CN108328611B - Self-supporting reduced graphene oxide roll network material and preparation method thereof - Google Patents

Self-supporting reduced graphene oxide roll network material and preparation method thereof Download PDF

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CN108328611B
CN108328611B CN201710302040.5A CN201710302040A CN108328611B CN 108328611 B CN108328611 B CN 108328611B CN 201710302040 A CN201710302040 A CN 201710302040A CN 108328611 B CN108328611 B CN 108328611B
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graphene oxide
reduced graphene
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network material
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CN108328611A (en
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陈辉亮
肖卓建
周维亚
王艳春
解思深
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Abstract

The invention provides a self-supporting reduced graphene oxide roll network material and a preparation method thereof, belonging to the field of nano material research. The preparation method comprises the following steps: preparing a mixed solution of a graphene oxide dispersion liquid and an additive; freeze-drying the mixed solution to obtain an unreduced graphene oxide roll network material; placing the unreduced graphene oxide roll network material in a protective gas atmosphere to be processed for a preset time at a preset temperature, so as to obtain a self-supporting partially reduced or completely reduced graphene oxide roll network material; repeatedly cleaning the self-supporting partially reduced or completely reduced graphene oxide roll network material to a preset degree, and then carrying out freeze drying treatment; obtaining the self-supporting reduced graphene oxide roll network material with low additive content. The method has the advantages of simplicity, easy implementation, low cost, large-scale industrial preparation and the like. The prepared graphene roll material has a completely self-supporting structure, different roll diameters and a wide application range.

Description

Self-supporting reduced graphene oxide roll network material and preparation method thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to a self-supporting reduced graphene oxide roll network material and a preparation method thereof.
Background
Graphene coils are one-dimensional structures formed by graphene rolling that resemble radially unclosed carbon nanotubes. The material between graphene and carbon nanotubes not only has high electron mobility and high mechanical strength, but also has unique and excellent electrical and mechanical properties different from the two. The structure not only avoids the problem that graphene sheet layers are easy to stack and agglomerate, keeps larger specific surface area, but also enables the rolled structure of the graphene rolled sheet layers to be easier to fill and compound other materials compared with the carbon nano tube with a closed structure, and has wide application value in the aspects of energy sources such as super capacitors, lithium batteries and the like. The conventional graphene roll preparation comprises electric arc discharge, high-energy ball milling and a chemical method; the former two are difficult to control the product to contain a large amount of graphite and amorphous carbon, so that the graphene roll is difficult to separate. In the chemical method, the graphene oxide is partially reduced and then is subjected to freeze drying to form a roll-shaped structure. The sample obtained by the method is generally dispersed graphene roll powder and cannot form a self-supporting structure, meanwhile, the graphene oxide roll cannot be prepared by the method, the roll diameter of the prepared graphene roll is generally below 1000nm, the component, structure and scale range of the prepared graphene roll are limited, and the application field of the graphene oxide roll is greatly influenced.
Therefore, how to design a graphene roll network material which is simple and easy to implement and low in cost and has a self-supporting structure is significant.
Disclosure of Invention
The invention aims to provide a preparation method of a self-supporting reduced graphene oxide roll network material, which aims to solve the problems that the currently prepared graphene roll can only be in a reduced state, the application range is limited, the graphene roll is powdery, the diameter of the graphene roll is limited, and the like. The method has the advantages of simplicity, easiness in implementation, low cost, large-scale industrial preparation and the like. Another object of the present invention is to provide a self-supporting reduced graphene oxide roll network material, which has a completely self-supporting structure, has different roll diameters, and has a wide application range.
Particularly, the self-supporting reduced graphene oxide roll network material provided by the invention is prepared by the preparation method, the self-supporting reduced graphene oxide roll network material is formed by mutually connecting and rolling a single layer to a plurality of layers of reduced graphene oxide sheets into a reduced graphene oxide roll, and the reduced graphene oxide rolls are mutually overlapped and lapped to form a self-supporting three-dimensional porous network structure; the self-supporting reduced graphene oxide roll network material contains an additive, has certain shape and flexibility, and can be processed or cut into any shape.
Further, the reduced graphene oxide roll can have different reduction degrees, the constituent elements of the reduced graphene oxide roll are carbon, hydrogen and oxygen, and the mass ratio of carbon to oxygen can be regulated and controlled;
alternatively, the reduced graphene oxide roll may be an unreduced graphene oxide roll;
alternatively, the roll of reduced graphene oxide may be a roll of partially reduced graphene oxide;
optionally, the reduced graphene oxide roll may be a completely reduced graphene oxide roll, and the content of oxygen element is less than or equal to 1%.
Furthermore, the porosity of the reduced graphene oxide roll network material is adjustable, and is preferably 10-99%.
Further, the density of the self-supporting reduced graphene oxide roll network material is adjustable, and is preferably less than 10mg/cm3. The diameter of the reduced graphene oxide roll network material is adjustable, and is preferably 1nm-10 μm.
Further, the aspect ratio of the reduced graphene oxide roll network material
Figure GDA0002885711540000021
The adjustment is carried out;
preferably, the aspect ratio
Figure GDA0002885711540000022
Greater than 5;
wherein, L is the length of the volume between two nodes of the graphene volume network, and d is the diameter of the graphene volume.
The invention also provides a preparation method of the self-supporting reduced graphene oxide roll network material, which comprises the following steps:
s1, preparing a uniformly mixed solution of the graphene oxide dispersion liquid and the additive according to a certain mass ratio;
s2, freeze-drying the mixed solution to obtain an unreduced graphene oxide roll network material;
s3, placing the unreduced graphene oxide roll network material in a protective gas atmosphere to be processed for a preset time at a preset temperature, and obtaining a self-supporting partially reduced or completely reduced graphene oxide roll network material;
s4, repeatedly cleaning the self-supporting partially-reduced graphene oxide roll network material to a preset degree, and then carrying out freeze drying treatment; obtaining the self-supporting partially reduced graphene oxide roll network material with low additive content.
Further, in the step S1, the mass ratio of the graphene oxide dispersion liquid to the additive is adjustable;
preferably, the mass ratio is 1:10-10: 1.
Further, in the step S1, the additive may be one or more of monosaccharide, disaccharide or polysaccharide;
preferably, the monosaccharide is one or more of glucose, fructose and galactose;
preferably, the disaccharide is one or more of sucrose, lactose and maltose;
preferably, the polysaccharide is one or more of glycogen and starch.
Further, in the step S3, the protective gas is an inert gas, a reducing gas or a mixed gas of the inert gas and the reducing gas;
preferably, the inert gas is nitrogen, argon or a mixed gas thereof;
preferably, the reducing gas is hydrogen.
Further, in the step S3, the predetermined time is greater than 0.1 h; the preset temperature is not lower than 50 ℃;
preferably, the predetermined temperature is 50-1000 ℃;
preferably, the predetermined time is 1 to 30 hours.
Further, in the step S4, the organic solvent used for the repeated washing is not limited, and is preferably one or more of ethanol, methanol and acetone.
The self-supporting reduced graphene oxide roll network structure material and the preparation method thereof provided by the invention have the following beneficial effects:
(1) the self-supporting reduced graphene oxide roll network structure material can have different components, namely completely unreduced graphene oxide and partially reduced and completely reduced graphene oxide, so that the graphene oxide can exert and utilize a larger specific surface area in different reduction states, and stacking among graphene sheet layers caused by the traditional suction filtration and other modes is avoided. The application range is wide, and the device can be applied to gas detectors, such as sulfur dioxide gas detectors; the lithium-sulfur battery can be applied to energy storage, and comprises a lithium-sulfur battery, a lithium-silicon battery, a super capacitor and the like.
(2) By regulating the mass fraction of the additive, the material shows different structures such as graphene roll diameter, network pore diameter and the like, and the application range of the graphene roll is further expanded;
the preparation method of the self-supporting reduced graphene oxide roll network structure material provided by the invention has the advantages of simple operation, low cost, strong controllability, large-scale industrial preparation and the like.
According to the preparation method of the self-supporting reduced graphene oxide roll network structure material, the self-supporting structures of graphene oxide rolls with different reduction degrees are prepared by using the mixed solution of the additive and the graphene oxide dispersion liquid and directly through a freeze drying technology. The structure avoids the stacking of graphene, utilizes the larger specific surface area of the graphene, has good connection between the rolls, and has certain flexibility, and the different reduction degrees can be applied to the fields which are not used.
The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the invention will be described in detail hereinafter, by way of illustration and not limitation, with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:
the drawings are not necessarily to scale. In the drawings:
FIG. 1 is a surface topography (SEM) of a scanning electron microscope of a self-supporting reduced graphene oxide roll network structure material according to one embodiment of the invention;
FIG. 2 is a surface topography (SEM) of a scanning electron microscope of a self-supporting reduced graphene oxide roll network structure material according to an embodiment of the invention;
FIG. 3 is a surface topography (SEM) of a scanning electron microscope of a free standing graphene roll prepared without additives;
fig. 4 is a schematic flow chart of a method for preparing a self-supporting reduced graphene oxide roll network structure material according to an embodiment of the present invention.
Detailed Description
The present invention is described in detail by way of embodiments, which are only used for further illustration of the present invention and are not to be construed as limiting the scope of the present invention, and other people who have made some non-essential changes and modifications according to the above disclosure belong to the scope of the present invention.
FIG. 1 is a surface topography (SEM) of a scanning electron microscope of a self-supporting reduced graphene oxide roll network structure material according to one embodiment of the invention;
fig. 2 is a surface topography (SEM image) of a scanning electron microscope of a self-supporting reduced graphene oxide roll network structure material according to an embodiment of the present invention.
As shown in fig. 1 and 2, the present invention provides a self-supporting reduced graphene oxide roll network material.
The self-supporting reduced graphene oxide roll network material provided by the invention is formed by mutually connecting and rolling a single layer to a plurality of layers of reduced graphene oxide sheets into a reduced graphene oxide roll, wherein the reduced graphene oxide rolls are mutually overlapped and lapped to form a self-supporting three-dimensional porous network structure; the self-supporting reduced graphene oxide roll network material contains an additive, has certain shape and flexibility, and can be processed or cut into any shape.
In particular, reduced graphene oxide rolls of a self-supporting reduced graphene oxide roll network material may have different degrees of reduction. The constituent elements of the reduced graphene oxide roll are carbon, hydrogen and oxygen. The mass ratio of carbon to oxygen can be controlled by controlling the additives and the mass fraction as well as the predetermined time and the predetermined temperature of the heat treatment.
In a particular embodiment, the reduced graphene oxide roll may be an unreduced graphene oxide roll. The appearance of the self-supporting reduced graphene oxide roll network material formed by the unreduced graphene oxide roll is non-black, including tan and brown. The constituent elements are carbon, hydrogen and oxygen.
In another specific embodiment, the roll of reduced graphene oxide may be a roll of partially reduced graphene oxide; the appearance of the self-supporting reduced graphene oxide roll network material formed by the partially reduced graphene oxide roll is black. The constituent elements are carbon, hydrogen and oxygen. The mass ratio of carbon to oxygen can be adjusted and is preferably between 2 and 100.
In another specific embodiment, the roll of reduced graphene oxide may be a roll of fully reduced graphene oxide. The constituent elements are carbon, hydrogen and oxygen, and the content of the oxygen element is less than or equal to 1 percent. The appearance of the self-supporting reduced graphene oxide roll network material formed by the completely reduced graphene oxide roll is black. The mass ratio of carbon to oxygen can be regulated and controlled. Preferably, the carbon to oxygen mass ratio is 100 or more.
The porosity of the self-supporting reduced graphene oxide roll network material is adjustable, and is preferably 10-99%. Optionally, the porosity of the reduced graphene oxide roll network structure material is 10-50%. Optionally, the porosity of the reduced graphene oxide roll network structure material is 50-99%.
Further, the density of the self-supporting reduced graphene oxide roll network material is adjustable, and is preferably less than 10mg/cm3。
Optionally, the density of the self-supporting reduced graphene oxide roll network material is adjustable and is less than 0.5mg/cm3。
Optionally, the density of the self-supporting reduced graphene oxide roll network material is adjustable and is 0.5-1mg/cm3。
Optionally, the density of the self-supporting reduced graphene oxide roll network material is adjustable and is 1-5mg/cm3。
Optionally, the density of the self-supporting reduced graphene oxide roll network material is adjustable and is 5-10mg/cm3. Optionally, the density of the self-supporting reduced graphene oxide roll network material is adjustable and is greater than 10mg/cm3。
Further, the diameter of the reduced graphene oxide roll of the self-supporting reduced graphene oxide roll network material is adjustable, preferably between 1nm and 10 μm.
Optionally, the reduced graphene oxide roll has a diameter between 1nm and 200 nm.
Alternatively, the reduced graphene oxide roll may have a diameter of 0.2-0.4 μm.
Alternatively, the reduced graphene oxide roll may have a diameter of 0.4-0.6 μm.
Optionally, the reduced graphene oxide roll has a diameter of 0.6-0.8 μm.
Optionally, the reduced graphene oxide roll has a diameter of 0.8-1 μm.
Optionally, the reduced graphene oxide roll has a diameter of 1-5 μm.
Optionally, the reduced graphene oxide roll has a diameter of 5-10 μm.
Further, the aspect ratio of the self-supporting reduced graphene oxide roll network material provided by the invention
Figure GDA0002885711540000061
Is adjustable. Preferably, the aspect ratio of the self-supporting reduced graphene oxide roll network material
Figure GDA0002885711540000062
Greater than 5. Wherein, L is the length of the volume between two nodes of the graphene volume network, and d is the diameter of the graphene volume.
Optionally, the aspect ratio of the self-supporting reduced graphene oxide roll network material is less than or equal to 20.
Optionally, the aspect ratio of the self-supporting reduced graphene oxide roll network material is in the range of 20-500.
Optionally, the aspect ratio of the self-supporting reduced graphene oxide roll network material is greater than 500.
Fig. 4 is a schematic flow chart of a method for preparing a self-supporting reduced graphene oxide roll network structure material according to an embodiment of the present invention. As shown in fig. 4, the method for preparing a self-supporting reduced graphene oxide roll network structure material provided by the present invention may generally include the following steps:
s1, preparing a uniformly mixed solution of the graphene oxide dispersion liquid and the additive according to a certain mass ratio;
s2, freeze-drying the mixed solution to obtain an unreduced graphene oxide roll network material;
s3, placing the unreduced graphene oxide roll network material in a protective gas atmosphere to be processed for a preset time at a preset temperature, and obtaining a self-supporting partially reduced or completely reduced graphene oxide roll network material;
s4, repeatedly cleaning the self-supporting partially-reduced graphene oxide roll network material to a preset degree, and then carrying out freeze drying treatment; obtaining the self-supporting partially reduced graphene oxide roll network material with low additive content.
Specifically, in step S1, the graphene oxide dispersion liquid may be obtained by oxidizing graphite with a strong acid, and the preparation method thereof may be any one of a Brodie method, a Staudenmaier method, and a Hummers method. The preparation process of the Hummers method has relatively good timeliness and is relatively safe, and the Hummers method is the most commonly used method at present. The Hummers method adopts potassium permanganate in concentrated sulfuric acid and graphite powder to carry out oxidation reaction to obtain brown graphite flakes with derived carboxylic acid groups at the edges and mainly phenolic hydroxyl groups and epoxy groups on the planes, the graphite flake layer can be stirred and peeled off violently by ultrasonic or high shear to form graphene oxide, and stable and light brown single-layer graphene oxide suspension is formed in water. Preferably, the graphene oxide dispersion liquid is prepared by a Hummers method. In step S1, the additive is a saccharide organic compound. The additive can be one or more of monosaccharide, disaccharide or polysaccharide. Optionally, the monosaccharide used in the additive may be one or more of glucose, fructose and galactose. Optionally, the disaccharide used in the additive is one or more of sucrose, lactose and maltose. Optionally, the polysaccharide used in the additive is one or more of glycogen and starch. Of course, the organic carbohydrate compounds used in the additive are not limited to the specific carbohydrates mentioned above, but may be other organic carbohydrate compounds or other biomacromolecules composed of C, H, O elements.
In step S3, the protective gas is an inert gas, a reducing gas, or a mixture of both. In a specific embodiment, the inert gas is nitrogen, argon, or a mixture thereof, and may be other gases that do not chemically react with the graphene oxide dispersion liquid and the additive. In a specific embodiment, the reducing gas is hydrogen. The reducing gas is used to partially or completely reduce the graphene oxide at the time of the heat treatment in step S3.
In step S4, the organic solvent used for repeated washing is not limited, and is preferably one or more of ethanol, methanol and acetone. Of course, other organic solvents may be used, and only the additives in the self-supporting reduced graphene oxide roll network material need to be cleaned.
Further, in the step S1, the mass ratio of the graphene oxide dispersion liquid to the additive is adjustable. In a preferred embodiment, the mass ratio of the graphene oxide dispersion liquid to the additive is 1:10 to 10: 1. In the process of preparing the self-supporting reduced graphene oxide roll network material, the microstructure of the prepared self-supporting reduced graphene oxide roll network material can be controlled by adjusting the mass ratio of the graphene oxide dispersion liquid to the additive, so that the prepared self-supporting reduced graphene oxide roll network material shows different graphene roll diameters, network pore diameters and the like, and the application range of the self-supporting reduced graphene oxide roll network material is further expanded.
Further, in the step S3, the predetermined time is not limited, alternatively, the predetermined time is not less than 0.1h, and the predetermined temperature is not lower than 50 ℃. Preferably, the predetermined time is 1-30 h. Preferably, the predetermined temperature is 50-1000 ℃. By controlling the preset time and the preset temperature of the heat treatment, the reduction degree of the prepared self-supporting reduced graphene oxide roll network material can be controlled.
For example, in one specific embodiment, in step S3, the solution is freeze-dried and then heat-treated at 50-500 ℃ for 1-30h to obtain a self-supporting partially reduced graphene oxide roll network structure.
In another specific embodiment, in step S3, the solution is freeze-dried and then heat-treated at 50-300 ℃ for 1-10h to obtain the self-supporting partially reduced graphene oxide roll network structure.
In another specific embodiment, in the step S3, the solution is heat-treated at 500 ℃ for 10-20h after being freeze-dried, so as to obtain the self-supporting partially-reduced graphene oxide roll network structure.
In another specific embodiment, in the step S3, the solution is heat-treated at 1000 ℃ for 1-30h after being freeze-dried, so as to obtain the self-supporting fully-reduced graphene oxide roll network structure.
In another specific embodiment, in the step S3, the solution is heat-treated at 300 ℃ > 700 ℃ for 1-100h after freeze-drying to obtain a self-supporting fully-reduced graphene oxide roll network structure.
In another specific embodiment, in the step S3, the solution is heat-treated at 700-1000 ℃ for 20-30h after being freeze-dried, so as to obtain the self-supporting fully-reduced graphene oxide roll network structure.
The principle that the reduced graphene oxide roll has the structure and the properties is as follows: after the additive is added in the step S1, the solution still keeps a uniform dispersion state, but the freezing point of the whole solution is lowered; meanwhile, due to the weak reduction effect of the additive, the acting force between graphene sheets is weakened, so that in the step S2 freeze drying process, the graphene roll-shaped structure which is overlapped and wound is finally formed by taking the ice crystals as a template; after this step S2, the additive is coated or partially coated on the surface of the graphene oxide sheet layer as a "mud" like state, and is attached to the gaps between the graphene oxide sheet layer and the sheet layer, so that the graphene roll can maintain a network structure without being loose or in a powder form. After the heat treatment of step S3, the graphene oxide as a "brick" becomes partially reduced graphene oxide or fully reduced graphene; the additive is partially pyrolyzed or completely carbonized into amorphous carbon and is coated on the surface of a completely reduced or partially reduced graphene oxide sheet layer (often also referred to as a graphene sheet layer) as "mud" or partially coated on the surface of the completely reduced or partially reduced graphene oxide sheet layer, and is filled or partially filled in gaps between the reduced or partially reduced graphene oxide sheet layer and the sheet layer to form a "brick mud structure", so that the nano-coil can maintain a self-supporting three-dimensional network structure; in step S4, after the partially reduced graphene oxide roll is cleaned, most of the additive heat treatment product on the surface of the partially reduced graphene oxide roll is cleaned, which is beneficial to reducing the density of the nanocolloid; and part of the additive heat treatment product filled in the gaps between the graphene sheet layers and the sheet layers as mud still exists between the graphene sheet layers and the sheet layers and is not washed away, which is probably due to the bonding or bridging effect between the additive heat treatment product and the graphene sheet layers caused by the reduction process, so that the graphene roll can maintain a self-supporting three-dimensional network structure without loosening or being in a powder shape. The graphene which is not added with the additive and is also processed in the step S2 cannot form a roll-like structure, and the sample does not have certain flexibility, but is fragile, loose in structure or powdery, and cannot form a stable macro-structure state.
The invention provides a preparation method of a self-supporting reduced graphene oxide roll network structure material, which comprises the following specific embodiments:
detailed description of the preferred embodiment 1
Preparing a self-supporting unreduced graphene oxide roll containing an additive by using glucose and graphene oxide:
1) taking a certain amount of concentrated H2SO4Graphite powder, NaNO3Stirring in an ice water bath; then KMnO was added4Stirring with deionized water in ice water bath, and adding H2O2And centrifuging and cleaning for multiple times to obtain the graphene oxide dispersion liquid.
2) And dissolving a certain mass of graphene oxide dispersion liquid and glucose in deionized water, and performing ultrasonic treatment, wherein the concentration of both the graphene oxide and the glucose is 0.5 mg/mL.
3) And (2) injecting the solution into a polytetrafluoroethylene material mold, immersing a part of the bottom of the mold into liquid nitrogen to form a temperature gradient difference, preparing the material by using an ice crystal template technology, and after the solution is completely solidified, putting the solution into a freeze dryer to dry for 36 hours, and taking out the solution to prepare the self-supported graphene oxide roll containing glucose.
In the method provided by this embodiment, graphene oxide with a certain concentration is ultrasonically mixed with an additive (in this embodiment, the additive is glucose, and the concentrations of graphene oxide and glucose are also 0.5mg/mL), at this time, the freezing point of the solution is lower than the freezing point when no additive is added, and the graphene oxide dispersion liquid is easy to form a three-dimensional graphene roll structure in a subsequent ice crystal template method; meanwhile, the additive solution is a non-electrolyte solution, so that the graphene oxide dispersion liquid cannot agglomerate, and graphene oxide sheets in the mixed solution are kept in a good dispersion state; then, injecting the solution into a container (the container can be made of glass, stainless steel, plastic and other materials which are insoluble in water, in this embodiment, polytetrafluoroethylene) and partially immersing the container into liquid nitrogen to form a temperature difference, using ice crystals as a template to prepare a graphene roll-shaped structure, and then removing the ice crystals by using a freezing technology (the freezing drying time is variable, in this embodiment, a freeze dryer is used for drying for 36 hours), so as to obtain a three-dimensional unreduced graphene oxide roll.
The graphene oxide roll prepared by the method can be self-supported, has certain macroscopic properties and is a cuttable three-dimensional network structure; the sample is brownish yellow in a macroscopic state, the diameter of the graphene roll is about 500nm, and the density of the graphene roll is about 1mg/cm3(by adjusting the concentration of the additive and the graphene dispersion liquid, the color similar to brown yellow in a macroscopic state and the difference between the diameter of the graphene roll and the density of the three-dimensional reduced graphene oxide roll can be obtained). The self-supporting unreduced graphene oxide roll network structure material reserves the larger specific surface area of graphene, can be applied to a gas sensor (such as a sulfur dioxide sensor), and can be used for preparing graphene oxide roll structures with different specifications, such as samples with different void ratios and different roll diameters, by adjusting the concentrations of the graphene oxide dispersion liquid and an additive.
Specific example 2
The difference between the embodiment and the embodiment 1 is that fructose is used as an additive, the concentration of the fructose is 0.25mg/mL, and finally, a self-supporting graphene oxide roll containing fructose is prepared, and the diameter of the graphene roll is about 300 nm. The rest is the same as embodiment 1.
Specific example 3
This example is different from embodiment 1 in that a self-supporting graphene oxide roll containing an additive is prepared by using sucrose and graphene oxide, the concentration of sucrose is 0.5mg/mL, and a self-supporting graphene oxide roll containing sucrose is prepared, and the diameter of the graphene roll is about 500 nm. The rest is the same as embodiment 1.
Specific example 4
This example differs from embodiment 1 in that maltose is used as an additive and the concentration is 1mg/mL, and finally a self-supporting graphene oxide roll containing maltose is prepared, the diameter of the graphene roll is about 1000 nm. The rest is the same as embodiment 1.
Specific example 5
Preparing a self-supporting fully reduced graphene oxide roll containing an additive by using glucose and graphene oxide:
1) and dissolving a certain mass of graphene oxide dispersion liquid and glucose in deionized water, and performing ultrasonic treatment, wherein the concentration of the graphene oxide and the concentration of the glucose are respectively 0.5mg/mL and 1 mg/mL.
2) And injecting the solution into a polytetrafluoroethylene material mold, freezing and solidifying by liquid nitrogen, putting into a freeze dryer, drying for 36h, and taking out.
3) Placing the material prepared by freeze drying into a tubular furnace, performing heat treatment for 8 hours at 800 ℃ in an argon atmosphere, and then naturally cooling to room temperature to obtain a self-supporting completely-reduced graphene oxide roll structure, wherein the completely-reduced graphene oxide roll is characterized by being black in a macroscopic state, as shown in figure 2; the diameter of the graphene roll at this point is about 500 nm.
In the method provided by this embodiment, graphene oxide with a certain concentration is ultrasonically mixed with an additive (in this embodiment, the additive is glucose, and the concentrations of graphene oxide and glucose are 0.5mg/mL and 1mg/mL respectively), at this time, the condensation point of the solution is lowered compared with the freezing point when no additive is added, and the graphene oxide dispersion liquid is easy to form a three-dimensional graphene roll structure in a subsequent ice crystal template method; meanwhile, the additive solution is a non-electrolyte solution, so that the graphene oxide dispersion liquid cannot agglomerate, and graphene oxide sheets in the mixed solution are kept in a good dispersion state; then, injecting the solution into a container (the container can be made of glass, stainless steel, plastic and other materials which are insoluble in water, in this embodiment, polytetrafluoroethylene) and partially immersing the container into liquid nitrogen to form a temperature difference, using ice crystals as a template to prepare a graphene roll-shaped structure, and then removing the ice crystals by using a freezing technology (the freezing drying time is variable, in this embodiment, a freeze dryer is used for drying for 36 hours), so as to obtain a three-dimensional unreduced graphene oxide roll. Then the prepared material is insulated from air and treated at high temperature for a period of time and then cooled (in the embodiment, the material is naturally cooled after being treated by heat in a tube furnace at 800 ℃ for 8 hours), at the moment, the additive contained in the material is carbonized, and the graphene oxide is completely reduced; the fully reduced graphene oxide roll prepared by the method can be self-supporting, has a certain macroscopic shape and is a cuttable three-dimensional network structure; the macroscopic state of the sample is black, and the diameter, the density and the like of the graphene roll can be adjusted according to the concentrations of the initial graphene oxide and the additive (in the embodiment, the diameter of the graphene roll is about 1000nm, and the density is about 0.5 mg/mL). The self-supporting graphite oxide roll keeps the larger specific surface area of graphene, has certain flexibility and smaller density, is a better conductive network structure material, and can be used as a substrate material of a super capacitor, a lithium silicon battery, a lithium sulfur battery and the like.
Specific example 6
The difference between the embodiment and the embodiment 5 is that galactose is used as an additive, the concentration of the galactose is 0.25mg/mL, and finally, a self-supporting fully reduced graphene oxide roll containing galactose is prepared, and the diameter of the graphene roll is about 300 nm; the rest is the same as embodiment 5.
Specific example 7
The difference between the embodiment and the embodiment 5 is that sucrose is used as an additive, the concentration of the sucrose is 1mg/mL, and finally, a self-supporting fully reduced graphene oxide roll containing sucrose is prepared, and the diameter of the graphene roll is about 1000 nm; the rest is the same as embodiment 5.
Fig. 3 is a scanning electron microscope surface topography (SEM image) of a free standing graphene roll prepared without additives. As shown in fig. 3, the present invention also uses a graphene oxide dispersion, and adopts a preparation method without adding an additive, so as to try to directly prepare a self-supporting graphene roll. The electron microscope observation of the prepared graphene material shows that when no additive is added by the preparation method disclosed by the invention, the prepared graphene material is in a strip shape and has no winding structure, and the specific process is as follows:
specific example 8
The method is characterized in that a graphene oxide dispersion liquid is utilized, no additive is added, and the process of directly preparing the self-supporting graphene roll is tried:
1) and (3) ultrasonically treating a certain mass of graphene oxide dispersion liquid in deionized water to prepare a solution with the graphene oxide concentration of 0.5 mg/mL.
2) And injecting the solution into a polytetrafluoroethylene material mold, freezing and solidifying by liquid nitrogen, putting into a freeze dryer, drying for 36h, and taking out.
3) As can be seen from the SEM image in fig. 3, the graphene is in a ribbon shape and has no winding structure.
Specific example 9
A self-supporting partially reduced graphene oxide roll network structure material is prepared and used for a lithium-sulfur battery.
1) And dissolving a certain mass of graphene oxide dispersion liquid and glucose in deionized water, and performing ultrasonic treatment, wherein the concentrations of the graphene oxide and the glucose are 1mg/mL and 0.5mg/mL respectively.
2) And injecting the solution into a polytetrafluoroethylene material mold, freezing and solidifying by liquid nitrogen, putting into a freeze dryer, drying for 36h, and taking out.
3) The material obtained by freeze drying is subjected to heat treatment at 180 ℃ in an argon atmosphere for 12h, and then is naturally cooled to room temperature.
4) Placing the prepared material in a mixed solution of deionized water and ethanol, heating for 2h at 60 ℃ in a water bath, wherein the volume ratio of water to ethanol is 1:1, and then replacing the mixed solution to treat under the same condition; the process is repeated for 5 times, and then deionized water is used for washing the sample for multiple times to remove the glucose heat treatment product on the graphene roll.
In the method provided by this embodiment, graphene oxide with a certain concentration is ultrasonically mixed with an additive (in this embodiment, the additive is glucose, and the concentrations of graphene oxide and glucose are 1mg/mL and 0.5mg/mL respectively), at this time, the condensation point of the solution is lowered compared with the freezing point when no additive is added, and the graphene oxide dispersion liquid is easy to form a three-dimensional graphene roll structure in a subsequent ice crystal template method; meanwhile, the additive solution is a non-electrolyte solution, so that the graphene oxide dispersion liquid cannot agglomerate, and graphene oxide sheets in the mixed solution are kept in a good dispersion state; then, injecting the solution into a container (the container can be made of glass, stainless steel, plastic and other materials which are insoluble in water, in this embodiment, polytetrafluoroethylene) and partially immersing the container into liquid nitrogen to form a temperature difference, using ice crystals as a template to prepare a graphene roll-shaped structure, and then removing the ice crystals by using a freezing technology (the freezing drying time is variable, in this embodiment, a freeze dryer is used for drying for 36 hours), so as to obtain a three-dimensional unreduced graphene oxide roll. The unreduced graphene oxide roll is subjected to thermal reduction at a lower temperature and then is naturally cooled (the example is treated at 180 ℃ for 12 hours), so that the partially reduced graphene oxide roll containing the additive is obtained. And further removing the additive (the embodiment adopts the repeated use of the mixed solution of deionized water and ethanol with the same volume in the water bath at 60 ℃ for 2h to remove the glucose heat treatment product by cleaning), so as to obtain the partially reduced graphene oxide roll without the additive. The partially reduced graphene roll may be further heat treated at a higher temperature for a period of time (e.g., above 500 ℃ for more than 5 hours), such that a fully reduced graphene oxide roll containing no additive reaction product is obtained.
The partially reduced graphene oxide roll prepared by the method can be self-supporting, has a certain macroscopic shape and is a cuttable three-dimensional network structure; the sample is black in macroscopic state, the diameter, the density and the like of the graphene roll can be adjusted according to the concentrations of the initial graphene oxide and the additive (the diameter of the graphene roll in the embodiment is about 1000nm, and the density is about 0.8mg/mL), and the graphene roll contains no or very little additive heat treatment product (the mass fraction of the additive heat treatment product in the embodiment is less than 1%). The self-supporting graphite oxide roll keeps larger specific surface area of graphene, has certain flexibility and smaller density, is a better conductive network structure material, has oxygen-containing functional groups (such as carboxyl, epoxy and the like) on the surface, and can effectively restrain polysulfide products generated in the discharge process of a battery when being applied to a lithium-sulfur battery so as to avoid shuttle effect caused by the fact that the polysulfide products are dissolved in electrolyte; the partially reduced graphene oxide roll further expands the application range of the reduced graphene oxide roll.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.

Claims (10)

1. The self-supporting reduced graphene oxide roll network material is characterized in that the self-supporting reduced graphene oxide roll network material is formed by mutually connecting and rolling a single layer to a plurality of layers of reduced graphene oxide sheets into a reduced graphene oxide roll, and the reduced graphene oxide rolls are mutually overlapped and lapped to form a self-supporting three-dimensional porous network structure; the self-supporting reduced graphene oxide roll network material contains an additive, has certain shape and flexibility, and can be processed or cut into any shape; the additive can be one or more of monosaccharide, disaccharide or polysaccharide;
the reduced graphene oxide roll can have different reduction degrees, the constituent elements of the reduced graphene oxide roll are carbon, hydrogen and oxygen, and the mass ratio of the carbon to the oxygen can be regulated and controlled;
the porosity of the reduced graphene oxide roll network material is adjustable;
the density of the reduced graphene oxide roll network material is adjustable;
the diameter of the reduced graphene oxide roll network material is adjustable;
the length-diameter ratio of the reduced graphene oxide roll network material
Figure FDA0002888124790000012
The utility model can be adjusted in a controllable way,wherein L is the length of the volume between two nodes of the graphene volume network, and d is the diameter of the graphene volume;
the additive is partially pyrolyzed or fully carbonized to amorphous carbon and coated or partially coated as a "mud" on the surface of fully or partially reduced graphene oxide lamellae, while filling or partially filling in the gaps between the reduced or partially reduced graphene oxide lamellae, forming a "brick mud structure" enabling the nanocolloid to maintain a self-supporting three-dimensional network structure.
2. The self-supporting reduced graphene oxide roll network material of claim 1,
the reduced graphene oxide roll is a partially reduced graphene oxide roll and/or a completely reduced graphene oxide roll, and the content of oxygen is less than or equal to 1%.
3. The self-supporting reduced graphene oxide roll network material of claim 1, wherein the reduced graphene oxide roll network material has a porosity of 10-99%;
the density of the reduced graphene oxide roll network material is less than 10mg/cm3；
The diameter of the reduced graphene oxide roll network material is 1nm-10 mu m.
4. The self-supporting reduced graphene oxide roll network material of claim 1, wherein the reduced graphene oxide roll network material has an aspect ratio
Figure FDA0002888124790000011
Greater than 5.
5. The preparation method of the self-supporting reduced graphene oxide roll network material applied to the claim 1 is characterized by comprising the following steps:
s1, preparing a uniformly mixed solution of the graphene oxide dispersion liquid and the additive according to a certain mass ratio;
s2, freeze-drying the mixed solution to obtain an unreduced graphene oxide roll network material;
s3, placing the unreduced graphene oxide roll network material in a protective gas atmosphere to be processed for a preset time at a preset temperature, and obtaining a self-supporting partially reduced or completely reduced graphene oxide roll network material;
s4, repeatedly cleaning the self-supporting partially-reduced graphene oxide roll network material to a preset degree, and then carrying out freeze drying treatment; obtaining a self-supporting partially reduced graphene oxide roll network material with low additive content;
the self-supporting reduced graphene oxide roll network material contains the additive, has certain shape and flexibility, and can be processed or cut into any shape;
the reduced graphene oxide roll can have different reduction degrees, the constituent elements of the reduced graphene oxide roll are carbon, hydrogen and oxygen, and the mass ratio of the carbon to the oxygen can be regulated and controlled;
the porosity of the reduced graphene oxide roll network material is adjustable;
the density of the reduced graphene oxide roll network material is adjustable;
the diameter of the reduced graphene oxide roll network material is adjustable;
the length-diameter ratio of the reduced graphene oxide roll network material
Figure FDA0002888124790000021
The method is adjustable, wherein L is the length of the graphene roll between two nodes of the graphene roll network, and d is the diameter of the graphene roll;
the additive can be one or more of monosaccharide, disaccharide or polysaccharide;
the concentration of the graphene oxide in the mixed solution is 0.5mg/ml or 1 mg/ml; the concentration of the additive is 0.25mg/ml or 0.5mg/ml or 1 mg/ml.
6. The method for preparing the self-supporting reduced graphene oxide roll network material according to claim 5, wherein in the step S1, the mass ratio of the graphene oxide dispersion liquid to the additive is adjustable;
the mass ratio is 1:10-10: 1.
7. The method of preparing a self-supporting reduced graphene oxide roll network material according to claim 5,
the monosaccharide is one or more of glucose, fructose and galactose;
the disaccharide is one or more of sucrose, lactose and maltose;
the polysaccharide is one or more of glycogen and starch.
8. The method for preparing a self-supporting graphene oxide roll network material according to claim 5, wherein in the step S3, the protective gas is an inert gas, a reducing gas or a mixed gas of the inert gas and the reducing gas; wherein the content of the first and second substances,
the inert gas is nitrogen, argon or a mixed gas thereof;
the reducing gas is hydrogen.
9. The method for preparing a self-supporting graphene oxide roll network material according to claim 5, wherein in the step S3, the predetermined temperature is not lower than 50 ℃; the preset time is not less than 0.1 h; wherein the content of the first and second substances,
the predetermined temperature is 50-1000 ℃;
the predetermined time is 1-30 h.
10. The method for preparing the self-supporting reduced graphene oxide roll network material according to claim 5, wherein in the step S4, the organic solvent used for repeated cleaning is not limited, and the organic solvent is one or more of ethanol, methanol and acetone.
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* Cited by examiner, † Cited by third party
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