Sulfur and oxygen co-doped graphene and preparation method and application thereof

Abstract

The application relates to the technical field of preparation of heteroatom-doped graphene, and discloses sulfur-oxygen co-doped graphene as well as a preparation method and application thereof, wherein the sulfur-oxygen co-doped graphene contains: a) 1-9% of sulfur element; and b) 5-13% of oxygen element in terms of weight percentage; and the specific surface area of the sulfur-oxygen co-doped graphene is 600 m 2 / g-1000 m 2 / g. The sulfur-oxygen co-doped graphene has the characteristics of simple preparation process, high specific surface area and good capacitance performance, and can be used for supercapacitor electrode materials.

Description

Technical Field

[0001] This invention relates to the field of preparation technology of heteroatom-doped graphene, specifically to a sulfur-oxygen co-doped graphene, its preparation method, and its application. Background Technology

[0002] Graphene is a type of poly(phosphorus) 2 A novel material with hybridized carbon atoms tightly packed into a single-layer two-dimensional honeycomb lattice structure possesses excellent optical, electrical, and mechanical properties. It has significant application prospects in materials science, micro-nano fabrication, energy, biomedicine, and drug delivery, and is considered a revolutionary material for the future.

[0003] Supercapacitors have advantages such as fast charging and discharging speed, high power density, good low-temperature performance, high safety, and long cycle life, and are widely used in electronic equipment, rail transportation, heavy machinery, and renewable energy.

[0004] Two-dimensional graphene possesses high electron mobility and a high specific surface area, making it suitable as an electrode material for supercapacitors. By doping the graphene lattice with sulfur and oxygen atoms, a pseudocapacitive effect can be generated during charge and discharge by reacting with the electrolyte through a redox reaction, thereby improving the specific capacitance and energy density of the supercapacitor.

[0005] Currently, the main methods for preparing sulfur-doped graphene include chemical vapor deposition, thermal annealing, solvothermal method, and mechanochemical method.

[0006] CN 105374573A discloses a method for preparing sulfur-doped graphene-based supercapacitor electrode materials. The method involves preparing graphene material using methane, argon, and hydrogen, coating the graphene surface with a dibenzyl disulfide solution, and annealing in an argon atmosphere to obtain the sulfur-doped graphene-based supercapacitor electrode material. This electrode material achieves a specific capacitance of 376.5 F / g in a 6 mol / L KOH electrolyte at a voltage scan rate of 2 mV / s. However, this method requires radio frequency plasma chemical vapor deposition, uses only metallic Ni / Pt / Cu as the current collector material, involves high reaction temperatures (600–800 °C), and has high production costs.

[0007] CN 104577141A discloses a sulfur-doped graphene-modified electrode, its preparation method, and its application. The method involves preparing sulfur-doped graphene by hydrothermal treatment of an aqueous solution of graphene oxide and sodium sulfide. This method requires heat treatment (180–210°C), and the hydrothermal product needs to be repeatedly washed with water, acetone, and ethanol sequentially.

[0008] While the aforementioned techniques can produce sulfur-doped graphene, chemical vapor deposition and thermal annealing are complex processes with high reaction temperatures, making them unsuitable for co-doping of sulfur and oxygen. Although the solvothermal method has a slightly lower heat treatment temperature, heating is still essential, and the product needs to be separated and purified. Solid-phase mechanical chemical reaction does not require heating, but the reaction time is long, the product needs to be separated and purified, and the specific surface area is low, resulting in low capacitance performance of the sulfur-doped graphene produced. Summary of the Invention

[0009] The purpose of this invention is to overcome the problems of complex preparation methods, low specific surface area, and poor capacitance performance of existing sulfur-oxygen co-doped graphene, and to provide a sulfur-oxygen co-doped graphene and its preparation method. This sulfur-oxygen co-doped graphene has the characteristics of simple process, high specific surface area, and good capacitance performance.

[0010] To achieve the above objectives, the present invention provides a sulfur-oxygen co-doped graphene, wherein, by weight percentage, the sulfur-oxygen co-doped graphene contains: a) 1% to 9% sulfur; b) 5% to 13% oxygen; and the specific surface area of ​​the sulfur-oxygen co-doped graphene is 600 m². 2 / g~1000m 2 / g.

[0011] The second aspect of the present invention provides a method for preparing sulfur-oxygen co-doped graphene according to the present invention, the method comprising: grinding graphite oxide and / or graphene oxide solid with hydrogen sulfide gas, wherein the grinding conditions include: a rotation speed of 1140 rpm to 1995 rpm and a vibration rate of 700 rpm to 1225 rpm.

[0012] This invention uses solid-phase graphene oxide and / or graphene oxide and gaseous hydrogen sulfide as raw materials. Under grinding conditions of 1140 rpm to 1995 rpm and vibration rate of 700 rpm to 1225 rpm, graphene oxide is rapidly exfoliated into graphene oxide. The oxygen-containing functional groups on the surface of the graphene oxide undergo a gas-solid phase doping reduction reaction with hydrogen sulfide to rapidly generate sulfur-oxygen co-doped graphene. The reaction products of this invention do not require separation and purification processes.

[0013] A third aspect of the present invention provides the application of the sulfur-oxygen co-doped graphene described herein as an electrode material for supercapacitors.

[0014] This invention increases the interlayer spacing of graphene by doping with sulfur and oxygen atoms, and the shorter reaction time of ball milling reduces the secondary agglomeration of graphene sheets, resulting in sulfur and oxygen-doped graphene with a high specific surface area. The double-layer capacitance formed by the high surface area and the pseudocapacitance formed by sulfur and oxygen doping give the supercapacitor excellent electrochemical performance. Attached Figure Description

[0015] Figure 1The X-ray diffraction patterns are those of natural graphite, graphite oxide used in Example 1, and sulfur-oxygen co-doped graphene prepared in Example 1.

[0016] Figure 2 This is a scanning electron microscope image of the sulfur-oxygen co-doped graphene prepared in Example 1.

[0017] Figure 3 This is a transmission electron microscope image of the sulfur-oxygen co-doped graphene prepared in Example 1.

[0018] Figure 4 The X-ray photoelectron spectra are those of the graphene oxide used in Example 1 and the sulfur-oxygen co-doped graphene prepared in Example 1.

[0019] Figure 5 This is the nitrogen adsorption isotherm of the sulfur-oxygen co-doped graphene prepared in Example 1. Detailed Implementation

[0020] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] This invention provides a sulfur-oxygen co-doped graphene, which, by weight percentage, contains: a) 1%–9% sulfur; b) 5%–13% oxygen; and has a specific surface area of ​​600 m². 2 / g~1000m 2 / g.

[0022] The sulfur-oxygen co-doped graphene of this invention has the characteristics of high specific surface area and good capacitance performance, making it particularly suitable for use as an electrode material for supercapacitors.

[0023] In this invention, sulfur-oxygen co-doped graphene possessing the aforementioned characteristics can achieve the objectives of this invention. There are no special requirements for the preparation method of the sulfur-oxygen co-doped graphene. According to a preferred embodiment of this invention, the preparation method of the sulfur-oxygen co-doped graphene includes:

[0024] The graphite oxide and / or graphene oxide were ground with hydrogen sulfide gas under the following conditions: a rotation speed of 1140 rpm to 1995 rpm and a vibration rate of 700 rpm to 1225 rpm.

[0025] According to a particularly preferred embodiment of the present invention, the ball milling is performed on a three-dimensional high-energy vibration ball mill, and the method for preparing the sulfur-oxygen co-doped graphene includes:

[0026] (1) Put graphite oxide and / or graphene oxide and grinding balls into the grinding jar, seal the grinding jar and then evacuate it;

[0027] (2) Then hydrogen sulfide gas is introduced into the grinding jar;

[0028] (3) Install the grinding jar from step (2) onto the three-dimensional high-energy vibration ball mill for grinding. Adjust the rotation speed of the three-dimensional high-energy vibration ball mill to 1140 rpm to 1995 rpm and the vibration rate to 700 rpm to 1225 rpm.

[0029] This invention uses solid-phase graphite oxide and gaseous hydrogen sulfide as raw materials. Under the action of three-dimensional synergistic mechanical forces, including high-speed oscillation, strong impact and vibration, in a three-dimensional high-energy vibrating ball mill, graphite oxide is rapidly exfoliated into graphene oxide. The oxygen-containing functional groups on the surface of graphene oxide undergo a gas-solid phase doping reduction reaction with hydrogen sulfide to rapidly generate sulfur-oxygen co-doped graphene.

[0030] In this invention, as long as the purpose of this invention can be achieved, there are no special requirements for the weight ratio of the grinding ball to graphite oxide and / or graphene oxide. According to a preferred embodiment of this invention, the weight ratio of the grinding ball to graphite oxide and / or graphene oxide in step (1) is (5-80):1.

[0031] In this invention, as long as the purpose of this invention can be achieved, there are no special requirements for the material of the grinding ball and the grinding jar. According to a preferred embodiment of this invention, the grinding ball and the grinding jar are made of agate.

[0032] In this invention, as long as the purpose of this invention can be achieved, the grinding conditions can be conventionally selected in the art. According to a preferred embodiment of this invention, the grinding conditions include: a grinding time of 2 minutes to 60 minutes.

[0033] According to a preferred embodiment of the present invention, the grinding conditions further include: a hydrogen sulfide gas pressure of 0.5 MPa to 3 MPa.

[0034] According to a preferred embodiment of the present invention, the three-dimensional high-energy vibration ball mill has a front-to-back amplitude of, for example, 59 mm and a left-to-right amplitude of 25 mm.

[0035] In this invention, as long as the objective of the invention can be achieved, there are no particular requirements on the weight ratio of hydrogen sulfide to graphite oxide and / or graphene oxide. According to a preferred embodiment of the invention, the weight ratio of hydrogen sulfide to graphite oxide and / or graphene oxide is (0.2–20):1. In this invention, as long as the objective of the invention can be achieved, there are no particular requirements on the oxygen percentage content of the graphite oxide and / or graphene oxide. According to a preferred embodiment of the invention, the oxygen percentage content in the graphite oxide and / or graphene oxide is 24%–48% by weight.

[0036] A third aspect of the present invention provides the application of the sulfur-oxygen co-doped graphene described herein as an electrode material for supercapacitors.

[0037] This invention increases the interlayer spacing of graphene by doping with sulfur and oxygen atoms, and the short reaction time of three-dimensional high-energy vibration ball milling reduces the secondary agglomeration of graphene sheets, resulting in sulfur and oxygen doped graphene with a high specific surface area. The double-layer capacitance formed by the high surface area and the pseudocapacitance formed by sulfur and oxygen doping make the supercapacitor have excellent electrochemical performance.

[0038] The present invention will be further described below through specific embodiments, but the scope of the present invention is not limited to the scope covered by the embodiments. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained through commercial channels.

[0039] Example 1

[0040] One gram of graphite oxide and 6.4 grams of agate grinding balls were placed in an agate grinding jar. The graphite oxide contained 30.2% oxygen by weight. After sealing, a vacuum was applied. 1.3 grams of hydrogen sulfide gas were introduced into the grinding jar, bringing the pressure inside to 2 MPa. The grinding jar was then mounted on a three-dimensional high-energy vibratory ball mill, and the milling was started at a speed of 1425 rpm, a vibration rate of 875 rpm, a front-to-back amplitude of 59 mm, and a left-to-right amplitude of 25 mm. The milling time was 10 minutes. The milled product was sulfur-oxygen co-doped graphene, containing 8.3% sulfur by weight, 5.82% oxygen by weight, and a specific surface area of ​​951 m². 2 / g.

[0041] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 480 F / g at a current density of 0.5 A / g.

[0042] Example 2

[0043] 0.5 g of graphene oxide and 6.4 g of agate grinding balls were placed in an agate grinding jar. The graphene oxide contained 30.2% oxygen by weight. After sealing, a vacuum was applied. 1.3 g of hydrogen sulfide gas was introduced into the grinding jar, and the pressure of the hydrogen sulfide gas inside the jar was 2 MPa. The grinding jar was then installed on a three-dimensional high-energy vibration ball mill, and the milling was started at a speed of 1725 rpm, a vibration rate of 1060 rpm, a front-to-back amplitude of 59 mm, and a left-to-right amplitude of 25 mm. The milling time was 20 minutes. The milling product was sulfur-oxygen co-doped graphene, with a sulfur weight percentage of 5.98%, an oxygen weight percentage of 10.88%, and a specific surface area of ​​653 m². 2 / g.

[0044] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 381 F / g at a current density of 0.5 A / g.

[0045] Example 3

[0046] One gram of graphene oxide and 6.4 grams of agate grinding balls were placed in an agate grinding jar. The graphene oxide contained 30.2% oxygen by weight. After sealing, a vacuum was applied. 1.3 grams of hydrogen sulfide gas was introduced into the grinding jar, and the pressure of the hydrogen sulfide gas inside the jar was 2 MPa. The grinding jar was then mounted on a three-dimensional high-energy vibratory ball mill, and the milling was started at a speed of 1425 rpm, a vibration rate of 875 rpm, a front-to-back amplitude of 59 mm, a left-to-right amplitude of 25 mm, and a milling time of 2 minutes. The milling product was sulfur-oxygen co-doped graphene, with a sulfur weight percentage of 1.51%, an oxygen weight percentage of 12.70%, and a specific surface area of ​​701 m². 2 / g.

[0047] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 367 F / g at a current density of 0.5 A / g.

[0048] Example 4

[0049] One gram of graphene oxide and 6.4 grams of agate grinding balls were placed in an agate grinding jar. The graphene oxide contained 30.2% oxygen by weight. After sealing, a vacuum was applied. 1.3 grams of hydrogen sulfide gas were introduced into the grinding jar, bringing the pressure inside to 2 MPa. The grinding jar was then mounted on a three-dimensional high-energy vibratory ball mill, and the milling was started at a speed of 1425 rpm, a vibration rate of 875 rpm, a front-to-back amplitude of 59 mm, and a left-to-right amplitude of 25 mm. The milling time was 50 minutes. The milled product was sulfur-oxygen co-doped graphene, containing 3.41% sulfur by weight, 5.51% oxygen by weight, and a specific surface area of ​​624 m². 2 / g.

[0050] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 293 F / g at a current density of 0.5 A / g.

[0051] Example 5

[0052] 0.3 g of graphene oxide and 6.4 g of agate grinding balls were placed in an agate grinding jar. The graphene oxide contained 30.2% oxygen by weight. After sealing, a vacuum was applied. 1.3 g of hydrogen sulfide gas was introduced into the grinding jar, and the pressure of the hydrogen sulfide gas inside the jar was 2 MPa. The grinding jar was then installed on a three-dimensional high-energy vibratory ball mill, and the milling was started at a speed of 1425 rpm, a vibration rate of 875 rpm, a front-to-back amplitude of 59 mm, a left-to-right amplitude of 25 mm, and a milling time of 10 minutes. The milling product was sulfur-oxygen co-doped graphene, with a sulfur weight percentage of 3.60%, an oxygen weight percentage of 9.72%, and a specific surface area of ​​761 m². 2 / g.

[0053] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 411 F / g at a current density of 0.5 A / g.

[0054] Example 6

[0055] 0.1 g of graphene oxide and 6.4 g of agate grinding balls were placed in an agate grinding jar. The graphene oxide contained 30.2% oxygen by weight. After sealing, a vacuum was applied. 1.95 g of hydrogen sulfide gas was introduced into the grinding jar, and the pressure of the hydrogen sulfide gas inside the jar was 3 MPa. The grinding jar was then installed on a three-dimensional high-energy vibration ball mill, and the milling was started at a speed of 1425 rpm, a vibration rate of 875 rpm, a front-to-back amplitude of 59 mm, a left-to-right amplitude of 25 mm, and a milling time of 30 minutes. The milling product was sulfur-oxygen co-doped graphene, with a sulfur weight percentage of 6.65%, an oxygen weight percentage of 5.94%, and a specific surface area of ​​881 m². 2 / g.

[0056] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 440 F / g at a current density of 0.5 A / g.

[0057] Example 7

[0058] One gram of graphene oxide and 6.4 grams of agate grinding balls were placed in an agate grinding jar. The graphene oxide contained 30.2% oxygen by weight. After sealing, a vacuum was applied. 0.65 grams of hydrogen sulfide gas was introduced into the grinding jar, and the pressure of the hydrogen sulfide gas inside the jar was 1 MPa. The grinding jar was then mounted on a three-dimensional high-energy vibratory ball mill, and the milling was started at a speed of 1725 rpm, a vibration rate of 1060 rpm, a front-to-back amplitude of 59 mm, and a left-to-right amplitude of 25 mm. The milling time was 10 minutes. The milled product was sulfur-oxygen co-doped graphene, with a sulfur weight percentage of 2.30%, an oxygen weight percentage of 6.32%, and a specific surface area of ​​910 m². 2 / g.

[0059] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 394 F / g at a current density of 0.5 A / g.

[0060] Example 8

[0061] One gram of graphene oxide and 6.4 grams of agate grinding balls were placed in an agate grinding jar. The graphene oxide contained 42.92% oxygen by weight. After sealing, a vacuum was applied. 1.3 grams of hydrogen sulfide gas were introduced into the grinding jar, bringing the pressure inside to 2 MPa. The grinding jar was then mounted on a three-dimensional high-energy vibration ball mill, and the milling process was started at a speed of 1425 rpm, a vibration rate of 875 rpm, a front-to-back amplitude of 59 mm, and a left-to-right amplitude of 25 mm. The milling time was 20 minutes. The milled product was sulfur-oxygen co-doped graphene, containing 7.76% sulfur by weight, 5.33% oxygen by weight, and a specific surface area of ​​895 m². 2 / g.

[0062] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 453 F / g at a current density of 0.5 A / g.

[0063] Example 9

[0064] 0.3 g of graphene oxide and 6.4 g of agate grinding balls were placed in an agate grinding jar. The graphene oxide contained 26.50% oxygen by weight. After sealing, a vacuum was applied. 1.95 g of hydrogen sulfide gas was introduced into the grinding jar, and the pressure of the hydrogen sulfide gas inside the jar was 3 MPa. The grinding jar was then installed on a three-dimensional high-energy vibratory ball mill, and the milling was started at a speed of 1725 rpm, a vibration rate of 1060 rpm, a front-to-back amplitude of 59 mm, and a left-to-right amplitude of 25 mm. The milling time was 10 minutes. The milling product was sulfur-oxygen co-doped graphene, with a sulfur weight percentage of 6.22%, an oxygen weight percentage of 10.20%, and a specific surface area of ​​674 m². 2 / g.

[0065] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 396 F / g at a current density of 0.5 A / g.

[0066] Comparative Example 1

[0067] One gram of graphite oxide and 160 grams of agate grinding balls were placed in an agate grinding jar, containing 280 agate balls with a diameter of 6 mm and 40 agate balls with a diameter of 10 mm. The jar was sealed and then evacuated. 7.5 grams of hydrogen sulfide gas were introduced into the grinding jar, and the pressure of the hydrogen sulfide gas inside the jar was 2 MPa. The grinding jar was then installed on a planetary ball mill, and the mill was started. The mill rotation speed was 500 rpm, the speed ratio (rotation:revolution) was 2, and the milling time was 8 hours. The milling product was sulfur-oxygen co-doped graphene, with a sulfur weight percentage of 5.98%, an oxygen weight percentage of 14.94%, and a specific surface area of ​​236 m². 2 / g.

[0068] Sulfur-oxygen co-doped graphene, acetylene black, and binder were mixed uniformly in a mass ratio of 8:1:1 and pressed onto a current collector to form a supercapacitor electrode material. Electrochemical performance was tested in a 1 mol / L H2SO4 electrolyte, and the specific capacitance was 160 F / g at a current density of 0.5 A / g.

[0069] In the attached diagram,

[0070] Figure 1 The X-ray diffraction patterns are those of natural graphite, graphite oxide used in Example 1, and sulfur-oxygen co-doped graphene prepared in Example 1. Figure 1 In the study, sulfur-oxygen co-doped graphene showed no obvious X-ray diffraction peaks at 2θ = 26.6° (attributed to graphite) and 2θ = 10.8° (attributed to graphite oxide), exhibiting the characteristics of graphene X-ray diffraction.

[0071] Figure 2 This is a scanning electron microscope image of the sulfur-oxygen co-doped graphene prepared in Example 1. Figure 2 In the process, transparent, silk-like graphene sheets are stacked on top of each other to form fluffy, porous graphene particles.

[0072] Figure 3 This is a transmission electron microscope image of the sulfur-oxygen co-doped graphene prepared in Example 1. Figure 3 In the process, graphene sheets are nearly transparent under electron beam irradiation, and their surface exhibits intrinsic wrinkles, with 1 to 5 graphene layers.

[0073] Figure 4 The X-ray photoelectron spectra are those of the graphene oxide used in Example 1 and the sulfur-oxygen co-doped graphene prepared in Example 1. Figure 4 In the graphene lattice, the peak at 284.6 eV corresponds to the C1s peak, the peak at 531.8 eV corresponds to the O1s peak, the peak at 163.5 eV corresponds to the S 2p peak, and the peak at 227.9 eV corresponds to the S 2s peak, indicating that some sulfur and oxygen atoms have replaced carbon atoms and entered the graphene lattice.

[0074] Figure 5 This is the nitrogen adsorption isotherm of the sulfur-oxygen co-doped graphene prepared in Example 1. Figure 5 In the study, nitrogen adsorption tests at 77K showed that sulfur-oxygen co-doped graphene contains a large number of micropores and mesopore interfaces.

[0075] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing sulfur-oxygen co-doped graphene, characterized in that, The method includes: Graphite oxide and / or graphene oxide are ground with hydrogen sulfide gas under the following conditions: rotation speed of 1140 rpm to 1995 rpm and vibration speed of 700 rpm to 1225 rpm. The sulfur-oxygen co-doped graphene contains, by weight percentage: a) 1%–9% sulfur; b) 5%–13% oxygen; and has a specific surface area of ​​600 m². 2 / g~1000 m 2 / g.

2. The preparation method according to claim 1, wherein, The method includes: (1) Put graphite oxide and / or graphene oxide and grinding balls into the grinding jar, seal the grinding jar and then evacuate it; (2) Then hydrogen sulfide gas is introduced into the grinding jar; (3) Install the grinding jar from step (2) onto the three-dimensional high-energy vibration ball mill for grinding. Adjust the rotation speed of the three-dimensional high-energy vibration ball mill to 1140 rpm to 1995 rpm and the vibration rate to 700 rpm to 1225 rpm.

3. The preparation method according to claim 2, wherein, The weight ratio of the grinding balls to graphite oxide and / or graphene oxide in step (1) is (5-80):

1.

4. The preparation method according to claim 2 or 3, wherein, The grinding balls and the grinding jar in step (1) are made of agate.

5. The preparation method according to claim 2 or 3, wherein, Grinding conditions include a time of 2 to 60 minutes.

6. The preparation method according to claim 2 or 3, wherein, The grinding conditions include a hydrogen sulfide gas pressure of 0.5 MPa to 3 MPa.

7. The preparation method according to claim 2 or 3, wherein the grinding conditions include: The weight ratio of hydrogen sulfide to the graphite oxide and / or graphene oxide is (0.2–20):

1.

8. The preparation method according to claim 2 or 3, wherein, The weight percentage of oxygen in graphite oxide and / or graphene oxide is 24% to 48%.

9. The application of sulfur-oxygen co-doped graphene obtained by the preparation method of claim 1 or 2 as an electrode material for supercapacitors.

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