CN115465860A - Preparation method of low-oxygen high-stripping graphene oxide and application of obtained product - Google Patents
Preparation method of low-oxygen high-stripping graphene oxide and application of obtained product Download PDFInfo
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Abstract
The invention provides a preparation method of low-oxygen high-stripping graphene oxide and application of an obtained product, belonging 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, vacuum filtering, drying, and pulverizing; 3) Mixing and ultrasonically treating a graphite sheet material with concentrated sulfuric acid, adding potassium permanganate, and ultrasonically treating for 0.1-0.5 h at the temperature lower than 10 ℃ to obtain a material to be reacted; 4) Heating the materials to be reacted to 30 ℃ for reaction for 2h, continuously heating to 40 ℃ for reaction for 1.5h, and then continuously heating to 50 ℃ for reaction for 1h; 5) Separating concentrated sulfuric acid, washing with water and filtering; 6) Acid washing and filtering to obtain solid materials after acid washing; 7) And (5) homogenizing to obtain the low-oxygen high-stripping graphene oxide. The product prepared by the method has low oxidation degree, good dispersibility and 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 high-exfoliation graphene oxide and application of the obtained product.
Background
Graphene (Graphene) is a new material with a monolayer sheet structure composed of carbon atoms. The hexagonal honeycomb-shaped planar thin film is a hexagonal honeycomb-shaped planar thin film formed by carbon atoms through sp2 hybridized orbitals. Graphene is a two-dimensional material with the thickness of only one carbon atom, has a plurality of excellent theoretical properties, is widely applied to energy storage materials, environmental engineering and sensitive sensing, is called as 'black gold' or 'king of new materials', has a wide potential application prospect, and has become a focus of attention and a research hotspot all over the world at present.
In the prior art, the graphene oxide is mainly prepared by a Hummers method to realize the industrial mass production of graphene. The preparation of graphene by graphene oxide 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 an oxidant, and the use of a large amount of acid can cause environmental pollution.
Meanwhile, the traditional graphene oxide product needs to be subjected to the working procedures of dispersing, coating, foaming, carbonizing, graphitizing, rolling, die cutting and the like to obtain a final graphene heat-conducting film product; in order to ensure the heat-conducting property of the graphene heat-conducting film, the graphene heat-conducting film needs to have higher single-layer rate, improve the transmission rate of interlayer phonons and reduce the loss. Theoretically, the higher the oxidation degree of the graphene oxide is, the easier the single-layer/few-layer graphene oxide can be prepared, so that high-oxidation and high-stripping products are adopted in the market. However, the higher the degree of oxidation, the better the dispersibility, the more difficult the separation process becomes, and the greater the viscosity of the concentrated end product becomes. This product is difficult to use due to its high viscosity. And because the oxygen content is high, the carbon content is relatively reduced, and when the graphene is prepared by reduction, the final product has high oxygen loss rate, high product loss rate and low product yield.
Disclosure of Invention
The invention provides a preparation method of low-oxygen high-stripping graphene oxide, an obtained product and application thereof.
In order to achieve the above object, the present invention provides a method for preparing low-oxygen high-exfoliation graphene oxide, comprising 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 filtering the dispersion liquid in sequence, drying and crushing solid materials obtained by 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 the mass-volume ratio of 1-30, carrying out ultrasonic treatment, adding potassium permanganate when the temperature of the material is reduced to below 10 ℃, and carrying out ultrasonic treatment for 0.1-0.5 h at the 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;
4) Heating the materials 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, and then continuously heating to 48-52 ℃ for reaction for 0.5-1.1 h to obtain reaction materials;
5) Separating concentrated sulfuric acid in the reaction material, and washing and filtering the obtained solid material to obtain a washed solid material;
6) Washing and filtering the washed solid material by adopting a sulfuric acid solution with the mass concentration of 0.5-2% to obtain an acid-washed solid material;
7) And homogenizing the acid-washed solid material to obtain the low-oxygen high-stripping graphene oxide.
Preferably, the volume ratio of the ethanol to the water is 7: 5; the expanded graphite accounts for 1-5% of the total mass of the ethanol and the water.
Preferably, the rotating speed of the shearing dispersion is 2000-3000 r/min, and the time is 0.5-1.0 h.
Preferably, the pressure for homogenizing in the step 2) is 150 to 200Mpa, and the times are 2 to 5 times.
Preferably, in the step 2), the drying temperature is 55-65 ℃.
Preferably, the pressure of the concentrated sulfuric acid in the step 5) during filtration and separation 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, the step 6) is washed by sulfuric acid solutions with mass concentrations of 2%, 1% and 0.5%, respectively.
Preferably, the pressure for homogenizing in the step 7) is 5-20 Mpa.
The invention also provides application of the low-oxygen high-peeling-off 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 is simple in process, short in reaction period and high in 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 less, the energy consumption is less, and the environment is more protected.
Meanwhile, the product prepared by the method has the advantages of low oxidation degree, complete lamella, few defects, high single-layer rate and low viscosity, and is convenient for application of subsequent downstream products.
Moreover, the low-oxygen high-stripping graphene oxide product has lower oxygen-containing group content, so that compared with a common high-oxygen graphene oxide product, the graphene oxide slurry with high solid content and good fluidity can be prepared more easily, and a heat-conducting film product with a thicker film and a larger heat flux can be prepared more easily, concisely and efficiently.
Furthermore, after the graphene oxide film with the same thickness (or quality) is coated and is subjected to the processes of foaming → carbonization → graphitization → calendering and the like, the low-oxygen and high-peeling product has lower oxygen content, lower product loss rate and thicker final film thickness, can provide higher heat flux, and has higher actual utilization rate and higher heat conduction efficiency.
Drawings
FIG. 1 is an SEM image of a raw material expanded graphite;
FIG. 2 is an SEM image of a thin, few-layer graphite flake 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 diagram of graphene oxide prepared in example 1;
fig. 8 is a TG diagram of graphene oxide prepared in comparative example 1;
fig. 9 is a TG diagram of graphene oxide prepared in comparative example 2;
fig. 10 is a TG diagram of graphene oxide prepared in comparative example 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of low-oxygen 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 filtering the dispersion liquid in sequence, drying and crushing solid materials obtained by 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 the mass-to-volume ratio of 1-30, carrying out ultrasonic treatment, adding potassium permanganate when the temperature of the material is reduced to below 10 ℃, and carrying out ultrasonic treatment for 0.1-0.5 h at the 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;
4) Heating the materials 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, and then continuously heating to 48-52 ℃ for reaction for 0.5-1.1 h to obtain reaction materials;
5) Separating concentrated sulfuric acid in the reaction material, and washing and filtering the obtained solid material to obtain a washed solid material;
6) Washing and filtering the washed solid material by adopting a sulfuric acid solution with the mass concentration of 0.5-2% to obtain an acid-washed solid material;
7) And homogenizing the solid material after the acid washing to obtain the low-oxygen high-stripping graphene oxide.
The method comprises the steps of mixing expanded graphite, ethanol and water, and shearing and dispersing the obtained mixture to obtain a dispersion liquid. In the present invention, the volume ratio of ethanol to water is preferably 7 to 5; the expanded graphite is preferably 1 to 5 percent of the total mass of the ethanol and the water. In the present invention, the rotation speed of the shear dispersion is preferably 2000 to 3000r/min, and the time is preferably 0.5 to 1.0h.
The invention mixes the expanded graphite, the ethanol and the water, 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 invention carries out homogenization and suction filtration on the dispersion liquid in sequence, and the solid material obtained by suction filtration is dried and crushed to obtain the thin-layer and few-layer graphite sheet material with the granularity of 20-30 mu m. In the present invention, the pressure for homogenization is preferably 150 to 200MPa, and the number of times is preferably 2 to 5 times. In the present invention, the temperature of the drying is preferably 55 to 65 ℃.
The invention adopts the expanded graphite, the interlamellar is more fluffy, 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, has larger subsequent liquid absorption amount, causes the increase of acid dosage and larger viscosity, and increases the operation difficulty in the preparation process. In the invention, the expanded graphite is dispersed, homogenized and filtered, so that the pores can be reduced, and the use amount of acid is further reduced. Furthermore, the invention homogenizes the dispersion liquid to obtain a thin-layer and few-layer graphite sheet material, achieves the effects of partial stripping, dispersion and pre-stripping, and further can reduce the consumption of concentrated sulfuric acid during the subsequent intercalation stripping.
After obtaining a graphite sheet material, mixing the graphite sheet material with concentrated sulfuric acid according to a mass-to-volume ratio of 1-30, carrying out ultrasonic treatment, adding potassium permanganate when the temperature of the material is reduced to below 10 ℃, and carrying out ultrasonic treatment for 0.1-0.5 h at the temperature lower than 10 ℃ to obtain a material to be reacted; heating the materials 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, and then continuously heating to 48-52 ℃ for reaction for 0.5-1.1 h to obtain the reaction materials. In the invention, the mass ratio of the potassium permanganate to the expanded graphite is 0.5-1.0. In the invention, the graphite sheet material can be intercalated and oxidized through the steps.
After the reaction material is obtained, the concentrated sulfuric acid in the reaction material is separated, and the obtained solid material is washed and filtered to obtain the washed solid material. In the present invention, concentrated sulfuric acid is preferably separated by a positive pressure filter. In the invention, the pressure of the concentrated sulfuric acid during filtration and separation is preferably not less than 0.1Mpa, and the recovery rate of the concentrated sulfuric acid is not less than 70%.
After the washed solid material is obtained, the washed solid material is washed and filtered by adopting a sulfuric acid solution with the mass concentration of 0.5-2% to obtain the acid-washed solid material. 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 method is convenient for the next step of application.
After the solid material after acid washing is obtained, homogenizing the solid material after acid washing to obtain the low-oxygen high-stripping graphene oxide. In the present invention, it is preferable to adjust the solid content by adding water to the solid material before homogenizing the solid material. The specific water addition amount is added according to the final use requirement of the product. Meanwhile, the solid material is added with water, so that the subsequent homogenization is facilitated. In the present invention, the pressure of the homogenization pressure is preferably 5 to 20Mpa. In the invention, the solid material after acid washing is homogenized, on one hand, graphite oxide which is not completely peeled and has overlapped sheets in the preparation process can be further peeled, and a better sheet peeling effect is achieved; on the other hand, the slurry has the function of homogenizing, so that the size distribution of the lamella is more concentrated, and the uniformity and the stability of the product are guaranteed.
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 a thin-layer and few-layer graphite sheet material, thereby achieving the effect of partial stripping, and then adopts an oxidation-reduction process to obtain a proper and controllable oxidation degree. By introducing various oxygen-containing functional groups, subsequent surface modification of the low-oxygen high-stripping graphene oxide product is increased, the product has complete lamella, few defects, high single-layer rate and low viscosity, and the subsequent downstream product application is facilitated. The method has the advantages of simple preparation process, short reaction period and high production efficiency. Meanwhile, the method only uses potassium permanganate and concentrated sulfuric acid, other impurities are not introduced, and the product purity is high. In addition, the acid consumption is less, the energy consumption is less, and the environment is more protected.
Theoretically, the higher the oxidation degree of graphene oxide, the easier it is to prepare single-layer/few-layer graphene oxide, but the higher the oxidation degree, the better the dispersibility, the more difficult the washing and separation process, and the higher the viscosity of the concentrated final product. Meanwhile, the oxidation degree of the high-oxidation product is high, the defects are more, the oxygen loss rate of the final product is high, the utilization rate of the product is low, and great waste is caused. In addition, in the aspect of downstream application, better dispersibility of graphene oxide is used, related graphene products are further obtained through subsequent processes, and finally the unique performance of graphene is used.
With the popularization and application of the 5G technology, the heat transfer rate directly influences the performance and the service life of the high-power electronic component. A thermally conductive film having a thicker film thickness and a wider heat flux is in urgent need of development. After the graphene oxide film with the same thickness (or quality) is coated and is subjected to the processes of foaming → carbonization → graphitization → calendering and the like, the low-oxygen and high-peel product has lower product loss rate and thicker final film thickness due to lower oxygen content, and can provide higher heat flux, higher actual utilization rate of the product and higher heat conduction efficiency. The low-oxygen high-stripping product prepared by the invention not only ensures that the product has higher stripping rate, but also endows a proper amount of oxygen-containing functional groups, ensures excellent dispersibility and usability, has adjustable solid content of the product, more importantly, improves the utilization rate of the product in downstream application, meets the current 'carbon peak reaching and carbon neutralizing' requirement in times by comprehensive consideration, and has higher applicability and popularization.
The invention also provides application of the low-oxygen high-peeling-off graphene oxide prepared by any one of the methods in preparation of a graphene heat-conducting film.
In order to further illustrate the present invention, the following embodiments are described in detail, 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 from Qingdao rock sea, and the concentrated sulfuric acid is 98% of industrial grade;
positive pressure filter source heluo membrane filtration equipment ltd, haining, inc;
a homogenizer device: shanghai Shenlu homogenizer (SRH 40-100).
Example 1
(1) Dissolving 60g of expanded graphite according to the proportion of 2 percent of solid content in 3000ml of ethanol and water mixed solution (volume ratio is 7;
(2) homogenizing the dispersion liquid by a high-pressure homogenizer (pressure 150 Mpa), circularly feeding for 3 times, carrying out suction filtration and separation on the obtained material, drying the solid material in a 60 ℃ oven to obtain a dried material, and recovering the filtrate for recycling;
(3) putting the dried material into a jet mill for crushing, and controlling the particle size of the material to be 20-30 um to obtain a thin-layer and few-layer graphite sheet material with the particle size of 20-30 mu m;
(4) thin layers with the granularity of 20-30 mu m, few-layer graphite sheet materials and concentrated sulfuric acid (industrial grade) are mixed according to the mass: mixing according to the volume ratio of 1: a thin layer with the granularity of 20-30 mu m and a few layers of graphite sheet layer materials are slowly added into a reaction system according to the proportion of 0.5, and the whole process is controlled below 10 ℃;
(5) after the step (4) is finished, reacting for 0.5h at the temperature of below 10 ℃, in an ultrasonic system, carrying out gradient heating reaction, reacting for 2h at the constant temperature of 30 ℃, reacting for 1.5h at the constant temperature of 40 ℃, and reacting for 1h at the constant temperature of 50 ℃ to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure type filter, and 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 recovery rate of the acid solution is 70%;
(7) mixing the solid material in the step (6): the mass volume ratio of the high-purity water is 1:1, washing with water to obtain a washed material, wherein the temperature in 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 2%, 1% and 0.5% dilute sulfuric acid (according to the volume amount of the high pure water added in the step) in batches for filtering and washing for three times;
(9) and (5) 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 percentage), and stripping and dispersing the slurry through a homogenizer at low pressure of 10Mpa to obtain a low-oxygen high-stripping graphene oxide product.
Example 2
(1) Dissolving 60g of expanded graphite in 1200ml of a mixed solution of ethanol and water according to the proportion of 5 percent of solid content (volume ratio is 7: 3), and shearing and dispersing for 60min at the rotating speed of 2000 r/min;
(2) homogenizing the dispersion liquid by a high-pressure homogenizer (pressure 150 Mpa), circularly feeding for 3 times, carrying out suction filtration and separation on the obtained material, drying the solid material in a 65 ℃ oven to obtain a dried material, and recovering the filtrate for recycling;
(3) putting the dried material into a jet mill for milling, and controlling the particle size of the material to be 20-30 um to obtain a thin-layer and few-layer graphite sheet material with the particle size of 20-30 mu m;
(4) thin layers with the granularity of 20-30 mu m, few-layer graphite sheet materials and concentrated sulfuric acid (industrial grade) are mixed according to the mass: mixing according to the volume ratio of 1: a thin layer with the granularity of 20-30 mu m and a few layers of graphite sheet layer materials are slowly added into a reaction system according to the proportion of 1.0, and the whole process is controlled below 10 ℃;
(5) after the step (4) is finished, reacting for 0.5h at the temperature of below 10 ℃, in an ultrasonic system, carrying out gradient heating reaction, reacting for 2h at the constant temperature of 30 ℃, reacting for 1.5h at the constant temperature of 40 ℃, and reacting for 1h at the constant temperature of 50 ℃ to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure filter, and 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 recovery rate of the acid solution is 70%;
(7) mixing the solid material in the step (6): high-purity water is mixed according to the mass volume ratio of 1:1, washing with water to obtain a washed material, wherein the temperature in 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 2%, 1% and 0.5% concentration dilute sulfuric acid (according to the volume amount of the high pure water obtained in the step) for three times for filtering and washing in batches;
(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 percentage), and stripping and dispersing the slurry through a homogenizer at low pressure of 10Mpa to obtain a low-oxygen high-stripping graphene oxide product.
Example 3
(1) Dissolving 60g of expanded graphite according to the proportion of 1 percent of solid content in 6000ml of ethanol and water mixed solution (volume ratio is 7;
(2) homogenizing the dispersion liquid with a high-pressure homogenizer (pressure 200 Mpa), circularly feeding for 2 times, performing suction filtration and separation on the obtained material, drying the solid material in a 55 ℃ oven to obtain a dried material, and recovering the filtrate for recycling;
(3) putting the dried material into a jet mill for crushing, and controlling the particle size of the material to be 20-30 um to obtain a thin-layer and few-layer graphite sheet material with the particle size of 20-30 mu m;
(4) thin layers with the granularity of 20-30 mu m, few-layer graphite sheet materials and concentrated sulfuric acid (industrial grade) are mixed according to the mass: mixing according to the volume ratio of 1: a thin layer with the granularity of 20-30 mu m and a few-layer graphite sheet material are slowly added into a reaction system according to the proportion of 0.5, and the whole process is controlled to be below 10 ℃;
(5) after the step (4) is finished, reacting for 0.5h at the temperature of below 10 ℃, in an ultrasonic system, carrying out gradient heating reaction, reacting for 2h at the constant temperature of 30 ℃, reacting for 1.5h at the constant temperature of 40 ℃, and reacting for 1h at the constant temperature of 50 ℃ to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure type filter, and filtering and separating the concentrated sulfuric acid solution to obtain a solid material, wherein the whole process is carried out for 1.0h, the working pressure is 0.1Mpa, and the recovery rate of the acid solution is 70%;
(7) mixing the solid material in the step (6): high-purity water is mixed according to the mass volume ratio of 1:1, washing with water to obtain a washed material, wherein the temperature in 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 2%, 1% and 0.5% dilute sulfuric acid (according to the volume amount of the high pure water added in the step) in batches for filtering and washing for three times;
(9) and (5) 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 percentage), and stripping and dispersing the slurry through a homogenizer at low pressure of 10Mpa to obtain a low-oxygen 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 and dispersing. The specific operation is as follows:
(1) 60g of expanded graphite and concentrated sulfuric acid (industrial grade) are mixed according to the mass ratio: mixing according to the volume ratio of 1: slowly adding the expanded graphite into a reaction system according to the mass ratio of 0.5;
(2) after the step (1) is finished, reacting for 0.5h at the temperature of below 10 ℃, in an ultrasonic system, carrying out gradient heating reaction, reacting for 2h at the constant temperature of 30 ℃, reacting for 1.5h at the constant temperature of 40 ℃, and reacting for 1h at the constant temperature of 50 ℃ to obtain a reaction material;
(3) pouring the reaction material obtained in the step (2) into a positive pressure type filter, and filtering and separating concentrated sulfuric acid solution to obtain a solid material, wherein the whole process is carried out for 0.5h, the working pressure is not less than 0.1MPa, and the recovery rate of the acid solution is not less than 70%;
(4) mixing the solid material in the step (3): high-purity water is mixed according to the mass volume ratio of 1:1, washing by water to obtain a washed material, wherein the temperature in 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 2%, 1% and 0.5% concentration dilute sulfuric acid (according to the volume amount of the high pure water obtained in the step) for three times for filtering and washing in batches;
(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 percentage), and stripping and dispersing the slurry through a homogenizer at low pressure of 10Mpa to obtain a graphene oxide product.
Comparative example 2
The difference from example 1 is that the operation step (9) was not carried out. The specific operation is as follows:
(1) dissolving 60g of expanded graphite according to the proportion of 2 percent of solid content in 3000ml of ethanol and water mixed solution (volume ratio is 7;
(2) homogenizing the dispersion liquid by a high-pressure homogenizer (pressure 150 Mpa), circularly feeding for 3 times, carrying out suction filtration and separation on the obtained material, drying the solid material in a 60 ℃ oven to obtain a dried material, and recovering the filtrate for recycling;
(3) putting the dried material into a jet mill for crushing, and controlling the particle size of the material to be 20-30 um to obtain a thin-layer and few-layer graphite sheet material with the particle size of 20-30 mu m;
(4) thin layer and few layer graphite sheet material with the granularity of 20-30 mu m and concentrated sulfuric acid (industrial grade) are mixed according to the mass: mixing according to the volume ratio of 1: slowly adding the thin layer and few-layer graphite sheet with the granularity of 20-30 mu m into a reaction system according to the mass ratio of 0.5;
(5) after the step (4) is finished, reacting for 0.5h at the temperature of below 10 ℃, in an ultrasonic system, carrying out gradient heating reaction, reacting for 2h at the constant temperature of 30 ℃, reacting for 1.5h at the constant temperature of 40 ℃, and reacting for 1h at the constant temperature of 50 ℃ to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure filter, and 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 not less than 0.1MPa, and the recovery rate of the sulfuric acid solution is not less than 70%;
(7) mixing the solid material in the step (6): high-purity water is mixed according to the mass volume ratio of 1:1, washing by water to obtain a washed material, wherein the temperature in the whole process is controlled below 60 ℃;
(8) and (4) pouring the water-washed material obtained in the step (7) into a positive pressure filter for filtering and washing, and then adding 2%, 1% and 0.5% dilute sulfuric acid (according to the volume amount of the high pure water obtained in the 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 flake graphite was used instead of expanded graphite. The specific operation is as follows:
(1) dissolving 60g of crystalline flake graphite according to the proportion of 2 percent of solid content in 3000ml of ethanol and water mixed solution (volume ratio is 7: 3), and shearing and dispersing for 30min at the rotating speed of 2500 r/min;
(2) homogenizing the dispersion liquid by a high-pressure homogenizer (pressure 150 Mpa), circularly feeding for 3 times, carrying out suction filtration and separation on the obtained material, drying the solid material in a 60 ℃ oven to obtain a dried material, and recovering the filtrate for recycling;
(3) crushing the dried material in a jet mill, and controlling the particle size of the material to be 20-30 um to obtain a flake graphite raw material subjected to high-pressure homogenization treatment (which shows that the flake graphite has stronger interlayer acting force and is more compact and difficult to be homogenized and peeled off compared with expanded graphite, and a thin-layer and few-layer graphite sheet layer material cannot be obtained);
(4) the scale graphite raw material and concentrated sulfuric acid (industrial grade) after high-pressure homogenization treatment are as follows: mixing according to the volume ratio of 1: slowly adding the high-pressure homogenized crystalline flake graphite raw material into a reaction system according to the mass ratio of 0.5;
(5) after the step (4) is finished, reacting for 0.5h at the temperature of below 10 ℃, in an ultrasonic system, carrying out gradient heating reaction, reacting for 2h at the constant temperature of 30 ℃, reacting for 1.5h at the constant temperature of 40 ℃, and reacting for 1h at the constant temperature of 50 ℃ to obtain a reaction material;
(6) pouring the reaction material obtained in the step (5) into a positive pressure filter, and 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 not less than 0.1MPa, and the recovery rate of the sulfuric acid solution is not less than 70%;
(7) and (3) mixing the solid material obtained in the step (6): high-purity water is mixed according to the mass volume ratio of 1:1, washing with water to obtain a washed material, wherein the temperature in 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 2%, 1% and 0.5% concentration dilute sulfuric acid (according to the volume amount of the high pure water obtained in the step) for three times for filtering and washing in batches;
(9) and (5) 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 through a homogenizer at low pressure of 10Mpa to obtain a graphene oxide product.
Performance test
1. SEM detection
SEM examination of the starting expanded graphite, the flake in example 1, the reduced graphite flake material, and 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, dripping the solution into a silicon wafer to prepare a sample, and placing the sample on the silicon wafer into a field emission scanning electron microscope to test SEM (scanning electron microscope), wherein the specific test result is shown in figures 1-6.
Wherein:
FIG. 1 shows the expanded graphite used as the raw material in the present invention, and it can be seen from FIG. 1 that the expanded graphite used as the raw material in the present invention is in the form of loose and porous worms.
FIG. 2 is a thin, few-layer graphite flake material obtained in example 1. As can be seen from fig. 2, after the high-pressure homogeneous exfoliation treatment of the expanded graphite, the interlayer exfoliation is complete and the sheet layer is thin.
Fig. 3 shows the low-oxygen and high-exfoliation graphene oxide product finally obtained in example 1. As can be seen from fig. 3, after the low oxidation treatment, the graphene oxide finally obtained has complete sheet layers, thinner thickness and high surface peeling degree.
Fig. 4 shows graphene oxide prepared in comparative example 1. As can be seen from FIG. 4, the expanded graphite is not subjected to high-pressure homogeneous 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 shows graphene oxide prepared in comparative example 2. As can be seen from FIG. 5, the final material was not subjected to low-pressure homogenization and stripping, and the distribution of the sheet diameter was not uniform, and the thickness was not uniform.
Fig. 6 shows graphene oxide prepared in comparative example 3. As can be seen from figure 6, the flake graphite is adopted as the raw material, and the flake graphite is more compact between layers, the high-pressure homogeneous physical stripping effect is poor, and the chemical stripping effect is poor and the lamella is thick after low-oxidation treatment.
2. Performing a Thermal Gravimetric (TG) test
The lower the oxygen content of the product, the higher the C content relatively, and the higher the residual amount after the carbonization/graphitization treatment. Therefore, the residual mass of the material can be characterized by analyzing the TG chart to determine the proportion of the oxygen content of the reaction product.
The products of example 1 and comparative examples 1 to 3 were subjected to a thermogravimetric test, and the specific results are shown in fig. 7 to 10.
Fig. 7 shows the low-oxygen and high-exfoliation graphene oxide prepared in example 1 of the present invention. As can be seen from fig. 7: the residue amount of the finally prepared graphene oxide is high, which shows that the graphene oxide prepared by the method is low in oxygen content and high in carbon content.
Fig. 8 shows graphene oxide prepared in comparative example 1 of the present invention. As can be seen from fig. 8: the finally obtained graphene oxide has low residual quantity in comparative example 1, which shows that the prepared graphene oxide has high oxygen content and low carbon content. The reason is that the expanded graphite raw material is loose and porous, so that the liquid absorption amount is large, the local oxidation degree is high, and the peeling degree and the integrity of the final product are greatly different from those of the final product in example 1 because the expanded graphite raw material is not subjected to high-pressure homogeneous pre-peeling combined with SEM representation.
Fig. 9 shows graphene oxide prepared in comparative example 2 according to the present invention. As can be seen from fig. 9: since the final material is not subjected to low-pressure homogenization treatment, the oxidation stratification degree of the material is not much different from that of the material in example 1, and the residue amount of the graphene oxide finally obtained in comparative example 2 is high, which indicates that the prepared graphene oxide is low in oxygen content and high in carbon content. However, in combination with the SEM characterization, it can be seen that, since the final product is not subjected to the low-pressure homogenization physical treatment, although the degree of oxidation of the graphene oxide of comparative example 2 is low, the difference between the material sheet diameter and the sheet layer of the final product is larger than that of example 1, and the final product performance is greatly affected.
Fig. 10 shows graphene oxide prepared in comparative example 3 according to the present invention. As can be seen from fig. 10: the finally prepared graphene oxide is low in residual quantity, which shows that the finally prepared graphene oxide is high in oxygen content and low in carbon content.
3. Thermal diffusion coefficient test
The products of examples 1 to 3 and comparative examples 1 to 3 were subjected to a thermal diffusivity test, specifically, a NETZSCH-LFA467 flash method thermal conductivity meter of the chi-tolerant scientific instruments commercial shanghai ltd. Specific results are shown in table 1.
TABLE 1 thermal diffusivity results
As can be seen from table 1, the low-oxygen and high-exfoliation graphene oxide prepared by the present invention exhibits good interfacial heat transfer efficiency. The low-oxygen high-exfoliation graphene oxide prepared by the method has higher sheet integrity, less oxidation defects and good interface heat transfer efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of low-oxygen high-stripping graphene oxide is characterized by comprising 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 filtering the dispersion liquid in sequence, drying and crushing solid materials obtained by 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 the mass-to-volume ratio of 1-30, carrying out ultrasonic treatment, adding potassium permanganate when the temperature of the material is reduced to below 10 ℃, and carrying out ultrasonic treatment for 0.1-0.5 h at the 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;
4) Heating the materials 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, and then continuously heating to 48-52 ℃ for reaction for 0.5-1.1 h to obtain reaction materials;
5) Separating concentrated sulfuric acid in the reaction material, and washing and filtering the obtained solid material to obtain a washed solid material;
6) Washing and filtering the solid material after water washing by adopting a sulfuric acid solution with the mass concentration of 0.5-2% to obtain an acid-washed solid material;
7) And homogenizing the acid-washed solid material to obtain the low-oxygen high-stripping graphene oxide.
2. The method according to claim 1, wherein the volume ratio of ethanol to water is 7: 5; the expanded graphite accounts for 1-5% of the total mass of the ethanol and the water.
3. The method of claim 1, wherein the shear dispersion is performed at a rotational speed of 2000 to 3000r/min for a period of 0.5 to 1.0h.
4. The method of claim 1, wherein the homogenization pressure in step 2) is 150 to 200Mpa, and the number of homogenization times is 2 to 5.
5. The method according to claim 1, wherein the drying temperature in the step 2) is 55 to 65 ℃.
6. The preparation method according to claim 1, wherein the pressure of the concentrated sulfuric acid 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 washing in step 6) is performed by using sulfuric acid solutions having a mass concentration of 2%, 1%, and 0.5%, respectively.
8. The method according to claim 1, wherein the homogenization pressure in the step 7) is 5 to 20Mpa.
9. The use of low-oxygen, high-exfoliation graphene oxide prepared by any of the methods of claims 1-8 in the preparation of graphene thermal films.
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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 |
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