CN108383115A

CN108383115A - A kind of method that room temperature is prepared on a large scale high-quality graphene

Info

Publication number: CN108383115A
Application number: CN201810382328.2A
Authority: CN
Inventors: 张瑞军; 刘孟杰; 吴文玉
Original assignee: Yanshan University
Current assignee: Yanshan University
Priority date: 2018-04-26
Filing date: 2018-04-26
Publication date: 2018-08-10
Anticipated expiration: 2038-04-26
Also published as: CN108383115B

Abstract

A kind of method that room temperature is prepared on a large scale high-quality graphene is mainly to be by volume with Peracetic acid by the concentrated sulfuric acid：1~20：1~10 ratio ultrasonic mixing is uniform, and mixed liquor is made；According to the ratio that 0.05~0.5g graphite is added in every 5ml mixed liquors, graphite and mixed liquor are stirred evenly into rear room temperature and stand 1~12h, neutral, drying is then washed to, graphene is made.The present invention realize oxidation, intercalation, it is puffing and stripping four be carried out at the same time, enormously simplify the preparation process of graphene；Whole preparation process is completed at normal temperatures, is not necessarily to high temperature or irradiation, energy saving；Whole process is easy to operate, saves labour, liberates the productive forces, and can be prepared on a large scale high-quality graphene, direction is provided for large-scale industrial production.

Description

A kind of method that room temperature is prepared on a large scale high-quality graphene

Technical field

The invention belongs to new material technology field, more particularly to a kind of preparation method of graphene.

Background technology

Graphene is a kind of two-dimensional material of single graphite linings, is carbon atom with sp²Hybrid form is formed cellular thin Film, graphene are theoretical most thin and most hard nano materials known today, it is almost transparent, only absorbs 2.3% Light；This new carbon simultaneously there is high-specific surface area and excellent conduction, the capacity of heat transmission, thermal coefficient to be up to 5300W/ (mK), it is higher than carbon nanotube and diamond, its electron mobility is more than 15000cm under room temperature²/ (Vs), and compare nano-sized carbon Pipe or silicon crystal are high, and resistivity only has about 10^-6Ω cm, it is lower than copper or silver, it is the material of world resistivity minimum.Graphite Alkene material is macroscopically showing " lamination shape " as shale；On microcosmic, structure cell atom arranges stratification in three dimensions inner plane Shape, with Covalent bonding together between atom in layer, and atom between the layers is then interacted with Van der Waals force, therefore former in layer Bonding action between son is far longer than the interaction of atom between layers, to make its compound (0 dimension compared with other dimensions Fullerene, 1 dimension carbon nanotube, 3 dimension graphite) have unique crystal structure and special light, electricity, sound, mechanical property, by Graphene is made to be considered to be photoelectric material, energy storage material, microelectronic component, multifunctional composite and life in above-mentioned characteristic The research of object medicine and other fields is preferred.In the near future, graphene will be obtained in various fields such as catalysis, electronics, the energy Commercialized application.And scientist has found that graphene has the special physical effects and performance such as abnormal quantum hall effect, It is generally considered the final substituted for silicon of meeting, to cause the revolution again of electronics industry.

Since the two scientist An Deliegaimu (Andre Geim) and Ke Siteya of Univ Manchester UK Nuo Wo disappears a kind of few layer graphene that very simple mechanical separation method obtains of love (Konstantin Novoselov) And after obtaining Nobel Prize in physics, academic research and industrial requirement about graphene make graphene big yield, High quality preparation becomes particularly important.In general, the method for preparing graphene has：Mechanical stripping method, oxidation-reduction method, liquid Phase stripping method, electrochemical process etc., the method for micromechanics stripping is to utilize photoresist repeatedly by mechanical means in the above-mentioned methods The method that stripping graphite obtains graphene, this method is simple, but time-consuming and laborious, poor repeatability, it is difficult to accurately control；Most often at present Method is oxide-reduction method, and basic principle is to handle graphite by strong strong protonic acid, forms compound between graphite layers, Then it is aoxidized with strong oxidizer, forms graphene oxide, then reducing agent redox graphene is added in reduction step and obtains stone Black alkene, this method is high to temperature requirement and operating process is more complicated, can all cause certain injury to personnel and equipment, make Cause the processing of later stage spent acid relatively difficult with excessive acid amount；Also a kind of common method is liquid phase stripping method, and this method makes Make to remove graphite under the auxiliary of ultrasonic means with surfactant, but this method ultrasound needs super some time, The relatively low size for being generally 5% and destroying the graphene obtained by seriously causing to graphite-structure of yield is smaller (generally≤5 μm).Later stage for the surfactant on graphene cleaning also but also whole operation is time-consuming and laborious, this is also for water instantly It is undoubtedly for the deficienter overall situation of resource and makes the matter worse.

Therefore the technology for high-quality graphene being prepared on a large scale under a kind of energy room temperature becomes domestic and international graphene scientific research work The most important thing of author investigation work.

Invention content

The purpose of the invention is to existing insufficient in view of the above technology, provide a kind of process it is easy to operate, without height The method that temperature or irradiation, energy saving room temperature are prepared on a large scale high-quality graphene.

The present invention is as follows：

(1) by the concentrated sulfuric acid and Peracetic acid by volume 1~20：1~10 ratio ultrasonic mixing is uniform, and mixing is made Liquid；

(2) according to the ratio that 0.05~0.5g graphite is added in every 5ml mixed liquors, by the mixed liquor of graphite and step (1) It stirs evenly rear room temperature and stands 1~12h, then, be washed to neutral, dry, obtained graphene.

The graphite is the natural flake graphite of 50~500 mesh.

Compared with the prior art, the present invention has the following advantages：

1, realize oxidation, intercalation, it is puffing and stripping four be carried out at the same time, enormously simplify the preparation process of graphene.

2, whole preparation process is completed at normal temperatures, is not necessarily to high temperature or irradiation, energy saving.

3, whole process is easy to operate, saves labour, liberates the productive forces, and can be prepared on a large scale high quality graphite Alkene.

Description of the drawings

Fig. 1 is graphene scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1.

Fig. 2 is graphene transmission electron microscope picture prepared by the embodiment of the present invention 1.

Specific implementation mode

Embodiment 1

The concentrated sulfuric acid of 5ml a concentration of 98% and the Peracetic acid ultrasonic mixing of 5ml a concentration of 26% is uniform, mixing is made Liquid stirs and evenly mixs rear room temperature in the mixed liquor in being put into the natural graphite of 50 mesh of 0.1g and stands 12h, be then washed to it is neutral, It is dry, you can to obtain graphene, the number of plies of gained graphene is about 8 layers.

As shown in Figure 1, by the high-degree of conversion by graphite to graphene, the size of gained graphene is also bigger and compares It is relatively transparent.

As shown in Fig. 2, further illustrating that the graphene of gained is more transparent, than relatively thin.

Embodiment 2

The concentrated sulfuric acid of 1ml a concentration of 98% and the Peracetic acid ultrasonic mixing of 10ml a concentration of 26% is uniform, it is made mixed Liquid is closed, room temperature stands 5h after being stirred in the mixed liquor during the natural graphite of 80 mesh of 0.55g is put into, and is then washed to neutral, dry It is dry, you can to obtain graphene, the number of plies of gained graphene is about 15 layers.

Embodiment 3

The concentrated sulfuric acid of 20ml a concentration of 98% and the Peracetic acid ultrasonic mixing of 10ml a concentration of 26% is uniform, it is made mixed Liquid is closed, room temperature stands 8h after being stirred in the mixed liquor during the natural graphite of 300 mesh of 1g is put into, and is then washed to neutral, dry It is dry, you can to obtain graphene, the number of plies of gained graphene is about 25 layers.

Embodiment 4

The concentrated sulfuric acid of 15ml a concentration of 98% and the Peracetic acid ultrasonic mixing of 1ml a concentration of 26% is uniform, it is made mixed Liquid is closed, room temperature stands 3h after being stirred in the mixed liquor during the natural graphite of 300 mesh of 0.3g is put into, and is then washed to neutral, dry It is dry, you can to obtain graphene, the number of plies of gained graphene is about 30 layers.

Embodiment 5

The concentrated sulfuric acid of 1ml a concentration of 98% and the Peracetic acid ultrasonic mixing of 5ml a concentration of 26% is uniform, mixing is made Liquid, room temperature stands 1h after stirring in the mixed liquor during the natural graphite of 500 mesh of 0.42g is put into, and is then washed to neutral, dry It is dry, you can to obtain graphene, the number of plies of gained graphene is about 20 layers.

Embodiment 6

The concentrated sulfuric acid of 20ml a concentration of 98% and the Peracetic acid ultrasonic mixing of 1ml a concentration of 26% is uniform, it is made mixed Close liquid, room temperature stands 9h after stirring in the mixed liquor during the natural graphite of 100 mesh of 1.68g is put into, be then washed to it is neutral, It is dry, you can to obtain graphene, the number of plies of gained graphene is about 15 layers.

Embodiment 7

The concentrated sulfuric acid of 15ml a concentration of 98% and the Peracetic acid ultrasonic mixing of 5ml a concentration of 26% is uniform, it is made mixed Liquid is closed, room temperature stands 12h after being stirred in the mixed liquor during the natural graphite of 50 mesh of 2g is put into, and is then washed to neutral, dry It is dry, you can to obtain graphene, the number of plies of gained graphene is about 10 layers.

Claims

1. a kind of method that room temperature is prepared on a large scale high-quality graphene, it is characterised in that：It includes the following steps：

(1) by the concentrated sulfuric acid and Peracetic acid by volume 1~20：1~10 ratio ultrasonic mixing is uniform, and mixed liquor is made；

(2) according to the ratio that 0.05~0.5g graphite is added in every 5ml mixed liquors, graphite and the mixed liquor in step (1) are stirred Room temperature stands 1~12h after mixing uniformly, is then washed to neutral, drying, graphene is made.

2. the method that room temperature according to claim 1 is prepared on a large scale high-quality graphene, it is characterised in that：The graphite For the natural flake graphite of 50~500 mesh.