CN111430082B - Core-shell packaging preparation method of silver nanowire composite transparent conductive film - Google Patents
Core-shell packaging preparation method of silver nanowire composite transparent conductive film Download PDFInfo
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- CN111430082B CN111430082B CN202010216477.9A CN202010216477A CN111430082B CN 111430082 B CN111430082 B CN 111430082B CN 202010216477 A CN202010216477 A CN 202010216477A CN 111430082 B CN111430082 B CN 111430082B
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Abstract
The invention discloses a core-shell packaging preparation method of a silver nanowire composite transparent conductive film, and belongs to the technical field of nano materials and flexible photoelectric films. The method mainly comprises the steps of adding 2-methylimidazole into silver nanowire dispersion liquid (Ag NWS), uniformly mixing, coating to form a film, then coating Zn (NO3) 2.6H 2O solution on the surface of the film, naturally drying in the air, and forming a crystal material which takes transition metal Zn as a connection point and 2-methylimidazole as an organic ligand, namely ZOF for short, on the surface of the silver nanowire through self-assembly. No polymer resin is used in the whole process and formula, so that the nano silver wire fully shows conductivity; the obtained transparent conductive film realizes node welding due to the deposition of ZOF at the nodes of the silver nanowires, and the conductivity of the transparent conductive film is improved; meanwhile, the chemical resistance, the thermal stability and the adhesive force of the silver nanowire are greatly improved due to a core-shell structure formed by the deposition of the ZOF on the surface of the silver nanowire.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a core-shell packaging preparation method of a silver nanowire composite transparent conductive film.
Background
The transparent conductive film is one of the core components of 3C electronic devices, and has extremely important application in the touch field. In recent years, silver nanowires have received extensive attention and much research as an important material to replace ITO (indium tin oxide). The optical performance and the conductivity are important points of research, at present, the photoelectric performance of the silver nanowire transparent conductive film is researched to a certain stage, and for enterprises, the photoelectric performance of the silver nanowire transparent conductive film meets basic industrial application, and more emphasis is placed on economic applicability, production simplicity and other performances matched with industrial application.
At present, in a commercial silver nanowire transparent conductive film, a solvent type capping layer (OC) is coated on a silver nanowire conductive layer to increase the adhesion and improve the chemical resistance and thermal stability. The OC-coated silver nanowire transparent conductive film inevitably covers a part of the silver nanowires, resulting in a decrease in conductivity; meanwhile, rainbow streak phenomenon can be brought, thereby greatly influencing the apparent performance. Researchers develop matched resins to improve the rainbow effect, but the rainbow effect cannot be well solved, in addition, more production processes and high cost are required for coating OC, and the environment is polluted when a large amount of organic solvent in OC volatilizes, which is not ideal for the comprehensive applicability of industrial production. Based on the characteristics, the resin matched with the silver nanowire coating liquid is not selected, the properties of the inner material and the outer material are integrated in a core-shell packaging mode, the defects of the inner material and the outer material are mutually compensated, and the adhesive force, the thermal stability and the chemical resistance of the composite nano material are improved through synergistic effect of the inner material and the outer material.
Disclosure of Invention
Technical problem to be solved
The problem that the OC-coated silver nanowire transparent conductive film inevitably covers a part of the silver nanowire, so that the conductivity is reduced is solved; meanwhile, rainbow texture phenomenon is brought, so that the apparent performance of the silver nanowire composite transparent conductive film is greatly influenced, in addition, more production processes and high cost are required for coating OC, and the environment is polluted when a large amount of organic solvent in OC volatilizes, which is not ideal for the comprehensive applicability of industrial production, and the core-shell packaging preparation method of the silver nanowire composite transparent conductive film is provided.
(II) technical scheme
A core-shell packaging preparation method of a silver nanowire composite transparent conductive film comprises the following steps:
1) firstly, adding 2-methylimidazole into silver nanowire dispersion liquid, uniformly mixing, and then coating on a substrate to form a film:
2) coating Zn (NO3) 2.6H 2O solution on the surface of a membrane, naturally drying, and forming a crystal material which takes transition metal Zn as a connection point and 2-methylimidazole as an organic ligand, namely Zn-organic frameworks, ZOF for short, by self-assembly on the surface of the silver nanowire:
as a preferred technical scheme, the amount of the silver nanowire dispersion liquid is 500 mL;
as a preferable technical scheme, the concentration of the 2-methylimidazole is 0.0556-0.556 mol/L;
as a preferable technical scheme, the concentration of Zn (NO3)2 & 6H2O is 0.0278-0.278 mol/L.
According to a preferable technical scheme, the solvent of the silver nanowire dispersion liquid is a mixed solvent of water, ethanol or isopropanol, and the concentration of the silver nanowire dispersion liquid is 0.05-0.25 mg/mL.
As a preferred solution, the substrate is glass or polyethylene terephthalate (PET).
Preferably, the silver nanowire coating liquid of 2-methylimidazole is one of a meyer bar coating method, a spray coating method, a vacuum suction filtration transfer method and a spin coating method.
As a preferable technical scheme, the method for coating the Zn (NO3) 2.6H 2O solution on the surface of the film is spraying.
(III) advantageous effects
The invention has the beneficial effects that:
(1) the preparation method comprises the steps of adding 2-methylimidazole into silver nanowire dispersion liquid, uniformly mixing, coating to form a film, coating Zn (NO3) 2.6H 2O solution on the surface of the film, and naturally drying in the air to obtain the composite transparent conductive film. No polymer resin is used in the whole process and formula, so that the nano silver wire fully shows conductivity; the obtained transparent conductive film realizes node welding due to the deposition of ZOF at the nodes of the silver nanowires, and the conductivity of the transparent conductive film is improved; meanwhile, the chemical resistance, the thermal stability and the adhesive force of the silver nanowire are greatly improved due to a core-shell structure formed by the deposition of the ZOF on the surface of the silver nanowire. The treatment method of the invention has the following advantages: the process is simple and the operation is easy; the method has the advantages of high economic applicability and environmental protection, and does not need to coat a solvent type capping layer (over coating) on the surface of the silver nanowire conducting layer for protection; the conductivity is good, and the thermal stability and chemical resistance are also greatly improved.
Drawings
FIG. 1 is a scanning electron micrograph and a transmission electron micrograph of a Ag @ ZOF film of example 1;
FIG. 2 is a scanning electron micrograph and a transmission electron micrograph of the Ag @ ZOF film of example 2;
FIG. 3 is a scanning electron micrograph and a transmission electron micrograph of the Ag @ ZOF film of example 3;
FIG. 4 is a scanning electron micrograph and a transmission electron micrograph of the Ag @ ZOF film of example 4;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments and drawings. However, these examples are not intended to limit the present invention, and those skilled in the art who have the above-mentioned invention will make various insubstantial modifications and adaptations to the invention without departing from the scope of the invention.
The embodiment provides a core-shell packaging preparation method of a silver nanowire composite transparent conductive film, which comprises the following specific implementation steps:
example 1
Firstly, adding 10mL of 0.139 mol/L2-methylimidazole into 500mL of 0.16mg/mL silver nanowire, uniformly mixing, and coating;
then 10mL of 0.078mol/L Zn (NO3) 2.6H 2O was applied to the surface and allowed to dry naturally to give Ag @ ZOF films, which were characterized by SEM and TEM and finally tested for adhesion (GB/T9286), conductivity (four-probe), chemical resistance (ethanol, toluene, nitric acid solution at pH 3, 100 wipes with 1kg force alcohol swabs), thermal stability (120 ℃, 240 hours). The test results are shown in the following table.
TABLE 1 comparison of conductivity, adhesion, and chemical resistance before and after core-shell encapsulation
Example 2
Firstly, adding 10mL of 0.278 mol/L2-methylimidazole into 500mL of 0.18mg/mL silver nanowire, uniformly mixing, and coating;
then 10mL of 0.112mol/L Zn (NO3) 2.6H 2O was applied to the surface, dried naturally to give Ag @ ZIF-8 films, characterized by SEM and TEM, and finally tested for adhesion (GB/T9286), conductivity (four-probe instrument), chemical resistance (ethanol, toluene, nitric acid solution with pH 3, 100 wipes with 1kg force alcohol swabs), thermal stability (120 ℃, 240 hours). The test results are shown in the following table.
TABLE 2 comparison of conductivity, adhesion, and chemical resistance before and after core-shell encapsulation
Example 3
Firstly, adding 10mL of 0.278 mol/L2-methylimidazole into 500mL of 0.18mg/mL silver nanowire, uniformly mixing, and coating;
then 10mL of 0.556mol/L Zn (NO3) 2.6H 2O was applied to the surface, dried naturally to give Ag @ ZIF-8 films, characterized by SEM and TEM, and finally tested for adhesion (GB/T9286), conductivity (four-probe instrument), chemical resistance (ethanol, toluene, nitric acid solution with pH 3, 100 wipes with 1kg force alcohol cotton swab), thermal stability (120 ℃, 240 hours). The test results are shown in the following table.
TABLE 3 comparison of conductivity, adhesion, and chemical resistance before and after core-shell encapsulation
Example 4
Firstly, adding 10mL of 0.112 mol/L2-methylimidazole into 500mL of 0.20mg/mL silver nanowire, uniformly mixing, and coating;
then 10mL of 0.556mol/L Zn (NO3) 2.6H 2O was applied to the surface, dried naturally to give Ag @ ZIF-8 films, characterized by SEM and TEM, and finally tested for adhesion (GB/T9286), conductivity (four-probe instrument), chemical resistance (ethanol, toluene, nitric acid solution with pH 3, 100 wipes with 1kg force alcohol cotton swab), thermal stability (120 ℃, 240 hours). The test results are shown in the following table.
TABLE 4 comparison of conductivity, adhesion, and chemical resistance before and after core-shell encapsulation
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. Other variations and modifications will be apparent to persons skilled in the art in light of the above teachings. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of this invention are intended to be included within the scope of the present invention.
Claims (5)
1. A core-shell packaging preparation method of a silver nanowire composite transparent conductive film is characterized by comprising the following steps:
1) firstly, adding 2-methylimidazole into silver nanowire dispersion liquid, uniformly mixing, and then coating on a substrate to form a film:
2) coating Zn (NO3) 2.6H 2O solution on the surface of a membrane, naturally drying, and forming a crystal material which takes transition metal Zn as a connection point and 2-methylimidazole as an organic ligand, namely Zn-organic frameworks, ZOF for short, by self-assembly on the surface of the silver nanowire:
the amount of the silver nanowire dispersion liquid is 500mL, and the concentration of the silver nanowire dispersion liquid is 0.05-0.25 mg/mL;
the amount of the 2-methylimidazole is 10ml, and the concentration of the 2-methylimidazole is 0.0556-0.556 mol/L;
the amount of Zn (NO3)2 & 6H2O is 10ml, and the concentration of Zn (NO3)2 & 6H2O is 0.0278-0.278 mol/L.
2. The core-shell packaging preparation method of the silver nanowire composite transparent conductive film according to claim 1, characterized by comprising the following steps: the solvent of the silver nanowire dispersion liquid is a mixed solvent of water, ethanol or isopropanol.
3. The core-shell packaging preparation method of the silver nanowire composite transparent conductive film according to claim 1, characterized by comprising the following steps: the substrate is glass or polyethylene terephthalate (PET).
4. The core-shell packaging preparation method of the silver nanowire composite transparent conductive film according to claim 1, characterized by comprising the following steps: the coating method of the silver nanowire coating liquid of the 2-methylimidazole is one of a meyer bar coating method, a spraying method, a vacuum filtration transfer method and a spin coating method.
5. The core-shell packaging preparation method of the silver nanowire composite transparent conductive film according to claim 1, characterized by comprising the following steps: the method for coating the Zn (NO3) 2.6H 2O solution on the surface of the film is spraying.
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| CN104992752B (en) * | 2015-07-16 | 2016-12-14 | 城步新鼎盛电子科技有限公司 | A kind of production method of nano-silver thread transparent conductive film |
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| CN109065214A (en) * | 2018-07-13 | 2018-12-21 | 华南理工大学 | A kind of preparation method of the flexible transparent conductive film of conduction homogenous silver nano line high adhesion force |
| CN109390080A (en) * | 2018-11-16 | 2019-02-26 | 顾氏纳米科技（浙江）有限公司 | A kind of silver nanowires and transparent conductive oxide composite transparent conductive film and its application |
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