CN115650214A - Low-energy-consumption extremely-fast efficient graphene oxide reduction method - Google Patents
Low-energy-consumption extremely-fast efficient graphene oxide reduction method Download PDFInfo
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Abstract
The invention discloses a method for reducing graphene oxide with low energy consumption, high speed and high efficiency, which comprises the steps of placing a reduction initiator on a heat source with the temperature of not lower than 180 ℃, and then contacting graphene oxide with the reduction initiator to start reaction to obtain reduced graphene oxide; or placing the graphene oxide coated with the reduction initiator on a heat source at 160-240 ℃ for reduction reaction to obtain the reduced graphene oxide. According to the invention, through selecting a proper reduction initiator and regulating and controlling the temperature of a heat source, the graphene oxide is reduced at a high speed and high efficiency.
Description
Technical Field
The invention belongs to the technical field of reduced graphene oxide preparation, relates to a preparation technology of high-conductivity reduced graphene oxide, and particularly relates to a method for quickly preparing reduced graphene oxide with good conductivity by using low-melting-point metal as an initiator.
Background
The direct preparation of graphene faces the main problems of low yield of single-layer graphene, insufficient micron-sized transverse dimension and the like.
At present, an indirect preparation process of firstly oxidizing graphite and then stripping the graphite into single-layer graphene oxide is adopted, the yield of the graphite can almost reach 100%, and the transverse dimension of the graphite can easily exceed the micron level. Therefore, the graphene prepared by reducing graphene oxide has great potential.
However, the current methods for reducing graphene oxide mainly include a chemical reduction method, a high-temperature annealing method and a microwave reduction method. A large amount of reducing agents are needed in the chemical reduction process, and the reducing agents comprise hydrazine hydrate, hydroiodic acid, high-temperature hydrogen and other toxic or dangerous substances; in the reduction process, due to the selectivity of the reducing agent and the strong interaction between the reducing agent and the functional group of the graphene oxide, the reduced graphene oxide prepared by the chemical reduction method often has the defects of discontinuous structure, high oxygen content, complex subsequent treatment and the like. Although the microwave reduction method can prepare reduced graphene oxide with fewer layers, a conductive agent and other pretreatment means need to be introduced in the reduction process, so that the reduced graphene oxide prepared by the microwave method has high impurity content and low product yield.
CN 111908455A discloses a method for reducing graphene oxide by using high-temperature hydrogen, which not only has high energy consumption and complex process, but also has a great risk.
CN 102153078B discloses a method for reducing graphene oxide by using acetone oxime, acetaldoxime or methyl ethyl ketoxime as a reducing agent, but all of the reducing agents have certain toxicity and are inevitably harmful to operators and the environment in the production process.
Therefore, a high-energy-consumption, low-efficiency and toxic reduction mode is not desirable in the process of producing reduced graphene oxide on a large scale, and does not accord with the current environmental protection development concept; prime for a novel reduction-oxidation graphene process to be developed, can realize the high-efficient preparation of reduction-oxidation graphene, can effectively reduce the energy consumption moreover, avoid the pollution to the environment simultaneously.
Disclosure of Invention
The invention aims to provide a method for reducing graphene oxide with low energy consumption, high speed and high efficiency aiming at the problems of high energy consumption, low efficiency, toxicity and the like in the traditional graphene oxide reduction method.
In order to achieve the purpose, the invention adopts the following technical scheme to realize.
The invention provides a low-energy-consumption extremely-fast efficient graphene oxide reduction method, which comprises two implementation modes:
a first implementation, comprising the steps of:
(A1) Placing the reduction initiator on a heat source at a temperature of not lower than 180 ℃;
(A2) Contacting the graphene oxide with a reduction initiator to start reaction to obtain reduced graphene oxide;
the second implementation mode comprises the following steps:
(B1) Coating graphene oxide in a reduction initiator;
(B2) And (3) placing the reduction initiator coated with the graphene oxide on a heat source at 160-240 ℃ for reduction reaction to obtain the reduced graphene oxide.
In both implementations, the reduction initiator may be any metal having a low melting point, such as lithium or tin, or an alloy of two or more metals; the melting point of the reducing initiator preferably ranges from 180 ℃ to 250 ℃.
In both implementations, there is no limitation on the preparation process of the graphene oxide, and the graphene oxide prepared by any method can be reduced by the method provided by the present invention and does not require any purification or complicated subsequent treatment. The shape of the graphene oxide is not required, and the graphene oxide can be in a foam shape, a film shape, a powder shape, a flocculent shape or other shapes with any size; in a preferred implementation, the water content in the graphene oxide is not more than 50%, and further, the water content is not more than 30%; when the water content in the graphene oxide is lower than 30%, the reaction is more easily initiated, so that the reduction is more thorough.
The foamy graphene oxide is obtained by freeze-drying aqueous dispersion containing graphene oxide; the foamed graphene oxide may be further subjected to pressure compression to obtain a layered graphene oxide. The film graphene oxide is obtained by drying aqueous dispersion containing graphene oxide; the thin film graphene oxide may be further compressed under pressure. The concentration of the graphene oxide in the aqueous dispersion containing the graphene oxide is 5-15mg/mL, and in a preferred implementation mode, the concentration of the graphene oxide in the aqueous dispersion containing the graphene oxide is 10mg/mL.
In the two implementation modes, no special requirement is required for a heat source, and the heat source can be an electric iron, a flat heater, a point heater, a baking lamp or a tube furnace and the like.
In the two implementation modes, the environmental atmosphere of the reduction initiator and the graphene oxide has no special requirement, and can be any atmosphere of air, inert gas, hydrogen, nitrogen and oxygen or the mixed atmosphere of more than two atmospheres; for example, an argon-hydrogen mixed gas atmosphere (hydrogen gas content of 1% to 15%). The ambient humidity is not higher than 80%, and in a preferred implementation, the ambient humidity is not higher than 50%.
In both implementations, the reduction rate of graphene oxide is greater than 0.1cm 2 /s。
In both implementations, the resistivity of the resulting reduced graphene oxide is no higher than 50 Ω · cm.
In two implementation manners, the carbon-oxygen ratio of the obtained reduced graphene oxide is 20:1 to 1:50; the carbon-oxygen ratio in the obtained reduced graphene oxide is 10-14: 1.
in the first implementation manner, the weight ratio of the graphene oxide to the reduction initiator is not limited, as long as the graphene oxide and the reduction initiator can be in point contact or surface contact at any angle within the range of 0-90 °; the graphene oxide may be in a flat, upright, or inclined posture with respect to the reduction initiator. In order to achieve sufficient reduction of graphene oxide, in a preferred embodiment, the area of the contact surface between graphene oxide and the reduction initiator is not less than the contact area between the graphene oxide and the reduction initiator.
In the first implementation mode, the temperature of the heat source is preferably 180-200 ℃, and the contact time of the graphene oxide and the reduction initiator is not less than 1s, so that the graphene oxide is completely reduced.
In a second implementation manner, the reduction initiator wraps all or part of the graphene oxide, and the wrapping area is not less than 5%. The reduction reaction time of the graphene oxide is not less than 1s, so that the graphene oxide is completely reduced.
The low-energy-consumption extremely-fast efficient graphene oxide reduction method provided by the invention has the following beneficial effects:
(1) The invention discloses a method for reducing graphene oxide only based on a heat source and a reduction initiator, which realizes the extremely-fast and efficient reduction of the graphene oxide by selecting the appropriate reduction initiator and regulating and controlling the temperature of the heat source, wherein the reduction rate is more than 0.1cm 2 /s。
(2) The method for reducing the graphene oxide provided by the invention has the advantages of simple preparation conditions and low environmental requirements, can be suitable for large-scale production, does not generate toxic substances, and meets the current environmental protection development concept.
Drawings
Fig. 1 is a schematic diagram of a foamy graphene oxide.
Fig. 2 is a schematic view of a layered graphene oxide pressed by using the foamed graphene oxide shown in fig. 1.
Fig. 3 is a schematic diagram of graphene oxide after drying.
Fig. 4 is a raman diagram of the foamy graphene oxide.
Fig. 5 is a raman diagram of layered graphene oxide pressed using the foamed graphene oxide shown in fig. 1.
Fig. 6 is an SEM image of the foamy graphene oxide.
Fig. 7 is a raman chart of the reduced graphene oxide obtained in example 2.
Fig. 8 is a schematic view of reduced graphene oxide obtained in example 9.
Fig. 9 is a raman diagram of reduced graphene oxide obtained in example 9.
Fig. 10 is an infrared image of reduced graphene oxide obtained in example 9.
Fig. 11 is a raman chart of reduced graphene oxide and graphene oxide obtained in example 13.
Fig. 12 is an infrared image of reduced graphene oxide obtained in example 13.
Fig. 13 is a raman chart of reduced graphene oxide and graphene oxide obtained in example 17.
Fig. 14 is an infrared image of reduced graphene oxide and graphene oxide obtained in example 17.
Fig. 15 is an SEM image of reduced graphene oxide obtained in example 17.
Fig. 16 is a TEM image of reduced graphene oxide obtained in example 17.
Fig. 17 is a raman chart of reduced graphene oxide obtained in comparative example 1.
Fig. 18 is an infrared image of reduced graphene oxide obtained in comparative example 1.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, belong to the present invention.
Graphene oxide and all reduction initiators used in the following examples were obtained commercially.
The preparation method of the foamy graphene oxide solid A in the following example is as follows: 200mL of graphene oxide aqueous solution (with the concentration of 5 mg/mL) is poured into an evaporation pan (a round glass evaporation pan with the radius of 9 cm), the evaporation pan is placed in a freeze dryer, and freeze drying is carried out for 36 hours, so that a foamy graphene oxide solid A (shown in figure 1) is obtained, and the water content is 10%.
The preparation method of the foamy graphene oxide solid B in the following examples is as follows: pouring 100mL of graphene oxide aqueous solution (with the concentration of 10 mg/mL) into an evaporating dish (a round glass evaporating dish with the radius of 9 cm), placing the evaporating dish into a freeze dryer, and freeze-drying for 36h to obtain a foamy graphene oxide solid B with the water content of 10%.
The preparation method of the thin-film graphene oxide solid a in the following example is as follows: 30mL of graphene oxide aqueous solution (with the concentration of 15 mg/mL) is poured into an evaporation dish (a round glass evaporation dish with the radius of 9 cm), the evaporation dish is gently shaken to enable the graphene oxide aqueous solution to completely cover the bottom of the evaporation dish, and the evaporation dish is placed in an oven with the temperature of 70 ℃ for processing for 5 hours to obtain a film-shaped graphene oxide solid A (shown in figure 3) with the water content of 10%.
The preparation method of the thin-film graphene oxide solid B in the following examples is: pouring 30mL of graphene oxide aqueous solution (with the concentration of 10 mg/mL) into an evaporation dish (a round glass evaporation dish with the radius of 9 cm), slightly shaking the evaporation dish to enable the graphene oxide aqueous solution to completely cover the bottom of the evaporation dish, and placing the evaporation dish in an oven with the temperature of 70 ℃ for processing for 5 hours to obtain a film-shaped graphene oxide solid B with the water content of 10%.
Example 1
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) 0.0778g (size 4 cm. Times.3 cm, thickness 0.5 cm) of the foamy graphene oxide solid A was taken and placed in an evaporation dish, and the evaporation dish was transferred to a dry environment with a humidity of less than 80% for standby.
(2) Heating an electric iron serving as a heat source to 180 ℃; contacting a heat source with metallic tin such that the heat source carries the metallic tin;
(3) And (2) continuously keeping the heating state, and then contacting the foamy graphene oxide solid A obtained in the step (1) with metal tin loaded by an electric soldering iron at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 2
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) 0.0732g (size: 4 cm. Times.3 cm) of the foamed graphene oxide solid A was taken and placed under a 40T electric tablet press for 5s (pressure: 10 MPa) to obtain layered graphene oxide with a thickness of 20 μm (as shown in FIG. 2), which was then placed in an evaporation dish and transferred to a dry environment with a humidity of less than 80% for use.
(2) Heating an electric iron serving as a heat source to 180 ℃; contacting a heat source with metallic tin such that the heat source carries the metallic tin;
(3) And (2) continuously keeping the heating state, and then contacting the layered graphene oxide obtained in the step (1) with metal tin loaded by an electric soldering iron at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 3
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) 0.0522g (size 4cm × 3cm, thickness 0.1 cm) of thin film graphene oxide solid A is taken and placed in an evaporation dish, and the evaporation dish is transferred to an environment with humidity lower than 80% for standby.
(2) Heating an electric iron serving as a heat source to 180 ℃; contacting a heat source with metallic tin such that the heat source carries the metallic tin;
(3) And (2) continuously keeping the heating state, and then contacting the film-shaped graphene oxide solid A obtained in the step (1) with metal tin loaded on an electric soldering iron at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 4
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) Taking 0.0516g (with the size of 4cm multiplied by 3 cm) of film-shaped graphene oxide solid A, placing the film-shaped graphene oxide solid A under a 40T electric tablet press for 5s (with the pressure of 10 MPa) to obtain a graphene oxide film with the thickness of 20 mu m, then placing the graphene oxide film in an evaporation dish, and transferring the evaporation dish to an environment with the humidity of lower than 80% for standby.
(2) Heating an electric iron serving as a heat source to 180 ℃; contacting a heat source with metallic tin such that the heat source carries the metallic tin;
(3) And (2) continuously keeping the heating state, and then contacting the graphene oxide film obtained in the step (1) with metal tin loaded by an electric soldering iron at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 5
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) 0.0807g (size 4cm multiplied by 3cm, thickness 0.5 cm) of foam graphene oxide solid A is taken and placed in an evaporation pan, and the evaporation pan is transferred to a glove box protected by nitrogen (purity is more than or equal to 99.999%) for standby (oxygen content in the glove box is less than 0.01ppm, and water content is less than 0.01 ppm).
(2) Heating an electric iron serving as a heat source to 200 ℃; contacting a heat source with metallic tin such that the heat source carries the metallic tin;
(3) And (2) continuously keeping the heating state, and then contacting the foamy graphene oxide solid A obtained in the step (1) with metal tin loaded by an electric soldering iron at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 6
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) Taking 0.0823g (with the size of 4cm multiplied by 3 cm) of the foamy graphene oxide solid A, placing the foamy graphene oxide solid A under a 40T electric tablet press for tabletting for 5s (with the pressure of 10 MPa), and obtaining the layered graphene oxide with the thickness of 20 mu m. Graphene oxide is placed in an evaporation dish and transferred into a glove box protected by nitrogen (the purity is more than or equal to 99.999%) for standby application (the oxygen content in the glove box is less than 0.01ppm, and the water content in the glove box is less than 0.01 ppm).
(2) Heating an electric iron serving as a heat source to 200 ℃; contacting a heat source with metallic tin such that the heat source carries the metallic tin;
(3) And (2) continuously keeping the heating state, and then contacting the layered graphene oxide obtained in the step (1) with iron-supported metal tin at 0 ° (namely, the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 7
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) 0.0547g (4 cm multiplied by 3cm in size and 0.1cm in thickness) of film-shaped graphene oxide solid A is taken and placed in an evaporation pan, and the evaporation pan is transferred to a glove box protected by nitrogen (the purity is more than or equal to 99.999%) for standby (the oxygen content in the glove box is less than 0.01ppm, and the water content in the glove box is less than 0.01 ppm).
(2) Heating an electric iron serving as a heat source to 200 ℃; contacting a heat source with metallic tin such that the heat source carries the metallic tin;
(3) And (2) continuously keeping the heating state, and then contacting the film-shaped graphene oxide solid A obtained in the step (1) with metal tin loaded by an electric soldering iron at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 8
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) 0.0478g (4 cm multiplied by 3cm in size) of the film-shaped graphene oxide solid A is placed under a 40T electric tablet press for 5s (pressure 10 MPa) to obtain a graphene oxide film with the thickness of 20 mu m, and then the graphene oxide film is placed in an evaporation dish, and the evaporation dish is transferred into a glove box protected by nitrogen (the purity is more than or equal to 99.999%) for standby (the oxygen content in the glove box is less than 0.01ppm, and the water content in the glove box is less than 0.01 ppm).
(2) Heating an electric iron serving as a heat source to 200 ℃; contacting a heat source with metallic tin such that the heat source carries the metallic tin;
(3) And (3) continuously keeping the heating state, and then contacting the graphene oxide film obtained in the step (1) with iron-loaded metal tin at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 9
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) 0.0807g (size 4cm × 3cm, thickness 0.5 cm) of the foamy graphene oxide solid B was taken and placed in an evaporation pan, and the evaporation pan was transferred into a glove box protected by argon (purity ≧ 99.999%) for later use (oxygen content < 0.01ppm and water content < 0.01ppm in the glove box).
(2) Placing metal lithium on a heating plate, and heating the heating plate to 200 ℃;
(3) And (3) continuously keeping the heating state, and then contacting the foamy graphene oxide solid B obtained in the step (1) with metal lithium on a heating plate at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide (as shown in FIG. 8).
Example 10
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) 0.0823g (4 cm multiplied by 3cm in size) of the foamy graphene oxide solid B is taken and placed under a 40T electric tablet machine to be tabletted for 5s (10 MPa of pressure), and the layered graphene oxide with the thickness of 20 mu m is obtained. The layered graphene oxide is placed in an evaporation dish and transferred into an argon (purity ≧ 99.999%) protective glove box for later use (oxygen content in the glove box is < 0.01ppm, water content is < 0.01 ppm).
(2) Placing lithium metal on a heating plate, and heating the heating plate to 200 ℃;
(3) And (2) continuously keeping the heating state, and then contacting the layered graphene oxide obtained in the step (1) with metal lithium on a heating plate at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 11
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) 0.0547g (size 4cm × 3cm, thickness 0.1 cm) of film-shaped graphene oxide solid B is taken and placed in an evaporation dish, and the evaporation dish is transferred to an argon (purity ≧ 99.999%) protective glove box for standby (oxygen content in the glove box is less than 0.01ppm, water content is less than 0.01 ppm).
(2) Placing metal lithium on a heating plate, and heating the heating plate to 200 ℃;
(3) And (3) continuously keeping the heating state, and then contacting the film-shaped graphene oxide solid B obtained in the step (1) with metal lithium on a heating plate at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 12
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) Taking 0.0478g (size of 4cm × 3 cm) of film-shaped graphene oxide solid B, placing the film-shaped graphene oxide solid B under a 40T electric tablet press for 5s (pressure of 10 MPa) to obtain a graphene oxide film with the thickness of 20 μm, then placing the graphene oxide film in an evaporation dish, and transferring the evaporation dish to a glove box protected by argon (purity ≧ 99.999%) for standby (oxygen content in the glove box is less than 0.01ppm, and water content is less than 0.01 ppm).
(2) Placing lithium metal on a heating plate, and heating the heating plate to 200 ℃;
(3) And (3) continuously keeping the heating state, and then contacting the graphene oxide film obtained in the step (1) with metal lithium on a heating plate at 0 degrees (namely the surface of the graphene oxide is parallel to the plane of a heat source) for 1s to obtain the reduced graphene oxide.
Example 13
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) 0.0832g (size 4cm x 3cm, thickness 0.5 cm) of solid foam graphene oxide B was placed in an evaporating dish and the dish was transferred to a dry environment with a humidity below 80% for use.
(2) Wrapping the foamy graphene oxide solid B obtained in the step (1) with an indium tin bismuth alloy (indium content: 50.2119%, tin content 16.3663%, bismuth content 32.3218, lead content 0.0153% and other metals 1.1%) with the size of 8cm × 3cm, placing the wrapped foamy graphene oxide solid B in a crucible, transferring the foamy graphene oxide solid B into a tube furnace for reaction, heating to 160 ℃ (the temperature rise rate is 10 ℃/min) under argon (the concentration is not less than 99.999%), and then directly cooling to room temperature to obtain the reduced graphene oxide.
Example 14
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) 0.0788g (size is 4cm multiplied by 3 cm) of foam graphene oxide solid B is taken and placed under a 40T electric tablet press to be tabletted for 5s (pressure is 10 MPa), and the layered graphene oxide with the thickness of 20 mu m is obtained. The layered graphene oxide is placed in an evaporation dish and transferred to a dry environment with humidity below 80% for standby.
(2) Wrapping the layered graphene oxide with the thickness of 20 microns obtained in the step (1) by using an indium tin bismuth alloy (indium content: 50.2119%, tin content 16.3663%, bismuth content 32.3218, lead content 0.0153% and other metals 1.1%) with the size of 8cm × 3cm, placing the layered graphene oxide in a crucible, transferring the layered graphene oxide into a tubular furnace for reaction, heating to 160 ℃ (the temperature rise rate is 10 ℃/min) under argon (the concentration is not less than 99.999%), and directly cooling to room temperature to obtain the reduced graphene oxide.
Example 15
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) 0.0462g (size 4cm × 3cm, thickness 0.1 cm) of thin film graphene oxide solid B was taken and placed in an evaporation dish, and the evaporation dish was transferred to an environment with humidity lower than 80% for standby.
(2) Wrapping the 0.1cm film-shaped graphene oxide solid B obtained in the step (1) by indium tin bismuth alloy (indium content: 50.2119%, tin content 16.3663%, bismuth content 32.3218, lead content 0.0153% and other metals 1.1%) with the size of 8cm × 3cm, placing the indium tin bismuth alloy in a crucible, transferring the crucible to a tubular furnace for reaction, heating to 160 ℃ (the temperature rise rate is 10 ℃/min) under argon (the concentration is not less than 99.999%), and directly cooling to room temperature to obtain the reduced graphene oxide.
Example 16
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) Taking 0.0506g (size is 4cm multiplied by 3 cm) of film-shaped graphene oxide solid B, placing the film-shaped graphene oxide solid B under a 40T electric tablet press for 5s (pressure is 10 MPa) to obtain a graphene oxide film with the thickness of 20 mu m, then placing the graphene oxide film in an evaporation dish, and transferring the evaporation dish to an environment with the humidity lower than 80% for standby.
(2) Wrapping the 20-micron graphene oxide film obtained in the step (1) by using an indium tin bismuth alloy (with indium content: 50.2119%, tin content 16.3663%, bismuth content 32.3218, lead content 0.0153% and other metals 1.1%) with the size of 8cm × 3cm, placing the film in a crucible, transferring the film into a tube furnace for reaction, heating the film to 160 ℃ (the temperature rise rate is 10 ℃/min) under argon (the concentration is not less than 99.999%), and directly cooling the film to room temperature to obtain the reduced graphene oxide.
Example 17
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) 0.0884g (4 cm × 3cm in size and 0.5cm in thickness) of the foamy graphene oxide solid B was taken and placed in an evaporation dish, and the evaporation dish was transferred to a dry environment with a humidity of less than 80% for standby.
(2) Covering the 0.5cm foamy graphene oxide solid B obtained in the step (1) with a tin sheet (with the size of 8cm multiplied by 3 cm) (with the tin content of 99.951%, the silver content of 0.0015%, the copper content of 0.0006%, the lead content of 0.0012%, the bismuth content of 0.0011%, the arsenic content of 0.0013% and other metals of 0.0433%) in a crucible, transferring the crucible into a tubular furnace for reaction, heating to 235 ℃ (the heating rate is 10 ℃/min) in the atmosphere of argon-hydrogen mixed gas, and then directly cooling to room temperature to obtain the reduced graphene oxide.
Example 18
The method for reducing graphene oxide at low energy consumption and high speed with high efficiency provided by the embodiment comprises the following steps:
(1) 0.0932g (size is 4cm multiplied by 3 cm) of foam graphene oxide solid B is taken and placed under a 40T electric tablet machine to be tabletted for 5s (pressure is 10 MPa), and the layered graphene oxide with the thickness of 20 mu m is obtained. The layered graphene oxide is placed in an evaporation dish and transferred to a dry environment with a humidity of less than 80% for use.
(2) Covering the layered graphene oxide with the thickness of 20 microns obtained in the step (1) with tin sheets (the tin content is 99.951%, the silver content is 0.0015%, the copper content is 0.0006%, the lead content is 0.0012%, the bismuth content is 0.0011%, the arsenic content is 0.0013%, and other metals are 0.0433%) with the size of 8cm multiplied by 3cm, placing the layered graphene oxide in a crucible, transferring the crucible into a tubular furnace for reaction, heating the layered graphene oxide to 235 ℃ (the heating rate is 10 ℃/min) in the atmosphere of argon-hydrogen mixed gas, and then directly cooling the layered graphene oxide to the room temperature to obtain the reduced graphene oxide.
Example 19
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) 0.0577g (size is 4cm multiplied by 3cm, thickness is 0.1 cm) of thin film graphene oxide solid B is taken and placed in an evaporation dish, and the evaporation dish is transferred to an environment with humidity lower than 80% for standby.
(2) And (2) wrapping the 0.1cm film-shaped graphene oxide solid B obtained in the step (1) by using a tin sheet (with the size of 8cm multiplied by 3 cm) (with the tin content of 99.951%, the silver content of 0.0015%, the copper content of 0.0006%, the lead content of 0.0012%, the bismuth content of 0.0011%, the arsenic content of 0.0013% and other metals of 0.0433%) in a crucible, transferring the crucible into a tubular furnace for reaction, heating to 235 ℃ (the heating rate is 10 ℃/min) in the argon-hydrogen mixed gas atmosphere (with the hydrogen content of 15%), and then directly cooling to the room temperature to obtain the reduced graphene oxide.
Example 20
The method for reducing graphene oxide at low energy consumption and high speed and high efficiency provided by the embodiment comprises the following steps:
(1) Taking 0.0653g (size is 4cm multiplied by 3 cm) of film-shaped graphene oxide solid B, placing the film-shaped graphene oxide solid B under a 40T electric tablet press for 5s (pressure is 10 MPa) to obtain a graphene oxide film with the thickness of 20 mu m, then placing the graphene oxide film in an evaporation dish, and transferring the evaporation dish to an environment with the humidity of lower than 80% for standby.
(2) Wrapping the 20-micron graphene oxide film obtained in the step (1) with a block-shaped tin sheet (with the size of 8cm multiplied by 3cm, the tin content is 99.951%, the silver content is 0.0015%, the copper content is 0.0006%, the lead content is 0.0012%, the bismuth content is 0.0011%, the arsenic content is 0.0013%, and other metals are 0.0433%) and placing the block-shaped tin sheet in a crucible, transferring the block-shaped tin sheet to a tubular furnace for reaction, heating the block-shaped tin sheet to 235 ℃ (the heating rate is 10 ℃/min) in the atmosphere of argon-hydrogen mixed gas, and directly cooling the block-shaped tin sheet to room temperature to obtain the reduced graphene oxide.
Comparative examples 1 to 20
Comparative example 1-comparative example 20 the steps for reducing graphene oxide are provided as follows: adding 70mL of deionized water into a graphene oxide aqueous solution for dilution, stirring for 30min, transferring into a 100mL round bottom flask, adding a condenser pipe into the round bottom flask, placing the round bottom flask into an oil bath, carrying out oil bath at the temperature of 65 ℃, adding ammonia water when the temperature of the graphene oxide aqueous solution in the round bottom flask reaches 65 ℃, fully stirring for 1min, then adding hydrazine hydrate, increasing the temperature of the oil bath to 95 ℃, stirring for full reaction (reaction time is 2.5 h), after the reaction is finished, carrying out suction filtration on the solution in the round bottom beaker to obtain a reduced graphene oxide precursor substance, then dissolving the reduced graphene oxide precursor into 100mL hydrochloric acid with the concentration of 5mol/L, fully stirring for 3h, carrying out suction filtration to remove the hydrochloric acid solution, then cleaning with a mixed solution of deionized water and ethanol (deionized water: ethanol = 3.
The amounts of the aqueous graphene oxide solution and the aqueous ammonia hydrazine hydrate used are shown in table 1.
TABLE 1 proportioning of raw materials in comparative examples 1 to 20
(I) statistical analysis of time required to reduce graphene oxide
The time required for reducing the graphene oxide is the time required for preparing the reduced graphene oxide by using the graphene oxide as a raw material.
Statistics of the time required for the reaction of the graphene oxides of examples 1 to 20 and comparative examples 1 to 20 show that, in the present invention, when the temperature of the heat source meets the requirement, the reaction starts as long as the graphene oxide contacts the reducing agent, and the reduction of the graphene oxide can be completed within 1s of the contact time; when the tube furnace is used as a heat source, the temperature can be directly reduced when the temperature is raised to the set temperature. Compared with the reaction time of 2.5h in the comparative example, the method for reducing the graphene oxide has extremely high reaction rate and extremely low energy consumption, and can realize the efficient preparation of the reduced graphene oxide.
Moreover, the method for reducing the graphene oxide provided by the invention reduces subsequent operations such as purification, washing, freeze-drying and the like, greatly simplifies the preparation process of the reduced graphene oxide, and is low in energy consumption, low in cost, short in processing period, high in processing efficiency and more suitable for industrial production.
(II) reduced graphene oxide structural analysis
SEM analysis and TEM analysis were performed on the graphene oxide foam used in the present invention and the reduced graphene oxide prepared in example 17, and the analysis results are shown in fig. 6, 15, and 16. As can be seen from the figure, the reduced graphene oxide prepared by the method does not change the structure of the graphene oxide.
Raman analysis was performed on graphene oxide foam, layered graphene oxide pressed from graphene oxide foam, the reduced graphene oxide obtained in example 2, the reduced graphene oxide obtained in example 9, the reduced graphene oxide obtained in example 13, the reduced graphene oxide obtained in example 17, and the reduced graphene oxide obtained in comparative example 1, and the analysis results are shown in fig. 4, fig. 5, fig. 7, fig. 9, fig. 11, fig. 13, and fig. 17. As can be seen from the figure, the reduced graphene oxide structure obtained by the method provided by the invention meets the requirements of target products.
Infrared analysis was performed on the reduced graphene oxide obtained in example 9, the reduced graphene oxide obtained in example 13, the reduced graphene oxide obtained in example 17, and the reduced graphene oxide obtained in comparative example 1, and the analysis results are shown in fig. 10, 12, 14, and 18. As can be seen from the figure, the reduced graphene oxide obtained by the method provided by the invention has a structure meeting the requirements of a target product, and compared with graphene oxide, the peak value of all oxygen functional groups of the reduced graphene oxide is significantly reduced or completely disappeared, because the formation of bond bonds and the recovery of even conjugation are promoted in the reduction process, so that high-quality reduced graphene oxide is obtained.
(II) analysis of reduced graphene oxide Property
Statistics of the performance of the reduced graphene oxides of examples 1 to 20 and comparative examples 1 to 20 are shown in table 2, which includes the resistance of the reduced graphene oxide, the mass of the reduced graphene oxide, and the carbon-to-oxygen ratio of the reduced graphene oxide.
TABLE 2 reduced graphene oxide Properties
| Examples | Resistivity (omega. Cm) | Mass (g) | Carbon to oxygen ratio | Comparative example | Resistivity (omega. Cm) | Quality (g) | Carbon to oxygen ratio |
| Example 1 | 4.32 | 0.0358 | 11:1 | Comparative example 1 | 650 | 0.0432 | 5:1 |
| Example 2 | 5.52 | 0.0345 | 10:1 | Comparative example 2 | 650 | 0.0422 | 5:1 |
| Example 3 | 6.78 | 0.0257 | 11:1 | Comparative example 3 | 650 | 0.0336 | 5:1 |
| Example 4 | 6.74 | 0.0238 | 12:1 | Comparative example 4 | 650 | 0.0327 | 5:1 |
| Example 5 | 2.33 | 0.0397 | 12:1 | Comparative example 5 | 650 | 0.0447 | 5:1 |
| Example 6 | 4.51 | 0.0417 | 11:1 | Comparative example 6 | 650 | 0.0445 | 5:1 |
| Example 7 | 5.37 | 0.0366 | 12:1 | Comparative example 7 | 650 | 0.0413 | 5:1 |
| Example 8 | 5.48 | 0.0388 | 10:1 | Comparative example 8 | 650 | 0.0425 | 5:1 |
| Example 9 | 1.57 | 0.0375 | 10:1 | Comparative example 9 | 650 | 0.0432 | 5:1 |
| Example 10 | 1.69 | 0.0342 | 10:1 | Comparative example 10 | 650 | 0.0456 | 5:1 |
| Example 11 | 2.45 | 0.0322 | 10:1 | Comparative example 11 | 650 | 0.0433 | 5:1 |
| Example 12 | 2.98 | 0.0327 | 11:1 | Comparative example 12 | 650 | 0.0426 | 5:1 |
| Example 13 | 0.97 | 0.0403 | 13:1 | Comparative example 13 | 650 | 0.0423 | 5:1 |
| Example 14 | 1.42 | 0.0358 | 12:1 | Comparative example 14 | 650 | 0.0447 | 5:1 |
| Example 15 | 1.52 | 0.0325 | 12:1 | Comparative example 15 | 650 | 0.0440 | 5:1 |
| Example 16 | 1.51 | 0.0327 | 11:1 | Comparative example 16 | 650 | 0.0430 | 5:1 |
| Example 17 | 0.42 | 0.0288 | 14:1 | Comparative example 17 | 650 | 0.0429 | 5:1 |
| Example 18 | 0.52 | 0.0458 | 13:1 | Comparative example 18 | 650 | 0.0431 | 5:1 |
| Example 19 | 0.88 | 0.0415 | 12:1 | Comparative example 19 | 650 | 0.0429 | 5:1 |
| Example 20 | 0.87 | 0.0432 | 12:1 | Comparative example 20 | 650 | 0.0432 | 5:1 |
Note: (1) The method for testing the resistance in the reduced graphene oxide comprises the following steps: placing the obtained reduced graphene oxide in a chromium steel die, and keeping the die for 10s under the pressure of 15MPa to obtain a reduced graphene oxide ceramic wafer with the diameter of about 12.0mm and the thickness of about 0.2 mm; measuring the resistivity by adopting a four-probe measuring instrument;
(2) The method for testing the carbon-oxygen ratio in the reduced graphene oxide comprises the following steps: and (4) carrying out XPS (X-ray diffraction) measurement on the reduced graphene oxide of the ceramic plate, and calculating the carbon-oxygen ratio of the ceramic plate according to the XPS result.
The resistance of the reduced graphene oxide, the quality of the reduced graphene oxide and the carbon-oxygen ratio of the reduced graphene oxide are analyzed, so that the reduced graphene oxide obtained by the method provided by the invention has lower resistivity and higher yield, and the carbon-oxygen ratio of the reduced graphene oxide is higher, so that the reduced graphene oxide can be obtained in a low-energy-consumption, high-efficiency and non-toxic reduction mode, which not only accords with the current environmental development concept, but also plays a certain role in promoting the industrial production of the reduced graphene oxide and the reduced graphene oxide.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (10)
1. A low-energy-consumption extremely-fast efficient graphene oxide reduction method is characterized by comprising two implementation modes:
a first implementation includes the steps of:
(A1) Placing the reduction initiator on a heat source at the temperature of not less than 180 ℃;
(A2) Contacting the graphene oxide with a reduction initiator to start reaction to obtain reduced graphene oxide;
the second implementation mode comprises the following steps:
(B1) Coating graphene oxide in a reduction initiator;
(B2) And (3) placing the reduction initiator coated with the graphene oxide on a heat source at 160-240 ℃ for reduction reaction to obtain the reduced graphene oxide.
2. The method as claimed in claim 1, wherein the reduction initiator is lithium or tin low melting point metal or its alloy.
3. The method for reducing graphene oxide with low energy consumption, high speed and high efficiency according to claim 1, wherein the graphene oxide structure is in a foam shape, a film shape, a powder shape or a flocculent shape.
4. The method of claim 1, wherein the heat source is an electric iron, a flat heater, a spot heater, a baking lamp, or a tube furnace.
5. The method for reducing graphene oxide at low energy consumption and high speed and high efficiency according to claim 4, wherein in the first implementation mode, the temperature of a heat source is 180-200 ℃, and the contact time of the graphene oxide and a reduction initiator is not less than 1s.
6. The method of claim 1, wherein in the second implementation mode, the reduction initiator completely or partially wraps the graphene oxide, and the wrapping area is not less than 5%.
7. The method as claimed in claim 1, wherein the ambient humidity of the reduction initiator and the graphene oxide is not higher than 80%.
8. The method for reducing graphene oxide with low energy consumption and high efficiency at a high speed according to any one of claims 1 to 7, wherein the resistivity of the reduced graphene oxide is not higher than 50 Ω -cm.
9. The method for reducing graphene oxide at low energy consumption and high speed and high efficiency according to any one of claims 1 to 7, wherein the carbon-oxygen ratio in the reduced graphene oxide is 20:1 to 1:50.
10. the method for reducing graphene oxide at low energy consumption and high speed and high efficiency according to claim 9, wherein the carbon-oxygen ratio in the obtained reduced graphene oxide is 10-14: 1.
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