CN108622883B - Preparation method of graphene powder material - Google Patents
Preparation method of graphene powder material Download PDFInfo
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- CN108622883B CN108622883B CN201710176915.1A CN201710176915A CN108622883B CN 108622883 B CN108622883 B CN 108622883B CN 201710176915 A CN201710176915 A CN 201710176915A CN 108622883 B CN108622883 B CN 108622883B
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Abstract
The invention discloses a preparation method of a graphene powder material, wherein the method comprises the following steps: mixing polyphenyl metal compound and nonmetal simple substance according to the proportion of 1: 0.01-1 mass proportion; placing the mixture of the polyphenyl metal compound and the nonmetal simple substance into a reaction furnace with a protective gas atmosphere, and heating to 500-800 ℃ at a heating rate of 1-3 ℃/min under normal pressure to ensure that the mixture fully reacts in a slow heating process to obtain a graphene powder material containing impurities and consisting of benzene ring active elements; and annealing and removing impurities to obtain the graphene powder material. The polyphenyl metal compound and the nonmetal simple substance are uniformly mixed, the nonmetal simple substance is fully reacted with hydrogen and metal in the polyphenyl metal compound at high temperature to obtain graphene consisting of benzene ring active elements, and impurities such as the metal compound, the nonmetal compound and the like remained in the reaction are removed at high temperature to obtain the graphene powder material which has high purity, large specific surface area and good quality.
Description
Technical Field
The invention relates to the field of preparation of graphene, in particular to a preparation method of a graphene powder material.
Background
As a novel nano carbon material, the graphene has the characteristics of unique two-dimensional structure, excellent conductivity, higher mechanical property, high specific surface area and the like. Due to various excellent characteristics of graphene, graphene has recently shown great application potential in many fields such as electronics, optics, magnetism, biomedicine, catalysis, energy storage and sensors, and has attracted high attention in the scientific and industrial fields. Graphene exists mainly in two forms, powder and thin film.
For graphene powder materials, oxidation methods (Hummers methods) are mainly adopted to prepare graphene powder materials and composite materials thereof at present. Typically by dissolving graphite in sulfuric acid (H)2SO4) Nitric acid (HNO)3) Perchloric acid (HClO)4) Under the action of an equal-strength oxidant or electrochemical peroxidation, graphite oxide is formed after hydrolysis, and the graphite oxide is stripped in water or other polar solvents under the action of external force such as ultrasonic waves to form a single-layer graphene powder material. However, the existing method for preparing graphene powder needs to use a large amount of strong acid and strong base, and the production cost is high; a plurality of cleaning processes are needed to remove acid and alkali, so that the preparation process is more, and the large-scale production is not facilitated; a large amount of acid-base waste can be generated, and environmental pollution is caused; the prepared graphene powder material is easy to have acid-base residues.
Therefore, the existing preparation method of graphene powder materials still needs to be improved.
Disclosure of Invention
The invention aims to solve the problems of more preparation procedures, high production cost, acid and alkali residues in the powder material, environmental pollution caused by the acid and alkali residues and the like in the existing preparation method of the graphene powder material; the preparation method of the graphene powder material is provided, and the graphene powder material is high in purity, large in specific surface area and good in quality; the preparation method has simple process, no pollution to the environment and easy large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a graphene powder material comprises the following steps: mixing polyphenyl metal compound and nonmetal simple substance according to the proportion of 1: 0.01-1 mass proportion; placing the mixture of the polyphenyl metal compound and the nonmetal simple substance into a reaction furnace with a protective gas atmosphere, and heating to 500-800 ℃ at a heating rate of 1-3 ℃/min under normal pressure to ensure that the mixture fully reacts in a slow heating process to obtain a graphene powder material containing impurities and consisting of benzene ring active elements; and annealing and removing impurities to obtain the graphene powder material.
Preferably, the polyphenyl metal compound is at least one of triphenyl tin, triphenyl bismuth, triphenyl thallium, iron tetraphenyl porphyrin, tetraphenyl tin, tetraphenyl germanium, tetraphenyl lead, pentaphenyl bismuth, hexaphenyl distannum, hexaphenyl digermum or hexaphenyl digermum.
Preferably, the non-metallic element is at least one of phosphorus, arsenic, sulfur, selenium, tellurium or polonium.
Preferably, the step of annealing and impurity removal to obtain the graphene powder material specifically comprises: keeping the graphene powder material containing impurities at constant temperature for 8-15h under the atmosphere of protective gas, and completely removing impurities such as metal and non-metal compounds; and finally, turning off the heating, and naturally cooling to room temperature to obtain the graphene powder material.
Preferably, the step of annealing and impurity removal to obtain the graphene powder material specifically comprises: keeping the graphene powder material containing impurities at constant temperature for 8-15h under the atmosphere of protective gas, and removing impurities such as metal and nonmetal compounds; and finally, closing the heating, and naturally cooling to room temperature to obtain the impurity-doped graphene powder material.
Preferably, the protective gas is at least one of hydrogen, argon or nitrogen.
Preferably, the gas purity of the protective gas is greater than 99.99%.
The preparation method comprises the steps of uniformly mixing a polyphenyl metal compound and a nonmetal simple substance according to a certain proportion, reacting the nonmetal simple substance with hydrogen and metal of the polyphenyl metal compound at a high temperature, and annealing to remove impurities such as the reacted metal compound and the nonmetal compound and leave the graphene powder material consisting of benzene ring active elements. Compared with the existing graphene powder material preparation technology, the preparation method has the following advantages:
(1) according to the method, the polyphenyl metal compound is used as a reaction source, the natural benzene ring active elements carried by the polyphenyl metal compound are left after the polyphenyl metal compound is mixed with non-metal simple substances and reacts at a high temperature to form graphene, and impurities such as residual metal and non-metal compounds are removed through high-temperature annealing, so that the obtained graphene powder material is high in purity, large in specific surface area and good in quality;
(2) according to the preparation method of the graphene powder material, the mixing amount of the polyphenyl metal compound and the nonmetal simple substance can be controlled, so that the nonmetal simple substance can completely react with hydrogen in the polyphenyl metal compound and can also completely or partially react with part of metal in the polyphenyl metal compound, and the non-doped or metal-doped graphene powder material can be prepared according to the requirement;
(3) the preparation method of the graphene powder material does not use strong acid, strong alkali and deacidification and dealkalization treatment, and has low production cost; no acid, alkali and other wastes, and no pollution to the environment; the preparation process is simple, the production procedures are few, and the large-scale production can be realized.
Drawings
Fig. 1 is a schematic process diagram of a preparation method of a graphene powder material provided by the invention;
fig. 2 is a schematic diagram of a synthesis principle of embodiment 1 of the graphene powder material provided by the invention;
fig. 3 is an SEM picture of the graphene powder material provided by the present invention;
fig. 4 is a TEM image of the graphene powder material provided by the present invention;
fig. 5 is an HRTEM image of the graphene powder material provided by the present invention;
fig. 6 is a raman spectrum of the graphene powder material provided by the present invention;
fig. 7 is a schematic diagram of a synthesis principle of embodiment 2 of the graphene powder material provided by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a graphene powder material, wherein the graphene is a small amount of metal-doped graphene or metal-free doped graphene; the graphene consists of benzene ring active elements, and has high purity, large specific surface area and good quality.
As shown in fig. 1, the preparation method of the graphene powder material comprises the following steps:
s101: polyphenyl metal compound and nonmetal simple substance are mixed according to the proportion of 1: 0.01-1 mass proportion;
wherein the polyphenyl metal compound is at least one of triphenyl tin, triphenyl bismuth, triphenyl thallium, tetraphenyl porphyrin iron, tetraphenyl tin, tetraphenyl germanium, tetraphenyl lead, pentaphenyl bismuth, hexaphenyl distannum, hexaphenyl digermum and hexaphenyl dipalmium; the nonmetal simple substance is at least one of phosphorus (P), arsenic (As), sulfur (S), selenium (Se), tellurium (Te) and polonium (Po);
s102: reacting the mixture in a high-temperature environment, putting the aromatic base metal compound and the non-metal simple substance mixture obtained in the step S101 into a reaction furnace in a protective gas atmosphere, and heating to 800 ℃ at the normal pressure at the heating rate of 1-3 ℃/min to ensure that the mixture fully reacts in the slow heating process, and the graphene consisting of benzene ring active elements is remained;
s103: annealing and removing impurities to obtain a graphene powder material;
keeping the reaction product obtained in the step S102 at constant temperature for 8-15h under the atmosphere of protective gas, and removing impurities such as metal compounds, nonmetal compounds and the like; finally, turning off heating, and naturally cooling to room temperature to obtain a graphene powder material; wherein the protective gas atmosphere in S102 and S103 is at least one of hydrogen, argon, nitrogen and the like, and the gas purity is more than 99.99%.
The following embodiments may be employed in the present invention:
example 1
Adding hexaphenyldigermum: the mass ratio of the simple substance phosphorus is 1: 0.1, uniformly mixing;
putting the obtained mixture of hexaphenyldigermum and elemental phosphorus into a reaction furnace with the purity of more than 99.99 percent in the protective atmosphere of hydrogen and argon, then heating to 600 ℃ at the heating rate of 1 ℃/min under normal pressure, so that the mixture is fully reacted in the slow heating process, and the reaction product germanium compound, phosphine and the like are sublimated at high temperature, and finally obtaining the graphene consisting of benzene ring active elements left by the reaction;
keeping the obtained reaction product at constant temperature for 14h under the protection of hydrogen and argon with the purity of more than 99.99%, and completely removing impurities such as germanium compounds, phosphorus compounds and the like; finally, turning off heating, and naturally cooling to room temperature to obtain a graphene powder material;
as can be seen from the schematic diagram of the synthetic principle of the graphene powder material shown in fig. 2, by reacting hydrogen (H) and germanium (Ge) in hexa-phenyl-digermanium with selenium (Se) at a high temperature, the reaction products of germanium selenide 23, germanium diselenide 24, hydrogen selenide 25, and the like are sublimated at a high temperature, and the remaining benzene ring active elements are bonded with each other through carbon-carbon bonds, so that graphene with carbon atoms arranged in a hexagon is obtained, wherein the graphene is pure graphene 22 completely composed of benzene rings.
As shown in fig. 3-6, it can be seen from the SEM and TEM photographs of the graphene powder material in fig. 3 and 4 that the graphene is in a flower-like shape and uniformly distributed, and the flake shape reaches micrometer or even tens of micrometers, which indicates that the specific surface area of the graphene is large; as can be seen from HRTEM of the graphene powder material in fig. 5 and raman in fig. 6, the number of graphene layers is less than 8, and is generally 2-6, which indicates that the graphene layers are few, high in purity and good in quality.
Example 2
As shown in fig. 7, unlike embodiment 1, in this embodiment, hydrogen (H) and germanium (Ge) in hexaphenyldigermanium are reacted with selenium (Se) at a high temperature, reaction products such as generated germanium selenide 23, germanium diselenide 24, hydrogen selenide 25, and the like are sublimated at a high temperature, part of germanium is left, and active elements of benzene rings are bonded to each other through carbon-carbon bonds, so that the metal-doped graphene 21 with part of germanium left and carbon atoms arranged in a hexagonal pattern is obtained.
Example 3
Mixing pentaphenyl bismuth: the mass ratio of the simple substance tellurium to tellurium is 1: 0.05, uniformly mixing;
putting the obtained mixture of pentaphenyl bismuth and simple substance tellurium into a reaction furnace with the purity of more than 99.99 percent in the protective atmosphere of hydrogen and argon, then heating to 700 ℃ at the heating rate of 2 ℃/min under normal pressure, leading the mixture to fully react in the slow heating process, subliming the reaction product bismuth compound, hydrogen telluride and the like at high temperature, and finally obtaining the graphene consisting of the benzene ring active elements left by the reaction;
keeping the obtained reaction product at constant temperature for 12h under the protection of hydrogen and argon with the purity of more than 99.99%, and further completely removing impurities such as bismuth compounds, tellurium compounds and the like; and finally, turning off heating, and naturally cooling to room temperature to obtain the high-quality graphene powder material.
The polyphenyl metal compound and the nonmetal simple substance are uniformly mixed, the nonmetal simple substance is fully reacted with hydrogen and metal in the polyphenyl metal compound at high temperature to obtain graphene consisting of benzene ring active elements, and impurities such as the metal compound, the nonmetal compound and the like which are remained in the reaction are removed at high temperature to obtain the graphene powder material which has high purity, large specific surface area and good quality; the preparation method can prepare the non-doped or metal-doped graphene powder material with controllable amount according to the requirement; meanwhile, the preparation method of the graphene powder material does not use strong acid, strong alkali and deacidification and dealkalization treatment, so that the production cost is low; no acid, alkali and other wastes, and no pollution to the environment; the preparation process is simple, the production procedures are few, and the large-scale production can be realized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A preparation method of a graphene powder material is characterized by comprising the following steps: the method comprises the following steps:
mixing polyphenyl metal compound and nonmetal simple substance according to the proportion of 1: 0.01-1 mass proportion;
placing the mixture of the polyphenyl metal compound and the nonmetal simple substance into a reaction furnace with a protective gas atmosphere, and heating to 500-800 ℃ at a heating rate of 1-3 ℃/min under normal pressure to ensure that the mixture fully reacts in a slow heating process to obtain a graphene powder material containing impurities and consisting of benzene ring active elements;
and annealing and removing impurities to obtain the graphene powder material.
2. The method for preparing the graphene powder material according to claim 1, wherein the method comprises the following steps: the polyphenyl metal compound is at least one of triphenyl tin, triphenyl bismuth, triphenyl thallium, tetraphenyl porphyrin iron, tetraphenyl tin, tetraphenyl germanium, tetraphenyl lead, pentaphenyl bismuth, hexaphenyl distannum, hexaphenyl digermum or hexaphenyl dipndusium.
3. The method for preparing the graphene powder material according to claim 1, wherein the method comprises the following steps: the nonmetal simple substance is at least one of phosphorus, arsenic, sulfur, selenium, tellurium or polonium.
4. The method for preparing the graphene powder material according to claim 1, wherein the method comprises the following steps: the step of annealing and impurity removal to obtain the graphene powder material specifically comprises the following steps: keeping the graphene powder material containing impurities at constant temperature for 8-15h under the atmosphere of protective gas, and completely removing impurities such as metal and non-metal compounds; and finally, turning off the heating, and naturally cooling to room temperature to obtain the graphene powder material.
5. The method for preparing the graphene powder material according to claim 1, wherein the method comprises the following steps: the step of annealing and impurity removal to obtain the graphene powder material specifically comprises the following steps: keeping the graphene powder material containing impurities at constant temperature for 8-15h under the atmosphere of protective gas, and removing impurities such as metal and nonmetal compounds; and finally, closing the heating, and naturally cooling to room temperature to obtain the impurity-doped graphene powder material.
6. The method for preparing the graphene powder material according to claim 4 or 5, wherein: the protective gas is at least one of hydrogen, argon or nitrogen.
7. The method for preparing the graphene powder material according to claim 4 or 5, wherein: the gas purity of the protective gas is greater than 99.99%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102433544A (en) * | 2012-01-11 | 2012-05-02 | 中国科学院上海微系统与信息技术研究所 | Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition |
| CN105478168A (en) * | 2016-02-01 | 2016-04-13 | 天津大学 | Photoinduced hydrogen production catalytic system taking graphene as electron mediator and containing iron-sulfur cluster compound and preparation method and application of catalytic system |
| CN105575674A (en) * | 2014-10-13 | 2016-05-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene/active carbon composite material, preparation method thereof, and supercapacitor |
| WO2016109830A2 (en) * | 2014-12-31 | 2016-07-07 | The Regents Of The University Of California | Quinolines, polyquinolines, molecular segments of fullerenes and graphene nanoribbons, and graphene nanoribbons and methods of their synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433544A (en) * | 2012-01-11 | 2012-05-02 | 中国科学院上海微系统与信息技术研究所 | Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition |
| CN105575674A (en) * | 2014-10-13 | 2016-05-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene/active carbon composite material, preparation method thereof, and supercapacitor |
| WO2016109830A2 (en) * | 2014-12-31 | 2016-07-07 | The Regents Of The University Of California | Quinolines, polyquinolines, molecular segments of fullerenes and graphene nanoribbons, and graphene nanoribbons and methods of their synthesis |
| CN105478168A (en) * | 2016-02-01 | 2016-04-13 | 天津大学 | Photoinduced hydrogen production catalytic system taking graphene as electron mediator and containing iron-sulfur cluster compound and preparation method and application of catalytic system |
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