CN115571874A - Large lamellar graphene oxide and preparation method thereof - Google Patents
Large lamellar graphene oxide and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 321
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 238000011282 treatment Methods 0.000 claims abstract description 84
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 239000000138 intercalating agent Substances 0.000 claims abstract description 7
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- -1 oleum Chemical compound 0.000 claims abstract description 4
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- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
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- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 3
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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Abstract
The application discloses a large lamellar graphene oxide and a preparation method thereof, relating to the field of carbon materials; the method aims to solve the technical problem of low stripping efficiency when the existing preparation technology is used for preparing large-lamellar graphene oxide; the preparation method of the large-sheet-layer graphene oxide comprises the following steps: carrying out intercalation treatment on original graphite by using an intercalation solvent to obtain intercalated graphite; the intercalation solvent comprises an acidic intercalating agent comprising at least one of sulfuric acid, oleum, nitric acid, and phosphoric acid; wherein the mixing ratio of the original graphite to the acidic intercalating agent is 1g; carrying out expansion treatment on the intercalated graphite to obtain expanded graphite; carrying out oxidation treatment on the expanded graphite to obtain graphite oxide; and stripping the graphite oxide to obtain single-layer graphene oxide.
Description
Technical Field
The application relates to the field of carbon materials, in particular to a large lamellar graphene oxide and a preparation method thereof.
Background
Graphene and its derivatives such as graphite oxide, graphene oxide, and graphene nanoplatelets have a wide application prospect in nanoelectronic devices, conductive inks, multifunctional fibers, functionalized films, energy materials, and the like. The mechanical, electric, heat conducting and liquid crystal properties of the sheet carbon-like material are closely related to the size of the sheet layer and the defect density of the sheet carbon-like material. Generally, the combination of properties of the large-lamellar flaky carbon material is more excellent. However, the stripping efficiency of the existing preparation method is low when the large-lamellar graphene oxide is prepared.
Disclosure of Invention
The application mainly aims to provide a large-lamellar graphene oxide and a preparation method thereof, and aims to solve the technical problem that the stripping efficiency is low when the large-lamellar graphene oxide is prepared by the existing preparation technology.
In order to solve the technical problem, the application provides: a preparation method of large lamellar graphene oxide comprises the following steps:
performing intercalation treatment on the original graphite by using an intercalation solvent to obtain intercalated graphite; the intercalation solvent comprises an acidic intercalating agent comprising at least one of sulfuric acid, oleum, nitric acid, and phosphoric acid; wherein the mixing ratio of the original graphite to the acidic intercalation agent is 1g;
carrying out expansion treatment on the intercalated graphite to obtain expanded graphite;
carrying out oxidation treatment on the expanded graphite to obtain graphite oxide;
and stripping the graphite oxide to obtain single-layer graphene oxide.
As some optional embodiments herein, the intercalation solvent further comprises: an intercalation facilitating agent comprising ammonium persulfate;
wherein the mixing ratio of the original graphite to the ammonium persulfate is 1g.
As some optional embodiments herein, the intercalation facilitating agent further comprises: potassium permanganate;
wherein the mixing ratio of the original graphite to the potassium permanganate is 1g.
As some optional embodiments of the present application, the intercalation temperature of the intercalation treatment is 25-100 ℃, and the intercalation time is 20 min-8 h.
As some optional embodiments of the present application, the expansion process comprises: at least one of microwave expansion treatment, hydrogen peroxide expansion treatment and electrochemical expansion treatment.
As some optional embodiments of the present application, when the expansion treatment is a microwave expansion treatment, the treatment power is 500-5000W, and the treatment time is 30 s-10 min.
As some optional embodiments of the present application, when the expansion treatment is hydrogen peroxide expansion treatment, the concentration of the hydrogen peroxide used is 20 to 80wt%, and the treatment time is 30min to 24h.
As some optional embodiments of the present application, when the expansion treatment is an electrochemical expansion treatment, the treatment voltage is 2-20V, and the treatment time is 30 s-30 min.
As some alternative embodiments herein, the oxidizing agent used when the oxidizing treatment is performed comprises at least one of sulfuric acid, fuming sulfuric acid, nitric acid, and phosphoric acid;
wherein the mixing ratio of the expanded graphite to the oxidant is 1g.
As some alternative embodiments herein, the oxidizing agent further comprises potassium permanganate;
wherein the mixing ratio of the expanded graphite to the potassium permanganate is 1g.
As some optional embodiments of the present application, the subjecting the expanded graphite to an oxidation treatment to obtain graphite oxide includes:
mixing the expanded graphite with the oxidant to obtain a mixed solution;
and heating the mixed solution to 25-60 ℃ and oxidizing for 30 min-4 h to obtain graphite oxide.
As some optional embodiments of the present application, the subjecting the expanded graphite to an oxidation treatment to obtain graphite oxide includes:
mixing the expanded graphite with the oxidant to obtain a mixed solution;
heating the mixed solution to 25-60 ℃ and oxidizing for 30 min-4 h to obtain first graphite oxide;
and mixing the first graphite oxide with the acidic solution, heating to 60-100 ℃, and oxidizing for 10-40 min to obtain second graphite oxide.
As some alternative embodiments of the present application, the stripping treatment comprises several centrifugal water washing treatments.
In order to solve the technical problem, the application also provides a large lamellar graphene oxide prepared by the method.
Compared with the prior art, the preparation method disclosed by the application comprises the steps of firstly carrying out intercalation treatment on original graphite by using an acidic intercalation agent, and then carrying out expansion treatment, so that the intercalation agent and oxygen-containing functional groups between graphite layers are decomposed to generate a large amount of gas, the gas has a certain acting force on the graphite sheet layer after escaping from the graphite layers, and when the acting force is greater than the pi-pi interaction force between the graphite layers, the graphite is expanded to form porous vermicular expanded graphite; compared with the original graphite, the specific surface area of the expanded graphite is greatly improved, so that the contact area of the expanded graphite and an oxidant is correspondingly and greatly increased in the subsequent oxidation process, the graphite is uniformly oxidized by the oxidant, the functional groups can increase the distance between graphite oxide layers, the interaction force between graphite oxide layers is weakened, the stripping efficiency of the graphene oxide is improved, and the prepared graphite oxide can be stripped into single-layer large-sheet graphene oxide without external force.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a large-lamellar graphene oxide according to an embodiment of the present application;
FIG. 2 is an atomic force electron microscope image of a large graphene oxide sheet prepared in the examples of the present application;
fig. 3 is a scanning electron microscope image of a large graphene oxide sheet prepared in an example of the present application.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
Graphene and its derivatives such as graphite oxide, graphene oxide, and graphene nanoplatelets have a wide application prospect in nano-electronic devices, conductive inks, multifunctional fibers, functionalized films, energy materials, and the like. The mechanical, electric, heat conducting and liquid crystal properties of the sheet carbon-like material are closely related to the size of the sheet layer and the defect density of the sheet carbon-like material. Generally, the combination of properties of the large-lamellar flaky carbon material is more excellent. For example, when graphene oxide self-assembles into a three-dimensional device, a suspension of large lamellar graphene oxide has better rheological properties, lower critical concentration of liquid crystal, and higher modulus and viscosity than a suspension of small lamellar graphene oxide. These advantages give the large-sheet graphene oxide better orientation performance in the device, and the obtained device has more excellent performance. Accordingly, similar size effects exist for graphene prepared by reduction of graphene oxide. Because large sheets of graphene have fewer intrinsic defects and fewer edges than small sheets of graphene. When graphene sheets are lapped over each other to form a device, fewer lap joint sites and a larger lap area mean lower contact and thermal resistance. Meanwhile, the intrinsic mechanical property, heat conduction property and electric conduction property of the large-layer graphene are also very excellent. However, the preparation of large sheets of graphene oxide is often difficult compared to small sheets of graphene oxide. The reason is that the preparation of the large-sheet graphene oxide needs to adopt large-sheet crystalline flake graphite with thicker thickness and more perfect lattice structure as an initial raw material, and the resistance of the oxidant in the process of diffusing from the edge of the large-sheet graphite to the middle is extremely large, so that the oxidation is difficult and the efficiency is low. According to the difference of the chemical and physical properties of graphene oxide with different lamella sizes, such as lamella size, pH sensitivity, liquid crystal behavior, sedimentation rate and the like, partial researchers separate the graphene oxide with large lamellae from the graphene oxide mixed with large and small lamellae by adopting a centrifugal, suction filtration or sedimentation grading means.
Meanwhile, in order to obtain the graphene oxide with large sheet layers, the most common peeling mode of ultrasonic wave which can cause severe damage to the graphene oxide sheet layers must be strictly controlled or even avoided. Therefore, some researchers have tried to reduce the damage to the graphene oxide sheet size as much as possible by mild peeling means such as slight shaking, freeze-thaw cycling, stirring, and turbulence. Although these researchers have obtained large sheets of graphene oxide using a variety of different methods, the methods are generally very complex and wasteful of resources and time, making it difficult to scale up the production in industry. How to reduce the oxidation difficulty of large-sheet graphite by adopting a simple and convenient mode, and directly producing the large-sheet graphene oxide becomes a difficult problem to be solved urgently in the industrial application of graphene.
Based on this, as shown in fig. 1, the present application provides a preparation method of a large sheet graphene oxide, including the following steps:
carrying out intercalation treatment on original graphite by using an intercalation solvent to obtain intercalated graphite; the intercalation solvent comprises an acidic intercalating agent comprising at least one of sulfuric acid, oleum, nitric acid, and phosphoric acid; wherein the mixing ratio of the original graphite to the acidic intercalating agent is 1g;
carrying out expansion treatment on the intercalated graphite to obtain expanded graphite;
carrying out oxidation treatment on the expanded graphite to obtain graphite oxide;
and stripping the graphite oxide to obtain single-layer graphene oxide.
Compared with the prior art, the preparation method disclosed by the application comprises the steps of firstly carrying out intercalation treatment on the original graphite by using an acidic intercalation agent, and then carrying out expansion treatment, so that the intercalation agent and the oxygen-containing functional groups between graphite layers are decomposed to generate a large amount of gas, the gas escaping from the graphite layers can have a certain acting force on the graphite layers, and when the acting force is greater than the pi-pi interaction force between the graphite layers, the graphite can expand to form porous vermicular expanded graphite; compared with the original graphite, the specific surface area of the expanded graphite is greatly improved, so that the contact area of the expanded graphite and an oxidant is correspondingly and greatly increased in the subsequent oxidation process, the graphite is uniformly oxidized by the oxidant, the functional groups can increase the distance between graphite oxide layers, the interaction force between graphite oxide layers is weakened, the stripping efficiency of the graphene oxide is improved, and the prepared graphite oxide can be stripped into single-layer large-sheet graphene oxide without external force.
This application is when carrying out the intercalation to original graphite and is handled, through adding the ammonium persulfate, introduces sulphur on original graphite to can be divided family and produce gas when making follow-up carry out expansion to the intercalation graphite, thereby increase the inflation degree of expanded graphite. That is, as some alternative embodiments herein, the intercalation solvent further comprises: an intercalation facilitating agent comprising ammonium persulfate;
wherein the mixing ratio of the original graphite to the ammonium persulfate is 1g.
In order to increase the intercalation amount of the acid intercalation agent in the original graphite, thereby being more beneficial to subsequent expansion treatment and oxidation treatment; as some optional embodiments herein, the intercalation facilitating agent further comprises: potassium permanganate;
wherein the mixing ratio of the original graphite to the potassium permanganate is 1g.
In order to increase the intercalation amount of the acid intercalation agent in the original graphite and obtain better interlayer spacing, thereby being more beneficial to subsequent expansion treatment and oxidation treatment; as some optional embodiments of the present application, the intercalation temperature of the intercalation treatment is 25-100 ℃, and the intercalation time is 20 min-8 h.
In order to decompose the intercalation agent and the oxygen-containing functional groups between the graphite layers and generate a large amount of gas, the gas has certain acting force on the graphite sheet layer when escaping from the graphite layers, and when the acting force is larger than the pi-pi interaction force between the graphite layers, the intercalated graphite is expanded to form porous vermicular expanded graphite; as some optional embodiments of the present application, the expansion process comprises: at least one of microwave expansion treatment, hydrogen peroxide expansion treatment and electrochemical expansion treatment. When the expansion treatment is microwave expansion treatment, the treatment power is 500-5000W, and the treatment time is 30 s-10 min. When the expansion treatment is hydrogen peroxide expansion treatment, the concentration of the hydrogen peroxide is 20-80 wt%, and the treatment time is 30 min-24 h. When the expansion treatment is electrochemical expansion treatment, the treatment voltage is 2-20V, and the treatment time is 30 s-30 min.
In order to improve the oxidation efficiency of the expanded graphite, a large number of oxygen-containing functional groups are contained between graphite sheets so as to increase the distance between graphite oxide layers and weaken the interaction force between the graphite oxide layers; as some alternative embodiments herein, the oxidizing agent used when the oxidizing treatment is performed comprises at least one of sulfuric acid, fuming sulfuric acid, nitric acid, and phosphoric acid; wherein the mixing ratio of the expanded graphite to the oxidant is 1g.
In order to improve the oxidation efficiency of the expanded graphite, a large number of oxygen-containing functional groups are contained between graphite sheets so as to increase the distance between graphite oxide layers and weaken the interaction force between the graphite oxide layers; as some alternative embodiments herein, the oxidizing agent further comprises potassium permanganate;
wherein the mixing ratio of the expanded graphite to the potassium permanganate is 1g to 8g.
In order to improve the oxidation efficiency of the expanded graphite, a large number of oxygen-containing functional groups are contained between graphite sheets so as to increase the distance between graphite oxide layers and weaken the interaction force between the graphite oxide layers; as some optional embodiments of the present application, the subjecting the expanded graphite to an oxidation treatment to obtain graphite oxide includes:
mixing the expanded graphite with the oxidant to obtain a mixed solution;
and heating the mixed solution to 25-60 ℃ and oxidizing for 30 min-4 h to obtain graphite oxide.
As some optional embodiments of the present application, the subjecting the expanded graphite to an oxidation treatment to obtain graphite oxide includes:
mixing the expanded graphite with the oxidant to obtain a mixed solution;
heating the mixed solution to 25-60 ℃ and oxidizing for 30 min-4 h to obtain first graphite oxide;
and mixing the first graphite oxide with the acidic solution, heating to 60-100 ℃, and oxidizing for 10-40 min to obtain second graphite oxide.
When the graphene oxide is subjected to stripping treatment to obtain single-layer graphene oxide, the single-layer large-sheet graphene oxide can be obtained through self-stripping without any external force, so that complex stripping modes such as slight oscillation, freeze-thaw cycle, stirring and turbulence and complex grading means such as suction filtration or sedimentation are avoided; as some alternative embodiments of the present application, the stripping treatment comprises several centrifugal water washing treatments.
In order to solve the technical problems, the application also provides a large lamellar graphene oxide prepared by the method. The method comprises the steps of intercalating original graphite with an intercalation agent to obtain intercalated graphite, expanding the intercalated graphite into expanded graphite by adopting an expansion means, and oxidizing the expanded graphite by using mixed acid and potassium permanganate to obtain graphite oxide; and then washing the graphite oxide with centrifugal water for many times. Compared with graphene oxide with small flake layers, the large-flake flaky carbon material is generally more excellent in overall performance. For example, when graphene oxide self-assembles into a three-dimensional device, a suspension of large lamellar graphene oxide has better rheological properties, lower critical concentration of liquid crystal, and higher modulus and viscosity than a suspension of small lamellar graphene oxide. These advantages give the large-sheet graphene oxide better orientation performance in the device, and the obtained device has more excellent performance.
The technical scheme of the present application is described in detail below with reference to specific examples:
example 1
Adding 25mL of concentrated sulfuric acid into 1g of original graphite, slowly adding 0.5g of potassium permanganate, uniformly stirring, performing intercalation for 4 hours at room temperature of 25 ℃ to obtain intercalated graphite, performing microwave expansion on the intercalated graphite for 30 seconds at 1000W to obtain expanded graphite, mixing the obtained 1g of expanded graphite with 50mL of concentrated sulfuric acid and 5g of potassium permanganate, heating the mixed solution to 35 ℃, oxidizing for 2 hours to obtain graphite oxide, and finally performing centrifugal washing for multiple times to obtain large-sheet graphene oxide.
As shown in fig. 2, when the graphene oxide of the large sheet layer obtained in this embodiment is tested by an atomic force electron microscope, it can be seen that the thickness of the graphene oxide of the large sheet layer is about 1nm, which indicates that the graphene oxide of the large sheet layer is a single layer.
As shown in FIG. 3, it can be seen that the weight-average lamella size of the large-lamellar graphene oxide obtained in this example is 2650 μm 2 Indicating that it is a large sheet layer of graphene oxide.
Example 2
Adding 30mL of concentrated sulfuric acid into 1g of original graphite, slowly adding 0.8g of potassium permanganate, uniformly stirring, intercalating at 25 ℃ for 4 hours to obtain intercalated graphite, performing microwave expansion on the intercalated graphite at 2000W for 30s to obtain expanded graphite, mixing the obtained 1g of expanded graphite with 50mL of concentrated sulfuric acid and 5g of potassium permanganate, heating the mixed solution to 35 ℃ to oxidize for 2 hours to obtain graphite oxide, and finally performing centrifugal washing for multiple times to obtain large-sheet graphene oxide.
Atomic force electron microscope tests show that the thickness of the graphene oxide sheet layer is about 1nm, which shows that the graphene oxide sheet layer is single-layer graphene oxide; scanning electron micrograph test shows that the weight average lamella size of the obtained graphene oxide is 2850 mu m 2 And is large lamellar graphene oxide.
Example 3
Adding 25mL of concentrated sulfuric acid into 1g of original graphite, intercalating for 4h at room temperature of 25 ℃ to obtain intercalated graphite, performing microwave expansion on the intercalated graphite at 1000W for 30s to obtain expanded graphite, mixing the obtained 1g of expanded graphite with 50mL of concentrated sulfuric acid and 5g of potassium permanganate, heating the mixed solution to 35 ℃ to oxidize for 2h to obtain graphite oxide, and finally performing centrifugal washing for multiple times to obtain large-sheet graphene oxide.
Atomic force electron microscope tests show that the thickness of the graphene oxide sheet layer is about 1nm, which shows that the graphene oxide sheet layer is single-layer graphene oxide; scanning electron micrograph test shows that the weight average lamella size of the obtained graphene oxide is 2820 mu m 2 And is large lamellar graphene oxide.
Example 4
Adding 25mL of concentrated sulfuric acid into 1g of original graphite, slowly adding 0.5g of potassium permanganate, uniformly stirring, intercalating at 25 ℃ for 4h to obtain intercalated graphite, performing 1000W microwave expansion on the intercalated graphite for 30s to obtain expanded graphite, mixing the obtained 1g of expanded graphite with 50mL of concentrated sulfuric acid and 5g of potassium permanganate, heating the mixed solution to 35 ℃ to oxidize for 2h to obtain graphite oxide, and finally performing centrifugal washing for multiple times to obtain large-sheet graphene oxide.
Atomic force electron microscope tests show that the thickness of the graphene oxide sheet layer is about 1nm, which shows that the graphene oxide sheet layer is single-layer graphene oxide; scanning electron micrograph test shows that the weight average lamella size of the obtained graphene oxide is 2770 mu m 2 I.e. it is shown to be a large sheet of graphene oxide.
Example 5
Adding 25mL of concentrated sulfuric acid into 1g of original graphite, slowly adding 0.5g of potassium permanganate, uniformly stirring, intercalating at 25 ℃ for 4 hours to obtain intercalated graphite, expanding the intercalated graphite in 60% hydrogen peroxide for 2 hours, mixing the obtained 1g of expanded graphite with 50mL of concentrated sulfuric acid and 5g of potassium permanganate, heating the mixed solution to 35 ℃ for oxidizing for 2 hours to obtain graphite oxide, and finally performing centrifugal washing for multiple times to obtain the large-sheet graphene oxide.
Atomic force electron microscope tests show that the thickness of the graphene oxide sheet layer is about 1nm, which shows that the graphene oxide sheet layer is single-layer graphene oxide; scanning electron micrograph test shows that the weight average lamella size of the obtained graphene oxide is 3120 mu m 2 I.e. it is shown to be a large sheet of graphene oxide.
Example 6
Adding 25mL of concentrated sulfuric acid into 1g of original graphite, slowly adding 0.5g of potassium permanganate, uniformly stirring, intercalating at 25 ℃ for 4h to obtain intercalated graphite, performing microwave expansion on the intercalated graphite at 1000W for 30s to obtain expanded graphite, mixing the obtained 1g of expanded graphite with 50mL of concentrated sulfuric acid and 5g of potassium permanganate, heating the mixed solution to 35 ℃ for oxidation for 2h to obtain graphite oxide, and finally performing centrifugal washing for multiple times to obtain large-sheet graphene oxide.
Atomic force electron microscope tests show that the thickness of the graphene oxide sheet layer is about 1nm, which shows that the graphene oxide sheet layer is single-layer graphene oxide; scanning electron micrograph test shows that the weight average lamella size of the obtained graphene oxide is 2350 mu m 2 I.e. it is shown to be a large sheet of graphene oxide.
Example 7
Adding 25mL of concentrated sulfuric acid into 1g of original graphite, slowly adding 0.5g of potassium permanganate, uniformly stirring, performing intercalation for 4 hours at room temperature of 25 ℃ to obtain intercalated graphite, performing microwave expansion on the intercalated graphite for 30 seconds at 1000W to obtain expanded graphite, mixing the obtained 1g of expanded graphite with 50mL of concentrated sulfuric acid and 8g of potassium permanganate, heating the mixed solution to 35 ℃, oxidizing for 2 hours to obtain graphite oxide, and finally performing centrifugal washing for multiple times to obtain large-sheet graphene oxide.
Atomic force electron microscope tests show that the thickness of the graphene oxide sheet layer is about 1nm, which shows that the graphene oxide sheet layer is single-layer graphene oxide; scanning electron micrograph test shows that the weight-average lamellar size of the obtained graphene oxide is 2460 mu m 2 I.e. it is shown to be a large sheet of graphene oxide.
Example 8
Adding 25mL of concentrated sulfuric acid into 1g of original graphite, slowly adding 0.5g of potassium permanganate, uniformly stirring, intercalating at 25 ℃ for 4h to obtain intercalated graphite, performing microwave expansion on the intercalated graphite at 1000W for 30s to obtain expanded graphite, mixing the obtained 1g of expanded graphite with 50mL of concentrated sulfuric acid and 8g of potassium permanganate, heating the mixed solution to 35 ℃ for oxidation for 2h, adding water for dilution (mixed acid: water = 1mL.
Atomic force electron microscope tests show that the thickness of the graphene oxide sheet layer is about 1nm, which shows that the graphene oxide sheet layer is single-layer graphene oxide; scanning electron micrograph test shows that the weight average lamella size of the obtained graphene oxide is 1960 mu m 2 I.e. it is shown to be a large sheet of graphene oxide.
Therefore, compared with the prior art, the preparation method disclosed by the application comprises the steps of firstly carrying out intercalation treatment on the original graphite by using an acidic intercalation agent and a small amount of potassium permanganate, and then carrying out expansion treatment, so that the intercalation agent and the oxygen-containing functional group between graphite layers are decomposed and generate a large amount of gas, the gas escaping from the graphite layers can have a certain acting force on the graphite sheet layers, and when the acting force is greater than the pi-pi interaction force between the graphite layers, the graphite can expand to form the porous worm-like expanded graphite; compared with the original graphite, the specific surface area of the expanded graphite is greatly improved, so that the contact area of the expanded graphite and an oxidant is correspondingly and greatly increased in the subsequent oxidation process, the graphite is uniformly oxidized by the oxidant, the functional groups can increase the distance between graphite oxide layers, the interaction force between graphite oxide layers is weakened, the stripping efficiency of the graphene oxide is improved, and the prepared graphite oxide can be stripped into single-layer large-sheet graphene oxide without external force.
The above description is only a preferred embodiment of the present application, and not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes, which are made by the contents of the specification and the drawings of the present application, or which are directly or indirectly applied to other related technical fields, are included in the scope of the present application.
Claims (14)
1. A preparation method of large-sheet graphene oxide is characterized by comprising the following steps:
carrying out intercalation treatment on original graphite by using an intercalation solvent to obtain intercalated graphite; the intercalation solvent comprises an acidic intercalating agent comprising at least one of sulfuric acid, oleum, nitric acid, and phosphoric acid; wherein the mixing ratio of the original graphite to the acidic intercalating agent is 1g;
carrying out expansion treatment on the intercalated graphite to obtain expanded graphite;
carrying out oxidation treatment on the expanded graphite to obtain graphite oxide;
and stripping the graphite oxide to obtain single-layer graphene oxide.
2. The method of preparing large-piece graphene oxide according to claim 1, wherein the intercalation solvent further comprises: an intercalation facilitating agent comprising ammonium persulfate;
wherein the mixing ratio of the original graphite to the ammonium persulfate is 1g.
3. The method for preparing large-piece graphene oxide according to claim 2, wherein the intercalation promoter further comprises: potassium permanganate;
wherein the mixing ratio of the original graphite to the potassium permanganate is 1g.
4. The preparation method of large-piece-layer graphene oxide according to claim 1, wherein the intercalation temperature of the intercalation treatment is 25-100 ℃, and the intercalation time is 20 min-8 h.
5. The method for preparing large-piece graphene oxide according to claim 1, wherein the expansion treatment comprises: at least one of microwave expansion treatment, hydrogen peroxide expansion treatment and electrochemical expansion treatment.
6. The method for preparing large-piece graphene oxide according to claim 5, wherein when the expansion treatment is a microwave expansion treatment, the treatment power is 500 to 5000W, and the treatment time is 30s to 10min.
7. The preparation method of large-sheet graphene oxide according to claim 5, wherein when the expansion treatment is hydrogen peroxide expansion treatment, the concentration of the hydrogen peroxide is 20-80 wt%, and the treatment time is 30 min-24 h.
8. The method for preparing large-piece graphene oxide according to claim 5, wherein when the expansion treatment is electrochemical expansion treatment, the treatment voltage is 2 to 20V, and the treatment time is 30s to 30min.
9. The method for producing large-piece graphene oxide according to claim 1, wherein when the oxidation treatment is performed, the oxidizing agent used includes at least one of sulfuric acid, fuming sulfuric acid, nitric acid, and phosphoric acid;
wherein the mixing ratio of the expanded graphite to the oxidant is 1g.
10. The method for preparing a large-piece graphene oxide according to claim 9, wherein the oxidizing agent further comprises potassium permanganate;
wherein the mixing ratio of the expanded graphite to the potassium permanganate is 1g to 8g.
11. The method for preparing large-piece graphene oxide according to claim 10, wherein the step of subjecting the expanded graphite to oxidation treatment to obtain graphite oxide comprises:
mixing the expanded graphite with the oxidant to obtain a mixed solution;
and heating the mixed solution to 25-60 ℃ and oxidizing for 30 min-4 h to obtain graphite oxide.
12. The method for preparing large-piece graphene oxide according to claim 10, wherein the step of subjecting the expanded graphite to oxidation treatment to obtain graphite oxide comprises:
mixing the expanded graphite with the oxidant to obtain a mixed solution;
heating the mixed solution to 25-60 ℃ and oxidizing for 30 min-4 h to obtain first graphite oxide;
and mixing the first graphite oxide with the acidic solution, heating to 60-100 ℃, and oxidizing for 10-40 min to obtain second graphite oxide.
13. The method for preparing large-piece graphene oxide according to claim 1, wherein the exfoliation treatment comprises several times of centrifugal water washing treatment.
14. A graphene oxide in large sheets, prepared by the method of any one of claims 1 to 13.
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| CN116161657A (en) * | 2023-03-02 | 2023-05-26 | 四川大学 | Spheroid hollow graphite and preparation method and application thereof |
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