CN115497689A - Preparation method of carbon nano tube transparent conductive film - Google Patents
Preparation method of carbon nano tube transparent conductive film Download PDFInfo
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Abstract
The invention belongs to the technical field of conductive films, and particularly relates to a preparation method of a carbon nano tube transparent conductive film, which comprises the following preparation steps: adding a carbon nano tube, a surfactant, a soluble metal salt and a film-forming agent into deionized water to prepare a carbon nano tube solution; step two, grinding and dispersing the carbon nanotube solution, and then filtering the dispersed carbon nanotube solution to obtain a carbon nanotube dispersion solution; step three, uniformly coating the carbon nano tube dispersion liquid on the surface of a transparent substrate, and then drying to form a transparent film; step four, taking a low-boiling-point alcohol solvent, respectively placing the low-boiling-point alcohol solvent and the transparent film in a closed container, and heating the low-boiling-point alcohol solvent for 1-2 hours; and fifthly, taking out the transparent film, and drying to remove the redundant solvent on the transparent film to obtain the carbon nano tube transparent conductive film. The transparent conductive film prepared by the preparation method has high conductivity and high light transmittance.
Description
Technical Field
The invention belongs to the technical field of conductive films, and particularly relates to a preparation method of a carbon nano tube transparent conductive film.
Background
The transparent conductive film is a functional film with good conductivity and good visible light transmittance, is an important photoelectric material, and is widely applied to the fields of touch screens, displays, solar cells and the like. Indium Tin Oxide (ITO) thin films have received much attention because of their low resistivity, transmittance of over 90%, and good stability and compatibility in dry or humid environments, and are currently the most common transparent conductive thin films. However, indium in ITO is a rare material, the total reserve is low, the cost is high, and ITO has low bending rate and poor flexibility, which limits its application in flexible devices, retractable devices, and wearable electronic devices. Therefore, the search for transparent conductive film materials with good flexibility and low cost becomes a research hotspot.
As a nano material, the carbon nano tube has good characteristics in the aspects of flexibility, electric conduction, light transmission and the like, and has the potential of preparing a flexible transparent conductive film with low cost. The fact proves that the transparent conductive film prepared by the carbon nano tube has stronger mechanical property and flexibility. At present, there are two main methods for preparing carbon nanotube transparent conductive films, the first method is a dry film preparation method, and the method comprises the following steps: drawing a film by using the carbon nano tube array or growing a carbon nano tube film in situ. The carbon nano tube transparent conductive film prepared by the method not only has complex preparation process, but also has extremely high requirements on equipment and process, and is not beneficial to large-scale industrial production. The second method is a wet film preparation method, which comprises the following steps: and depositing the carbon nano tube dispersion liquid on a substrate, and drying to form a film.
In order to further improve the conductivity of the conductive film, in the prior art, after the nano metal and the carbon nano tube are mixed to prepare the dispersion liquid, the dispersion liquid is deposited on the substrate, but because the nano metal powder and the carbon nano tube are easy to agglomerate and are difficult to disperse, the prepared conductive film is difficult to realize the common improvement of the conductivity and the transparency.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon nano tube transparent conductive film, which aims to solve the problem that a conductive agent of the transparent conductive film is difficult to disperse and improve the conductivity and the transparency of the conductive film.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a carbon nano tube transparent conductive film, which comprises the following preparation steps:
adding a carbon nano tube, a surfactant, a soluble metal salt and a film-forming agent into deionized water to prepare a carbon nano tube solution;
step two, grinding and dispersing the carbon nano tube solution, and then filtering the dispersed carbon nano tube solution to obtain a carbon nano tube dispersion liquid;
step three, uniformly coating the carbon nano tube dispersion liquid on the surface of a transparent substrate, and then drying to form a transparent film;
step four, taking a low-boiling-point alcohol solvent, respectively placing the low-boiling-point alcohol solvent and the transparent film in a closed container, and heating the low-boiling-point alcohol solvent for 1-2 hours;
and fifthly, taking out the transparent film, and drying to remove the redundant solvent on the transparent film to obtain the carbon nano tube transparent conductive film.
In the first step, the carbon nanotube solution comprises the following components in percentage by mass: 0.1-0.5% of carbon nano tube, 0.3-1.5% of surfactant, 0.01-1% of soluble metal salt, 0.1-1% of film-forming agent and the balance of deionized water.
In the first step, before preparing the carbon nanotube solution, plasma treatment is carried out on the carbon nanotubes in a mixed atmosphere of ammonia gas and nitrogen gas, wherein the volume ratio of the ammonia gas to the nitrogen gas is 1:4-9, the treatment power is 100-150W, and the treatment time is 30-60 min.
Wherein the surfactant is at least one of sodium cholate, sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, BYK-2015, sodium dodecyl sulfate, tween 80, hydroxypropyl cellulose and polyvinylidene fluoride.
Wherein the soluble metal salt is a soluble silver salt.
Wherein, in the second step, the rotation speed during grinding is 1500-2000 r/min, and the grinding time is 2-4h.
Wherein, in the second step, a filter membrane with the aperture of 1-5 μm is adopted for filtration.
In the fourth step, the low-boiling-point alcohol solvent is at least one of ethanol, propanol and isopropanol.
Wherein, in the fourth step, the heating temperature is 90-150 ℃.
The invention has the beneficial effects that:
the preparation method solves the technical problem that when the carbon nano tube transparent conductive film is prepared by a wet method, the nano metal simple substance in the dispersion liquid is easy to agglomerate, so that the prepared transparent conductive film is poor in conductivity and transparency.
The preparation method comprises the steps of firstly mixing soluble metal salt with carbon nano tubes, a surfactant, a film forming agent and deionized water to prepare a carbon nano tube dispersion liquid, then coating the dispersion liquid on the surface of a transparent base material, enabling the soluble metal salt to be attached to a dried carbon nano tube transparent film, then respectively placing a low-boiling-point alcohol solvent and the transparent film into a closed container, enabling the low-boiling-point alcohol solvent and the transparent film not to be in direct contact with each other, evaporating the low-boiling-point alcohol solvent to form steam under the condition of heating the low-boiling-point alcohol solvent, and enabling the steam to fall onto the transparent film to form small liquid drops.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. The examples do not indicate specific conditions, and the conventional conditions or conditions suggested by the manufacturer are followed; the reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
In the description of the present invention, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the description of the present invention, "at least one" means one or more, and "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly dictates otherwise, expressions in the singular form of a word should be understood to include the plural form of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides a preparation method of a carbon nano tube transparent conductive film, which comprises the following preparation steps:
adding a carbon nano tube, a surfactant, a soluble metal salt and a film-forming agent into deionized water to prepare a carbon nano tube solution;
step two, grinding and dispersing the carbon nanotube solution, and then filtering the dispersed carbon nanotube solution to obtain a carbon nanotube dispersion solution;
step three, uniformly coating the carbon nano tube dispersion liquid on the surface of a transparent substrate, and then drying to form a transparent film;
step four, taking a low-boiling-point alcohol solvent, respectively placing the low-boiling-point alcohol solvent and the transparent film in a closed container, and heating the low-boiling-point alcohol solvent for 1-2 hours;
and fifthly, taking out the transparent film, and drying to remove the redundant solvent on the transparent film to obtain the carbon nano tube transparent conductive film.
The preparation method comprises the steps of firstly mixing soluble metal salt with the carbon nano tube, the surfactant, the film forming agent and deionized water to prepare a carbon nano tube dispersion liquid, then coating the dispersion liquid on the surface of a transparent base material, enabling the dried carbon nano tube transparent film to be attached with the soluble metal salt, then respectively placing a low-boiling-point alcohol solvent and the transparent film in a closed container, enabling the low-boiling-point alcohol solvent and the transparent film not to be in direct contact with each other, evaporating the low-boiling-point alcohol solvent to form steam under the condition of heating the low-boiling-point alcohol solvent, and enabling the steam to fall on the transparent film to form small liquid drops.
According to the invention, the surfactant is added, and the carbon nanotube solution is ground, so that the dispersibility and stability of the carbon nanotubes in the solution are improved, the carbon nanotubes are not easy to agglomerate, and the conductivity and the light transmittance of the transparent conductive film are improved. The addition of the film-forming agent enables the carbon nano tube dispersion liquid to have good film-forming performance, the dispersion liquid is convenient to coat on a base material, the conductive agent of the prepared transparent conductive film is not easy to separate from the base material, on the other hand, the film-forming agent can prevent the metal simple substance from agglomerating into a spherical shape when the soluble metal salt is reduced into the metal simple substance, the size of metal simple substance particles can be controlled, and the film-forming agent plays a role of a stabilizing agent.
The invention coats the treated carbon nano tube dispersion liquid on a transparent substrate, and dries the carbon nano tube dispersion liquid to form a transparent film, tiny soluble metal salt particles are uniformly distributed on the formed transparent film, then a low-boiling-point alcohol solvent and the transparent film formed after primary drying are respectively placed in a closed container, and the low-boiling-point alcohol solvent is heated to evaporate the low-boiling-point alcohol solvent to form steam, the steam falls on the transparent film in a closed environment to form small droplets, the small droplets are contacted with the soluble metal salt particles on the transparent film and dissolve the soluble metal salt, because the alcohol steam formed by heating has a certain temperature, and the alcohol solvent has reducibility, metal ions can be reduced into metal simple substances, and the metal ions are contacted with the carbon nano tubes to form a conductive network, thereby improving the conductivity of the film. The concentration of the soluble metal salt in the dispersion liquid is low, and when the soluble metal salt and the dispersion liquid are coated on the base material, the soluble metal salt is uniformly coated on each position on the base material, so that the agglomeration phenomenon is difficult to form when the metal salt is reduced into a metal simple substance, and the metal salt can be uniformly distributed on each position on the base material after reduction to form a nano metal simple substance and a carbon nano tube to form a conductive network.
According to the preparation method, the soluble metal salt is dissolved in the carbon nano tube dispersion liquid and coated on the transparent substrate, the soluble metal salt is uniformly embedded in the transparent film formed after the coating is dried, the alcohol steam with a certain temperature is formed by heating the low-boiling-point alcohol solvent in the closed container, the metal salt is dissolved on the substrate and reacts with the alcohol steam, so that the metal salt is reduced into the metal simple substance, the particle size of the produced metal simple substance is controlled by controlling the concentration of the metal salt and the concentration of the film forming agent, the nano metal simple substance is finally formed and uniformly distributed at each position of the film, and the nano metal simple substance does not influence the transparency of the film. And the formation of the nano metal simple substance is beneficial to converting Schottky contact in the contact resistance of the carbon nano tube and the carbon nano tube into ohmic contact, further reducing the bending of a semiconductor energy band at the contact interface of the metal carbon nano tube and the semiconductor carbon nano tube caused by the Schottky contact, forming a Schottky barrier and leading the interface resistance to be larger than the resistance of the semiconductor, and the nano metal simple substance can effectively reduce the contact of the metal carbon nano tube on the surface of the film and the semiconductor carbon nano tube, increase the contact points between the nano metal simple substance and the metal carbon nano tube and between the metal simple substance and the metal simple substance, form multi-ohmic contact and further increase the conductivity of the film.
In conclusion, the preparation method solves the technical problem that when the carbon nano tube transparent conductive film is prepared by a wet method, the nano metal simple substance in the dispersion liquid is easy to agglomerate, so that the prepared transparent conductive film is poor in conductivity and transparency.
The carbon nano tube solution prepared in the first step comprises the following specific preparation steps: firstly adding carbon nano tubes and a surfactant into deionized water, stirring for 20-30min at a rotation speed of 500-800r/min, then adding soluble metal salt, stirring until the soluble metal salt is completely dissolved, then adding a film-forming agent, and stirring for 20-30min at a rotation speed of 500-800r/min to obtain a carbon nano tube solution.
The carbon nano tube and the surfactant are added into the deionized water, the stirring speed and the stirring time are controlled, and the surfactant can wrap the surface of the carbon nano tube, so that the carbon nano tube is not easy to agglomerate in the deionized water, and the dispersion effect of a carbon nano tube solution is improved.
In the first step, the carbon nanotube solution comprises the following components in percentage by mass: 0.1 to 0.5 percent of carbon nano tube, 0.3 to 1.5 percent of surfactant, 0.01 to 1 percent of soluble metal salt, 0.1 to 1 percent of film forming agent and the balance of deionized water.
According to the invention, the addition amount of each component is controlled according to the mass percentage, so that the carbon nano tube can be uniformly dispersed in the solution, the dispersion liquid is convenient to coat on the transparent base material, the carbon nano tube on the finally formed transparent conductive film after drying and the produced metal simple substance are firmly combined with the transparent base material and are not easy to fall off, and the prepared transparent conductive film has good conductivity and transparency.
In the first step, before preparing the carbon nanotube solution, plasma treatment is carried out on the carbon nanotubes in a mixed atmosphere of ammonia gas and nitrogen gas, wherein the volume ratio of the ammonia gas to the nitrogen gas is 1:4-9, the treatment power is 100-150W, and the treatment time is 30-60 min. The carbon nano tube treated by the plasma treatment technology is easier to disperse in the solution, which is more beneficial to improving the dispersion effect of the carbon nano tube in the solution and leading the prepared conductive film to have better light transmittance and conductivity.
Wherein, the carbon nanotube can be at least one of a single-wall carbon nanotube and a multi-wall carbon nanotube.
The surface active agent is at least one of sodium cholate, sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, BYK-2015, sodium dodecyl sulfate, tween 80, hydroxypropyl cellulose and polyvinylidene fluoride, and the surface active agent has a good dispersing effect on the carbon nano tubes and is beneficial to improving the conductivity and light transmittance of the transparent conductive film.
Wherein the soluble metal salt is a soluble silver salt. The soluble silver salt can be reduced into silver simple substance, the silver simple substance has good conductivity, and the conductivity of the transparent conductive film can be improved. Specifically, the soluble silver salt may be at least one of silver nitrate, silver fluoride, silver chlorate and silver perchlorate, and is preferably silver nitrate.
Wherein the film forming agent is at least one of sodium polyvinylbenzene sulfonate, polyvinylpyrrolidone and sodium carboxymethylcellulose.
The transparent substrate can be but is not limited to transparent glass and a PET film, has high light transmittance and is more favorable for preparing a transparent conductive film with high light transmittance
In the second step, the rotation speed during grinding is 1500-2000 r/min, the grinding time is 2-4h, and the grinding speed and the grinding time are controlled, so that the dispersion effect of the carbon nanotube solution can be effectively improved, the carbon nanotubes are uniformly and stably distributed in the solution system, and the conductivity and the light transmittance of the prepared transparent conductive film are improved. Specifically, in other embodiments, the grinding speed may be, but is not limited to, 1500r/min, 1600r/min, 1700r/min, 1800r/min, 1900r/min, 2000r/min.
In the second step, a filter membrane with the aperture of 1-5 microns is adopted for filtering, so that larger particulate matters which are not dispersed in the solution can be filtered, the uniform dispersion of all the matters in the dispersion liquid is ensured, and the improvement of the conductivity and the light transmittance of the transparent conductive film is facilitated. Specifically, in other embodiments, the pore size of the filter membrane can be, but is not limited to, 1 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 5 μm.
Wherein, in the third step, the carbon nano tube dispersion liquid is evenly coated on the surface of the transparent base material by adopting a wire bar coating machine, the wire bar in the wire bar coating machine adopts a wire bar with the diameter of 4-8 microns, the coating speed is 100-200 mm/s, and the deionized water is washed for 5 times, 5-10 ml each time. And by adopting a wire rod coating mode, the thickness of the film is easy to control, the equipment is simple to operate, and the large-size film preparation is easy. Specifically, in other embodiments, the diameter of the wire rod may be, but is not limited to, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, and the coating speed may be, but is not limited to, 100mm/s, 110mm/s, 120mm/s, 130mm/s, 140mm/s, 150mm/s, 160mm/s, 170mm/s, 180mm/s, 190mm/s.
In the fourth step, the low-boiling-point alcohol solvent is at least one of ethanol, propanol and isopropanol, and the solvents have low boiling points, can be evaporated at a lower temperature to form steam, and react with the soluble metal salt on the film.
Wherein, in the fourth step, the heating temperature is 90-150 ℃, specifically, in other embodiments, the heating temperature can be, but is not limited to, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 150 ℃.
In order to clearly understand the details of the above-described implementation and operation of the present invention for those skilled in the art and to significantly embody the advanced performance of the embodiments of the present invention, the above-described technical solution is illustrated by a plurality of embodiments below.
Example 1
A preparation method of a carbon nano tube transparent conductive film comprises the following preparation steps:
s1, weighing the component reagents according to the following mass percent for later use, wherein the component reagents comprise 0.3 percent of carbon nano tube, 0.9 percent of sodium dodecyl benzene sulfonate, 0.5 percent of silver nitrate, 0.5 percent of polyvinylpyrrolidone and the balance of deionized water.
S2, carrying out plasma treatment on the carbon nano tube in a mixed atmosphere of ammonia gas and nitrogen gas, wherein the volume ratio of the ammonia gas to the nitrogen gas is 1:6.5, the plasma treatment power is 125W, and the treatment time is 45min;
s3, adding the carbon nano tube subjected to plasma treatment and sodium dodecyl benzene sulfonate into deionized water, stirring for 25min at a rotation speed of 650r/min, then adding silver nitrate, stirring until the silver nitrate is completely dissolved, then adding polyvinylpyrrolidone, and stirring for 20-30min at a rotation speed of 650r/min to obtain a carbon nano tube solution;
s4, grinding and dispersing the carbon nanotube solution, wherein the rotation speed during grinding is 1750r/min, the grinding time is 3h, and then filtering the dispersed carbon nanotube solution by using a filter membrane with the aperture of 3 mu m to obtain a carbon nanotube dispersion liquid;
s5, uniformly coating the carbon nanotube dispersion liquid on the surface of the PET film substrate by using a wire bar coating machine, wherein a wire bar in the wire bar coating machine is washed for 5 times with deionized water at the coating speed of 150mm/S and 7.5ml each time, and then drying to form a transparent film;
s6, taking an ethanol solvent, respectively placing the ethanol solvent and the transparent film in two mutually communicated closed containers, and heating the ethanol solvent for 1.5 hours at the temperature of 120 ℃;
and S7, taking out the transparent film, and drying to remove the redundant solvent on the transparent film to obtain the carbon nano tube transparent conductive film.
Example 2
A preparation method of a carbon nano tube transparent conductive film comprises the following preparation steps:
s1, weighing the component reagents according to the following mass percent for later use, wherein the component reagents comprise 0.1 percent of carbon nano tube, 0.3 percent of hexadecyl trimethyl ammonium bromide, 0.01 percent of silver nitrate, 0.1 percent of sodium polystyrene sulfonate and the balance of deionized water.
S2, carrying out plasma treatment on the carbon nano tube in a mixed atmosphere of ammonia gas and nitrogen gas, wherein the volume ratio of the ammonia gas to the nitrogen gas is 1:4, the plasma treatment power is 100W, and the treatment time is 30min;
s3, adding the carbon nano tube subjected to plasma treatment and hexadecyl trimethyl ammonium bromide into deionized water, stirring for 20min at a rotation speed of 500r/min, then adding silver nitrate, stirring until the silver nitrate is completely dissolved, then adding sodium polystyrene sulfonate, and stirring for 20min at a rotation speed of 50r/min to obtain a carbon nano tube solution;
s4, grinding and dispersing the carbon nanotube solution, wherein the rotation speed during grinding is 1500r/min, the grinding time is 2h, and then filtering the dispersed carbon nanotube solution by adopting a filter membrane with the aperture of 1 mu m to obtain a carbon nanotube dispersion liquid;
s5, uniformly coating the carbon nanotube dispersion liquid on the surface of the PET film substrate by using a wire bar coating machine, wherein a wire bar in the wire bar coating machine is used for washing 5 times with deionized water at a coating speed of 100mm/S, 5ml each time, and then drying to form a transparent film;
s6, taking an ethanol solvent, respectively placing the ethanol solvent and the transparent film in two mutually communicated closed containers, and heating the ethanol solvent for 1h at the temperature of 90 ℃;
and S7, taking out the transparent film, and drying to remove the redundant solvent on the transparent film to obtain the carbon nano tube transparent conductive film.
Example 3
A preparation method of a carbon nano tube transparent conductive film comprises the following preparation steps:
s1, weighing the component reagents according to the following mass percent for later use, wherein the component reagents comprise 0.5 percent of carbon nano tube, 1.5 percent of sodium dodecyl sulfate, 1 percent of silver nitrate, 1 percent of sodium carboxymethyl cellulose, and the balance of deionized water.
S2, carrying out plasma treatment on the carbon nano tube in a mixed atmosphere of ammonia gas and nitrogen gas, wherein the volume ratio of the ammonia gas to the nitrogen gas is 1:9, the plasma processing power is 150W, and the processing time is 60min;
s3, adding the carbon nano tube subjected to plasma treatment and sodium dodecyl sulfate into deionized water, stirring at a rotation speed of 800r/min for 30min, then adding silver nitrate, stirring until the silver nitrate is completely dissolved, then adding sodium carboxymethyl cellulose, and stirring at a rotation speed of 800r/min for 30min to obtain a carbon nano tube solution;
s4, grinding and dispersing the carbon nanotube solution, wherein the rotating speed during grinding is 2000r/min, the grinding time is 4h, and then filtering the dispersed carbon nanotube solution by adopting a filter membrane with the aperture of 5 mu m to obtain a carbon nanotube dispersion liquid;
s5, uniformly coating the carbon nanotube dispersion liquid on the surface of the PET film substrate by using a wire bar coating machine, wherein the wire bar in the wire bar coating machine has the diameter of 8 microns, the coating speed is 200mm/S, the coating is washed for 5 times by using deionized water, 10ml of deionized water is used for each time, and then the deionized water is dried to form a transparent film;
s6, taking an ethanol solvent, respectively placing the ethanol solvent and the transparent film in two mutually communicated closed containers, and heating the ethanol solvent for 2 hours at the temperature of 150 ℃;
and S7, taking out the transparent film, and drying to remove the redundant solvent on the transparent film to obtain the carbon nano tube transparent conductive film.
Comparative example 1
A preparation method of a carbon nano tube transparent conductive film comprises the following preparation steps:
s1, weighing the components according to the following mass percentage, namely 0.3 percent of carbon nano tube, 0.9 percent of sodium dodecyl benzene sulfonate, 0.5 percent of nano silver particles, 0.5 percent of polyvinylpyrrolidone and the balance of deionized water for later use.
S2, carrying out plasma treatment on the carbon nano tube in a mixed atmosphere of ammonia gas and nitrogen gas, wherein the volume ratio of the ammonia gas to the nitrogen gas is 1:6.5, the plasma treatment power is 125W, and the treatment time is 45min;
s3, adding the carbon nano tube subjected to plasma treatment and sodium dodecyl benzene sulfonate into deionized water, stirring for 25min at a rotation speed of 650r/min, then adding nano silver particles, stirring until the nano silver particles are completely dissolved, then adding polyvinylpyrrolidone, and stirring for 20-30min at a rotation speed of 650r/min to obtain a carbon nano tube solution;
s4, grinding and dispersing the carbon nano tube solution, wherein the rotation speed during grinding is 1750r/min, the grinding time is 3h, and then filtering the dispersed carbon nano tube solution by adopting a filter membrane with the aperture of 3 mu m to obtain a carbon nano tube dispersion liquid;
and S5, uniformly coating the carbon nanotube dispersion liquid on the surface of the PET film substrate by using a wire bar coating machine, wherein the wire bar coating machine is used for washing 5 times with deionized water, 7.5ml each time, and drying to form the carbon nanotube transparent conductive film, and the diameter of the wire bar is 6 microns.
Comparative example 2
A preparation method of a carbon nano tube transparent conductive film is characterized in that a film-forming agent is not added in a comparative example 2, and other preparation steps are the same as those in the example 1, which are not repeated herein.
Performance test
The carbon nanotube transparent conductive coatings obtained in examples 1 to 3 and comparative examples 1 to 2 were measured for resistance and transmittance in the same manner, and the results are shown in the following table.
TABLE 1 Performance test results of each transparent conductive film
| Group of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Square resistance (omega/sq) | 218 | 252 | 238 | 341 | 384 |
| Light transmittance (%) | 85.6 | 86.0 | 85.1 | 50.8 | 65.1 |
According to the test result, the transparent conductive film prepared by the preparation method has high conductivity and high light transmittance, the square resistance is 218-252 omega/sq, and the light transmittance is 85-86%. The sheet resistance of the comparative example 1 is 341 Ω/sq, the light transmittance is 50.8%, and the conductivity and the light transmittance of the comparative example 1 are both inferior to those of the present invention, because the comparative example 1 directly adopts the nano metal particles and the carbon nano tubes to prepare the dispersion liquid, the carbon nano tubes and the nano metal particles are both easy to agglomerate and are difficult to disperse, and the distribution of nano metals in the prepared carbon nano tube conductive film is uneven compared with the present invention, and the agglomeration condition is more serious than that of the present invention, so the conductivity and the light transmittance of the transparent conductive film prepared by the comparative example are both inferior to those of the present invention, while the comparative example 2 is not added with the film-forming agent, and the film-forming effect of the dispersion liquid on the substrate is poor, when the soluble metal salt is reduced into the metal simple substance, due to the blocking effect of the film-forming agent being reduced, a small part of the metal simple substance is easy to agglomerate, thereby affecting the conductivity and the light transmittance of the transparent conductive film.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. A preparation method of a carbon nano tube transparent conductive film is characterized by comprising the following preparation steps:
adding a carbon nano tube, a surfactant, a soluble metal salt and a film-forming agent into deionized water to prepare a carbon nano tube solution;
step two, grinding and dispersing the carbon nanotube solution, and then filtering the dispersed carbon nanotube solution to obtain a carbon nanotube dispersion solution;
step three, uniformly coating the carbon nano tube dispersion liquid on the surface of a transparent substrate, and then drying to form a transparent film;
step four, taking a low-boiling-point alcohol solvent, respectively placing the low-boiling-point alcohol solvent and the transparent film in a closed container, and heating the low-boiling-point alcohol solvent for 1-2 hours;
and fifthly, taking out the transparent film, and drying to remove the redundant solvent on the transparent film to obtain the carbon nano tube transparent conductive film.
2. The method for preparing a carbon nanotube transparent conductive film according to claim 1, wherein in the first step, the carbon nanotube solution comprises the following components by mass percent: 0.1-0.5% of carbon nano tube, 0.3-1.5% of surfactant, 0.01-1% of soluble metal salt, 0.1-1% of film-forming agent and the balance of deionized water.
3. The method for preparing a carbon nanotube transparent conductive film according to claim 1, wherein in the first step, before preparing the carbon nanotube solution, the carbon nanotubes are subjected to plasma treatment in a mixed atmosphere of ammonia and nitrogen, and the volume ratio of ammonia to nitrogen is 1:4-9, the treatment power is 100-150W, and the treatment time is 30-60 min.
4. The method of claim 1, wherein the surfactant is at least one selected from the group consisting of sodium cholate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, BYK-2015, sodium dodecylsulfate, tween 80, hydroxypropylcellulose, and polyvinylidene fluoride.
5. The method as claimed in claim 1, wherein the soluble metal salt is a soluble silver salt.
6. The method for preparing a carbon nanotube transparent conductive film according to claim 1, wherein in the second step, the rotation speed during grinding is 1500-2000 r/min, and the grinding time is 2-4h.
7. The method for preparing a carbon nanotube transparent conductive film as claimed in claim 1, wherein in the second step, the filtration is performed by using a filter membrane with a pore size of 1-5 μm.
8. The method for preparing a carbon nanotube transparent conductive film according to claim 1, wherein in the fourth step, the low-boiling-point alcohol solvent is at least one of ethanol, propanol and isopropanol.
9. The method for preparing a carbon nanotube transparent conductive film as claimed in claim 1, wherein in the fourth step, the heating temperature is 90-150 ℃.
10. The method of claim 1, wherein the transparent substrate is transparent glass or PET film.
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