CN114368741A - Preparation method of graphene/carbon nanotube/silicon dioxide aerogel material - Google Patents
Preparation method of graphene/carbon nanotube/silicon dioxide aerogel material Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene/carbon nanotube/silicon dioxide aerogel material, which comprises the steps of putting graphene oxide, a carbon nanotube, water glass, silica gel, polydopamine and urea into a stirring tank according to a certain proportion, uniformly stirring and mixing, obtaining a dispersion liquid after dispersion treatment, then adding the dispersion liquid into an oil bath pot for heating, and then carrying out freeze drying treatment, acid washing and sintering to obtain the graphene/carbon nanotube/silicon dioxide aerogel material. Graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed and stirred, and are subjected to discharge plasma sintering after being heated and dried to obtain the graphene/carbon nanotube/silicon dioxide aerogel material, the method is simple, the process is controllable, no alcohol solvent is required to be added in the preparation process, the environment is protected, no waste liquid is required to be treated, the production cost is reduced, the industrial continuous production can be favorably realized, and the prepared composite aerogel material can tolerate the high temperature of more than 500 ℃.
Description
Technical Field
The invention relates to the technical field of aerogels, in particular to a preparation method of a graphene/carbon nanotube/silicon dioxide aerogel material.
Background
The lithium ion battery has the characteristics of high voltage, high specific energy, no memory effect, no environmental pollution and the like, and becomes one of the main choices of green batteries in the 21 st century. The lithium ion battery cathode material which is commercially used at present is mainly a carbon-based cathode material, the actual specific capacity of the lithium ion battery cathode material is close to the theoretical capacity 372mAh/g of carbon, and the lithium ion battery cathode material is difficult to have a space for improvement. Facing this limitation, numerous new materials are emerging in succession, with silicon anode materials being one of the most promising anode materials. When Si forms Li with Li4In the case of the 4Si structure, the theoretical specific capacity can reach 4200mAh/g, however, the volume expansion of the Si negative electrode in a charging state can reach 300%, which becomes the biggest obstacle in stopping the application of the Si negative electrode. Meanwhile, the silicon dioxide aerogel is a light nano porous amorphous solid material with low density and high porosity, and the aerogel contains a nano-scale pore structure (1-100nm) and has a very large specific surface area (200 plus 1000 m)2A/g), a very high porosity (80-99.8%), a very low density (1-500 kg/m)3) Small thermal conductivity coefficient, and the like, and shows mechanical, acoustic, thermal, optical and other aspectsUnique properties. Therefore, the unique properties and applications of silica aerogel have attracted great interest to a great number of physicists, chemists and materials scientists, and relevant researchers have begun to make relevant researches on whether silica aerogel can be used for preparing negative electrode materials for lithium ion batteries with excellent electrical properties.
The method for preparing the aerogel disclosed in chinese patent CN107032360B can be referred to, a large amount of ethanol solvent is used for solvent replacement, waste liquid is generated, the waste liquid needs to be treated subsequently in order to not pollute the environment, the production cost is increased, and the method is not suitable for industrial continuous production. Therefore, there is a need for improvements in the existing methods of aerogel production.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing graphene/carbon nanotube/silica aerogel material, which is environment-friendly without adding alcohol solvent in the preparation process, and does not need to treat waste liquid, thereby reducing the production cost and facilitating the realization of industrial continuous production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a graphene/carbon nanotube/silicon dioxide aerogel material comprises the following steps:
(1) mixing: mixing graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea according to the proportion of 1: (0.25-1.5): (2-4): (1-3): (3-5): (3-8) putting the mixture into a stirring tank according to the mass ratio, uniformly stirring and mixing, and performing dispersion treatment to obtain a dispersion liquid;
(2) heating: adding the dispersion liquid obtained in the step (1) into an oil bath pot, and heating at the temperature of 60-110 ℃ for 20-50min to obtain a graphene/carbon nanotube/silicon dioxide aerogel mixture;
(3) and (3) drying: carrying out freeze drying treatment on the graphene/carbon nanotube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank;
(4) acid washing: washing the blank obtained in the step (3) with aqua regia, removing impurity ions, washing with deionized water until the pH is neutral, and drying to obtain graphene/carbon nanotube/silicon dioxide aerogel;
(5) and (3) sintering: and (5) performing discharge plasma sintering on the graphene/carbon nanotube/silicon dioxide aerogel obtained in the step (4), using nitrogen as a protective gas, and performing temperature of 500-700 ℃ for 0.5-8min to obtain the graphene/carbon nanotube/silicon dioxide aerogel material.
Preferably, the number of layers of the graphene oxide is less than or equal to 10, and the transverse dimension of the graphene oxide is greater than 10 μm.
As a preferred scheme, the carbon nanotube is a single-walled carbon nanotube or a multi-walled carbon nanotube, the diameter of the carbon nanotube is less than or equal to 60nm, and the length of the carbon nanotube is 10-30 μm.
As a preferable scheme, the stirring speed in the step (1) is 300-1400rpm, and the stirring time is 1-5 h.
Preferably, the dispersion treatment in step (1) is performed by one or more of a colloid mill, a homogenizer and an emulsification pump, the rotation speed is 1000-2800rpm, and the dispersion time is 0.5-1 h.
As a preferable scheme, the drying treatment in the step (3) is hot air drying treatment, the temperature is 60-100 ℃, and the time is 10-30 min.
As a preferable scheme, the aqua regia in the step (4) is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3: 1.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea are mixed and stirred, discharge plasma sintering is carried out after heating and drying, and the graphene/carbon nano tube/silicon dioxide aerogel material is obtained.
To more clearly illustrate the features and effects of the present invention, the present invention is described in detail below with reference to specific examples.
Detailed Description
The invention discloses a preparation method of a graphene/carbon nanotube/silicon dioxide aerogel material, which comprises the following steps:
(1) mixing: mixing graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea according to the proportion of 1: (0.25-1.5): (2-4): (1-3): (3-5): (3-8) putting the mixture into a stirring tank according to the mass ratio, uniformly stirring and mixing, and performing dispersion treatment to obtain a dispersion liquid; the number of layers of the graphene oxide is less than or equal to 10, and the transverse size of the graphene oxide is greater than 10 micrometers; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter of the carbon nano tube is less than or equal to 60nm, and the length of the carbon nano tube is 10-30 mu m; the stirring speed is 300-1400rpm, the stirring time is 1-5h, the dispersion treatment is performed by one or more of a colloid mill, a homogenizer and an emulsification pump, the rotating speed is 1000-2800rpm, and the dispersion time is 0.5-1 h.
(2) Heating: and (2) adding the dispersion liquid obtained in the step (1) into an oil bath pot, and heating at the temperature of 60-110 ℃ for 20-50min to obtain a graphene/carbon nanotube/silicon dioxide aerogel mixture.
(3) And (3) drying: carrying out freeze drying treatment on the graphene/carbon nanotube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment at 60-100 deg.C for 10-30 min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia, removing impurity ions, washing with deionized water until the pH is neutral, and drying to obtain graphene/carbon nanotube/silicon dioxide aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3: 1.
(5) And (3) sintering: and (5) performing discharge plasma sintering on the graphene/carbon nanotube/silicon dioxide aerogel obtained in the step (4), using nitrogen as a protective gas, and performing temperature of 500-700 ℃ for 0.5-8min to obtain the graphene/carbon nanotube/silicon dioxide aerogel material.
The invention is illustrated in more detail below in the following examples:
example 1
(1) Mixing: mixing graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea according to the proportion of 1: 0.25: 2: 1: 3: 3, putting the mixture into a stirring tank, uniformly stirring and mixing, and performing dispersion treatment to obtain a dispersion liquid; the number of layers of the graphene oxide is less than or equal to 10, and the transverse size of the graphene oxide is greater than 10 micrometers; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter of the carbon nano tube is less than or equal to 60nm, and the length of the carbon nano tube is 10-30 mu m; the stirring speed is 300rpm, the stirring time is 1h, the dispersion treatment is dispersion by a colloid mill, the rotating speed is 1000rpm, and the dispersion time is 0.5 h.
(2) Heating: and (2) adding the dispersion liquid obtained in the step (1) into an oil bath pot, and heating at 70 ℃ for 30min to obtain a graphene/carbon nanotube/silicon dioxide aerogel mixture.
(3) And (3) drying: carrying out freeze drying treatment on the graphene/carbon nanotube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment at 65 deg.C for 18 min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia, removing impurity ions, washing with deionized water until the pH is neutral, and drying to obtain graphene/carbon nanotube/silicon dioxide aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3: 1.
(5) And (3) sintering: and (4) performing discharge plasma sintering on the graphene/carbon nanotube/silicon dioxide aerogel obtained in the step (4), using nitrogen as a protective gas, and keeping the temperature at 500 ℃ for 5min to obtain the graphene/carbon nanotube/silicon dioxide aerogel material.
Example 2
(1) Mixing: mixing graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea according to the proportion of 1: 1.5: 4: 3: 5: 8, putting the mixture into a stirring tank, stirring and mixing the mixture uniformly, and performing dispersion treatment to obtain a dispersion liquid; the number of layers of the graphene oxide is less than or equal to 10, and the transverse size of the graphene oxide is greater than 10 micrometers; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter of the carbon nano tube is less than or equal to 60nm, and the length of the carbon nano tube is 10-30 mu m; the stirring speed was 1400rpm, the stirring time was 5 hours, and the dispersion treatment was dispersion by a homogenizer at 2800rpm for 1 hour.
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath pot, and heating at 90 ℃ for 20min to obtain a graphene/carbon nanotube/silicon dioxide aerogel mixture;
(3) and (3) drying: carrying out freeze drying treatment on the graphene/carbon nanotube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment at 90 deg.C for 20 min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia, removing impurity ions, washing with deionized water until the pH is neutral, and drying to obtain graphene/carbon nanotube/silicon dioxide aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3: 1.
(5) And (3) sintering: and (4) performing discharge plasma sintering on the graphene/carbon nanotube/silicon dioxide aerogel obtained in the step (4), using nitrogen as a protective gas, and keeping the temperature at 700 ℃ for 1min to obtain the graphene/carbon nanotube/silicon dioxide aerogel material.
Example 3
(1) Mixing: mixing graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea according to the proportion of 1: 1: 3: 2: 4: 6, putting the mixture into a stirring tank, stirring and mixing the mixture uniformly, and performing dispersion treatment to obtain a dispersion liquid; the number of layers of the graphene oxide is less than or equal to 10, and the transverse size of the graphene oxide is greater than 10 micrometers; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter of the carbon nano tube is less than or equal to 60nm, and the length of the carbon nano tube is 10-30 mu m; the stirring speed is 700rpm, the stirring time is 3h, the dispersing treatment is dispersing by an emulsification pump, the rotating speed is 1800rpm, and the dispersing time is 0.8 h.
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath pot, and heating at the temperature of 60 ℃ for 20min to obtain a graphene/carbon nanotube/silicon dioxide aerogel mixture;
(3) and (3) drying: carrying out freeze drying treatment on the graphene/carbon nanotube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment at 80 deg.C for 15 min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia, removing impurity ions, washing with deionized water until the pH is neutral, and drying to obtain graphene/carbon nanotube/silicon dioxide aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3: 1.
(5) And (3) sintering: and (4) performing discharge plasma sintering on the graphene/carbon nanotube/silicon dioxide aerogel obtained in the step (4), using nitrogen as a protective gas, and keeping the temperature at 500 ℃ for 8min to obtain the graphene/carbon nanotube/silicon dioxide aerogel material.
Example 4
(1) Mixing: mixing graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea according to the proportion of 1: 1.2: 3.5: 2.6: 3.8: 6.2, uniformly stirring and mixing the materials in a stirring tank, and performing dispersion treatment to obtain a dispersion liquid; the number of layers of the graphene oxide is less than or equal to 10, and the transverse size of the graphene oxide is greater than 10 micrometers; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter of the carbon nano tube is less than or equal to 60nm, and the length of the carbon nano tube is 10-30 mu m; the stirring speed is 1200rpm, the stirring time is 4.5h, the dispersion treatment is to sequentially carry out dispersion by a colloid mill and a homogenizer, the rotating speed is 2600rpm, and the dispersion time is 0.8 h.
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath pot, and heating at the temperature of 110 ℃ for 50min to obtain a graphene/carbon nanotube/silicon dioxide aerogel mixture;
(3) and (3) drying: carrying out freeze drying treatment on the graphene/carbon nanotube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment at 75 deg.C for 16 min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia, removing impurity ions, washing with deionized water until the pH is neutral, and drying to obtain graphene/carbon nanotube/silicon dioxide aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3: 1.
(5) And (3) sintering: and (4) performing discharge plasma sintering on the graphene/carbon nanotube/silicon dioxide aerogel obtained in the step (4), using nitrogen as a protective gas, and keeping the temperature at 700 ℃ for 0.5min to obtain the graphene/carbon nanotube/silicon dioxide aerogel material.
Example 5
(1) Mixing: mixing graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea according to the proportion of 1: 0.5: 2.6: 2.2: 4: 7, putting the mixture into a stirring tank, uniformly stirring and mixing, and performing dispersion treatment to obtain a dispersion liquid; the number of layers of the graphene oxide is less than or equal to 10, and the transverse size of the graphene oxide is greater than 10 micrometers; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter of the carbon nano tube is less than or equal to 60nm, and the length of the carbon nano tube is 10-30 mu m; the stirring speed is 1000rpm, the stirring time is 2h, the dispersing treatment is dispersing by an emulsification pump, the rotating speed is 1800rpm, and the dispersing time is 0.9 h.
(2) Heating: and (2) adding the dispersion liquid obtained in the step (1) into an oil bath pot, and heating at 100 ℃ for 46min to obtain a graphene/carbon nanotube/silicon dioxide aerogel mixture.
(3) And (3) drying: carrying out freeze drying treatment on the graphene/carbon nanotube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment at 60 deg.C for 30 min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia, removing impurity ions, washing with deionized water until the pH is neutral, and drying to obtain graphene/carbon nanotube/silicon dioxide aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3: 1.
(5) And (3) sintering: and (4) performing discharge plasma sintering on the graphene/carbon nanotube/silicon dioxide aerogel obtained in the step (4), using nitrogen as a protective gas, and keeping the temperature at 650 ℃ for 5min to obtain the graphene/carbon nanotube/silicon dioxide aerogel material.
Example 6
(1) Mixing: mixing graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea according to the proportion of 1: 1.4: 3.8: 2.6: 3.8: 6.8, uniformly stirring and mixing the materials in a stirring tank, and performing dispersion treatment to obtain a dispersion liquid; the number of layers of the graphene oxide is less than or equal to 10, and the transverse size of the graphene oxide is greater than 10 micrometers; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter of the carbon nano tube is less than or equal to 60nm, and the length of the carbon nano tube is 26 mu m; the stirring speed is 700rpm, the stirring time is 3.6h, the dispersion treatment is dispersion by a colloid mill, the rotating speed is 2500rpm, and the dispersion time is 0.6 h.
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath pot, and heating at 100 ℃ for 43min to obtain a graphene/carbon nanotube/silicon dioxide aerogel mixture;
(3) and (3) drying: carrying out freeze drying treatment on the graphene/carbon nanotube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment at 100 deg.C for 10 min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia, removing impurity ions, washing with deionized water until the pH is neutral, and drying to obtain graphene/carbon nanotube/silicon dioxide aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3: 1.
(5) And (3) sintering: and (4) performing discharge plasma sintering on the graphene/carbon nanotube/silicon dioxide aerogel obtained in the step (4), using nitrogen as a protective gas, and keeping the temperature at 570 ℃ for 4min to obtain the graphene/carbon nanotube/silicon dioxide aerogel material.
The graphene/carbon nanotube/silica aerogel material prepared in the above embodiments is subjected to performance tests, and the test standards are as follows:
coefficient of thermal conductivity: testing the heat conductivity coefficient by adopting a transient hot wire method;
the results of the above tests are shown in table 1 below:
TABLE 1
As can be seen from tables 1 and 2, the graphene/carbon nanotube/silica aerogel material prepared in the above embodiments has a thermal conductivity coefficient at room temperature that is not much different from the thermal conductivity coefficient at 500 ℃ and the thermal conductivity coefficient at 650 ℃, and can normally operate at a high temperature of 500 ℃ or higher.
The design of the invention is characterized in that: graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea are mixed and stirred, discharge plasma sintering is carried out after heating and drying, and the graphene/carbon nano tube/silicon dioxide aerogel material is obtained.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (7)
1. A preparation method of a graphene/carbon nanotube/silicon dioxide aerogel material is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing: mixing graphene oxide, carbon nano tubes, water glass, silica gel, polydopamine and urea according to the proportion of 1: (0.25-1.5): (2-4): (1-3): (3-5): (3-8) putting the mixture into a stirring tank according to the mass ratio, uniformly stirring and mixing, and performing dispersion treatment to obtain a dispersion liquid;
(2) heating: adding the dispersion liquid obtained in the step (1) into an oil bath pot, and heating at the temperature of 60-110 ℃ for 20-50min to obtain a graphene/carbon nanotube/silicon dioxide aerogel mixture;
(3) and (3) drying: carrying out freeze drying treatment on the graphene/carbon nanotube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank;
(4) acid washing: washing the blank obtained in the step (3) with aqua regia, removing impurity ions, washing with deionized water until the pH is neutral, and drying to obtain graphene/carbon nanotube/silicon dioxide aerogel;
(5) and (3) sintering: and (5) performing discharge plasma sintering on the graphene/carbon nanotube/silicon dioxide aerogel obtained in the step (4), using nitrogen as a protective gas, and performing temperature of 500-700 ℃ for 0.5-8min to obtain the graphene/carbon nanotube/silicon dioxide aerogel material.
2. The method for preparing graphene/carbon nanotube/silica aerogel material according to claim 1, wherein: the number of layers of the graphene oxide is less than or equal to 10, and the transverse size of the graphene oxide is greater than 10 micrometers.
3. The method for preparing graphene/carbon nanotube/silica aerogel material according to claim 1, wherein: the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter of the carbon nano tube is less than or equal to 60nm, and the length of the carbon nano tube is 10-30 mu m.
4. The method for preparing graphene/carbon nanotube/silica aerogel material according to claim 1, wherein: the stirring speed in the step (1) is 300-1400rpm, and the stirring time is 1-5 h.
5. The method for preparing graphene/carbon nanotube/silica aerogel material according to claim 1, wherein: the dispersion treatment in the step (1) is to disperse by one or more of a colloid mill, a homogenizer and an emulsification pump, the rotating speed is 1000 and 2800rpm, and the dispersion time is 0.5-1 h.
6. The method for preparing graphene/carbon nanotube/silica aerogel material according to claim 1, wherein: the drying treatment in the step (3) is hot air drying treatment, the temperature is 60-100 ℃, and the time is 10-30 min.
7. The method for preparing graphene/carbon nanotube/silica aerogel material according to claim 1, wherein: and (3) the aqua regia in the step (4) is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3: 1.
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