CN212050552U - Graphite intercalation thing preparation system - Google Patents
Graphite intercalation thing preparation system Download PDFInfo
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- CN212050552U CN212050552U CN202020279394.XU CN202020279394U CN212050552U CN 212050552 U CN212050552 U CN 212050552U CN 202020279394 U CN202020279394 U CN 202020279394U CN 212050552 U CN212050552 U CN 212050552U
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Abstract
The utility model relates to a graphite intercalation thing preparation system belongs to graphite material preparation technical field. The system comprises a mixing kettle, a slurry pump, an electrolytic bath and a gas-liquid separator which are sequentially communicated, wherein: the top of the mixing kettle is provided with a graphite feed inlet and a liquid feed inlet, and the bottom of the mixing kettle is connected with a slurry pump and is used for pumping the slurry suspension into an electrolytic cell through a cooler; the electrolytic bath comprises an anode plate and a cathode plate which are oppositely arranged, and an anode chamber and a cathode chamber which are separated by an anion exchange membrane; the top of vapour and liquid separator is provided with the tail gas export, and the bottom is connected to the slurry pump. The utility model carries out forced circulation to the slurry suspension liquid through the slurry pump, thereby being convenient for the multi-angle intercalation of the intercalation medium to the graphite flake and avoiding the problems of intercalation dead angle and intercalation unevenness; the circulating suspension can discharge bubbles generated in the reaction process in time, and the current density per unit area is prevented from greatly fluctuating due to accumulation in the electrolytic cell.
Description
Technical Field
The utility model relates to a graphite material preparation system technical field specifically provides a graphite intercalation thing preparation system.
Background
Graphene is a two-dimensional crystal, and common graphite is formed by stacking planar carbon atoms which are orderly arranged in a honeycomb shape layer by layer, the interlayer acting force of the graphite is weak, the graphite can be easily peeled off from each other, and the graphene is obtained after the graphite sheets are peeled into a single layer or a plurality of layers.
The electrochemical method is one of the mature graphene production methods, and the electrochemical oxidation method is mainly used for batch production: graphite intercalation materials (materials in which graphite is intercalated by a liquid-phase medium are called) are formed by taking cheap graphite as a raw material and inserting graphite flakes in a liquid phase by utilizing an exfoliation medium (mainly comprising sulfuric acid, nitric acid, hydrogen peroxide, potassium permanganate and the like) with an oxidation effect under the action of an electric field. In the intercalation process, partial carbon atoms in the graphite structure are oxidized, and meanwhile, nitric acid and sulfuric acid molecules are embedded into gaps between graphite layers. The decomposition of the graphite intercalation is finished at a high temperature of 800-1200 ℃, the gaps between graphite layers rapidly release decomposed gaseous products at the high temperature, and the crystal lattice rapidly expands under the action of air pressure to prepare the graphene powder product. The electrochemical oxidation method for preparing the graphite intercalation has the advantages of low cost and high yield, and has the defects of low chemical purity and a large number of structural defects in a graphene layer, mainly because the products have oxygen atoms, sulfur atoms and the like which are chemically connected, so that most of the mechanical and electronic properties of the material are seriously degraded and reduced.
Another method for electrochemically preparing graphite intercalation material is to prepare graphene by anode and cathode oxidation stripping, namely, a graphite rod is used as an anode or a cathode, ions in electrolyte move to the anode or the cathode when a power supply works, anions and cations enter the anode or cathode graphite rod respectively to cause the graphite to be intercalated and expand in volume, and when the volume of the graphite electrode is increased to a certain degree, the graphite electrode finally falls off from the graphite rod block due to the reduction of van der waals interaction force between layers to form a layered graphite intercalation material with certain oxygen-containing functional groups. The method can prepare the graphite intercalation material with better performance for producing the graphene, but the working area in the electrolysis process is too small, so that the method is not beneficial to mass production.
Meanwhile, in the prior art, in the process of electrochemically preparing the graphite intercalation material, because the shape of the electrolytic cell or gas generated in the electrolytic process cannot be discharged in time, the electric field in the electrolytic cell is easy to be uneven, and adverse effects can be caused on the electrolytic process and the product quality.
SUMMERY OF THE UTILITY MODEL
In order to solve the problems in the prior art, the utility model provides a graphite intercalation preparation system; in the graphite intercalation preparation system of the utility model, the circular slurry suspension can discharge the bubbles generated in the reaction process in time, thereby preventing the accumulation in the electrolytic bath from leading to the current density per unit area to fluctuate greatly.
In order to solve the technical problem, the utility model provides a technical scheme as follows:
the utility model provides a graphite intercalation thing preparation system, including the material mixing cauldron, slurry pump, electrolysis trough and vapour and liquid separator that communicate in proper order, wherein:
the top of the mixing kettle is provided with a graphite feed port and a liquid feed port, materials are uniformly mixed in the mixing kettle, and the bottom of the mixing kettle is connected with the slurry pump and is used for pumping slurry suspension into the electrolytic cell through a cooler;
the electrolytic cell comprises an anode plate and a cathode plate which are oppositely arranged, and an anode chamber and a cathode chamber which are separated by an anion exchange membrane;
the top of vapour and liquid separator is provided with the tail gas export, and the bottom is connected to the slurry pump makes suspension be in circulate between slurry pump, cooler, electrolysis trough and vapour and liquid separator.
Further, the anode chamber is a space formed between the anode plate and the anion exchange membrane, and the cathode chamber is a space formed between the cathode plate and the anion exchange membrane.
Further, a slurry suspension is arranged in the anode chamber, and a perchloric acid solution with the concentration of 30-50% is arranged in the cathode chamber.
Further, the feed inlet of electrolysis trough is located the lower part of anode chamber, the discharge gate of electrolysis trough is located the upper portion of anode chamber, the gas outlet is located the top in cathode chamber.
Furthermore, the top of the anode plate is provided with an anode hanging lug which is used for connecting the anode of a power supply; and the top of the negative plate is provided with a negative hanging lug for connecting a negative pole of a power supply.
Further, the bottom of the gas-liquid separator is also connected with a reaction liquid slurry pump for pumping the slurry after the reaction to a subsequent treatment system.
Furthermore, the subsequent treatment system comprises a filtering device, a washing device, a filter press and an air flow dryer which are arranged in sequence.
Further, the cooler is a conventional cooler, preferably a water cooler or an electric refrigeration cooler.
The aggregation and discharge processes of the gas can cause partial graphite powder to separate from the liquid phase, so that the electrolysis and intercalation processes can not be effectively finished. Therefore, the material in the anode chamber is forcibly circulated by a slurry pump: pumping the circulating suspension into the lower part of the anode chamber, discharging the bubbles generated in the chamber and the circulating liquid out of the anode chamber, removing the bubbles through a gas-liquid separator, adjusting the acidity of the degassed suspension, pumping the suspension into the lower part of the anode chamber through a pump, cooling the suspension through a cooler, and then feeding the cooled suspension into an electrolytic cell to form material circulation, wherein the temperature is kept below 50 ℃.
At low temperature, the oxidability of the perchloric acid of less than 50 percent is weak, the perchloric acid does not react with graphite carbon atoms, and the electrochemical performance and the physical performance of the obtained powder graphene product have obvious superiority compared with an acid oxidation method.
The separated gas is washed and purified by sodium carbonate solution and then is discharged, and the washed product sodium hypochlorite can be recycled as industrial salt.
The hydrogen generated by the cathode in the electrolysis process is discharged through a gas outlet and sent to a gas furnace for combustion, or is collected by a gas collecting pipe and sent to a washing tower for washing by alkali liquor, and the hydrogen is pressurized by a compressor and can be sold as a product.
In the application, the graphite intercalation prepared by the system can be treated by hot gas at the temperature of 300-700 ℃ to obtain graphene.
When the graphite intercalation powder is used for producing graphene, the powder material is fed into a graphene generator through a feeder, and under the action of hot gas flow at the temperature of 300-700 ℃, the intercalated perchloric acid generates a large amount of gas, and the formula is shown as follows.
4HClO4＝2H2O+7O2+2Cl2
Because the gas is released and rapidly diffused, the volume of the intercalation between the graphite layers is increased by thousands of times, the van der Waals force between the graphite layers is overcome, the graphite layers are directly stripped in a non-oxidation mode, the graphene layers are opened and the interlayer distance is pulled, and the graphene product with the specific surface area more than 300 times that of the graphite flakes and several layers or single layers is obtained. Chemical bonds among carbon atoms in the product are not damaged, and the graphene has a basically complete structure, so that the graphene has excellent electrochemical performance and physical performance. Therefore, the product can be applied to the electronic fields such as super capacitors, high-energy batteries and the like with obvious defects of graphene obtained by an oxidation method.
Compared with the prior art, the utility model discloses following beneficial effect has:
the solution in the electrolytic cell is continuously circulated, the graphite flake is not fixed in a certain state, so that the multi-angle intercalation of the intercalation medium to the graphite flake is facilitated, and the problems of intercalation dead angle and non-uniform intercalation are avoided. The circulating suspension can discharge bubbles generated in the reaction process in time, and the current density per unit area is prevented from greatly fluctuating due to accumulation in the electrolytic cell. Meanwhile, the intercalation process of the intercalation medium to graphite is completed by using cheap graphite flakes and a liquid medium without strong oxidation, and the graphite intercalation material for producing high-quality graphene is prepared in batches.
Drawings
Fig. 1 is a schematic structural diagram of a graphite intercalation preparation system of embodiment 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The utility model provides a graphite intercalation thing preparation system, the concrete embodiment is as follows.
A graphite intercalation thing preparation system, see figure 1, including the material mixing cauldron 3, slurry pump 4, electrolysis trough 6 and vapour and liquid separator 15 that communicate in proper order, wherein:
the top of the mixing kettle 3 is provided with a graphite feed port 1 and a liquid feed port 2, the materials are uniformly mixed in the mixing kettle 3, and the bottom of the mixing kettle 3 is connected with a slurry pump 4 for pumping slurry suspension into an electrolytic bath 6 through a cooler 5;
the electrolytic cell 6 comprises an anode plate 7 and a cathode plate 8 which are oppositely arranged, and an anode chamber and a cathode chamber which are separated by an anion exchange membrane;
the top of the gas-liquid separator 15 is provided with a tail gas outlet 16 and the bottom is connected to the slurry pump 4, so that the suspension circulates between the slurry pump 4, the cooler 5, the electrolytic bath 6 and the gas-liquid separator 15.
The utility model forces the slurry suspension to circulate through the slurry pump, so that the graphite flake is not fixed in a certain state, thereby facilitating the multi-angle intercalation of the intercalation medium on the graphite flake and avoiding the occurrence of intercalation dead angle and intercalation unevenness; the circulating suspension can discharge bubbles generated in the reaction process in time, and the current density per unit area is prevented from greatly fluctuating due to accumulation in the electrolytic cell.
Further, the anode chamber is a space formed between the anode plate 7 and the anion exchange membrane, and the cathode chamber is a space formed between the cathode plate 8 and the anion exchange membrane; a slurry suspension is arranged in the anode chamber, the anode chamber is a slurry working chamber, and a perchloric acid solution with the concentration of 30-50% can be arranged in the cathode chamber; the feed inlet 10 of the electrolytic cell 6 is positioned at the lower part of the anode chamber; the discharge port 11 of the electrolytic cell 6 is positioned at the upper part of the anode chamber, and the gas outlet 14 is positioned at the top of the cathode chamber, so that the gas in the electrolytic process can be directly discharged, and the problems of electrolytic cell explosion and the like caused by gas accumulation can be prevented. Before the electrolytic cell works, the cathode chamber is filled with acid liquor through the gas outlet 14, and hydrogen generated in the cathode chamber is discharged in normal operation.
Further, the top of the anode plate 7 can be provided with an anode hanging lug 12 for connecting with the positive pole of a power supply; the top of the cathode plate 8 may be provided with a cathode hanger 13 for connecting to the negative pole of a power supply.
Further, the bottom of the gas-liquid separator 15 may be further connected to a reaction slurry pump 17, and the reaction slurry pump 17 is configured to pump the slurry after the reaction to a subsequent treatment system 18.
Further, the post-treatment system 18 may include a filtering device, a washing device, a filter press, and a pneumatic dryer, which are sequentially disposed to purify and dry the graphite intercalation compound.
Further, the cooler 5 is a conventional cooler, preferably a water cooler or an electrically refrigerated cooler.
Preferably, after the completion of the electrolytic reaction, the slurry after the completion of the reaction in the electrolytic bath may be transferred to the gas-liquid separator by being replaced with the acid solution recovered by the filtering device.
The temperature of the circulating feed liquid is controlled to be less than 50 ℃ by a cooler, so that the suspension, the sediment and the liquid form uniform and stable suspension with certain viscosity, the ion flow resistance in the acid liquid in the suspension is increased, the intercalation ions are forced to move towards the solid-phase graphite layers, and the intercalation effect is improved. All be provided with the valve between above-mentioned each device, convenient operation.
The method for preparing the graphite intercalation substance by using the system comprises the following steps:
step 1: sequentially adding a perchloric acid solution with the concentration of 40% and powdery graphite flakes with the size of 80-120 meshes into a mixing kettle, controlling the solid-liquid (volume) ratio to be 1:8, immersing the powdery graphite flakes into the perchloric acid solution by stirring, and uniformly stirring to obtain a suspension;
step 2: the slurry pump pumps the suspension into an anode chamber of the electrolytic cell, and the suspension is cooled by a cooler to keep the temperature of the suspension below 30 ℃;
and step 3: connecting the anode and the cathode of the electrolytic cell with the anode and the cathode of a direct current power supply respectively, and forming an electric field between the two polar plates after electrifying;
and 4, step 4: to pairElectrolyzing the suspension at 10V and 90mA/cm current density2(ii) a The suspension after electrolysis is subjected to gas-liquid separation through a gas-liquid separator, the liquid is sent to a slurry pump, and enters the anode chamber of the electrolytic cell again for electrolysis after passing through a cooler; circulating the suspension among the electrolytic bath, the gas-liquid separator and the cooler by using a slurry pump;
and 5: repeating the step 4 until the suspension is electrolyzed for 5 hours, and finishing the reaction process;
step 6: filtering the final residual suspension liquid of the gas-liquid separator to recover residual acid, then washing with desalted water, press-filtering with a press filter, and then drying with air flow, wherein the moisture of the dried graphite intercalation is controlled to be less than 1%.
During the period, the bubbles generated in the anode chamber are discharged out of the anode chamber together with the circulating liquid, the bubbles are removed by the gas-liquid separator, and the solution is pumped into the lower part of the anode chamber by the pump to form material circulation after the acidity of the solution is adjusted. In the process, a small amount of acid liquor with high concentration is added to keep the concentration of the acid liquor in the electrolytic cell unchanged. The separated gas is discharged after being washed and purified by alkali liquor.
The gas such as hydrogen generated by the cathode in the electrolysis process is collected by the gas collecting pipe and sent to the washing tower to be washed by alkali liquor, and the hydrogen is pressurized by the compressor and can be used as a product for sale.
Respectively carrying out hot air flow expansion reaction on the graphite intercalation substances prepared in the above embodiments at 650 ℃ to obtain graphene, wherein the conductivity of the graphene reaches 1 x 105s/m or more, and a specific surface area of 500m or more2More than g, the graphene is distributed in 5-9 layers, and the diameter of the tablet is 40 microns.
In conclusion, the slurry suspension circulating in the graphite intercalation preparation system of the utility model can discharge the bubbles generated in the reaction process in time, and prevent the current density per unit area from fluctuating greatly due to accumulation in the electrolytic bath. Meanwhile, the intercalation process of the intercalation medium to graphite is completed by using cheap graphite flakes and a liquid medium without strong oxidation, and the graphite intercalation material for producing high-quality graphene is prepared in batches.
The foregoing is a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the present invention, and these improvements and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The utility model provides a graphite intercalation preparation system which characterized in that, including the material mixing cauldron, slurry pump, electrolysis trough and vapour and liquid separator that communicate in proper order, wherein:
the top of the mixing kettle is provided with a graphite feed port and a liquid feed port, materials are uniformly mixed in the mixing kettle, and the bottom of the mixing kettle is connected with the slurry pump and is used for pumping slurry suspension into the electrolytic cell through a cooler;
the electrolytic cell comprises an anode plate and a cathode plate which are oppositely arranged, and an anode chamber and a cathode chamber which are separated by an anion exchange membrane;
the top of vapour and liquid separator is provided with the tail gas export, and the bottom is connected to the slurry pump makes suspension be in circulate between slurry pump, cooler, electrolysis trough and vapour and liquid separator.
2. The system of claim 1, wherein the anode compartment is a space formed between the anode plate and an anion exchange membrane, and the cathode compartment is a space formed between the cathode plate and an anion exchange membrane.
3. The system of claim 2, wherein a slurry suspension is disposed in the anode chamber and a perchloric acid solution having a concentration of 30-50% is disposed in the cathode chamber.
4. The graphite intercalation preparation system of claim 3, wherein the feed inlet of the cell is located in the lower portion of the anode chamber and the discharge outlet of the cell is located in the upper portion of the anode chamber, and the top of the cathode chamber is provided with a gas outlet.
5. The system for preparing the graphite intercalation substance according to claim 1, wherein the top of the anode plate is provided with an anode hanger for connecting with the positive electrode of a power supply; and the top of the negative plate is provided with a negative hanging lug for connecting a negative pole of a power supply.
6. The system for preparing a graphite intercalation material according to claim 1, wherein the bottom of the gas-liquid separator is further connected with a reaction liquid slurry pump for pumping the suspension after the reaction to a subsequent treatment system.
7. The system for preparing a graphite intercalation material according to claim 6, wherein the post-treatment system includes a filtering apparatus, a washing apparatus, a filter press and a pneumatic dryer, which are arranged in this order.
8. The system for preparing a graphite intercalation material according to claim 1, wherein the cooler is a water cooler or an electrically-cooled cooler.
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| CN202020279394.XU CN212050552U (en) | 2020-03-09 | 2020-03-09 | Graphite intercalation thing preparation system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113666367A (en) * | 2021-08-30 | 2021-11-19 | 山东恒华新材料有限公司 | Electrolytic tank for preparing graphite intercalation and preparation method of graphite intercalation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113666367A (en) * | 2021-08-30 | 2021-11-19 | 山东恒华新材料有限公司 | Electrolytic tank for preparing graphite intercalation and preparation method of graphite intercalation |
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