CN114956059B - Temperature control and convection homogenizing device and method for preparing graphene by electrochemical stripping of graphite - Google Patents
Temperature control and convection homogenizing device and method for preparing graphene by electrochemical stripping of graphite Download PDFInfo
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- CN114956059B CN114956059B CN202210789145.9A CN202210789145A CN114956059B CN 114956059 B CN114956059 B CN 114956059B CN 202210789145 A CN202210789145 A CN 202210789145A CN 114956059 B CN114956059 B CN 114956059B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 43
- 239000010439 graphite Substances 0.000 title claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000007921 spray Substances 0.000 claims abstract description 85
- 239000003792 electrolyte Substances 0.000 claims abstract description 79
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000000265 homogenisation Methods 0.000 claims description 33
- 239000012530 fluid Substances 0.000 claims description 29
- 239000000523 sample Substances 0.000 claims description 28
- 230000008859 change Effects 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 9
- 238000005452 bending Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000000429 assembly Methods 0.000 claims description 6
- 230000000712 assembly Effects 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 3
- 230000002262 irrigation Effects 0.000 claims description 3
- 238000003973 irrigation Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000012544 monitoring process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/135—Carbon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
- C25B15/023—Measuring, analysing or testing during electrolytic production
- C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
- C25B15/027—Temperature
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/67—Heating or cooling means
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention belongs to the technical field of graphene preparation by electrochemical stripping, and provides a temperature control and convection homogenizing device and method for preparing graphene by electrochemical stripping graphite, wherein the device comprises an electrolytic tank, a graphite electrode for stripping, a first jet flow assembly, a second jet flow assembly, a first output pipe, a circulating pump and a pressurizing pump; the first jet assembly comprises a first jet main pipe and a first jet pipe, and the second jet assembly comprises a second jet main pipe, a second jet branch pipe and a second jet pipe nozzle; one end port of the first output pipe is positioned at the bottom in the electrolytic tank, the other end of the first output pipe is connected with a liquid inlet of the circulating pump, a liquid outlet of the circulating pump is connected with a first port of the three-way valve, a second port of the three-way valve is connected with the first spray header pipe through a pipeline, a third port of the three-way valve is connected with the pressurizing pump through a pipeline, and the pressurizing pump is connected with the second spray header pipe through a second backflow pipeline. The invention ensures the uniformity of the temperature and the concentration of the electrolyte at all positions in the tank, and improves the batch stability and the quality reliability of graphene products.
Description
Technical Field
The invention relates to the technical field of graphene preparation by electrochemical stripping, in particular to a temperature control and convection homogenizing device and method for graphene preparation by electrochemical stripping of graphite.
Background
Graphene is a honeycomb hexagonal plane two-dimensional crystal formed by single-layer sp 2 hybridized carbon atoms, on the two-dimensional plane, sp 2 hybridized carbon atoms are connected with three adjacent carbon atoms through strong sigma bonds, and the rest P electron orbits are perpendicular to the graphene plane and form large pi bonds with surrounding atoms, so that the graphene has good electric conduction, heat conduction and mechanical properties, electron mobility is up to 200,000cm 2/V.s, electric conductivity is up to 106S/m, heat conductivity can be up to 5000W/m.K, and strength can be up to 130GPa. The excellent characteristics of the graphene lead the graphene to have great potential application prospects in the fields of optoelectronic devices, chemical power sources (such as solar cells and lithium ion batteries), gas sensors, antistatic and heat dissipation materials and the like. This requires that the quality of graphene is good enough and that it can be produced on a large scale.
However, the preparation of graphene has a great challenge to industrial application at present. Firstly, a high-quality graphene material can be obtained by a method for preparing graphene through a micromolecular thermal decomposition carbon atom recombination growth method, such as a chemical vapor deposition technology and an epitaxial growth method, but the yield is low, the energy consumption is high, the transfer is difficult, the technical threshold is high, the product is widely applied to the field of graphene films, and the wide application of the scale is limited; in the method for obtaining the graphene material by stripping the graphite, besides a micromechanical stripping method, a chemical oxidation-reduction method and a liquid phase stripping method can be used for preparing the graphene on a large scale, but a large amount of oxygen-containing groups are connected to graphene sheets by the chemical oxidation-reduction method, so that a large amount of structural defects are caused, the electric conductivity and the heat conductivity of the graphene are greatly reduced, and a large amount of strong oxidizing reagents and toxic reagents with strong reducibility are used in the preparation process, so that the environmental protection is not facilitated. The liquid phase stripping method can obtain high-quality graphene materials without using strong acid or strong oxidant, but solvents and auxiliaries used in the stripping process are not easy to remove, and the product has small sheet diameter, low yield, low efficiency, large pollution and high cost. The prior art has a low-cost macro preparation method that graphite and a compound containing carboxylic acid or carbonyl are used as additives to perform local or intercalation reaction, boundary functional groups of the graphite or form intercalated graphite, and then the graphite is stripped by a ball milling or ultrasonic method to obtain high-quality graphene.
Aiming at the current state of the art, the graphene material bottleneck can be broken through by a large-scale, high-quality, low-cost, green and pollution-free preparation technology which is required by the development of the graphene industry, wherein the preparation technology is high in quality, low in yield and high in cost or is low in quality, high in yield and heavy in pollution. Electrochemical methods for preparing graphene are one of the possible ways. Compared with the redox method, the electrochemical method does not need a strong oxidant, and instead, the electric field intercalation stripping is carried out; compared with chemical vapor deposition, the electrochemical yield is far higher than that of the vapor deposition technology, the technical threshold is low, and the quality of graphene is easy to regulate and control; the electrochemical stripping yield may be in excess of 90% compared to less than 5% for liquid phase stripping. However, in the process of preparing graphene in a large scale by adopting an electrochemical method, partial electric energy and chemical energy are inevitably converted into heat energy, so that the temperature of an electrolytic cell cannot be continuously stable and form fluctuation, the batch consistency and stability of stripping are affected, the production is not facilitated, and in the electrolytic process, the concentration difference between electrodes is polarized, and the batch consistency and stability of a product are also affected. In order to solve the above problems, the present invention provides a temperature control and convection homogenizing device for electrochemical stripping preparation of an array graphite electrode.
Disclosure of Invention
The invention aims at: aiming at the problems, the invention provides a temperature control and convection homogenizing device for preparing graphene by electrochemically stripping graphite, which has the characteristic of strictly controlling the temperature, can realize the rapid homogenization of the temperature of main electrolyte and electrode side electrolyte in an electrolytic tank, and can reduce the concentration difference polarization between electrodes in the tank, thereby ensuring the batch consistency and the product stability of graphene stripping.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A temperature control and convection homogenizing device for preparing graphene by electrochemically stripping graphite comprises an electrolytic tank body, a plurality of graphite electrodes for stripping, a first jet flow assembly, a second jet flow assembly, a first output pipe, a circulating pump and a pressurizing pump; the plurality of graphite electrodes for stripping are arranged in parallel in the electrolytic tank, and adjacent graphite electrodes for stripping form a space; the first jet assembly comprises a first jet main pipe and first jet pipes, the first jet main pipe is transversely arranged along one side wall in the electrolytic tank, the side wall is parallel to the connecting lines of the plurality of graphite electrodes for stripping, the same side of the first jet main pipe is connected and communicated with the plurality of first jet pipes at intervals, one ends of the plurality of first jet pipes, far away from the first jet main pipe, extend upwards and then bend downwards to form a hook-shaped bent pipe, and the pipe orifice of the first jet pipe, far away from the first jet main pipe, faces into the electrolytic tank; the second jet assembly comprises a second jet main pipe, second jet branch pipes and second jet pipe spray heads, the second jet main pipe is formed into a square frame shape at the bottom of the electrolytic tank, two ends of a plurality of second jet branch pipes are connected to different edges of the second jet main pipe and are communicated with the interior of the second jet main pipe, and each second jet branch pipe is respectively provided with a plurality of second jet pipe spray heads with upward spray directions; one end port of the first output pipe is positioned at the bottom in the electrolytic tank, the other end of the first output pipe is connected with a liquid inlet of the circulating pump, a liquid outlet of the circulating pump is connected with a first port of the three-way valve through a pipeline, a second port of the three-way valve is connected with and communicated with a first spray header pipe through a first backflow pipeline, a third port of the three-way valve is connected with and communicated with a second backflow pipeline through a pipeline, and the second backflow pipeline is connected with and communicated with a second spray header pipe.
In the present invention, preferably, the device further comprises a transverse jet pipe, wherein the transverse jet pipe is connected and communicated with the first jet main pipe, and the transverse jet pipe is horizontally arranged.
In the present invention, preferably, the device further includes a central controller, the three-way valve is a three-way electromagnetic valve, and the central controller is connected with the circulating pump and the three-way electromagnetic valve through circuit control respectively.
In the present invention, preferably, the apparatus further comprises a temperature detection assembly, a central controller, and a heat exchanger; the temperature detection assembly comprises a fixing frame, an electric telescopic rod and a temperature probe, wherein the fixing frame is positioned at the outer side of the electrolytic tank, the fixing end of the electric telescopic rod is rotatably arranged on the fixing frame, the rotation direction is in a vertical direction, the telescopic end of the electric telescopic rod is close to and extends to the upper side of the electrolytic tank, and the temperature probe is fixed by the telescopic end of the electric telescopic rod through a mounting block; the temperature detection assemblies are provided with a plurality of groups, and each temperature probe is respectively positioned in the interval formed by the adjacent graphite electrodes for stripping; the second port of the three-way valve is connected with the liquid inlet of the heat exchanger through a pipeline, the liquid outlet of the heat exchanger is connected with one end of a second backflow pipeline, a booster pump is arranged on the second backflow pipeline, and the liquid outlet of the second backflow pipeline is connected and communicated with a second spray header pipe; the three-way valve is a three-way electromagnetic valve, and the central controller is respectively connected with the temperature probe, the electric telescopic rod, the heat exchanger, the booster pump, the circulating pump and the three-way electromagnetic valve through circuit control.
In the invention, preferably, the first backflow pipeline is a hose, and the first jet assembly is connected with the side wall of the electrolytic tank in a hanging way through a plurality of hanging assemblies with different heights, so that the first jet assembly can be hung at different heights of the electrolytic tank.
In the present invention, preferably, the first jet pipe is of a swingable structure, and is driven to swing horizontally by the first driving component.
In the present invention, preferably, the second jet pipe nozzle has a swingable structure, and the second driving unit drives the second jet pipe nozzle to change the direction of the jet.
In the present invention, preferably, the lateral nozzle is of a swingable structure, and the third driving assembly drives the spray direction to change.
In the present invention, preferably, the first driving assembly includes a first motor, a first crank shaft lever, a first connection block, a second connection block, a movable lever and a connecting rod; the first jet pipe is formed by connecting a vertical part and a hook part, the vertical part and the hook part are in sealing rotation connection and are communicated, the rotation direction of the hook part is in a horizontal direction, the hook part is connected with one end of a connecting rod through a connecting piece, the one end of the connecting rod is movably hinged with the connecting piece, the other ends of a plurality of connecting rods are fixedly connected with the same movable rod, a first connecting block is movably sleeved on the outer side of the movable rod, a bending section of a first bent shaft rod is fixedly connected on the first connecting block, one end of the first bent shaft rod is connected with an output shaft of a first motor and is driven by the first motor to rotate in the horizontal direction, and the other end of the first bent shaft rod is rotationally connected on a second connecting block; the first motor is arranged on the electrolytic tank or outside the electrolytic tank through a first motor bracket; the second connecting block is fixed on the first motor bracket or the electrolytic tank; the first motor is electrically connected with the central controller.
In the invention, preferably, the lower end of the second jet flow pipe nozzle is a spherical pipe, a round groove matched with the spherical pipe is arranged on the second jet flow branch pipe, and the lower end of the second jet flow pipe nozzle is rotatably arranged in the round groove on the second jet flow branch pipe through the spherical pipe; the second driving assembly comprises a power grid, a second crankshaft rod and a second motor, wherein the power grid consists of an outer frame and a plurality of parting strips connected in the outer frame, each parting strip is provided with a power hole, the power grid is movably arranged on the second jet pipe, and each second jet pipe nozzle is sleeved on the inner side of one power hole; the bending section of the second crank shaft rod is fixedly connected with the outer frame of the power grid, the upper end of the second crank shaft rod is connected with the output shaft of the second motor and is driven by the second motor to rotate in the horizontal direction, and the lower end of the second crank shaft rod is rotationally connected to the third connecting block; the second motor is fixed on the electrolytic tank or outside the electrolytic tank through a second motor bracket; the third connecting block is fixed in the electrolytic tank; the second motor is electrically connected with the central controller.
In the invention, preferably, one end of the transverse spray pipe is a spherical pipe, the inner side of the other end of the first spray header pipe is provided with a circular groove matched with the spherical pipe, and the transverse spray pipe is rotatably arranged in the circular groove at the other end of the first spray header pipe through the spherical pipe; the third driving assembly comprises a third motor bracket, a hydraulic rod, a third motor and a third crankshaft rod; a fourth connecting block is fixedly arranged on the third motor support, a rotating supporting rod is hinged to the fourth connecting block, the rotating direction of the rotating supporting rod is vertical, a third motor is fixedly arranged on the rotating supporting rod, an output shaft of the third motor is connected with one end of a third crankshaft rod, and the bent end of the third crankshaft rod is fixedly connected with a transverse spray pipe; one end of the hydraulic rod is hinged with a third motor bracket, and the other end of the hydraulic rod is hinged with a rotating support rod; the third motor is electrically connected with the central controller; the first spray header pipe or the transverse spray pipe is provided with a fluid control valve for controlling the flow of the transverse spray pipe, and the fluid control valve is electrically connected with the central controller.
In the invention, preferably, the inner side wall of the electrolytic tank is provided with fixed temperature probes fixed at different positions and different depths through hooks.
In the invention, preferably, an electrolyte buffer tank is arranged between the liquid outlet of the heat exchanger and the second jet main pipe, and the volume ratio of the buffer tank to the electrolyte in the electrolytic tank is 1:3.
In the present invention, it is preferable that the outer cover of each graphite electrode for peeling is provided with a filter bag or a filter frame, and the first spout pipe is directed into the filter bag or the filter frame away from the orifice of the first spout pipe.
The invention also provides a temperature control and convection homogenization method for preparing graphene by electrochemically stripping graphite, which comprises the following steps of:
After the electrolyte in the electrolytic tank body is pumped out through a circulating pump, the electrolyte is split through a three-way valve, a part of the electrolyte is conveyed to a heat exchanger, and after heat exchange, the electrolyte flows back into the electrolytic tank body through a second jet main pipe, so that upward fluid is formed to homogenize the electrolyte; the other part directly flows back into the electrolytic tank through the first return pipe, the first main flow pipe and the first jet pipe and is used as main power and medium for convection in the tank to form downward fluid; the output power can be directly increased or reduced by respectively adjusting the outlet valves of the circulating pump and the pressurizing pump, so that the convection intensity in the electrolytic tank is controlled as a whole, the concentration of the electrolyte in the electrolytic tank is uniform, and the concentration range is reduced;
For temperature regulation and control, through the flexible of electric telescopic rod, temperature probe can remove to measure the temperature variation of different positions between each electrode in the peeling process of graphite electrode, fixed temperature probe can test the electrolyte temperature near the electrolysis trough lateral wall, and central controller is after comparing each position, can control the delivery flow of force (forcing) pump, the delivery flow of circulating pump, the work of heat exchanger, the switching of tee bend valve, the opening and shutting of fluid control valve more accurately according to the size of each position temperature difference, thereby makes first spout pipe, second spout pipe shower nozzle, the flow increase or reduce of horizontal sprinkling irrigation regulate and control convection's intensity, in order to realize quick fluid temperature and the quick homogenization of concentration.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. According to the invention, through the arrangement of the first jet flow assembly, the second jet flow assembly, the first output pipe and the circulating pump, the circulating homogenization of the electrolyte can be realized, after the electrolyte is split by the three-way valve, one part of the electrolyte flows back into the electrolytic tank to form downward flowing fluid, the other part of the electrolyte flows back to form upward flowing fluid, and the two parts enable the electrolyte in the electrolytic tank to form stable convection, so that the temperature and the concentration of the electrolyte are better homogenized.
2. According to the invention, the temperature detection assembly, the central controller and the heat exchanger are arranged, so that the temperature of the electrolyte at multiple points in the electrolytic tank can be monitored, when the temperature difference exceeds a certain value, the power of the circulating pump and the power of the pressurizing pump are adjusted to adjust the convection intensity, and the temperature of the electrolyte is raised or lowered through the heat exchanger, so that the homogenization and the temperature homogenization of the electrolyte are realized more quickly.
3. The invention can further enlarge the spraying range by arranging the first spraying component, the second spraying component and the transverse spraying pipe into a structure capable of adjusting the spraying direction so as to realize the homogenization and the temperature homogenization of the electrolyte.
Drawings
FIG. 1 is an overall layout of the present invention;
FIG. 2 is a perspective view of an electrolytic cell according to the present invention;
FIG. 3 is a schematic illustration of a first jet assembly, a second jet assembly, a lateral nozzle, and a corresponding drive arrangement in accordance with the present invention;
FIG. 4 is a schematic diagram of a first driving assembly according to the present invention;
FIG. 5 is a schematic diagram of a temperature detecting assembly according to the present invention;
fig. 6 is a control schematic diagram in the present invention.
FIG. 7 shows the pH change of the electrolyte at a monitoring point before temperature and convection homogenization are not performed;
FIG. 8 shows the pH change of the electrolyte at the same monitoring point after mild and convective homogenization;
FIG. 9 shows the temperature change at a monitoring point before temperature and convection homogenization are not performed;
FIG. 10 shows the temperature change of the same monitoring point after temperature and convection homogenization;
FIG. 11 shows the temperature change of the electrolytic cell at a certain point when the temperature control and homogenizing cycle system are continuously operated;
FIG. 12 stripping effect of pole piece without temperature and convection homogenization;
FIG. 13 shows the stripping effect of the pole piece when the pole piece is opened after mild convection homogenization.
1-Cell body, 2-graphite electrode, 3-first jet assembly, 301-first jet manifold, 302-first jet pipe, 4-second jet assembly, 401-second jet manifold, 402-second jet manifold, 403-second jet pipe nozzle, 404-bulb pipe, 5-fluid control valve, 6-lateral nozzle, 7-electrode load-bearing bar, 8-temperature probe assembly, 801-mount, 802-electric telescopic bar, 803-temperature probe, 9-circulation pump, 10-three-way valve, 11-booster pump, 12-temperature display, 13-fixed temperature probe, 14-pipe shut-off valve, 15-heat exchanger, 16-central controller, 17-first output pipe, 18-first return pipe, 19-second return pipe, 20-filter frame, 21-first drive assembly, 2101-first motor, 2102-first connecting block, 2103-second connecting block, 2104-movable rod, 2105-connecting rod, 2106-first motor bracket, 2107-first crankshaft rod, 22-second drive assembly, 2201-power grid, 2202-second crankshaft rod, 2203-second motor, 2204-third connecting block, 2205-second motor bracket, 24-third drive assembly, 2401-third motor bracket, 2402-hydraulic rod, 2403-third motor, 2404-third crankshaft rod, 2405-rotary strut.
Detailed Description
The present invention will be further described with reference to the following examples in order to more clearly illustrate the present invention.
The invention provides a temperature control and convection homogenizing device for preparing graphene by electrochemically stripping graphite, which realizes the uniformity of electrolyte concentration and temperature in the electrolysis process through structural improvement, thereby realizing the batch consistency and product stability of graphene products. The invention comprises an electrolytic bath body 1, a plurality of graphite electrodes 2 for stripping, a first jet assembly 3, a second jet assembly 4, a first output pipe 17, a circulating pump 9 and a pressurizing pump 11; the electrolytic tank body 1 of the invention is a conventional product structure and comprises the electrolytic tank body 1, an electrolytic tank current conducting bus, a conductive terminal, an electrode bearing rod 7, an electrolytic cathode part and the like, the conventional part is not improved by the invention, and the electrolytic tank foundation structure capable of realizing electrochemical stripping is well known to the person skilled in the art, so the invention is not described in detail, and the figure is used for clearly expressing the improved part of the invention, so that the person skilled in the art can understand that the invention has all basic structures for realizing electrolysis. In the present invention, a plurality of graphite electrodes 2 for separation are installed in parallel in an electrolytic cell via electrode-supporting bars 7, adjacent graphite electrodes 2 for separation are spaced apart, and an electrolytic cathode is provided between adjacent graphite electrodes 2 to form an electrolytic electrode pair. Referring to fig. 1-3, the improvement of the invention is that the first spray assembly 3 comprises a first spray header 301 and a first spray pipe 302, the first spray header 301 is transversely arranged along a side wall in the electrolytic tank, the side wall is parallel to the connecting lines of the plurality of graphite electrodes 2 for stripping, the transverse arrangement is not required to be in a horizontal state, the same side (in particular to the upper side) of the first spray header 301 is connected and communicated with a plurality of first spray pipes 302 at intervals, one end of the plurality of first spray pipes 302 far away from the first spray header 301 extends upwards and then bends downwards to form a hook-shaped bent pipe, and the pipe orifice of the first spray pipe 302 far away from the first spray header 301 faces into the electrolytic tank for backflow of electrolyte into the electrolytic tank to form downward flowing fluid; the second spray assembly 4 comprises a second spray header 401, second spray branch pipes 402 and second spray pipe spray nozzles 403, the second spray header 401 is formed into a square frame shape at the bottom of the electrolytic tank, two ends of a plurality of second spray branch pipes 402 are connected on different sides of the second spray header 401 and are communicated with the inside of the second spray header 401, two sides of the second spray branch pipes 402 can be connected on adjacent sides, more preferably on opposite sides of the square frame shape, and each second spray branch pipe 402 is respectively provided with a plurality of second spray pipe spray nozzles 403 with upward spray directions for spraying electrolyte upwards to form upward flowing fluid, wherein the upward direction can be vertical upward, inclined upward or the like; one end port of the first output pipe 17 is positioned at the bottom in the electrolytic tank, the other end is connected with a liquid inlet of the circulating pump 9, a liquid outlet of the circulating pump 9 is connected with a first port of the three-way valve 10, a second port of the three-way valve 10 is connected and communicated with the first spray header 301 through a first backflow pipeline 18, a third port of the three-way valve 10 is connected with the second backflow pipeline 19 through a pipeline, and the second backflow pipeline 19 is connected and communicated with the second spray header 401. Each pipe is provided with a pipe shut-off valve 14.
Through the arrangement, when electrochemical stripping is carried out, electrolyte is injected into the electrolytic tank to a preset liquid level, after the circulating pump 9 is started, the electrolyte in the electrolytic tank can enter the three-way valve 10 through the circulating pump 9 under the action of the circulating pump 9, the three-way valve 10 shunts the electrolyte, part of the electrolyte enters the first jet manifold 301 through the first return pipeline 18, enters the first jet manifold 302 through the first jet manifold 301 and then flows back into the electrolytic tank to form downward flowing fluid, the other part of the electrolyte enters the second jet manifold 401 through the pipeline and the second return pipeline 19, and then the electrolyte is sprayed upwards through the second jet pipe spray nozzle 403 to form upward flowing fluid, so that the electrolyte in the electrolytic tank forms stable convection, and the temperature and the concentration of the electrolyte are better uniform. And the intensity of convection can be controlled by adjusting the flow rate of the circulation pump 9.
In some preferred embodiments of the present invention, the device further comprises a transverse jet pipe 6, the transverse jet pipe 6 is connected to and communicates with the first jet main 301, and a fluid control valve 5 for controlling the flow rate of the transverse jet pipe 6 is arranged on the first jet main 301 or the transverse jet pipe 6; the transverse jet pipe 6 is horizontally arranged. When the circulating pump 9 works, the electrolyte flowing back in the first jet main 301 can flow out through the transverse jet pipe 6, so that horizontal flow is formed, better uniformity of the temperature and concentration of the electrolyte is further promoted, and the flow intensity of the fluid can be controlled by controlling the opening and closing degree of the fluid control valve 5.
In some preferred embodiments of the invention, the device further comprises a temperature detection assembly 8, a central controller 16 and a heat exchanger 15; referring to fig. 1,2, 3 and 5, the temperature detecting assembly 8 includes a fixing frame 801, an electric telescopic rod 802 and a temperature probe 803, the fixing frame 801 is located at the outer side of the electrolytic tank, a fixed end of the electric telescopic rod 802 is rotatably mounted on the fixing frame 801, the rotation direction is a vertical direction, a telescopic end of the electric telescopic rod 802 is close to and extends above the electrolytic tank, and the telescopic end of the electric telescopic rod 802 is fixed with the temperature probe 803 through a mounting block; the temperature detection assemblies 8 are provided with a plurality of groups, and each temperature probe 803 is respectively positioned in a space formed by the adjacent graphite electrodes 2 for stripping; the second port of the three-way valve 10 is connected with the liquid inlet of the heat exchanger 15 through a pipeline, the liquid outlet of the heat exchanger 15 is connected with one end of a second backflow pipeline 19, the second backflow pipeline 19 is provided with a booster pump 11, and the liquid outlet of the second backflow pipeline 19 is connected with and communicated with a second spray header 401; the three-way valve 10 is a three-way electromagnetic valve, the central controller 16 is respectively connected with the temperature probe 803, the electric telescopic rod 802, the heat exchanger 15, the booster pump 11, the circulating pump 9 and the three-way electromagnetic valve through circuit control, and the temperature is displayed through the temperature display 13.
Through the arrangement, when electrochemical stripping is carried out, the temperature probe 803 measures the temperature of the electrolyte in real time, the electric telescopic rod 802 can quickly move the temperature probe 803 to the two sides and the middle position of the electrode by stretching or shortening, and the temperature change of different parts between the electrodes in the stripping process of the graphite electrode 2 for stripping is measured, so that the PLC central controller 16 collects accurate temperature values of the parts, and when the temperature difference is large, the central controller 16 increases the convective intensity of the electrolyte by controlling the power of the pressurizing pump 11 and the circulating pump 9, thereby promoting the rapid homogenization of the temperature and the concentration of the electrolyte. Meanwhile, the PLC central controller 16 controls the speed of the heat exchanger 15 for carrying out temperature exchange on the electrolyte according to the temperature value, so as to accelerate temperature homogenization. For example, when the temperature at the electrode side is high, the central controller 16 increases the convection intensity of the electrolyte by controlling the power of the pressurizing pump 11 and the circulating pump 9, and controls the heat exchanger 15 to cool the electrolyte, and after the cooled electrolyte enters the electrolytic tank through the spray head of the first spray pipe 302, the temperature can be more quickly homogenized through a heat exchange mode. Based on this, the invention also preferably fixes the fixed temperature probe 13 through the hook at different positions and different depths of the inner side wall of the electrolytic tank, the fixed temperature probe 13 is electrically connected with the central controller 16, thus can test the electrolyte temperature near the side wall of the electrolytic tank, know the temperature condition of more points, the central controller 16 can control the power of the booster pump 11, the circulating pump 9 and the work of the heat exchanger 15 more accurately after comparing each part, achieve faster electrolyte homogenization.
In the invention, an electrolyte buffer tank (not shown) is arranged between the liquid outlet of the heat exchanger 15 and the second spray header 401, and the volume ratio of the buffer tank to the electrolyte in the electrolytic tank is 1:3; the electrode liquid entering the buffer tank from the heat exchanger 15 is used for reducing the temperature of the electrolyte in the electrolytic tank, and the temperature is lower than the temperature in the tank by 15-25 ℃.
In some preferred embodiments of the present invention, the outer cover of each graphite electrode 2 for peeling is provided with a filter bag or filter frame 20, and the first spout pipe 302 is directed toward the inside of the filter bag or filter frame 20 away from the orifice of the first spout pipe 301. By this arrangement, the fluid ejected from the first jet pipe 302 can form a turbulent layer with strong convection on the surface of the graphite electrode 2, and the homogenization of the electrode surface and the temperature can be quickly achieved.
In some preferred embodiments of the present invention, the first jet pipe 302 is of a swingable structure, and is driven to swing horizontally by the first driving assembly 21. Preferably, the first driving assembly 21 includes a first motor 2101, a first crank shaft 2107, a first connecting block 2102, a second connecting block 2103, a movable rod 2104 and a connecting rod 2105; the first jet pipe 302 is formed by connecting a vertical part and a hook part, the vertical part and the hook part are connected in a sealing and rotating way and communicated, the rotating direction is the horizontal direction, the hook part is connected with one end of a connecting rod 2105 through a connecting piece, the one end of the connecting rod 2105 is movably hinged with the connecting piece, the other ends of a plurality of connecting rods 2105 are fixedly connected with a same movable rod 2104, a first connecting block 2102 is movably sleeved on the outer side of the movable rod 2104, a bending section of a first crank rod 2107 is fixedly connected on the first connecting block 2102, one end of the first crank rod 2107 is connected with an output shaft of a first motor 2101 and is driven by the first motor 2101 to rotate in the horizontal direction, and the other end of the first crank rod 2107 is rotatably connected with a second connecting block 2103; the first motor 2101 is arranged on the electrolytic bath or outside the electrolytic bath through a first motor bracket 2106; the second connecting block 2103 is fixed on the first motor bracket 2106 or the electrolytic tank. Through this setting, at first motor 2101 during operation, the output shaft drives first bent axle pole 2107 horizontal rotation to drive first connecting piece 2102, movable rod 2104 and connecting rod 2105 respectively and do circular motion, thereby drive hook-like portion and carry out horizontal oscillation, can remove the spout position on the horizontal plane, increase the injection range of electrolyte, promote the homogeneity and the temperature homogeneity of electrolyte more soon. The first motor 2101 is electrically connected to the central controller 16 through a circuit, so that automatic adjustment can be further realized.
In some preferred embodiments of the present invention, the second jet pipe nozzle 403 is of a swingable construction, and the direction of the spray is varied by the second drive assembly 22. Preferably, the lower end of the second jet pipe nozzle 403 is a spherical pipe, a circular groove matched with the spherical pipe is arranged on the second jet pipe branch 402, the lower end of the second jet pipe nozzle 403 is rotatably arranged in the circular groove on the second jet pipe branch 402 through the spherical pipe, and a sealing gasket can be arranged at the joint of the spherical pipe and the circular groove to enhance the sealing effect; the second driving assembly 22 includes a power grid 2201, a second crank shaft 2202 and a second motor 2203, the power grid 2201 is composed of an outer frame and a plurality of parting strips connected in the outer frame, each parting strip is provided with a power hole, the power grid 2201 is movably placed on the second jet pipe, and each second jet pipe nozzle 403 is sleeved on the inner side of one power hole; the bending section of the second crank shaft 2202 is movably connected with the outer frame of the power grid 2201, the upper end of the second crank shaft 2202 is connected with the output shaft of the second motor 2203 and drives the second crank shaft 2202 to rotate along the horizontal direction by the second motor, and the lower end of the second crank shaft 2202 is rotatably connected with the third connecting block 2204; the second motor 2203 is fixed on the electrolytic cell or fixed outside the electrolytic cell through a second motor bracket 2205; the third connection block 2204 is fixed in the electrolytic cell. Through this setting, at second motor 2203 during operation, the output shaft drives second bent axle pole 2202 horizontal rotation to drive power grid 2201 and do circular motion, thereby drive the upper portion of second jet pipe shower nozzle 403 and do circular motion, the injection direction of shower nozzle can carry out three-dimensional direction adjustment in the electrolysis trough, increases the injection range of electrolyte, promotes the homogeneity and the temperature homogeneity of electrolyte more rapidly. The second motor 2203 is electrically connected to the central controller 16 through a circuit, so that automatic adjustment can be further realized.
In some preferred embodiments of the invention, the lateral nozzle 6 is of a swingable construction, the direction of the spray being driven by a third drive assembly 24. Preferably, one end of the transverse spray pipe 6 is a spherical pipe, a round groove matched with the spherical pipe is formed in the inner side of the other end of the first spray header 301, and the transverse spray pipe 6 is rotatably arranged in the round groove at the other end of the first spray header 301 through the spherical pipe; the third drive assembly 24 includes a third motor bracket 2401, a hydraulic rod 2402, a third motor 2403, and a third crankshaft rod 2404; a fourth connecting block is fixedly arranged on the third motor bracket 2401, the fourth connecting block is hinged with a rotating strut 2405, the rotating direction of the rotating strut 2405 is a vertical direction, a third motor 2403 is fixedly arranged on the rotating strut 2405, an output shaft of the third motor 2403 is connected with one end of a third crankshaft rod 2404, and a bending end of the third crankshaft rod 2404 is fixedly connected with a transverse spray pipe 6; one end of the hydraulic rod 2402 is hinged with a third motor bracket 2401, and the other end is hinged with a rotating strut 2405. Through the arrangement, when the third motor 2403 works, only reciprocating rotation of less than 180 degrees is carried out, the output shaft drives the third crankshaft rod 2404 to reciprocate, so that the bending section of the third crankshaft rod 2404 drives the transverse spray pipe 6 to horizontally oscillate, and the spraying direction of the transverse spray pipe 6 can be adjusted in a three-dimensional direction in the electrolytic bath; when the hydraulic rod 2402 stretches, the up-down position of the third motor 2403 can be driven to change, so that the up-down position of the third crank rod 2404 and the transverse spray pipe 6 are also driven to change; thereby increasing the spraying range of the electrolyte and promoting the homogenization and temperature uniformity of the electrolyte more quickly. The third motor 2403 is electrically connected to the central controller 16 through a circuit, so that automatic adjustment can be further realized.
In some preferred embodiments of the present invention, the first return conduit 18 is a hose, and the first jet assembly 3 is suspended from the side wall of the electrolyzer by a plurality of sets of suspension assemblies having different heights, so that the first jet assembly 3 can be suspended at different heights of the electrolyzer. Correspondingly, the first motor bracket 2106 has a structure capable of correspondingly lifting. Fig. 4 shows an embodiment, in which the bottom of the first motor bracket 2106 is connected with a movable end of an electric lifting rod, the fixed end of the electric lifting rod is fixed on a base, and the first motor bracket 2106 is slidably connected in sliding grooves on two sides of the base, so that the stability of the structure is maintained.
The working principle of the invention is as follows:
The first spray header 301 and the second spray header 401 of the electrolytic tank are respectively provided with independent fluid delivery pumps, and the fluid delivery quantity of the circulating pump 9 of the first spray header 301 is far greater than that of the pressurizing pump 11 of the second spray header 401. In general, after the electrolyte in the electrolytic tank body 1 is pumped out by the circulating pump 9, the electrolyte is split by the three-way valve 10, part of the electrolyte is conveyed to the heat exchanger, and after heat exchange, the electrolyte flows back into the electrolytic tank body 1 by the second jet main 401 to form upward fluid for homogenizing the electrolyte; the other part directly flows back into the electrolytic tank through the first return pipe, the first spray header 301 and the first spray pipe 302 and is used as main power and medium for convection in the tank to form downward fluid; the output power can be directly increased or reduced by respectively adjusting the outlet valves of the circulating pump 9 and the pressurizing pump 11, so that the convection intensity in the electrolytic tank is controlled as a whole, the concentration of the electrolyte in the electrolytic tank is uniform, and the concentration is extremely poor.
For temperature regulation and control, the temperature probe 803 can move through the expansion and contraction of the electric expansion rod 802, and measure the temperature change of different parts between the electrodes in the stripping process of the graphite electrode 2, the fixed temperature probe 13 can test the electrolyte temperature near the side wall of the electrolytic tank, and the central controller 16 can more accurately control the conveying flow of the booster pump 11, the conveying flow of the circulating pump 9, the work of the heat exchanger 15, the opening and closing of the three-way valve 10 and the opening and closing of the fluid control valve 5 according to the temperature difference of each part after comparing the electrolyte temperature of each part, so that the flow of the first jet pipe 302, the second jet pipe jet 403 and the transverse sprinkling irrigation is increased or reduced to regulate the convection intensity, and the rapid homogenization of the fluid temperature and the concentration is realized.
The device is adopted to electrochemically strip graphite to prepare graphene, the pH change condition of the electrolyte is shown in figure 7 before mild and convective homogenization is not carried out, and the pH change condition of the electrolyte is shown in figure 8 after mild and convective homogenization is carried out; the vertical axis represents the pH value, and the horizontal axis represents the time, so that the electrolyte pH floating range of the same monitoring point is smaller, and the electrolyte property is more stable and uniform after the device is adopted for controlling temperature and carrying out convection homogenization.
Before temperature control and convection homogenization are not performed, the temperature change condition of each monitoring point is shown in fig. 9, after temperature control and convection homogenization, the temperature change condition of a certain monitoring point is shown in fig. 10, and when the temperature control circulation system continuously operates, the temperature change condition of an electrolytic tank at a certain point is shown in fig. 11; it can be seen that after the device is adopted for carrying out mild convection homogenization, the fluctuation range of the electrolyte temperature at the same monitoring point is smaller, and the electrolyte temperature is more stable and uniform.
Under the condition that the temperature and convection homogenization are not carried out, the stripping effect of the pole piece is shown in figure 12, and the stripping effect of the pole piece when the de-slotting temperature control system is started is shown in figure 13. It can be seen that uniform stability of product performance can be improved by controlling temperature and convection homogenization.
The results of the random sampling and comparison of the stripping of the production electrode of the electrolytic cell with or without the temperature control system are shown in Table 1, and can be seen that the stripping is more uniform and the phenomena of cracking and slag falling are reduced through the temperature control and the convection homogenization.
TABLE 1
The comparison result of the oxygen content of the material sample test obtained by the production of the electrolytic tank with or without the temperature control system is shown in table 2, and it can be seen that the product performance is more stable through temperature control and convection homogenization.
TABLE 2
In summary, compared with the existing device, the graphene stripping device disclosed by the invention can be used for promoting the homogenization and temperature uniformity of the electrolyte more quickly, and reducing the concentration difference polarization between the electrodes in the tank, so that the batch consistency and the product stability of graphene stripping can be ensured.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (15)
1. Temperature control and convection homogenizing device for preparing graphene by electrochemical stripping of graphite is characterized in that: comprises an electrolytic bath body, a plurality of graphite electrodes for stripping, a first jet assembly, a second jet assembly, a first output pipe, a circulating pump and a booster pump; the plurality of graphite electrodes for stripping are arranged in parallel in the electrolytic tank, and adjacent graphite electrodes for stripping form a space; the first jet assembly comprises a first jet main pipe and first jet pipes, the first jet main pipe is transversely arranged along one side wall in the electrolytic tank, the side wall is parallel to the connecting lines of the plurality of graphite electrodes for stripping, the same side of the first jet main pipe is connected and communicated with the plurality of first jet pipes at intervals, one ends of the plurality of first jet pipes, far away from the first jet main pipe, extend upwards and then bend downwards to form a hook-shaped bent pipe, and the pipe orifice of the first jet pipe, far away from the first jet main pipe, faces into the electrolytic tank; the second jet assembly comprises a second jet main pipe, second jet branch pipes and second jet pipe spray heads, the second jet main pipe is formed into a square frame shape at the bottom of the electrolytic tank, two ends of a plurality of second jet branch pipes are connected to different edges of the second jet main pipe and are communicated with the interior of the second jet main pipe, and each second jet branch pipe is respectively provided with a plurality of second jet pipe spray heads with upward spray directions; one end port of the first output pipe is positioned at the bottom in the electrolytic tank, the other end of the first output pipe is connected with a liquid inlet of the circulating pump, a liquid outlet of the circulating pump is connected with a first interface of the three-way valve, a second interface of the three-way valve is connected and communicated with the first spray header pipe through a first backflow pipeline, a third interface of the three-way valve is connected with a second backflow pipeline through a pipeline, and the second backflow pipeline is connected and communicated with the second spray header pipe.
2. The apparatus according to claim 1, wherein: the horizontal spray pipe is connected with and communicated with the first spray header pipe, and is horizontally arranged.
3. The apparatus according to claim 1 or 2, characterized in that: the three-way valve is a three-way electromagnetic valve, and the central controller is respectively connected with the circulating pump and the three-way electromagnetic valve through circuit control.
4. The apparatus according to claim 1 or 2, characterized in that: the system also comprises a temperature detection assembly, a central controller and a heat exchanger; the temperature detection assembly comprises a fixing frame, an electric telescopic rod and a temperature probe, wherein the fixing frame is positioned at the outer side of the electrolytic tank, the fixing end of the electric telescopic rod is rotatably arranged on the fixing frame, the rotation direction is in a vertical direction, the telescopic end of the electric telescopic rod is close to and extends to the upper side of the electrolytic tank, and the temperature probe is fixed by the telescopic end of the electric telescopic rod through a mounting block; the temperature detection assemblies are provided with a plurality of groups, and each temperature probe is respectively positioned in the interval formed by the adjacent graphite electrodes for stripping; the second port of the three-way valve is connected with the liquid inlet of the heat exchanger through a pipeline, the liquid outlet of the heat exchanger is connected with one end of a second backflow pipeline, a booster pump is arranged on the second backflow pipeline, and the liquid outlet of the second backflow pipeline is connected and communicated with a second spray header pipe; the three-way valve is a three-way electromagnetic valve, and the central controller is respectively connected with the temperature probe, the electric telescopic rod, the heat exchanger, the booster pump, the circulating pump and the three-way electromagnetic valve through circuit control.
5. The apparatus according to claim 1, wherein: the first backflow pipeline is a hose, and the first jet assembly is suspended and connected with the side wall of the electrolytic tank through a plurality of groups of suspension assemblies with different heights, so that the first jet assembly is suspended at different heights of the electrolytic tank.
6. The apparatus according to claim 4, wherein: the first jet pipe is of a swinging structure, and is driven to swing horizontally by the first driving component.
7. The apparatus according to claim 4, wherein: the second jet flow pipe spray head is of a swinging structure, and the spraying direction of the second jet flow pipe spray head is driven by the second driving assembly to change.
8. The apparatus according to claim 4, wherein: the transverse spray pipe is of a swinging structure, and the third driving component drives the spraying direction to change.
9. The apparatus according to claim 6, wherein: the first driving assembly comprises a first motor, a first crankshaft rod, a first connecting block, a second connecting block, a movable rod and a connecting rod; the first jet pipe is formed by connecting a vertical part and a hook part, the vertical part and the hook part are in sealing rotation connection and are communicated, the rotation direction of the hook part is in a horizontal direction, the hook part is connected with one end of a connecting rod through a connecting piece, the one end of the connecting rod is movably hinged with the connecting piece, the other ends of a plurality of connecting rods are fixedly connected with the same movable rod, a first connecting block is movably sleeved on the outer side of the movable rod, a bending section of a first bent shaft rod is fixedly connected on the first connecting block, one end of the first bent shaft rod is connected with an output shaft of a first motor and is driven by the first motor to rotate in the horizontal direction, and the other end of the first bent shaft rod is rotationally connected on a second connecting block; the first motor is arranged on the electrolytic tank or outside the electrolytic tank through a first motor bracket; the second connecting block is fixed on the first motor bracket or the electrolytic tank; the first motor is electrically connected with the central controller.
10. The apparatus according to claim 7, wherein: the lower end of the second jet flow pipe spray head is a spherical pipe, a round groove matched with the spherical pipe is formed in the second jet flow branch pipe, and the lower end of the second jet flow pipe spray head is rotatably arranged in the round groove on the second jet flow branch pipe through the spherical pipe; the second driving assembly comprises a power grid, a second crankshaft rod and a second motor, wherein the power grid consists of an outer frame and a plurality of parting strips connected in the outer frame, each parting strip is provided with a power hole, the power grid is movably arranged on the second jet pipe, and each second jet pipe nozzle is sleeved on the inner side of one power hole; the bending section of the second crank shaft rod is movably connected with the outer frame of the power grid, the upper end of the second crank shaft rod is connected with the output shaft of the second motor, the second crank shaft rod is driven by the second motor to rotate in the horizontal direction, and the lower end of the second crank shaft rod is rotationally connected to the third connecting block; the second motor is fixed on the electrolytic tank or outside the electrolytic tank through a second motor bracket; the third connecting block is fixed in the electrolytic tank; the second motor is electrically connected with the central controller.
11. The apparatus according to claim 8, wherein: one end of the transverse spray pipe is a spherical pipe, a round groove matched with the spherical pipe is formed in the inner side of the other end of the first spray header pipe, and the transverse spray pipe is rotatably arranged in the round groove at the other end of the first spray header pipe through the spherical pipe; the third driving assembly comprises a third motor bracket, a hydraulic rod, a third motor and a third crankshaft rod; a fourth connecting block is fixedly arranged on the third motor support, a rotating supporting rod is hinged to the fourth connecting block, the rotating direction of the rotating supporting rod is vertical, a third motor is fixedly arranged on the rotating supporting rod, an output shaft of the third motor is connected with one end of a third crankshaft rod, and the bent end of the third crankshaft rod is fixedly connected with a transverse spray pipe; one end of the hydraulic rod is hinged with a third motor bracket, and the other end of the hydraulic rod is hinged with a rotating support rod; the third motor is electrically connected with the central controller; the first spray header pipe or the transverse spray pipe is provided with a fluid control valve for controlling the flow of the transverse spray pipe, and the fluid control valve is electrically connected with the central controller.
12. A device according to claim 3, characterized in that: the inner side wall of the electrolytic tank is provided with fixed temperature probes which are fixed at different positions and different depths through hooks.
13. The apparatus according to claim 4, wherein: an electrolyte buffer tank is arranged between the liquid outlet of the heat exchanger and the second jet main pipe, and the volume ratio of the buffer tank to the electrolyte in the electrolytic tank is 1:3.
14. A device according to claim 3, characterized in that: the outer cover of each graphite electrode for stripping is provided with a filter bag or a filter frame, and the pipe orifice of the first jet pipe far away from the first jet pipe faces into the filter bag or the filter frame.
15. A temperature control and convection homogenization method for preparing graphene by electrochemically stripping graphite, which is characterized in that the device of any one of claims 1-14 is utilized, and the specific method is as follows:
After the electrolyte in the electrolytic tank body is pumped out through a circulating pump, the electrolyte is split through a three-way valve, a part of the electrolyte is conveyed to a heat exchanger, and after heat exchange, the electrolyte flows back into the electrolytic tank body through a second jet main pipe, so that upward fluid is formed to homogenize the electrolyte; the other part directly flows back into the electrolytic tank through the first return pipe, the first main flow pipe and the first jet pipe and is used as main power and medium for convection in the tank to form downward fluid; the output power is directly increased or reduced by respectively adjusting the outlet valves of the circulating pump and the pressurizing pump, so that the convection intensity in the electrolytic tank is controlled as a whole, the concentration of the electrolyte in the electrolytic tank is uniform, and the concentration range is reduced;
For temperature regulation and control, through the flexible of electric telescopic rod, temperature probe removes to measure the temperature variation of graphite electrode at different positions between each electrode in the stripping process, fixed temperature probe test electrolysis bath lateral wall near electrolyte temperature, central controller is after comparing each position, the transport flow of force (forcing) pump, the transport flow of circulating pump, the work of heat exchanger, the switching of tee bend valve, the switching of fluid control valve more accurately is controlled to the size of each position temperature difference, thereby makes first spout pipe, second spout pipe shower nozzle, transverse sprinkling irrigation's flow increase or reduce and regulate and control the intensity of convection, in order to realize quick fluid temperature and quick homogenization of concentration.
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| CN217756908U (en) * | 2022-07-06 | 2022-11-08 | 广西师范大学 | Electrolyte circulation temperature control device for preparing graphene electrolytic cell by electrochemical method |
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| CN114956059A (en) | 2022-08-30 |
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Inventor after: Jiang Juantao Inventor after: Qiu Zhian Inventor after: Zheng Fenghua Inventor after: Huang Youguo Inventor after: Han Jinlu Inventor after: Wang Hongqiang Inventor after: Li Qingyu Inventor before: Qiu Zhian Inventor before: Han Jinlu Inventor before: Jiang Juantao Inventor before: Zheng Fenghua Inventor before: Huang Youguo Inventor before: Wang Hongqiang Inventor before: Li Qingyu |
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