Preparation method and application of sulfur-doped graphene and derivatives thereof

Abstract

The invention relates to a preparation method of sulfur-doped graphene and derivatives thereof. The method includes the following steps: 1) uniformly mixing a solution of the graphene and the derivatives thereof with an sulfur-containing ionic group solution to prepare a suspension liquid; 2) freeze-drying the suspension liquid to obtain a solid mixture of the graphene and the derivatives thereof with the sulfur-containing ionic salt; 3) under protective atmosphere, calcining the solid mixture of the graphene and the derivatives thereof with the sulfur-containing ionic salt to obtain an intermediate of the sulfur-doped graphene and derivatives thereof; and 4) cooling, washing and drying the intermediate to obtain a finish product of the sulfur-doped graphene and derivatives thereof. The preparation method is simple in operation, employs common devices, is low in cost and achieves industrial production. The sulfur-doped graphene and derivatives thereof has very high specific surface area, has penetrated porous structure and has high pore capacity and high electric conductivity.

Description

technical field

[0001] The invention belongs to the field of graphene, and relates to a sulfur-doped graphene, a sulfur-doped graphene derivative, a preparation method and an application thereof, in particular to a preparation method of doping graphene and its derivatives with inorganic sulfur-containing substances Sulfur-doped graphene method. Background technique

[0002] Graphene is a sp 2 The periodic honeycomb two-dimensional carbonaceous new material formed by hybridized carbon atoms arranged in a hexagon has ultra-high hardness and its theoretical specific surface area is as high as 2630m 2 / g, and are currently being widely used as raw materials for sensors, batteries, supercapacitors, etc.

[0003] Doping can change the electronic structure of graphene, effectively changing the band gap of graphene. The incorporation of heteroatoms into the graphene lattice can not only effectively introduce a band gap, but also increase the defects and local reactivity of graphe...

Examples

Embodiment 1

[0045]A preparation method of sulfur-doped graphene material, comprising the steps of:

[0046] (1) In the potassium sulfate solution 100mL containing 10g / L, add the graphene solution 1mL that concentration is 10g / L, and mix uniformly, obtain mixed suspension; The mass ratio of graphene and potassium sulfate in the suspension is 0.01:1 ;

[0047] (2) freeze-drying the suspension that step (1) obtains, obtains the solid mixture of graphene and potassium sulfate;

[0048] (3) in N 2 Under the protection of gas, the solid mixture of the obtained graphene and potassium sulfate was calcined at a high temperature of 300 ° C for 30 h to obtain a sulfur-doped graphene intermediate product;

[0049] (4) Cool the sulfur-doped graphene intermediate product to 20° C., wash with ultrapure water, and then dry to obtain the sulfur-doped graphene final product.

[0050] The sulfur-doped graphene that embodiment 1 obtains is carried out transmission electron microscope scanning on Hitachi J...

Embodiment 2

[0054] A preparation method of sulfur-doped graphene material, comprising the steps of:

[0055] (1) in the potassium sulfate solution 10mL that contains 0.1g / L, add the graphene solution 5mL that concentration is 10g / L, and mix uniformly, obtain mixed suspension, the mass ratio of graphene and potassium sulfate in the suspension is 5: 1;

[0056] (2) freeze-drying the suspension that step (1) obtains, obtains the solid mixture of graphene and potassium sulfate;

[0057] (3) in N 2 Under the protection of gas, the obtained graphene and potassium sulfate solid were calcined at a high temperature of 1200 ° C for 2 hours to obtain a sulfur-doped graphene intermediate product;

[0058] (4) Cool the obtained sulfur-doped graphene intermediate product to 30° C., wash with ultrapure water, and then dry to obtain the sulfur-doped graphene final product.

[0059] The sulfur-doped graphene that embodiment 2 obtains is carried out transmission electron microscope scanning, and scannin...

Embodiment 3

[0061] A preparation method of sulfur-doped graphene material, comprising the steps of:

[0062] (1) in the magnesium sulfate solution 100mL that contains 0.1g / L, add the graphene solution 1mL that concentration is 10g / L, and mix uniformly, obtain mixed suspension, the mass ratio of graphene and magnesium sulfate in the suspension is 1: 1;

[0063] (2) the suspension obtained in step (1) is freeze-dried to obtain a solid mixture of graphene oxide and magnesium sulfate;

[0064] (3) in N 2 Under the protection of gas, the solid mixture of the obtained graphene and magnesium sulfate was calcined at a high temperature of 800 ° C for 2 hours to obtain a sulfur-doped graphene intermediate product;

[0065] (4) After the obtained product is cooled to 30°C, it is washed with ultrapure water and dried.

[0066] The sulfur-doped graphene obtained in Example 3 is scanned by a transmission electron microscope, and the scanning conditions are the same as in Example 1; the test results ...

technical field

[0001] The invention belongs to the field of graphene, and relates to a sulfur-doped graphene, a sulfur-doped graphene derivative, a preparation method and an application thereof, in particular to a preparation method of doping graphene and its derivatives with inorganic sulfur-containing substances Sulfur-doped graphene method. Background technique

[0002] Graphene is a sp 2 The periodic honeycomb two-dimensional carbonaceous new material formed by hybridized carbon atoms arranged in a hexagon has ultra-high hardness and its theoretical specific surface area is as high as 2630m 2 / g, and are currently being widely used as raw materials for sensors, batteries, supercapacitors, etc.

[0003] Doping can change the electronic structure of graphene, effectively changing the band gap of graphene. The incorporation of heteroatoms into the graphene lattice can not only effectively introduce a band gap, but also increase the defects and local reactivity of graphe...

Examples

Embodiment 1

[0045]A preparation method of sulfur-doped graphene material, comprising the steps of:

[0046] (1) In the potassium sulfate solution 100mL containing 10g / L, add the graphene solution 1mL that concentration is 10g / L, and mix uniformly, obtain mixed suspension; The mass ratio of graphene and potassium sulfate in the suspension is 0.01:1 ;

[0047] (2) freeze-drying the suspension that step (1) obtains, obtains the solid mixture of graphene and potassium sulfate;

[0048] (3) in N 2 Under the protection of gas, the solid mixture of the obtained graphene and potassium sulfate was calcined at a high temperature of 300 ° C for 30 h to obtain a sulfur-doped graphene intermediate product;

[0049] (4) Cool the sulfur-doped graphene intermediate product to 20° C., wash with ultrapure water, and then dry to obtain the sulfur-doped graphene final product.

[0050] The sulfur-doped graphene that embodiment 1 obtains is carried out transmission electron microscope scanning on Hitachi J...

Embodiment 2

[0054] A preparation method of sulfur-doped graphene material, comprising the steps of:

[0055] (1) in the potassium sulfate solution 10mL that contains 0.1g / L, add the graphene solution 5mL that concentration is 10g / L, and mix uniformly, obtain mixed suspension, the mass ratio of graphene and potassium sulfate in the suspension is 5: 1;

[0056] (2) freeze-drying the suspension that step (1) obtains, obtains the solid mixture of graphene and potassium sulfate;

[0057] (3) in N 2 Under the protection of gas, the obtained graphene and potassium sulfate solid were calcined at a high temperature of 1200 ° C for 2 hours to obtain a sulfur-doped graphene intermediate product;

[0058] (4) Cool the obtained sulfur-doped graphene intermediate product to 30° C., wash with ultrapure water, and then dry to obtain the sulfur-doped graphene final product.

[0059] The sulfur-doped graphene that embodiment 2 obtains is carried out transmission electron microscope scanning, and scannin...

Embodiment 3

[0061] A preparation method of sulfur-doped graphene material, comprising the steps of:

[0062] (1) in the magnesium sulfate solution 100mL that contains 0.1g / L, add the graphene solution 1mL that concentration is 10g / L, and mix uniformly, obtain mixed suspension, the mass ratio of graphene and magnesium sulfate in the suspension is 1: 1;

[0063] (2) the suspension obtained in step (1) is freeze-dried to obtain a solid mixture of graphene oxide and magnesium sulfate;

[0064] (3) in N 2 Under the protection of gas, the solid mixture of the obtained graphene and magnesium sulfate was calcined at a high temperature of 800 ° C for 2 hours to obtain a sulfur-doped graphene intermediate product;

[0065] (4) After the obtained product is cooled to 30°C, it is washed with ultrapure water and dried.

[0066] The sulfur-doped graphene obtained in Example 3 is scanned by a transmission electron microscope, and the scanning conditions are the same as in Example 1; the test results ...

Images