CN115432697B - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN115432697B CN115432697B CN202210975330.7A CN202210975330A CN115432697B CN 115432697 B CN115432697 B CN 115432697B CN 202210975330 A CN202210975330 A CN 202210975330A CN 115432697 B CN115432697 B CN 115432697B
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Abstract
The invention provides a preparation method of graphene, which comprises the steps of introducing carbon dioxide-containing gas into gallium-based liquid alloy at a certain reaction temperature, and regulating and controlling the reaction temperature and the flow rate of the gas to control the generation of graphene, wherein the amount of the gallium-based liquid alloy is excessive relative to the amount of carbon dioxide in the gas. The invention uses gallium in gallium-based liquid metal to make CO 2 Activated at room temperature to decompose into solid carbon, the process utilizes CO 2 Synthesizing graphene can enable the mass production of graphene, and simultaneously can reduce CO emission to the atmosphere 2 . The method has the advantages of high yield, no pollution, simple operation and the like.
Description
Technical Field
The invention relates to graphene, in particular to a preparation method of graphene.
Background
Graphene is a novel two-dimensional inorganic nano material and has wide application prospects in various fields of chemistry, physics, materials, electronics and the like. The methods for preparing graphene, which are widely used at present, can be roughly divided into the following categories: mechanical stripping, epitaxial growth, chemical vapor deposition, chemical synthesis, reduction of graphene oxide, and longitudinal cutting of carbon tubes. However, none of the above methods is suitable for mass production, which is an important factor restricting the wide application and industrial production of graphene.
Disclosure of Invention
The invention aims to provide a preparation method of graphene, which solves the current situation that the large-scale production of graphene cannot be realized by the existing scheme.
In order to achieve the above purpose, the present invention proposes the following technical scheme:
a preparation method of graphene comprises the steps of introducing carbon dioxide-containing gas into gallium-based liquid alloy at a certain reaction temperature, and regulating and controlling the reaction temperature and the flow rate of the gas to control the generation of graphene, wherein the amount of the gallium-based liquid alloy is excessive relative to the amount of carbon dioxide in the gas.
Further, under the condition that the amount of carbon dioxide in the gas is fixed, regulating and controlling the flow rate of the gas to be smaller than or equal to a certain preset flow rate optimal value at a certain reaction temperature, wherein the certain preset flow rate optimal value is the flow rate when the flow rate reaches a peak value of the graphene generating rate at a certain corresponding reaction temperature.
Further, the optimal flow rate value is inversely related to the reaction temperature.
Further, the peak rate of graphene formation is positively correlated with the reaction temperature.
Further, the reaction temperature is 80-400 ℃, and the flow rate of the gas is 20-400 ml/min according to the carbon dioxide therein.
Further, when the reaction temperature is 200 ℃, the flow rate of the gas is 30 ml/min-450 ml/min based on the carbon dioxide therein, and the optimal value of the flow rate is 200ml/min based on the carbon dioxide therein.
Further, when the reaction temperature is 100 ℃, the flow rate of the gas is 45 ml/min-550 ml/min based on carbon dioxide therein, and the optimal flow rate is 280ml/min based on carbon dioxide therein.
Further, under the condition that the amount of carbon dioxide in the gas is fixed, regulating and controlling the reaction temperature to be less than or equal to a certain preset temperature optimal value under the condition that the flow rate of a certain gas is fixed, wherein the certain preset temperature optimal value is the temperature when the flow rate of a certain corresponding gas reaches the peak value of the graphene generating rate.
Further, the temperature optimum is positively correlated to the flow rate of the gas.
Further, the peak rate of graphene generation is positively correlated to the flow rate of the gas.
Further, the optimum value of the temperature is 300℃when the flow rate of the gas is 150ml/min in terms of carbon dioxide therein.
Further, the optimum value of the temperature is 220℃when the flow rate of the gas is 250ml/min in terms of carbon dioxide therein.
The beneficial effects are that:
according to the technical scheme, the preparation method of the graphene is provided, carbon dioxide-containing gas is introduced into the gallium-based liquid alloy at a certain reaction temperature, and the reaction temperature and the flow rate of the gas are regulated so as to control the generation of the graphene, wherein the amount of the gallium-based liquid alloy is excessive relative to the amount of carbon dioxide in the gas.
Through the scheme, the gallium in the gallium-based liquid metal is utilized to make CO 2 Activated at room temperature to decompose into solid carbon, the process utilizes CO 2 Synthesizing graphene can enable the mass production of graphene, and simultaneously can reduce CO emission to the atmosphere 2 . The method has the advantages of high yield, no pollution, simple operation and the like.
It should be understood that all combinations of the foregoing concepts, as well as additional concepts described in more detail below, may be considered a part of the inventive subject matter of the present disclosure as long as such concepts are not mutually inconsistent.
The foregoing and other aspects, embodiments, and features of the present teachings will be more fully understood from the following description, taken together with the accompanying drawings. Other additional aspects of the invention, such as features and/or advantages of the exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of the embodiments according to the teachings of the invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a morphology of a graphene material obtained according to a method in an embodiment of the present invention in a liquid metal;
fig. 2 is a graph of graphene morphology obtained according to a method in an embodiment of the present invention.
Detailed Description
For a better understanding of the technical content of the present invention, specific examples are set forth below, along with the accompanying drawings.
Aspects of the invention are described in this disclosure with reference to the drawings, in which are shown a number of illustrative embodiments. The embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be understood that the various concepts and embodiments described above, as well as those described in more detail below, may be implemented in any of a number of ways, as the disclosed concepts and embodiments are not limited to any implementation. Additionally, some aspects of the disclosure may be used alone or in any suitable combination with other aspects of the disclosure.
The method aims at solving the problems that the production process of graphene in the prior art, such as the traditional chemical method (such as methane decomposition method), cannot be suitable for large-scale industrial production, and the main reason for analysis is that the dynamics speed is extremely low, solid surface deposition is needed, so that stable-scale production cannot be realized.
The liquid metal decomposition has the great advantage that the mobility of the liquid metal and the non-wettability between the graphene and the liquid metal are utilized, so that the graphene generated by the reaction can migrate to the surface, is independent of solid surface deposition, is convenient to collect, realizes continuous production, and is a possible way for realizing industrial mass production.
However, the decomposition of carbon dioxide products by liquid metal may be a variety of, including but not limited to, weakening graphene, graphite, etc., which is an important factor limiting the realization of mass production in the manner described above. The examples of the present invention have found that the different forms of the product described above are related to the kinetics of the decomposition reaction, mainly the mechanism of carbon atom deposition during chemical decomposition. In order to quickly obtain high-purity graphene in a liquid metal decomposition process, an equilibrium point between the free energy state of a unit volume of single-layer graphene and the interface energy of graphene/liquid metal can be established according to the energy states of different carbon atom structures, so that a process interval for generating graphene is obtained, and the core index in the process is found to be the reaction temperature and the carbon dioxide concentration. Based on the above-mentioned thought, the reaction temperature and carbon dioxide concentration can be adjusted as required to produce other products.
Based on the above thought, the present embodiment provides a preparation method of graphene, which includes:
and introducing carbon dioxide-containing gas into the gallium-based liquid alloy at a certain reaction temperature, and regulating the reaction temperature and the flow rate of the gas to control the generation of graphene, wherein the amount of the gallium-based liquid alloy is excessive relative to the amount of carbon dioxide in the gas.
The above-mentioned carbon dioxide concentration is the total amount of carbon dioxide relative to the content of the gallium-based liquid alloy, provided that the amount of the gallium-based liquid alloy is excessive relative to the amount of carbon dioxide in the gas. Because the reaction is that the gas is introduced into the liquid, the concentration parameter is converted into the flow rate of the gas so as to be convenient to control. The gas may be pure carbon dioxide gas or a mixed gas containing carbon dioxide and other inert gases. However, since the control of the amount of the reactant is based on the amount of carbon dioxide, even though the mixed gas is introduced, the flow rate of the gas is calculated as carbon dioxide therein, that is, assuming that the carbon dioxide content of the mixed gas is 50%, the flow rate of the gas is calculated as V1 as carbon dioxide therein, and the flow rate of the gas is actually 2V1 for convenience of description. A higher gas flow rate results in a shorter time for the carbon dioxide to be fully charged into the liquid alloy, whereas a lower gas flow rate results in a longer time for the carbon dioxide to be fully charged into the liquid alloy.
Compared with the traditional catalytic method for graphene production, the method has the advantages that the graphene production rate is controllable, the graphene is convenient to collect, continuous production can be realized, the process temperature is lower, and the energy consumption, the process and the equipment cost are extremely low.
In the above embodiment, when the amount of carbon dioxide is fixed, the total amount of theoretically generated graphene is determined, and on the basis of this, in order to obtain a higher graphene production rate, two variables, namely, a reaction temperature and a gas flow rate, are mainly involved.
The first regulation mode is to control the reaction temperature unchanged and regulate the flow velocity of the gas
Specifically, in this embodiment, under the condition that the amount of carbon dioxide in the gas is fixed, the flow rate of the gas is regulated and controlled to be less than or equal to a certain preset flow rate optimal value at a certain reaction temperature, where the certain preset flow rate optimal value is a flow rate when reaching a peak rate of graphene generation at a certain corresponding reaction temperature.
Therefore, it is preferable that the flow rate of the non-gas is larger than the optimum value of the flow rate, and graphite is easily generated.
And, the optimal flow rate value is inversely related to the reaction temperature. That is, if the reaction temperatures are T1 and T2, respectively, and T1 is smaller than T2, the optimum flow velocity V1 corresponding to the temperature T1 and the optimum flow velocity V2 corresponding to the temperature T2 are, respectively, and V1 is larger than V2.
Further, the peak rate of graphene formation is positively correlated with the reaction temperature. Therefore, in order to be able to obtain a faster production rate of graphene, a reaction temperature having a higher temperature should be selected as much as possible within a reasonable temperature range, i.e. a temperature range in which pure graphene can be produced.
In this embodiment, the reaction temperature in the reasonable temperature range is 80-400 ℃, and the flow rate of the gas capable of generating pure graphene by matching with different reaction temperatures is 20-400 ml/min based on the carbon dioxide therein.
Hereinafter, the processes at 2 specific reaction temperatures are given.
Example 1,
When the reaction temperature is 200 ℃, the flow rate of the gas is 30 ml/min-450 ml/min based on carbon dioxide therein, and the optimal value of the flow rate is 200ml/min based on carbon dioxide therein. Namely, when the reaction temperature is 200 ℃ and the gas flow rate is 200ml/min, the reaction effect is that the graphene with the highest rate and purity is generated at the temperature. Beyond the gas flow rate, graphite is formed.
EXAMPLE 2,
When the reaction temperature is 100 ℃, the flow rate of the gas is 45 ml/min-550 ml/min based on carbon dioxide therein, and the optimal value of the flow rate is 280ml/min based on carbon dioxide therein. Namely, when the reaction temperature is 100 ℃ and the gas flow rate is 280ml/min, the reaction effect is that the graphene with the highest rate and purity is generated at the temperature. Beyond the gas flow rate, graphite is formed.
Regulating mode II, controlling the flow rate of gas unchanged, regulating reaction temperature
Specifically, in this embodiment, under the condition that the amount of carbon dioxide in the gas is fixed, the reaction temperature is regulated to be less than or equal to a certain preset temperature optimum value under the condition that the flow rate of a certain gas, where the certain preset temperature optimum value is the temperature at which the corresponding flow rate of the certain gas reaches the peak of the rate of graphene generation.
Therefore, the higher the reaction temperature is, the better, and the more than the above-mentioned temperature optimum value, graphite is likely to be generated.
And, the temperature optimum is positively correlated with the flow rate of the gas. That is, if the flow rates of the gases are V3 and V4, respectively, and V3 is smaller than V4, there are a temperature optimum value T3 corresponding to the flow rate of the V3 gas and a temperature optimum value T4 corresponding to the flow rate of the V4 gas, and T3 is smaller than T4.
Further, the peak rate of graphene generation is positively correlated to the flow rate of the gas.
Hereinafter, the process at 2 specific gas flow rates is given.
EXAMPLE 3,
The optimum value of the temperature was 300℃when the flow rate of the gas was 150ml/min in terms of carbon dioxide therein. Namely, when the gas flow rate is 150ml/min and the reaction temperature is 300 ℃, the reaction effect is that the graphene with the fastest rate and purity is generated under the gas flow rate. When the reaction temperature exceeds the above reaction temperature, graphite is formed.
EXAMPLE 4,
The optimum value of the temperature was 220℃when the flow rate of the gas was 250ml/min in terms of carbon dioxide therein. When the gas flow rate is 250ml/min and the temperature is gradually increased from 80 ℃ to 220 ℃, the graphene generation rate is increased along with the temperature increase, and when the gas flow rate is 250ml/min and the reaction temperature is 220 ℃, the reaction effect is that the graphene with the highest rate and purity is generated under the gas flow rate. Beyond the reaction temperature, graphene or graphite formation may be weakened, and the graphene formation rate may start to decrease. When the temperature reaches 400 ℃, other side reactions are accompanied, and CO is generated.
Since the various embodiments described above refer to more specific raw materials and preparation processes, a more specific process for the present embodiment described above is provided:
and S1, preparing gallium-based liquid metal alloy.
In the step, the gallium-based liquid metal alloy can be GaIn alloy, gaSn alloy or GaInSn alloy, and the proportion range is as follows: ga. The weight ratio of In to Sn is (50-95): 0-50): 0-30.
And S2, introducing CO2 gas into the liquid metal alloy.
In the step, the gas is pure CO2 gas or mixed gas of CO2 and other inert gases, and the reaction temperature is adjusted to be 80-400 ℃.
And S3, separating the liquid metal alloy from the graphene by a separation and extraction or physical separation method after the reaction is completed, so as to obtain the graphene material.
In this step, an acid solution or an alkali solution is used for the separation and extraction, wherein the acid solution includes but is not limited to nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, etc., and the alkali solution includes but is not limited to sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, etc.; in addition to the above-mentioned chemical separation method, a physical separation method such as centrifugation or direct taping, or the like may be used. For industrial large-scale application, separation extraction and centrifugation are generally used.
In the framework of the specific operating steps described above, the following two specific examples are given:
EXAMPLE 5,
Heating 69.5 parts of Ga, 20.5 parts of In and 10 parts of Sn to 80 ℃ for smelting to obtain the liquid metal alloy; wherein the smelting time is 1-2h, and the mixture is cooled to room temperature for standby after smelting;
a second step of transferring the materials obtained in the first step to a first reaction vessel and introducing CO 2 Adjusting the reaction temperature to 120 ℃ and the ventilation time to 2.5h;
stopping ventilation after the reaction is finished, cooling to room temperature, transferring the material into a second reaction container, adding nitric acid solution, heating to 80 ℃, dissolving the liquid metal alloy, and washing and drying to obtain the high-purity graphene material.
As shown in fig. 1 and fig. 2, the morphology of the graphene material obtained by the method in this embodiment in liquid metal and the morphology of the dried graphene are shown, and it can be known from the graph that a single-layer-structure high-quality graphene with good structural integrity and less structural defects is synthesized by the process.
EXAMPLE 6,
Heating 68 parts of Ga, 22 parts of In and 10 parts of Sn to 80 ℃ for smelting to obtain the liquid metal alloy; wherein the smelting time is 1-2h, and the mixture is cooled to room temperature for standby after smelting;
a second step of transferring the materials obtained in the first step to a first reaction vessel and introducing CO 2 Adjusting the reaction temperature to 150 ℃ and the ventilation time to 6 hours;
stopping ventilation after the reaction is finished, cooling to room temperature, transferring the material into a second reaction container, adding sodium hydroxide solution, heating to 80 ℃, dissolving the liquid metal alloy, and washing and drying to obtain the high-purity graphene material.
In the embodiment, the reaction temperature is slightly long, but the obtained graphene has the characteristics of better structural integrity and high quality of a single-layer structure with fewer structural defects as in the embodiment 5.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (6)
1. A preparation method of graphene is characterized by comprising the following steps: introducing carbon dioxide-containing gas into the gallium-based liquid alloy at a certain reaction temperature, and regulating the reaction temperature and the flow rate of the gas to control the generation of graphene, wherein the amount of the gallium-based liquid alloy is excessive relative to the amount of carbon dioxide in the gas;
under the condition that the amount of carbon dioxide in the gas is fixed, regulating and controlling the flow rate of the gas to be smaller than or equal to a certain preset flow rate optimal value at a certain reaction temperature, wherein the certain preset flow rate optimal value is the flow rate when reaching a speed peak value for generating graphene at a certain corresponding reaction temperature;
the optimal flow rate value is inversely related to the reaction temperature; the peak value of the graphene generation rate is positively correlated with the reaction temperature;
the reaction temperature is 80-400 ℃, and the flow rate of the gas is 20-400 ml/min according to the carbon dioxide.
2. The method according to claim 1, characterized in that: when the reaction temperature is 200 ℃, the flow rate of the gas is 30 ml/min-450 ml/min according to the carbon dioxide therein.
3. The method according to claim 2, characterized in that: the optimum flow rate was 200ml/min in terms of carbon dioxide at 200℃for the reaction temperature.
4. The method according to claim 1, characterized in that: when the reaction temperature is 100 ℃, the flow rate of the gas is 45 ml/min-550 ml/min according to the carbon dioxide therein.
5. The method according to claim 4, wherein: the optimum flow rate was 280ml/min in terms of carbon dioxide at 100℃for the reaction temperature.
6. A preparation method of graphene is characterized by comprising the following steps: introducing carbon dioxide-containing gas into the gallium-based liquid alloy at a certain reaction temperature, and regulating the reaction temperature and the flow rate of the gas to control the generation of graphene, wherein the amount of the gallium-based liquid alloy is excessive relative to the amount of carbon dioxide in the gas;
under the condition that the amount of carbon dioxide in the gas is fixed, regulating and controlling the reaction temperature to be less than or equal to a certain preset temperature optimal value under the condition that the flow rate of a certain gas is fixed, wherein the certain preset temperature optimal value is the temperature when the flow rate of a certain corresponding gas reaches the peak value of the rate for generating graphene;
the temperature optimum is positively correlated to the flow rate of the gas; the rate peak value of the generated graphene is positively correlated with the flow rate of the gas;
wherein the optimal value of the temperature is 300 ℃ when the flow rate of the gas is 150ml/min based on carbon dioxide therein;
wherein the optimal value of the temperature is 220 ℃ when the flow rate of the gas is 250ml/min based on carbon dioxide therein.
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