CN114368741B - Preparation method of graphene/carbon nano tube/silicon dioxide aerogel material - Google Patents
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Abstract
The invention discloses a preparation method of graphene/carbon nano tube/silicon dioxide aerogel material, which comprises the steps of putting graphene oxide, carbon nano tube, water glass, silica gel, polydopamine and urea into a stirring tank according to a proportion, stirring and mixing uniformly, obtaining a dispersion liquid after dispersion treatment, 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 nano tube/silicon dioxide aerogel material. Graphene oxide, carbon nano tube, water glass, silica gel, polydopamine and urea are mixed and stirred, and discharge plasma sintering is carried out after heating and drying to obtain the graphene/carbon nano tube/silica aerogel material, so that the method is simple, the process is controllable, an alcohol solvent is not required to be added in the preparation process, the preparation method is environment-friendly, waste liquid is not required to be treated, the production cost is reduced, industrial continuous production is facilitated, and the prepared composite aerogel material can resist high temperature of more than 500 ℃.
Description
Technical Field
The invention relates to the technical field of aerogel, in particular to a preparation method of graphene/carbon nano tube/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 has become one of the main choices of the 21 st century green battery. The current lithium ion battery cathode material used commercially is mainly a carbon cathode material, the actual specific capacity of the material is close to the theoretical capacity 372mAh/g of carbon, and the material is difficult to have a lifting space. In face of this limitation, many new materials continue to emerge, with silicon anode materials being one of the most promising anode materials. When Si forms Li with Li 4 When the 4Si structure is adopted, the theoretical specific capacity can reach 4200mAh/g, however, the Si anode volume expansion in the charged state can reach 300%, which becomes the biggest obstacle to Si anode application. 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 hole structure (1-100 nm) and has extremely large specific surface area (200-1000 m 2 Per gram), very high porosity (80-99.8%), very low density (1-500 kg/m) 3 ) And the characteristics of small heat conductivity coefficient, etc., and the material has unique properties in mechanical, acoustic, thermal, optical, etc. Therefore, the unique properties and uses of silica aerogel have attracted great interest to a wide range of physicists, chemists and materialists, and related researchers have begun to conduct related researches on whether silica aerogel can be prepared into negative electrode materials for lithium ion batteries having excellent electrical properties.
The method for preparing the graphene/silicon dioxide composite aerogel disclosed in the Chinese patent CN107032360B requires a large amount of ethanol solvent to be used for solvent replacement, so that waste liquid is generated, and the waste liquid is treated later so as not to pollute the environment, thereby increasing the production cost and being not beneficial to industrial continuous production. Thus, there is a need for improvements in existing methods of aerogel preparation.
Disclosure of Invention
In view of the above, the present invention aims at overcoming the drawbacks of the prior art, and its main objective is to provide a preparation method of graphene/carbon nanotube/silica aerogel material, which does not need to add alcohol solvent in the preparation process, is environment-friendly, does not need to treat waste liquid, reduces production cost, and is beneficial to realizing industrial continuous production.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the graphene/carbon nano tube/silicon dioxide aerogel material comprises the following steps:
(1) Mixing: graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed according to the following ratio of 1: (0.25-1.5): (2-4): (1-3): (3-5): the mass ratio of (3-8) is put into a stirring tank to be stirred and mixed uniformly, and dispersion treatment is carried out to obtain dispersion liquid;
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath kettle for heating, wherein the heating temperature is 60-110 ℃, and the heating time is 20-50min, so as to obtain a graphene/carbon nano tube/silicon dioxide aerogel mixture;
(3) And (3) drying: performing freeze drying treatment on the graphene/carbon nano tube/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 to remove foreign ions, washing with deionized water to neutral pH, and drying to obtain graphene/carbon nanotube/silica aerogel;
(5) Sintering: and (3) performing spark plasma sintering on the graphene/carbon nano tube/silicon dioxide aerogel obtained in the step (4), and using nitrogen as a protective gas, wherein the temperature is 500-700 ℃ and the time is 0.5-8min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel material.
As a preferable scheme, the number of layers of the graphene oxide is less than or equal to 10, and the transverse dimension of the graphene oxide is more than 10 mu m.
As a preferable scheme, the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter is less than or equal to 60nm, and the length is 10-30 mu m.
As a preferable scheme, the stirring speed in the step (1) is 300-1400rpm, and the stirring time is 1-5h.
As a preferable scheme, the dispersing treatment in the step (1) is carried out by one or more modes of a colloid mill, a homogenizer and an emulsion pump, the rotating speed is 1000-2800rpm, and the dispersing time is 0.5-1h.
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 10-30min.
As a preferable scheme, the aqua regia in the step (4) is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to a volume ratio of 3:1.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and in particular, the technical scheme can be as follows:
graphene oxide, carbon nano tube, water glass, silica gel, polydopamine and urea are mixed and stirred, and discharge plasma sintering is carried out after heating and drying to obtain the graphene/carbon nano tube/silica aerogel material, so that the method is simple, the process is controllable, an alcohol solvent is not required to be added in the preparation process, the preparation method is environment-friendly, waste liquid is not required to be treated, the production cost is reduced, industrial continuous production is facilitated, and the prepared graphene/carbon nano tube/silica aerogel composite material can resist high temperature of more than 500 ℃.
In order to more clearly illustrate the features and effects of the present invention, the present invention will be described in detail with reference to specific examples.
Detailed Description
The invention discloses a preparation method of a graphene/carbon nano tube/silicon dioxide aerogel material, which comprises the following steps:
(1) Mixing: graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed according to the following ratio of 1: (0.25-1.5): (2-4): (1-3): (3-5): the mass ratio of (3-8) is put into a stirring tank to be stirred and mixed uniformly, and dispersion treatment is carried out to obtain dispersion liquid; the number of layers of the graphene oxide is less than or equal to 10, and the transverse dimension of the graphene oxide is more than 10 mu m; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter is less than or equal to 60nm, and the length is 10-30 mu m; the stirring speed is 300-1400rpm, the stirring time is 1-5h, the dispersing treatment is carried out by one or more modes of a colloid mill, a homogenizer and an emulsifying pump, the rotating speed is 1000-2800rpm, and the dispersing time is 0.5-1h.
(2) Heating: and (3) adding the dispersion liquid obtained in the step (1) into an oil bath kettle, heating at 60-110 ℃ for 20-50min to obtain a graphene/carbon nano tube/silicon dioxide aerogel mixture.
(3) And (3) drying: performing freeze drying treatment on the graphene/carbon nano tube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment, the temperature is 60-100 ℃, and the time is 10-30min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia to remove foreign ions, washing with deionized water to neutral pH, and drying to obtain graphene/carbon nanotube/silica aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3:1.
(5) Sintering: and (3) performing spark plasma sintering on the graphene/carbon nano tube/silicon dioxide aerogel obtained in the step (4), and using nitrogen as a protective gas, wherein the temperature is 500-700 ℃ and the time is 0.5-8min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel material.
The invention is described in further detail below in a number of examples:
example 1
(1) Mixing: graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed according to the following ratio of 1:0.25:2:1:3:3, placing the mixture in a stirring tank for stirring and mixing uniformly, and obtaining a dispersion liquid after dispersion treatment; the number of layers of the graphene oxide is less than or equal to 10, and the transverse dimension of the graphene oxide is more than 10 mu m; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter is less than or equal to 60nm, and the length is 10-30 mu m; the stirring rate was 300rpm, the stirring time was 1h, the dispersion treatment was carried out by a colloid mill at a rotation speed of 1000rpm for 0.5h.
(2) Heating: and (3) adding the dispersion liquid obtained in the step (1) into an oil bath kettle for heating, wherein the heating temperature is 70 ℃, and the heating time is 30min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel mixture.
(3) And (3) drying: performing freeze drying treatment on the graphene/carbon nano tube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment, the temperature is 65 ℃, and the time is 18min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia to remove foreign ions, washing with deionized water to neutral pH, and drying to obtain graphene/carbon nanotube/silica aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3:1.
(5) Sintering: and (3) performing spark plasma sintering on the graphene/carbon nano tube/silicon dioxide aerogel obtained in the step (4), and using nitrogen as a protective gas, wherein the temperature is 500 ℃, and the time is 5min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel material.
Example 2
(1) Mixing: graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed according to the following ratio of 1:1.5:4:3:5:8, placing the mixture into a stirring tank for stirring and mixing uniformly, and obtaining a dispersion liquid after dispersion treatment; the number of layers of the graphene oxide is less than or equal to 10, and the transverse dimension of the graphene oxide is more than 10 mu m; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter is less than or equal to 60nm, and the length is 10-30 mu m; the stirring rate was 1400rpm, the stirring time was 5 hours, the dispersion treatment was carried out by a homogenizer at a rotation speed of 2800rpm, and the dispersion time was 1 hour.
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath kettle for heating, wherein the heating temperature is 90 ℃, and the heating time is 20min, so as to obtain a graphene/carbon nano tube/silicon dioxide aerogel mixture;
(3) And (3) drying: performing freeze drying treatment on the graphene/carbon nano tube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment, the temperature is 90 ℃, and the time is 20min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia to remove foreign ions, washing with deionized water to neutral pH, and drying to obtain graphene/carbon nanotube/silica aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3:1.
(5) Sintering: and (3) performing spark plasma sintering on the graphene/carbon nano tube/silicon dioxide aerogel obtained in the step (4), and using nitrogen as a protective gas, wherein the temperature is 700 ℃ and the time is 1min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel material.
Example 3
(1) Mixing: graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed according to the following ratio of 1:1:3:2:4:6, placing the mixture in a stirring tank according to the mass ratio, stirring and uniformly mixing the mixture, and obtaining a dispersion liquid after dispersion treatment; the number of layers of the graphene oxide is less than or equal to 10, and the transverse dimension of the graphene oxide is more than 10 mu m; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter is less than or equal to 60nm, and the length is 10-30 mu m; the stirring rate was 700rpm, the stirring time was 3 hours, the dispersion treatment was carried out by an emulsification pump, the rotation speed was 1800rpm, and the dispersion time was 0.8 hours.
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath kettle for heating, wherein the heating temperature is 60 ℃, and the heating time is 20min, so as to obtain a graphene/carbon nano tube/silicon dioxide aerogel mixture;
(3) And (3) drying: performing freeze drying treatment on the graphene/carbon nano tube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment, the temperature is 80 ℃, and the time is 15min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia to remove foreign ions, washing with deionized water to neutral pH, and drying to obtain graphene/carbon nanotube/silica aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3:1.
(5) Sintering: and (3) performing spark plasma sintering on the graphene/carbon nano tube/silicon dioxide aerogel obtained in the step (4), and using nitrogen as a protective gas, wherein the temperature is 500 ℃, and the time is 8min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel material.
Example 4
(1) Mixing: graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed according to the following ratio of 1:1.2:3.5:2.6:3.8:6.2, placing the mixture into a stirring tank for stirring and mixing uniformly, and obtaining dispersion after dispersion treatment; the number of layers of the graphene oxide is less than or equal to 10, and the transverse dimension of the graphene oxide is more than 10 mu m; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter is less than or equal to 60nm, and the length is 10-30 mu m; the stirring speed is 1200rpm, the stirring time is 4.5h, the dispersing treatment is that the materials are dispersed by a colloid mill and a homogenizer in sequence, the rotating speed is 2600rpm, and the dispersing time is 0.8h.
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath kettle for heating, wherein the heating temperature is 110 ℃, and the heating time is 50min, so as to obtain a graphene/carbon nano tube/silicon dioxide aerogel mixture;
(3) And (3) drying: performing freeze drying treatment on the graphene/carbon nano tube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment, the temperature is 75 ℃, and the time is 16min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia to remove foreign ions, washing with deionized water to neutral pH, and drying to obtain graphene/carbon nanotube/silica aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3:1.
(5) Sintering: and (3) performing spark plasma sintering on the graphene/carbon nano tube/silicon dioxide aerogel obtained in the step (4), and using nitrogen as a protective gas, wherein the temperature is 700 ℃, and the time is 0.5min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel material.
Example 5
(1) Mixing: graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed according to the following ratio of 1:0.5:2.6:2.2:4:7, placing the mixture into a stirring tank for stirring and mixing uniformly, and obtaining a dispersion liquid after dispersion treatment; the number of layers of the graphene oxide is less than or equal to 10, and the transverse dimension of the graphene oxide is more than 10 mu m; the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube, the tube diameter is less than or equal to 60nm, and the length is 10-30 mu m; the stirring rate was 1000rpm, the stirring time was 2 hours, the dispersion treatment was carried out by an emulsification pump, the rotation speed was 1800rpm, and the dispersion time was 0.9 hours.
(2) Heating: and (3) adding the dispersion liquid obtained in the step (1) into an oil bath kettle for heating, wherein the heating temperature is 100 ℃, and the heating time is 46min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel mixture.
(3) And (3) drying: performing freeze drying treatment on the graphene/carbon nano tube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment, the temperature is 60 ℃, and the time is 30min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia to remove foreign ions, washing with deionized water to neutral pH, and drying to obtain graphene/carbon nanotube/silica aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3:1.
(5) Sintering: and (3) performing spark plasma sintering on the graphene/carbon nano tube/silicon dioxide aerogel obtained in the step (4), and using nitrogen as a protective gas, wherein the temperature is 650 ℃ and the time is 5min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel material.
Example 6
(1) Mixing: graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed according to the following ratio of 1:1.4:3.8:2.6:3.8:6.8, placing the mixture into a stirring tank for stirring and mixing uniformly, and obtaining dispersion after dispersion treatment; the number of layers of the graphene oxide is less than or equal to 10, and the transverse dimension of the graphene oxide is more than 10 mu m; 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 rate was 700rpm, the stirring time was 3.6 hours, the dispersion treatment was carried out by a colloid mill at 2500rpm, and the dispersing time was 0.6 hours.
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath kettle for heating, wherein the heating temperature is 100 ℃, and the heating time is 43 minutes, so as to obtain a graphene/carbon nano tube/silicon dioxide aerogel mixture;
(3) And (3) drying: performing freeze drying treatment on the graphene/carbon nano tube/silicon dioxide aerogel mixture obtained in the step (2) to obtain a blank; the drying treatment is hot air drying treatment, the temperature is 100 ℃, and the time is 10min.
(4) Acid washing: washing the blank obtained in the step (3) with aqua regia to remove foreign ions, washing with deionized water to neutral pH, and drying to obtain graphene/carbon nanotube/silica aerogel; the aqua regia is a mixture of concentrated hydrochloric acid and concentrated nitric acid according to the volume ratio of 3:1.
(5) Sintering: and (3) performing spark plasma sintering on the graphene/carbon nano tube/silicon dioxide aerogel obtained in the step (4), and using nitrogen as a protective gas, wherein the temperature is 570 ℃, and the time is 4min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel material.
Performance tests are carried out on the graphene/carbon nano tube/silicon dioxide aerogel materials prepared by the above embodiments, and the test standards are as follows:
thermal conductivity coefficient: 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 the above tables 1 and 2, the graphene/carbon nanotube/silica aerogel material prepared in the above examples has a thermal conductivity at room temperature which is not much different from that of the graphene/carbon nanotube/silica aerogel material at 500 ℃ and that of the graphene/carbon nanotube/silica aerogel material at 650 ℃ and can normally operate at a high temperature of 500 ℃ or higher.
The design focus of the invention is that: graphene oxide, carbon nano tube, water glass, silica gel, polydopamine and urea are mixed and stirred, and discharge plasma sintering is carried out after heating and drying to obtain the graphene/carbon nano tube/silica aerogel material, so that the method is simple, the process is controllable, an alcohol solvent is not required to be added in the preparation process, the preparation method is environment-friendly, waste liquid is not required to be treated, the production cost is reduced, industrial continuous production is facilitated, and the prepared graphene/carbon nano tube/silica aerogel composite material can resist high temperature of more than 500 ℃.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical principles of the present invention are still within the scope of the technical solutions of the present invention.
Claims (7)
1. A preparation method of a graphene/carbon nano tube/silicon dioxide aerogel material is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) Mixing: graphene oxide, carbon nanotubes, water glass, silica gel, polydopamine and urea are mixed according to the following ratio of 1: (0.25-1.5): (2-4): (1-3): (3-5): the mass ratio of (3-8) is put into a stirring tank to be stirred and mixed uniformly, and dispersion treatment is carried out to obtain dispersion liquid;
(2) Heating: adding the dispersion liquid obtained in the step (1) into an oil bath kettle for heating, wherein the heating temperature is 60-110 ℃, and the heating time is 20-50min, so as to obtain a graphene/carbon nano tube/silicon dioxide aerogel mixture;
(3) And (3) drying: performing freeze drying treatment on the graphene/carbon nano tube/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 to remove foreign ions, washing with deionized water to neutral pH, and drying to obtain graphene/carbon nanotube/silica aerogel;
(5) Sintering: and (3) performing spark plasma sintering on the graphene/carbon nano tube/silicon dioxide aerogel obtained in the step (4), and using nitrogen as a protective gas, wherein the temperature is 500-700 ℃ and the time is 0.5-8min, so as to obtain the graphene/carbon nano tube/silicon dioxide aerogel material.
2. The method for preparing the 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 dimension of the graphene oxide is more than 10 mu m.
3. The method for preparing the 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 is less than or equal to 60nm, and the length is 10-30 mu m.
4. The method for preparing the 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 1-5h.
5. The method for preparing the graphene/carbon nanotube/silica aerogel material according to claim 1, wherein: the dispersion treatment in the step (1) is carried out by one or more modes of a colloid mill, a homogenizer and an emulsion pump, the rotating speed is 1000-2800rpm, and the dispersion time is 0.5-1h.
6. The method for preparing the 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 10-30min.
7. The method for preparing the graphene/carbon nanotube/silica aerogel material according to claim 1, wherein: 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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