Device for graphene surface modification or metal deposition

Abstract

The invention provides a device for graphene surface modification or metal deposition, the device comprises an outer tank cylinder, an electrolytic tank, an inner electrode and an outer electrode, the electrolytic tank comprises an inner tank cylinder, and an electrolytic reaction of graphene occurs in the inner tank cylinder; the submersible pump is fixedly mounted at the bottom of the inner tank cylinder and is used for creating a circulation condition in the inner tank cylinder in a jet manner, so that graphene continuously circulates along with the electrolyte in the inner tank cylinder and collides with the electrode; a water flow pipeline is arranged in the water flow circulation module, and the bottom of the water flow circulation module is opposite to a submersible pump water outlet; and the water flow baffle is used for blocking the electrolyte sprayed out of the water flow pipeline, so that the electrolyte falls into the bottom of the inner tank cylinder again and enters the submersible pump again, and internal circulation of the electrolyte is formed. In the device for graphene surface modification or metal deposition, circulation conditions are created in the inner pool cylinder through the submersible pump in a jet mode, so that graphene continuously circulates in the inner pool cylinder along with the electrolyte and collides with the electrode.

Description

Technical Field

[0001] This invention relates to the field of graphene, and more particularly to an apparatus for graphene surface modification or metal deposition. Background Technology

[0002] Graphene is a novel two-dimensional carbon material with extremely high tensile strength, specific stiffness, electrical conductivity, and thermal conductivity. As an additive, it can improve the mechanical, electrical, and thermal properties of various materials such as polymers, metals, and ceramics.

[0003] However, graphene exhibits poor dispersibility, necessitating surface modification to improve its dispersion in most applications. Oxidation is a common modification method, but traditional oxidation requires strong acids and oxidants, resulting in low efficiency and significant pollution. Furthermore, electroless plating, a common method for metallizing graphene surfaces, also requires strong acids and formaldehyde. Electrochemical methods, with their advantages of simplicity, low cost, relatively environmentally friendly approach, and high efficiency, are ideal for modifying graphene powder.

[0004] Existing electrochemical devices can only be used for the electrochemical exfoliation of graphene, but cannot modify existing graphene powder. Therefore, there is an urgent need for a simple and efficient electrochemical device that can achieve electrochemical exfoliation while also meeting the needs of graphene modification for various applications, improving the dispersibility of graphene and its affinity with the substrate. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide an apparatus for graphene surface modification or metal deposition.

[0006] The technical solution of this invention is: an apparatus for graphene surface modification or metal deposition, characterized in that the apparatus comprises: an outer cell cylinder, an electrolytic cell disposed inside the outer cell cylinder, an inner electrode fixed inside the electrolytic cell, and an outer electrode disposed between the electrolytic cell and the outer cell cylinder, wherein the electrolytic cell comprises: The inner tank consists of a hollow cylinder and a cover installed on the top of the tank. The tank has a cylindrical structure, and the electrolytic reaction of graphene occurs inside the inner tank. A submersible pump is fixedly installed at the bottom of the inner tank to create circulation conditions in the inner tank using a jet method, so that the graphene continuously circulates with the electrolyte and collides with the electrodes in the inner tank. The water circulation module has an internal water pipe, and its bottom is opposite to the outlet of the submersible pump, which is used to transport the electrolyte ejected by the submersible pump; The water flow baffle is fixed below the top cover and placed above the water flow circulation module. It is used to block the electrolyte sprayed out of the water flow pipe, so that the electrolyte falls back into the bottom of the inner tank and re-enters the submersible pump to form an internal circulation of the electrolyte.

[0007] Preferably, the bottom of the inner pool cylinder is an inverted conical inner pool sludge hopper connected to the cylinder body, and the submersible pump is placed at the bottom of the inner pool sludge hopper.

[0008] Preferably, the water circulation module is in the shape of a double cone assembly, with the outer surface angle of the upper cone matching the inner surface angle of the water flow baffle, and the outer surface angle of the lower cone matching the inverted cone angle of the inner tank sludge hopper. Furthermore, small cylinders are set at the top and bottom respectively. After the water pipe passes through the lower small cylinder, it passes through the lower cone, the upper cone, and the upper small cylinder in sequence.

[0009] Preferably, the water flow baffle has a conical structure that is narrow at the top and wide at the bottom.

[0010] Preferably, the inner tank cylinder has several exchange windows arranged around the middle of its body.

[0011] Preferably, the interval angle of the exchange window is 90 degrees.

[0012] Preferably, the exchange window is embedded with a PTEE filter membrane.

[0013] Preferably, the outer electrode includes an annular electrode that surrounds the inner tank cylinder and two barbed electrodes fixed on the annular electrode, with the two barbs hooked upside down onto the outer tank cylinder.

[0014] Preferably, the inner electrode is disposed on the inner wall of the inner pool sludge hopper and has an inverted conical structure. The inner electrode also includes four upwardly extending connecting rods.

[0015] The above technical solution has the following advantages or beneficial effects: In the above-mentioned device for graphene surface modification or metal deposition, a submersible pump creates circulation conditions in the inner tank using a jet method, allowing the graphene to continuously circulate and collide with the electrodes in the inner tank along with the electrolyte. In the electrolytic cell, when the graphene collides with the inner tank electrodes, it becomes a microparticle electrode, increasing the specific surface area of ​​the electrode and improving current efficiency. The inner and outer tanks of this device can be interchanged as needed. When the inner tank is the cathode, a reduction reaction occurs on the graphene surface, which can be used for electrodeposition of metals such as copper, nickel, and zinc on the graphene surface; when the inner tank is the anode, an oxidation reaction occurs on the graphene surface, which can be used for graphene surface oxidation modification, creating active sites and preparing graphene oxide. In the aforementioned device, two different effects can be achieved by changing the anode and cathode: graphene oxidation or surface metal coating. This device can improve the efficiency and uniformity of graphene modification, while the process has less environmental pollution and lower energy consumption, making it an environmentally friendly graphene modification device. The modified graphene prepared by this device can be used for a variety of purposes. Attached Figure Description

[0017] Embodiments of the invention will be described more fully with reference to the accompanying drawings. However, the drawings are for illustration and explanation only and do not constitute a limitation on the scope of the invention.

[0018] Figure 1 This is a schematic diagram of the overall structure of a device for graphene surface modification or metal deposition according to the present invention. Figure 2 This is a schematic diagram of the outer tank in an apparatus for graphene surface modification or metal deposition according to the present invention. Figure 3 This is a schematic diagram of the electrolytic cell in an apparatus for graphene surface modification or metal deposition according to the present invention. Figure 4 This is a schematic diagram of the submersible pump in a device for graphene surface modification or metal deposition according to the present invention. Figure 5 This is a schematic diagram of the water circulation module in a device for graphene surface modification or metal deposition according to the present invention. Figure 6 This is a cross-sectional view of the water circulation module and water flow baffle in an apparatus for graphene surface modification or metal deposition according to the present invention. Figure 7 This is a schematic diagram of the water flow baffle in an apparatus for graphene surface modification or metal deposition according to the present invention. Figure 8 This is a schematic diagram of the structure of the external electrode in a device for graphene surface modification or metal deposition according to the present invention. Figure 9This is a schematic diagram of the internal electrode structure in a device for graphene surface modification or metal deposition according to the present invention. In the attached diagram: 1. Outer tank cylinder; 2. Electrolytic cell; 21. Inner tank cylinder; 211. Inner tank sludge hopper; 212. Cylinder body; 213. Exchange window; 214. Top cover; 22. Submersible pump; 23. Water circulation module; 231. Water flow pipe; 24. Water flow baffle; 3. Inner electrode; 4. Outer electrode; 41. Annular electrode; 42. Barbed electrode. Detailed Implementation

[0019] The following describes in detail an apparatus for graphene surface modification or metal deposition according to the present invention, with reference to the accompanying drawings and specific embodiments.

[0020] In the description of this invention, it should be understood that the terms "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicating orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention. Similarly, the terms "first," "second," etc., are only used to distinguish the names of various components and do not have a primary or secondary relationship, and therefore should not be construed as a limitation of this invention.

[0021] Example 1 like Figure 1 As shown, an apparatus for graphene surface modification or metal deposition includes: an outer cell cylinder 1, an electrolytic cell 2 disposed inside the outer cell cylinder 1, an inner electrode 3 fixed inside the electrolytic cell 2, and an outer electrode 4 disposed between the electrolytic cell 2 and the outer cell cylinder 1, wherein the electrolytic cell 2 includes: The inner tank cylinder 21 includes a hollow cylinder 212 and an upper cover 214 installed on the upper part of the tank body. The tank body has a cylindrical structure, and the electrolysis reaction of graphene occurs inside the inner tank cylinder 21. Submersible pump 22 is fixedly installed at the bottom of inner tank cylinder 21 and is used to create circulation conditions in inner tank cylinder 21 by means of jet, so that graphene continuously circulates in inner tank cylinder 21 with electrolyte and collides with electrodes. The water circulation module 23 has a water pipe 231 inside, and its bottom is opposite to the water outlet of the submersible pump 22, which is used to transport the electrolyte ejected by the submersible pump 22. The water flow baffle 24 is fixed below the upper cover 214 and placed above the water flow circulation module 23. It is used to block the electrolyte sprayed out of the water flow pipe 231, so that the electrolyte falls back into the bottom of the inner tank cylinder 21 and re-enters the submersible pump 22 to form an internal circulation of the electrolyte.

[0022] In the aforementioned apparatus for graphene surface modification or metal deposition, the graphene treatment is primarily carried out in an electrolytic cell 2, which is surrounded by an outer cylinder 1. The upper cover 214 of the electrolytic cell 2 is positioned above the inner cylinder 21, and a water flow baffle 24 is installed below the upper cover 214. The electrolyte ejected by the submersible pump 22 is sprayed through the water flow circulation module 23 onto the water flow baffle 24, then falls back to the bottom of the inner cylinder 21 and is circulated again by the submersible pump 22. The inner electrode 3 and outer electrode 4, located inside and outside the electrolytic cell 2, can be interchanged as needed. When the inner electrode 3 is the cathode, a reduction reaction occurs on the graphene surface, which can be used for electrodeposition of metals such as copper, nickel, and zinc. When the inner electrode 3 is the anode, an oxidation reaction occurs on the graphene surface, which can be used for oxidative modification of the graphene surface, creating active sites and preparing graphene oxide.

[0023] Furthermore, such as Figure 2 As shown, the inner tank cylinder 21 has several exchange windows 213 arranged around the middle of its body 212 for ion exchange and electron flow between the inner and outer tanks. The exchange windows 213 help ensure that ions can be replenished to the inner tank in a timely manner during electrolysis, thus ensuring electrolysis efficiency.

[0024] Furthermore, such as Figure 3 As shown, an exchange window 213 is provided every 90° in each ring of the inner tank cylinder 21 body 212. The exchange window 213 is embedded with a PTFE filter membrane (polytetrafluoroethylene filter membrane). This material is chemically stable and does not easily decompose during electrolysis. It is used for ion exchange of electrolyte in the inner and outer tanks and to prevent graphene from flowing out of the inner tank.

[0025] Furthermore, such as Figure 4 As shown, the bottom of the inner tank cylinder 21 is an inverted conical inner tank sludge hopper 211 connected to the cylinder body 212, and the submersible pump 22 is placed at the bottom of the inner tank sludge hopper 211. The inverted conical structure facilitates faster centralized recovery of graphene after it circulates back, which is then absorbed by the submersible pump 22, promoting circulation.

[0026] Furthermore, such as Figure 5 and 6 As shown, the water circulation module 23 is a double-cone assembly, with small cylinders at the top and bottom. The water pipe 231 passes through the lower small cylinder and then sequentially passes through the lower cone, the upper cone, and the upper small cylinder. This double-cone assembly structure helps the electrolyte to fall back into the inner tank sludge hopper 211 more quickly. Furthermore, the outer surface angle of the upper cone matches the inner surface angle of the water flow baffle 24, and the outer surface angle of the lower cone matches the angle of the inverted cone shape of the inner tank sludge hopper 211, facilitating electrolyte circulation and ensuring electrolysis efficiency.

[0027] Furthermore, such as Figure 7As shown, the water flow baffle 24 has a conical structure that is narrow at the top and wide at the bottom. That is, its inner surface is narrow and its bottom is wide. This structure can maximize the contact area after the electrolyte is sprayed, and it can also help the electrolyte fall back quickly.

[0028] Furthermore, such as Figure 8 As shown, the outer electrode 4 includes an annular electrode 41 surrounding the inner cell cylinder 21 and two barbed electrodes 42 fixed on the annular electrode 41. The two barbed electrodes 42 are inverted and attached to the outer cell cylinder 1 to fix the outer electrode 4 and facilitate power connection. Furthermore, the inner diameter of the annular structure of the outer electrode 4 is 1.1-3.5 times the outer diameter of the inner cell cylinder, preferably 2 times, which facilitates operation and saves electrolyte material.

[0029] Furthermore, such as Figure 9 As shown, the inner electrode 3 is disposed on the inner wall of the inner pool mud hopper 211 and has an inverted conical structure, which is the same as the inner wall structure of the inner pool mud hopper 211. The inner electrode 3 also includes four upwardly extending connecting rods for connecting to the power supply.

[0030] It is worth noting that the outer electrode 4 corresponds to the inner electrode 3, forming a radial current, which allows the current to be evenly distributed in the electrolytic cell 2, thereby promoting the uniform electrolysis of graphene and improving working efficiency.

[0031] Furthermore, the cathode uses highly conductive materials such as copper and graphite, while the anode uses titanium plated with anti-oxidation materials such as iridium-tantalum or ruthenium-iridium, which can be selected according to the composition of the plating solution. When the inner tank is used as a cathode tank, the inner electrode 3 is the cathode, and the outer tank is the anode tank, with the outer electrode 4 acting as the anode; conversely, when the inner tank is used as an anode tank, the inner electrode 3 is the anode, and the outer tank is the cathode tank, with the outer electrode 4 acting as the cathode.

[0032] In the aforementioned apparatus for graphene surface modification or metal deposition, a submersible pump 22 creates circulation conditions in the inner tank 21 using a jet flow method, allowing the graphene to continuously circulate and collide with the electrodes within the inner tank 21 along with the electrolyte. In the electrolytic cell 2, when the graphene collides with the inner tank electrodes, it becomes a microparticle electrode, increasing the specific surface area of ​​the electrode and improving current efficiency. The inner and outer tanks of this apparatus can be interchanged as needed. When the inner tank is the cathode, a reduction reaction occurs on the graphene surface, which can be used for electrodeposition of metals such as copper, nickel, and zinc. When the inner tank is the anode, an oxidation reaction occurs on the graphene surface, which can be used for graphene surface oxidation modification, creating active sites and preparing graphene oxide. In the aforementioned device, two different effects can be achieved by changing the anode and cathode: graphene oxidation or surface metal coating. This device can improve the efficiency and uniformity of graphene modification, while the process has less environmental pollution and lower energy consumption, making it an environmentally friendly graphene modification device. The modified graphene prepared by this device can be used for a variety of purposes.

[0033] Example 2 10g of graphene powder with a D50 of 2.0μm prepared by physical method was placed in a mixing tank, along with 30L of deionized water and 10L of ethanol. A small amount of concentrated sulfuric acid was added to adjust the pH to 1.5, and the mixture was stirred for 60 minutes to obtain the electrolyte. A conical iridium-tantalum-titanium plated anode was placed on the inner tank sludge hopper 211, and a submersible pump 22 was placed below the inner tank sludge hopper 211. A copper anode was hung between the inner and outer tanks. The stirred electrolyte was poured into the inner tank, and a portion of the liquid flowed into the outer tank through the filter membrane on the exchange window 213. The top cover 214 was then secured. The submersible pump 22 was powered on to ensure that the graphene began to circulate in the inner tank under the action of the jet from the submersible pump 22. The cathode and anode were then connected to the power supply. The power supply was switched to constant current mode, and the current was adjusted to 1.5A. The mixture was run for 2 hours.

[0034] Graphene and electrolyte were extracted from electrolytic cell 2, filtered, and washed multiple times to obtain I. D / I G Approximately 0.5% graphene oxide.

[0035] Example 3 15g of graphene powder with a D50 of 8.5μm prepared by physical method was placed in a mixing tank, along with 30L of deionized water and 10L of ethanol. A small amount of concentrated sulfuric acid was added to adjust the pH to 1.2, and the mixture was stirred for 60 minutes to obtain the electrolyte. A conical iridium-tantalum-titanium plated anode was placed on the inner tank sludge hopper 211, and a submersible pump 22 was placed below the inner tank sludge hopper 211. A copper anode was hung between the inner and outer tanks. The stirred electrolyte was poured into the inner tank, and a portion of the liquid flowed into the outer tank through the filter membrane on the exchange window 213. The top cover 214 was then secured. The submersible pump 22 was powered on to ensure that the graphene began to circulate in the inner tank under the action of the jet from the submersible pump 22. The cathode and anode were then connected to the power supply. The power supply was switched to constant current mode, and the current was adjusted to 5A. The mixture was run for 4 hours.

[0036] Graphene and electrolyte were extracted from electrolytic cell 2, filtered, and washed multiple times to obtain I. D / I G Approximately 1.2 ppm of graphene oxide.

[0037] Example 4 10g of graphene powder with a D50 of 7.5μm prepared by physical method was placed in a mixing tank, along with 620g CuSO4·5H2O, 1g hexadecyltrimethylammonium bromide, and 40L deionized water. A small amount of concentrated sulfuric acid was added to adjust the pH to 2.0. The mixture was stirred for 60 minutes to obtain the electrolyte. A conical copper cathode was placed on the inner tank sludge hopper 211, and a submersible pump 22 was placed below the inner tank sludge hopper 211. An iridium-plated tantalum-titanium basket anode was hung between the inner and outer tanks. The stirred electrolyte was poured into the inner tank, and a portion of the liquid flowed into the outer tank through the filter membrane on the exchange window 213. The top cover 214 was then secured. The submersible pump 22 was powered on to ensure that the graphene began to circulate in the inner tank under the action of the jet from the submersible pump 22. The cathode and anode were then connected to the power supply. The power supply was switched to constant current mode, and the current was adjusted to 3A. The mixture was run for 4 hours.

[0038] The graphene and electrolyte were extracted from electrolytic cell 2, filtered, and washed multiple times to obtain copper-plated graphene. The graphene content was approximately 30% by mass.

[0039] For those skilled in the art, various changes and modifications will undoubtedly be apparent after reading the above description. Therefore, the appended claims should be construed as covering all changes and modifications that encompass the true intent and scope of the invention. Any and all equivalent scope and content within the scope of the claims should be considered to remain within the intent and scope of the invention.

Claims

1. An apparatus for graphene surface modification or metal deposition, characterized in that, The device includes: an outer cell cylinder (1), an electrolytic cell (2) placed inside the outer cell cylinder (1), an inner electrode (3) fixed inside the electrolytic cell (2), and an outer electrode (4) placed between the electrolytic cell (2) and the outer cell cylinder (1), wherein the electrolytic cell (2) includes: The inner tank cylinder (21) includes a hollow cylinder (212) and an upper cover (214) installed on the upper part of the tank body. The tank body has a columnar structure, and the electrolytic reaction of graphene occurs inside the inner tank cylinder (21). A submersible pump (22) is fixedly installed at the bottom of the inner tank (21) to create circulation conditions in the inner tank (21) by means of jet, so that the graphene circulates continuously with the electrolyte in the inner tank (21) and collides with the electrodes. The water circulation module (23) has a water pipe (231) inside, and its bottom is opposite to the outlet of the submersible pump (22) to transport the electrolyte sprayed by the submersible pump (22); The water flow baffle (24) is fixed below the upper cover (214) and placed above the water flow circulation module (23). It is used to block the electrolyte sprayed out of the water flow pipe (231), so that the electrolyte falls back into the bottom of the inner tank cylinder (21) and re-enters the submersible pump (22) to form an internal circulation of the electrolyte.

2. The apparatus for graphene surface modification or metal deposition according to claim 1, characterized in that, The bottom of the inner pool cylinder (21) is an inverted conical inner pool mud hopper (211) connected to the cylinder body (212), and the submersible pump (22) is placed at the bottom of the inner pool mud hopper (211).

3. The apparatus for graphene surface modification or metal deposition according to claim 2, characterized in that, The water circulation module (23) is in the shape of a double cone. The outer surface angle of the upper cone is consistent with the inner surface angle of the water flow baffle (24), and the outer surface angle of the lower cone is consistent with the inverted cone angle of the inner pool mud hopper (211). Small cylinders are provided at the top and bottom respectively. After the water flow pipe (231) passes through the lower small cylinder, it passes through the lower cone, the upper cone, and the upper small cylinder in sequence.

4. The apparatus for graphene surface modification or metal deposition according to claim 3, characterized in that, The water flow baffle (24) has a conical structure that is narrow at the top and wide at the bottom.

5. The apparatus for graphene surface modification or metal deposition according to claim 2, characterized in that, The inner tank cylinder (21) has several exchange windows (213) arranged around the middle of the cylinder body (212).

6. The apparatus for graphene surface modification or metal deposition according to claim 5, characterized in that, The interval angle of the exchange window (213) is 90 degrees.

7. The apparatus for graphene surface modification or metal deposition according to claim 6, characterized in that, The exchange window (213) is fitted with a PTEE filter membrane.

8. The apparatus for graphene surface modification or metal deposition according to claim 2, characterized in that, The outer electrode (4) includes an annular electrode (41) that surrounds the inner tank cylinder (21) and two barbed electrodes (42) fixed on the annular electrode (41), with the two barbed electrodes (42) upside down on the outer tank cylinder (1).

9. The apparatus for graphene surface modification or metal deposition according to claim 2, characterized in that, The inner electrode (3) is disposed on the inner wall of the inner pool mud hopper (211) and has an inverted conical structure. The inner electrode (3) also includes four upwardly extending connecting rods.

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