CN113666367B - Electrolytic tank for preparing graphite intercalation and preparation method of graphite intercalation - Google Patents
Electrolytic tank for preparing graphite intercalation and preparation method of graphite intercalation Download PDFInfo
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Abstract
The invention relates to an electrolytic cell for preparing a graphite intercalation and a preparation method of the graphite intercalation, belonging to the technical field of electrochemical preparation of graphene. The electrolytic tank comprises a cathode plate, an ion exchange membrane and a composite anode plate which are horizontally arranged from top to bottom, wherein a space formed between the cathode plate and the ion exchange membrane is a cathode chamber, and a space formed between the composite anode plate and the ion exchange membrane is an anode chamber; the composite anode plate is a plate-shaped structure with a metal plate at the bottom and a graphite plate at the upper surface, and is prepared by supporting the metal plate in a press and pressing after mixing graphite flakes and an organic binder. In the invention, the GIC generated in the oxidation process of the composite anode plate still remains in the electric field, and the density and the thickness of the material layer are basically consistent, so that the intercalation of the graphite flake is more thorough, the uniform current density in the electrolytic cell can be ensured, the probability of the intercalation of the graphite flake in the electrolytic cell by the electrolyte ions is uniform, and the consistency of the product is facilitated.
Description
Technical Field
The invention relates to the technical field of graphene electrochemical preparation, and particularly provides an electrolytic cell for preparing a graphite intercalation and a preparation method of the graphite intercalation.
Background
Compared with a redox method, a hydrothermal method, a physical mechanical method and the like, the electrochemical stripping method is a method for preparing graphene with high speed, high efficiency, environmental protection, low cost and high quality. The basic principle of the method is as follows: in different electrolytes, graphite is used as an anode (or a cathode), ions are driven to be inserted into a graphite electrode under the action of an electric field to form a Graphite Intercalation Compound (GIC), so that the volume of the electrode is expanded to reduce the van der Waals force between layers, and the diffusion force of gas is generated through GIC oxidation or reduction reaction to ensure that the microstructure of the graphite layer is expanded in a large proportion and effectively exfoliated, and finally the single-layer or few-layer graphene is obtained through exfoliation.
The method is mainly characterized in that: (1) graphite is generally used as a raw material, so that the price is low and the reserves are abundant; (2) the reaction condition is mild, the operation is simple, and the preparation cost is low; (3) compared with a chemical graphite oxide reduction method, the method reduces the oxidation degree of graphite, so that the original structure of the graphite is kept to a great extent; (4) the experimental parameters such as voltage and current can be accurately adjusted, and the repeatability and controllability of graphene preparation are guaranteed.
At present, the intercalation of graphite cathode is still in the research stage, the graphite anode oxidation method is gradually applied industrially, and the structure of the electrolytic cell for graphite anode oxidation is shown in the figure 1-2. The advantages of the graphite anodizing process are numerous, but the disadvantages are also evident: (1) in the electrolytic process, the graphite anode falls off from the anode plate randomly after forming a Graphite Intercalation Compound (GIC) in the oxidation reaction process, and the layer number and the sheet diameter are uncontrollable, so that the consistency of the product is poor; (2) the detached GIC falls to the bottom of the electrolytic cell, and if the GIC is out of the electric field, no intercalation chance exists. If the GIC is accumulated at the bottom of the electric field, there is also an opportunity for intercalation of the GIC, but the working environment of the whole electric field is changed: the resistance of the conductive ions flowing in some GIC regions is increased, so that the current density in different upper and lower regions in an electric field is not uniform, and the GIC generated by the upper and lower reactions of an anode plate is not uniform. Negatively affects the consistency and yield of graphite intercalation.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an electrolytic cell for preparing a graphite intercalation and a preparation method of the graphite intercalation, and the invention enables the fallen GIC to be continuously remained in an electric field by horizontally arranging a composite anode plate in the electrolytic cell, so that the thicker GIC has the opportunity of further intercalation and the intercalation quality of the GIC is improved; and in the preparation process of the GIC, the current density on each comparable layer is uniform, and the reaction opportunities of unit anode plates are equal.
In order to solve the technical problems, the invention provides the following technical scheme:
in one aspect, the invention provides an electrolytic cell for preparing a graphite intercalation substance, which comprises a cathode plate, an ion exchange membrane and a composite anode plate which are horizontally arranged from top to bottom, wherein a space formed between the cathode plate and the ion exchange membrane is a cathode chamber, and a space formed between the composite anode plate and the ion exchange membrane is an anode chamber;
the composite anode plate is a plate-shaped structure with a metal plate at the bottom and a graphite plate at the upper surface, and is prepared by supporting a metal plate in a press after mixing graphite flakes and an organic binder;
the metal plate at the bottom of the composite anode plate is communicated with the anode of a power supply through an anode plate joint embedded at the bottom of the electrolytic cell; the negative plate is directly communicated with the negative electrode of the power supply.
Furthermore, metal mesh plates are arranged on the upper surface and the lower surface of the ion exchange membrane and are embedded in the electrolytic bath. The ion exchange membrane allows charged ions in the electrolyte to pass through, whereas bubbles in the solution cannot pass through but are discharged with the liquid stream from the outlet.
Further, the cathode plate is a graphite electrode plate.
Furthermore, one end of the anode chamber and one end of the cathode chamber are respectively provided with an anolyte inlet and a catholyte inlet, and the other end of the anode chamber and the other end of the cathode chamber are respectively provided with an anolyte gas outlet and a catholyte gas outlet.
On the other hand, the invention also provides a preparation method of the graphite intercalation substance, which is used for preparing the graphene intercalation substance by using the electrolytic cell and specifically comprises the following steps:
step 1: preparing a composite anode plate:
firstly, uniformly mixing graphite flakes with an organic binder, then uniformly paving the mixture on a metal plate, and pressing the mixture into a plate-shaped structure by using a press to obtain a composite anode plate;
and 2, step: assembling the electrolytic cell by using the composite anode plate in the step 1;
and 3, step 3: adding electrolyte into the anode chamber and the cathode chamber through an anolyte inlet and a catholyte inlet respectively until a small amount of electrolyte continuously flows out from an anolyte gas outlet and a catholyte gas outlet respectively, and fixing the flow rate of the electrolyte;
and 4, step 4: connecting the two polar plates with a DC power supply, controlling the voltage of the electrolytic bath to 3-8VThe flow density is 30-100mA/cm 2 Electrolyzing for 1-5 hours;
and 5: after electrolysis, stopping supplying electrolyte to the electrolytic cell, opening the electrolytic cell, taking out the composite anode plate, collecting the graphite intercalation on the composite anode plate, washing the graphite intercalation with deionized water for 4-7 times, filtering, and drying at low temperature.
Further, in the step 1, the organic binder is acrylic resin, and the amount of the organic binder is 0.2-0.5wt% of the graphite flakes; the particle size of the graphite flake is 80-200 meshes.
Further, the surface of the metal plate is a titanium plate plated with ruthenium; the thickness is 2mm; the thickness of the composite anode plate is 10-20mm.
Further, in the step 3, the electrolyte is a mixture of an acid solution and an auxiliary reagent, and the acid solution is sulfuric acid and/or perchloric acid; the auxiliary reagent is oxalic acid, and the addition amount of the auxiliary reagent is 10-20wt% of the total amount of the electrolyte; the acid liquor concentration is 50-70%.
Preferably, in the step 5, the drying temperature is 80-100 ℃.
In the invention, the cathode chamber and the anode chamber are clamped by a mechanical device, the two chambers are sealed by sealing rings, and a small amount of electrolyte is controlled to enter the electrolytic cell from the upper part and the lower part of the ion exchange membrane during operation, so that the concentration of the electrolyte in the electrolytic cell is kept consistent, the temperature is not required to change greatly, and bubbles generated by electrolysis can be taken out at any time.
When in normal operation, the composite anode plate in the electrolytic tank is arranged, and the metal plate at the bottom of the anode plate is attached to the anode plate joint and has the electric conduction capability. Adding an auxiliary reagent into a mixed inorganic salt (or acid or a mixed solution thereof) solution to serve as an electrolyte, adding the electrolyte into the electrolytic cell from an inlet of the electrolytic cell through an electrolyte pump, and continuously flowing out a small amount of electrolyte from a gas-liquid outlet of the cathode and a gas-liquid outlet of the anode.
Connecting the two electrode plate connectors with a DC power supply according to the wiring requirement, controlling the voltage of the electrolytic cell to be 3-8V, and controlling the current density to be 30-100mA/cm 2 。
The liquid and gas discharged from the cathode and anode gas-liquid outlets are separated by the gas-liquid separator, the electrolyte returns to the electrolyte storage tank, and the cathode gas can be recovered as fuel gas.
After electrolysis for a period of time, the dropped GIC material is accumulated on the anode plate, so that the resistance of the conductive ion movement is increased, the total current is possibly reduced, the voltage can be regulated within a limited voltage range, and the current density is ensured to be basically at a constant value.
And after the anode graphite plate is reacted, continuously electrolyzing for 1-5 hours, stopping supplying the electric conduction liquid by the electrolytic cell, opening the electrolytic cell, collecting GIC in the anode chamber, and then carrying out subsequent processing on the graphene intermediate product.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the process of oxidizing the composite anode plate, the generated GIC still remains in an electric field, and the density and the thickness of a material layer are basically consistent, so that the intercalation of the graphite flake is more thorough, the uniform current density in the electrolytic cell can be ensured, the probability of the intercalation of the graphite flake in the electrolytic cell by electrolyte ions is uniform, and the consistency of products is facilitated.
(2) The composite anode plate is formed by compounding a metal plate and graphite flakes, and the metal plate can continuously provide stable electrolysis conditions for GIC intercalation after the graphite oxidation reaction is finished.
Drawings
FIG. 1 is a front view of a prior art electrolytic cell construction;
FIG. 2 is a side view of a prior art electrolytic cell construction;
FIG. 3 is a schematic view of the structure of the electrolytic cell before electrolysis according to the present invention;
FIG. 4 is a schematic view of the electrolytic cell structure after electrolysis according to 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 is made with reference to the accompanying drawings and specific embodiments.
The materials used in the present invention are commercially available unless otherwise specified.
Example 1
An electrolytic cell for preparing graphite intercalation, as shown in fig. 3-4, comprises a cathode plate 1, an ion exchange membrane 2 and a composite anode plate 3 which are horizontally arranged from top to bottom, wherein a space formed between the cathode plate 1 and the ion exchange membrane 2 is a cathode chamber 4, and a space formed between the composite anode plate 3 and the ion exchange membrane 2 is an anode chamber 5; the composite anode plate 3 is a plate-shaped structure which is prepared by mixing graphite flakes with an organic binder, supporting a metal plate 6 in a press and pressing the mixture into a plate-shaped structure with a metal plate 6 at the bottom and a graphite plate 7 at the top;
the metal plate 6 at the bottom of the composite anode plate 3 is communicated with the anode of a power supply through an anode plate joint 8 embedded at the bottom of the electrolytic cell; the cathode plate 1 is directly communicated with the cathode of the power supply.
In the process of oxidizing the composite anode plate, the generated GIC still remains in an electric field, and the density and the thickness of a material layer are basically consistent, so that the intercalation of the graphite flake is more thorough, the uniform current density in the electrolytic cell can be ensured, the probability of the intercalation of the graphite flake in the electrolytic cell by electrolyte ions is uniform, and the consistency of products is facilitated. The composite anode plate is formed by compounding a metal plate and graphite flakes, and the metal plate can continuously provide stable electrolysis conditions for GIC intercalation after the graphite oxidation reaction is finished.
In the prior art, an anodic graphene oxide electrolytic cell is structurally shown in fig. 1-2, a cathode plate 1 'and an anode plate 3' are vertically placed in the electrolytic cell, the graphite anode plate is at the anode, and after intercalation, a graphite intercalation substance peels off a graphite plate and is accumulated at the bottom of the electrolytic cell, so that the intercalation is uneven.
Furthermore, metal mesh plates 9 are arranged on the upper surface and the lower surface of the ion exchange membrane 2 and are embedded in the electrolytic cell. The ion exchange membrane 2 allows charged ions in the electrolyte to pass through, whereas bubbles in the solution cannot pass through but are discharged with the liquid flow from the outlet. The cathode plate 1 is a graphite electrode plate.
Furthermore, one end of the anode chamber 5 and one end of the cathode chamber 4 are respectively provided with an anolyte inlet 10 and a catholyte inlet 11, and the other end of the anode chamber 5 and the other end of the cathode chamber 4 are respectively provided with an anolyte gas outlet 12 and a catholyte gas outlet 13. The liquid and gas discharged from the cathode and anode outlets are separated by gas-liquid separator, the electrolyte is returned to the electrolyte storage tank, and the cathode gas can be used as fuel gas for recovery.
In the invention, the cathode chamber and the anode chamber are clamped by a mechanical device, the two chambers are sealed by sealing rings, and a small amount of electrolyte is controlled to enter the electrolytic cell from the upper part and the lower part of the ion exchange membrane during operation, so that the concentration of the electrolyte in the electrolytic cell is kept consistent, the temperature is not required to change greatly, and bubbles generated by electrolysis can be taken out at any time. When in normal operation, the composite anode plate in the electrolytic tank is arranged, and the metal plate at the bottom of the anode plate is attached to the anode plate joint and has the electric conduction capability. Adding an auxiliary reagent into a mixed inorganic salt (or acid or mixed solution thereof) solution to serve as an electrolyte, adding the electrolyte into an electrolytic cell from an inlet of the electrolytic cell through an electrolyte pump, and continuously flowing out a small amount of electrolyte from a gas-liquid outlet of a cathode to a gas-liquid outlet of an anode.
Example 2
A preparation method of a graphite intercalation substance, which utilizes the electrolytic cell to prepare the graphene intercalation substance, comprises the following steps:
step 1: preparing a composite anode plate:
firstly, uniformly mixing graphite flakes (with the grain diameter of 80-200 meshes) with organic binder acrylic resin, wherein the use amount of the organic binder is 0.2wt% of the graphite flakes. Then uniformly paving the mixture on a 2mm metal plate (ruthenium is plated on the surface of a titanium plate), and pressing the mixture into a plate-shaped structure with the thickness of 10mm by using a press machine to obtain a composite anode plate;
and 2, step: placing the composite anode plate in the step 1 into the electrolytic cell of the embodiment 1;
and step 3: electrolyte is respectively added into the anode chamber and the cathode chamber through an anolyte inlet and a catholyte inlet until a small amount of electrolyte continuously flows out from an anolyte gas outlet and a catholyte gas outlet respectively, and the flow rate of the electrolyte is fixed; the electrolyte is a mixture of acid liquor and an auxiliary reagent, and the acid liquor is sulfuric acid; the auxiliary reagent is oxalic acid, and the addition amount of the auxiliary reagent is 15wt% of the total amount of the electrolyte; the acid solution concentration is 50%.
And 4, step 4: connecting the two electrode plates with a DC power supply, controlling the voltage of the electrolytic bath to 5V and the current density to 50mA/cm 2 Electrolyzing for 3 hours;
and 5: after electrolysis, stopping supplying electrolyte to the electrolytic cell, opening the electrolytic cell, taking out the composite anode plate, collecting the graphite intercalation on the composite anode plate, washing the graphite intercalation with deionized water for 4-7 times, filtering, and drying at the low temperature of 80 ℃.
Example 3
A preparation method of a graphite intercalation substance, which utilizes the electrolytic cell to prepare the graphene intercalation substance, comprises the following steps:
step 1: preparing a composite anode plate:
firstly, uniformly mixing graphite flakes (with the grain diameter of 80-200 meshes) with organic binder acrylic resin, wherein the dosage of the organic binder is 0.3wt% of the graphite flakes. Then uniformly paving the mixture on a 2mm metal plate (plating ruthenium on the surface of a titanium plate), and pressing the mixture into a plate-shaped structure with the thickness of 12mm by using a press to obtain a composite anode plate;
step 2: placing the composite anode plate in the step 1 into the electrolytic cell of the embodiment 1;
and step 3: adding electrolyte into the anode chamber and the cathode chamber through an anolyte inlet and a catholyte inlet respectively until a small amount of electrolyte continuously flows out from an anolyte gas outlet and a catholyte gas outlet respectively, and fixing the flow rate of the electrolyte; the electrolyte is a mixture of acid liquor and an auxiliary reagent, and the acid liquor is perchloric acid; the auxiliary reagent is oxalic acid, and the addition amount of the auxiliary reagent is 10wt% of the total amount of the electrolyte; the acid liquor concentration is 60%.
And 4, step 4: connecting the two electrode plates with a DC power supply, controlling the voltage of the electrolytic tank to 3V and the current density to 30mA/cm 2 Electrolyzing for 1 hour;
and 5: after electrolysis, stopping supplying electrolyte to the electrolytic cell, opening the electrolytic cell, taking out the composite anode plate, collecting the graphite intercalation on the composite anode plate, washing the graphite intercalation for 4-7 times by using deionized water, filtering, and drying at the low temperature of 90 ℃.
Example 4
A preparation method of a graphite intercalation substance, which utilizes the electrolytic cell to prepare the graphene intercalation substance, comprises the following steps:
step 1: preparing a composite anode plate:
firstly, uniformly mixing graphite flakes (with the grain diameter of 80-200 meshes) with organic binder acrylic resin, wherein the use amount of the organic binder is 0.4wt% of the graphite flakes. Then uniformly paving the mixture on a 2mm metal plate (ruthenium is plated on the surface of a titanium plate), and pressing the mixture into a plate-shaped structure with the thickness of 15mm by using a press machine to obtain a composite anode plate;
step 2: placing the composite anode plate in the step 1 in an electrolytic tank similar to the electrolytic tank in the embodiment 1;
and step 3: electrolyte is respectively added into the anode chamber and the cathode chamber through an anolyte inlet and a catholyte inlet until a small amount of electrolyte continuously flows out from an anolyte gas outlet and a catholyte gas outlet respectively, and the flow rate of the electrolyte is fixed; the electrolyte is a mixture of acid liquor and an auxiliary reagent, and the acid liquor is equal to sulfuric acid and perchloric acid; the auxiliary reagent is oxalic acid, and the addition amount of the auxiliary reagent is 20wt% of the total amount of the electrolyte; the acid solution concentration is 70%.
And 4, step 4: connecting the two electrode plates with a DC power supply, controlling the voltage of the electrolytic bath to 6V and the current density to 80mA/cm 2 When electrolyzing for 5 hours;
and 5: after electrolysis, stopping supplying electrolyte to the electrolytic cell, opening the electrolytic cell, taking out the composite anode plate, collecting the graphite intercalation on the composite anode plate, washing the graphite intercalation with deionized water for 4-7 times, filtering, and drying at the low temperature of 100 ℃.
Example 5
A preparation method of a graphite intercalation substance utilizes the electrolytic cell to prepare the graphene intercalation substance, and specifically comprises the following steps:
step 1: preparing a composite anode plate:
firstly, uniformly mixing graphite flakes (with the grain diameter of 80-200 meshes) with organic binder acrylic resin, wherein the dosage of the organic binder is 0.5wt% of the graphite flakes. Then uniformly paving the mixture on a 2mm metal plate (plating ruthenium on the surface of a titanium plate), and pressing the mixture into a plate-shaped structure with the thickness of 20mm by using a press to obtain a composite anode plate;
step 2: placing the composite anode plate in the step 1 in an electrolytic tank similar to the electrolytic tank in the embodiment 1;
and 3, step 3: electrolyte is respectively added into the anode chamber and the cathode chamber through an anolyte inlet and a catholyte inlet until a small amount of electrolyte continuously flows out from an anolyte gas outlet and a catholyte gas outlet respectively, and the flow rate of the electrolyte is fixed; the electrolyte is a mixture of acid liquor and an auxiliary reagent, and the acid liquor is sulfuric acid and/or perchloric acid; the auxiliary reagent is oxalic acid, and the addition amount of the auxiliary reagent is 18wt% of the total amount of the electrolyte; the acid liquor concentration is 70%.
And 4, step 4: connecting the two electrode plates with a DC power supply, controlling the voltage of the electrolytic tank to 8V and the current density to 100mA/cm 2 Electrolyzing for 4 hours;
and 5: after electrolysis, stopping supplying electrolyte to the electrolytic cell, opening the electrolytic cell, taking out the composite anode plate, collecting the graphite intercalation on the composite anode plate, washing the graphite intercalation for 4-7 times by using deionized water, filtering, and drying at the low temperature of 90 ℃.
Example 6
A process for preparing graphite intercalation materials, step 4 electrolysis time 4 hours, the rest conditions were the same as in example 4.
Example 7
A graphite intercalation preparation method, step 4 electrolysis time is 3 hours, the other conditions are the same as example 4.
To further illustrate the beneficial effects of the present invention, a comparative example was constructed as follows, only taking example 4 as an example, for space limitation.
Comparative example 1
The composite anode plate prepared in example 4 was placed in an electrolytic cell as shown in FIGS. 1-2 for electrolysis according to the prior art, and the electrolysis conditions were the same as in example 4.
Comparative example 2
The composite anode plate of example 4 was replaced with a graphite plate of the same thickness, and the rest of the conditions were the same as in example 4.
The graphite intercalation materials prepared in the above examples 1 to 7 and comparative examples 1 to 2 were subjected to thermal decomposition at 900 ℃ in an inert gas or vacuum environment to obtain graphene powder.
The performance of the graphene powder is detected, and the results are shown in table 1.
TABLE 1
| Serial number | Electrical conductivity (s/m) | Specific surface area (m) 2 /g) | Number of layers |
| Example 2 | 75000 | 174 | 1-7 |
| Example 3 | 78000 | 156 | 1-6 |
| Example 4 | 70000 | 300 | 1-3 |
| Example 5 | 74000 | 287 | 1-5 |
| Example 6 | 76000 | 248 | 1-5 |
| Example 7 | 80000 | 180 | 1-7 |
| Comparative example 1 | 75000 | 61 | 3-12 |
| Comparative example 2 | 65000 | 103 | 2-10 |
As can be seen from table 1, in the electrolytic cell of the present invention, the graphite flakes and the metal plate are compounded to prepare the composite anode plate, and the composite anode plate is horizontally placed at the bottom of the electrolytic cell, such that a stable electrolysis condition can be continuously provided, an intercalation material is prevented from being accumulated at the bottom of the electrolytic cell, uniform intercalation of the graphite flakes by electrolyte ions is ensured, a specific surface area for preparing graphene can be effectively increased, and the number of layers for preparing graphene is reduced.
Different from the prior art that electrodes are vertically placed in an electrolytic cell (comparative example 1), in the prior art, graphite flakes can settle at the bottom of the electrolytic cell after intercalation, so that the current density distribution in the electrolytic cell is uneven, the intercalation reaction is uneven, and the uniformity of graphene is poor.
Compared with comparative example 2, the existence of the metal plate can ensure the electrolysis condition and improve the intercalation uniformity.
In conclusion, the dropped GICs are continuously remained in the electric field by horizontally arranging the composite anode plate in the electrolytic cell, so that thicker GICs have the opportunity of further intercalation, and the intercalation quality of the GICs is improved.
While the foregoing is directed to the preferred embodiment of the present invention, it will be appreciated by those skilled in the art that various changes and modifications may be made therein without departing from the principles of the invention as set forth in the appended claims.
Claims (8)
1. The electrolytic cell for preparing the graphite intercalation substances is characterized by comprising a cathode plate, an ion exchange membrane and a composite anode plate which are horizontally arranged from top to bottom, wherein a space formed between the cathode plate and the ion exchange membrane is a cathode chamber, and a space formed between the composite anode plate and the ion exchange membrane is an anode chamber;
the composite anode plate is a plate-shaped structure with a metal plate at the bottom and a graphite plate at the upper surface, and is prepared by supporting a metal plate in a press after mixing graphite flakes and an organic binder;
the metal plate at the bottom of the composite anode plate is communicated with the positive electrode of a power supply through an anode plate joint embedded at the bottom of the electrolytic tank; the negative plate is directly communicated with the negative electrode of the power supply;
the upper surface and the lower surface of the ion exchange membrane are both provided with metal mesh plates which are embedded in the electrolytic bath.
2. The electrolyzer of claim 1 characterized in that the cathode plate is a graphite electrode plate.
3. The electrolyzer for preparing a graphite intercalation material according to claim 2, characterized in that one end of the anode chamber and the cathode chamber is provided with an anolyte inlet and a catholyte inlet, respectively, and the other end of the anode chamber and the cathode chamber is provided with an anolyte gas outlet and a catholyte gas outlet, respectively.
4. A method for preparing a graphite intercalation, characterized in that the method for preparing a graphite intercalation by using the electrolytic cell of any one of claims 1 to 3 comprises the following steps:
step 1: preparing a composite anode plate:
firstly, uniformly mixing graphite flakes with an organic binder, then uniformly paving the mixture on a metal plate, and pressing the mixture into a plate-shaped structure by using a press to obtain a composite anode plate;
step 2: assembling the electrolytic cell of any one of claims 1-3 using the composite anode plate of step 1;
and 3, step 3: electrolyte is respectively added into the anode chamber and the cathode chamber through an anolyte inlet and a catholyte inlet until a small amount of electrolyte continuously flows out from an anolyte gas outlet and a catholyte gas outlet respectively, and the flow rate of the electrolyte is fixed;
and 4, step 4: connecting the two electrode plates with a DC power supply, controlling the voltage of the electrolytic bath to 3-8V and the current density to 30-100mA/cm 2 Electrolyzing for 1-5 hours;
and 5: after electrolysis, stopping supplying electrolyte to the electrolytic cell, opening the electrolytic cell, taking out the composite anode plate, collecting the graphite intercalation on the composite anode plate, washing the graphite intercalation for 4-7 times by using deionized water, filtering and drying at low temperature.
5. The method for preparing a graphite intercalation material according to claim 4, wherein in step 1, the organic binder is acrylic resin, and the amount of the organic binder is 0.2-0.5wt% of the graphite flake; the particle size of the graphite flake is 80-200 meshes.
6. The method for preparing a graphite intercalation material according to claim 4, wherein the metal plate is a titanium plate with ruthenium plated on the surface; the thickness is 2mm; the thickness of the composite anode plate is 10-20mm.
7. The method for preparing a graphite intercalation product according to claim 4, wherein in step 3, the electrolyte is a mixture of an acid solution and an auxiliary reagent, the acid solution is sulfuric acid and/or perchloric acid; the auxiliary reagent is oxalic acid, and the addition amount of the auxiliary reagent is 10-20wt% of the total amount of the electrolyte; the acid liquor concentration is 50-70%.
8. The method for preparing a graphite intercalation material according to claim 4, wherein the baking temperature in step 5 is 80-100 ℃.
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| JPS5690989A (en) * | 1979-12-14 | 1981-07-23 | Nobuatsu Watanabe | Manufacture of interlaminar compound of graphite |
| US8524067B2 (en) * | 2007-07-27 | 2013-09-03 | Nanotek Instruments, Inc. | Electrochemical method of producing nano-scaled graphene platelets |
| CN104477892B (en) * | 2014-12-12 | 2016-08-24 | 盐城市新能源化学储能与动力电源研究中心 | Flaky graphite alkene device prepared by the preparation method of a kind of flaky graphite alkene and use the method |
| US11168404B2 (en) * | 2016-02-17 | 2021-11-09 | Global Graphene Group, Inc. | Electrochemical method of producing single-layer or few-layer graphene sheets |
| CN109573993A (en) * | 2019-01-18 | 2019-04-05 | 上海华普汽车有限公司 | A kind of preparation method of multi-layer graphene |
| CN112239203B (en) * | 2019-07-16 | 2022-09-09 | 中国科学院上海微***与信息技术研究所 | Electrochemical preparation method of porous graphene dispersion liquid |
| CN110316729B (en) * | 2019-08-14 | 2020-10-30 | 中国科学院兰州化学物理研究所 | Method for preparing graphene based on high-concentration organic salt aqueous solution electrochemical intercalation |
| CN212050552U (en) * | 2020-03-09 | 2020-12-01 | 山东恒华新材料有限公司 | Graphite intercalation thing preparation system |
| CN113060722A (en) * | 2021-03-17 | 2021-07-02 | 中国科学院上海微***与信息技术研究所 | Electrochemical preparation method of high-quality graphene material |
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