Continuous electrochemical stripping device for preparing graphene oxide
By designing a continuous electrochemical peeling device including a reactor cylinder, a support base, a perforated cover plate and a movable base plate, the problems of long oxidation time, high oxidant risk and device susceptible to thermal expansion in the existing graphene oxide preparation methods are solved, and the rapid, efficient and low-cost preparation of graphene oxide is achieved, and it is suitable for large-scale production.
Patent Information
- Application Number
- CN202420931714.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-30
- Publication Date
- 2025-04-18
- Estimated Expiration
- 2034-04-30
AI Technical Summary
In the existing preparation methods for graphene oxide, the oxidation time is long, the oxidant is at high risk, the toxic gas is generated during the reaction, and the device is prone to heat expansion and cracking, making it difficult to achieve fast speed, high yield, low cost and large-scale production.
A continuous electrochemical peeling device is designed, including a reactor cylinder, a support base, a perforated cover plate and a movable base plate. The contact with the electrolyte is carried out through the platinum wire, and graphene oxide is prepared by electrochemical reactions, and the device deformation caused by thermal expansion is prevented by the design of the movable base plate and a support spring.
The rapid preparation, high yield, low cost of graphene oxide is achieved, and easy to produce on a large scale, while avoiding the risk of device deformation due to thermal expansion.
Smart Images
Figure CN222770971U_ABST
Abstract
Description
Technical field:
[0001] The utility model relates to the technical field of graphene oxide manufacturing equipment, in particular to a continuous electrochemical stripping device for preparing graphene oxide with high speed, high yield, low cost and easy scale. Background technology:
[0002] Graphene oxide has a two-dimensional honeycomb structure similar to that of pristine graphene, and contains functional groups such as carboxyl and hydroxyl in its structure. In addition to properties similar to those of graphene, the presence of these functional groups also creates some additional properties, such as hydrophilicity, which makes this material easily dispersed in water and some organic solvents. These oxygen-containing functional groups can also be covalently linked to polymers or small molecules to regulate surface functionalization, so graphene oxide plays a role in many fields such as electrochemical energy devices, polymer composites, and sensors. There are currently three main methods for preparing graphene oxide. The Brodie method uses KClO3 as an oxidant and continuously stirs the reaction in the HNO3 system from 0°C for 20 to 24 hours. This method has a long oxidation time and KClO3 is more dangerous as an oxidant, and more toxic gases are produced during the reaction. The Staudenmaier method is similar to the Brodie method, using HNO3 and KClO3 as oxidants and reacting in the H2SO4 system. This method also requires multiple oxidation treatments, and more toxic gases are produced during the reaction. The Hummers law uses KMnO4 as an oxidant, and reacts in three stages in the H2SO4+NaNO3 system at low temperature (4°C), medium temperature (about 35°) and high temperature (below 98°). Although it is safer than the first two methods and has a shorter oxidation time, there are more process factors that need to be controlled during the reaction. Jianuo Chen et al. prepared graphene oxide using electrochemical exfoliation and published it in the Journal of Power Sources, but the reaction space inside the device cannot be changed, the bottom plate cannot move up and down after the reaction starts, and the reaction device is very likely to cause the reactor to bulge due to the exothermic electrochemical reaction. Therefore, this patent aims to solve this problem and design a flexible reactor device. Summary of the invention:
[0003] In view of the shortcomings and deficiencies in the prior art, the utility model proposes a continuous electrochemical stripping device for preparing graphene oxide with high speed, high yield, low cost and easy scale-up.
[0004] The utility model achieves this through the following measures:
[0005] A continuous electrochemical stripping device for preparing graphene oxide, characterized in that a reactor barrel for accommodating an electrolyte is provided, a support base coaxially arranged with the reactor barrel is provided in the reactor barrel, the support base is in the shape of a cylindrical tube with a closed bottom, a hole groove connected to the reactor barrel is provided on the side wall of the support base, the upper end of the support base is rotatably connected or separated with a perforated cover plate through a mortise and tenon component, a through hole is provided in the center of the perforated cover plate, a plug body for closing the through hole is provided on the upper end of the perforated cover plate, a hole for passing a wire into the device is left on the plug body, a hole groove array is provided around the central through hole on the perforated cover plate, a movable bottom plate is provided below the perforated cover plate, the lower part of the movable bottom plate is connected to a support spring, after the perforated cover plate is buckled on the upper end of the support base, the movable bottom plate and the spring are placed in the support base, and a limiting boss for limiting the downward position of the movable bottom plate in the support base is provided on the inner wall of the support base; a platinum wire extends into the support base along the top of the perforated cover plate to contact the electrolyte.
[0006] The utility model discloses a sleeve body is arranged above the perforated cover plate corresponding to the central through hole, springs are symmetrically arranged on both sides of the upper end of the sleeve body, and a plug body seals the upper end of the sleeve body to seal the reaction container.
[0007] The utility model discloses a guide column for guiding and positioning a support spring in the center of the inner bottom plate of the support base. Furthermore, the upper end of the support spring is connected to the movable bottom plate via the guide column.
[0008] The side wall of the support base of the utility model is provided with more than two vertical strip-shaped slots in a centrally symmetrical manner to realize the circulation of the electrolyte.
[0009] The upper bottom and the lower bottom of the perforated cover plate of the utility model are at an angle of 15°, so that the bubbles generated in the reaction can escape through their own buoyancy instead of being attached to the reactor to hinder the continuation of the reaction. The diameter of the holes on the perforated cover plate is 0.5 mm, which ensures that the electrolyte enters the perforated cover plate and fully contacts the graphite sheet, and prevents the outflow of the contents.
[0010] The support spring of the utility model is coated with a polymer corrosion-resistant material, and the movable bottom plate is located at the uppermost part at the initial stage of the reaction, so as to ensure sufficient movable space during thermal expansion, thereby preventing the deformation of the perforated cover plate.
[0011] In the utility model, the reactor cylinder is placed vertically; the support base is placed in the cylinder, and the fixed buckle is located on the top of the support base to limit the upward movement of the perforated cover plate; the support spring connects the movable bottom plate and the support base, and enables the movable bottom plate to move freely downward to prevent the thermal expansion during the reaction from causing the perforated cover plate to be lifted up or deformed; the plug is connected to the perforated cover plate through a spring, and the reactant is pressed into the cavity of the perforated cover plate. Compared with the prior art, the speed is fast, the yield is high, the cost is low, and it is easy to scale up. Description of the drawings:
[0012] Attached Figure 1 It is a structural schematic diagram of the utility model.
[0013] Attached Figure 2 It is a structural schematic diagram of the utility model in another state.
[0014] Attached Figure 3 It is a structural schematic diagram of the support base of the utility model.
[0015] Attached Figure 4 It is a cutaway view of the utility model.
[0016] Figure numerals: reactor cylinder 1, support base 2, fixing clip 2.1, electrolyte 3, support spring 4, platinum wire immersed in electrolyte 5, perforated cover plate 7, small spring 8, plug 9, movable bottom plate 11. Specific implementation method:
[0017] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.
[0018] Example:
[0019] This example provides a reaction device for preparing graphene oxide by continuous electrochemical exfoliation, comprising: a reactor barrel 1, a support base 2, an electrolyte 3, a support spring 4, a platinum wire 5 immersed in the electrolyte, a perforated cover plate 7, a small spring 8, a plug 9, a movable bottom plate 11 and a fixing buckle 2.1;
[0020] The reactor cylinder 1 provides a reaction site and contains electrolyte; the support base 2 and the perforated cover plate 7 are connected to each other by a mortise and tenon structure through a fixed buckle 2.1, and can be locked or separated by rotation. At the same time, the movable bottom plate 11 can move within a certain range under the support of the support spring 4, and the fixed buckle 2.1 limits its maximum activity limit. The space between the support base 2, the perforated cover plate 7 and the movable bottom plate is the place where the graphite flakes are electrochemically stripped to prepare graphene oxide. The plug 9 is connected to the movable bottom plate 11 to seal the reactor, and the two springs apply pressure to the graphene flakes.
[0021] The reactor cylinder 1 contains electrolyte 3, wherein the electrolyte 3 is a 0.1-1 mol ammonium sulfate solution; the graphite sheet is in the space between the support base 2, the perforated cover plate 7 and the movable bottom plate. The wire is introduced into the perforated cover plate 7 through the hole on the plug 9 and contacts the graphite sheet, and an external 10V voltage is connected. The electrolyte level is below the wire and does not contact the wire;
[0022] Furthermore, when the reaction proceeds, the reactor expands and generates bubbles. At this time, due to the increase in the volume of the contents, a force is applied to the movable bottom plate 11 to move it downward, and the space in the reactor becomes larger. The bubbles escape by their own buoyancy.
[0023] After the reaction is completed, the contents are vacuum filtered 3-5 times with deionized water until the washing liquid is neutral, and the ammonium sulfate residue has been removed. The mixture is dispersed in deionized water and ultrasonicated for 10 minutes to complete the stripping and uniform dispersion. Finally, the product is centrifuged at 1500 rpm for 15 minutes to separate the product.
[0024] In the utility model, the reactor cylinder is placed vertically; the support base is placed in the cylinder, and the fixed buckle is located on the top of the support base to limit the upward movement of the perforated cover plate; the support spring connects the movable bottom plate and the support base, and enables the movable bottom plate to move freely downward to prevent the thermal expansion during the reaction from causing the perforated cover plate to be lifted up or deformed; the plug is connected to the perforated cover plate through a spring, and the reactant is pressed into the cavity of the perforated cover plate. Compared with the prior art, the speed is fast, the yield is high, the cost is low, and it is easy to scale up.
Claims
1. A continuous electrochemical stripping device for preparing graphene oxide, characterized in that: A reactor cylinder for accommodating an electrolyte is provided, a support base coaxially arranged with the reactor cylinder is provided in the reactor cylinder, the support base is in the shape of a cylindrical tube with a closed bottom, a hole groove connected to the reactor cylinder is provided on the side wall of the support base, the upper end of the support base is rotatably connected or separated with the perforated cover plate through mortise and tenon parts, a through hole is provided in the center of the perforated cover plate, a plug body for closing the through hole is provided on the upper end of the perforated cover plate, a hole for passing a wire into the interior of the device is reserved on the plug body, an array of hole grooves is provided around the central through hole on the perforated cover plate, a movable bottom plate is provided below the perforated cover plate, the lower part of the movable bottom plate is connected to a support spring, after the perforated cover plate is buckled on the upper end of the support base, the movable bottom plate and the spring are placed in the support base, and a limiting boss for limiting the downward position of the movable bottom plate in the support base is provided on the inner wall of the support base; the platinum wire extends into the support base along the top of the perforated cover plate to contact the electrolyte.
2. A continuous electrochemical stripping device for preparing graphene oxide according to claim 1, characterized in that: A sleeve body is arranged above the perforated cover plate corresponding to the central through hole, springs are symmetrically arranged on both sides of the upper end of the sleeve body, and a plug body seals the upper end of the sleeve body to seal the reaction container.
3. A continuous electrochemical stripping device for preparing graphene oxide according to claim 1, characterized in that: A guide column for guiding and positioning the support spring is arranged in the center of the inner bottom plate of the support base, and the upper end of the support spring is connected to the movable bottom plate via the guide column.
4. A continuous electrochemical stripping device for preparing graphene oxide according to claim 1, characterized in that: More than two vertical strip-shaped slots are centrally symmetrically provided on the side wall of the support base to realize the circulation of the electrolyte.
5. The continuous electrochemical stripping device for preparing graphene oxide according to claim 1, characterized in that: The upper and lower bottoms of the perforated cover plate are at an angle of 15°, so that the bubbles generated in the reaction can escape through their own buoyancy instead of being attached to the reactor and hindering the continuation of the reaction. The diameter of the holes on the perforated cover plate is 0.5 mm, which ensures that the electrolyte enters the perforated cover plate and fully contacts the graphite sheet, and prevents the outflow of the contents.
6. A continuous electrochemical stripping device for preparing graphene oxide according to claim 1, characterized in that: The support spring is coated with a polymer corrosion-resistant material, and the movable bottom plate is located at the uppermost part at the initial stage of the reaction, so as to ensure sufficient movable space during thermal expansion, thereby preventing deformation of the perforated cover plate.