WO2021026888A1

WO2021026888A1 - Graphene surface plasma modification treatment device and treatment method

Info

Publication number: WO2021026888A1
Application number: PCT/CN2019/100790
Authority: WO
Inventors: 张波; 金旭栋; 朱理瀚; 虞文武; 马雯雯; 聂俊; 刘凯凯
Original assignee: 常州机电职业技术学院
Priority date: 2019-08-15
Filing date: 2019-08-15
Publication date: 2021-02-18

Abstract

Provided are a graphene surface plasma modification treatment device and a treatment method, which belong to the technical field of graphene surface modification, and solve the problems in the prior art that in methods for treating graphene by means of ultrasonic wave, heating or airflow etc. the productivity is low, sheets are severely agglomerated, a lot of structural defects of graphene are induced by long-time ultrasound treatment, and more surfactants or surface active substances need to be introduced, and the problem that the existing plasma treatment method can only act on a surface layer on which graphene is accumulated. Said treatment device comprises a vacuum chamber, a glass container, a radio frequency power supply system, a counter electrode and a rotation mechanism; the vacuum chamber is of a horizontal structure, the counter electrode is of a circular arc structure, a cylindrical glass container is placed in the middle of the counter electrode, and the glass container is connected to the rotation mechanism. A corresponding treatment method is provided. The invention is mainly used for surface modification treatment of graphene.

Description

[Name of invention formulated by ISA according to Rule 37.2] 　Graphene surface plasma modification treatment device and treatment method

Technical field

The invention belongs to the technical field of graphene surface modification, and particularly relates to a graphene surface plasma modification treatment device and a treatment method.

Background technique

Plasma technology is often used for surface modification of materials. Graphene is also widely used in various fields. Effectively dispersing surfactant-free graphene in an aqueous solution has always been a dream desire of materials scientists. However, due to the hydrophobicity of the surface of graphene, it is difficult Evenly dispersed in water, it is easy to agglomerate, which limits the application and development of graphene. At present, graphene solutions are mainly obtained by ultrasonic, heating or airflow. However, these methods also have low yield and serious lamella agglomeration. , Long-term ultrasound causes a large number of structural defects in graphene, the need to introduce more surfactants or surface activators, etc., which greatly restricts these preparation methods. At present, there are also related researches on the surface modification of graphene. However, in general, graphene is stacked in a flat manner. The plasma can only act on the surface layer of the graphene stack, and the graphene inside cannot be modified. There is an urgent need for a device and processing method that can realize industrial production. The plasma modification device and treatment method for improving the hydrophilicity of the graphene surface are beneficial to the modification and application of the graphene surface.

Summary of the invention

In order to solve the problems in the prior art, the present invention proposes a graphene surface plasma modification treatment device and treatment method.

In order to achieve the above objectives, the present invention adopts the following technical solutions: a graphene surface plasma modification treatment device, which includes a vacuum chamber, a glass container, a radio frequency power supply system, a counter electrode and a rotating mechanism, and the vacuum chamber has a horizontal structure The vacuum chamber is provided with gas-filling holes and exhaust holes, the counter electrode is connected to the radio frequency power supply system, the counter electrode has an arc-shaped structure, the inner arc part is a discharge layer, the middle part is an insulating layer, and the outer circle The arc part is a shielding layer. A cylindrical glass container is placed in the middle of the counter electrode. The counter electrode is fixed on the inner wall of the vacuum chamber by a polytetrafluoroethylene block and is coaxial with the center of the glass container. The glass container is connected to the rotating mechanism. Connected, one end of the glass container is provided with a through hole.

Furthermore, a shielded observation window is opened on the vacuum chamber, and the vacuum chamber includes a vacuum chamber body and a vacuum chamber head, and the vacuum chamber body and the vacuum chamber head are detachably connected. The vacuum chamber has a horizontal rectangular structure with a length of 1500 mm, a width of 1200 mm, and a height of 1000 mm.

Furthermore, the glass container includes a container body and a container head, and the container body and the container head are detachably connected. The glass container has a length of 1000 mm, an inner diameter of 600 mm, and a thickness of 5 mm.

Furthermore, the inflation hole is connected with a ventilation control system, and the suction hole is connected with a ventilation control system.

Furthermore, the rotating mechanism includes a rotating shaft and an active motor, the output end of the active motor is connected to the rotating shaft, and the rotating shaft is connected to the glass container.

Furthermore, the maximum power of the radio frequency power supply system is 1000 W and the frequency is 13.56 MHz.

Furthermore, the discharge layer is made of 304 stainless steel, the insulating layer is made of polytetrafluoroethylene, and the shielding layer is made of 304 stainless steel.

Furthermore, the thickness of the discharge layer is 3 mm, the thickness of the insulating layer is 50 mm, and the thickness of the shielding layer is 3 mm.

The present invention also provides a plasma modification treatment method for the graphene surface, which includes the following steps:

Step 1: Put the graphene to be processed into the glass container, close the container head and the vacuum chamber head, start the pumping control system, and keep the background vacuum of the vacuum chamber 0.01-1Pa;

Step 2: Turn on the ventilation control system, fill the vacuum chamber with mixed gas, maintain the vacuum and inflation state of the vacuum chamber, keep the working vacuum in the vacuum chamber stable at 10-20Pa, turn on the radio frequency power supply system to make the glow discharge area Tethered in a glass container;

Step 3: Turn on the active motor, rotate the glass container through the rotating shaft drive, and drive the graphene placed inside the glass container to continuously roll in the glow discharge area. The processing time is 2-5min, and the discharge RF power is 80-120W;

Step 4: After the processing is completed, turn off the radio frequency power supply system, the ventilation control system, and the exhaust control system, vent air to atmospheric pressure, and take out the processed graphene.

Furthermore, in the second step, the mixed gas is oxygen and helium, and the volume ratio of oxygen and helium is 10:1 to 5:1.

Compared with the prior art, the present invention has the following beneficial effects: the present invention solves the problem of low yield, serious lamellar agglomeration, and a large number of structural defects of graphene caused by long-term ultrasound. , The problem of the need to introduce more surfactants or surface activators, and the problem that the existing plasma treatment method can only act on the surface layer of graphene accumulation. The invention is used to improve the hydrophilicity of the graphene surface, and is beneficial to realize the modification treatment of the graphene surface. The device has a reasonable structure, good stability, and simple operation. The treatment method is a pure physical modification and the treatment method is environmentally friendly. There is no need to introduce surfactants or surface activators, the processing results are reproducible and the production efficiency is high.

Description of the drawings

Figure 1 is a schematic diagram of the structure of a graphene surface plasma modification treatment device according to the present invention

2 is a schematic diagram of a cross-sectional structure of a graphene surface plasma modification treatment device according to the present invention

Figure 3 is a schematic diagram of the counter electrode structure of the present invention

1-Vacuum chamber, 2-Glass container, 3-Container head, 4-Vacuum chamber head, 5-Inflatable hole, 6-Exhaust hole, 7-Rotating shaft, 8-Active motor, 9-RF power system, 10 -Counter electrode, 11-through hole, 12-PTFE block, 13-discharge layer, 14-insulating layer, 15-shielding layer

detailed description

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention.

Referring to Figures 1-3 to illustrate this embodiment, a graphene surface plasma modification treatment device includes a vacuum chamber 1, a glass container 2, a radio frequency power system 9, a counter electrode 10, and a rotating mechanism. The vacuum chamber 1 is In a horizontal structure, the vacuum chamber 1 is provided with an inflatable hole 5 and an exhaust hole 6, the counter electrode 10 is connected to the radio frequency power supply system 9, the counter electrode 10 has an arc-shaped structure, and the inner arc part is a discharge layer 13. The middle part is the insulating layer 14, the outer arc part is the shielding layer 15, the cylindrical glass container 2 is placed in the middle of the counter electrode 10, and the counter electrode 10 is fixed on the inner wall of the vacuum chamber 1 through a polytetrafluoroethylene block 12 The glass container 2 is connected to the rotating mechanism, and a through hole 11 is provided at one end of the glass container 2.

The vacuum chamber 1 of this embodiment realizes the glow discharge of the radio frequency power system 9 through the arc-shaped counter electrode 10 under the set vacuum condition, so that the plasma glow discharge area is confined in the glass container 2 to improve the effectiveness of graphene processing The glass container 2 is driven to rotate through the rotating mechanism, thereby driving the graphene filled inside to continuously roll, and the graphene is uniformly surface treated. The through hole 11 is used to realize the communication between the vacuum chamber 1 and the glass container 2. The vacuum degree of the vacuum chamber 1 is ensured through the inflation hole 5 and the suction hole 6.

The vacuum chamber 1 of this embodiment is provided with a shielded observation window. The vacuum chamber 1 includes a vacuum chamber body and a vacuum chamber head 4, and the vacuum chamber body and the vacuum chamber head 4 are detachably connected. The vacuum chamber 1 has a horizontal rectangular structure with a length of 1500mm, a width of 1200mm, and a height of 1000mm. The shielded observation window can be used to observe the transmission and glow discharge conditions in the vacuum chamber 1. The shielded observation window can be set in On the vacuum chamber head 4, the structure in which the vacuum chamber body and the vacuum chamber head 4 are detachably connected is convenient for the installation inside the vacuum chamber 1 and the opening and closing of the vacuum chamber; the glass container 2 includes the container body and the container head 3, so The container body and the container head 3 are detachably connected. The glass container 2 has a length of 1000 mm, an inner diameter of 600 mm, and a thickness of 5 mm. The container body and the container head 3 are detachably connected to facilitate the taking and placing of graphene; the gas filling hole 5 is connected to the ventilation control system, and the air extraction hole 6 is connected with the air extraction control system, and the vacuum degree of the vacuum chamber 1 is ensured through the ventilation control system and the air extraction control system; the rotating mechanism includes a rotating shaft 7 and an active motor 8, the output end of the active motor 8 and the rotating shaft 7 The rotating shaft 7 is connected to the glass container 2, and the rotation speed is adjustable to control the rotation of the cylinder and the continuous rolling of graphene; the maximum power of the radio frequency power system 9 is 1000W, the frequency is 13.56MHz, and it can be adjusted according to needs. Realize glow discharge at different powers; the discharge layer 13 is made of 304 stainless steel, the insulating layer 14 is made of polytetrafluoroethylene, the shielding layer 15 is made of 304 stainless steel, and the thickness of the discharge layer 13 is 3mm, The thickness of the insulating layer 14 is 50 mm, the thickness of the shielding layer 15 is 3 mm, the number of through holes 11 is multiple, and the multiple through holes 11 are uniformly distributed along the center of the glass container 2.

Step 1: Put the graphene to be processed into the glass container 2, close the container head 3 and the vacuum chamber head 4, start the air extraction control system, and keep the background vacuum of the vacuum chamber 1 0.01-1Pa;

Step 2: Turn on the ventilation control system, fill the vacuum chamber 1 with mixed gas, maintain the vacuum and inflation state of the vacuum chamber 1, and keep the working vacuum in the vacuum chamber 1 stable at 10-20 Pa, and turn on the radio frequency power system 9 , So that the glow discharge area is bound in the glass container 2;

Step 3: Turn on the active motor 8 and drive the glass container 2 through the rotating shaft 7 to drive the graphene placed inside the glass container 2 to continuously roll in the glow discharge area. The processing time is 2-5min, and the discharge RF power is 80-120W ；

Step 4: After the processing is completed, turn off the radio frequency power supply system 9, the ventilation control system and the exhaust control system, vent air to atmospheric pressure, and take out the processed graphene.

In the second step of this embodiment, the mixed gas is oxygen and helium, and the volume ratio of oxygen and helium is 10:1 to 5:1.

The above is a detailed introduction to the graphene surface plasma modification treatment device and treatment method provided by the present invention. Specific examples are used in this article to illustrate the principle and implementation of the present invention. The description of the above examples is only It is used to help understand the method and core idea of the present invention; at the same time, for those of ordinary skill in the art, according to the idea of the present invention, there will be changes in the specific implementation and the scope of application. In summary, this The contents of the description should not be construed as limiting the present invention.

Claims

A graphene surface plasma modification treatment device, which is characterized in that it comprises a vacuum chamber (1), a glass container (2), a radio frequency power supply system (9), a counter electrode (10) and a rotating mechanism. The vacuum chamber (1) is a horizontal structure, the vacuum chamber (1) is provided with a gas-filling hole (5) and a suction hole (6), the counter electrode (10) is connected to the radio frequency power supply system (9), and the counter electrode (10) is a circular arc structure, the inner arc part is the discharge layer (13), the middle part is the insulating layer (14), the outer arc part is the shielding layer (15), and the counter electrode (10) is placed in the middle Cylindrical glass container (2), the counter electrode (10) is fixed on the inner wall of the vacuum chamber (1) through a polytetrafluoroethylene block (12) and is coaxial with the center of the glass container (2). 2) Connected with a rotating mechanism, and one end of the glass container (2) is provided with a through hole (11).
A graphene surface plasma modification treatment device according to claim 1, wherein the vacuum chamber (1) is provided with a shielded observation window, and the vacuum chamber (1) includes a vacuum chamber body and The vacuum chamber head (4), the vacuum chamber body and the vacuum chamber head (4) are detachably connected. The vacuum chamber (1) has a horizontal rectangular structure with a length of 1500mm, a width of 1200mm, and a height of 1000mm.
The graphene surface plasma modification treatment device according to claim 1, wherein the glass container (2) comprises a container body and a container head (3), and the container body and the container head ( 3) It is a detachable connection. The glass container (2) has a length of 1000 mm, an inner diameter of 600 mm, and a thickness of 5 mm.
The graphene surface plasma modification treatment device according to claim 1, characterized in that: the gas filling hole (5) is connected with a ventilation control system, and the suction hole (6) is connected with a gas extraction control system.
The graphene surface plasma modification treatment device according to claim 1, wherein the rotating mechanism comprises a rotating shaft (7) and an active motor (8), and the output end of the active motor (8) It is connected with the rotating shaft (7), and the rotating shaft (7) is connected with the glass container (2).
The graphene surface plasma modification treatment device according to claim 1, wherein the maximum power of the radio frequency power supply system (9) is 1000 W and the frequency is 13.56 MHz.
The graphene surface plasma modification treatment device according to claim 1, wherein the discharge layer (13) is made of 304 stainless steel, and the insulating layer (14) is made of polytetrafluoroethylene. The shielding layer (15) is made of 304 stainless steel.
The graphene surface plasma modification treatment device according to claim 7, characterized in that: the thickness of the discharge layer (13) is 3mm, the thickness of the insulating layer (14) is 50mm, and the shielding layer ( 15) The thickness is 3mm.
A treatment method of a graphene surface plasma modification treatment device according to claim 1, characterized in that it comprises the following steps:

Step 1: Put the graphene to be processed into the glass container (2), close the container head (3) and the vacuum chamber head (4), start the pumping control system, and maintain the background vacuum of the vacuum chamber (1) Degree 0.01-1Pa;

Step 2: Turn on the ventilation control system, fill the vacuum chamber (1) with mixed gas, maintain the vacuum chamber (1) pumping and inflating state, and keep the working vacuum in the vacuum chamber (1) stable at 10-20Pa , Turn on the radio frequency power supply system (9), so that the glow discharge area is bound in the glass container (2);

Step 3: Turn on the active motor (8), drive the glass container (2) to rotate through the rotating shaft (7), and drive the graphene placed inside the glass container (2) to continuously roll in the glow discharge area, and the processing time is 2-5min , The discharge RF power is 80-120W;

Step 4: After the processing is completed, turn off the radio frequency power supply system (9), the ventilation control system and the air extraction control system, vent air to atmospheric pressure, and take out the processed graphene.
The method for modifying the surface of graphene by plasma modification according to claim 9, wherein the mixed gas in the second step is oxygen and helium, and the volume ratio of oxygen and helium is 10:1-5: 1.