阅读说明：本技术 一种石墨烯纳米孔阵列及其制备方法和应用 (Graphene nanopore array and preparation method and application thereof ) 是由 吴丹丹 袁志山 王成勇 于 2019-08-08 设计创作，主要内容包括：本发明涉及一种石墨烯纳米孔阵列及其制备方法和应用。所述快速可控制备方法包括如下步骤：S1：将表面分布有纳针的基底薄膜作为模具；S2：向模具上旋涂石墨烯悬浮液,使得石墨烯悬浮液分布于基底薄膜和纳针表面,固化得石墨烯薄膜；S3：对基底薄膜施加力,使得纳针的针尖刺破石墨烯薄膜,即得所述石墨烯纳米孔阵列。本发明利用纳针刺破石墨烯薄膜的方式来得到石墨烯纳米孔阵列,石墨烯纳米孔阵列的纳米孔直径及分布与模具上的纳针针尖直径和分布相对应,尺寸、密度可控。本发明提供的制备方法简单,高效,成本较低,所需设备简单,解决了传统纳米孔阵列制备中的成本高,低效等问题。(The invention relates to a graphene nanopore array and a preparation method and application thereof. The rapid and controllable preparation method comprises the following steps: s1: taking a substrate film with nano needles distributed on the surface as a mould; s2: rotationally coating the graphene suspension liquid on the mold to enable the graphene suspension liquid to be distributed on the surfaces of the substrate film and the nano needle, and curing to obtain the graphene film; s3: and applying force to the substrate film to enable the needle point of the nano needle to puncture the graphene film, so as to obtain the graphene nanopore array. According to the method, the graphene nanopore array is obtained by puncturing the graphene film by the nano needles, the diameters and the distribution of the nano holes of the graphene nanopore array correspond to the diameters and the distribution of the needle tips of the nano needles on the mold, and the size and the density are controllable. The preparation method provided by the invention is simple, efficient, low in cost and simple in required equipment, and solves the problems of high cost, low efficiency and the like in the traditional nanopore array preparation.)

1. A rapid and controllable preparation method of a graphene nanopore array is characterized by comprising the following steps:

s1: taking a substrate film with nano needles distributed on the surface as a mould;

S2: rotationally coating the graphene suspension liquid on the mold to enable the graphene suspension liquid to be distributed on the surfaces of the substrate film and the nano needle, and curing to obtain the graphene film;

s3: and applying force to the substrate film to enable the needle point of the nano needle to puncture the graphene film, so as to obtain the graphene nanopore array.

2. the method according to claim 1, wherein the height of the nanoneedle protruding from the base film is 50nm to 500 μm.

3. The preparation method according to claim 1, wherein the needle tip diameter of the nanoneedle is 10-100 nm; the distance between the adjacent nano needles is 10-200 nm.

4. the preparation method according to claim 1, wherein the substrate film is one or more of a silicon nitride film, a silicon film or a metal film; the nano needle is one or more of a silicon nitride nano needle, a silicon nano needle or a metal nano needle.

5. The method of claim 1, wherein the mold in S1 is manufactured by a micro-machining process.

6. The preparation method according to claim 1, wherein the mass concentration of graphene in the graphene suspension in S2 is 2-10 mg/mL.

7. The method according to claim 1, wherein the graphene thin film in S2 has a thickness of 10 to 100 nm.

8. A graphene nanopore array, characterized by being prepared by the preparation method of any one of claims 1 to 7.

9. The graphene nanopore array according to claim 8, wherein the pore diameter of the nanopore in the graphene nanopore array is 10-100 nm.

10. Use of the graphene nanopore array of any one of claims 8 to 9 in the preparation of a graphene battery.

Technical Field

the invention belongs to the technical field of micro-nano device preparation and application, and particularly relates to a graphene nanopore array and a preparation method and application thereof.

background

The graphene battery is a new energy battery developed by utilizing the characteristic that lithium ions rapidly shuttle and move in a large quantity between the surface of graphene and an electrode. Such new batteries can be charged for hours down to as short as one minute, and their charge-discharge rate is becoming a focus of attention. From a microscopic perspective, the charge and discharge process of the storage battery is actually a process of "embedding" and "detaching" on the positive ion re-electrode, so that the more pores on the electrode material, the smaller the pores, and the higher the charge and discharge speed is represented macroscopically. Therefore, in the research of graphene batteries, how to prepare graphene with many large-area holes and small size becomes a key.

At present, various methods for preparing graphene nanopores exist internationally, but how to rapidly and controllably prepare a large-area graphene nanopore array is still not effectively solved. By utilizing the traditional stamping technology, uniform holes (such as CN108410136A) with the diameter of 0.1-1 mm can be obtained by stamping on the graphene film by using an industrial punch, and the holes with smaller diameters prepared on the graphene film by the technology are still difficult to break through. Reportedly, with the help of a Helium Ion Microscope (HIM), high-quality graphene nanopores with the diameter of 5-30 nanometers and capable of being used for biomolecule detection are prepared on a graphene film, and progress is made in the aspect of accurate preparation technology research of the graphene nanopores. But the method by means of Helium Ion Microscopy (HIM) has not yet achieved fast and controllable fabrication of large area graphene nanopore arrays. Therefore, how to rapidly and controllably prepare a large-area graphene nanopore array is a great challenge for the research of graphene batteries to the micro-nano manufacturing technology. Therefore, the research on the rapid and controllable preparation of the graphene nanopore array has very important significance.

Disclosure of Invention

The invention aims to overcome the defects and shortcomings that the large-area graphene nanopore array cannot be rapidly and controllably manufactured in the prior art, and provides a rapid and controllable preparation method of the graphene nanopore array. According to the invention, the graphene nanopore array can be prepared by using a specific mould, and the size and the density of the graphene nanopore array are controllable; the preparation method provided by the invention is simple, efficient and low in cost.

Another object of the present invention is to provide a graphene nanopore array.

The invention also aims to provide application of the graphene nanopore array in preparation of a graphene battery.

in order to achieve the purpose, the invention adopts the following technical scheme:

A rapid and controllable preparation method of a graphene nanopore array comprises the following steps:

S1: taking a substrate film with nano needles distributed on the surface as a mould;

S2: rotationally coating the graphene suspension liquid on the mold to enable the graphene suspension liquid to be distributed on the surfaces of the substrate film and the nano needle, and curing to obtain the graphene film;

S3: and applying force to the substrate film to enable the needle point of the nano needle to puncture the graphene film, so as to obtain the graphene nanopore array.

According to the method, the graphene nanopore array is obtained by puncturing the graphene film by the nano needles, the diameters and the distribution of the nano holes of the graphene nanopore array correspond to the diameters and the distribution of the needle tips of the nano needles on the mold, and the size and the density are controllable.

The preparation method provided by the invention is simple, efficient, low in cost and simple in required equipment, and solves the problems of high cost, low efficiency and the like in the traditional nanopore array preparation.

The height of the nano needle protruding out of the substrate film can be selected according to actual conditions, can be in a micron-scale or a nanometer-scale, and can be used for puncturing the graphene film when external force is applied.

Preferably, the height of the nano-needle protruding from the base film is 50 nm-500 μm.

The diameter and the distribution of the needle tips of the nano needles determine the diameter and the distribution of holes in the graphene nanopore array, and can be adjusted according to actual needs.

Preferably, the diameter of the needle point of the nano needle is 10-100 nm; the distance between the adjacent nano needles is 10-200 nm.

It should be understood that pitch refers to the closest distance between adjacent nanoneedle edges.

More preferably, the diameter of the needle point of the nano needle is 10-50 nm.

Preferably, the substrate film is one or more of a silicon nitride film, a silicon film or a metal film; the nano needle is one or more of a silicon nitride nano needle, a silicon nano needle or a metal nano needle.

More preferably, the substrate film is a silicon nitride film, and the nano-needle is a silicon nitride nano-needle.

preferably, the mold in S1 is made by a micro-machining process.

specifically, taking a silicon nitride film with silicon nitride nanoneedles distributed on the surface as an example, the preparation process is described as follows: firstly, performing thermal oxidation treatment on a silicon nitride film, gluing, exposing, performing body etching to obtain a cylindrical silicon nitride array, and then performing body etching to obtain nano needles.

The concentration requirement of the graphene suspension can be regulated and controlled according to the conventional requirement.

Preferably, the mass concentration of graphene in the graphene suspension in S2 is 2-10 mg/mL.

Graphene is either commercially available or can be obtained using conventional redox methods.

preferably, the thickness of the graphene film in S2 is 10-100 nm.

A graphene nanopore array is prepared by the preparation method.

Preferably, the pore diameter of the nanopore in the graphene nanopore array is 10-100 nm.

More preferably, the pore diameter of the nanopore in the graphene nanopore array is 10-50 nm.

the application of the graphene nanopore array in the preparation of the graphene battery is also within the protection scope of the invention.

Compared with the prior art, the invention has the following beneficial effects:

According to the method, the graphene nanopore array is obtained by puncturing the graphene film by the nano needles, the diameters and the distribution of the nano holes of the graphene nanopore array correspond to the diameters and the distribution of the needle tips of the nano needles on the mold, and the size and the density are controllable.

The preparation method provided by the invention is simple, efficient, low in cost and simple in required equipment, and solves the problems of high cost, low efficiency and the like in the traditional nanopore array preparation.

drawings

Fig. 1 is a process flow diagram of a rapid and controllable preparation method of a graphene nanopore array provided in example 1;

fig. 2 is a schematic view of a mold required in the method for rapidly and controllably preparing a graphene nanopore array provided in example 1;

Fig. 3 is a schematic structural diagram presented in step 2) of the rapid and controllable preparation method of a graphene nanopore array provided in example 1;

Fig. 4 is a schematic structural diagram presented in step 3) of the rapid and controllable preparation method of a graphene nanopore array provided in embodiment 1;

Fig. 5 is a schematic structural diagram presented in step 4) of the rapid and controllable preparation method of a graphene nanopore array provided in embodiment 1;

Wherein 1 is a silicon nitride film, 2 is a silicon nitride nanoneedle, 3 is a graphene suspension, and 4 is a graphene nanopore array film.

Detailed Description

the invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.