Device and method for continuously preparing high-quality graphene

Abstract

The invention relates to a device and method for continuously preparing high-quality graphene, and belongs to the technical field of new materials.The device comprises an upper support, a fixed mounting plate, a lower rack and a reaction kettle, and is characterized in that the upper support and the lower rack are connected through the fixed mounting plate, an electrode lifting structure is mounted in the upper support, and the electrode lifting structure is connected with the reaction kettle; the lower rack supports a reaction kettle of which the outer wall can be cooled and circulated, the electrode lifting structure is connected with a sliding table electrode connecting piece for mounting an electrode assembly body, and a stirring module and a counterweight module are also mounted in the upper bracket. According to the equipment and the method, graphite flakes and fixing gaskets are stacked on a plurality of independent metal screw rods layer by layer by adopting a method of stringing sugar-coated haws on sticks, and then through a certain electrode structure and transmission design, continuous and stable production of high-quality graphene / graphene oxide is realized; and the production efficiency and the product quality of the graphene are greatly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of new materials, and in particular relates to a device and method for continuously preparing high-quality graphene. Background Art

[0002] Graphene has excellent optical, electrical and mechanical properties and has important application prospects in materials science, micro-nano processing, energy, biomedicine and drug delivery. The electrochemical method directly prepares high-quality graphene sheets, i.e. high-quality graphene, by inducing electrochemical reactions between graphite layers to produce gases to exfoliate the graphite sheets.

[0003] Due to its simple process, clean and pollution-free, low cost, and stripping efficiency up to about 85%, which is significantly better than liquid phase stripping, electrochemical stripping is currently the most promising technology for large-scale controllable preparation of high-quality graphene. In 2011, Su (Acs Nano, 2011, 2332-2339 (5)) and other researchers successfully prepared thin layers of graphene by electrolyzing highly oriented pyrolytic graphite and ordinary graphite in dilute sulfuric acid electrolyte (0.5M, pH = 0.3); Yang (Angewandte Chemie-International Edition, 2017, 6669-6675 (56)) and others used square wave alternating voltage for electrolysis (±10V, 0.1Hz) to obtain high-yield graphene preparation (20g h -1 ); Cao (Journal of the American Chemical Society, 2017, 17446-17456 (139)) et al. obtained a few-layer graphene oxide powder by a two-step electrochemical exfoliation method. These methods have proposed many original methods in regulating the electrochemical exfoliation process and improving the graphene yield, but there are still 15-25% of graphene sheets in the product that need to be removed, which is still not conducive to large-scale preparation.

[0004] If traditional graphene oxide is prepared using the Hummers method, it is usually stripped with the help of polluting chemical raw materials such as concentrated sulfuric acid, potassium permanganate, sodium nitrate and hydrogen peroxide, which will produce a large amount of pollutants. Compared with the Hummers method for preparing graphene oxide, the electrochemical method for preparing graphene is clean and pollution-free. However, the difficulty of electrochemical stripping of graphene lies in continuous production. Continuous production requires continuous feeding of materials. At present, the electrochemical method for preparing graphene still lacks equipment and methods for mass production.

[0005] Due to the uniqueness of the electrochemical preparation of graphene process, the traditional confined electrochemical preparation of graphene requires relatively harsh reaction conditions, which makes it difficult to produce continuously. For example, high voltage, specific concentration of electrolyte, and strictly controlled temperature and pH value. These conditions have high requirements for experimental environment and equipment, which limits its continuous production capacity on an industrial scale. In addition, there are many steps in the electrochemical preparation of graphene, and the electrolysis step is only the first step. If graphene can be prepared continuously and efficiently by electrolysis, it will be more helpful to cooperate with the subsequent steps to achieve mass production of graphene.

[0006] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention

[0007] The purpose of the present invention is to provide a device and method for continuously preparing high-quality graphene, which can fundamentally solve the technical problem that traditional confined electrochemical preparation of graphene requires relatively harsh reaction conditions, resulting in difficulty in continuous production, and greatly improve the quality and uniformity of confined electrochemical mass production.

[0008] To achieve the above-mentioned purpose, the present invention provides a device for continuously preparing high-quality graphene, comprising: an upper bracket, which is composed of an outer structure bracket located at the periphery to form a main frame, a stirring paddle bracket horizontally fixed at the center of the outer structure bracket, and a counterweight pulley bracket fixed on one side above the stirring paddle bracket; a fixed mounting plate, which is used to fix the upper bracket located above it and the lower frame located below it; the lower frame is used to support the reactor, and a pulley can be installed at the bottom of the lower frame to facilitate the movement of the entire device; the reactor is used to perform an electrolytic reaction inside it, and a discharge port can be provided below it to facilitate the outflow of materials; a counterweight module is fixed to the outer structure The inner side of the lower part of the structure bracket is supported by a counterweight pulley bracket, which is used to balance the force when the balance device is running; the electrode assembly, in which the positive and negative electrodes and the reaction raw materials can be installed by bolts, and it is installed on the slide electrode connector and rises and falls with the electrode lifting structure; the electrode lifting structure controls the lifting time and rate of the slide electrode connector structure inside it, and further controls the electrode assembly to slowly enter the reactor for electrolysis reaction; the stirring module is fixed on the stirring paddle bracket, and is used to stir the electrolyte and the product during the electrolysis reaction to ensure uniform reaction; the device also includes a cooling device, which is connected to the outer wall of the reactor.

[0009] Furthermore, the fixed mounting plate includes an upper bracket mounting hole, a lifting slide mounting hole, a lower rack mounting hole and a wiring opening; wherein, the upper bracket is connected to the fixed mounting plate through the upper bracket mounting hole on the outer edge of the fixed mounting plate; the lower rack is connected to the fixed mounting plate through the lower rack mounting hole inside the fixed mounting plate; the lifting slide mounting holes are multiple slots located on one side of the short side of the fixed mounting plate.

[0010] Furthermore, the counterweight module includes an optical axis slide fixed to the inner side of the lower side of the external structure support by bolts, a counterweight block installed on the optical axis slide, an electrode assembly hook installed on the slide electrode connector, a frame pulley and a counterweight wire rope installed on the counterweight pulley mounting frame; the weight of the counterweight block is half of the total weight of the electrode assembly and the slide electrode connector; one end of the counterweight wire rope is connected to the hook on the counterweight block, and the other end passes through the frame pulley and is connected to the electrode assembly hook.

[0011] Furthermore, the electrode assembly includes an anode guide ring, an electrode positioning plate, a cathode connecting column, a cathode mesh tube, a plurality of anode feeding rods, a cathode guide ring, a cathode quick-plug ear, an anode quick-plug ear and an electrode connecting bolt pair; the anode guide ring and the cathode guide ring are fixed to the electrode positioning plate by an electrode connecting bolt pair; the cathode quick-plug ear and the anode quick-plug ear are respectively installed on the cathode guide ring and the anode guide ring through threaded holes; the lower ends of the six cathode connecting columns are connected to the cathode mesh tube, and the upper ends are installed on the cathode guide ring through threaded holes after passing through the electrode positioning plate; the anode feeding rod is installed on the anode guide ring through threaded holes after passing through the electrode positioning plate; the cathode guide ring, anode guide ring, cathode connecting column and cathode mesh tube are made of inert conductive metal materials; the electrode positioning plate is made of insulating material; the cathode guide ring and the anode guide ring do not contact each other; the cathode quick-plug ear and the anode quick-plug ear are respectively connected to the cathode and anode of an external power supply when an electrolysis reaction is required.

[0012] Furthermore, the anode feeding rod is composed of a plurality of fixed nuts, a plurality of fixed spring washers, a plurality of fixed gaskets and a plurality of graphite sheets tightly mounted on the full-thread screw in a fixed order; the full-thread screw has a periodic candied-haws structure of 1 fixed nut, 1 fixed spring washer, (1 fixed gasket, 1 graphite sheet)×N, 1 fixed spring washer, and 1 fixed nut from top to bottom, and the range of N is 5 to 20; the full-thread screw is made of an inert conductive metal material.

[0013] Furthermore, the electrode lifting structure includes a stepping motor and a ball slide installed on the inner side of the upper end of the outer structure support, and a slide electrode connector fixedly connected to the ball slide.

[0014] Furthermore, the stirring module includes a stirring motor connecting plate fixed above the stirring paddle bracket by angle codes and bolts, a stirring motor fixed on the stirring motor connecting plate, a stirring rod with one end connected to the stirring motor and the other end passing through the stirring motor connecting plate to enter the reactor, and a plurality of detachable stirring blades that can be installed on the stirring rod; the stirring rod and the detachable stirring blades are made of stainless steel coated with polytetrafluoroethylene.

[0015] The present invention also provides a method for continuously preparing high-quality graphene, comprising the following steps:

[0016] 1) preparing raw graphite sheets by a sheet cutting device or a molding process;

[0017] 2) Assemble the anode feeding rod and install it on the electrode assembly;

[0018] 3) Prepare the electrolyte, pour it into the reactor and turn on the cooling device to set the cooling temperature, and turn on the stirring motor to set the stirring speed;

[0019] 4) The electrode assembly is first raised to the highest point by the electrode lifting structure, and then slowly lowered into the electrolyte in the reactor by setting the descending speed and the total reaction time, and fully electrolyzed to generate graphene under a certain electrolysis voltage and current;

[0020] 5) Collecting the prepared graphene and sequentially cleaning and post-processing it to obtain a graphene solution.

[0021] Furthermore, in the step 1), the raw graphite is prepared into a graphite sheet with an inner diameter matching the full-thread screw and an outer diameter matching the fixed gasket by a cutting device or a molding process; when the raw graphite is graphite paper, a cutting device is used, and when the raw graphite is graphite powder, flake graphite, and worm graphite, a molding process is used; the inner diameter of the graphite sheet is 4 to 6 mm, the outer diameter is 16 to 20 mm, and the thickness is 0.5 to 2 mm; in the step 2), the installation order on the full-thread screw in the anode feeding rod is, from top to bottom, 1 fixed nut, 1 fixed spring washer, (1 The periodic candied haws structure is 1000× ...

[0022] Furthermore, the post-treatment method in step 5) is at least one of ultrasonic dispersion treatment and shear homogenization treatment; the ultrasonic power range of the ultrasonic dispersion is 30 to 3000 W, preferably 1000 to 2000 W; the ultrasonic time of the ultrasonic dispersion is 0.5 to 5 h, preferably 1 to 2 h; the rotation speed of the shear homogenization is 1000 to 5000 rpm.

[0023] Compared with the prior art, the device and method for continuously preparing high-quality graphene according to the present invention, wherein, by adopting the "candied haws on a string" method, graphite sheets and fixed gaskets are stacked layer by layer on several independent metal screws, and then through a certain electrode structure and transmission design, a continuous and stable production of high-quality graphene / graphene oxide equipment and method is achieved, which greatly improves the production efficiency and product quality of graphene. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic structural diagram of a device for continuously preparing high-quality graphene according to the present invention;

[0025] Figure 2 It is a schematic diagram of the three-dimensional structure of the upper support part of the device for continuously preparing high-quality graphene of the present invention;

[0026] Figure 3It is a structural schematic diagram of a fixed mounting plate portion in the device for continuously preparing high-quality graphene of the present invention;

[0027] Figure 4 It is a structural schematic diagram of a counterweight module part in the device for continuously preparing high-quality graphene of the present invention;

[0028] Figure 5 It is a schematic diagram of the three-dimensional structure of the electrode assembly part in the device for continuously preparing high-quality graphene of the present invention;

[0029] Figure 6 It is a schematic structural diagram of the anode loading rod part in the device for continuously preparing high-quality graphene of the present invention;

[0030] Figure 7 It is a partial enlarged view of the anode feeding rod part in the device for continuously preparing high-quality graphene of the present invention;

[0031] Figure 8 It is a schematic diagram of the three-dimensional structure of the electrode elevator part in the device for continuously preparing high-quality graphene of the present invention;

[0032] Fig. 9 It is a schematic diagram of the three-dimensional structure of the stirring module part in the device for continuously preparing high-quality graphene of the present invention;

[0033] Fig.10 This is an atomic force microscope image of graphene obtained in Example 1 of the present invention.

[0034] Description of reference numerals:

[0035] 1. Upper bracket; 1-1. External structure bracket; 1-2. Agitator bracket; 1-3. Counterweight pulley bracket;

[0036] 2. Fixed mounting plate; 2-1. Upper bracket mounting hole; 2-2. Lifting slide mounting hole; 2-3. Lower rack mounting hole; 2-4. Wiring opening;

[0037] 3. Lower the rack;

[0038] 4. Reactor;

[0039] 5. Counterweight module; 5-1. Optical axis slide; 5-2. Counterweight block; 5-3. Electrode assembly hook; 5-4. Frame pulley; 5-5. Counterweight wire rope;

[0040] 6. Electrode assembly; 6-1. Anode guide ring; 6-2. Electrode positioning plate; 6-3. Cathode connecting column; 6-4. Cathode mesh cylinder; 6-5. Anode feeding rod; 6-5-1. Full-thread screw; 6-5-2. Fixing nut; 6-5-3. Fixing spring washer; 6-5-4. Fixing gasket; 6-5-5. Graphite sheet; 6-6. Cathode guide ring; 6-7. Cathode quick-plug lug; 6-8. Anode quick-plug lug; 6-9. Electrode connecting bolt pair;

[0041] 7. Electrode lifting structure; 7-1. Stepping motor; 7-2. Ball slide; 7-3. Slide electrode connector;

[0042] 8. Electrode lifting structure; 8-1. Stirring motor; 8-2. Stirring motor connecting plate; 8-3. Stirring rod; 8-4. Removable stirring blade. DETAILED DESCRIPTION

[0043] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0044] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.

[0045] like Figures 1 to 9The figure shows a schematic diagram of the structure of a graphene preparation device according to a preferred embodiment of the present invention and a partial enlarged diagram thereof. The present invention provides a device for continuously preparing high-quality graphene, comprising: an upper bracket 1, which is composed of an outer structural bracket 1-1 located on the periphery to form a main frame, a stirring paddle bracket 1-2 horizontally fixed at the central position of the outer structural bracket 1-1, and a counterweight pulley bracket 1-3 fixed on one side above the stirring paddle bracket 1-2; a fixed mounting plate 2, which is used to fix the upper bracket 1 located above it and the lower frame 3 located below it; the lower frame 3 is used to support a reactor 4, and a pulley can be installed at the bottom of the lower frame 3 to facilitate the movement of the entire device; the reactor 4 is used to perform an electrolytic reaction inside it, and a discharge port can be provided below it to facilitate the discharge of materials outflow; a counterweight module 5, fixed on the inner side below the outer structure support 1-1 and supported by a counterweight pulley support 1-3, is used to balance the force during the operation of the balancing device; an electrode assembly 6, in which positive and negative electrodes and reaction raw materials can be installed by bolts, which is installed on the slide electrode connector 7-3 and rises and falls with the electrode lifting structure 7; the electrode lifting structure 7, by controlling the lifting time and rate of the slide electrode connector 7-3 structure therein, further controls the electrode assembly 6 to slowly enter the reactor 4 for electrolysis reaction; a stirring module 8, fixed on the stirring paddle support 1-2, is used to stir the electrolyte and the product during the electrolysis reaction to ensure uniform reaction; the device also includes a cooling device, which is connected to the outer wall of the reactor 4.

[0046] Furthermore, the fixed mounting plate 2 includes an upper bracket mounting hole 2-1, a lifting slide mounting hole 2-2, a lower rack mounting hole 2-3 and a wiring opening 2-4; wherein, the upper bracket 1 is connected to the fixed mounting plate 2 through the upper bracket mounting hole 2-1 on the outer edge of the fixed mounting plate 2; the lower rack 3 is connected to the fixed mounting plate 2 through the lower rack mounting hole 2-3 inside the fixed mounting plate 2; the lifting slide mounting hole 2-2 is a plurality of slots located on one side of the short side of the fixed mounting plate 2.

[0047] Furthermore, the counterweight module 5 includes an optical axis slide 5-1 fixed to the inner side below the external structure support 1-1 by bolts, a counterweight block 5-2 installed on the optical axis slide 5-1, an electrode assembly hook 5-3 installed on the slide electrode connector 7-3, a frame pulley 5-4 and a counterweight wire rope 5-5 installed on the counterweight pulley mounting frame 1-3; the weight of the counterweight block 5-2 is half of the total weight of the electrode assembly 6 and the slide electrode connector 7-3; one end of the counterweight wire rope 5-5 is connected to the hook on the counterweight block 5-2, and the other end passes through the frame pulley 5-4 and is connected to the electrode assembly hook 5-3.

[0048] Furthermore, the electrode assembly 6 includes an anode guide ring 6-1, an electrode positioning plate 6-2, a cathode connecting column 6-3, a cathode mesh tube 6-4, a plurality of anode feeding rods 6-5, a cathode guide ring 6-6, a cathode quick-plug lug 6-7, an anode quick-plug lug 6-8 and an electrode connecting bolt pair 6-9; the anode guide ring 6-1 and the cathode guide ring 6-6 are fixed to the electrode positioning plate 6-2 by the electrode connecting bolt pair 6-9; the cathode quick-plug lug 6-7 and the anode quick-plug lug 6-8 are respectively installed on the cathode guide ring 6-6 and the anode guide ring 6-1 through threaded holes; the lower ends of the six cathode connecting columns 6-3 are The cathode mesh cylinder 6-4 is connected, and the upper end passes through the electrode positioning plate 6-2 and is installed on the cathode guide ring 6-6 through a threaded hole; the anode feeding rod 6-5 passes through the electrode positioning plate 6-2 and is installed on the anode guide ring 6-1 through a threaded hole; the cathode guide ring 6-6, the anode guide ring 6-1, the cathode connecting column 6-3 and the cathode mesh cylinder 6-4 are made of inert conductive metal materials; the electrode positioning plate 6-2 is made of insulating material; the cathode guide ring 6-6 and the anode guide ring 6-1 do not contact each other; the cathode quick-plug lug 6-7 and the anode quick-plug lug 6-8 are respectively connected to the cathode and anode of an external power supply when an electrolysis reaction is required.

[0049] Furthermore, the anode feeding rod 6-5 is composed of a plurality of fixed nuts 6-5-2, a plurality of fixed spring washers 6-5-3, a plurality of fixed gaskets 6-5-4 and a plurality of graphite sheets 6-5-5 which are tightly mounted on the full-thread screw 6-5-1 and combined in a fixed order; the full-thread screw 6-5-1 has a periodic candied haws structure of 1 fixed nut (6-5-2), 1 fixed spring washer 6-5-3, (1 fixed gasket 6-5-4, 1 graphite sheet 6-5-5)×N, 1 fixed spring washer 6-5-3, and 1 fixed nut 6-5-2 from top to bottom, and the range of N is 5 to 20; the full-thread screw 6-5-1 is an inert conductive metal material.

[0050] Furthermore, the electrode lifting structure 7 includes a stepper motor 7-1 and a ball slide 7-2 installed on the inner side of the upper end of the outer structure support 1-1, and a slide electrode connector 7-3 fixedly connected to the ball slide 7-2.

[0051] Furthermore, the stirring module 8 includes a stirring motor connecting plate 8-2 fixedly installed above the stirring paddle bracket 1-2 by angle codes and bolts, a stirring motor 8-1 fixed on the stirring motor connecting plate 8-2, a stirring rod 8-3 with one end connected to the stirring motor 8-1 and the other end passing through the stirring motor connecting plate 8-2 to enter the reactor 4, and a plurality of detachable stirring blades 8-4 that can be installed on the stirring rod 8-3; the stirring rod 8-3 and the detachable stirring blades 8-4 are made of stainless steel coated with polytetrafluoroethylene.

[0052] The present invention also provides a method for continuously preparing high-quality graphene, comprising the following steps:

[0053] 1) preparing a raw graphite sheet 6-5-5 by a sheet cutting device or a molding process;

[0054] 2) Assembling the anode feeding rod 6-5 and installing it on the electrode assembly 6;

[0055] 3) Prepare the electrolyte, pour it into the reactor 4 and turn on the cooling device to set the cooling temperature, and turn on the stirring motor 8-1 to set the stirring speed;

[0056] 4) The electrode assembly 6 is first raised to the highest point by the electrode lifting structure 7, and then slowly lowered into the electrolyte in the reactor 4 by setting the descending speed and the total reaction time, and fully electrolyzed to generate graphene under a certain electrolysis voltage and current;

[0057] 5) collecting the prepared graphene and sequentially cleaning and post-processing it to obtain a graphene solution.

[0058] Further, in the step 1), the raw graphite is prepared into a graphite sheet 6-5-5 with an inner diameter matching the full-thread screw 6-5-1 and an outer diameter matching the fixed gasket 6-5-4 by a cutting device or a molding process; when the raw graphite is graphite paper, a cutting device is used, and when the raw graphite is graphite powder, flake graphite, and worm graphite, a molding process is used; the inner diameter of the graphite sheet 6-5-5 is 4 to 6 mm, the outer diameter is 16 to 20 mm, and the thickness is 0.5 to 2 mm; in the step 2), the installation order on the full-thread screw 6-5-1 in the anode feeding rod 6-5 is from top to bottom 1 fixed nut 6-5-2, 1 fixed spring washer 6-5-3, (1 fixed gasket 6-5-4, 1 graphite sheet 6-5-5)×N, 1 fixed spring washer 6-5-3, 1 fixed nut 6-5- 2 of the periodic sugar-coated haws structure, N ranges from 5 to 20; the electrolyte in the step 3) is one or a combination of sulfuric acid, sulfate, bisulfate, persulfate, phosphate, oxalic acid, citric acid, and nitric acid, and is adjusted by ammonia and hydroxide corresponding system cation base; the cooling temperature in the step 3) is set to 5 to 40°C, preferably 10 to 25°C; the stirring speed in the step 3) is 50 to 150 rpm, preferably 60 to 100 rpm; the descending speed in the step 4) is in the range of 1 to 20 mm / h, preferably 2 to 5 mm / h; the total reaction time in the step 4) is 1-1000 h; the voltage in the step 4) is set to 5 to 100 V, preferably 10 to 50 V; the current is set to 100 to 500 A, preferably 200 to 300 A.

[0059] Furthermore, the post-treatment method in step 5) is at least one of ultrasonic dispersion treatment and shear homogenization treatment; the ultrasonic power range of the ultrasonic dispersion is 30 to 3000 W, preferably 1000 to 2000 W; the ultrasonic time of the ultrasonic dispersion is 0.5 to 5 h, preferably 1 to 2 h; the rotation speed of the shear homogenization is 1000 to 5000 rpm.

[0060] In this embodiment, the design of the device realizes uniform and continuous raw material input, which ensures the continuation of the confined electrolysis reaction to the greatest extent and improves the quality and uniformity of the product.

[0061] In the following Examples 1 to 16, the preparation processes of the present invention under different preparation environments are specifically described:

[0062] Embodiment 1, a method for continuously preparing high-quality graphene, comprising:

[0063] The raw graphite powder is pressed into graphite sheets 6-5-5 by a molding process, with a specification of φ6×16mm, and a gasket of matching size is used. Five graphite sheets 6-5-5 are used as a confined period and evenly installed on the anode feeding rod 6-5. A single anode feeding rod 6-5 is equipped with 120 graphite sheets 6-5-5. There are 36 anode feeding rods 6-5, which are evenly installed under the anode guide ring 6-1. 0.8M ammonium sulfate + 0.2M sodium sulfate is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 2mm / h. The voltage is set to 10V and the current is 250A. The reaction temperature is set to 10℃. The stirring paddle speed is 60rpm. The total reaction time is 720h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 50mpas. It is subjected to 1000W ultrasound for 1h and then centrifuged to obtain high-quality graphene with an average number of 1 to 3 layers.

[0064] Embodiment 2, a method for continuously preparing high-quality graphene, comprising:

[0065] Cut graphite paper into annular graphite sheets 6-5-5 with a specification of φ5×18mm, and use gaskets of matching size, with 6 graphite sheets 6-5-5 as the confined period, evenly installed on the anode feeding rod 6-5, a single anode feeding rod 6-5 is equipped with 110 graphite sheets 6-5-5, and a total of 34 anode feeding rods 6-5 are evenly installed under the anode guide ring 6-1. 0.7M ammonium sulfate + 0.3M sulfuric acid is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 3mm / h. Set the voltage to 12V and the current to 280A. The reaction temperature is set to 12℃. The stirring paddle speed is 65rpm. The total reaction time is 680h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 55mpas. It is ultrasonically treated at 1200W for 1.2h and then centrifuged to obtain high-quality graphene with an average number of 2 to 4 layers.

[0066] Embodiment 3, a method for continuously preparing high-quality graphene, comprising:

[0067] The raw graphite powder is pressed into graphite sheets 6-5-5 by a molding process, with a specification of φ4×20mm, and a gasket of matching size is used. Seven graphite sheets 6-5-5 are used as a confined period and evenly installed on the anode feeding rod 6-5. A single anode feeding rod 6-5 is equipped with 100 graphite sheets 6-5-5. There are 32 anode feeding rods 6-5, which are evenly installed under the anode guide ring 6-1. 0.6M ammonium sulfate + 0.4M sodium sulfate is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 4mm / h. The voltage is set to 14V and the current is 300A. The reaction temperature is set to 14℃. The stirring paddle speed is 70rpm. The total reaction time is 640h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 60mpas. It is ultrasonically treated at 1400W for 1.4h and then centrifuged to obtain high-quality graphene with an average number of 1 to 3 layers.

[0068] Embodiment 4, a method for continuously preparing high-quality graphene, comprising:

[0069] Cut graphite paper into annular graphite sheets 6-5-5 with a specification of φ6×18mm, and use gaskets of matching size, with 8 graphite sheets 6-5-5 as the confined period, evenly installed on the anode feeding rod 6-5, and 90 graphite sheets 6-5-5 are installed on a single anode feeding rod 6-5. There are 30 anode feeding rods 6-5, evenly installed under the anode guide ring 6-1. 0.5M sodium persulfate + 0.5M sodium sulfate is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 5mm / h. Set the voltage to 16V and the current to 320A. The reaction temperature is set to 16℃. The stirring paddle speed is 75rpm. The total reaction time is 600h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 65mpas. It is ultrasonically treated at 1600W for 1.6 hours and then centrifuged to obtain high-quality graphene with an average number of 2 to 4 layers.

[0070] Embodiment 5, a method for continuously preparing high-quality graphene, comprising:

[0071] The raw graphite powder is pressed into graphite sheets 6-5-5 by a molding process, with a specification of φ5×19mm, and a gasket of matching size is used. With 9 graphite sheets 6-5-5 as the confined period, they are evenly installed on the anode feeding rod 6-5. A single anode feeding rod 6-5 is equipped with 80 graphite sheets 6-5-5. There are 28 anode feeding rods 6-5 in total, which are evenly installed under the anode guide ring 6-1. 0.4M ammonium sulfate + 0.6M sodium sulfate is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 6mm / h. The voltage is set to 18V and the current is 340A. The reaction temperature is set to 18℃. The stirring paddle speed is 80rpm. The total reaction time is 560h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 70mpas. It is ultrasonically treated at 1800W for 1.8h and then centrifuged to obtain high-quality graphene with an average number of 1 to 3 layers.

[0072] Embodiment 6, a method for continuously preparing high-quality graphene, comprising:

[0073] Cut graphite paper into annular graphite sheets 6-5-5 with a specification of φ4×17mm, and use gaskets of matching size, with 10 graphite sheets 6-5-5 as the confined period, evenly installed on the anode feeding rod 6-5, a single anode feeding rod 6-5 is equipped with 70 graphite sheets 6-5-5, and a total of 26 anode feeding rods 6-5 are evenly installed under the anode guide ring 6-1. 0.3M ammonium sulfate + 0.7M sodium sulfate is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 7mm / h. Set the voltage to 20V and the current to 360A. The reaction temperature is set to 20℃. The stirring paddle speed is 85rpm. The total reaction time is 520h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 75mpas. It is ultrasonicated at 2000W for 2h and then centrifuged to obtain high-quality graphene with an average number of 2 to 4 layers.

[0074] Embodiment 7, a method for continuously preparing high-quality graphene, comprising:

[0075] The raw graphite powder is pressed into graphite sheets 6-5-5 by a molding process, with a specification of φ6×19mm, and a gasket of matching size is used. 11 graphite sheets 6-5-5 are used as a confined period and evenly installed on the anode feeding rod 6-5. A single anode feeding rod 6-5 is equipped with 65 graphite sheets 6-5-5. There are 24 anode feeding rods 6-5, which are evenly installed under the anode guide ring 6-1. 0.2M ammonium sulfate + 0.8M sodium sulfate is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 8mm / h. The voltage is set to 22V and the current is 380A. The reaction temperature is set to 22℃. The stirring paddle speed is 90rpm. The total reaction time is 480h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 80mpas. It is ultrasonicated at 2200W for 2.2h and then separated by centrifugation to obtain high-quality graphene with an average number of 1 to 3 layers.

[0076] Embodiment 8, a method for continuously preparing high-quality graphene, comprising:

[0077] Cut graphite paper into annular graphite sheets 6-5-5 with a specification of φ5×20mm, and use gaskets of matching size, with 12 graphite sheets 6-5-5 as the confined period, evenly installed on the anode feeding rod 6-5, a single anode feeding rod 6-5 is equipped with 60 graphite sheets 6-5-5, and a total of 22 anode feeding rods 6-5 are evenly installed under the anode guide ring 6-1. 0.1M ammonium sulfate + 0.9M citric acid is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 9mm / h. Set the voltage to 24V and the current to 400A. The reaction temperature is set to 24℃. The stirring paddle speed is 95rpm. The total reaction time is 440h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 85mpas. It is ultrasonicated at 2400W for 2.4h and then separated by centrifugation to obtain high-quality graphene with an average number of 2 to 4 layers.

[0078] Embodiment 9, a method for continuously preparing high-quality graphene, comprising:

[0079] The raw graphite powder is pressed into graphite sheets 6-5-5 with a specification of φ4×18mm by a molding process, and a gasket of matching size is used. 13 graphite sheets 6-5-5 are used as a confined period and evenly installed on the anode feeding rod 6-5. A single anode feeding rod 6-5 is equipped with 55 graphite sheets 6-5-5. There are 20 anode feeding rods 6-5, which are evenly installed under the anode guide ring 6-1. 0.05M ammonium sulfate + 0.95M sodium sulfate is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 10mm / h. The voltage is set to 26V and the current is 420A. The reaction temperature is set to 26℃. The stirring paddle speed is 100rpm. The total reaction time is 400h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 90mpas. It is ultrasonicated at 2600W for 2.6h and then separated by centrifugation to obtain high-quality graphene with an average number of 1 to 3 layers.

[0080] Embodiment 10, a method for continuously preparing high-quality graphene, comprising:

[0081] Cut graphite paper into annular graphite sheets 6-5-5 with a specification of φ6×20mm, and use gaskets of matching size, with 14 graphite sheets 6-5-5 as the confined period, evenly installed on the anode feeding rod 6-5, a single anode feeding rod 6-5 is equipped with 50 graphite sheets 6-5-5, and a total of 18 anode feeding rods 6-5 are evenly installed under the anode guide ring 6-1. 0.8M sodium bisulfate + 0.2M potassium sulfate is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 11mm / h. Set the voltage to 28V and the current to 440A. The reaction temperature is set to 28℃. The stirring paddle speed is 105rpm. The total reaction time is 360h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 95mpas. It is ultrasonicated at 2800W for 2.8h and then separated by centrifugation to obtain high-quality graphene with an average number of 2 to 4 layers.

[0082] Embodiment 11, a method for continuously preparing high-quality graphene, comprising:

[0083] The raw graphite powder is pressed into graphite sheets 6-5-5 by a molding process, with a specification of φ5×17mm, and a gasket of matching size is used. 15 graphite sheets 6-5-5 are used as a confined period and evenly installed on the anode feeding rod 6-5. A single anode feeding rod 6-5 is equipped with 45 graphite sheets 6-5-5. There are 16 anode feeding rods 6-5-5 in total, which are evenly installed under the anode guide ring 6-1. 0.7M ammonium sulfate + 0.3M oxalic acid is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 12mm / h. The voltage is set to 30V and the current is 460A. The reaction temperature is set to 30℃. The stirring paddle speed is 110rpm. The total reaction time is 320h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 100 mpas. It is ultrasonicated at 3000 W for 3 hours and then centrifuged to obtain high-quality graphene with an average number of 1 to 3 layers.

[0084] Embodiment 12, a method for continuously preparing high-quality graphene, comprising:

[0085] Cut the graphite sheet 6-5-5 to φ4×19mm, and use a gasket of matching size, with 16 graphite sheets 6-5-5 as the confined period, evenly installed on the anode feeding rod 6-5, a single anode feeding rod 6-5 is equipped with 40 graphite sheets 6-5-5, and a total of 14 anode feeding rods 6-5 are evenly installed under the anode guide ring 6-1. 0.6M ammonium sulfate + 0.4M citric acid is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 13mm / h. Set the voltage to 32V and the current to 480A. Set the reaction temperature to 32℃. The stirring paddle speed is 115rpm. The total reaction time is 280h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 50mpas. It is subjected to 1000W ultrasound for 1h and then centrifuged to obtain high-quality graphene with an average number of 2 to 4 layers.

[0086] Embodiment 13, a method for continuously preparing high-quality graphene, comprising:

[0087] The raw graphite powder is pressed into graphite sheets 6-5-5 with a specification of φ6×18mm through a molding process, and a gasket of matching size is used. 17 graphite sheets 6-5-5 are used as a confined period and evenly installed on the anode feeding rod 6-5. A single anode feeding rod 6-5 is equipped with 35 graphite sheets 6-5-5. There are 12 anode feeding rods 6-5 in total, which are evenly installed under the anode guide ring 6-1. 0.5M ammonium sulfate + 0.5M nitric acid is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 14mm / h. The voltage is set to 34V and the current is 500A. The reaction temperature is set to 34℃. The stirring paddle speed is 120rpm. The total reaction time is 240h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 55mpas. It is ultrasonically treated at 1200W for 1.2h and then centrifuged to obtain high-quality graphene with an average number of 1 to 3 layers.

[0088] Embodiment 14, a method for continuously preparing high-quality graphene, comprising:

[0089] Cut the graphite sheet 6-5-5 to φ5×16mm, and use a gasket of matching size, with 18 graphite sheets 6-5-5 as the confined period, evenly installed on the anode feeding rod 6-5, a single anode feeding rod 6-5 is equipped with 30 graphite sheets 6-5-5, and a total of 10 anode feeding rods 6-5 are evenly installed under the anode guide ring 6-1. 0.4M ammonium sulfate + 0.6M phosphoric acid is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 15mm / h. Set the voltage to 36V and the current to 520A. Set the reaction temperature to 36℃. The stirring paddle speed is 125rpm. The total reaction time is 200h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 60mpas. It is ultrasonicated at 1400W for 1.4h and then separated by centrifugation to obtain high-quality graphene with an average number of 2 to 4 layers.

[0090] Embodiment 15, a method for continuously preparing high-quality graphene, comprising:

[0091] The raw graphite powder is pressed into graphite sheets 6-5-5 with a specification of φ4×15mm by a molding process, and a gasket of matching size is used. 19 graphite sheets 6-5-5 are used as a confined period and evenly installed on the anode feeding rod 6-5. A single anode feeding rod 6-5 is equipped with 25 graphite sheets 6-5-5. There are 8 anode feeding rods 6-5 in total, which are evenly installed under the anode guide ring 6-1. 0.3M ammonium sulfate + 0.7M sodium persulfate are selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 16mm / h. The voltage is set to 38V and the current is 540A. The reaction temperature is set to 38℃. The stirring paddle speed is 130rpm. The total reaction time is 160h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 65mpas. It is ultrasonically treated at 1600W for 1.6 hours and then centrifuged to obtain high-quality graphene with an average number of 1 to 3 layers.

[0092] Embodiment 16, a method for continuously preparing high-quality graphene, comprising:

[0093] Cut the graphite sheet 6-5-5 into φ6×16mm, and use the gasket with matching size, with 5 graphite sheets 6-5-5 as the confined period, evenly install them on the anode feeding rod 6-5, and install 120 graphite sheets 6-5-5 on a single anode feeding rod 6-5. There are 36 anode feeding rods 6-5, evenly installed under the anode guide ring 6-1. 0.8M ammonium sulfate + 0.2M sodium sulfate is selected as the electrolyte. The descending rate of the slide electrode connector 7-3 is 2mm / h. Set the voltage to 10V and the current to 200A. Set the reaction temperature to 10℃. The stirring paddle speed is 60rpm. The total reaction time is 720h. After the electrolysis is completed, the mixed liquid is cleaned by centrifugation, the electrolyte is recycled, and the solid is reconfigured with industrial-grade pure water to a mixed liquid with a viscosity of 50mpas. It is subjected to 1000W ultrasound for 1h and then centrifuged to obtain high-quality graphene with an average number of 1 to 3 layers.

Claims

1. A device for continuously preparing high-quality graphene, comprising an upper support (1), a fixed mounting plate (2), a lower frame (3) and a reaction kettle (4), characterized in that: The upper bracket (1) and the lower frame (3) are connected up and down through the fixed mounting plate (2) and fixed by standard angle brackets and bolts; the upper bracket (1) is composed of an outer structure bracket (1-1) located on the periphery and constituting a main frame, a stirring paddle bracket (1-2) horizontally fixed at the center of the outer structure bracket (1-1), and a counterweight pulley bracket (1-3) fixed on one side above the stirring paddle bracket (1-2); the reaction kettle (4) is supported by the lower frame (3) and is limited to the center of the fixed mounting plate (2) by bolts; The upper bracket (1) is also equipped with a counterweight module (5) fixed to the inner side below the outer structure bracket (1-1) and supported by the counterweight pulley bracket (1-3), an electrode lifting structure (7) fixed to the inner side above the outer structure bracket (1-1), and a stirring module (8) fixed to the stirring paddle bracket (1-2); the electrode lifting structure (7) is also connected to a slide electrode connector (7-3) for mounting an electrode assembly (6); the device also includes a cooling device, which is connected to the outer wall of the reactor (4).

2. The device according to claim 1, characterized in that The fixed mounting plate (2) comprises an upper bracket mounting hole (2-1), a lifting slide mounting hole (2-2), a lower rack mounting hole (2-3) and a wiring opening (2-4); wherein the upper bracket (1) is connected to the fixed mounting plate (2) via the upper bracket mounting hole (2-1) at the outer edge of the fixed mounting plate (2); the lower rack (3) is connected to the fixed mounting plate (2) via the lower rack mounting hole (2-3) inside the fixed mounting plate (2); the lifting slide mounting hole (2-2) is a plurality of notches located on one side of the short side of the fixed mounting plate (2).

3. The device according to claim 1, characterized in that The counterweight module (5) comprises an optical axis slide (5-1) fixed to the inner side below the external structure support (1-1) by bolts, a counterweight block (5-2) mounted on the optical axis slide (5-1), an electrode assembly hook (5-3) mounted on the slide electrode connector (7-3), a frame pulley (5-4) and a counterweight wire rope (5-5) mounted on the counterweight pulley mounting frame (1-3); the weight of the counterweight block (5-2) is half of the total weight of the electrode assembly (6) and the slide electrode connector (7-3); one end of the counterweight wire rope (5-5) is connected to the hook on the counterweight block (5-2), and the other end passes through the frame pulley (5-4) and is connected to the electrode assembly hook (5-3).

4. The device according to claim 1, characterized in that The electrode assembly (6) comprises an anode guide ring (6-1), an electrode positioning plate (6-2), a cathode connecting column (6-3), a cathode mesh tube (6-4), a plurality of anode feeding rods (6-5), a cathode guide ring (6-6), a cathode quick-plug lug (6-7), an anode quick-plug lug (6-8) and an electrode connecting bolt pair (6-9); the anode guide ring (6-1) and the cathode guide ring (6-6) are fixed to the electrode positioning plate (6-2) through the electrode connecting bolt pair (6-9); the cathode quick-plug lug (6-7) and the anode quick-plug lug (6-8) are respectively installed on the cathode guide ring (6-6) and the anode guide ring (6-8) through threaded holes. 6-1); the lower ends of the six cathode connecting columns (6-3) are connected to the cathode net cylinder (6-4), and the upper ends pass through the electrode positioning plate (6-2) and are installed on the cathode guide ring (6-6) through the threaded hole; the anode loading rod (6-5) passes through the electrode positioning plate (6-2) and is installed on the anode guide ring (6-1) through the threaded hole; the cathode guide ring (6-6), the anode guide ring (6-1), the cathode connecting columns (6-3) and the cathode net cylinder (6-4) are made of inert conductive metal materials; the electrode positioning plate (6-2) is made of insulating material; the cathode guide ring (6-6) and the anode guide ring (6-1) do not contact each other.

5. The device according to claim 4, characterized in that The anode feeding rod (6-5) is composed of a plurality of fixed nuts (6-5-2), a plurality of fixed spring washers (6-5-3), a plurality of fixed gaskets (6-5-4) and a plurality of graphite sheets (6-5-5) which are tightly mounted on a full-thread screw (6-5-1) and combined in a fixed order; the full-thread screw (6-5-1) has a periodic candied haws structure of 1 fixed nut (6-5-2), 1 fixed spring washer (6-5-3), (1 fixed gasket (6-5-4), 1 graphite sheet (6-5-5))×N, 1 fixed spring washer (6-5-3), 1 fixed nut (6-5-2), and N ranges from 5 to 20; the full-thread screw (6-5-1) is made of an inert conductive metal material.

6. The device according to claim 1, characterized in that The electrode lifting structure (7) comprises a stepping motor (7-1) and a ball slide (7-2) mounted on the inner side of the upper end of the external structure support (1-1), and a slide electrode connector (7-3) fixedly connected to the ball slide (7-2).

7. The device according to claim 1, characterized in that The stirring module (8) comprises a stirring motor connecting plate (8-2) fixedly mounted above the stirring paddle bracket (1-2) by means of angle brackets and bolts, a stirring motor (8-1) fixed on the stirring motor connecting plate (8-2), a stirring rod (8-3) having one end connected to the stirring motor (8-1) and the other end passing through the stirring motor connecting plate (8-2) and entering the reaction kettle (4), and a plurality of detachable stirring blades (8-4) that can be mounted on the stirring rod (8-3); the stirring rod (8-3) and the detachable stirring blades (8-4) are made of stainless steel coated with polytetrafluoroethylene.

8. A method for continuously preparing high-quality graphene using the apparatus of claims 1 to 7, characterized in that: The following steps are involved: 1) preparing the graphite sheet (6-5-5) by a sheet cutting device or a molding process; 2) assembling the anode loading rod (6-5) and installing it on the electrode assembly (6); 3) preparing an electrolyte, pouring it into the reactor (4) and turning on the cooling device to set the cooling temperature, while turning on the stirring motor (8-1) to set the stirring speed; 4) The electrode assembly (6) is first raised to the highest point by the electrode lifting structure (7), and then slowly lowered into the electrolyte in the reactor (4) by setting the descending speed and the total reaction time, and fully electrolyzed to generate graphene at a certain electrolysis voltage and current; 5) Collecting the prepared graphene and sequentially cleaning and post-processing it to obtain a graphene solution.

9. The method according to claim 8, characterized in that In the step 1), when the raw graphite is graphite paper, a cutting device is used, and when the raw graphite is graphite powder, flake graphite, worm graphite, etc., a molding process is used; the inner diameter of the graphite sheet (6-5-5) is 4 to 6 mm, the outer diameter is 16 to 20 mm, and the thickness is 0.5 to 2 mm; in the step 3), the electrolyte is one or a combination of sulfuric acid, sulfate, hydrogen sulfate, persulfate, phosphate, oxalic acid, citric acid, and nitric acid, and is adjusted by ammonia water and a hydroxide corresponding system cation base; the step 3) the cooling temperature is set to 5-40°C, preferably 10-25°C; the stirring speed in step 3) is 50-150rpm, preferably 60-100rpm; the descending speed in step 4) is in the range of 1-20mm / h, preferably 2-5mm / h; the total reaction time in step 4) is 1-1000h; the voltage in step 4) is set to 5-100V, preferably 10-50V; the current is set to 100-500A, preferably 200-300A.

10. The method according to claim 8, characterized in that The post-treatment method in step 5) is at least one of ultrasonic dispersion treatment and shear homogenization treatment; the ultrasonic power range of the ultrasonic dispersion is 30 to 3000 W, preferably 1000 to 2000 W; the ultrasonic time of the ultrasonic dispersion is 0.5 to 5 h, preferably 1 to 2 h; the rotation speed of the shear homogenization is 1000 to 5000 rpm.

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