CN111254718A - Self-cleaning graphene carbon fiber non-woven fabric and preparation method thereof - Google Patents
Self-cleaning graphene carbon fiber non-woven fabric and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-cleaning graphene carbon fiber non-woven fabric and a preparation method thereof, wherein the self-cleaning graphene carbon fiber non-woven fabric comprises a self-cleaning coating and graphene carbon fiber base cloth; the self-cleaning coating is prepared from the following raw materials: nano silicon oxide, graphene powder, methyltrimethoxysilane, methanol and water; the graphene carbon fiber base fabric is prepared from the following raw materials: graphene oxide, carbon fibers and nano-silver fibers. According to the self-cleaning graphene carbon fiber non-woven fabric, the self-cleaning coating is sprayed on the graphene carbon fiber base fabric, so that the hydrophobicity of the surface of the graphene carbon fiber non-woven fabric is improved, the surface of the graphene carbon fiber non-woven fabric has a larger contact angle, the self-cleaning performance is good, and the surface of the non-woven fabric can be kept clean and pollution-free for a long time.
Description
Technical Field
The invention relates to the technical field of non-woven fabrics, in particular to a self-cleaning graphene carbon fiber non-woven fabric and a preparation method thereof.
Background
The self-cleaning surface with the lotus leaf effect has good super-hydrophobicity and strong anti-pollution capability. The self-cleaning surface has the advantages of water saving, energy saving, environmental protection and the like, and is more and more concerned by people.
The graphene fiber non-woven fabric is a novel non-woven fabric made of graphene fibers, has excellent performances of electric conduction, heat conduction and the like due to the mutual fusion of the graphene fibers at the lap joint and the excellent characteristics of the graphene, and can be widely applied to the field of energy storage devices such as capacitors, batteries and the like as a flexible fabric electrode.
At present, the existing graphene fiber non-woven fabric is good in flexibility and high in conductivity, but the graphene fiber non-woven fabric is poor in self-cleaning performance and cannot keep the surface of the non-woven fabric clean for a long time.
Chinese patent CN106192201B discloses a graphene fiber non-woven fabric and a preparation method thereof, the non-woven fabric is obtained by filtering, depositing, drying and reducing graphene short fiber dispersion liquid through a filter screen, so that the structural units of the non-woven fabric are graphene short fibers which are stacked disorderly and bonded with each other, and a large number of holes through which liquid or gas can pass are formed by lapping the fibers. The graphene fiber non-woven fabric has good mechanical strength and toughness, is completely composed of graphene fibers, does not contain high polymer materials as a framework or an adhesive and the like, has excellent electric and heat conducting performance after a network structure formed by overlapping the graphene fibers is reduced, and can be used as a multifunctional high-performance fabric. However, the structural units of the graphene fiber non-woven fabric are randomly stacked and mutually bonded graphene short fibers, and the graphene fiber non-woven fabric has high surface energy and does not have self-cleaning property.
Chinese patent CN106436016B discloses a graphene fiber flame-retardant conductive non-woven fabric and a preparation method thereof. The paint is prepared from the following components: 5% graphene conductive paste, flame-retardant polyester staple fibers, chopped carbon fibers, a dispersing agent and a dye-guiding agent. The strength and the flame retardance of the conductive fibers are improved, the safety performance of products is improved, the water resistance of the heating material is improved, the damage rate of the heating material is reduced, the failure rate is reduced, the air permeability is improved, and the adhesive permeability and the bonding strength between the conductive fibers and the insulating material are enhanced. However, the graphene fiber flame-retardant conductive non-woven fabric is not modified by low-surface-energy substances, so that the self-cleaning performance of the product is poor.
Therefore, the invention provides the self-cleaning graphene carbon fiber non-woven fabric and the preparation method thereof, which change the proportion of the graphene carbon fiber base fabric and perform surface modification on the base fabric to realize the self-cleaning property of the graphene carbon fiber non-woven fabric.
Disclosure of Invention
Aiming at the problems, the invention provides a self-cleaning graphene carbon fiber non-woven fabric and a preparation method thereof.
The technical scheme adopted by the invention for solving the problems is as follows: a self-cleaning graphene carbon fiber non-woven fabric comprises a self-cleaning coating and graphene carbon fiber base cloth; the self-cleaning coating is prepared from the following raw materials in parts by weight: 0.5-1.5 parts of nano silicon oxide, 1.2-1.6 parts of graphene powder, 4.0-8.0 parts of methyltrimethoxysilane, 30-35 parts of methanol and 60-70 parts of water; the graphene carbon fiber base cloth is prepared from the following raw materials in parts by weight: 200 to 300 parts of graphene oxide, 65 to 105 parts of carbon fiber and 0.5 to 1.0 part of nano-silver fiber.
Further, the self-cleaning coating is prepared from the following raw materials in parts by weight: 0.8-1.2 parts of nano silicon oxide, 1.3-1.5 parts of graphene powder, 5.0-7.0 parts of methyltrimethoxysilane, 31-34 parts of methanol and 62-68 parts of water; the graphene carbon fiber base cloth is prepared from the following raw materials in parts by weight: 220 to 280 parts of graphene oxide, 75 to 95 parts of carbon fiber and 0.6 to 0.9 part of nano-silver fiber.
According to the self-cleaning graphene carbon fiber non-woven fabric, after methyl trimethoxy silane in the self-cleaning layer is hydrolyzed, the contact angle is larger, the transparency is high, the thermal stability is good, the hydrophobicity of the self-cleaning graphene carbon fiber non-woven fabric is further enhanced by adding nano silicon oxide and graphene powder, and the smoothness of the surface and the mechanical strength of the surface are improved; graphene oxide fibers and carbon fibers are selected from the graphene carbon fiber base cloth to be compounded, so that the flexibility of the graphene oxide fibers can be kept, the toughness of the graphene oxide fibers can be enhanced, the nano-silver fibers are used as the auxiliary materials, the antibacterial and bacteriostatic properties of the base cloth are improved, and meanwhile, the graphene oxide carbon fiber base cloth is filled in the middle of the graphene oxide fibers, so that the formability and the comprehensive performance are improved.
Furthermore, the particle size of the graphene powder is 10 nm-20 nm.
Another object of the present invention is to provide a method for preparing the self-cleaning graphene carbon fiber non-woven fabric, comprising the following steps:
step I, self-cleaning suspension preparation: hydrolyzing the methyltrimethoxysilane in parts by weight in the mixed solution of methanol and water in parts by weight, adding the nano silicon oxide in parts by weight for the first ultrasonic dispersion for 40-60 minutes, adding the graphite powder in parts by weight, and performing the second ultrasonic dispersion for 45-50 minutes to obtain a self-cleaning suspension;
step II, preparing graphene oxide fibers: dispersing the graphene oxide in water by weight to prepare 15-20 mg/mL of spinning solution, and then spinning by a wet method to obtain graphene oxide fibers;
step III, preparing graphene carbon fiber base cloth: shearing and dispersing the graphene oxide fibers obtained in the step II in water for 30-35 minutes for the first time, then adding the carbon fibers and the nano-silver fibers in parts by weight, shearing and dispersing for 20-30 minutes for the second time, and filtering, depositing and drying the obtained suspension liquid through a filter screen to obtain graphene carbon fiber base cloth;
step IV, preparing a self-cleaning graphene carbon fiber non-woven fabric: and (3) spraying the self-cleaning suspension obtained in the step (I) on the surface of the graphene carbon fiber base fabric obtained in the step (III) to form a self-cleaning coating, and then drying for 3-4 hours at normal temperature to obtain the self-cleaning graphene carbon fiber non-woven fabric.
Further, in the step I, the hydrolysis temperature is 38-42 ℃.
Further, in the step I, the pH value of the mixed solution of methanol and water is 3.00-3.05.
Further, in the step III, the length of the fiber in the suspension is 0.5 mm-1.5 mm.
Further, in the step III, the graphene carbon fiber base cloth further comprises thermal reduction at the temperature of 300-600 ℃.
Furthermore, in the step IV, the thickness of the self-cleaning coating is 15-25 μm.
The invention has the advantages that:
(1) according to the self-cleaning graphene carbon fiber non-woven fabric, the self-cleaning coating is sprayed on the graphene carbon fiber base fabric, so that the hydrophobicity of the surface of the graphene carbon fiber non-woven fabric is improved, the surface of the graphene carbon fiber non-woven fabric has a larger contact angle, the self-cleaning performance is good, and the surface of the non-woven fabric can be kept clean and pollution-free for a long time;
(2) according to the self-cleaning graphene carbon fiber non-woven fabric, the self-cleaning layer and the graphene carbon fiber base cloth layer have good surface formability and mechanical strength, good stability, certain antibacterial and bacteriostatic effects and high use safety;
(3) the self-cleaning graphene carbon fiber non-woven fabric disclosed by the invention is excellent in electric and heat conducting properties, simple in preparation method, long in service life, high in practical value and wide in application range.
Detailed Description
The following detailed description of embodiments of the invention, but the invention can be practiced in many different ways, as defined and covered by the claims.
Example 1
Self-cleaning graphene carbon fiber non-woven fabric
Comprises a self-cleaning coating and graphene carbon fiber base cloth; the self-cleaning coating is prepared from the following raw materials in parts by weight: 0.5kg of nano silicon oxide, 1.2kg of graphene powder, 4.0kg of methyltrimethoxysilane, 30kg of methanol and 60kg of water; the graphene carbon fiber base cloth is prepared from the following raw materials in parts by weight: 200kg of graphene oxide, 65kg of carbon fiber and 0.5kg of nano-silver fiber; wherein the particle size of the graphene powder is 10 nm.
The preparation method comprises the following steps:
step I, self-cleaning suspension preparation: hydrolyzing the methyltrimethoxysilane in parts by weight in the mixed solution of methanol and water in parts by weight, adding the nano silicon oxide in parts by weight for the first ultrasonic dispersion for 40 minutes, adding the graphite powder in parts by weight, and performing the second ultrasonic dispersion for 45 minutes to obtain a self-cleaning suspension; wherein, the hydrolysis temperature is 38 ℃; the pH value of the mixed solution of methanol and water is 3.00;
step II, preparing graphene oxide fibers: dispersing the graphene oxide in water by weight part to prepare a spinning solution of 15mg/mL, and then spinning by a wet method to obtain graphene oxide fibers;
step III, preparing graphene carbon fiber base cloth: shearing and dispersing the graphene oxide fibers obtained in the step II in water for 30 minutes for the first time, then adding the carbon fibers and the nano-silver fibers in parts by weight, shearing and dispersing for 20 minutes for the second time, filtering and depositing the obtained suspension by using a filter screen, drying, and carrying out thermal reduction at the temperature of 300 ℃ to obtain graphene carbon fiber base cloth; wherein the length of the fiber in the suspension is 0.5 mm;
step IV, preparing a self-cleaning graphene carbon fiber non-woven fabric: and (3) spraying the self-cleaning suspension obtained in the step (I) on the surface of the graphene carbon fiber base cloth obtained in the step (III) to form a self-cleaning coating with the thickness of 15 mu m, and then drying at normal temperature for 3 hours to obtain the self-cleaning graphene carbon fiber non-woven fabric.
Example 2
Self-cleaning graphene carbon fiber non-woven fabric
Comprises a self-cleaning coating and graphene carbon fiber base cloth; the self-cleaning coating is prepared from the following raw materials in parts by weight: 1.5kg of nano silicon oxide, 1.6kg of graphene powder, 8.0kg of methyltrimethoxysilane, 35kg of methanol and 70kg of water; the graphene carbon fiber base cloth is prepared from the following raw materials in parts by weight: 300kg of graphene oxide, 105kg of carbon fiber and 1.0kg of nano-silver fiber; wherein the particle size of the graphene powder is 20 nm.
The preparation method comprises the following steps:
step I, self-cleaning suspension preparation: hydrolyzing the methyltrimethoxysilane in parts by weight in the mixed solution of methanol and water in parts by weight, adding the nano silicon oxide in parts by weight for the first ultrasonic dispersion for 60 minutes, adding the graphite powder in parts by weight, and performing the second ultrasonic dispersion for 50 minutes to obtain a self-cleaning suspension; wherein, the hydrolysis temperature is 42 ℃; the pH value of the mixed solution of methanol and water is 3.05;
step II, preparing graphene oxide fibers: dispersing the graphene oxide in water by weight part to prepare a spinning solution of 20mg/mL, and then spinning by a wet method to obtain graphene oxide fibers;
step III, preparing graphene carbon fiber base cloth: shearing and dispersing the graphene oxide fibers obtained in the step II in water for 35 minutes for the first time, then adding the carbon fibers and the nano-silver fibers in parts by weight, shearing and dispersing for 30 minutes for the second time, filtering and depositing the obtained suspension liquid through a filter screen, drying, and carrying out thermal reduction at the temperature of 600 ℃ to obtain graphene carbon fiber base cloth; wherein the length of the fiber in the suspension is 1.5 mm;
step IV, preparing a self-cleaning graphene carbon fiber non-woven fabric: and (3) spraying the self-cleaning suspension obtained in the step (I) on the surface of the graphene carbon fiber base cloth obtained in the step (III) to form a self-cleaning coating with the thickness of 25 mu m, and then drying at normal temperature for 4 hours to obtain the self-cleaning graphene carbon fiber non-woven fabric.
Example 3
Self-cleaning graphene carbon fiber non-woven fabric
Comprises a self-cleaning coating and graphene carbon fiber base cloth; the self-cleaning coating is prepared from the following raw materials in parts by weight: 0.8kg of nano silicon oxide, 1.3kg of graphene powder, 5.0kg of methyltrimethoxysilane, 31kg of methanol and 62kg of water; the graphene carbon fiber base cloth is prepared from the following raw materials in parts by weight: 220kg of graphene oxide, 75kg of carbon fiber and 0.6kg of nano-silver fiber; wherein the particle size of the graphene powder is 12 nm.
The preparation method comprises the following steps:
step I, self-cleaning suspension preparation: hydrolyzing the methyltrimethoxysilane in parts by weight in the mixed solution of methanol and water in parts by weight, adding the nano silicon oxide in parts by weight for ultrasonic dispersion for 45 minutes for the first time, adding the graphite powder in parts by weight, and performing ultrasonic dispersion for 46 minutes for the second time to obtain a self-cleaning suspension; wherein, the hydrolysis temperature is 39 ℃; the pH value of the mixed solution of methanol and water is 3.01;
step II, preparing graphene oxide fibers: dispersing the graphene oxide in water by weight part to prepare a spinning solution of 16mg/mL, and then spinning by a wet method to obtain graphene oxide fibers;
step III, preparing graphene carbon fiber base cloth: shearing and dispersing the graphene oxide fibers obtained in the step II in water for 31 minutes for the first time, then adding the carbon fibers and the nano-silver fibers in parts by weight, shearing and dispersing for 22 minutes for the second time, filtering and depositing the obtained suspension liquid through a filter screen, drying, and carrying out thermal reduction at the temperature of 400 ℃ to obtain graphene carbon fiber base cloth; wherein the length of the fiber in the suspension is 0.8 mm;
step IV, preparing a self-cleaning graphene carbon fiber non-woven fabric: and (3) spraying the self-cleaning suspension obtained in the step (I) on the surface of the graphene carbon fiber base cloth obtained in the step (III) to form a self-cleaning coating with the thickness of 17 mu m, and then drying at normal temperature for 4 hours to obtain the self-cleaning graphene carbon fiber non-woven fabric.
Example 4
Self-cleaning graphene carbon fiber non-woven fabric
Comprises a self-cleaning coating and graphene carbon fiber base cloth; the self-cleaning coating is prepared from the following raw materials in parts by weight: 1.2kg of nano silicon oxide, 1.5kg of graphene powder, 7.0kg of methyltrimethoxysilane, 34kg of methanol and 68kg of water; the graphene carbon fiber base cloth is prepared from the following raw materials in parts by weight: 280kg of graphene oxide, 95kg of carbon fiber and 0.9kg of nano-silver fiber; wherein the particle size of the graphene powder is 18 nm.
The preparation method comprises the following steps:
step I, self-cleaning suspension preparation: hydrolyzing the methyltrimethoxysilane in parts by weight in the mixed solution of methanol and water in parts by weight, adding the nano silicon oxide in parts by weight for the first ultrasonic dispersion for 55 minutes, adding the graphite powder in parts by weight, and performing the second ultrasonic dispersion for 49 minutes to obtain a self-cleaning suspension; wherein the hydrolysis temperature is 41 ℃; the pH value of the mixed solution of methanol and water is 3.04;
step II, preparing graphene oxide fibers: dispersing the graphene oxide in water by weight part to prepare 19mg/mL spinning solution, and then spinning by a wet method to obtain graphene oxide fibers;
step III, preparing graphene carbon fiber base cloth: shearing and dispersing the graphene oxide fibers obtained in the step II in water for 34 minutes for the first time, then adding the carbon fibers and the nano-silver fibers in parts by weight, shearing and dispersing for 28 minutes for the second time, filtering and depositing the obtained suspension liquid through a filter screen, drying, and carrying out thermal reduction at the temperature of 500 ℃ to obtain graphene carbon fiber base cloth; wherein the length of the fiber in the suspension is 1.3 mm;
step IV, preparing a self-cleaning graphene carbon fiber non-woven fabric: and (3) spraying the self-cleaning suspension obtained in the step (I) on the surface of the graphene carbon fiber base cloth obtained in the step (III) to form a self-cleaning coating with the thickness of 22 mu m, and then drying at normal temperature for 3 hours to obtain the self-cleaning graphene carbon fiber non-woven fabric.
Example 5
Self-cleaning graphene carbon fiber non-woven fabric
Comprises a self-cleaning coating and graphene carbon fiber base cloth; the self-cleaning coating is prepared from the following raw materials in parts by weight: 1.0kg of nano silicon oxide, 1.4kg of graphene powder, 6.0kg of methyltrimethoxysilane, 33kg of methanol and 65kg of water; the graphene carbon fiber base cloth is prepared from the following raw materials in parts by weight: 260kg of graphene oxide, 85kg of carbon fiber and 0.8kg of nano-silver fiber; wherein the particle size of the graphene powder is 15 nm.
The preparation method comprises the following steps:
step I, self-cleaning suspension preparation: hydrolyzing the methyltrimethoxysilane in parts by weight in the mixed solution of methanol and water in parts by weight, adding the nano silicon oxide in parts by weight for the first ultrasonic dispersion for 50 minutes, adding the graphite powder in parts by weight, and performing the second ultrasonic dispersion for 48 minutes to obtain a self-cleaning suspension; wherein the hydrolysis temperature is 40 ℃; the pH value of the mixed solution of methanol and water is 3.02;
step II, preparing graphene oxide fibers: dispersing the graphene oxide in water by weight part to prepare a spinning solution of 18mg/mL, and then spinning by a wet method to obtain graphene oxide fibers;
step III, preparing graphene carbon fiber base cloth: the graphene oxide fiber obtained in the step II is sheared and dispersed in water for the first time for 33 minutes, then the carbon fiber and the nano-silver fiber in parts by weight are added, the shearing and dispersion are carried out for the second time for 25 minutes, and the obtained suspension is filtered, deposited and dried by a filter screen and is thermally reduced at the temperature of 450 ℃ to obtain graphene carbon fiber base cloth; wherein the length of the fiber in the suspension is 1.0 mm;
step IV, preparing a self-cleaning graphene carbon fiber non-woven fabric: and (3) spraying the self-cleaning suspension obtained in the step (I) on the surface of the graphene carbon fiber base cloth obtained in the step (III) to form a self-cleaning coating with the thickness of 20 microns, and then drying at normal temperature for 3.5 hours to obtain the self-cleaning graphene carbon fiber non-woven fabric.
Examples of the experiments
To further illustrate the improvement of the self-cleaning graphene carbon fiber nonwoven fabrics prepared in embodiments 1 to 5 of the present invention, the following tests are performed.
The contact angle tester is used for measuring the static contact angle between the surface of the self-cleaning graphene carbon fiber non-woven fabric prepared in the embodiment 1-5 and deionized water, the experimental temperature is 23 ℃, the relative humidity is 50%, and the injection volume is 4 mu L. For each example, the surface of the sample was measured at 5 points, and the average value was taken as the test result, which is summarized in the following table 1:
table 1 performance test of self-cleaning graphene carbon fiber nonwoven fabric prepared in embodiments 1 to 5 of the present invention
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Contact angle (°) | 165 | 170 | 168 | 172 | 177 |
The above results show that the self-cleaning graphene carbon fiber non-woven fabric prepared in the embodiments 1 to 5 has a large contact angle and a good self-cleaning effect; in addition, the self-cleaning layer of the self-cleaning graphene carbon fiber non-woven fabric prepared in the embodiments 1-5 of the invention has good transparency, high stability and long service life.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A self-cleaning graphene carbon fiber non-woven fabric is characterized by comprising a self-cleaning coating and a graphene carbon fiber base fabric; the self-cleaning coating is prepared from the following raw materials in parts by weight: 0.5-1.5 parts of nano silicon oxide, 1.2-1.6 parts of graphene powder, 4.0-8.0 parts of methyltrimethoxysilane, 30-35 parts of methanol and 60-70 parts of water; the graphene carbon fiber base cloth is prepared from the following raw materials in parts by weight: 200 to 300 parts of graphene oxide, 65 to 105 parts of carbon fiber and 0.5 to 1.0 part of nano-silver fiber.
2. The self-cleaning graphene carbon fiber non-woven fabric according to claim 1, wherein the self-cleaning coating is prepared from the following raw materials in parts by weight: 0.8-1.2 parts of nano silicon oxide, 1.3-1.5 parts of graphene powder, 5.0-7.0 parts of methyltrimethoxysilane, 31-34 parts of methanol and 62-68 parts of water; the graphene carbon fiber base cloth is prepared from the following raw materials in parts by weight: 220 to 280 parts of graphene oxide, 75 to 95 parts of carbon fiber and 0.6 to 0.9 part of nano-silver fiber.
3. The self-cleaning graphene carbon fiber non-woven fabric according to claim 1, wherein the particle size of the graphene powder is 10nm to 20 nm.
4. The preparation method of the self-cleaning graphene carbon fiber non-woven fabric according to claims 1 to 3, characterized by comprising the following steps:
step I, self-cleaning suspension preparation: hydrolyzing the methyltrimethoxysilane in parts by weight in the mixed solution of methanol and water in parts by weight, adding the nano silicon oxide in parts by weight for the first ultrasonic dispersion for 40-60 minutes, adding the graphite powder in parts by weight, and performing the second ultrasonic dispersion for 45-50 minutes to obtain a self-cleaning suspension;
step II, preparing graphene oxide fibers: dispersing the graphene oxide in water by weight to prepare 15-20 mg/mL of spinning solution, and then spinning by a wet method to obtain graphene oxide fibers;
step III, preparing graphene carbon fiber base cloth: shearing and dispersing the graphene oxide fibers obtained in the step II in water for 30-35 minutes for the first time, then adding the carbon fibers and the nano-silver fibers in parts by weight, shearing and dispersing for 20-30 minutes for the second time, and filtering, depositing and drying the obtained suspension liquid through a filter screen to obtain graphene carbon fiber base cloth;
step IV, preparing a self-cleaning graphene carbon fiber non-woven fabric: and (3) spraying the self-cleaning suspension obtained in the step (I) on the surface of the graphene carbon fiber base fabric obtained in the step (III) to form a self-cleaning coating, and then drying for 3-4 hours at normal temperature to obtain the self-cleaning graphene carbon fiber non-woven fabric.
5. The method according to claim 4, wherein the hydrolysis temperature in step I is 38-42 ℃.
6. The method according to claim 4, wherein the pH of the mixed solution of methanol and water in step I is 3.00 to 3.05.
7. The method according to claim 4, wherein in step III, the length of the fibers in the suspension is 0.5mm to 1.5 mm.
8. The preparation method according to claim 4, wherein in the step III, the graphene carbon fiber base fabric is further subjected to thermal reduction at a temperature of 300-600 ℃.
9. The method according to claim 4, wherein in step IV, the thickness of the self-cleaning coating is 15 μm to 25 μm.
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