minutes.

在浆料中的氧化石墨剥离之后，形成氧化石墨烯浆料。氧化石墨烯浆料可以包含单层和/或几层形式的氧化石墨烯。很少层的形式可以包括2至10个基于石墨烯的片。After the graphite oxide in the slurry is exfoliated, a graphene oxide slurry is formed. The graphene oxide slurry may contain graphene oxide in the form of a single layer and/or several layers. Few-layer forms can include 2 to 10 graphene-based sheets.

氧化石墨烯浆料中的至少一些氧化石墨烯包含至少一个孔。在一些实施方案中，浆液中至少一些氧化石墨烯包含多个孔。孔隙的产生可能是由于引入氧化石墨烯片中的缺陷引起的。At least some of the graphene oxide in the graphene oxide slurry contains at least one pore. In some embodiments, at least some of the graphene oxide in the slurry contains a plurality of pores. The generation of pores may be caused by the defects introduced into the graphene oxide sheets.

氧化石墨烯浆料可以用于形成多孔氧化石墨烯膜。可以使用本领域技术人员已知的常规成膜技术来制备氧化石墨烯膜。Graphene oxide slurries can be used to form porous graphene oxide films. Graphene oxide films can be prepared using conventional film forming techniques known to those skilled in the art.

多孔氧化石墨烯膜的形成Formation of Porous Graphene Oxide Films

可以通过本领域技术人员已知的成膜技术来形成氧化石墨烯膜。The graphene oxide film can be formed by film forming techniques known to those skilled in the art.

在一些实施方案中，多孔氧化石墨烯膜的形成涉及将氧化石墨烯溶液施加到基底上以形成涂层，并从涂层中除去溶剂以在基底上留下多孔氧化石墨烯膜。如果需要，可以从基底上剥离所得的氧化石墨烯膜。例如，可以将膜从基板上剥离。In some embodiments, the formation of the porous graphene oxide film involves applying a graphene oxide solution to the substrate to form a coating, and removing the solvent from the coating to leave the porous graphene oxide film on the substrate. The resulting graphene oxide film can be exfoliated from the substrate if desired. For example, the film can be peeled off from the substrate.

冷冻干燥方法Freeze drying method

在该实施方案中，形成多孔氧化石墨烯膜涉及冷冻干燥过程。在这样的实施方案中，可以将氧化石墨烯浆料滴到基材上以在基材上形成涂层。所述氧化石墨烯浆料是在冰箱低温(例如-25℃)冷冻一段时间(例如10小时)，然后真空干燥，以除去涂层中的溶剂，形成3D多孔氧化石墨烯膜。衬底的尺寸和/或液滴的尺寸可以确定多孔氧化石墨烯膜的尺寸。氧化石墨烯膜的厚度可以由浆料中氧化石墨烯的浓度和量确定。In this embodiment, forming the porous graphene oxide film involves a freeze-drying process. In such embodiments, the graphene oxide slurry can be dropped onto the substrate to form a coating on the substrate. The graphene oxide slurry is frozen for a period of time (for example, 10 hours) at a low temperature in a refrigerator (for example, -25° C.), and then vacuum-dried to remove the solvent in the coating to form a 3D porous graphene oxide film. The size of the substrate and/or the size of the droplets can determine the size of the porous graphene oxide film. The thickness of the graphene oxide film can be determined by the concentration and amount of graphene oxide in the slurry.

压缩氧化石墨烯膜Compressed Graphene Oxide Film

在一些实施方案中，所述多孔氧化石墨烯膜可以涉及用一定的压力(例如1200psi压缩处理)，以进一步降低氧化石墨烯膜的厚度和控制孔径的大小。压缩的氧化石墨烯膜的最终厚度和孔径可能取决于施加的压力。In some embodiments, the porous graphene oxide film may involve compression treatment with a certain pressure (eg, 1200 psi compression) to further reduce the thickness of the graphene oxide film and control the size of the pore size. The final thickness and pore size of the compressed graphene oxide film may depend on the applied pressure.

还原氧化石墨烯的制备Preparation of reduced graphene oxide

实施方案的方法包括将氧化石墨烯膜进行预还原和完全还原以最终制备还原氧化石墨烯膜。预还原包括用光束照射氧化石墨烯膜。完全还原包括用微波辐照预还原的氧化石墨烯膜。用于预还原氧化石墨烯的照射方法在下文也可以称为“光还原”或“激光三维打印”。用于完全还原氧化石墨烯的照射方法在下文也可以称为“微波还原”。The method of an embodiment includes pre-reducing and fully reducing the graphene oxide film to finally produce a reduced graphene oxide film. Prereduction involves irradiating the graphene oxide film with a light beam. Complete reduction involves irradiating pre-reduced graphene oxide films with microwaves. The irradiation method for pre-reduction of graphene oxide may also be referred to hereinafter as "photoreduction" or "laser three-dimensional printing". The irradiation method for complete reduction of graphene oxide may also be referred to as "microwave reduction" hereinafter.

所述预还原和完全还原过程可降低存在于多孔氧化石墨烯膜中的一个或多个氧化石墨烯片的一个或更多的含氧官能团。在一些实施方案中，还原过程还原多个氧化石墨烯片中的至少一个含氧官能团。The pre-reduction and full reduction process can reduce one or more oxygen-containing functional groups present in one or more graphene oxide sheets in the porous graphene oxide film. In some embodiments, the reduction process reduces at least one oxygen-containing functional group in the plurality of graphene oxide sheets.

在实施方案的预还原或完全还原过程中，位于(i)氧化石墨烯片的孔中和/或(i i)两个或多个氧化石墨烯片之间的含氧官能团被还原。During pre-reduction or full reduction of embodiments, oxygen-containing functional groups located (i) in the pores of the graphene oxide sheets and/or (ii) between two or more graphene oxide sheets are reduced.

所述预还原和完全还原过程可还原位于氧化石墨烯片的孔中或在氧化石墨烯层间的含氧官能团。并且在一些实施方案中，照射至少还原了在氧化石墨烯片层之间的部分含氧官能团。The pre-reduction and full reduction process can reduce oxygen-containing functional groups located in the pores of graphene oxide sheets or between graphene oxide layers. And in some embodiments, the irradiation reduces at least a portion of the oxygen-containing functional groups between the graphene oxide sheets.

含氧官能团的预还原和完全还原从氧化石墨烯片上除去了该官能团，并形成了还原氧化石墨烯片。Pre-reduction and complete reduction of oxygen-containing functional groups removed the functional groups from the graphene oxide sheets and formed reduced graphene oxide sheets.

在还原过程之后，产生多孔的预还原或完全还原的氧化石墨烯膜。多孔的预还原或完全还原的氧化石墨烯膜包括至少一个还原的氧化石墨烯片，并且可以包括多个还原的氧化石墨烯片。当氧化石墨烯片中的至少一个含氧官能团被还原和去除时，形成还原的氧化石墨烯片。After the reduction process, a porous pre-reduced or fully reduced graphene oxide film is produced. The porous pre-reduced or fully reduced graphene oxide film includes at least one reduced graphene oxide sheet, and can include a plurality of reduced graphene oxide sheets. Reduced graphene oxide sheets are formed when at least one oxygen-containing functional group in the graphene oxide sheets is reduced and removed.

在一个实施方案中，预还原和/或完全还原在基本上无氧的环境中进行，例如在真空中或在惰性气氛例如氮气或氩气气氛中。In one embodiment, the pre-reduction and/or full reduction is performed in a substantially oxygen-free environment, such as in a vacuum or in an inert atmosphere such as nitrogen or argon.

本领域技术人员将理解，对于实施方案而言，并非必须预先还原或完全还原多孔氧化石墨烯膜中的所有氧化石墨烯片。然而，实施方案的方法提供了膜中至少一个氧化石墨烯片被还原。Those skilled in the art will understand that for embodiments, it is not necessary to pre-reduce or fully reduce all graphene oxide sheets in the porous graphene oxide film. However, the methods of the embodiments provide that at least one graphene oxide sheet in the film is reduced.

在一些实施方案中，多孔氧化石墨烯膜中的氧化石墨烯片的一部分被预先还原或完全还原。在这样的实施方案中，所得膜包含氧化石墨烯片和还原的氧化石墨烯片的混合物。In some embodiments, a portion of the graphene oxide sheets in the porous graphene oxide film are pre-reduced or fully reduced. In such embodiments, the resulting film comprises a mixture of graphene oxide sheets and reduced graphene oxide sheets.

本领域技术人员技术人员会理解，可以调节预还原和完全还原的工艺条件，以改变被还原的含氧官能团的量，从而改变还原的程度。Those skilled in the art will appreciate that the pre-reduction and full reduction process conditions can be adjusted to vary the amount of oxygen-containing functional groups that are reduced, and thus the degree of reduction.

孔径和/或层间距的任何变化是通过与还原工艺之前多孔氧化石墨烯膜中存在的相应氧化石墨烯片进行比较来确定的。Any changes in pore size and/or interlayer spacing were determined by comparison with the corresponding graphene oxide sheets present in the porous graphene oxide film prior to the reduction process.

如前面提到的，使用光束照射氧化石墨烯膜实现对氧化石墨烯膜的预还原。光辐射可引起热(即光热)或化学(即光化学)效应，其还原存在于多孔氧化石墨烯膜中的至少一个含氧官能团。在光热还原中，光或辐射可以包括不同形式的电磁辐射，包括光学辐射。As mentioned earlier, pre-reduction of the graphene oxide film is achieved by irradiating the graphene oxide film with a light beam. Optical radiation can induce thermal (ie, photothermal) or chemical (ie, photochemical) effects that reduce at least one oxygen-containing functional group present in the porous graphene oxide film. In photothermal reduction, light or radiation can include different forms of electromagnetic radiation, including optical radiation.

可以使用任何合适波长的光或辐射来进行光热还原。合适的波长可以从紫外线范围(约10nm)到红外线范围(约100μm)不等。Photothermal reduction can be performed using any suitable wavelength of light or radiation. Suitable wavelengths may vary from the ultraviolet range (about 10 nm) to the infrared range (about 100 μm).

在一些实施例中，来自CO ₂激光器的合适波长可以是从大约248nm到高达10.6μm。 In some embodiments, suitable wavelengths from a CO ₂ laser may be from about 248 nm up to 10.6 μm.

可以使用任何合适类型的光或辐射源进行光热还原。合适的光源或辐射源优选具有足够的功率以产生最小量的热量。在一些实施方案中，合适的光源或辐射源具有足够的功率以在还原过程中将多孔氧化石墨烯膜加热至至少约200℃的温度。可以用来促进光热还原的光源的一些示例包括但不限于紫外线灯，聚焦的日光和闪光灯。Photothermal reduction can be performed using any suitable type of light or radiation source. A suitable light source or radiation source preferably has sufficient power to generate a minimum amount of heat. In some embodiments, a suitable light source or radiation source has sufficient power to heat the porous graphene oxide film to a temperature of at least about 200°C during the reduction process. Some examples of light sources that can be used to facilitate photothermal recovery include, but are not limited to, UV lamps, focused sunlight, and flashlights.

如前面提到的，氧化石墨烯膜照射微波以完全还原氧化石墨烯膜。微波照射产生热效应，从而还原了存在于多孔氧化石墨烯膜的至少一个含氧官能团。As mentioned earlier, the graphene oxide film was irradiated with microwaves to completely reduce the graphene oxide film. The microwave irradiation produces a thermal effect that reduces at least one oxygen-containing functional group present in the porous graphene oxide film.

微波还原涉及使用微波辐射多孔氧化石墨烯膜(有和没有预还原)并在膜中产生局部热量。辐照后产生的热量取决于微波源和氧化石墨烯膜的热性能。Microwave reduction involves the use of microwaves to irradiate porous graphene oxide membranes (with and without prereduction) and generate localized heat in the membranes. The heat generated after irradiation depends on the microwave source and the thermal properties of the graphene oxide film.

孔径控制Aperture control

还原氧化石墨烯材料的孔径大小最初由冷冻干燥氧化石墨烯浆料的浓度和所述压缩过程的压力控制。在这个过程中，其趋势是越高浓度的浆料所产生的孔径越小，同时，越高的压力所产生的孔径越小。同时，还原氧化石墨烯材料的孔径的控制可以通过控制还原过程实现。通过还原(包括预还原和完全还原)可以除去含氧官能团，并且可以形成疏水性石墨烯结构域。在该方法中，由于去除了多个氧化石墨烯片层之间的氧官能团和水，可能产生诸如CO、CO ₂和H ₂O蒸气的气体。在还原过程中，气体可能会高速加热，这会导致气体体积膨胀，从而在各层之间产生孔隙。 The pore size of the reduced graphene oxide material is initially controlled by the concentration of the freeze-dried graphene oxide slurry and the pressure of the compression process. In this process, the trend is that the higher the concentration of the slurry, the smaller the pore size is, and the higher the pressure, the smaller the pore size is. Meanwhile, the control of the pore size of the reduced graphene oxide material can be achieved by controlling the reduction process. Oxygen-containing functional groups can be removed by reduction, including pre-reduction and full reduction, and hydrophobic graphene domains can be formed. In this method, gases such as CO, CO ₂ and H ₂ O vapor may be generated due to the removal of oxygen functional groups and water between the multiple graphene oxide sheets. During the reduction process, the gas may heat up at a high rate, which causes the gas volume to expand, creating pores between the layers.

电导率控制Conductivity Control

可以通过选择或控制还原参数来控制还原氧化石墨烯材料的电导率。通过还原(包括预还原和完全还原)氧官能团被除去，石墨烯的sp2网络结构恢复，其结果提高电导率。The conductivity of the reduced graphene oxide material can be controlled by selecting or controlling the reduction parameters. Through reduction (including pre-reduction and full reduction) the oxygen functional group is removed, the sp2 network structure of graphene is restored, and as a result, the electrical conductivity is improved.

使用还原氧化石墨烯电极的超级电容器Supercapacitors using reduced graphene oxide electrodes

根据上述方法生成的还原氧化石墨烯结构可以用于包括制造超级电容器的电极在内的一系列应用。The reduced graphene oxide structures produced according to the methods described above can be used for a range of applications including the fabrication of electrodes for supercapacitors.

根据上述方法生成的还原氧化石墨烯结构可以用于制造超级电容器的电极。The reduced graphene oxide structure produced according to the above method can be used to fabricate electrodes for supercapacitors.

使用上述方法制备的包括还原氧化石墨烯结构电极的超级电容器(以下被称为“还原氧化石墨烯超级电容器”)可以具有三明治结构。The supercapacitor including the reduced graphene oxide structured electrode (hereinafter referred to as "reduced graphene oxide supercapacitor") prepared using the above method may have a sandwich structure.

具有三明治结构的超级电容器Supercapacitor with sandwich structure

在一些实施例中，还原氧化石墨烯超级电容器可以具有三明治结构。In some embodiments, the reduced graphene oxide supercapacitor may have a sandwich structure.

每个三明治结构包括两个电极，夹在两个电极之间的隔膜以及连接到电极的一对集流器。Each sandwich structure includes two electrodes, a separator sandwiched between the two electrodes, and a pair of current collectors connected to the electrodes.

在还原氧化石墨烯超级电容器中，具有孔的还原氧化石墨烯电极被夹在两个金属集流器之间，两个金属集流器由隔膜(例如，电介质隔膜)隔开。可以使用如上所述的工艺来制造还原氧化石墨烯电极。In reduced graphene oxide supercapacitors, a reduced graphene oxide electrode with pores is sandwiched between two metal current collectors separated by a separator (eg, a dielectric separator). Reduced graphene oxide electrodes can be fabricated using the processes described above.

用夹层结构制造还原氧化石墨烯超级电容器的方法可以包括以下步骤：The method of fabricating a reduced graphene oxide supercapacitor with a sandwich structure may include the following steps:

(1)制造还原氧化石墨烯结构，其将用作超级电容器的电极；和(1) Fabrication of reduced graphene oxide structures that will be used as electrodes for supercapacitors; and

(2)将电极与金属集流器和隔膜进行组装。(2) Assemble the electrodes with metal current collectors and separators.

制作还原氧化石墨烯超级电容器的方法可以进一步包括使用本领域技术人员已知的制作超级电容器的任何其他步骤。The method of making a reduced graphene oxide supercapacitor may further include using any other steps known to those skilled in the art to make a supercapacitor.

隔膜和集流器可以通过本领域技术人员已知的任何常规方法来制造。在一些实施例中，隔膜可以由根据上述方法制造的氧化石墨烯膜制成。The membranes and current collectors can be fabricated by any conventional method known to those skilled in the art. In some embodiments, the separator may be made of a graphene oxide film fabricated according to the methods described above.

示例的处理方法Example processing method

如图1所示，根据一些实施例，形成还原氧化石墨烯的方法100开始于步骤102。As shown in FIG. 1 , according to some embodiments, a method 100 of forming reduced graphene oxide begins at step 102 .

在步骤104，石墨被氧化以产生氧化石墨。然后在步骤106剥落生成的氧化石墨以形成氧化石墨烯浆液。在步骤108，通过冷冻干燥法形成多孔氧化石墨烯膜。At step 104, the graphite is oxidized to produce graphite oxide. The resulting graphite oxide is then exfoliated at step 106 to form a graphene oxide slurry. At step 108, a porous graphene oxide film is formed by freeze-drying.

然后，在步骤110对在步骤108形成的多孔氧化石墨烯薄膜进行压缩。在步骤112中，对氧化石墨烯膜照射光束以预还原多孔氧化石墨烯膜。在步骤114中，用微波辐照预还原的氧化石墨烯膜以形成还原氧化石墨烯结构，该结构将用作还原氧化石墨烯超级电容器中的电极。Then, at step 110, the porous graphene oxide film formed at step 108 is compressed. In step 112, the graphene oxide film is irradiated with a light beam to prereduce the porous graphene oxide film. In step 114, the pre-reduced graphene oxide film is irradiated with microwaves to form a reduced graphene oxide structure that will be used as an electrode in a reduced graphene oxide supercapacitor.

在步骤116，将形成的还原氧化石墨烯结构与金属集流体组装在一起，以形成还原氧化石墨烯超级电容器。At step 116, the formed reduced graphene oxide structure is assembled with a metal current collector to form a reduced graphene oxide supercapacitor.

应用示例Application example

根据上述方法制造的还原氧化石墨烯(RGO)结构，还原氧化石墨烯电极或还原氧化石墨烯超级电容器可以提供许多优点或技术效果。能量密度可以类似于锂电池的能量密度。氧化石墨烯浆料可以直接从大型石墨材料与氧化剂合成，并且氧化石墨烯膜通过使用低成本的合成技术制造，如所述的冷冻干燥技术。氧化石墨烯材料的预还原可以使用便宜的激光二极管来实现，并且完全还原过程可以使用廉价的微波炉来实现。这个过程可以允许还原氧化石墨超级电容器方便地与其它电子设备集成，例如与太阳能电池板集成。超高功率密度可以为电子设备提供高电流，而还原氧化石墨烯超级电容器的充电可以在很短的时间内完成。还原氧化石墨烯超级电容器可具有热稳定性和化学惰性，因此可以在苛刻的环境中使用。还原氧化石墨烯膜可能对高温、氧化剂、强酸性/碱性试剂或有机溶剂具有较高的耐受性。还原氧化石墨烯膜可具有很高的机械强度。由于具有较高的机械强度、热和化学稳定性，因此还原氧化石墨烯超级电容器的使用寿命可以比现有超级电容器更长。According to the reduced graphene oxide (RGO) structures fabricated by the above methods, reduced graphene oxide electrodes or reduced graphene oxide supercapacitors can provide many advantages or technical effects. The energy density can be similar to that of lithium batteries. Graphene oxide slurries can be synthesized directly from large graphitic materials with oxidizing agents, and graphene oxide films are fabricated by using low-cost synthesis techniques, such as the described freeze-drying technique. Pre-reduction of graphene oxide materials can be achieved using inexpensive laser diodes, and the full reduction process can be achieved using inexpensive microwave ovens. This process could allow reduced graphite oxide supercapacitors to be easily integrated with other electronic devices, such as solar panels. The ultra-high power density can provide high current for electronic devices, and the charging of the reduced graphene oxide supercapacitor can be completed in a very short time. Reduced graphene oxide supercapacitors can be thermally stable and chemically inert, so they can be used in harsh environments. Reduced graphene oxide films may have high resistance to high temperatures, oxidizing agents, strongly acidic/basic reagents, or organic solvents. The reduced graphene oxide film can have high mechanical strength. Due to its high mechanical strength, thermal and chemical stability, reduced graphene oxide supercapacitors can last longer than existing supercapacitors.

RGO结构、RGO电极和RGO超级电容器可以采用环保的溶剂以环保的方式制备。此外，RGO膜可以是无毒的并且与生物样品相容。RGO structures, RGO electrodes, and RGO supercapacitors can be fabricated in an environmentally friendly manner using environmentally friendly solvents. Furthermore, RGO membranes can be non-toxic and compatible with biological samples.

使用如上所述的方法制造的超级电容器可以用于合适的应用，包括以下中的一个或多个：可直接储能的太阳能电池(例如，通过将超级电容器与太阳能电池板集成)；无人机电源；电动自行车或车辆的电源；夜视镜电源；军用无线电电源；军事GPS设备的电源；用于太阳能道路照明的电源；太阳能灌溉***的电源；移动房屋的电源；在生物医学应用中，例如生物植入物的电源；消费电子产品的电源，例如手机电池；轻轨和电车的电源；聪明的微电网；生物传感器；可充电的外套，用于为个人设备供电；为个人设备供电的可充电袋；带内置头灯的可充电自行车头盔；以及用于温室或其他种植相关应用的电源。Supercapacitors fabricated using the methods described above can be used in suitable applications, including one or more of the following: solar cells that can store energy directly (eg, by integrating the supercapacitor with solar panels); drones power supply; power supply for electric bicycles or vehicles; power supply for night vision goggles; power supply for military radios; power supply for military GPS equipment; power supply for solar road lighting; power supply for solar irrigation systems; power supply for mobile homes; in biomedical applications such as Power for biological implants; power for consumer electronics such as cell phone batteries; power for light rail and trams; smart microgrids; biosensors; rechargeable jackets for powering personal devices; rechargeables for powering personal devices bags; rechargeable bike helmets with built-in headlights; and power supplies for greenhouses or other grow-related applications.

使用如上所述的方法制造的超级电容器可以通过已知的电化学技术来表征，例如，以下技术中的任何一种或多种：循环伏安法，循环充电放电，泄漏电流测量，自放电测量和电化学阻抗谱。Supercapacitors fabricated using the methods described above can be characterized by known electrochemical techniques, for example, any one or more of the following techniques: cyclic voltammetry, cyclic charge-discharge, leakage current measurements, self-discharge measurements and electrochemical impedance spectroscopy.

该实施例现在将参考以下示例中描述。然而，应当理解，这些示例是通过举例说明实施方案的方式提供的，它们绝不限制本发明的范围。This embodiment will now be described with reference to the following examples. It should be understood, however, that these examples are provided by way of illustrative embodiments and in no way limit the scope of the invention.

实施例Example

下面描述的示例性实验涉及制造还原氧化石墨烯(RGO)结构和还原氧化石墨烯(RGO)超级电容器的过程，以及相应的实验结果。The exemplary experiments described below relate to the process of fabricating reduced graphene oxide (RGO) structures and reduced graphene oxide (RGO) supercapacitors, as well as the corresponding experimental results.

氧化石墨烯浆料的制备Preparation of graphene oxide slurry

将天然石墨粉(SP-1，Bay Carbon)(20克)放入80℃的浓H ₂SO ₄(30mL)，K ₂S ₂O ₈(10g)和P ₂O ₅(10克)的溶液中。将所得深蓝色混合物热分离，并在6小时内冷却至室温。然后将混合物用蒸馏水小心稀释，过滤，并在过滤器上洗涤直至冲洗水的pH值变为中性。将产物在环境温度下在空气中干燥过夜。然后，该过氧化的石墨通过Hummers法进行氧化。将氧化的石墨粉末(20g)放入冷(0℃)浓H ₂SO ₄(460mL)中。在搅拌和冷却下逐渐加入KMnO ₄(60g)，使得混合物的温度低于20℃。然后将混合物在35℃搅拌2小时，并加入蒸馏水(920mL)。在15分钟内，通过添加大量蒸馏水(2.8L)和30％H ₂O ₂溶液(50mL)终止反应，然后混合物的颜色变为亮黄色。过滤混合物，并用1:10HCl溶液(5L)洗涤，以除去金属离子。将氧化石墨产物悬浮在蒸馏水中，得到粘稠的棕色2％分散体，将其进行渗析以完全除去金属离子和酸。将合成后的氧化石墨悬浮在水中，得到褐色分散体，将其进行渗析以完全除去残留的盐和酸。所有实验均使用Ultrapure Milli-Q水。然后将纯化后的氧化石墨悬浮液分散在水中以产生0.05wt％的分散体。通过使用Brandson Digital Sonifier(S450D，500W，30％振幅)对分散液进行超声处理30分钟，将氧化石墨剥落成氧化石墨烯。然后使用转子半径为14cm的Eppendorf5702离心机，将获得的棕色分散体以3000rpm的速度离心30分钟，以除去任何未剥落的氧化石墨(通常存在的量非常少)。 Natural graphite powder (SP-1, Bay Carbon) (20 g) was put into a solution of concentrated H ₂ SO ₄ (30 mL), K ₂ S ₂ O ₈ (10 g) and P ₂ O ₅ (10 g) at 80°C middle. The resulting dark blue mixture was thermally separated and cooled to room temperature over 6 hours. The mixture was then carefully diluted with distilled water, filtered, and washed on the filter until the pH of the rinse water became neutral. The product was dried in air at ambient temperature overnight. Then, the peroxidized graphite is oxidized by the Hummers method. The oxidized graphite powder (20 g) was placed in cold ( ₀ °C) concentrated _H2SO4 (460 mL). KMnO4 ₍ 60 g) was gradually added with stirring and cooling so that the temperature of the mixture was below 20°C. The mixture was then stirred at 35°C for 2 hours, and distilled water (920 mL) was added. The reaction was quenched by adding copious distilled water (2.8 L) and 30% H2O2 solution (50 mL ₎ within ₁₅ minutes, then the color of the mixture changed to bright yellow. The mixture was filtered and washed with 1:10 HCl solution (5 L) to remove metal ions. The graphite oxide product was suspended in distilled water to give a viscous brown 2% dispersion which was dialyzed to completely remove metal ions and acids. The synthesized graphite oxide was suspended in water to obtain a brown dispersion, which was dialyzed to completely remove residual salts and acids. Ultrapure Milli-Q water was used for all experiments. The purified graphite oxide suspension was then dispersed in water to yield a 0.05 wt% dispersion. The graphite oxide was exfoliated to graphene oxide by sonicating the dispersion using a Brandson Digital Sonifier (S450D, 500W, 30% amplitude) for 30 minutes. The resulting brown dispersion was then centrifuged at 3000 rpm for 30 minutes using an Eppendorf 5702 centrifuge with a rotor radius of 14 cm to remove any unexfoliated graphite oxide (usually present in very small amounts).

多孔还原氧化石墨烯膜的制备：Preparation of Porous Reduced Graphene Oxide Films:

将氧化石墨烯浆液在-25℃的冰箱中冷冻10小时，然后真空干燥，得到多孔结构的氧化石墨烯膜。然后该氧化石墨烯膜在1200PSI的压力下压缩数次到氧化石墨烯薄层，以增强氧化石墨烯薄膜的机械强度。冷冻干燥的氧化石墨烯膜在玻璃基板上的照片如图2所示。然后将这些膜从基板上剥离下来以形成独立的氧化石墨烯膜，也可以将这些膜撕碎成小块。The graphene oxide slurry was frozen in a refrigerator at -25 °C for 10 hours, and then vacuum-dried to obtain a graphene oxide film with a porous structure. Then the graphene oxide film was compressed several times to the graphene oxide thin layer under the pressure of 1200 PSI to enhance the mechanical strength of the graphene oxide film. Photographs of freeze-dried graphene oxide films on glass substrates are shown in Figure 2. These films are then peeled off the substrate to form free-standing graphene oxide films, which can also be shredded into small pieces.

将压缩的氧化石墨烯薄层放置在氮气室中，并在此处引入红外(IR)激光以预还原氧化石墨烯层。仅用不到1秒的激光照射，整个氧化石墨烯层将被约200W/cm ²的激光功率(功率：1.6W，激光光斑尺寸：直径100微米)完全还原,计算的激光相对于薄膜的移动速度为10毫米/秒，这是由于自传播的类似多米诺骨牌反应的速度非常快。将激光预还原的氧化石墨烯薄层转移到石英玻璃容器中，并充入氮气，以消除其他气体的影响。然后将膜放入商用微波炉中，以全功率(1000W)还原30秒。所述的还原后的冷冻干燥氧化石墨烯膜的扫描电子显微镜(SEM)图像示于图3。 The compressed graphene oxide thin layer was placed in a nitrogen chamber, where an infrared (IR) laser was introduced to prereduce the graphene oxide layer. With less than 1 second of laser irradiation, the entire graphene oxide layer will be completely reduced by a laser power of about 200W/ ^cm2 (power: 1.6W, laser spot size: 100 μm in diameter), the calculated movement of the laser relative to the film The speed is 10 mm/s, which is due to the very fast speed of the self-propagating domino-like reaction. The laser-prereduced graphene oxide thin layer was transferred into a quartz glass container and filled with nitrogen to eliminate the influence of other gases. The membrane was then placed in a commercial microwave oven and reduced at full power (1000 W) for 30 seconds. A scanning electron microscope (SEM) image of the reduced freeze-dried graphene oxide film is shown in FIG. 3 .

结果result

通过拉曼光谱分析在以上实施例中制备的多孔还原氧化石墨烯膜。一些结果在下面讨论。The porous reduced graphene oxide films prepared in the above examples were analyzed by Raman spectroscopy. Some results are discussed below.

通过抽滤技术生产的氧化石墨烯膜的拉曼光谱如图4所示。在图4中分别示出了通过用激光二极管(LD)照射和用LD与微波结合照射产生的多孔还原氧化石墨烯膜的光谱。该结合的还原方式的光谱的I _D/I _G的比率显著下降，对应于缺陷密度的明显降低。所述还原氧化石墨烯膜也应用了元素分析进行表征，其原子重量的柱状图如图5所示。 The Raman spectrum of the graphene oxide film produced by the suction filtration technique is shown in Figure 4. Spectra of the porous reduced graphene oxide films produced by irradiation with a laser diode (LD) and irradiation with LD in combination with microwaves are shown in Figure 4, respectively. The ratio of ID/ _IG of the _spectrum of this combined reduction mode decreases significantly, corresponding to a significant decrease in defect density. The reduced graphene oxide film was also characterized by elemental analysis, and the histogram of its atomic weight is shown in FIG. 5 .

使用电化学工作站(Metro Autolab N系列恒电位仪/恒电流仪)测量具有不同浓度(例如169.9mg/ml，72mg/ml)的氧化石墨烯浆料制成的超级电容器的性能。其中1-乙基-3-甲基咪唑四氟硼酸盐(EMIMBF4)/AN作为电解液。结果如图6至图15所示。循环伏安法(CV)测试显示了在宽电压扫描速率范围内从0至3.5V的矩形曲线。恒电流在不同电流密度下的充/放电曲线。相应的电容最高为250F/g。放电开始时的电压降为0.034V(对于0.5A/g的电流密度)，表明测试电池中的ESR非常低。对从500kHz到1MHz的频率范围进行频率响应分析(FRA)可以得出以电阻抗谱(EIS)表示的Nyquist图。该图显示为一调近似垂直的曲线，表明近乎理想的电容行为。The performance of supercapacitors made of graphene oxide slurries with different concentrations (eg, 169.9 mg/ml, 72 mg/ml) was measured using an electrochemical workstation (Metro Autolab N-series potentiostat/galvanostat). Among them, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4)/AN was used as electrolyte. The results are shown in Figures 6 to 15. Cyclic voltammetry (CV) testing showed a rectangular curve from 0 to 3.5V over a wide voltage scan rate range. Galvanostatic charge/discharge curves at different current densities. The corresponding capacitance is up to 250F/g. The voltage drop at the onset of discharge was 0.034V (for a current density of 0.5A/g), indicating very low ESR in the test cells. A frequency response analysis (FRA) over the frequency range from 500kHz to 1MHz yields a Nyquist plot expressed as an electrical impedance spectrum (EIS). The graph is shown as a tonal near-vertical curve, indicating near-ideal capacitive behavior.

解释与定义Explanation and Definition

术语“约”和通常使用的范围，无论是否由术语“大约”限定，都意味着所理解的数字不限于本文所述的确切数字，并且旨在指代基本上在所引用范围内的范围。而不脱离本发明的范围。如本文中所使用的，“约”将被本领域普通技术人员理解，并且将在使用它的上下文中在某种程度上变化。如果给定使用上下文的术语的使用对本领域普通技术人员而言尚不清楚，则“约”表示特定术语的正负10％。The term "about" and commonly used ranges, whether defined by the term "about" or not, mean that the understood number is not limited to the exact number recited herein, and is intended to refer to a range substantially within the recited range. without departing from the scope of the present invention. As used herein, "about" will be understood by one of ordinary skill in the art and will vary to some extent in the context in which it is used. "About" means plus or minus 10% of the particular term if the usage of the term in a given context of use is not clear to one of ordinary skill in the art.

除非另有说明，否则本文所指的百分比(％)基于重量百分比(w/w或w/v)。Unless otherwise stated, the percentages (%) referred to herein are based on weight percentages (w/w or w/v).

本说明书中对任何先前出版物(或从其衍生的信息)或任何已知事项的引用均不是，也不应该被视为对该先前出版物(或信息)的承认或认可或任何形式的暗示。本说明书所涉及的研究领域中的公知常识的一部分。Reference in this specification to any prior publication (or information derived therefrom) or to any known matter is not and should not be construed as an acknowledgement or endorsement or implication of any kind of such prior publication (or information) . Part of the common general knowledge in the research field to which this specification relates.

在整个说明书和随后的权利要求书中，除非上下文另有要求，否则词语“包括”以及诸如“包括”和“包含”之类的变体将被理解为暗示包括所述整数或步骤或整数组。或步骤，但不排除任何其他整数或步骤或一组整数或步骤。Throughout the specification and the claims that follow, unless the context requires otherwise, the word "comprising" and variations such as "comprising" and "comprising" will be understood to imply the inclusion of the stated integer or step or group of integers . or steps, but does not exclude any other integer or step or set of integers or steps.

在不脱离本发明范围的情况下，许多修改对于本领域技术人员将是显而易见的。Numerous modifications will be apparent to those skilled in the art without departing from the scope of the present invention.

Claims

一种用于制备多孔石墨烯膜的方法，包括：A method for preparing a porous graphene membrane, comprising:

冷冻干燥氧化石墨烯浆料以形成多孔氧化石墨烯膜，并使用光束和微波照射多孔氧化石墨烯膜以形成多孔还原氧化石墨烯膜。The graphene oxide slurry was freeze-dried to form a porous graphene oxide film, and the porous graphene oxide film was irradiated with a light beam and microwaves to form a porous reduced graphene oxide film.
根据权利要求1所述的方法，其中，所述氧化石墨烯包括一层或多层多孔氧化石墨烯膜。The method of claim 1, wherein the graphene oxide comprises one or more layers of porous graphene oxide film.
根据权利要求2所述的方法，其中，所述多孔氧化石墨烯膜的每一层包括：The method of claim 2, wherein each layer of the porous graphene oxide film comprises:

多层的多孔氧化石墨烯片；和multilayered porous graphene oxide sheets; and

位于两个或多个氧化石墨烯片之间的氧官能团。Oxygen functional groups located between two or more graphene oxide sheets.
根据权利要求3所述的方法，其中，包括使用光或者微波照射除去氧化石墨烯片之间的至少一部分含氧官能团。The method of claim 3, comprising removing at least a portion of the oxygen-containing functional groups between the graphene oxide sheets using light or microwave irradiation.
根据权利要求3所述的方法，其中，包括通过照射所述多孔氧化石墨烯膜在所述多孔氧化石墨烯膜中进一步产生孔洞。4. The method of claim 3, comprising further creating pores in the porous graphene oxide film by irradiating the porous graphene oxide film.
根据权利要求2所述的方法，其中，包括在照射期间移动所述光束或者辐射束相对于所述多孔氧化石墨烯膜的位置。3. The method of claim 2, comprising moving the position of the light beam or radiation beam relative to the porous graphene oxide film during irradiation.
根据权利要求2所述的方法，其中，氧化石墨烯包括多层多孔氧化石墨烯膜，由透明绝缘介电材料隔离。3. The method of claim 2, wherein the graphene oxide comprises a multilayer porous graphene oxide film separated by a transparent insulating dielectric material.
根据权利要求7所述的方法，其中，通过照射同时还原所述多层氧化石墨烯膜。The method of claim 7, wherein the multilayered graphene oxide film is simultaneously reduced by irradiation.
根据权利要求1所述的方法，其中，所述氧化石墨烯包括氧化石墨烯溶液。The method of claim 1, wherein the graphene oxide comprises a graphene oxide solution.
根据权利要求9所述的方法，其中，还包括：The method of claim 9, further comprising:

将石墨氧化以形成氧化石墨；并在溶剂中剥离氧化石墨以形成氧化石墨烯浆料。The graphite is oxidized to form graphite oxide; and the graphite oxide is exfoliated in a solvent to form a graphene oxide slurry.
根据权利要求1所述的方法，其中，所述光束或辐射束包括连续波(CW)激光束或脉冲激光束。The method of claim 1, wherein the beam or beam of radiation comprises a continuous wave (CW) laser beam or a pulsed laser beam.
根据权利要求1所述的方法，还包括：The method of claim 1, further comprising:

使用形成的还原氧化石墨烯制作还原氧化石墨烯电极。A reduced graphene oxide electrode is fabricated using the formed reduced graphene oxide.
根据权利要求1所述的方法，其中，还包括：The method of claim 1, further comprising:

辐射后将集流器连接到还原氧化石墨烯。The current collectors were attached to the reduced graphene oxide after irradiation.
一种多孔还原氧化石墨烯膜，其通过权利要求1-11中的任一项的方法制得。A porous reduced graphene oxide film obtained by the method of any one of claims 1-11.
一种还原氧化石墨烯电极，其通过权利要求1-14中任一项的方法制得。A reduced graphene oxide electrode prepared by the method of any one of claims 1-14.
一种电容器，其通过权利要求1至14中任一项所述的方法制造。A capacitor manufactured by the method of any one of claims 1 to 14.
根据权利要求16所述的电容器，其中，所述电容器是超级电容器。The capacitor of claim 16, wherein the capacitor is a supercapacitor.