CN115403036A - Device and method for continuous electrochemical stripping and application - Google Patents

Abstract

The invention relates to a device and a method for continuous electrochemical stripping and application, and belongs to the technical field of new materials. The continuous electrochemical peeling apparatus of the present invention comprises: the anode barrel is internally provided with an anode electrode, the cathode barrel is internally provided with a cathode electrode, the anode barrel is separated from the cathode barrel through a multilayer partition, and the anode barrel is internally provided with an electrolytic compaction column. The anode barrel and the cathode barrel are separated by a multilayer partition, an anode electrolysis reaction area is communicated with the feed inlet, the bottom of the cathode barrel is correspondingly provided with the discharge outlet, electrolyte containing raw materials enters the electrolysis reaction area from the feed inlet under the action of external driving force, an electrolyzed product passes through the multilayer partition under the driving of the electrolyte and enters the cathode barrel to be discharged and collected from the discharge outlet, and the external driving force drives the electrolyte containing the raw materials to circularly flow, so that the continuous feeding of the raw materials and the continuous taking-out of the product are realized, and the continuous electrochemical stripping is realized.

Description

Device and method for continuous electrochemical stripping and application

Technical Field

The invention belongs to the technical field of new materials, and particularly relates to a device and a method for continuous electrochemical stripping and application of the device and the method.

Background

The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. The electrochemical method directly prepares the graphene sheet layer with high lattice quality, namely the high-quality graphene by initiating an electrochemical reaction between graphite layers to generate gas to strip the graphite sheet layer.

The method has the characteristics of simple process, cleanness, no pollution, low cost and the like, and the stripping efficiency can reach about 85 percent at most, which is obviously superior to a liquid phase stripping method, so that the electrochemical stripping method is the most promising technology for realizing large-scale controllable preparation of high-quality graphene at present. In 2011, researchers such as Su (Acs Nano,2011,2332-2339 (5)) successfully prepared thin-layer graphene by electrolyzing highly oriented pyrolytic graphite and common graphite in dilute sulfuric acid electrolyte (0.5 m, ph = 0.3); yang (Angewandte Chemie-International Edition,2017,6669-6675 (56)) et al used square wave alternating voltage to perform electrolysis (+ -10V, 0.1 Hz) to obtain high yield graphene preparation (20 g h) ^-1 ) (ii) a Cao (Journal of the American Chemical Society,2017,17446-17456 (139)) et al obtained few-layer graphene oxide powder by a two-step electrochemical exfoliation method. The methods provide a plurality of original methods in the aspects of regulating and controlling the electrochemical stripping process and improving the graphene yield, but 15-25% of graphite sheets still exist in the product and need to be removed, and the method is still not beneficial to large-scale preparation.

When the conventional graphene oxide is prepared, the Hummers method is generally adopted, and stripping is performed by using polluting chemical raw materials such as concentrated sulfuric acid, potassium permanganate, sodium nitrate and hydrogen peroxide, so that a large amount of pollutants are generated. Compared with the Hummers method for preparing graphene oxide, the electrochemical method for preparing graphene is clean and pollution-free, but the electrochemical stripping method for preparing graphene has the difficulty of continuous production, continuous production requires continuous feeding of materials, and the existing electrochemical method for preparing graphene is still lack of equipment and methods for batch production.

Due to the uniqueness of the electrochemical graphene stripping process, most of the existing electrochemical graphene stripping processes use self-supporting materials such as graphite paper as electrodes, but the graphite paper has high cost, and the yield of the graphene process route obtained based on the graphite paper electrolysis process is relatively low due to the characteristics of the graphite paper. Therefore, innovations in electrochemical devices and processes are urgently needed to develop a simple and efficient device and strategy for electrochemically stripping graphene so as to improve the stripping efficiency of graphite in the electrochemical stripping process. In addition, the number of steps for stripping graphene by an electrolytic method is large, the electrolytic step is only the first step, and if a graphene precursor can be efficiently prepared, the method is favorable for realizing mass production of graphene.

The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is already known to a person skilled in the art.

Disclosure of Invention

In order to solve the technical problems of long time consumption, low productivity and difficulty in continuous production of the electrochemical stripping technology in the prior art, the invention provides a device and a method for continuous electrochemical stripping and application thereof.

The invention provides a continuous electrochemical stripping device, which comprises an anode barrel and a cathode barrel, wherein an anode electrode is arranged in the anode barrel, a cathode electrode is arranged in the cathode barrel, the anode barrel and the cathode barrel are separated by a multilayer partition, and an electrolytic compaction column is arranged in the anode barrel. Preferably, the anode barrel and the cathode barrel are in an up-down structure and are separated by a plurality of layers of partitions, so that the anode electrode and the cathode electrode are prevented from being in direct contact.

In some embodiments, the anode electrode and the multi-layer partition form an electrolysis reaction zone, and the electrolysis reaction zone is communicated with the feed inlet. The electrolytic reaction area is communicated with the feed inlet, so that continuous feeding in the reaction process is facilitated.

Preferably, the anode electrode is divided into two parts, one part is a hollow disc and is used for participating in electrolytic reaction, the other part is a hollow cylinder and is used for filling reactants such as raw materials and electrolyte, the hollow disc and the hollow cylinder are made of inert metal materials, the bottom of the hollow cylinder is welded with the hollow part of the hollow disc, a through hole matched with the hollow cylinder is formed in the center of the electrolytic compaction column, and the hollow cylinder penetrates through the electrolytic compaction column to be clamped with the feed inlet, so that the electrolytic reaction area is communicated with the feed inlet. Because the hollow cylinder is connected with the feed inlet in a clamping way, the replacement and the maintenance of the electrode are convenient. Wherein, in order to be adapted to the up-and-down movement of the electrolytic compaction column communicated anode electrode, the material of the feed inlet of the device comprises but is not limited to stainless steel corrugated pipe, polytetrafluoroethylene corrugated pipe, PU corrugated pipe, PVC corrugated pipe and the like.

Further preferably, the anode electrode is provided with an anode connecting buckle, and the anode connecting buckle is provided with an anode connecting terminal for connecting an anode power supply. In addition, the separation design also facilitates replacement and maintenance of the electrolysis.

In some embodiments, the electrolytic compaction column is provided on the back surface of the anode electrode reaction surface. The electrolytic compaction column and the anode electrode are fixedly installed and used for compacting the anode electrode and further compacting the raw materials in the electrolytic reaction area so as to ensure the sufficient and comprehensive contact between the electrolytic raw materials and the electrode and promote the reaction to be carried out. The material of the electrolytic compaction column is acid and alkali resistant solid material, such as polytetrafluoroethylene, PVC plate, etc.

In some embodiments, a lifting device is connected to the electrolytic compaction column; preferably, the lifting device comprises a screw rod connecting flange, one end of the screw rod connecting flange is fixed on the electrolytic compaction column, the other end of the screw rod connecting flange is connected with a lifting screw rod, the up-down distance of the electrolytic compaction column is adjusted through the lifting screw rod, the compaction pressure in the electrolytic process is adjusted, and the electrolytic process is further regulated and controlled; the lifting screw rod is fixed on the outer support frame through a screw rod fixing support, a support side opening is formed in the side face of the outer support frame, fixing bolts can be conveniently installed through the support side opening, and a composite pulley is arranged at the bottom of the outer support frame; preferably, the screw rod fixing support is fixed on the outer support frame through a screw rod fixing hole, wherein the screw rod fixing support is provided with a plurality of key slots for adjusting the horizontal position of the lifting screw rod; more preferably, the screw fixing hole includes a plurality of array holes, so as to adjust the height of the screw fixing bracket.

In some embodiments, the multi-layer partition comprises an anode bucket mounting disk and a cathode bucket mounting disk with a filter cloth and/or a porous support disk disposed therebetween.

The anode barrel mounting disc and the cathode barrel mounting disc are respectively used for fixing the shell of the anode barrel and the shell of the cathode barrel; the porous support disc plays a role in supporting raw materials, preferably, filter cloth is arranged on the porous support disc, wherein the filter cloth is acid-alkali-resistant flexible nylon filter cloth or fiber filter cloth, the mesh number of the filter cloth is about 50 meshes smaller than that of raw materials (such as graphite powder and flake graphite), so that the raw materials can be well prevented from leaking to a lower barrel before unreacted, and meanwhile, the size-reduced product can smoothly pass through after reaction, so that the function of screening materials before and after reaction is realized, and the filter cloth can be detached and replaced; further preferably, the thickness of the porous supporting disk is 10-20 mm, the deformation of the porous supporting disk is not more than 1% under the pressure of 10-30 kg, a plurality of small holes are formed in the porous supporting disk, the diameter of each hole is not less than 1cm and not more than 2cm, the porous supporting disk is made of a PVC plate, a pressure-resistant ceramic plate and the like, and the porous supporting disk can be detached and replaced; when no filter cloth is arranged, the porous support disc not only can better prevent the raw materials from leaking into the lower barrel before the raw materials are not reacted, but also can ensure the products after electrolysis to smoothly pass through and fall into the lower cathode barrel; in order to prevent the electrolyte from leaking, a waterproof gasket is further installed between the anode barrel installation disk and the cathode barrel installation disk.

In some embodiments, the cathode electrode is fixed on the inner wall of the cathode barrel through a cathode snap-fit connection piece, a cathode connection terminal is arranged on the cathode snap-fit connection piece, and the cathode connection terminal is arranged on the outer wall of the cathode barrel; preferably, the cathode electrode is a disk structure, and all disks of the cathode electrode are effective reaction surfaces; the cathode electrode is provided with a plurality of cathode meshes, and preferably, the diameter of the apertures of the cathode meshes is about 1cm, so that products generated after electrolysis on the cathode electrode are prevented from falling and accumulating.

In some embodiments, the bottom of the cathode barrel is provided with a discharge hole; and discharging the electrolyzed product from the discharge hole along with the electrolyte under the action of an external driving force. In the external circulating system, only the electrolyte is collected and circulated, and the electrolyzed product can be filtered and extracted and does not enter the electrolytic circulation.

In some embodiments, the cathode barrel is provided with barrel support legs below for supporting the whole barrel body, and preferably, the bottom of the barrel support legs is provided with composite rollers.

In a second aspect, the present invention provides a method of continuous electrochemical stripping, said method comprising: electrolyzing the electrolysis raw material in a compressed state and in a circulating flowing electrolyte; preferably, the method is carried out on the basis of the apparatus described above.

The third aspect of the invention provides an application of a continuous electrochemical stripping device in batch preparation of graphene precursors.

The fourth aspect of the present invention provides a method for preparing a graphene precursor, wherein the graphene precursor is prepared by the above apparatus or the above method;

in some embodiments, the compaction pressure is from 1 to 30 kilograms;

and/or the voltage of the electrolysis is 10-1000V;

and/or the electrolysis time is 1-100 h;

and/or the electrolytic electrolyte is a strong acid salt solution; preferably, the strong acid salt is selected from one or more of sulfate, nitrate, perchlorate and phosphate; more preferably, the concentration of the strong acid salt solution is 0.1 to 5M;

and/or, the graphite raw material: strong acid salt solution = 1; preferably, the graphite raw material is flake graphite and/or graphite powder.

Compared with the prior art, the invention achieves the following technical effects:

(1) The anode barrel and the cathode barrel are separated by the multilayer partition, the anode electrolysis reaction area is communicated with the feeding hole, the bottom of the cathode barrel is correspondingly provided with the discharging hole, the electrolyte containing the raw materials enters the electrolysis reaction area from the feeding hole under the action of external driving force, the electrolyzed product passes through the multilayer partition under the driving of the electrolyte and enters the cathode barrel to be discharged and collected from the discharging hole, and the external driving force drives the electrolyte containing the raw materials to circularly flow, so that the continuous feeding of the raw materials and the continuous taking-out of the product are realized, and the continuous electrochemical stripping is realized.

(2) The invention solves the historical problem that the electrochemical stripping is difficult to be continuous, and greatly improves the productivity of the electrochemical stripping.

(3) The continuous electrochemical stripping device and the method are simple, have universality, are particularly suitable for batch preparation of the graphene precursor, improve the productivity of the graphene precursor and are beneficial to realizing batch production of graphene.

(4) The method for preparing the graphene precursor in batch takes cheap graphite flakes and graphite powder as raw materials, replaces the traditional graphite paper raw material, and greatly reduces the cost.

(5) The graphene precursor obtained by the method has the characteristics of good hydrophilicity, larger average size and higher yield, and is easy to carry out post-treatment; the graphene precursor obtained by the invention can be used as a precursor for preparing graphene by other methods, including but not limited to physical methods, liquid-phase stripping methods, redox methods and other graphene preparation processes.

Drawings

FIG. 1 is a schematic structural diagram of an apparatus in examples 1 and 2 of the present invention;

FIG. 2 is a schematic diagram of the structure associated with the anode electrode of FIG. 1;

FIG. 3 is a schematic cross-sectional view of the device of FIG. 1 after being rotated 90 degrees clockwise;

FIG. 4 is a schematic diagram of the structure of the cathode electrode shown in FIG. 1;

FIG. 5 is a schematic view of the structure of the outer supporting frame of FIG. 1;

FIG. 6 is a schematic view of the screw fixing bracket of FIG. 1;

FIG. 7 is a schematic view of the screw fixing hole of FIG. 1;

description of reference numerals:

i, an anode barrel; II, a cathode barrel;

1-a feed inlet; 2-anode connecting buckle; 21-an anode connection terminal; 3-anode barrel outer shell; 4-an anode electrode; 41-a hollow disc; 42-hollow cylinder; 5-electrolytic compaction column; 6-a cathode electrode; 61-cathode snap connection; 612-cathode connection terminals; 62-cathode mesh; 7-cathode can shell; 8-barrel body supporting legs; 9-a discharge hole; 10-a compound roller; 11-multilayer partition; 111-anode barrel mounting plate; 112-waterproof gasket; 113-filter cloth; 114-aperture support disk; 115-cathode barrel mounting plate; 116-fastening bolts; 12-an outer support frame; 13-a screw rod connecting flange; 14-lifting screw rod; 15-lead screw fixing support 15; 151-keyway; 16-a screw rod fixing hole; 17-electrolytic reaction zone.

Detailed Description

The technical scheme of the invention is explained by specific embodiments in the following with reference to the attached drawings. It is to be understood that one or more of the steps referred to in the present application do not exclude the presence of other methods or steps before or after the combination of steps, or that other methods or steps may be intervening between those steps specifically referred to. It should also be understood that these examples are for illustration only and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the steps, and is not intended to limit the scope of the invention, the relative relationship between the steps may be changed or adjusted without substantial technical change.

The raw materials and apparatuses used in the examples are not particularly limited in their sources, and may be purchased from the market or prepared according to a conventional method well known to those skilled in the art.

Example 1: continuous electrochemical stripping device

As shown in fig. 1, a continuous electrochemical stripping device comprises an anode barrel I and a cathode barrel II, wherein an anode electrode 4 is arranged in the anode barrel I, a cathode electrode 6 is arranged in the cathode barrel II, the anode barrel I and the cathode barrel II are in an up-down structure and are separated by a multilayer partition 11, so that the anode electrode 4 and the cathode electrode 6 are prevented from being in direct contact; an electrolytic reaction region 17 is formed between the anode 4 and the multilayer partition 11, and the raw material is electrolyzed in the reaction region.

Be equipped with electrolysis compaction post 5 in the above-mentioned positive pole bucket I, above-mentioned electrolysis compaction post 5 sets up the back at above-mentioned anode electrode 4 reaction surface, and electrolysis compaction post 5 is used for compressing tightly anode electrode 4, and then compresses tightly the raw materials of electrolysis reaction zone 17 to guarantee the abundant, comprehensive contact of electrolytic raw materials and anode electrode 4, promote the reaction and go on. The electrolytic compaction column 5 is made of polytetrafluoroethylene.

The electrolytic reaction area 17 is communicated with the feed inlet 1, so that continuous feeding is facilitated in the reaction process. The electrolytic reaction zone 17 is communicated with the feeding hole 1 through the anode electrode 4, and is realized through the following modes: the anode electrode 4 is divided into two parts (as shown in fig. 2), one part is a hollow disc 41, one surface of the hollow disc 41 is fixed with the electrolytic compaction column 5, the other surface is a reaction surface for participating in electrolytic reaction, the other part is a hollow cylinder 42 for filling reactants such as raw materials and electrolyte, the hollow disc 41 and the hollow cylinder 42 are made of inert metal materials, the bottom of the hollow cylinder 42 is welded with the hollow part of the hollow disc 41, the center of the electrolytic compaction column 5 is provided with a through hole matched with the hollow cylinder 42, and the hollow cylinder 42 penetrates through the electrolytic compaction column 5 to be clamped with the feed port 1, so that the electrolytic reaction area 17 is communicated with the feed port 1. The hollow cylinder 42 is connected with the feed inlet 1 in a clamping manner, so that the replacement and maintenance of the electrode are facilitated. Wherein, the feed inlet 1 is a flexible corrugated steel pipe which can adapt to the up-and-down movement of the barrel body.

As shown in fig. 2, the anode electrode 4 is provided with an anode connecting buckle 2 at the part exposed out of the electrolytic compaction column 5, and the anode connecting buckle 2 is provided with an anode connecting terminal 21 for connecting an anode power supply. In addition, the separation design also facilitates replacement and maintenance of the electrolysis.

As shown in fig. 3, the multi-layer partition 11 includes an anode tub installation plate 111 and a cathode tub installation plate 115, and a filter cloth 113 and a porous support plate 114 are disposed between the anode tub installation plate 111 and the cathode tub installation plate 115.

The anode barrel mounting disk 111 and the cathode barrel mounting disk 115 are used for fixing the anode barrel casing 3 and the cathode barrel casing 7, respectively; the porous support disc 114 plays a role in supporting raw materials, the filter cloth 113 is arranged on the porous support disc 114, the filter cloth 113 is an acid-base-resistant flexible nylon filter cloth, the mesh number of the filter cloth 113 is required to be 50 meshes smaller than that of the raw materials (such as graphite powder and flake graphite), so that the raw materials can be well prevented from leaking to a lower barrel before the raw materials are unreacted, and meanwhile, the size-reduced product can smoothly pass through after the reaction, so that the functions of screening the materials before and after the reaction can be realized, and the filter cloth can be detached and replaced; the thickness of the porous supporting disk 114 is 15mm, the deformation of the porous supporting disk 114 is not more than 1% under the pressure within the range of 30 kilograms, a plurality of small holes are formed in the porous supporting disk 114, the diameter of each hole is 1.5cm, and the porous supporting disk is made of a PVC plate and can be detached and replaced; in order to prevent the electrolyte from leaking, a waterproof gasket 112 is further installed between the anode barrel mounting disk 111 and the cathode barrel mounting disk 115; the anode barrel installation disc 111, the waterproof gasket 112, the filter cloth 113, the porous support disc 114 and the cathode barrel installation disc 115 are sequentially arranged from top to bottom and are fixed through a plurality of fastening bolts 116.

As shown in fig. 4, the cathode electrode 6 is fixed on the inner wall of the cathode barrel casing 7 by a cathode snap-fit connector 61, a cathode terminal 612 is arranged on the cathode snap-fit connector 61, and the cathode terminal 612 is arranged on the outer wall of the cathode barrel ii through the cathode barrel casing 7; the cathode electrode 6 is a disc structure, and all discs of the cathode electrode 6 are effective reaction surfaces; the cathode electrode 6 is provided with a plurality of cathode meshes 62, and the aperture diameter of the cathode meshes 62 is about 1cm, so that products after the electrolysis at the upper part is finished are prevented from falling and accumulating. In order to enhance the stability of the cathode electrode 6, a support frame (not shown) may be installed on the cathode electrode 6, and the support frame is made of an acid-resistant, alkali-resistant, and non-conductive material.

The bottom of the cathode barrel II is provided with a discharge hole 9; the products after electrolysis are discharged from the discharge port 9 along with the electrolyte under the action of external driving force. In the external circulation system, only electrolyte is collected and circulated, and the electrolyzed material can be filtered and extracted and does not enter the electrolysis circulation.

Example 2: continuous electrochemical stripping device

In this embodiment, devices such as a lifting device, a support device, and a moving device are provided in addition to embodiment 1, and the other parts are the same as embodiment 1.

A continuous electrochemical stripping device comprises the continuous electrochemical stripping device in embodiment 1, and the device comprises a lifting device, wherein the lifting device comprises a screw rod connecting flange 13, one end of the screw rod connecting flange 13 is fixed on the electrolytic compaction column 5, the other end of the screw rod connecting flange 13 is connected with a lifting screw rod 14, the lifting screw rod 14 is used for adjusting the distance between the upper part and the lower part of the electrolytic compaction column 5, adjusting the compaction pressure in the electrolytic process and further regulating and controlling the electrolytic process; the lifting screw rod 14 is fixed on the outer support frame 12 through a screw rod fixing support 15, a support side opening 121 is arranged on the side surface of the outer support frame 12 to facilitate the installation of a fixing bolt (as shown in fig. 5), and a composite pulley 10 is arranged at the bottom of the outer support frame 12; the screw rod fixing bracket 15 is fixed on the outer support frame 12 through a screw rod fixing hole 16, wherein a plurality of key slots 151 (shown in fig. 6) are arranged on the screw rod fixing bracket 15 and used for adjusting the horizontal position of the lifting screw rod 14; the lead screw fixing hole 16 includes a plurality of holes (as shown in fig. 7) in an array so as to adjust the height at which the lead screw fixing bracket 15 is installed.

Above-mentioned cathode drum below is equipped with staving supporting leg 8 for support whole staving, staving supporting leg 8 bottom is equipped with compound gyro wheel 10.

Example 3: working method of apparatus for continuous electrochemical stripping in example 1

The feeding port 1 and the discharging port 9 of the continuous electrochemical stripping device in embodiment 1 are respectively connected with two ends of a circulating pump, under the action of a driving force of the circulating pump, an electrolyte containing a raw material enters an electrolytic reaction area 17 through the feeding port 1 via a hollow cylinder 42 of an anode electrode 4, the electrolyte passes through a multilayer partition 11, the electrolytic raw material is deposited in the electrolytic reaction area 17, the anode electrode 4 is pressed by an electrolytic compaction column 5, and further the raw material of the electrolytic reaction area 17 is pressed, the pressing pressure is 25 kg, so as to ensure the sufficient and comprehensive contact between the electrolytic raw material and the anode electrode 4, promote the electrolytic reaction, and obtain a product after electrolysis, which passes through the layered partition 11 along with the flow of the electrolyte to enter a cathode barrel ii, and then the product is collected by filtration to obtain a target product.

Example 4: working method of apparatus for continuous electrochemical stripping in example 2

The working method of the device main body is the same as that of the embodiment 3, except that when the electrolytic compaction column 5 is compacted, the lifting screw rod 14 is driven by the motor to ascend or descend to realize the decompression or compaction of the electrolytic compaction column 5, and/or the installation position of the screw rod fixing hole 16 is adjusted by adjusting the screw rod fixing support 15; the horizontal position of the device body can be adjusted by a key groove on the screw rod fixing bracket 15.

Example 5: continuous electrochemical stripping method

A method of continuous electrochemical stripping comprising: the electrolysis of the starting materials was carried out in a compact and circulating electrolyte, the method being carried out on the basis of the continuous electrochemical stripping apparatus described in example 2.

Example 6: device for preparing graphene precursors in batches

An apparatus for batch preparation of a graphene precursor was the apparatus for continuous electrochemical exfoliation described in example 2 above.

Example 7: method for preparing graphene precursors in batches

A method for preparing a graphene precursor in batch is implemented on the basis of the device in embodiment 6, and specifically comprises the following steps:

preparing a mixed electrolysis raw material: graphite powder is used as a raw material, 2M sodium sulfate is used as an electrolyte, and the electrolyte is prepared from the following raw materials in parts by weight: mixing the electrolyte solution =1 in a ratio of 50 to obtain an electrolytic slurry;

electrolytic voltage: 500V;

and (3) electrolysis time: 50h;

electrolytic compaction column compaction pressure: 30 kilograms;

the size of the graphite powder raw material after the electrolysis is finished can be reduced, and after the size of the graphite powder raw material is smaller than the pore diameter of the filter cloth, a product can pass through the multilayer partition along with the flowing of the electrolyte and then fall into the cathode barrel body below. And then filtering and collecting to obtain the graphene precursor.

The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. The utility model provides a device that continuous electrochemistry was peeled off, includes positive pole bucket (I) and negative pole bucket (II), be equipped with anode electrode (4) in positive pole bucket (I), be equipped with cathode electrode (6) in negative pole bucket (II), its characterized in that, positive pole bucket (I) with negative pole bucket (II) separate through multilayer wall (11), anode electrode (4) with form electrolysis reaction zone (17) between multilayer wall (11), be equipped with electrolysis compaction post (5) in positive pole bucket (I).

2. The device according to claim 1, characterized in that the electrolytic reaction zone (17) communicates with the feed inlet (1).

3. The device according to claim 1 or 2, characterized in that the electrolytic compaction column (5) is arranged on the back of the reaction side of the anode electrode (4).

4. The apparatus according to claim 1 or 2, wherein a lifting device is connected to the electrolytic compaction column (5); preferably, the lifting device comprises a screw rod connecting flange (13), one end of the screw rod connecting flange (13) is fixed on the electrolytic compaction column (5), the other end of the screw rod connecting flange is connected with a lifting screw rod (14), and the lifting screw rod (14) is fixed on the outer support frame (12) through a screw rod fixing support (15); preferably, the screw rod fixing bracket (15) is fixed on the outer support frame (12) through a screw rod fixing hole (16); more preferably, the screw fixation hole (16) comprises a plurality of array holes.

5. The apparatus according to claim 1, wherein the multi-layer partition (11) comprises an anode bucket mounting disk (111) and a cathode bucket mounting disk (115), and a filter cloth (113) and/or a porous support disk (114) is/are arranged between the anode bucket mounting disk (111) and the cathode bucket mounting disk (115).

6. The device according to claim 1, characterized in that the cathode electrode (6) is fixed on the inner wall of the cathode barrel (II) through a cathode snap connector (61), a cathode connecting terminal (612) is arranged on the cathode snap connector (61), and the cathode connecting terminal (612) is arranged on the outer wall of the cathode barrel (II); preferably, a plurality of cathode meshes (62) are arranged on the cathode electrode (6);

and/or a discharge hole (9) is formed in the bottom of the cathode barrel (II);

and/or bucket body supporting legs (8) are arranged below the cathode bucket (II).

7. A method of continuous electrochemical stripping, the method comprising: electrolyzing an electrolysis raw material in a compressed state and in a circularly flowing electrolyte; preferably, the method is carried out on the basis of the device according to any one of claims 1 to 6.

8. Use of the apparatus for continuous electrochemical exfoliation according to any of claims 1-6 in the mass production of graphene precursors.

9. Use of the method for continuous electrochemical exfoliation according to claim 7 for mass production of graphene precursors.

10. A method for producing a graphene precursor, characterized by being produced by the apparatus according to any one of claims 1 to 6 or the method according to claim 7; preferably, the following components:

the pressing pressure is 1-30 kg;

and/or the voltage of the electrolysis is 10-1000V;

and/or the electrolysis time is 1-100 h;

and/or the electrolytic electrolyte is a strong acid salt solution; preferably, the strong acid salt is selected from one or more of sulfate, nitrate, perchlorate and phosphate; more preferably, the concentration of the strong acid salt solution is 0.1 to 5M;

and/or, the graphite raw material: the ratio of the strong acid salt solution = 1; preferably, the graphite raw material is crystalline flake graphite and/or graphite powder.

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