CN104692364A - Method for preparing ultra-dispersible graphene through liquid nitrogen cold quenching - Google Patents
Method for preparing ultra-dispersible graphene through liquid nitrogen cold quenching Download PDFInfo
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- CN104692364A CN104692364A CN201310649418.0A CN201310649418A CN104692364A CN 104692364 A CN104692364 A CN 104692364A CN 201310649418 A CN201310649418 A CN 201310649418A CN 104692364 A CN104692364 A CN 104692364A
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Abstract
The invention discloses a method for preparing ultra-dispersible graphene through liquid nitrogen cold quenching. Oxidized graphene with different sizes is prepared by adopting a chemical method, an oxidized graphene solution is heated and then cold-quenched in liquid nitrogen, and thus ultra-dispersible oxidized graphene is prepared; and then, the ultra-dispersible oxidized graphene is reduced by a heating or chemical reduction way, to obtain the ultra-dispersible graphene. The method has the advantages of low cost and simple flow path, can shorten the preparation period (mainly shortens the period of sample freeze drying), and is suitable for mass preparation of the ultra-dispersive graphene.
Description
Technical field
The present invention relates to the technology of preparing of Graphene, be specially cold quenching graphene oxide solution under liquid nitrogen environment and prepare oversubscription and to fall apart the method for Graphene, be applicable to oversubscription and fall apart the preparation in macroscopic quantity of Graphene.
Background technology
Graphene is a kind of novel nano Carbon Materials that research is the most popular at present, this material has a lot of excellent performance, as: peculiar quantum hall effect, high Young's modulus (~ 1,100 GPa), high elastic coefficient (130 GPa), good (~ 5,000 Wm of thermal conductivity
-1k
-1), high (200,000 cm of electronic mobility
2v
-1s
-1), high-specific surface area (calculated value, 2,630 m
2g
-1), light transmission is good, be easy to functionalization etc.The performance of these excellences also make Graphene have broad application prospects in a lot of field such as nanometer electronic device, nesa coating, electrode materials, matrix material (
nat. Mater. 2007,
6, 183;
science 2009,
324, 1530.).
Preparation is the key affecting Graphene development, relative to other preparation methods of Graphene, as mechanically peel method, SiC substrate surface epitaxial growth method, chemical Vapor deposition process etc., chemical method is simple to production unit relative requirement, it is the method most possibly realizing Graphene preparation in macroscopic quantity at present, chemical method is prepared Graphene and is mainly adopted modification Hummers method, first obtain graphite oxide, graphene oxide is obtained by ultrasonic disperse, and then obtain Graphene by the method for reduction, graphene sheet layer prepared by the method is thinner, preparation cost is low, it is one of method preparing Graphene comparatively commonly used at present.But the method is prepared Graphene and be there is defect, main manifestations is that preparation cycle is long, and the stacking quality of Graphene prepared that makes can occur again graphene oxide in cryodesiccated process decreases, these all hinder the development that chemical method prepares Graphene.That has also attempted at present that certain methods attempts to stop Graphene in preparation process is again stacking, and modal method is in the graphene oxide or graphene dispersing solution of preparation, add tensio-active agent to stop the again stacking of graphene oxide or graphene sheet layer.But this method also also exists defect, owing to the addition of tensio-active agent in this process, therefore in subsequent preparation process, also need surfactivity to remove, this turn increases the preparation cycle of Graphene undoubtedly, and if tensio-active agent is not removed completely, the quality preparing Graphene will be affected.Therefore, if can invent a kind of simple, quick, efficiently method stop Graphene in preparation process again stacking, and the preparation cycle that simultaneously can reduce Graphene is prepared magnanimity Graphene for chemical method and is had very important significance.
Summary of the invention
A kind of oversubscription of preparing under liquid nitrogen environment is the object of the present invention is to provide to fall apart the method for Graphene.
Technical scheme of the present invention is:
The present invention adopts chemical method to prepare the graphene oxide of different size, carries out cold quenching after graphene oxide solution being heated in liquid nitrogen, and preparation oversubscription is fallen apart graphene oxide.Then reduced by heating or the mode of chemical reduction oversubscription fallen apart graphene oxide, the Graphene thus preparation oversubscription is fallen apart.
Liquid nitrogen cold quenching is prepared oversubscription and to be fallen apart the method for Graphene, it is characterized in that the method step is:
A, graphene oxide solution cold quenching in liquid nitrogen: be put into liquid nitrogen cold quenching after the graphene oxide solution of 0.5 mg/ml ~ 8 mg/ml is heated to 30 DEG C ~ 100 DEG C by concentration, until solution is taken out after freezing completely, carry out In-situ condensation and be dried to graphene oxide complete drying;
B, oversubscription are fallen apart graphene oxide reduction: the mode of the graphene oxide of drying by heating or chemical reduction removed by oxygen-containing functional group wherein, thus obtain oversubscription and to fall apart graphene powder.
In step, the preferred concentration of graphene oxide solution is 0.5 mg/ml ~ 6 mg/ml.
In step, the preferable temperature of heating is 30 DEG C ~ 60 DEG C.
In stepb, the Heating temperature of described thermal reduction is 300 DEG C ~ 900 DEG C.
In stepb, hydrazine hydrate steam reduction is selected in chemical reduction, and the time of chemical reduction is 8 h ~ 16 h.
Fall apart graphene oxide or Graphene of oversubscription refers to that graphene oxide or Graphene can not occur again to reunite under the state of powder, still can keep the distribution of well less layer or individual layer, the present invention can obtain oversubscription by the mode of liquid nitrogen cold quenching and to fall apart graphene oxide or Graphene.
It is low that the present invention has cost, and flow process is simple, can shorten the advantages such as preparation cycle (main shorten the sample cryodesiccated cycle), therefore can be used as a kind of preparation in macroscopic quantity oversubscription that is suitable for and to fall apart the Perfected process of Graphene.
Feature of the present invention and beneficial effect are:
The present invention by will the mode of graphene oxide solution cold quenching in liquid nitrogen of heating, prevents again stacking in freezing dry process of graphene oxide, and preparation oversubscription is fallen apart graphene oxide, and and then prepared oversubscription and to have fallen apart Graphene; Present invention reduces the Graphene chemical method preparation process situ cryodesiccated cycle, reaction process is controlled, and technique is simple, preparation cycle is short, cost is low and it is high to prepare Graphene quality, has promoted the technological development that chemical method prepares magnanimity Graphene.
Accompanying drawing explanation
Fig. 1 is that oversubscription prepared by low-concentration oxidizing graphene solution is fallen apart the stereoscan photograph of Graphene.
Fig. 2 is that oversubscription prepared by high density graphene oxide solution is fallen apart the stereoscan photograph of Graphene.
Embodiment
Embodiment 1
32 order natural flake graphites are adopted to utilize the Hummers legal system of modification for graphite oxide.Crystalline flake graphite is 35 DEG C in oxidizing temperature, and oxidization time is prepare graphite oxide under the condition of 2 h, is dispersed in water by graphite oxide, the ultrasonic time is 10 min, ultrasonic power is 600 W, then removes visible particles by centrifugal rotational speed 3000 rpm, obtains graphene oxide solution.
Be that the graphene oxide solution of 0.5 mg/ml is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching by concentration, until solution is completely icing, then carried out In-situ condensation drying.Obtain oversubscription after drying to fall apart graphene oxide composite material, then by its 900 DEG C of reduction under Ar gas shielded, thus obtain oversubscription and to fall apart Graphene.
Electron microscopic observation result shows: in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 90% to be in few layer of dispersion state under such condition.As shown in Figure 1,0.5 mg/ml graphene oxide solution directly puts into liquid nitrogen cold quenching after being heated to 40 DEG C, can be found out by the photo of scanning electron microscope, and through the process of liquid nitrogen cold quenching, graphene sheet layer keeps very thin super dispersion state.
Embodiment 2
The preparation method of graphene oxide solution is with embodiment 1.
Be that the graphene oxide solution of 2 mg/ml is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching by concentration, until solution is completely icing, then carried out In-situ condensation drying.Obtain oversubscription after drying to fall apart graphene oxide composite material, then by its 900 DEG C of reduction under Ar gas shielded, thus obtain oversubscription and to fall apart Graphene.
Electron microscopic observation result shows: in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 85% to be in few layer of dispersion state under such condition.
Embodiment 3
The preparation method of graphene oxide solution is with embodiment 1.
Be that the graphene oxide solution of 6 mg/ml is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching by concentration, until solution is completely icing, then carried out In-situ condensation drying.Obtain oversubscription after drying to fall apart graphene oxide composite material, then by its 900 DEG C of reduction under Ar gas shielded, thus obtain oversubscription and to fall apart Graphene.
Electron microscopic observation result shows: in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 80% to be in few layer of dispersion state under such condition.As shown in Figure 2,6 mg/ml graphene oxide solution directly put into liquid nitrogen cold quenching after being heated to 40 DEG C, can be found out by the photo of scanning electron microscope, the graphene oxide solution of high density is through cold quenching process, and graphene sheet layer also can keep very thin super dispersion state.
Embodiment 4
The preparation method of graphene oxide solution is with embodiment 1.
Be that the graphene oxide solution of 8 mg/ml is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching by concentration, until solution is completely icing, then carried out In-situ condensation drying.Obtain oversubscription after drying to fall apart graphene oxide composite material, then by its 900 DEG C of reduction under Ar gas shielded, thus obtain oversubscription and to fall apart Graphene.
Electron microscopic observation result shows: in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 78% to be in few layer of dispersion state under such condition.
Embodiment 5
325 order natural flake graphites are adopted to utilize the Hummers legal system of modification for graphite oxide.Crystalline flake graphite is 60 DEG C in oxidizing temperature, and oxidization time is prepare graphite oxide under the condition of 6h, is dispersed in water by graphite oxide, the ultrasonic time is 10 min, ultrasonic power is 600 W, then removes visible particles by centrifugal rotational speed 4000 rpm, obtains graphene oxide solution.
Be that the small size graphene oxide solution of 0.5 mg/ml is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching by concentration, until solution is completely icing, then carried out In-situ condensation drying.Obtain oversubscription after drying to fall apart graphene oxide composite material, then by its 900 DEG C of reduction under Ar gas shielded, thus obtain oversubscription and to fall apart Graphene.
Electron microscopic observation result shows: in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 95% to be in few layer of dispersion state under such condition.
Embodiment 6
The preparation method of graphene oxide solution is with embodiment 5.
Be that the graphene oxide solution of 6 mg/ml is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching by concentration, until solution is completely icing, then carried out In-situ condensation drying.Obtain oversubscription after drying to fall apart graphene oxide composite material, then by its 900 DEG C of reduction under Ar gas shielded, thus obtain oversubscription and to fall apart Graphene.
Electron microscopic observation result shows: in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 85% to be in few layer of dispersion state under such condition.
Embodiment 7
The preparation method of graphene oxide solution is with embodiment 1.
Be that the graphene oxide solution of 0.5 mg/ml is heated to 80 DEG C and directly puts into liquid nitrogen cold quenching by concentration, until solution is completely icing, then carried out In-situ condensation drying.Obtain oversubscription after drying to fall apart graphene oxide composite material, then by its 900 DEG C of reduction under Ar gas shielded, thus obtain oversubscription and to fall apart Graphene.
Electron microscopic observation result shows: in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 60% to be in few layer of dispersion state under such condition, and other generations are curling.
Embodiment 8
The preparation method of graphene oxide solution is with embodiment 1.
Be that the graphene oxide solution of 0.5 mg/ml is heated to 100 DEG C and directly puts into liquid nitrogen cold quenching by concentration, until solution is completely icing, then carried out In-situ condensation drying.Obtain oversubscription after drying to fall apart graphene oxide composite material, then by its 900 DEG C of reduction under Ar gas shielded, thus obtain oversubscription and to fall apart Graphene.
Electron microscopic observation result shows: in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 50% to be in few layer of dispersion state under such condition, and other generations are curling.
Claims (5)
1. liquid nitrogen cold quenching is prepared oversubscription and to be fallen apart the method for Graphene, it is characterized in that the method step is:
A, graphene oxide solution cold quenching in liquid nitrogen: be put into liquid nitrogen cold quenching after the graphene oxide solution of 0.5 mg/ml ~ 8 mg/ml is heated to 30 DEG C ~ 100 DEG C by concentration, until solution is taken out after freezing completely, carry out In-situ condensation and be dried to graphene oxide complete drying;
B, oversubscription are fallen apart graphene oxide reduction: the mode of the graphene oxide of drying by heating or chemical reduction removed by oxygen-containing functional group wherein, thus obtain oversubscription and to fall apart graphene powder.
2. the method for claim 1, is characterized in that the concentration of graphene oxide solution in steps A is 0.5 mg/ml ~ 6 mg/ml.
3. the method for claim 1, is characterized in that the temperature heated in steps A is 30 DEG C ~ 60 DEG C.
4. the method for claim 1, is characterized in that the Heating temperature of thermal reduction in step B is 300 DEG C ~ 900 DEG C.
5. the method for claim 1, it is characterized in that in step B, hydrazine hydrate steam reduction is selected in chemical reduction, the time of chemical reduction is 8 h ~ 16 h.
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Cited By (7)
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| CN105967181A (en) * | 2016-07-21 | 2016-09-28 | 苏州协鑫集成科技工业应用研究院有限公司 | Graphene and preparation method thereof |
| CN106986330A (en) * | 2017-03-30 | 2017-07-28 | 周口师范学院 | A kind of grapheme material preparation method of ordered structure |
| CN108394897A (en) * | 2018-05-25 | 2018-08-14 | 清华-伯克利深圳学院筹备办公室 | A kind of magnanimity preparation method of porous oxidation graphene |
| CN110155961A (en) * | 2018-06-25 | 2019-08-23 | 中国科学院物理研究所 | A method of preparing stratified material fold |
| CN110436448A (en) * | 2019-08-26 | 2019-11-12 | 上海利物盛纳米科技有限公司 | A kind of method of ultralow temperature preparation small size graphene dispersing solution |
| CN110577210A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | preparation method of powder of graphene and graphene derivative |
| CN110885077A (en) * | 2018-09-10 | 2020-03-17 | 北京大学深圳研究生院 | Preparation method of high-thermal-conductivity graphene and coating thereof |
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| CN103396586A (en) * | 2013-08-09 | 2013-11-20 | 中国科学院宁波材料技术与工程研究所 | Graphene oxide fiber, preparation method, and preparation method of graphene oxide fiber composite material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105967181A (en) * | 2016-07-21 | 2016-09-28 | 苏州协鑫集成科技工业应用研究院有限公司 | Graphene and preparation method thereof |
| CN106986330A (en) * | 2017-03-30 | 2017-07-28 | 周口师范学院 | A kind of grapheme material preparation method of ordered structure |
| CN108394897A (en) * | 2018-05-25 | 2018-08-14 | 清华-伯克利深圳学院筹备办公室 | A kind of magnanimity preparation method of porous oxidation graphene |
| CN110577210A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | preparation method of powder of graphene and graphene derivative |
| CN110577210B (en) * | 2018-06-07 | 2023-04-25 | 山东欧铂新材料有限公司 | Preparation method of graphene and graphene derivative powder |
| CN110155961A (en) * | 2018-06-25 | 2019-08-23 | 中国科学院物理研究所 | A method of preparing stratified material fold |
| CN110155961B (en) * | 2018-06-25 | 2020-11-10 | 中国科学院物理研究所 | Method for preparing laminar material folds |
| CN110885077A (en) * | 2018-09-10 | 2020-03-17 | 北京大学深圳研究生院 | Preparation method of high-thermal-conductivity graphene and coating thereof |
| CN110436448A (en) * | 2019-08-26 | 2019-11-12 | 上海利物盛纳米科技有限公司 | A kind of method of ultralow temperature preparation small size graphene dispersing solution |
| CN110436448B (en) * | 2019-08-26 | 2021-07-02 | 上海利物盛纳米科技有限公司 | Method for preparing small-size graphene dispersion liquid at ultralow temperature |
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