CN115465860B - Preparation method of low-oxygen and high-stripping graphene oxide and application of obtained product - Google Patents
Preparation method of low-oxygen and high-stripping graphene oxide and application of obtained product Download PDFInfo
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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Abstract
The invention provides a preparation method of low-oxygen and high-peel graphene oxide and application of an obtained product, and belongs to the technical field of graphene preparation, wherein the preparation method comprises the following steps: 1) Mixing expanded graphite, ethanol and water, and shearing and dispersing the obtained mixture; 2) Homogenizing, filtering, drying and pulverizing; 3) Mixing graphite sheet material with concentrated sulfuric acid, performing ultrasonic treatment, adding potassium permanganate, and performing ultrasonic treatment for 0.1-0.5 h at a temperature lower than 10 ℃ to obtain a material to be reacted; 4) Heating the material to be reacted to 30 ℃ for reaction for 2 hours, continuously heating to 40 ℃ for reaction for 1.5 hours, and continuously heating to 50 ℃ for reaction for 1 hour; 5) Separating concentrated sulfuric acid, washing with water, and filtering; 6) Acid washing and filtering to obtain a solid material after acid washing; 7) Homogenizing to obtain graphene oxide with low oxygen content and high peeling. The product prepared by the method has low oxidation degree, good dispersibility and more environmental protection.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to a preparation method of low-oxygen and high-stripping graphene oxide and application of an obtained product.
Background
Graphene (Graphene) is a new material of a single-layer sheet structure composed of carbon atoms. It is a planar film with hexagonal honeycomb lattice composed of carbon atoms in sp2 hybridized orbitals. Graphene is a two-dimensional material with a thickness of only one carbon atom, has many excellent theoretical properties, is widely applied to energy storage materials, environmental engineering and sensitive sensing, is called "black gold" or "king of new materials", has wide potential application prospect, and is currently a focus of attention and research hotspot worldwide.
In the prior art, graphene oxide is mainly prepared by adopting a Hummers method to realize industrialized mass production of graphene. The preparation of graphene by oxidizing graphene can be roughly divided into three steps of graphite oxidation, stripping and reduction. The traditional Hummers method needs to use a large amount of mixed acid liquid and oxidant, and the use of a large amount of acid can cause environmental pollution, and the method has the advantages of long reaction period, complicated preparation process and higher energy consumption, and does not meet the current requirements of carbon peak reaching and carbon neutralization.
Meanwhile, the traditional graphene oxide product needs to be subjected to the procedures of dispersing, film coating, foaming, carbonization, graphitization, calendaring, die cutting and the like to obtain a final graphene heat conduction film product; in order to ensure the heat conducting performance of the graphene heat conducting film, the graphene heat conducting film is required to have higher single-layer rate, so that the interlayer 'phonon' transfer rate is improved, and the loss is reduced. In theory, the higher the oxidation degree of the graphene oxide is, the easier the single-layer/few-layer graphene oxide is prepared, so that the single-layer/few-layer graphene oxide is widely used in the market, and the products with high oxidation and high stripping are widely used. However, the higher the degree of oxidation, the better the dispersibility, the more difficult the washing separation process, and the greater the viscosity of the concentrated final product. The product has high viscosity and is difficult to use. And because the oxygen content is high, the carbon content is relatively reduced, and when graphene is prepared by reduction, the oxygen loss rate of the final product is high, the product loss rate is high, and the product yield is lower.
Disclosure of Invention
The invention provides a preparation method of low-oxygen high-peel graphene oxide, a product and application thereof, and the method has the advantages that the energy consumption in the reaction process is low, the environment-friendly requirement is met, and the prepared graphene oxide has low oxidation degree and good dispersibility.
In order to achieve the above purpose, the invention provides a preparation method of low-oxygen and high-stripping graphene oxide, which comprises the following steps:
1) Mixing expanded graphite, ethanol and water, and shearing and dispersing the obtained mixture to obtain a dispersion liquid;
2) Homogenizing and suction filtering the dispersion liquid sequentially, drying and crushing the solid material obtained by suction filtering to obtain a thin-layer and few-layer graphite sheet material with the granularity of 20-30 mu m;
3) Mixing the graphite sheet material with concentrated sulfuric acid according to a mass-volume ratio of 1:15-30, performing ultrasonic treatment, adding potassium permanganate when the temperature of the material is reduced to below 10 ℃, and performing ultrasonic treatment for 0.1-0.5 h at a temperature lower than 10 ℃ to obtain a material to be reacted; the mass ratio of the potassium permanganate to the expanded graphite is 0.5-1.0:1;
4) Heating the material to be reacted to 28-32 ℃ for reaction for 1.9-2.1 h, continuously heating to 38-42 ℃ for reaction for 1.4-1.6 h, continuously heating to 48-52 ℃ for reaction for 0.5-1.1 h, and obtaining a reaction material;
5) Separating concentrated sulfuric acid in the reaction materials, and washing and filtering the obtained solid materials to obtain washed solid materials;
6) Washing the washed solid material by adopting sulfuric acid solution with the mass concentration of 0.5% -2%, and filtering to obtain a washed solid material;
7) Homogenizing the pickled solid material to obtain the graphene oxide with low oxygen and high stripping.
Preferably, the volume ratio of the ethanol to the water is 7:3-5: 5, a step of; the expanded graphite accounts for 1 to 5 percent of the total mass of the ethanol and the water.
Preferably, the rotation speed of the shearing dispersion is 2000-3000 r/min, and the time is 0.5-1.0 h.
Preferably, the homogenizing pressure in the step 2) is 150-200 Mpa, and the times are 2-5 times.
Preferably, in the step 2), the drying temperature is 55 to 65 ℃.
Preferably, the pressure in the step 5) of filtering and separating the concentrated sulfuric acid is more than or equal to 0.1Mpa, and the recovery rate of the concentrated sulfuric acid is more than or equal to 70%.
Preferably, in the step 6), sulfuric acid solutions with mass concentration of 2%, 1% and 0.5% are used for washing respectively in sequence.
Preferably, the homogenizing pressure in the step 7) is 5-20 Mpa.
The invention also provides application of the low-oxygen and high-stripping graphene oxide prepared by any one of the methods in preparation of a graphene heat-conducting film.
Compared with the prior art, the invention has the advantages and positive effects that:
the method for preparing the low-oxygen high-stripping graphene oxide provided by the invention has the advantages of simple process, short reaction period and high production efficiency. The method only uses potassium permanganate and concentrated sulfuric acid, does not introduce other impurities, and has high product purity. And the acid consumption is small, the energy consumption is small, and the environment is protected.
Meanwhile, the product prepared by the method has the advantages of low oxidation degree, complete sheet layer, few defects, higher single-layer rate and lower viscosity, and is convenient for subsequent downstream product application.
In addition, the graphene oxide product with low oxygen content and high peeling strength is easier to prepare graphene oxide slurry with high solid content and good fluidity compared with the common graphene oxide product due to lower oxygen-containing group content, so that the heat conduction film product with thicker film and larger heat flux is easier, simpler and more efficient to prepare.
Further, after the graphene oxide film with the same thickness (or mass) is coated, the graphene oxide film is subjected to foaming, carbonization, graphitization, calendaring and other processes, the low-oxygen and high-stripping product has lower oxygen content, lower product loss rate, thicker final film thickness, higher heat flux, higher actual utilization rate of the product and higher heat conduction efficiency.
Drawings
FIG. 1 is an SEM image of raw expanded graphite;
FIG. 2 is an SEM image of a thin, few-layer graphite platelet material of example 1;
fig. 3 is an SEM image of graphene oxide prepared in example 1;
fig. 4 is an SEM image of graphene oxide prepared in comparative example 1;
FIG. 5 is an SEM image of graphene oxide prepared in comparative example 2;
FIG. 6 is an SEM image of graphene oxide prepared in comparative example 3;
FIG. 7 is a TG pattern of graphene oxide obtained in example 1;
FIG. 8 is a TG pattern of graphene oxide prepared in comparative example 1;
FIG. 9 is a TG pattern of graphene oxide prepared in comparative example 2;
fig. 10 is a TG chart of graphene oxide prepared in comparative example 3.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of low-oxygen and high-peel graphene oxide, which comprises the following steps:
1) Mixing expanded graphite, ethanol and water, and shearing and dispersing the obtained mixture to obtain a dispersion liquid;
2) Homogenizing and suction filtering the dispersion liquid sequentially, drying and crushing the solid material obtained by suction filtering to obtain a thin-layer and few-layer graphite sheet material with the granularity of 20-30 mu m;
3) Mixing the graphite sheet material with concentrated sulfuric acid according to a mass-volume ratio of 1:15-30, performing ultrasonic treatment, adding potassium permanganate when the temperature of the material is reduced to below 10 ℃, and performing ultrasonic treatment for 0.1-0.5 h at a temperature lower than 10 ℃ to obtain a material to be reacted; the mass ratio of the potassium permanganate to the expanded graphite is 0.5-1.0:1;
4) Heating the material to be reacted to 28-32 ℃ for reaction for 1.9-2.1 h, continuously heating to 38-42 ℃ for reaction for 1.4-1.6 h, continuously heating to 48-52 ℃ for reaction for 0.5-1.1 h, and obtaining a reaction material;
5) Separating concentrated sulfuric acid in the reaction materials, and washing and filtering the obtained solid materials to obtain washed solid materials;
6) Washing the washed solid material by adopting sulfuric acid solution with the mass concentration of 0.5% -2%, and filtering to obtain a washed solid material;
7) Homogenizing the pickled solid material to obtain the graphene oxide with low oxygen and high stripping.
The invention mixes the expanded graphite, ethanol and water, and the obtained mixture is sheared and dispersed to obtain dispersion liquid. In the invention, the volume ratio of the ethanol to the water is preferably 7:3-5:5; the expanded graphite is preferably 1% -5% of the total mass of ethanol and water. In the invention, the rotation speed of the shearing dispersion is preferably 2000-3000 r/min, and the time is preferably 0.5-1.0 h.
The invention mixes the expanded graphite, ethanol and water, which can increase the polarity of the expanded graphite, and further can fully disperse and dissolve the expanded graphite.
After the dispersion liquid is obtained, the dispersion liquid is sequentially homogenized and filtered by suction, and the solid material obtained by suction filtration is dried and crushed to obtain the thin-layer and few-layer graphite sheet materials with the granularity of 20-30 mu m. In the present invention, the homogenizing pressure is preferably 150 to 200Mpa, and the number of times is preferably 2 to 5. In the present invention, the drying temperature is preferably 55 to 65 ℃.
The invention adopts the expanded graphite, the interlayer of the sheet is fluffier, and the thin layer/few layer graphite raw material is easier to obtain through high-pressure homogenization treatment under the infiltration of the solvent, thereby being beneficial to the subsequent oxidation intercalation treatment. The expanded graphite is in an expanded worm shape, has more pores, and has larger subsequent liquid absorption amount, so that the acid consumption is increased, the viscosity is higher, and the operation difficulty in the preparation process is increased. In the invention, the expanded graphite is firstly dispersed, homogenized and filtered, so that the pores can be reduced, and the use amount of acid is further reduced. Furthermore, the dispersion liquid is homogenized to obtain thin-layer and few-layer graphite sheet materials, so that the effects of partial stripping, dispersion and pre-stripping are achieved, and the consumption of concentrated sulfuric acid in the subsequent intercalation stripping process can be reduced.
After obtaining a graphite sheet material, mixing the graphite sheet material with concentrated sulfuric acid according to a mass-volume ratio of 1:15-30, performing ultrasonic treatment, adding potassium permanganate when the temperature of the material is reduced to below 10 ℃, and performing ultrasonic treatment for 0.1-0.5 h at a temperature lower than 10 ℃ to obtain a material to be reacted; and heating the material to be reacted to 28-32 ℃ for 1.9-2.1 h, continuously heating to 38-42 ℃ for 1.4-1.6 h, continuously heating to 48-52 ℃ for 0.5-1.1 h, and obtaining the reaction material. In the invention, the mass ratio of the potassium permanganate to the expanded graphite is 0.5-1.0:1. In the invention, the graphite sheet material can be intercalated and oxidized through the steps.
After the reaction materials are obtained, concentrated sulfuric acid in the reaction materials is separated, and the obtained solid materials are subjected to water washing and filtering to obtain the washed solid materials. In the present invention, the concentrated sulfuric acid is preferably separated by a positive pressure filter. In the invention, the pressure during the filtration and separation of the concentrated sulfuric acid is preferably more than or equal to 0.1Mpa, and the recovery rate of the concentrated sulfuric acid is more than or equal to 70%.
After the washed solid material is obtained, the washed solid material is washed and filtered by adopting sulfuric acid solution with the mass concentration of 0.5% -2%, so that the acid-washed solid material is obtained. In the present invention, it is preferable to wash with sulfuric acid solutions having mass concentrations of 2%, 1% and 0.5%, respectively, in this order. In the invention, the sulfuric acid solution with the mass concentration of 0.5-2% is adopted for washing, so that nitrogen, sulfur and trace elements in the material can be reduced, and the next application is facilitated.
After the pickled solid material is obtained, homogenizing the pickled solid material to obtain the low-oxygen and high-stripping graphene oxide. In the present invention, the solid material is preferably adjusted by adding water to the solid material before homogenizing the solid material. The specific water adding amount is added according to the final use requirement of the product. Meanwhile, the water is added to the solid material, which is favorable for subsequent homogenization. In the present invention, the pressure of the homogenizing pressure is preferably 5 to 20Mpa. In the invention, the acid-washed solid material is homogenized, on one hand, the graphite oxide which is not completely stripped and overlapped in the sheet layer in the preparation process can be further stripped, and a better sheet layer stripping effect is achieved; on the other hand, the homogenization function is realized, so that the size distribution of the lamellar is more concentrated, and the uniformity and the stability of the product are ensured.
The invention firstly carries out pre-stripping on the expanded graphite by physical methods such as dispersion, high-pressure homogenization and the like on the expanded graphite to obtain thin-layer and few-layer graphite sheet materials, achieves the effect of partial stripping, and then adopts an oxidation-reduction process to obtain proper and controllable oxidation degree. By introducing various oxygen-containing functional groups, the subsequent surface modification and modification of the low-oxygen high-peel graphene oxide product are increased, the product has complete lamellar, few defects, higher monolayer rate and lower viscosity, and the subsequent downstream product application is facilitated. The preparation method is simple in preparation process, short in reaction period and capable of improving production efficiency. Meanwhile, the method only uses potassium permanganate and concentrated sulfuric acid, does not introduce other impurities, and has high product purity. In addition, the acid consumption is small, the energy consumption is small, and the environment is protected.
In theory, the higher the oxidation degree of graphene oxide is, the easier the single-layer/few-layer graphene oxide is prepared, but the higher the oxidation degree is, the better the dispersibility is, the more difficult the washing separation process is, and the higher the viscosity of the concentrated final product is. Meanwhile, the high oxidation degree of the product is high, the more defects are, the high oxygen loss rate of the final product is achieved, the low utilization rate of the product is achieved, and great waste is caused. In addition, in the aspect of downstream application, graphene oxide is better in dispersibility, related graphene products are further obtained through subsequent processes, and finally unique properties of the graphene are used.
With the popularization and application of 5G technology, the heat transfer rate directly affects the performance and service life of high-power electronic components. The development of a heat conductive film with thicker film thickness and wider heat flux is needed. After the graphene oxide film with the same thickness (or mass) is coated, the graphene oxide film is subjected to foaming, carbonization, graphitization, calendaring and other processes, and the low-oxygen and high-stripping product has lower oxygen content, lower product loss rate, thicker final film thickness, higher heat flux, higher actual utilization rate of the product and higher heat conduction efficiency. The low-oxygen high-stripping product prepared by the method ensures that the product has higher stripping rate, is endowed with proper oxygen-containing functional groups, ensures excellent dispersibility and usability, has adjustable solid content, and more importantly, improves the utilization rate of the product in downstream application, and comprehensively considers meeting the current 'carbon peak and carbon neutralization' as the time requirement, thereby having higher applicability and popularization.
The invention also provides application of the low-oxygen and high-stripping graphene oxide prepared by any one of the methods in preparation of a graphene heat-conducting film.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
The raw materials used in the following examples are as follows:
the expanded graphite is 60 meshes, is derived from Qingdao rock sea, and the concentrated sulfuric acid is 98% industrial grade;
positive pressure filter was from Haining Corp Membrane filtration plant Co., ltd;
homogenizer device: shanghai Shen Lu homogenizer (SRH 40-100).
Example 1
(1) 60g of expanded graphite is dissolved in 3000ml of ethanol and water mixed solution (volume ratio is 7:3) according to the proportion of 2 percent of solid content, and is sheared and dispersed for 30 minutes at the rotating speed of 2500 r/min;
(2) homogenizing the dispersion liquid by a high-pressure homogenizer (the pressure is 150 Mpa), circularly feeding for 3 times, carrying out suction filtration and separation on the obtained material, putting the solid material into a 60 ℃ oven for drying to obtain a dried material, and recycling filtrate;
(3) crushing the dried material in an air flow crusher, controlling the granularity of the material to be 20-30 mu m, and obtaining a thin-layer and less-layer graphite sheet material with the granularity of 20-30 mu m;
(4) the thin layer with granularity of 20-30 mu m, few graphite flake materials and concentrated sulfuric acid (industrial grade) are mixed according to the mass: mixing in a volume ratio of 1:25, and cooling to below 10 ℃ in an ultrasonic system, wherein the potassium permanganate is prepared by the following steps: slowly adding a thin layer with granularity of 20-30 mu m and a few graphite flakes in a ratio of 0.5:1 into a reaction system, wherein the whole process is controlled below 10 ℃;
(5) after the step (4) is finished, reacting for 0.5h at the temperature below 10 ℃, and reacting for 2h at the constant temperature of 30 ℃ and 1.5h at the constant temperature of 40 ℃ and 1h at the constant temperature of 50 ℃ in an ultrasonic system to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure filter, filtering and separating the concentrated sulfuric acid solution to obtain a solid material, wherein the whole process is carried out for 0.5h, the working pressure is 0.1Mpa, and the acid liquor recovery rate is 70%;
(7) the solid material in the step (6) is: high purity water according to the mass volume ratio of 1:1, washing to obtain a washed material, wherein the temperature of the whole process is controlled below 60 ℃;
(8) pouring the water-washed material obtained in the step (7) into a positive pressure filter for filtering and washing, and then adding dilute sulfuric acid with concentration of 2%, 1% and 0.5% (according to the volume of the heightened pure water in the previous step) in batches for filtering and washing for three times;
(9) and (3) adding water into the solid material obtained in the step (8) to dilute the solid material into slurry with the solid content of 5% (mass percent), and stripping and dispersing the slurry at low pressure of 10Mpa by a homogenizer to obtain a low-oxygen and high-stripping graphene oxide product.
Example 2
(1) 60g of expanded graphite is dissolved in 1200ml of ethanol and water mixed solution (volume ratio is 7:3) according to the proportion of 5 percent of solid content, and is sheared and dispersed for 60 minutes at the rotating speed of 2000 r/min;
(2) homogenizing the dispersion liquid by a high-pressure homogenizer (the pressure is 150 Mpa), circularly feeding for 3 times, carrying out suction filtration and separation on the obtained material, putting the solid material into a 65 ℃ oven for drying to obtain a dried material, and recycling filtrate;
(3) crushing the dried material in an air flow crusher, controlling the granularity of the material to be 20-30 mu m, and obtaining a thin-layer and less-layer graphite sheet material with the granularity of 20-30 mu m;
(4) the thin layer with granularity of 20-30 mu m, few graphite flake materials and concentrated sulfuric acid (industrial grade) are mixed according to the mass: mixing in a volume ratio of 1:15, and cooling to below 10 ℃ in an ultrasonic system, wherein the potassium permanganate is prepared by the following steps: slowly adding a thin layer and a few layer graphite sheet materials with granularity of 20-30 mu m into a reaction system in a ratio of 1.0:1, and controlling the whole process to be below 10 ℃;
(5) after the step (4) is finished, reacting for 0.5h at the temperature below 10 ℃, and reacting for 2h at the constant temperature of 30 ℃ and 1.5h at the constant temperature of 40 ℃ and 1h at the constant temperature of 50 ℃ in an ultrasonic system to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure filter, filtering and separating the concentrated sulfuric acid solution to obtain a solid material, wherein the whole process is carried out for 0.5h, the working pressure is 0.1Mpa, and the acid liquor recovery rate is 70%;
(7) the solid material in the step (6) is: high purity water according to the mass volume ratio of 1:1, washing to obtain a washed material, wherein the temperature of the whole process is controlled below 60 ℃;
(8) pouring the water-washed material obtained in the step (7) into a positive pressure filter for filtering and washing, and then adding dilute sulfuric acid with concentration of 2%, 1% and 0.5% (according to the volume of the heightened pure water in the previous step) in batches for filtering and washing for three times;
(9) and (3) adding water into the solid material obtained in the step (8) to dilute the solid material into slurry with the solid content of 5% (mass percent), and stripping and dispersing the slurry at low pressure of 10Mpa by a homogenizer to obtain a low-oxygen and high-stripping graphene oxide product.
Example 3
(1) 60g of expanded graphite is dissolved in 6000ml of ethanol and water mixed solution (volume ratio is 7:3) according to the proportion of 1 percent of solid content, and is sheared and dispersed for 30 minutes at the rotating speed of 3000 r/min;
(2) homogenizing the dispersion liquid by a high-pressure homogenizer (the pressure is 200 Mpa), circularly feeding for 2 times, carrying out suction filtration and separation on the obtained material, putting the solid material into a 55 ℃ oven for drying to obtain a dried material, and recycling filtrate;
(3) crushing the dried material in an air flow crusher, controlling the granularity of the material to be 20-30 mu m, and obtaining a thin-layer and less-layer graphite sheet material with the granularity of 20-30 mu m;
(4) the thin layer with granularity of 20-30 mu m, few graphite flake materials and concentrated sulfuric acid (industrial grade) are mixed according to the mass: mixing in a volume ratio of 1:30, and cooling to below 10 ℃ in an ultrasonic system, wherein the potassium permanganate is prepared by the following steps: slowly adding a thin layer with granularity of 20-30 mu m and a few graphite flakes in a ratio of 0.5:1 into a reaction system, wherein the whole process is controlled below 10 ℃;
(5) after the step (4) is finished, reacting for 0.5h at the temperature below 10 ℃, and reacting for 2h at the constant temperature of 30 ℃ and 1.5h at the constant temperature of 40 ℃ and 1h at the constant temperature of 50 ℃ in an ultrasonic system to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure filter, filtering and separating the concentrated sulfuric acid solution to obtain a solid material, wherein the whole process is 1.0h, the working pressure is 0.1Mpa, and the acid liquor recovery rate is 70%;
(7) the solid material in the step (6) is: high purity water according to the mass volume ratio of 1:1, washing to obtain a washed material, wherein the temperature of the whole process is controlled below 60 ℃;
(8) pouring the water-washed material obtained in the step (7) into a positive pressure filter for filtering and washing, and then adding dilute sulfuric acid with concentration of 2%, 1% and 0.5% (according to the volume of the heightened pure water in the previous step) in batches for filtering and washing for three times;
(9) and (3) adding water into the solid material obtained in the step (8) to dilute the solid material into slurry with the solid content of 5% (mass percent), and stripping and dispersing the slurry at low pressure of 10Mpa by a homogenizer to obtain a low-oxygen and high-stripping graphene oxide product.
Comparative example 1
The difference from example 1 is that the expanded graphite is directly reacted with concentrated sulfuric acid without shearing, homogenizing, drying, dispersing. The specific operation is as follows:
(1) 60g of expanded graphite and concentrated sulfuric acid (technical grade) are mixed according to mass: mixing in a volume ratio of 1:25, and cooling to below 10 ℃ in an ultrasonic system, wherein the potassium permanganate is prepared by the following steps: slowly adding the expanded graphite into a reaction system according to the mass ratio of 0.5:1, and controlling the whole process below 10 ℃;
(2) after the step (1) is finished, reacting for 0.5h at the temperature below 10 ℃, and reacting for 2h at the constant temperature of 30 ℃ and 1.5h at the constant temperature of 40 ℃ and 1h at the constant temperature of 50 ℃ in an ultrasonic system to obtain a reaction material;
(3) pouring the reaction material obtained in the step (2) into a positive pressure filter, filtering and separating the concentrated sulfuric acid solution to obtain a solid material, wherein the whole process is carried out for 0.5h, the working pressure is more than or equal to 0.1Mpa, and the acid liquor recovery rate is more than or equal to 70%;
(4) the solid material in the step (3) is: high purity water according to the mass volume ratio of 1:1, washing to obtain a washed material, wherein the temperature of the whole process is controlled below 60 ℃;
(5) pouring the water-washed material obtained in the step (4) into a positive pressure filter for filtering and washing, and then adding dilute sulfuric acid with concentration of 2%, 1% and 0.5% (according to the volume of the heightened pure water in the previous step) in batches for filtering and washing for three times;
(6) and (3) adding water into the solid material obtained in the step (5) to dilute the solid material into slurry with the solid content of 5% (mass percent), and stripping and dispersing the slurry at low pressure of 10Mpa by a homogenizer to obtain the graphene oxide product.
Comparative example 2
The difference from example 1 is that the operation (9) was not performed. The specific operation is as follows:
(1) 60g of expanded graphite is dissolved in 3000ml of ethanol and water mixed solution (volume ratio is 7:3) according to the proportion of 2 percent of solid content, and is sheared and dispersed for 30 minutes at the rotating speed of 2500 r/min;
(2) homogenizing the dispersion liquid by a high-pressure homogenizer (the pressure is 150 Mpa), circularly feeding for 3 times, carrying out suction filtration and separation on the obtained material, putting the solid material into a 60 ℃ oven for drying to obtain a dried material, and recycling filtrate;
(3) crushing the dried material in an air flow crusher, controlling the granularity of the material to be 20-30 mu m, and obtaining a thin-layer and less-layer graphite sheet material with the granularity of 20-30 mu m;
(4) the thin layer with granularity of 20-30 mu m, few graphite flake materials and concentrated sulfuric acid (industrial grade) are mixed according to the mass: mixing in a volume ratio of 1:25, and cooling to below 10 ℃ in an ultrasonic system, wherein the potassium permanganate is prepared by the following steps: slowly adding a thin layer with granularity of 20-30 mu m and a few graphite flakes into a reaction system according to the mass ratio of 0.5:1, wherein the whole process is controlled below 10 ℃;
(5) after the step (4) is finished, reacting for 0.5h at the temperature below 10 ℃, and reacting for 2h at the constant temperature of 30 ℃ and 1.5h at the constant temperature of 40 ℃ and 1h at the constant temperature of 50 ℃ in an ultrasonic system to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure filter, filtering and separating the concentrated sulfuric acid solution to obtain a solid material, wherein the whole process is carried out for 0.5h, the working pressure is more than or equal to 0.1Mpa, and the acid liquor recovery rate is more than or equal to 70%;
(7) the solid material in the step (6) is: high purity water according to the mass volume ratio of 1:1, washing to obtain a washed material, wherein the temperature of the whole process is controlled below 60 ℃;
(8) and (3) pouring the water washing material obtained in the step (7) into a positive pressure filter for filtering and washing, and then adding 2%, 1% and 0.5% concentration dilute sulfuric acid (according to the volume of the high-purity water in the previous step) in batches for three times for filtering and washing to obtain a graphene oxide product.
Comparative example 3
The difference from example 1 is that crystalline flake graphite is used instead of expanded graphite. The specific operation is as follows:
(1) 60g of flake graphite is dissolved in 3000ml of ethanol and water mixed solution (volume ratio is 7:3) according to the proportion of 2 percent of solid content, and is sheared and dispersed for 30 minutes at the rotating speed of 2500 r/min;
(2) homogenizing the dispersion liquid by a high-pressure homogenizer (the pressure is 150 Mpa), circularly feeding for 3 times, carrying out suction filtration and separation on the obtained material, putting the solid material into a 60 ℃ oven for drying to obtain a dried material, and recycling filtrate;
(3) the dried material is put into an air flow pulverizer to be pulverized, the granularity of the material is controlled to be 20-30 um, and the flake graphite raw material after high-pressure homogenization treatment is obtained (which means that the flake graphite has stronger interlayer acting force and is more compact than the expanded graphite, and is not easy to be peeled off in a homogenizing way, and the thin-layer and less-layer graphite flake material cannot be obtained);
(4) the high-pressure homogenized crystalline flake graphite raw material and concentrated sulfuric acid (industrial grade) are prepared according to the following mass: mixing in a volume ratio of 1:25, and cooling to below 10 ℃ in an ultrasonic system, wherein the potassium permanganate is prepared by the following steps: slowly adding the flake graphite raw materials subjected to high-pressure homogenization treatment into a reaction system in a mass ratio of 0.5:1, wherein the whole process is controlled below 10 ℃;
(5) after the step (4) is finished, reacting for 0.5h at the temperature below 10 ℃, and reacting for 2h at the constant temperature of 30 ℃ and 1.5h at the constant temperature of 40 ℃ and 1h at the constant temperature of 50 ℃ in an ultrasonic system to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure filter, filtering and separating the concentrated sulfuric acid solution to obtain a solid material, wherein the whole process is carried out for 0.5h, the working pressure is more than or equal to 0.1Mpa, and the acid liquor recovery rate is more than or equal to 70%;
(7) the solid material in the step (6) is: high purity water according to the mass volume ratio of 1:1, washing to obtain a washed material, wherein the temperature of the whole process is controlled below 60 ℃;
(8) pouring the water-washed material obtained in the step (7) into a positive pressure filter for filtering and washing, and then adding dilute sulfuric acid with concentration of 2%, 1% and 0.5% (according to the volume of the heightened pure water in the previous step) in batches for filtering and washing for three times;
(9) and (3) adding water into the solid material obtained in the step (8) to dilute the solid material into slurry with the solid content of 5% (mass percent), and stripping and dispersing the slurry at low pressure of 10Mpa by a homogenizer to obtain the graphene oxide product.
Performance testing
1. SEM examination
SEM examination was performed on the raw expanded graphite, the thin layer of example 1, the few-layer graphite platelet material, the end products of example 1 and comparative example, respectively. The specific operation method comprises the following steps: diluting an object to be tested into a solution with the solid content of 0.1-0.01% by using ethanol, performing ultrasonic dispersion for 10 minutes, then dripping the solution into a silicon wafer for sample preparation, and placing the sample on the silicon wafer into a field emission scanning electron microscope for SEM (scanning electron microscope) test, wherein the specific test results are shown in figures 1-6.
Wherein:
FIG. 1 shows the raw expanded graphite used in the present invention, and as can be seen from FIG. 1, the raw expanded graphite used in the present invention is in the form of loose porous worms.
FIG. 2 is a sheet of material of the thin and few-layer graphite sheets obtained in example 1. As can be seen from fig. 2, the expanded graphite is subjected to high-pressure homogenization delamination, delamination is complete, and the sheets are thin.
Fig. 3 is a low oxygen, high exfoliation graphene oxide product resulting from example 1. As can be seen from fig. 3, after the low oxidation treatment, the finally obtained graphene oxide sheet is complete, thinner and has high surface peeling degree.
Fig. 4 is graphene oxide prepared in comparative example 1. As can be seen from fig. 4, since the expanded graphite is not subjected to high-pressure homogenization stripping, the material is still in an expanded loose state, and the subsequent chemical oxidation stripping effect is poor due to the low-oxidation treatment.
Fig. 5 is graphene oxide prepared in comparative example 2. As can be seen from FIG. 5, since the final material was not subjected to low-pressure homogenization stripping, the sheet diameter distribution was not uniform and the thickness was not uniform.
Fig. 6 is graphene oxide prepared in comparative example 3. As can be seen from fig. 6, since the crystalline flake graphite is used as the raw material, the high-pressure homogenization physical stripping effect is poor due to the compactness between the crystalline flake graphite layers, and the chemical stripping effect is poor after the low-oxidation treatment, and the crystalline flake is thicker.
2. Thermal Gravity (TG) testing
When the oxygen content of the product is lower, the C content is relatively higher, and the residual amount is higher after carbonization/graphitization treatment. Thus, the ratio of the oxygen content of the product can be reacted by analyzing the residual mass of the TG profile characterizing material.
The products of example 1 and comparative examples 1 to 3 were subjected to thermogravimetric tests, and the specific results are shown in fig. 7 to 10.
Fig. 7 shows low-oxygen, high-exfoliation graphene oxide prepared in example 1 of the present invention. As can be seen from fig. 7: the graphene oxide prepared finally by the method has high residue, which indicates that the graphene oxide prepared by the method has lower oxygen content and higher carbon content.
Fig. 8 is graphene oxide prepared in comparative example 1 of the present invention. As can be seen from fig. 8: the graphene oxide obtained in comparative example 1 has low residual amount, which indicates that the prepared graphene oxide has higher oxygen content and lower carbon content. This is because the expanded graphite material is porous and porous in nature, has a large liquid absorption and a high degree of local oxidation, and, in combination with SEM characterization, it can be seen that the degree of exfoliation and the integrity of the final product differ significantly from those of example 1, since the expanded graphite material is not pre-exfoliated by high pressure homogenization.
Fig. 9 is graphene oxide prepared in comparative example 2 of the present invention. As can be seen from fig. 9: as the final material is not subjected to low-pressure slurry homogenization treatment, the oxidation degree of the material is not greatly different from that of the material in the example 1, and the graphene oxide finally obtained in the comparative example 2 has high residue, which shows that the prepared graphene oxide has lower oxygen content and higher carbon content. However, as can be seen from SEM characterization, the graphene oxide of comparative example 2 has a lower degree of oxidation, but the difference between the material sheet diameter and the sheet layer of the final product is larger than that of example 1, and the effect on the final product performance is larger, because the final product is not subjected to low-pressure slurry homogenization physical treatment.
Fig. 10 is graphene oxide prepared in comparative example 3 of the present invention. As can be seen from fig. 10: the residual amount of the finally prepared graphene oxide is low, which indicates that the finally prepared graphene oxide has higher oxygen content and lower carbon content.
3. Thermal diffusivity test
The products of examples 1 to 3 and comparative examples 1 to 3 were subjected to thermal diffusivity tests using a NETZSCH-LFA467 flash thermal conductivity meter, commercially available from Shanghai Co., ltd. The specific results are shown in Table 1.
TABLE 1 thermal diffusivity results
As can be seen from table 1, the low-oxygen, high-exfoliation graphene oxide prepared by the method of the present invention shows good interfacial heat transfer efficiency. The low-oxygen high-peel graphene oxide prepared by the method has higher sheet integrity, fewer oxidation defects and good interface heat transfer efficiency.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the low-oxygen and high-peel graphene oxide is characterized by comprising the following steps of:
1) Mixing expanded graphite, ethanol and water, and shearing and dispersing the obtained mixture to obtain a dispersion liquid;
2) Homogenizing and suction filtering the dispersion liquid sequentially, drying and crushing the solid material obtained by suction filtering to obtain a thin-layer and few-layer graphite sheet material with the granularity of 20-30 mu m;
3) Mixing the graphite sheet material with concentrated sulfuric acid according to a mass-volume ratio of 1:15-30, performing ultrasonic treatment, adding potassium permanganate when the temperature of the material is reduced to below 10 ℃, and performing ultrasonic treatment for 0.1-0.5 h at a temperature lower than 10 ℃ to obtain a material to be reacted; the mass ratio of the potassium permanganate to the expanded graphite is 0.5-1.0:1;
4) Heating the material to be reacted to 28-32 ℃ for reaction for 1.9-2.1 h, continuously heating to 38-42 ℃ for reaction for 1.4-1.6 h, continuously heating to 48-52 ℃ for reaction for 0.5-1.1 h, and obtaining a reaction material;
5) Separating concentrated sulfuric acid in the reaction materials, and washing and filtering the obtained solid materials to obtain washed solid materials;
6) Washing the washed solid material by adopting sulfuric acid solution with the mass concentration of 0.5% -2%, and filtering to obtain a washed solid material;
7) Homogenizing the pickled solid material to obtain the graphene oxide with low oxygen and high stripping.
2. The preparation method according to claim 1, wherein the volume ratio of ethanol to water is 7:3-5: 5, a step of; the expanded graphite accounts for 1 to 5 percent of the total mass of the ethanol and the water.
3. The method according to claim 1, wherein the rotational speed of the shear dispersion is 2000-3000 r/min for 0.5-1.0 h.
4. The method according to claim 1, wherein the homogenizing pressure in the step 2) is 150 to 200Mpa and the number of times is 2 to 5.
5. The method according to claim 1, wherein in the step 2), the drying temperature is 55 to 65 ℃.
6. The method according to claim 1, wherein the pressure in the step 5) is not less than 0.1Mpa, and the recovery rate of the concentrated sulfuric acid is not less than 70%.
7. The method according to claim 1, wherein the step 6) is sequentially performed with sulfuric acid solutions having mass concentrations of 2%, 1% and 0.5%, respectively.
8. The method according to claim 1, wherein the homogenizing pressure in the step 7) is 5 to 20Mpa.
9. Use of low-oxygen and high-peel graphene oxide prepared by the method of any one of claims 1 to 8 in preparation of graphene heat-conducting films.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015109916A1 (en) * | 2014-01-22 | 2015-07-30 | 智慧城市***服务（中国）有限公司 | Method for preparing graphene |
| CN105540575A (en) * | 2016-01-28 | 2016-05-04 | 成都新柯力化工科技有限公司 | Method for preparing graphene by using high-pressure homogenizer delamination |
| CN105542333A (en) * | 2015-12-15 | 2016-05-04 | 东华大学 | Reduced graphene oxide composite film and preparation method thereof |
| KR20160107030A (en) * | 2015-03-03 | 2016-09-13 | 주식회사 나노솔루션 | Method for manufacturing graphene and grphene using the methode |
| CA2999904A1 (en) * | 2015-09-25 | 2017-03-30 | Suzhou Cstar Graphene Technology Co., Ltd. | Industrial method for preparing large-sized graphene |
| CN109319771A (en) * | 2018-12-03 | 2019-02-12 | 青岛岩海碳材料有限公司 | A kind of preparation method of graphene |
| WO2020009421A1 (en) * | 2018-07-03 | 2020-01-09 | 전북대학교산학협력단 | Method for producing graphite oxide and graphene oxide in eco-friendly manner by using hydroxylation reaction |
| CN112978722A (en) * | 2019-12-17 | 2021-06-18 | 山东海科创新研究院有限公司 | Small-diameter graphene powder, graphene conductive paste, and preparation methods and applications thereof |
| CN113213458A (en) * | 2021-05-12 | 2021-08-06 | 江苏烯望新材料科技有限公司 | Preparation method of high-performance low-defect graphene heat dissipation film |
| CN113443620A (en) * | 2021-08-30 | 2021-09-28 | 湖南金阳烯碳新材料有限公司 | Preparation method and application of few-layer graphene powder |
| CN113830757A (en) * | 2020-06-24 | 2021-12-24 | 四川烯时代新材料有限公司 | Method for preparing low-defect graphene by thermal stripping of low-graphite oxide after intercalation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015193268A1 (en) * | 2014-06-20 | 2015-12-23 | Directa Plus S.P.A. | Process for preparing graphene nanoplatelets. |
| US10654721B2 (en) * | 2015-09-18 | 2020-05-19 | Toray Industries, Inc. | Graphene dispersion, process for producing same, process for producing particles of graphene/active material composite, and process for producing electrode paste |
| CN105293476B (en) * | 2015-11-16 | 2018-07-10 | 复旦大学 | A kind of preparation method of large scale graphene oxide or graphene |
| US10163540B2 (en) * | 2015-12-03 | 2018-12-25 | Nanotek Instruments, Inc. | Production process for highly conducting and oriented graphene film |
-
2022
- 2022-07-06 CN CN202210787593.5A patent/CN115465860B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015109916A1 (en) * | 2014-01-22 | 2015-07-30 | 智慧城市***服务（中国）有限公司 | Method for preparing graphene |
| KR20160107030A (en) * | 2015-03-03 | 2016-09-13 | 주식회사 나노솔루션 | Method for manufacturing graphene and grphene using the methode |
| CA2999904A1 (en) * | 2015-09-25 | 2017-03-30 | Suzhou Cstar Graphene Technology Co., Ltd. | Industrial method for preparing large-sized graphene |
| CN105542333A (en) * | 2015-12-15 | 2016-05-04 | 东华大学 | Reduced graphene oxide composite film and preparation method thereof |
| CN105540575A (en) * | 2016-01-28 | 2016-05-04 | 成都新柯力化工科技有限公司 | Method for preparing graphene by using high-pressure homogenizer delamination |
| WO2020009421A1 (en) * | 2018-07-03 | 2020-01-09 | 전북대학교산학협력단 | Method for producing graphite oxide and graphene oxide in eco-friendly manner by using hydroxylation reaction |
| CN109319771A (en) * | 2018-12-03 | 2019-02-12 | 青岛岩海碳材料有限公司 | A kind of preparation method of graphene |
| CN112978722A (en) * | 2019-12-17 | 2021-06-18 | 山东海科创新研究院有限公司 | Small-diameter graphene powder, graphene conductive paste, and preparation methods and applications thereof |
| CN113830757A (en) * | 2020-06-24 | 2021-12-24 | 四川烯时代新材料有限公司 | Method for preparing low-defect graphene by thermal stripping of low-graphite oxide after intercalation |
| CN113213458A (en) * | 2021-05-12 | 2021-08-06 | 江苏烯望新材料科技有限公司 | Preparation method of high-performance low-defect graphene heat dissipation film |
| CN113443620A (en) * | 2021-08-30 | 2021-09-28 | 湖南金阳烯碳新材料有限公司 | Preparation method and application of few-layer graphene powder |
Non-Patent Citations (1)
| Title |
|---|
| 石墨烯的液相剥离制备及在 磷酸铁锂正极中的应用;南文争;材料工程;第48卷(第11期);108-115 * |
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Application publication date: 20221213 Assignee: Haike Technology Innovation Service (Jiangsu) Co.,Ltd. Assignor: Shandong Haike Innovation Research Institute Co.,Ltd. Contract record no.: X2023980046100 Denomination of invention: A preparation method for low oxygen and high stripping oxygen graphene and the application of the resulting product Granted publication date: 20230616 License type: Common License Record date: 20231110 |