CN104692364B - A kind of liquid nitrogen cold quenching is prepared the method for the loose Graphene of oversubscription - Google Patents
A kind of liquid nitrogen cold quenching is prepared the method for the loose Graphene of oversubscription Download PDFInfo
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Abstract
The invention discloses a kind of liquid nitrogen cold quenching and prepare the method for the loose Graphene of oversubscription. The present invention adopts chemical method to prepare the graphene oxide of different size, will after the heating of graphene oxide solution, carry out cold quenching in liquid nitrogen, the loose graphene oxide of preparation oversubscription. Then by the mode of heating or electronation, loose oversubscription graphene oxide is reduced, thus the loose Graphene of preparation oversubscription. It is low that the method has cost, and flow process is simple, can shorten the advantages such as manufacturing cycle (mainly shortening the cryodesiccated cycle of sample), is suitable for the loose Graphene of preparation in macroscopic quantity oversubscription.
Description
Technical field
The present invention relates to the technology of preparing of Graphene, be specially the method that under liquid nitrogen environment cold quenching graphene oxide solution is prepared the loose Graphene of oversubscription, be applicable to the preparation in macroscopic quantity of the loose Graphene of oversubscription.
Background technology
Graphene is the most popular a kind of novel nano Carbon Materials of research at present, this material has the performance of a lot of excellences, as: peculiar quantum hall effect, high Young's modulus (～1,100GPa), high elastic modulus (130GPa), good (～5, the 000Wm of thermal conductivity-1K-1), high (200, the 000cm of electron mobility2V-1s-1), high-specific surface area (calculated value, 2,630m2g-1), light transmission is good, be easy to functionalization etc. These excellent performances also make Graphene have broad application prospects in a lot of fields such as nanometer electronic device, nesa coating, electrode material, composite (Nat.Mater. 2007,6,183；Science 2009,324,1530.)。
Preparation is the key that affects Graphene development, with respect to other preparation methods of Graphene, as mechanical stripping method, SiC substrate surface epitaxial growth method, chemical vapour deposition technique etc., chemical method requires simple to production equipment relatively, it is the method that most possibly realizes Graphene preparation in macroscopic quantity at present, chemical method is prepared Graphene and is mainly adopted modification Hummers method, first obtain graphite oxide, obtain graphene oxide by ultrasonic dispersion, and then obtain Graphene by the method for reduction, graphene sheet layer prepared by the method is thinner, preparation cost is low, it is current comparatively conventional one of method of Graphene of preparing. but the method is prepared Graphene and is existed defect, main manifestations is that manufacturing cycle is long, and graphene oxide the stacking quality of Graphene that makes preparation can occur again in cryodesiccated process and decreases, these have all hindered the development that chemical method is prepared Graphene. also attempted at present certain methods and attempted to stop again stacking in preparation process of Graphene, modal method is in the graphene oxide of preparation or graphene dispersing solution, to add surfactant to stop the again stacking of graphene oxide or graphene sheet layer. but this method also exists defect, owing to having added surfactant in this process, therefore in subsequent preparation process, also need surface-active to remove, this has increased again the manufacturing cycle of Graphene undoubtedly, and if surfactant is not removed completely, will affect the quality of preparing Graphene. therefore, if can invent a kind of simple, quick, method stops again stacking in preparation process of Graphene efficiently, and the manufacturing cycle that can reduce Graphene is simultaneously prepared magnanimity Graphene for chemical method and is had very important significance.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing the loose Graphene of oversubscription under liquid nitrogen environment.
Technical scheme of the present invention is:
The present invention adopts chemical method to prepare the graphene oxide of different size, will after the heating of graphene oxide solution, carry out cold quenching in liquid nitrogen, the loose graphene oxide of preparation oversubscription. Then by the mode of heating or electronation, loose oversubscription graphene oxide is reduced, thus the loose Graphene of preparation oversubscription.
Liquid nitrogen cold quenching is prepared a method for the loose Graphene of oversubscription, it is characterized in that the method step is:
A, graphene oxide solution cold quenching in liquid nitrogen: the graphene oxide solution that is 0.5mg/ml～8mg/ml by concentration is put into liquid nitrogen cold quenching after being heated to 30 DEG C～100 DEG C, until solution is taken out after freezing completely, carry out In-situ condensation and be dried to graphene oxide bone dry;
B, the loose graphene oxide reduction of oversubscription: dry graphene oxide is removed oxygen-containing functional group wherein by the mode of heating or electronation, thereby obtained the loose graphene powder of oversubscription.
In steps A, the preferred concentration of graphene oxide solution is 0.5mg/ml～6mg/ml.
In steps A, the preferred temperature of heating is 30 DEG C～60 DEG C.
In step B, the heating-up temperature of described thermal reduction is 300 DEG C～900 DEG C.
In step B, hydrazine hydrate steam reduction is selected in electronation, and the time of electronation is 8h～16h.
The loose graphene oxide of oversubscription or Graphene refer to that graphene oxide or Graphene can not occur again to reunite under the state of powder, still can keep the distribution of good few layer or individual layer, the present invention can obtain the loose graphene oxide of oversubscription or Graphene by the mode of liquid nitrogen cold quenching.
It is low that the present invention has cost, and flow process is simple, can shorten the advantages such as manufacturing cycle (mainly shortening the cryodesiccated cycle of sample), therefore can be used as a kind of Perfected process that is suitable for the loose Graphene of preparation in macroscopic quantity oversubscription.
Feature of the present invention and beneficial effect are:
The present invention is by by the mode of graphene oxide solution cold quenching in liquid nitrogen of heating, stoped again stacking in freezing dry process of graphene oxide, the loose graphene oxide of preparation oversubscription, and and then prepared the loose Graphene of oversubscription; The present invention has shortened the Graphene chemical method preparation process cryodesiccated cycle of situ, and course of reaction is controlled, technique is simple, manufacturing cycle is short, cost is low and it is high to prepare Graphene quality, has promoted the technological development that chemical method is prepared magnanimity Graphene.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the loose Graphene of the oversubscription prepared of low concentration oxygen functionalized graphene solution.
Fig. 2 is the stereoscan photograph of the loose Graphene of the oversubscription prepared of high concentration oxygen functionalized graphene solution.
Detailed description of the invention
Embodiment 1
Adopt 32 order natural flake graphites to utilize the Hummers legal system of modification for graphite oxide. Crystalline flake graphite is 35 DEG C in oxidizing temperature, under the condition that oxidization time is 2h, prepares graphite oxide, and graphite oxide is dispersed in water, the ultrasonic time is 10min, ultrasonic power is 600W, then removes visible particles by centrifugal rotational speed 3000rpm, obtains graphene oxide solution.
The graphene oxide solution that is 0.5mg/ml by concentration is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching, until solution is completely icing, is then carried out In-situ condensation and is dried. After dry, obtain the loose graphene oxide material of oversubscription, then by its 900 DEG C of reduction under the protection of Ar gas, thereby the loose Graphene of oversubscription obtained.
Electron microscopic observation result shows: under this kind of condition, in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 90% in few layer of dispersity. As shown in Figure 1,0.5mg/ml graphene oxide solution is directly put into liquid nitrogen cold quenching being heated to after 40 DEG C, can find out by the photo of ESEM, and through the processing of liquid nitrogen cold quenching, graphene sheet layer keeps very thin super dispersity.
Embodiment 2
The preparation method of graphene oxide solution is with embodiment 1.
The graphene oxide solution that is 2mg/ml by concentration is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching, until solution is completely icing, is then carried out In-situ condensation and is dried. After dry, obtain the loose graphene oxide material of oversubscription, then by its 900 DEG C of reduction under the protection of Ar gas, thereby the loose Graphene of oversubscription obtained.
Electron microscopic observation result shows: under this kind of condition, in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 85% in few layer of dispersity.
Embodiment 3
The preparation method of graphene oxide solution is with embodiment 1.
The graphene oxide solution that is 6mg/ml by concentration is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching, until solution is completely icing, is then carried out In-situ condensation and is dried. After dry, obtain the loose graphene oxide material of oversubscription, then by its 900 DEG C of reduction under the protection of Ar gas, thereby the loose Graphene of oversubscription obtained.
Electron microscopic observation result shows: under this kind of condition, in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 80% in few layer of dispersity. As shown in Figure 2,6mg/ml graphene oxide solution is directly put into liquid nitrogen cold quenching being heated to after 40 DEG C, photo by ESEM can be found out, the graphene oxide solution process cold quenching processing of high concentration, and graphene sheet layer also can keep very thin super dispersity.
Embodiment 4
The preparation method of graphene oxide solution is with embodiment 1.
The graphene oxide solution that is 8mg/ml by concentration is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching, until solution is completely icing, is then carried out In-situ condensation and is dried. After dry, obtain the loose graphene oxide material of oversubscription, then by its 900 DEG C of reduction under the protection of Ar gas, thereby the loose Graphene of oversubscription obtained.
Electron microscopic observation result shows: under this kind of condition, in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 78% in few layer of dispersity.
Embodiment 5
Adopt 325 order natural flake graphites to utilize the Hummers legal system of modification for graphite oxide. Crystalline flake graphite is 60 DEG C in oxidizing temperature, under the condition that oxidization time is 6h, prepares graphite oxide, and graphite oxide is dispersed in water, the ultrasonic time is 10min, ultrasonic power is 600W, then removes visible particles by centrifugal rotational speed 4000rpm, obtains graphene oxide solution.
The small size graphene oxide solution that is 0.5mg/ml by concentration is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching, until solution is completely icing, is then carried out In-situ condensation and is dried. After dry, obtain the loose graphene oxide material of oversubscription, then by its 900 DEG C of reduction under the protection of Ar gas, thereby the loose Graphene of oversubscription obtained.
Electron microscopic observation result shows: under this kind of condition, in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 95% in few layer of dispersity.
Embodiment 6
The preparation method of graphene oxide solution is with embodiment 5.
The graphene oxide solution that is 6mg/ml by concentration is heated to 40 DEG C and directly puts into liquid nitrogen cold quenching, until solution is completely icing, is then carried out In-situ condensation and is dried. After dry, obtain the loose graphene oxide material of oversubscription, then by its 900 DEG C of reduction under the protection of Ar gas, thereby the loose Graphene of oversubscription obtained.
Electron microscopic observation result shows: under this kind of condition, in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 85% in few layer of dispersity.
Embodiment 7
The preparation method of graphene oxide solution is with embodiment 1.
The graphene oxide solution that is 0.5mg/ml by concentration is heated to 80 DEG C and directly puts into liquid nitrogen cold quenching, until solution is completely icing, is then carried out In-situ condensation and is dried. After dry, obtain the loose graphene oxide material of oversubscription, then by its 900 DEG C of reduction under the protection of Ar gas, thereby the loose Graphene of oversubscription obtained.
Electron microscopic observation result shows: under this kind of condition, in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 60% in few layer of dispersity, and other generations are curling.
Embodiment 8
The preparation method of graphene oxide solution is with embodiment 1.
The graphene oxide solution that is 0.5mg/ml by concentration is heated to 100 DEG C and directly puts into liquid nitrogen cold quenching, until solution is completely icing, is then carried out In-situ condensation and is dried. After dry, obtain the loose graphene oxide material of oversubscription, then by its 900 DEG C of reduction under the protection of Ar gas, thereby the loose Graphene of oversubscription obtained.
Electron microscopic observation result shows: under this kind of condition, in graphene powder, Graphene agreement that contracts a film or TV play to an actor or actress has more than 50% in few layer of dispersity, and other generations are curling.
Claims (5)
1. liquid nitrogen cold quenching is prepared a method for the loose Graphene of oversubscription, it is characterized in that the method step is:
A, graphene oxide solution cold quenching in liquid nitrogen: the graphene oxide solution that is 0.5mg/ml～8mg/ml by concentration is put into liquid nitrogen cold quenching after being heated to 30 DEG C～100 DEG C, until solution is taken out after freezing completely, carry out In-situ condensation and be dried to graphene oxide bone dry;
B, the loose graphene oxide reduction of oversubscription: dry graphene oxide is removed oxygen-containing functional group wherein by the mode of heating or electronation, thereby obtained the loose graphene powder of oversubscription.
2. the method for claim 1, the concentration that it is characterized in that graphene oxide solution in steps A is 0.5mg/ml～6mg/ml.
3. the method for claim 1, is characterized in that the temperature heating in steps A is 30 DEG C～60 DEG C.
4. the method for claim 1, the heating-up temperature that it is characterized in that thermal reduction in step B is 300 DEG C～900 DEG C.
5. the method for claim 1, is characterized in that in step B, hydrazine hydrate steam reduction is selected in electronation, and the time of electronation is 8h～16h.
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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 |
| CN108394897B (en) * | 2018-05-25 | 2020-12-08 | 清华-伯克利深圳学院筹备办公室 | Macroscopic preparation method of porous graphene oxide |
| 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 |
| 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 |
| 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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