KR102289961B1 - Method of manufacturing transparent electrode film having improved conductivity through alkaline solution spraying process - Google Patents

Abstract

The present invention relates to a method for manufacturing a transparent conductive electrode film with improved conductivity, and more particularly, a capping agent or surfactant used in synthesizing silver nanowires by spraying a basic solution such as potassium hydroxide or sodium hydroxide aqueous solution on the electrode surface. It relates to a method for producing a transparent conductive electrode film having improved conductivity by decomposing it.

Description

Manufacturing method of transparent conductive electrode film with improved conductivity through basic solution spraying process

The present invention relates to a method for manufacturing a transparent conductive electrode film with improved conductivity, and more particularly, a capping agent or surfactant used in synthesizing silver nanowires by spraying a basic solution such as potassium hydroxide or sodium hydroxide aqueous solution on the electrode surface. It relates to a method for producing a transparent conductive electrode film having improved conductivity by decomposing it.

Transparent electrodes with electrical conductivity by applying nanowire particles to a transparent polymer film are widely used in displays, electronic products, and commercial glass. The materials are coated in the form of a thin film and used. Among them, silver (Ag) has the best electrical and thermal conductivity properties among metals, and is useful because it has high stability and excellent transparency when controlled with nanoparticles. However, these types of electrodes have many difficulties in improving properties due to the limitations of the inherent electrical conductivity of the coated metal particles and the effects of added surfactants and capping agents, limiting product development and performance advancement. there was

In order to solve this problem, a technique using a specific solvent to improve dispersibility during nanowire deposition has been proposed, but there is a limit to improving electrical conductivity. Although possible, there was a problem that it is not preferable because it damages the polymer substrate on which the nanowire electrode is formed.

In addition, in the prior art, it is reported that most of the materials required for synthesis are directly purchased, so resource, environmental, and economic problems follow one after another.

International Patent Publication WO2015/130965 A1 Japanese Laid-Open Patent P2001-316736A

The technical problem to be achieved by the present invention is to spray a basic solution on the surface of a transparent conductive electrode made of silver nanowires to decompose the capping agent or surfactant used for the purpose of shape control when synthesizing silver nanowires through a chemical reaction. It is to provide a method to improve the conductivity.

Another technical object of the present invention is to provide a method of manufacturing a transparent electrode that is environmentally friendly and has reduced process cost through the process of recovering silver from waste scrap, synthesizing silver nanowires, and manufacturing the same as an electrode.

In order to solve the above problems, the present invention comprises the steps of: a) reducing silver nitrate (AgNO ₃ ) in a polyol process using a reducing solvent containing a capping agent to prepare a silver nanowire; b) dispersing the silver nanowires in a solvent and depositing them on a film; c) removing the solvent by drying the film on which the silver nanowires are deposited; And d) provides a method for producing a transparent conductive electrode film comprising the step of modifying the surface by spraying a basic solution on the film surface.

The present invention also provides a method of synthesizing silver nanowires using silver recovered from waste scrap, and manufacturing a transparent conductive electrode film using the silver nanowires obtained in this way.

The present invention synthesizes silver nanowires using a polyol process through silver recovery through a wet recovery process using waste scrap containing various metals. Since synthetic materials are directly recovered from waste scraps discarded at industrial sites, it is eco-friendly and, in particular, is the most realistically feasible solution to the resource depletion problem approaching the present generation. In addition, since there is no need to directly purchase materials and reagents required for synthesis, there is an effect of reducing the total process cost.

In addition, the present invention prepares a conductive transparent electrode film by applying silver nanowires to a polymer substrate in the form of a thin film through a particle production and size control process, and chemical reaction by spraying an aqueous solution of potassium hydroxide or sodium hydroxide on the electrode surface Conductivity was improved by inducing a reaction that decomposes the surfactant used for the purpose of shape control when synthesizing silver nanowires.

The present invention is not limited to one material type of a substrate to be coated in the transparent electrode and material process currently in progress, but has the advantage that it can be applied to various types of substrates such as glass, ceramic, and carbon. In addition, when using a polymer-based substrate vulnerable to high temperature, it is very effective in improving electrode conductivity even if it does not react at a high temperature, so an effect of reducing process cost can be expected. Although silver nanowires are used in the present invention, they are also not limited to one metal and can be applied to various types of metals and shapes.

1 shows an XRD analysis result of waste scrap (left) and an XRD analysis result of leached AgCl particles (right) according to an embodiment of the present invention.
2 is an SEM analysis image (left) taken in the intermediate stage of silver nanowire synthesis according to an embodiment of the present invention, and an SEM analysis image (right) taken after nanowire synthesis.
3 is a SEM analysis image of silver nanowires deposited on the surface of a PET film prepared according to an embodiment of the present invention.
4 is an SEM analysis image of the electrode surface after application of an aqueous potassium hydroxide solution according to an embodiment of the present invention.
5 is an SEM analysis image of the electrode surface after application of an aqueous sodium hydroxide solution according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples and drawings.

The present invention is a method of improving the electrical conductivity of a transparent electrode by spraying a basic solution on the surface of a transparent conductive electrode made of silver nanowires and decomposing a capping agent or surfactant used for shape control purposes when synthesizing silver nanowires through a chemical reaction In particular, it provides a method of manufacturing a transparent electrode that is environmentally friendly and has reduced process cost through the process of recovering silver from waste scrap, synthesizing silver nanowires, and manufacturing it as an electrode.

In the present invention, silver particles were first recovered from waste scrap. The scrap contained Cu, Ag, Si, and Al metals, and all metals except aluminum were dissolved by leaching them in nitric acid. After that, hydrochloric acid was added to induce a double substitution reaction and leached using the low solubility of silver chloride (AgCl). After that, the AgCl particles obtained were reduced to Ag particles, and then leached in nitric acid to obtain silver nitrate (AgNO _{3 )} . Then, silver nanowires were synthesized using _{AgNO 3} as a precursor by a bottom-up method. The nanowire thus obtained was coated on a PET film using a spray coating technique, and the conductivity of the prepared electrode was measured. After that, in order to improve the electrical conductivity of the applied thin-film silver nanowires, the PVP capping agent present on the surface of the nanowires is decomposed and peeled off to increase the contact area between the silver nanowire particles, thereby inducing more active current movement. The principle was applied. Accordingly, in the present invention, a 0.03% basic mixed aqueous solution is directly sprayed on the surface of the applied silver nanowire thin film on the surface, and then a chemical reaction is induced to remove the PVP surfactant present on the surface, thereby the contact area between the Ag nanowires. As a result, it was possible to manufacture an improved electrode that lowered the surface resistivity and can transmit current more smoothly and quickly.

The manufacturing method of the transparent conductive electrode film according to the present invention is viewed step by step, comprising the steps of: a) reducing silver nitrate (AgNO ₃ ) by a polyol process using a reducing solvent containing a capping agent to prepare silver nanowires; b) dispersing the silver nanowires in a solvent and depositing them on a film; c) removing the solvent by drying the film on which the silver nanowires are deposited; and d) spraying a basic solution on the surface of the film to modify the surface.

At this time, the basic solution that can be used is preferably sodium hydroxide (NaOH), potassium hydroxide (KOH), or a mixed aqueous solution thereof, but is not limited thereto, and any basic solution capable of removing the capping agent or surfactant can be used. can When sodium hydroxide (NaOH), potassium hydroxide (KOH), or a mixed aqueous solution thereof is used as the basic solution, the appropriate concentration for spraying the electrode surface is preferably in the range of 0.01% w/v to 0.05% w/v, and 0.028% w/v More preferably, it is in the range of v to 0.03% w/v. When spraying an aqueous solution exceeding this concentration, there is an effect of reducing the resistance of the transparent electrode, but there is a risk of damaging a specific substrate (PET, Silicon, etc.) due to strong basicity.

In addition, in the present invention, the polyol solvent used for synthesizing silver nanowires serves as a solvent and a reducing agent, and usable reducing solvents include ethylene glycol, 1,2-propylene glycol, At least one selected from the group consisting of 1,3-propylene glycol, glycerin, glycerol, glucose, isosorbide, and polypropylene glycol, Among them, ethylene glycol is generally oxidized to glycol aldehyde easily at low cost and high temperature and has a strong reducing power.

In addition, a capping agent is used in the synthesis of silver nanowires of the present invention, and since the capping agent serves to prevent the coalescence of nuclei in the initial growth stage of the nanowire, it is very useful for controlling the shape and size of nanoparticles. Examples of usable capping agents include at least one selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylamide (PAA), etc., but is not particularly limited thereto, All common capping agents used in the polyol process can be used. Among them, polyvinylpyrrolidone (PVP) is more preferable because it serves as a binder that enables anisotropy by preferentially binding to the side surface of the grown nanowire.

Meanwhile, in the polyol process for synthesizing silver nanowires, a process method of adding an additive (mediated agent) is called a mediated agent process method, and a process method without adding an additive is called a self-seeding process method. was synthesized. In this case, the usable additives may _{be selected from the group consisting of halogen catalysts such as FeCl 3} , NaCl, AgCl, CuCl ₂ and the like, but is not limited thereto, and various additives used in the polyol process may be used.

In addition, the present invention is environmentally friendly and economical in that the silver nanowires used for the production of the transparent conductive electrode film are synthesized using silver directly recovered from waste scrap. Specifically, i) leaching the waste scrap into nitric acid, ii) adding hydrochloric acid after the leaching to obtain silver chloride (AgCl), iii) reducing the silver chloride (AgCl) to obtain silver (Ag) particles, iv ) are is by obtaining a silver nitrate (AgNO ₃₎ by leaching the particles (Ag) nitrate is produced of silver nitrate (AgNO ₃₎ required for nanowire synthesis.

The silver nanowire prepared in the present invention can be used as a conductive transparent electrode by depositing it on a PET film. In the manufacture of such a transparent electrode, there are also various methods for coating the nanowires on the film, representatively spin-coating method, spray coating method, doctor blading method, sputtering method, vacuum deposition method, etc. There is a difference in the deposited characteristics and shape for each process method, and the spray coating method is more preferable because it has a low process cost and easy operation, and it is very easy to control the deposition thickness during particle deposition.

Hereinafter, the present invention will be described in more detail through specific examples. However, the following examples are provided by way of illustration to help the understanding of the present invention, and the scope of the present invention should not be construed as being limited thereto.

Example 1: from waste scrap silver (Ag) recovery process

In this embodiment, a process for recovering Ag from waste scrap containing Ag was first performed. [Table 1] below describes the formulas showing the chemical reactions in each step. Scrap containing Cu, Al, Si, Ag was _{leached in nitric acid (HNO 3} , 70%, DAEJUNG) to dissolve Cu, Si, and Ag (Equation 1) and then reacted with hydrochloric acid (HCl, 35%, DAEJUNG) By inducing a double substitution, AgCl with very low solubility was leached (Equation 2). After dissolving the recovered AgCl using ammonia water (NH ₄ OH, 25-28%, DAEJUNG) (Equation 3), hydrazine (N ₂ H ₄ , DAEJUNG) was reduced to Ag particles using a reducing agent (Equation 4) After leaching and dissolving in nitric acid in a supersaturated state at a temperature of 90°C, the temperature was reduced to 25°C _{to synthesize crystallized AgNO 3} (Equation 5). 1 shows the results of XRD analysis of waste scrap (left) and XRD analysis results of leached AgCl particles (right).

One Ag + HNO ₃ → AgNO ₃ + NO ₂ + H ₂ O 2 AgNO ₃ + HCl → AgCl + HNO ₃ 3 AgCl + 2 NH ₄ OH → Ag(NH ₃ ) ₂ Cl + 2 H ₂ O 4 N ₂ H ₄ + Ag(NH ₃ ) ₂ Cl → Ag 5 Ag + HNO ₃ → AgNO ₃ + NO + 2 H ₂ O

Example 2: silver of nanowires synthesis

Silver nanowires were synthesized through a polyol process. As a precursor, the recovered silver nitrate (Silver nitrate, AgNO ₃ ) was used to induce nanowire growth, and the process is as follows.

In 100 ml of ethylene glycol (99.0%), 55K and 360K polyvinylpyrrolidone (PVP, Aldrich) of 0.027M, respectively, was injected and dissolved. At this time, ethyl glycol was used as a reducing agent and solvent, and PVP was used as a capping agent and binder. The use of PVP is a necessary step in synthesizing silver nanowires, and it is useful for controlling the shape and size of nanoparticles because it prevents the coalescence of nuclei in the initial growth stage of nanowires. It also serves as a binder that enables anisotropy by preferentially binding to the side of the

The length of the chain varies depending on the molecular weight of PVP. PVP with high molecular weight is mainly used for wire synthesis. By doing so, it is preferable to add two kinds of PVP having different molecular weights, since it induces bonding with the side surface of the silver nanowire and can prevent the side growth of the wire.

In an ethyl glycol solution in which PVP is dissolved, AgNO _{3 0.023M as a precursor and FeCl 3} (Aldrich, 99%) 40 μM as a mediated agent are used to induce the growth of silver nanoparticles wire. First, FeCl ₃ was first dissolved in the solution, and then AgNO ₃ was dissolved. Thereafter, the reaction was stirred at 130° C. for 8 hours, and then the precipitated silver nanowires were recovered using a centrifuge. Thereafter, it was washed again using a centrifuge using distilled water, and after washing with ethanol, the nanowires dispersed in ethanol were dried to a weight ratio of 2 wt%.

2 shows an SEM analysis image (left) taken in the intermediate stage of synthesizing silver nanowires of this embodiment and an SEM analysis image (right) taken after wire synthesis.

Example 3: Preparation of transparent conductive electrode film

The silver nanowires prepared in Example 2 may be deposited on a PET film and used as a conductive transparent electrode. In this example, after diluting the prepared nanowires in ethanol at a weight ratio of 2 wt%, spraying and depositing them on the deposition film using a spray coating technique, and then drying in a drying oven at a temperature of about 45° C. for about 15 minutes to remove the solvent. removed. The deposited nanowire film was checked for electrical conductivity by measuring the resistance of the surface using a multimeter measuring device. At this time, it was difficult to achieve a very uniform coating due to the nature of the spray coating, so the resistance of the silver nanowire film was confirmed by measuring the resistance of 5 to 10 times on one film using a multimeter measuring instrument and averaging it.

Example 4: Basic solution spray experiment and surface resistance measurement result

The film on which the silver nanowires are deposited has high transparency, flexibility, and electrical conductivity as a transparent electrode and is already used in many industries. could Referring to the SEM analysis image (FIG. 3) of the deposited nanowires on the film, it can be seen that the nanowires are irregular and deposited in various directions. As such, the PVP surfactant injected for shape control in the combination of such a wide and large cross-sectional area and irregular nanowires is deposited on the surface of the nanowires, so the contact area between the silver nanowires is very low, and as a result, the resistance of the electrode surface is expected to be high. It was predicted. Therefore, since the silver (Ag) contact area between the wires is substantially reduced due to the PVP structure surrounding the wire particles, smooth movement of electrons between the wires is inevitably difficult.

To solve this problem, a solution capable of inducing a chemical reaction is sprayed directly onto the surface on which the wire is deposited to remove and decompose the existing PVP to increase the surface contact area, thereby lowering the surface resistance of the electrode. An experiment was conducted for Various aqueous solutions were sprayed on the electrode surface, and an experiment was performed according to the following procedure to measure the effect thereof.

1. Spray on the coated film surface using various sprays. The aqueous solution sprayed to improve the electrode surface conductivity performance is shown in [Table 2] below.

reagent name molecular formula density Sodium Hydroxide NaOH 0.028% (7.144mM) Potassium Hydroxide KOH 0.03% (5.917 mM) Sodium Hydroxide + Potassium Hydroxide NaOH + KOH Mix NaOH and KOH 1:1

2. For each experimental step, perform the washing step using distilled water and ethanol separately.

3. Dry the distributed solution in a dry oven for 15 minutes.

4. Measure and compare the coating film surface resistance using a multimeter.

As a result of the experiment, it was confirmed that when an aqueous solution of potassium hydroxide and sodium hydroxide was directly sprayed on the electrode surface, the surface resistance value of the electrode was effectively reduced. [Fig. 4] shows an SEM analysis image of the electrode surface after application of an aqueous solution of potassium hydroxide, and [Fig. 5] shows an image of an SEM analysis of the surface of an electrode after application of an aqueous solution of sodium hydroxide. As a result of surface analysis through SEM, it was confirmed that there was no difference in the shape change of the nanowires before and after solution application.

Meanwhile, as a result of analyzing the resistance of the coated electrode surface using a multimeter, it was confirmed that the resistance was significantly reduced compared to that of the uncoated electrode, and both aqueous solutions of sodium hydroxide and potassium hydroxide showed similar resistance reduction effects. The following [Table 3] shows the surface measured resistance values before and after the sodium hydroxide aqueous solution treatment, [Table 4] shows the surface measured resistance values before and after the potassium hydroxide aqueous solution treatment, and [Table 5] shows the measured resistance values of sodium hydroxide and potassium hydroxide The surface measurement resistance values before and after the mixed aqueous solution treatment are shown.

solution number before processing after processing result Sodium Hydroxide
(7.144 mM) One 4 kΩ 171.6 Ω 96% reduction 2 4.64 kΩ 233.3 Ω 95% reduction 3 1.62 MΩ 245.6 Ω 99% reduction 4 0.767 MΩ 171.5 Ω 99% reduction 5 1.69 MΩ 254.9 Ω 99% reduction Average Avg 817.128 kΩ 215.38 Ω 99% reduction

solution number before processing after processing result Potassium Hydroxide
(5.917 mM) One 1.366 kΩ 126 Ω 91% reduction 2 3.45 kΩ 140 Ω 96% reduction 3 0.776 kΩ 139 Ω 82% reduction 4 3.81 kΩ 134.4 Ω 97% reduction 5 0.84 kΩ 66.7 Ω 92% reduction Average Avg 2.046 kΩ 121.22 Ω 94% reduction

solution number before processing after processing result Sodium Hydroxide (7.144 mM) + Potassium Hydroxide (5.917 mM) One 154 kΩ 6.20 kΩ 96% reduction 2 170.5 kΩ 9.82 kΩ 95% reduction 3 392 kΩ 7.03 kΩ 99% reduction 4 6050 kΩ 17.53 kΩ 99% reduction 5 4040 kΩ 5.87 kΩ 99% reduction Average Avg 2200 kΩ 9.29 kΩ 99% reduction

In addition, in order to compare the change in conductivity properties on the electrode during treatment with other types of solutions, measurements were made after spraying a non-basic solution and other solutions (distilled water, toluene). The following [Table 6] shows the surface measurement resistance values before and after the distilled water treatment, and the following [Table 7] shows the surface measurement resistance values before and after the toluene treatment.

solution number before processing after processing result Distilled Water One 0.55 MΩ 7.1 MΩ 11.9 times increase 2 0.39 MΩ 31.27 MΩ 79.2 times increase 3 3 MΩ 7.85 MΩ 1.6 times increase 4 1.34 MΩ 14.1 MΩ 9.5 times increase 5 0.81 MΩ 26.55 MΩ 31.7 times increase Average Avg 1.218 MΩ 17.374 kΩ 13.3 times increase

solution number before processing after processing result Toluene
(DAEJUNG, C ₆ H ₅ CH ₃ , 99.5%) One 61.7 Ω 43.5 Ω 29% reduction 2 47.5 Ω 33.3 Ω 29% reduction 3 66.8 Ω 32.7 Ω 51% reduction 4 57.4 Ω 44.6 Ω 22% reduction 5 52.7 Ω 30.2 Ω 42% reduction Average Avg 57.22 Ω 36.86 Ω 35% reduction

When measuring the electrode surface resistance, each step was measured 10 times within the same electrode, and the results were averaged and recorded. As a result, the electrode surface resistance of the electrodes treated with the strong alkaline aqueous solution was reduced by an average of 97.3% compared to before. On the other hand, in the case of distilled water, the resistance did not decrease, but increased on average by 13 times compared to the electrode resistance before treatment, and in the case of toluene aqueous solution, it was confirmed that the resistance decreased by 34%. When used, there is a risk of damaging the polymer substrate, and the effect of reducing resistance is insignificant compared to other solutions.

PVP is known to be soluble in water. In addition, there is a process method that removes the PVP polymer layers through a washing process using a centrifuge several times using not only water but also various solvents (chloroform, glycerin, IPA, methylene, etc.) It is reported that it is difficult to completely remove PVPs. However, as shown in the results of this example, when a strong basic aqueous solution is sprayed, it was confirmed that the remaining PVP is decomposed and separated more effectively than using general water, and the reason for this is as follows.

(1) Basic hydrolysis

PVP is a polymer with Pendant Lactam Group. Here, lactam means lactone that forms a cyclic amide, lactone is a molecule that has a carboxyl ester and amide bond, and Lactam group of PVP forms a molecular group attached to the backbone chain of a long molecule of pendant. When a strong alkaline solution penetrates the PVP bonding structure, the PVP undergoes hydrolysis in the internal bonding. PVP hydrolysis progressed was exhibit symptoms of decomposing a carbonyl bond C = O of the inner coupling wherein O is bonded because of the oxygen atom and the orbital bond energy: Ag ⁺ binding also from the PVP, which is the remaining naturally decomposes Ag are separated The bonding structure of PVP and Ag is shown in [Formula 1].

(2) Reaction according to difference in ionization tendency and difference in reduction potential

In the case of PVP remaining after the washing process, a weak bond is formed by orbital binding energy between ^{oxygen and Ag +} on the surface of the silver nanowire by the internal carbonyl group (C=O). [Table 8] shows standard reduction potential tables for Ag, Na, and K.

Half-Reaction Standard Potential(v) Ag ^{2 +} + e ^- → Ag ⁺ 1.99 Na ⁺ + e ^- → Na -2.71 K ⁺ + e ^- → K -2.92

As such, silver shows a dominant tendency in reducing properties, and according to the ionization tendency table, potassium and sodium have a much higher ionization tendency than silver. Therefore, Ag ^+, which is a combination and when the injection of potassium hydroxide or sodium hydroxide to the electrode surface by passing the ionization tendency is high K or Na E to Ag ⁺ PVP receives the electronic was, wherein ions there is a reduction to Ag ⁰ Ag is decomposed with an oxygen atom, and K ⁺ ions, which are highly reactive with oxygen, are combined, so that the remaining PVP is separated from the silver nanowire, and the resistance of the silver nanowire itself is inevitably lowered.

In addition, it was confirmed that the conduction efficiency was higher by performing an additional PVP removal operation through additional drying and washing operations using distilled water and ethanol as well as spraying the aqueous solution. In addition, even considering the case where the remaining PVP is not completely removed by this process, it has the characteristic of improving the ionic conductivity under the influence of ^{K +} or Na ^{+ bonded to PVP instead of Ag, so the electrical conductivity of PVP itself is reduced.} There is also the possibility of contributing to the improvement of the conductivity of the overall silver nanowire electrode as a result of increasing the effect can be expected.

As described above, in the present invention, Ag was recovered from waste scrap in an environmentally friendly manner _{, synthesized up to AgNO 3} , and using this as a precursor, silver nanowires were synthesized through a polyol process. The nanowires synthesized in this way were sprayed onto the PET film by spray spraying and then coated to make a transparent electrode. After the washing process, the PVP, which remained in a small amount by bonding to the surface of the silver nanowires, was mixed with strong alkaline solutions potassium hydroxide, sodium hydroxide, and potassium hydroxide. A mixed aqueous solution of sodium hydroxide was sprayed to cause PVP hydrolysis, and at the same time, an elemental bond substitution reaction was induced by inducing ionization and reduction by the sprayed solution to separate the remaining PVP from the silver nanowires. Since the PVP-decomposed silver nanowire itself lost resistance (PVP) in the movement of current itself, it was predicted that the electrode electrical conductivity would be improved, and this was confirmed as a result of the experiment. In addition, there is an advantage that is not limited to the type of the electrode substrate and the shape of the metal particles used in the present invention, there is an advantage that the cost is low compared to other processes.

Claims (9)

a) preparing silver nanowires by reducing _{silver nitrate (AgNO 3} ) by a polyol process using a reducing solvent including a capping agent;
b) dispersing the silver nanowires in a solvent and depositing them on a film;
c) removing the solvent by drying the film on which the silver nanowires are deposited; and
d) The surface of the film is selected from sodium hydroxide (NaOH), potassium hydroxide (KOH), or a mixed aqueous solution thereof, and a basic solution having a concentration in the range of 0.01% w / v to 0.05% w / v is sprayed to modify the surface A method of manufacturing a transparent conductive electrode film comprising the steps of. delete delete According to claim 1,
The reducing solvent of step a) is ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerin, glycerol, glucose, isobide, characterized in that at least one selected from the group consisting of polypropylene glycol A method for producing a transparent conductive electrode film. According to claim 1,
The capping agent is a method of manufacturing a transparent conductive electrode film, characterized in that at least one selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and polyacrylamide (PAA). According to claim 1,
The reduction solvent of step a) FeCl ₃ , AgCl, NaCl, CuCl ₂ Method of manufacturing a transparent conductive electrode film, characterized in that it further comprises one or more additives (mediated agent) selected from the group consisting of. According to claim 1,
The silver nitrate (AgNO ₃ ) is a method of manufacturing a transparent conductive electrode film, characterized in that it is prepared using silver recovered from waste scrap. 8. The method of claim 7,
The silver nitrate (AgNO ₃ ) is obtained by i) leaching the waste scrap into nitric acid, ii) adding hydrochloric acid after the leaching to obtain silver chloride (AgCl), iii) reducing the silver chloride (AgCl) to obtain silver (Ag) particles Obtaining a, iv) leaching silver (Ag) particles in nitric acid to obtain silver nitrate (AgNO ₃ ) Method for producing a transparent conductive electrode film, characterized in that prepared by the step. According to claim 1,
The method of depositing the silver nanowires on the film in step b) is a method of manufacturing a transparent conductive electrode film, characterized in that it is performed by a method selected from a spin coating method, a spray coating method, a doctor blading method, a sputtering method, and a vacuum deposition method .

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