CN112723353B - Graphite intercalation compound and preparation method and application thereof - Google Patents
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Abstract
Providing a method for preparing a graphite intercalation compound, carrying out intercalation reaction on gasified intercalation agent and graphite in a reaction kettle at a temperature higher than the gasification temperature of the intercalation agent, and discharging the intercalation agent in a gas state after the reaction is finished so as to obtain the graphite intercalation compound; wherein the graphite is placed in a container in the reaction kettle, and the intercalation agent is placed at the kettle bottom of the reaction kettle. The invention also provides a graphite intercalation compound prepared by the method and application thereof. The method of the invention adopts the gasified intercalation agent to react with the graphite, and the gaseous intercalation agent is discharged after the reaction is finished. The method does not need to remove redundant intercalation agent, saves the separation step, has less consumption of the intercalation agent and saves water. In the raw material adding stage, the intercalation agent and the raw material graphite are respectively placed in places which are not in mutual contact, and are not in mutual contact, so that the loading and unloading are convenient, the raw material graphite can occupy more than 1/3 of the volume of the reaction kettle, the handling capacity is large, and the industrial mass production is easy.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a method for preparing a graphite intercalation compound and a hydrocarbon oxidation method.
Background
The graphite crystal is a laminated structure of hexagonal ring-shaped (carbon atom spacing is 0.142nm) sheet bodies formed by combining carbon atoms by covalent bonds, the distance between layer surfaces is large (0.335nm), various molecules, atoms or ions are inserted between the layer surfaces of the graphite crystal by a chemical or physical method without damaging the two-dimensional structure, but the layer surface spacing is increased, and a compound which is special for graphite is formed and is called as a graphite intercalation compound, and is also called as a graphite intercalation compound. The graphite intercalation compound has higher conductivity and stable chemical property compared with graphite, and in addition, the graphite intercalation compound can be further processed by a physical and chemical method to obtain high-quality graphene, so the graphite intercalation compound is attracted by people. The existing graphite intercalation compound mostly adopts a double-chamber method and a solvent method, wherein the former has harsh reaction conditions and low yield, and the latter is difficult to obtain low-order products or pure products and has the phenomenon of solvent co-insertion, so that another method, namely a mixing method, is developed in recent years.
A chinese patent (application No. 201310581859.1) discloses a magnetic iron-based graphite intercalation compound and a method thereof, wherein the magnetic iron-based graphite intercalation compound is synthesized by taking graphite micro powder as a raw material through the processes of pre-oxidation, ferric chloride mixing, drying, intercalation, acid washing and reduction. The raw materials used in the invention are cheap and easy to obtain, the method is simple and efficient, the obtained product has good magnetic permeability of the iron-based magnetic substance and good conductivity of the graphite substrate, the intercalation structure of the product endows the iron-based intercalation compound with excellent stability, but the technical process comprises pre-oxidation and later-stage acid washing, the method is complex, and the acid washing has great influence on the environment.
In addition, a chinese patent (application No. 201510186358.2) discloses a synthesis process of a graphite intercalation compound, comprising the following steps: firstly, drying a graphite raw material and a reaction kettle; adding graphite and an intercalation agent into the reaction kettle, wherein the mass ratio of the graphite to the intercalation agent is 1: 0.5-10; stirring and mixing the graphite in the reaction kettle and the intercalation agent uniformly, and pumping out the air in the kettle, wherein the vacuum degree is less than 500 Pa; heating the reaction kettle, continuously reacting for 1-10 hours when the temperature in the kettle body rises to 280-550 ℃, and then cooling to obtain the stable graphite intercalation compound. After the graphite intercalation compound in the kettle body in the step (4) is cooled, the graphite intercalation compound is flushed out of the kettle body by pure water and collected, and then the graphite intercalation compound is washed to be neutral. Although the description indicates that the graphite intercalation compound is cleaned by pure water, the obtained filtrate is pure intercalation solution, can be recycled and has no influence on the environment. However, the intercalation solution has low concentration, great recycling difficulty, especially high energy consumption, and has great practical environmental problems.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of a graphite intercalation compound and a hydrocarbon oxidation method.
The invention provides a method for preparing graphite intercalation compound, which comprises the steps of carrying out intercalation reaction on gasified intercalation agent and graphite in a reaction kettle at a temperature higher than the gasification temperature of the intercalation agent, and discharging gaseous intercalation agent after the reaction is finished so as to obtain the graphite intercalation compound; the graphite is placed in a container in the reaction kettle, and the intercalation agent is placed at the kettle bottom of the reaction kettle.
According to another embodiment of the invention, before the intercalation reaction, the air in the reaction kettle is replaced by nitrogen and then sealed; the volume content of oxygen gas in the reaction kettle is less than 5 percent, and the content of water vapor is less than 1 percent.
According to another embodiment of the present invention, the graphite occupies more than 1/3 of the volume of the reaction vessel, and the intercalation agent is gasified and then introduced into the vessel containing the graphite for intercalation reaction.
According to another embodiment of the present invention, the intercalating agent is used in an amount of 1 to 500 parts by weight, preferably 2 to 200 parts by weight, more preferably 5 to 100 parts by weight, relative to 100 parts by weight of the graphite.
According to another embodiment of the present invention, the graphite is one or more selected from the group consisting of flake graphite, amorphous graphite, artificial graphite, spheroidal graphite, and aphanitic graphite; the intercalation agent is selected from one or more of alkali metals, alkaline earth metals, rare earth metals and alloys thereof, composite halides, metal halides, oxides of halogens, acid anhydrides, halogens and fluorides of halogens.
According to another embodiment of the invention, the intercalation is carried out for 1 to 48 h; the intercalation reaction is carried out at a temperature of 200 ℃ and 500 ℃ under autogenous pressure.
According to another embodiment of the present invention, the method further comprises the step of recovering the intercalant after the completion of the intercalation reaction.
According to another embodiment of the invention, the step of recovering the intercalant comprises adsorbing the gaseous intercalant below the intercalant boiling or sublimation point; the point below the boiling or sublimation point of the intercalant includes where the intercalant is placed.
In a second aspect, the present invention provides a graphite intercalation compound prepared by the above-described process.
The invention also provides application of the graphite intercalation compound prepared by the method as a catalyst in organic matter oxidation reaction.
According to an embodiment of the present invention, the organic substance is selected from one or more of alkanes, aromatic hydrocarbons, ether alcohols and halogenated hydrocarbons; preferably one or more of alkanes and aromatics, more preferably C 1 -C 6 Further preferably butane; the mass ratio of the organic matter to the oxygen is 1: 1-10, preferably 1: 2-8.
According to another embodiment of the present invention, the oxidation reaction is performed at a temperature of 200-500 ℃; preferably, the oxidation reaction is carried out at 250-450 ℃; more preferably, the oxidation reaction is carried out at 300-350 ℃; the oxidation reaction is carried out in a fixed bed reactor with a gas feed volume flow rate of 2 to 500mL/min, preferably 10 to 300mL/min, more preferably 15 to 100mL/min per 100mL of fixed bed reactor volume.
The method of the invention adopts the gasified intercalation agent to react with the graphite, and the intercalation agent in a gas state is discharged after the reaction is finished. The method does not need to remove the redundant intercalating agent by methods such as water washing and the like after the intercalation reaction, saves the steps of water washing, solid-liquid separation and the like, has less loss of the intercalating agent, and saves water. Furthermore, in the raw material adding stage, the intercalation agent and the raw material graphite are respectively placed in places which are not in contact with each other, the materials are not mixed and are not in direct contact with each other, the loading and unloading are convenient, the mixing step is omitted, the raw material graphite can occupy more than 1/3 of the volume of the reaction kettle, the processing capacity is large, and the industrial mass production is easy. The utilization rate of the intercalation agent in the traditional method is generally less than 50 percent, and the utilization rate of the intercalation agent in the method can reach more than 90 percent, thereby obviously improving the utilization rate of the intercalation agent.
The graphite intercalation compound prepared by the invention is used as a catalyst to effectively improve the catalytic activity of the oxidation reaction, particularly the complete oxidation reaction of organic matters, particularly hydrocarbon substances.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to the first aspect of the invention, the invention discloses a method for preparing a graphite intercalation compound, which utilizes gasified intercalation agent and graphite to carry out intercalation reaction at the temperature higher than the gasification temperature of the intercalation agent, and discharges the intercalation agent in a gas state after the reaction is finished. Wherein, the graphite and the intercalation agent can be subjected to intercalation reaction in a reaction kettle, and the graphite is placed in a container in the reaction kettle. The container can be a common liquid-bearing inner member, the inner member capable of bearing liquid in the reaction kettle is a small single-opening container or an inner member which is placed in the reaction kettle and used for containing graphite, and the inner member can be a common beaker, flask, enamel bowl, polytetrafluoroethylene lining, crucible, magnetic boat and the like, or a special inner member specially prepared according to process design. In particular, a small polytetrafluoroethylene liner may be placed in the reaction vessel for intercalation. The intercalation agent is put in the position which is not the position for putting the graphite in the reaction kettle, for example, the intercalation agent is put at the bottom of the reaction kettle. Other placements are possible as long as the intercalant and graphite are not in direct contact prior to reaction. After the reaction kettle is sealed, the temperature is raised to gasify the intercalation agent and the intercalation agent is contacted with graphite to generate intercalation reaction. And the gaseous intercalation agent is discharged after the reaction is finished, so that the obtained graphite intercalation compound does not contain free redundant intercalation agent, an additional separation and purification step is not needed, and the process is simplified. The intercalation agent and the raw material graphite are respectively placed in places which are not in contact with each other, the materials are not mixed and are not in direct contact with each other, the loading and unloading are convenient, the separation step is omitted, and the utilization rate of the intercalation agent can be improved.
The intercalation agent can be gasified first, and then the gasified intercalation agent is introduced into a container containing graphite to carry out intercalation reaction.
Wherein, after the intercalation reaction is finished, the gaseous intercalation agent is discharged, if necessary, the negative pressure exhaust is assisted, or inert gas such as nitrogen is used for replacing the gas in the reaction vessel, and the intercalation agent which is not inserted between the graphite particle layers and is in a free state is separated from the graphite intercalation compound, so as to obtain the graphite intercalation compound. Thus, the obtained graphite intercalation compound does not need to be washed, and can be directly used as a catalyst for oxidation reaction of organic substances such as hydrocarbons.
After the intercalation reaction is finished, the gaseous intercalant is discharged, and the intercalant which is remained on the surface of the graphite intercalation compound and is not inserted into the graphite particle layers in a free state can be recycled. The gaseous intercalant may be adsorbed below the boiling point or sublimation point of the intercalant, and the temperature difference between the site of adsorption and the environment is used to promote the directional flow of the intercalant in the gaseous state to the site of adsorption and to liquefy or desublimate at the site of adsorption for recovery. In order to promote the flow of the gaseous intercalation agent, the environment temperature outside the adsorption position can be increased, the temperature difference between the environment and the adsorption position is increased, the flow of the gaseous intercalation agent is accelerated, and the recovery efficiency and the recovery quality are further improved. Specifically, the temperature at which the intercalant is placed can be lowered by maintaining or slightly raising the temperature at which the graphite is placed (the graphite intercalation compound), such that the intercalant in the free state that is not intercalated between the graphite particle layers diffuses back to where it is placed, or such that the intercalant in the free state that is not intercalated between the graphite particle layers diffuses into a vessel below the boiling or sublimation point of the intercalant, allowing for simple and efficient recycling of this portion of the intercalant.
The raw graphite for intercalation may be any of the commonly used graphite materials, such as one or more of flake graphite, amorphous graphite, artificial graphite, spheroidal graphite, and aphanitic graphite.
The intercalating agent can be any of the commonly used intercalating agents such as one or more of alkali metals, alkaline earth metals, rare earth metals and alloys thereof, complex halides, metal halides, oxides of halogens, anhydrides, halogens, fluorides of halogens other than fluorine, and the like.
The amount of the intercalating agent is 1 to 500 parts by weight, preferably 2 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the raw material graphite in the reaction vessel. The appropriate ratio may be preferred by those skilled in the art, depending on the type of intercalant.
In order to achieve a sufficient reaction, the intercalation may be carried out under non-stirred conditions. The intercalation reaction may also be carried out under stirring.
The intercalation reaction is carried out for 1-48h, the temperature of the intercalation reaction can be 200-500 ℃, and the pressure can be the pressure generated by the gaseous state of the intercalation agent in the reaction kettle.
The volume of graphite added to the reactor may be greater than 1/3 of the reactor volume. In order to achieve a better intercalation effect, the contact area between the graphite and the intercalation agent can be enlarged, for example, the graphite is spread and dispersed as much as possible, and for example, the graphite can move relative to the reaction kettle, for example, auxiliary stirring is performed.
Before intercalation reaction, after replacing air in the reaction kettle with nitrogen, and sealing. Preferably, during the intercalation reaction, the volume content of oxygen gas in the reaction kettle is preferably less than 1%, and the water vapor content is preferably less than 1%.
The graphite intercalation compound prepared by the method can be used as a catalyst in organic matter oxidation reaction. The conversion rate and selectivity of organic oxidation can be improved.
The organic substance may be selected from one or more of alkanes, aromatic hydrocarbons, ether alcohols and halogenated hydrocarbons. Preferably one or more of alkanes and aromatics. More preferably C 1 -C 6 Of (a) an alkane. Still more preferred is butane.
The oxidation of the organic material is carried out at a temperature sufficient to oxidize the organic material, preferably at a temperature of 200-500 ℃. The graphite intercalation compound prepared by the method of the invention is used as a catalyst, has improved catalytic activity, and can obtain higher hydrocarbon substance conversion rate even if the reaction is carried out at lower temperature. Preferably, the oxidation reaction is carried out at 250-450 ℃. More preferably, the oxidation reaction is carried out at 300-350 ℃.
In the oxidation reaction of the organic substance, the mass ratio of the organic substance to the oxygen can be selected according to the actual reaction requirement, and is, for example, 1: 1-10, preferably 1: 2-8.
The oxidation reaction of the organic matter according to the present invention may be carried out in a conventional reactor, preferably in a fixed bed reactor. When the oxidation reaction is carried out in a fixed bed reactor, the volumetric flow rate of the gas feed to the fixed bed reactor may be 2 to 500mL/min, preferably 10 to 300mL/min, and more preferably 15 to 100mL/min, per 100mL of the volume of the fixed bed reactor.
The graphite intercalation compound prepared by the method of the invention can be used as a catalyst for selective oxidation reaction and complete oxidation reaction, and is preferably completely oxidized. The term "complete oxidation reaction" as used herein refers to an oxidation reaction in which organic matter, such as hydrocarbons, is oxidized to carbon dioxide and water; the oxidation to other specific intermediates is a "selective oxidation reaction".
The present invention will be described in detail with reference to examples.
The reagents used in the following synthetic examples, examples and comparative examples are all commercially available chemical reagents unless otherwise specified.
Example 1
Firstly, 40g of flake graphite serving as a raw material is put into a 100ml of polytetrafluoroethylene inner liner, then 15g of intercalation agent ferric chloride is put into the bottom of a 250ml reaction kettle, then 100ml of polytetrafluoroethylene inner liner filled with the flake graphite is put into the reaction kettle, and the reaction kettle is sealed after air in the reaction kettle is replaced by nitrogen. Then heating to 350 ℃ to carry out intercalation reaction under the autogenous pressure at the temperature, opening a vent valve after the reaction time reaches 12h, discharging the residual intercalation agent in the gas phase and recovering for later use, opening the reaction kettle in a hot state and then quickly taking out the polytetrafluoroethylene lining to further obtain the graphite intercalation compound.
Example 2
An intercalated compound was synthesized in the same manner as in example 1, except that the temperature was 250 deg.C, thereby obtaining an intercalated compound according to the present invention.
Example 3
An intercalated compound was synthesized in the same manner as in example 1, except that the reaction time was 2 hours, thereby obtaining an intercalated compound according to the present invention.
Example 4
An intercalated compound was synthesized in the same manner as in example 1, except that the raw material was artificial graphite, thereby obtaining an intercalated compound according to the present invention.
Example 5
An intercalation compound was synthesized in the same manner as in example 1, except that the amount of the raw material flake graphite was 5g, thereby obtaining an intercalation compound according to the invention.
Example 6
An intercalated compound was synthesized in the same manner as in example 1, except that the amount of the raw material intercalant, ferric chloride, was 5g, to thereby obtain an intercalated compound according to the present invention.
Example 7
An intercalated compound was synthesized in the same manner as in example 1, except that the reaction was conducted by direct sealing heating without replacing the air in the reaction vessel with nitrogen, thereby obtaining an intercalated compound according to the present invention.
Example 8
An intercalated compound was synthesized in the same manner as in example 1, except that after the reaction, a vent valve was opened to release the residual intercalant in the gas phase, and finally the liner of the reactor was rapidly taken out in a state of being cooled to 100 ℃ or lower, thereby obtaining a graphite intercalated compound.
Comparative example 1
Putting 40g of flake graphite serving as a raw material and 15g of intercalation agent ferric chloride into a 250ml reaction kettle, preheating to 150 ℃, after stabilizing for a period of time, removing air in the kettle, keeping the vacuum degree of the kettle below 1000Pa, sealing, heating to 350 ℃, carrying out intercalation reaction at the temperature, cooling after the reaction time reaches 12 hours, obtaining a graphite intercalation compound in the reaction kettle, then washing and filtering for more than 3 times by using 2000ml of water until the filtrate is nearly neutral, and carrying out solid-liquid separation to obtain the graphite intercalation compound.
Comparing examples 1-8 with comparative example 1, it can be seen that in the process of the present invention, the gasified intercalant is reacted with graphite and the intercalant is discharged in gaseous form after the reaction is completed. The graphite intercalation compound obtained by the method basically does not contain free intercalation agent on the surface, does not need the extra step of removing the redundant intercalation agent, particularly can save the steps of washing and solid-liquid separation, saves water, greatly reduces the waste water discharge and even can achieve the purpose of no waste water discharge; the effective utilization rate of the intercalation agent is improved, the dosage of the raw material intercalation agent is less, and the raw material consumption cost is reduced. Further, in the raw material adding stage, the intercalation agent and the graphite are respectively placed at places which are not in contact with each other, and are not in direct contact with each other, so that the loading and unloading are convenient, the materials are not mixed, the consumption of the intercalation agent is greatly reduced, the steps of washing and separating are omitted, meanwhile, the raw material graphite can occupy more than 1/3 of the volume of the reaction kettle, the processing capacity is large, and the industrial mass production is easy. The utilization rate of the intercalation agent in the traditional method is generally less than 50 percent (for example, the utilization rate of the intercalation agent in comparative example 1 is only 36 percent), the utilization rate of the intercalation agent in the method can reach more than 90 percent (for example, the utilization rate of the intercalation agent in example 1 is 94 percent), and the utilization rate of the intercalation agent is obviously improved. The intercalator utilization here is calculated as follows:
the utilization ratio of the intercalant is the intercalant mass in the graphite intercalation compound/the total intercalant addition mass multiplied by 100%.
Test examples
This test example is intended to explain the catalytic effect of the graphite intercalation compound produced by the method of the present invention as a catalyst for the oxidation reaction of organic substances.
The following methods were used to evaluate the catalytic performance of the graphite intercalation compounds prepared in examples 1-8 and comparative example 1, and the raw materials ferric chloride and graphite in hydrocarbon oxidation reactions.
0.25g of graphite intercalation compound (or raw materials of ferric chloride and graphite) is filled in a 100mL fixed bed micro quartz tube reactor, quartz sand is sealed at two ends of the micro quartz tube reactor, gas containing normal butane and oxygen (the mass concentration of the normal butane is 0.675 percent, the mass ratio of the normal butane to the oxygen is 1: 5, and the rest is nitrogen serving as carrier gas) is introduced into the reactor at the total gas volume flow rate of 25mL/min for reaction under the conditions that the pressure is 0.5MPa and the temperature is 350 ℃, and the reaction is continuously carried out for 8 hours. The composition of the reaction mixture withdrawn from the reactor was continuously monitored by gas chromatography (sampled and analyzed once per hour), and the n-butane conversion and the selectivity for carbon dioxide as a product were calculated by the following formulas, respectively, wherein the higher the selectivity for carbon dioxide, the better the complete oxidation of the material was indicated.
Table 1 lists the results of the experiment when the reaction was carried out for 5 hours.
N-butane conversion (%) - ((initial concentration of n-butane-concentration of n-butane in the reaction mixture output from the reactor)/initial concentration of n-butane) × 100%;
carbon dioxide selectivity (%) × 100% (concentration of carbon dioxide in the reaction mixture output from the reactor/(initial concentration of n-butane-concentration of n-butane in the reaction mixture output from the reactor) × 4%).
TABLE 1
It can be seen from the results of table 1 that the graphite intercalation compound prepared by the process of the present invention shows improved full oxidation activity in the catalytic full oxidation reaction of organic substances, particularly hydrocarbon substances.
The present invention may, of course, be carried out in other embodiments, and it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A method for preparing graphite intercalation compound, utilize gasification intercalator and graphite to carry on the intercalation reaction at the temperature greater than said intercalator gasification in the reaction kettle, discharge gaseous intercalator after the reaction, and then get said graphite intercalation compound; wherein the graphite is placed in a container in the reaction kettle, and the intercalation agent is placed at the kettle bottom of the reaction kettle;
after the intercalation reaction is finished, the step of recovering the intercalating agent is also included, and the step of recovering the intercalating agent comprises the step of adsorbing the gaseous intercalating agent to a temperature lower than the boiling point or sublimation point of the intercalating agent; the point below the boiling or sublimation point of the intercalant includes where the intercalant is placed.
2. The process of claim 1, wherein the autoclave is hermetically sealed after replacing the atmosphere with nitrogen prior to the intercalation reaction; the volume content of oxygen gas in the reaction kettle is less than 5 percent, and the content of water vapor is less than 1 percent.
3. The process of claim 1 wherein said graphite occupies more than 1/3 of said reactor volume and said intercalant is vaporized and introduced into said vessel containing said graphite for intercalation.
4. The process of claim 1, wherein the intercalant is used in an amount of 1 to 500 parts by weight per 100 parts by weight of the graphite.
5. The process of claim 4, wherein the intercalating agent is used in an amount of 2-200 parts by weight.
6. The process of claim 5, wherein the intercalating agent is present in an amount of 5-100 parts by weight.
7. The method of claim 1, wherein the graphite is one or more selected from the group consisting of flake graphite, amorphous graphite, artificial graphite, spheroidal graphite, and aphanitic graphite; the intercalation agent is selected from one or more of alkali metals, alkaline earth metals, rare earth metals and alloys thereof, complex halides, metal halides, oxides of halogens, acid anhydrides, halogens, fluorides of halogens other than fluorine.
8. The process of claim 1, wherein the intercalation is carried out for 1-48 h; the intercalation reaction is carried out at a temperature of 200 ℃ and 500 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817074A (en) * | 2015-04-20 | 2015-08-05 | 德阳烯碳科技有限公司 | Process for preparing graphite intercalation compound |
| CN107032345A (en) * | 2017-05-12 | 2017-08-11 | 湖南大学 | A kind of preparation method of compound between graphite layers |
| CN107934945A (en) * | 2017-12-07 | 2018-04-20 | 西南交通大学 | A kind of method for preparing magnetic graphene using molysite gas phase intercalation and microwave technology |
| CN108314025A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of preparation method of bilayer graphene intercalation compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101652788B1 (en) * | 2009-02-17 | 2016-09-09 | 삼성전자주식회사 | Graphene sheet comprising intercalation compounds and process for preparing the same |
-
2019
- 2019-10-29 CN CN201911038862.2A patent/CN112723353B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817074A (en) * | 2015-04-20 | 2015-08-05 | 德阳烯碳科技有限公司 | Process for preparing graphite intercalation compound |
| CN107032345A (en) * | 2017-05-12 | 2017-08-11 | 湖南大学 | A kind of preparation method of compound between graphite layers |
| CN107934945A (en) * | 2017-12-07 | 2018-04-20 | 西南交通大学 | A kind of method for preparing magnetic graphene using molysite gas phase intercalation and microwave technology |
| CN108314025A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of preparation method of bilayer graphene intercalation compound |
Non-Patent Citations (2)
| Title |
|---|
| "石墨插层化合物的可控合成及表征";张艳;《中国优秀博士学位论文全文数据库（工程科技Ⅰ辑）》;20110215;第6、9页 * |
| "石墨插层技术的筛选和应用现状";罗立群 等;《现代化工》;20161115;第36卷(第11期);全文 * |
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