CN115403036B - Device, method and application for continuous electrochemical stripping - Google Patents
Device, method and application for continuous electrochemical stripping Download PDFInfo
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- CN115403036B CN115403036B CN202211045669.3A CN202211045669A CN115403036B CN 115403036 B CN115403036 B CN 115403036B CN 202211045669 A CN202211045669 A CN 202211045669A CN 115403036 B CN115403036 B CN 115403036B
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Abstract
The invention relates to a device, a method and application of continuous electrochemical stripping, and belongs to the technical field of new materials. The continuous electrochemical stripping device of the present invention comprises: the electrolytic compression device 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 through a plurality of layers of partitions, and an electrolytic compression column is arranged in the anode barrel. According to the invention, the anode barrel and the cathode barrel are separated through the multi-layer partition, the anode electrolytic reaction zone is communicated with the feed inlet, the bottom of the cathode barrel is correspondingly provided with the discharge outlet, the electrolyte containing raw materials enters the electrolytic reaction zone from the feed inlet under the action of external driving force, the electrolyzed product passes through the multi-layer partition and enters the cathode barrel under the driving of the electrolyte, and is discharged and collected from the discharge outlet, and the external driving force drives the electrolyte containing 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
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a continuous electrochemical stripping device, a continuous electrochemical stripping method and application.
Background
The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of material science, micro-nano processing, energy sources, biomedicine, drug delivery and the like, and is considered as a revolutionary material in the future. The electrochemical method directly prepares the graphene sheets with high lattice quality, namely high-quality graphene, by triggering the electrochemical reaction between graphite layers to generate gas to strip the graphene sheets.
The electrochemical stripping method is the most promising realization of high quality at present because the method has the characteristics of simple process, clean and pollution-free process, low cost and the like, and the stripping efficiency can reach about 85 percent at the highest, and is obviously superior to the liquid phase stripping methodAnd (3) preparing the graphene in a large-scale controllable manner. In 2011, researchers such as Su (Acs Nano,2011,2332-2339 (5)) successfully prepared thin graphene by electrolyzing highly oriented pyrolytic graphite and ordinary graphite in dilute sulfuric acid electrolyte (0.5 m, ph=0.3); yang (Angewandte Chemie-International Edition,2017,6669-6675 (56)) et al uses square wave alternating voltages for electrolysis (+ -10V, 0.1 Hz) to obtain high yields of graphene preparation (20 g h) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the Cao (Journal of the American Chemical Society,2017,17446-17456 (139)) et al obtained a few-layered graphene oxide powder by a two-step electrochemical stripping process. The methods provide a plurality of original methods in the aspects of regulating and controlling the electrochemical stripping process and improving the yield of the graphene, but 15-25% of graphite flakes still exist in the product to be removed, which is still unfavorable for large-scale preparation.
If conventional graphene oxide is used, the Hummers method is generally adopted, and the graphene oxide is peeled off by means of pollution chemical raw materials such as concentrated sulfuric acid, potassium permanganate, sodium nitrate, hydrogen peroxide and the like, so that a large amount of pollutants are generated. Compared with the method of preparing graphene oxide by Hummers, the method of preparing graphene by electrochemical method is clean and pollution-free, but the electrochemical stripping method of preparing graphene has the difficulty of continuous production, continuous production requires continuous material feeding, and the current electrochemical method of preparing graphene still lacks equipment and method for batch production.
Most of electrochemical stripping graphene is currently made of self-supporting materials such as graphite paper and the like as electrodes due to the uniqueness of the electrochemical stripping graphene process, but the cost of the graphite paper is high, and the productivity of a graphene process route obtained based on the graphite paper electrolysis process is relatively low due to the characteristics of the graphite paper. Therefore, innovation is needed in the aspects of electrochemical equipment and process, and a simple and efficient device and strategy for electrochemical stripping of graphene are developed so as to improve the stripping efficiency of graphite in the electrochemical stripping process. In addition, the electrolytic method has a plurality of graphene stripping procedures, and the electrolytic procedure is only the first step, so that if the graphene precursor can be efficiently prepared, the mass production of graphene can be realized.
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 already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention provides a continuous electrochemical stripping device, a continuous electrochemical stripping method and application, and aims to solve the technical problems that in the prior art, the electrochemical stripping technology is long in time consumption and low in productivity and is difficult to continuously produce.
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 plurality of layers of partitions, 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 directly contacted.
In some embodiments, an electrolytic reaction zone is formed between the anode electrode and the multi-layer partition, the electrolytic reaction zone being in communication with the feed inlet. The electrolytic reaction zone 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 used for participating in electrolytic reaction, the other part is a hollow cylinder and used for filling reactants such as raw materials, electrolyte and the like, 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 arranged at the center of the electrolytic compaction column, and the hollow cylinder passes through the electrolytic compaction column and is clamped with the feed inlet, so that the communication between the electrolytic reaction area and the feed inlet is realized. 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 suitable for the up-and-down movement of the electrolytic compaction column communicated with the anode electrode, the material of the feed inlet of the device comprises, but is not limited to, a stainless steel corrugated pipe, a polytetrafluoroethylene corrugated pipe, a PU corrugated pipe, a PVC corrugated pipe and the like.
Further preferably, an anode connecting buckle is arranged on the anode electrode, and an anode wiring terminal is arranged on the anode connecting buckle and used for connecting an anode power supply. In addition, the separation design is also convenient for the replacement and maintenance of the electrolysis.
In some embodiments, the electrolytic compaction column is disposed on a back side of the anode electrode reaction surface. The electrolytic compaction column is fixedly arranged with the anode electrode and is used for compacting the anode electrode, so as to compact the raw materials of the electrolytic reaction zone, ensure the full and comprehensive contact between the electrolyzed raw materials and the electrode and promote the reaction. The electrolytic compaction column is made of solid materials with acid resistance and alkali resistance, such as polytetrafluoroethylene, PVC plates and the like.
In some embodiments, the electrolytic compaction column is connected with a lifting device; 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 lifting screw rod is used for adjusting the vertical distance of the electrolytic compaction column, the compaction pressure in the electrolytic process is adjusted, and the electrolytic process is further adjusted 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 so as to be convenient for installing a fixing bolt, and a composite pulley is arranged at the bottom of the outer support frame; preferably, the screw rod fixing bracket is fixed on the outer support frame through a screw rod fixing hole, wherein a plurality of key grooves are formed in the screw rod fixing bracket and used 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 mounting height of the screw fixing bracket.
In some embodiments, the multi-layer partition includes an anode bucket mounting plate and a cathode bucket mounting plate, with a filter cloth and/or a porous support plate disposed therebetween.
The anode barrel mounting plate and the cathode barrel mounting plate are respectively used for fixing the shell of the anode barrel and the shell of the cathode barrel; the porous supporting disc plays a role in supporting raw materials, and preferably, the filter cloth is arranged on the porous supporting disc, wherein the filter cloth is acid-base resistant flexible nylon filter cloth or fiber filter cloth, the mesh number of the filter cloth is about 50 meshes smaller than that of the raw materials (such as graphite powder and flake graphite), so that the raw materials can be prevented from leaking to a barrel below before unreacted, and products with reduced sizes can be ensured to smoothly pass through after reaction, so that the effect of screening the materials before and after the reaction can be realized, and the filter cloth can be detached and replaced; further preferably, the thickness of the porous supporting disc is between 10 and 20mm, the deformation is not more than 1% under the pressure within the range of 10 kg to 30 kg, a plurality of small holes are formed in the disc, the diameter of the hole is not less than 1cm and not more than 2cm, and the porous supporting disc is made of PVC plates, pressure-resistant ceramic plates and the like and can be detached and replaced; when the filter cloth is not arranged, the porous supporting disc not only ensures that raw materials can be better prevented from leaking into the lower barrel before unreacted materials, but also ensures that products after electrolysis smoothly pass through and fall into the lower cathode barrel; in order to prevent electrolyte leakage, a waterproof gasket is also arranged between the anode barrel mounting plate and the cathode barrel mounting plate.
In some embodiments, the cathode electrode is fixed on the inner wall of the cathode barrel through a cathode buckle connector, a cathode connecting terminal is arranged on the cathode buckle connector, and the cathode connecting terminal is arranged on the outer wall of the cathode barrel; preferably, the cathode electrode has a disc structure, and the cathode electrode discs are all effective reaction surfaces; the cathode electrode is provided with a plurality of cathode meshes, and further preferably, the aperture diameter of the cathode meshes is about 1cm, so that products after the electrolysis above are prevented from falling and accumulating.
In some embodiments, a discharge hole is formed at the bottom of the cathode barrel; the product after the electrolysis is discharged from the discharge hole along with the electrolyte under the action of external driving force. In the external circulation system, only the electrolyte is collected and circulated, and the electrolyzed product can be filtered and extracted and does not enter the electrolysis circulation.
In some embodiments, a barrel supporting leg is arranged below the cathode barrel and is used for supporting the whole barrel, and preferably, a composite roller is arranged at the bottom of the barrel supporting leg.
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 the electrolyte which circularly flows; preferably, the above method is carried out based on the above device.
The third aspect of the invention provides an application of a continuous electrochemical stripping device in preparing graphene precursors in batches.
The fourth aspect of the present invention provides a method for preparing a graphene precursor, which is prepared by the above device or the above method;
in some embodiments, the compacting pressure is 1 to 30 kg;
and/or the voltage of the electrolysis is 10-1000V;
and/or the electrolysis time is 1-100 h;
and/or the electrolyte for electrolysis 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=1:10 to 1:100; preferably, the graphite raw material is flake graphite and/or graphite powder.
Compared with the prior art, the invention has the following technical effects:
(1) According to the invention, the anode barrel and the cathode barrel are separated through the multi-layer partition, the anode electrolytic reaction zone is communicated with the feed inlet, the bottom of the cathode barrel is correspondingly provided with the discharge outlet, the electrolyte containing raw materials enters the electrolytic reaction zone from the feed inlet under the action of external driving force, the electrolyzed product passes through the multi-layer partition and enters the cathode barrel under the driving of the electrolyte, and is discharged and collected from the discharge outlet, and the external driving force drives the electrolyte containing 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 electrochemical stripping is difficult to be continuous, and greatly improves the productivity of electrochemical stripping.
(3) The continuous electrochemical stripping device and the continuous electrochemical stripping method are simple, have universality, are particularly suitable for batch preparation of graphene precursors, improve the productivity of the graphene precursors, and are beneficial to realizing batch production of graphene.
(4) The graphene precursor prepared in batches uses cheap graphite flakes and graphite powder as raw materials, replaces the traditional graphite paper raw materials, 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 method can be used as a precursor for preparing graphene by other methods, including but not limited to a physical method, a liquid phase stripping method, a redox method and other graphene preparation processes.
Drawings
FIG. 1 is a schematic diagram of the apparatus in embodiment 1 and embodiment 2 of the present invention;
FIG. 2 is a schematic view of the structure of the anode electrode of FIG. 1;
FIG. 3 is a schematic cross-sectional view of the device of FIG. 1 rotated 90 degrees clockwise;
FIG. 4 is a schematic view of the cathode electrode related structure of FIG. 1;
FIG. 5 is a schematic view of the outer support 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 structure of the screw fixing hole in FIG. 1;
reference numerals illustrate:
i-anode barrels; II, a cathode barrel;
1-a feed inlet; 2-anode connecting buckle; 21-an anode connection terminal; 3-anode barrel housing; 4-an anode electrode; 41-hollow discs; 42-hollow cylinder; 5-electrolytic compaction column; 6-a cathode electrode; 61-cathode snap-fit connection; 612-cathode connection terminal; 62-cathode mesh; 7-cathode barrel housing; 8-barrel support legs; 9, a discharge hole; 10-a composite roller; 11-multi-layer partition; 111-anode barrel mounting plate; 112-waterproof gasket; 113-filtering cloth; 114-hole support plate; 115-cathode tub mounting plate; 116-fastening bolts; 12-an outer support frame; 13-a screw rod connecting flange; 14-lifting screw rods; 15-a screw rod fixing bracket 15; 151-keyway; 16-screw rod fixing holes; 17-electrolytic reaction zone.
Detailed Description
The technical scheme of the invention is described below through specific embodiments with reference to the accompanying drawings. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
Example 1: continuous electrochemical stripping device
As shown in figure 1, the device for continuous electrochemical stripping 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 multi-layer partition 11, and the anode electrode 4 and the cathode electrode 6 are prevented from being in direct contact; an electrolytic reaction zone 17 is formed between the anode electrode 4 and the multilayer partition 11, and the raw material is electrolyzed in the reaction zone.
An electrolytic compaction column 5 is arranged in the anode barrel I, the electrolytic compaction column 5 is arranged on the back surface of the reaction surface of the anode electrode 4, the electrolytic compaction column 5 is used for compacting the anode electrode 4, and then compacting the raw materials of the electrolytic reaction zone 17, so that the full and comprehensive contact between the electrolyzed raw materials and the anode electrode 4 is ensured, and the reaction is promoted. The electrolytic compaction column 5 is made of polytetrafluoroethylene.
The electrolytic reaction zone 17 is communicated with the feed inlet 1, so that continuous feeding in the reaction process is facilitated. The electrolytic reaction zone 17 is in communication with the feed inlet 1 via the anode electrode 4, in particular by: 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 and is used for participating in electrolytic reaction, the other part is a hollow cylinder 42 and is used for filling reactants such as raw materials, electrolyte and the like, 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, a through hole matched with the hollow cylinder 42 is arranged in the center of the electrolytic compaction column 5, and the hollow cylinder 42 passes through the electrolytic compaction column 5 and is clamped with the feed inlet 1, so that the communication between the electrolytic reaction area 17 and the feed inlet 1 is realized. The hollow cylinder 42 is connected with the feeding hole 1 in a clamping way, so that the replacement and maintenance of the electrode are facilitated. Wherein, the feed inlet 1 is a flexible stainless steel corrugated pipe which can adapt to the up-and-down movement of the barrel body.
As shown in fig. 2, the portion of the anode electrode 4 exposed out of the electrolytic compaction column 5 is provided with an anode connecting buckle 2, and the anode connecting buckle 2 is provided with an anode wiring terminal 21 for connecting an anode power supply. In addition, the separation design is also convenient for the replacement and maintenance of the electrolysis.
As shown in fig. 3, the multi-layered partition 11 includes an anode tub mounting plate 111 and a cathode tub mounting plate 115, and a filter cloth 113 and a porous support plate 114 are provided between the anode tub mounting plate 111 and the cathode tub mounting plate 115.
The anode barrel housing 3 and the cathode barrel housing 7 are respectively fixed by an anode barrel mounting plate 111 and a cathode barrel mounting plate 115; the porous support plate 114 plays a role in supporting raw materials, the filter cloth 113 is arranged on the porous support plate 114, wherein the filter cloth 113 is acid and alkali resistant flexible nylon filter cloth, the mesh number is required to be smaller than 50 meshes of the raw materials (such as graphite powder and flake graphite) so as to ensure that the raw materials can be better prevented from leaking to a barrel below before unreacted and the products with reduced size can be ensured to pass smoothly after reaction, so that the effect of screening the materials before and after reaction can be realized, and the materials can be detached and replaced; the thickness of the porous support plate 114 is 15mm, the deformation is not more than 1% under the pressure within the range of 30 kg, a plurality of small holes are formed in the porous support plate 114, the diameter of the holes is 1.5cm, and the porous support plate is made of PVC plates and can be detached and replaced; in order to prevent leakage of electrolyte, a waterproof gasket 112 is further installed between the anode tub mounting plate 111 and the cathode tub mounting plate 115; the anode barrel installation plate 111, the waterproof gasket 112, the filter cloth 113, the porous support plate 114 and the cathode barrel installation plate 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 to the inner wall of the cathode barrel housing 7 by a cathode snap connector 61, a cathode connection terminal 612 is provided on the cathode snap connector 61, and the cathode connection terminal 612 is provided on the outer wall of the cathode barrel ii through the cathode barrel housing 7; the cathode electrode 6 is in 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, the diameter of the aperture of the cathode meshes 62 is about 1cm, and products after the electrolysis above are prevented from falling and accumulating. In order to enhance the stability of the cathode electrode 6, a supporting frame (not shown) may be mounted on the cathode electrode 6, and the supporting frame is made of an acid-resistant, alkali-resistant or non-conductive material.
A discharge hole 9 is arranged at the bottom of the cathode barrel II; the product after electrolysis is discharged from the discharge hole 9 along with electrolyte under the action of external driving force. In the external circulation system, only electrolyte is collected and circulated, and the electrolyzed materials are filtered and extracted and do not enter the electrolysis circulation.
Example 2: continuous electrochemical stripping device
This embodiment is provided with a lifting device, a support, a movement device, and the like in addition to embodiment 1, and the other is the same as embodiment 1.
The continuous electrochemical stripping device comprises the continuous electrochemical stripping device in the embodiment 1, wherein the device comprises a lifting device, 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, 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, and the compacting pressure in the electrolytic process is adjusted so as to adjust 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 so as to be convenient for installing 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 fixing bracket 15 is fixed on the outer support frame 12 through screw fixing holes 16, wherein a plurality of key grooves 151 (as shown in fig. 6) are formed in the screw fixing bracket 15 for adjusting the horizontal position of the lifting screw 14; the screw fixing holes 16 include a plurality of array holes (as shown in fig. 7) so as to adjust the height of the screw fixing bracket 15.
The cathode barrel is provided with a barrel supporting leg 8 below, which is used for supporting the whole barrel, and a composite roller 10 is arranged at the bottom of the barrel supporting leg 8.
Example 3: method of operating the continuous electrochemical stripping device of example 1
The feed inlet 1 and the discharge outlet 9 of the continuous electrochemical stripping device described in embodiment 1 are respectively connected with two ends of a circulating pump, under the action of the driving force of the circulating pump, the electrolyte containing raw materials enters the electrolytic reaction zone 17 through the hollow cylinder 42 of the anode electrode 4 through the feed inlet 1, the electrolyte passes through the multi-layer partition 11, the electrolytic raw materials are deposited in the electrolytic reaction zone 17, the anode electrode 4 is compressed by the electrolytic compaction column 5, the raw materials in the electrolytic reaction zone 17 are compressed, the compression pressure is 25 kg, so that the full and comprehensive contact between the electrolytic raw materials and the anode electrode 4 is ensured, the electrolytic reaction is promoted, the product obtained after the electrolysis passes through the layered partition 11 to enter the cathode barrel II along with the flow of the electrolyte, and then the product is filtered and collected, so as to obtain the target product.
Example 4: method of operating the continuous electrochemical stripping device of 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 a motor to lift or lower so as to realize the decompression or compaction of the electrolytic compaction column 5, and/or the installation position of the screw rod fixing support 15 in the screw rod fixing hole 16 is adjusted; the horizontal position of the device body can be adjusted through a key groove on the screw rod fixing support 15.
Example 5: continuous electrochemical stripping method
A method of continuous electrochemical stripping comprising: the electrolysis raw material was electrolyzed in a compressed state and in a circulating electrolyte, and the method was carried out based on the continuous electrochemical stripping apparatus described in example 2.
Example 6: device for preparing graphene precursors in batches
The apparatus for batch preparation of graphene precursors was the apparatus for continuous electrochemical stripping described in example 2.
Example 7: method for preparing graphene precursors in batches
A method for preparing graphene precursors in batches, which is implemented based on the apparatus described in embodiment 6, specifically comprises:
preparing mixed electrolysis raw materials: graphite powder is used as a raw material, 2M sodium sulfate is used as electrolyte, and the raw materials of the graphite powder are as follows: mixing electrolyte=1:50 to obtain electrolytic slurry;
electrolytic voltage: 500V;
electrolysis time: 50h;
electrolytic compaction column compaction pressure: 30 kg;
when the size of the graphite powder raw material after the electrolysis is completed is reduced, and when the size is smaller than the pore diameter of the filter cloth, products can pass through the multi-layer partition along with the flow of the electrolyte and then fall into the barrel body of the cathode barrel below. And then filtering and collecting to obtain the graphene precursor.
The foregoing descriptions of specific exemplary embodiments of the present invention are 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 the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various 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 device for continuous electrochemical stripping comprises an anode barrel (I) and a cathode barrel (II), wherein an anode electrode (4) is arranged in the anode barrel (I), and a cathode electrode (6) is arranged in the cathode barrel (II), and the device is characterized in that the anode barrel (I) and the cathode barrel (II) are in an up-down structure, the anode barrel (I) and the cathode barrel (II) are separated by a multi-layer partition (11), the anode electrode (4) is divided into two parts, one part is a hollow disc (41), and the other part is a hollow cylinder (42); an electrolytic reaction zone (17) is formed between the anode electrode (4) and the multi-layer partition (11), and the electrolytic reaction zone (17) is communicated with the feed inlet (1);
the multi-layer partition (11) comprises an anode barrel mounting plate (111) and a cathode barrel mounting plate (115), wherein filter cloth (113) and a porous supporting plate (114) are arranged between the anode barrel mounting plate (111) and the cathode barrel mounting plate (115), and the mesh number of the filter cloth is required to be 50 meshes smaller than that of the raw materials;
an electrolytic compaction column (5) is arranged in the anode barrel (I);
a discharge hole (9) is formed in the bottom of the cathode barrel (II);
the electrolytic compaction column (5) is arranged on the back surface of the reaction surface of the anode electrode (4);
the electrolytic compaction column (5) is connected with a lifting device.
2. The device according to claim 1, characterized in that the lifting device comprises a screw connecting flange (13), one end of the screw connecting flange (13) is fixed on the electrolytic compaction column (5), the other end is connected with a lifting screw (14), and the lifting screw (14) is fixed on the outer support frame (12) through a screw fixing bracket (15).
3. The device according to claim 2, characterized in that the screw fixation bracket (15) is fixed to the outer support frame (12) through screw fixation holes (16); the screw rod fixing holes (16) comprise a plurality of array holes.
4. The device according to claim 1, characterized in that the cathode electrode (6) is fixed on the inner wall of the cathode barrel (ii) by a cathode snap connection (61), a cathode connection terminal (612) is provided on the cathode snap connection (61), and the cathode connection terminal (612) is provided on the outer wall of the cathode barrel (ii).
5. The device according to claim 1, characterized in that the cathode electrode (6) is provided with a number of cathode meshes (62);
and/or a barrel body supporting leg (8) is arranged below the cathode barrel (II).
6. A method of continuous electrochemical stripping, the method comprising: electrolyzing the electrolysis raw material in a compressed state and in the electrolyte which circularly flows; the method is carried out on the basis of the device according to any one of claims 1 to 5.
7. Use of a continuous electrochemical stripping apparatus according to any one of claims 1-5 for the batch preparation of graphene precursors.
8. Use of the method of continuous electrochemical stripping according to claim 6 for the batch preparation of graphene precursors.
9. A method for preparing a graphene precursor, characterized in that it is prepared by the apparatus according to any one of claims 1 to 5 or the method according to claim 6.
10. The method for preparing a graphene precursor according to claim 9, wherein,
the compacting 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 electrolyzed electrolyte is a strong acid salt solution; the strong acid salt is selected from one or more of sulfate, nitrate, perchlorate and phosphate; the concentration of the strong acid salt solution is 0.1-5M;
and/or, graphite starting materials: strong acid salt solution=1:10 to 1:100; the graphite raw material is flake graphite and/or graphite powder.
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| CN202211045669.3A CN115403036B (en) | 2022-08-30 | 2022-08-30 | Device, method and application for continuous electrochemical stripping |
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