KR102399432B1 - Hybrid structure including metal thin film layer coated on surface of conductive polymer structure and method of preparing the same - Google Patents

Abstract

The present application relates to a hybrid structure comprising a metal thin film layer coated on the surface of a conductive polymer structure, and a method for manufacturing the same.

Description

A hybrid structure comprising a metal thin film layer coated on the surface of a conductive polymer structure, and a method for manufacturing the same

The present application relates to a hybrid structure comprising a metal thin film layer coated on the surface of a conductive polymer structure, and a method for manufacturing the same.

With the rapid development of the information society, research is being conducted to apply a conductive polymer film having high electrical conductivity to various fields. For example, the conductive polymer film can be used in various applications such as transparent electrodes, solar cells, diodes, and thermoelectric devices. For this purpose, research on composite materials using metal nanostructures, conductive polymers, carbon structures, etc. is being actively conducted. The conductive polymer is lightweight, has high transparency, is a flexible material, and has several advantages in that it is easy to produce at a relatively low price. In general, a conductive polymer that conducts electricity is a polymer having a conjugated double bond as a main chain that does not dissolve well in general organic solvents and does not melt even thermally. The conductive polymer has been attracting attention for its electrochemical properties as a role of inhibiting oxidation and corrosion of metals in addition to conductivity from the early stage of development.

Among the conductive polymers, polyaniline, in particular, has received great attention because it is light, inexpensive, and stable in air, and is known to most effectively exhibit anti-oxidation and anti-corrosion functions. It is known that the conductive polymer forms a film with a polymer to cause anodic protection as a result of charge transfer between the metal and the polymer in addition to the simple barrier effect of suppressing oxidation and corrosion of the metal. As the metal is oxidized and the conductive polymer is reduced, the corrosion potential moves and anode protection is achieved. However, compared to metals, when the conductive polymer is actually applied, physical properties are deteriorated due to low thermal stability, the range of applications is limited due to relatively low electrical conductivity, and there are problems in insolubility and poor solubility in solvents.

The research results reported so far have adopted a method of coating a metal surface with a conductive polymer to block physical contact with oxygen and, at the same time, inhibit oxidation and corrosion by an electrochemical mechanism. If the above method is followed, it is effective in preventing oxidation and corrosion, but the polymer is coated on the metal, so the thermal and electrical conductivity, which is a characteristic of the metal, is lowered, and the processing temperature is increased to remove the polymer layer during sintering. . In addition, most nano-sized metals have various uses because the melting point decreases with size and the processing temperature is lowered to the level of the plastic processing temperature, but the above-mentioned oxidation and corrosion problems follow. accompanied by serious problems.

Korean Patent Publication No. 10-2016-0147037

The present application relates to a hybrid structure comprising a metal thin film layer coated on the surface of a conductive polymer structure, and a method for manufacturing the same.

However, the problems to be solved of the present application are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application, (a) forming a conductive polymer structure; (b) primary reduction of the metal precursor by stirring a solution containing the conductive polymer structure, the metal precursor, a first reducing agent, and a dispersion solvent; (c) a hybrid structure comprising a metal thin film layer coated on the surface of the conductive polymer structure by coating the metal on the surface of the conductive polymer structure by secondary reduction of the firstly reduced metal precursor using a second reducing agent A method for preparing a hybrid construct is provided, comprising obtaining.

A second aspect of the present application provides a hybrid structure manufactured by the method for manufacturing the hybrid structure according to the first aspect.

In the manufacturing method of the hybrid structure according to the embodiments of the present application, the conductive polymer can be nano-dispersed by stirring the conductive polymer structure and the first reducing agent through a microfluidizer, and the conductive polymer structure is formed through the microfluidizer. When nano-dispersed, there is an effect of realizing excellent uniformity of the conductive polymer and metal particles in the prepared hybrid structure.

In the method for manufacturing a hybrid structure according to the embodiments of the present application, the yield of the hybrid structure is improved by improving the synthesis method by using a microfluidic device in which optimal conditions are set, and energy can be saved by lowering the sintering temperature. It works.

In the method for manufacturing a hybrid structure according to the embodiments of the present application, unlike the prior art, a metal thin film is uniformly coated on the surface of the conductive polymer structure by secondary reduction of the metal precursor using a second reducing agent. There is an effect that can improve the yield.

The method for manufacturing a hybrid structure according to the embodiments of the present application is to further perform sintering after coating a metal on the surface of the conductive polymer structure, and by identifying the optimum sintering temperature and time, a hybrid structure having a low surface resistance value It has the advantage of being able to manufacture

In the embodiments of the present application, the hybrid structure comprising a metal thin film layer coated on the surface of the conductive polymer structure is manufactured using a method of coating a metal on the surface of the conductive polymer structure by inhibiting further oxidation of the metal There is an effect that the oxidation resistance of the conductive polymer is improved.

Figure 1a, in one embodiment of the present application, is an image of polyaniline without MF treatment.
Figure 1b, in one embodiment of the present application, is an image of polyaniline treated MF 5 times.
Figure 1c, in one embodiment of the present application, is an image of polyaniline treated MF 10 times.
Figure 2 is, in an embodiment of the present application, before (left) adding hydrazine monohydrate (Hydrazine monohydrate) dropwise, after adding the hydrazine monohydrate (Hydrazine monohydrate) dropwise (right) is a photograph.
FIG. 3a is an FE-SEM image of a Copper PANI composite (70 parts by weight of a PANi structure and 30 parts by weight of copper, polymerization of EB at 10° C.) synthesized at 60° C. according to an embodiment of the present application.
3b is an FE-SEM image of a Copper PANI composite (70 parts by weight of a PANi structure and 30 parts by weight of copper, polymerization of EB at -10°C) synthesized at 80°C according to an embodiment of the present application.
FIG. 4a is a FE-TEM image of a Copper PANI composite (70 parts by weight of a PANi structure and 30 parts by weight of copper, polymerization of EB at 10° C.) synthesized at 60° C. according to an embodiment of the present application.
FIG. 4b is a FE-TEM image of a Copper PANI composite (70 parts by weight of a PANi structure and 30 parts by weight of copper, polymerization of EB at -10°C) synthesized at 80° C. according to an embodiment of the present application.
5 is, in one embodiment of the present application, XRD of the Copper PANI composite powder.
Figure 6a, in one embodiment of the present application, before the heat treatment of the copper PANI composite powder XRD.
Figure 6b is, in one embodiment of the present application, XRD after heat treatment of the Copper PANI composite powder.
Figure 7a, in one embodiment of the present application, copper PANI composite powder (using EB polymerized at 10 ° C, PANi structure 70 parts by weight and copper 30 parts by weight) by temperature (250 ° C., 280 ° C., 300 ° C., 320 ℃) is an image of pellet molding.
Figure 7b, in one embodiment of the present application, Copper PANI composite powder (using EB polymerized at 10 ° C, 70 parts by weight of PANi structure and 30 parts by weight of copper) by temperature (250 ° C., 280 ° C., 300 ° C., 320 ℃) is an image of pellet molding.
Figure 7c, in one embodiment of the present application, Copper PANI composite powder (using EB polymerized at -10 ℃, PANi structure 70 parts by weight and copper 30 parts by weight) by temperature (250 ℃, 280 ℃, 300 ℃, 320 ℃) is an image of pellet molding.
Figure 7d, in one embodiment of the present application, Copper PANI composite powder (using EB polymerized at -10 ℃, PANi structure 70 parts by weight and copper 30 parts by weight) by temperature (250 ℃, 280 ℃, 300 ℃, 320 ℃) is an image of pellet molding.
8a is an XRD image before sintering of the Copper PANI composite pellets in one embodiment of the present application;
8B is an XRD image of the Copper PANI composite pellets after sintering according to an embodiment of the present application.
9 is an SEM image of the pellet surface and the pellet cross-section before and after sintering, according to an embodiment of the present application.

Hereinafter, embodiments and implementations of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily carry out. However, the present application may be embodied in several different forms and is not limited to the embodiments and examples described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout this specification, when a part is "connected" with another part, this includes not only the case where it is "directly connected" but also the case where it is "electrically connected" with another element interposed therebetween. do.

Throughout this specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout this specification, when a part "includes" a certain element, it means that other elements may be further included, rather than excluding other elements, unless otherwise stated.

As used herein, the terms "about," "substantially," and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and to aid in the understanding of the present application. It is used to prevent an unconscionable infringer from using the mentioned disclosure in an unreasonable way.

As used throughout this specification, the term “step of doing” or “step of” does not mean “step for”.

Throughout this specification, the term "combination(s) of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, reference to “A and/or B” means “A or B, or A and B”.

Hereinafter, embodiments and examples of the present application will be described in detail with reference to the accompanying drawings. However, the present application is not limited to these embodiments and examples and drawings.

A first aspect of the present application, (a) forming a conductive polymer structure; (b) primary reduction of the metal precursor by stirring a solution containing the conductive polymer structure, the metal precursor, a first reducing agent, and a dispersion solvent; (c) a hybrid structure comprising a metal thin film layer coated on the surface of the conductive polymer structure by coating the metal on the surface of the conductive polymer structure by secondary reduction of the firstly reduced metal precursor using a second reducing agent A method for preparing a hybrid construct is provided, comprising obtaining.

In one embodiment of the present application, in step (a), the conductive polymer structure may include a conductive polymer in the form of an emeraldine base. The emeraldine base is a structure represented by the following formula (1):

[Formula 1]

.

.

In the above formula, x and y are the mole fractions of the quinonediamine structure and the methylenediamine structural unit, respectively, x is an integer from 0 to 1.0, y is an integer from 0 to 1, x+y=1 is satisfied, and n is an integer greater than or equal to 1.

In one embodiment of the present application, the conductive polymer structure may have any possible shape such as a spherical shape, an oval shape, a rod shape, a nanorod, a nanoneedle, or a nanofiber (fiber).

In one embodiment of the present application, the conductive polymer structure may include a conductive polymer selected from polyaniline, polypyrrole, polythiophene, poly(3,4-ethylene dioxythiophene), polyacetylene, and combinations thereof. , but is not limited thereto. Specifically, polyaniline has received great attention because it is light, inexpensive, and stable in air compared to metals, and it most effectively exhibits a corrosion-preventing function among conductive polymers.

In one embodiment of the present application, the metal precursor may include one selected from Fe compound, Cu compound, Ag compound, Cr compound, Mn compound, Co compound, Ni compound, Ga compound, and combinations thereof. It is not limited. Specifically, the metal precursor may include a Cu compound, and the Cu compound may include copper(II) nitrate trihydrate, copper(I) chloride, copper(II) chloride, copper(I) iodide, and copper nitrate. rate, copper sulfate, copper acetate, copper cyanide, and combinations thereof. Specifically, the metal precursor may include copper (II) nitrate trihydrate. Copper is very useful because of its low price and high conductivity, but as it becomes finer in nano size, it is easily oxidized in air, so its use is extremely limited, so the effect of the present invention can be maximized.

In one embodiment of the present application, before the step (b), it may further include pretreatment of the conductive polymer structure, but is not limited thereto.

In one embodiment of the present application, the material used for pretreatment of the conductive polymer structure is polyethylene glycol, sodium polyacrylate, polyvinylpyrrolidone, poly(vinyl cap). lactam) (poly(vinyl caprolactam)), poly(sodium 4-styrenesulfonate), SnCl2, PdCl2, and combinations thereof. not. The pretreatment material controls the coating range of the metal thin film layer of the hybrid structure and keeps the dispersion solvent stable.

In one embodiment of the present application, the first reducing agent used in step (b) is a polyhydric alcohol including ethylene glycol, diethylene glycol, propylene glycol, butanediol or pentanediol, ascorbic acid, glycine, di -malic acid (di-malic acid), sodium tartrate (sodium tartrate), ammonium acetate (ammonium acetate), and may include one selected from a combination thereof. Specifically, the first reducing agent may be ethylene glycol, and the ethylene glycol may help to form a uniform metal thin film layer.

In one embodiment of the present application, the dispersion solvent used in step (b) is ethylene glycol, water, acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, tetrahydrofuran, dimethylform In amide, dimethylacetamide, N-methyl-2-pyrrolidone, hexane, cyclohexanone, toluene, chloroform, distilled water, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, ethyl acetate, and combinations thereof It may include, but is not limited to. Specifically, the dispersion solvent may be the ethylene glycol, and the ethylene glycol may be used as a dispersion solvent to disperse the solution and at the same time be used as a first reducing agent.

In one embodiment of the present application, the ultrasonic treatment may be performed in step (b).

In one embodiment of the present application, in the step (b), the sum of the conductive polymer structure and the metal precursor: the content ratio of the first reducing agent may be about 1 mol: 0.5 to 12 mol. Specifically, the sum of the conductive polymer structure and the metal precursor: the content ratio of the first reducing agent is about 1 mol: 0.5 mol to 12 mol, about 1 mol: 0.5 mol to 10 mol, about 1 mol: 0.5 mol to 8 mole, about 1 mole: 0.5 moles to 6 moles, about 1 mole: 0.5 moles to 4 moles, about 1 mole: 0.5 moles to 2 moles, or about 1 mole: 1 mole to 2 moles. When the content of the first reducing agent is larger than the above range, the reduction proceeds excessively, and the properties of the conductive polymer in the hybrid structure become insignificant. can

In one embodiment of the present application, after stirring the conductive polymer structure and the first reducing agent through a microfluidizer in step (b), the metal precursor and the dispersion solvent may be added. .

In one embodiment of the present application, the microfluidic device may be performed at a pressure of about 10,000 psi to about 20,000 psi. For example, the microfluidic device may be from about 10,000 psi to about 20,000 psi, from about 10,000 psi to about 18,000 psi, from about 10,000 psi to about 16,000 psi, from about 12,000 psi to about 20,000 psi, from about 12,000 psi to about 18,000 psi, about 12,000 psi to about 16,000 psi, about 14,000 psi to about 20,000 psi, about 14,000 psi to about 18,000 psi, or about 14,000 psi to about 16,000 psi.

In one embodiment of the present application, the stirring in the microfluidic device may be performed about 1 to about 8 times. For example, the agitation in the microfluidic device is about 1 to about 8 times, about 1 to about 7 times, about 1 to about 6 times, about 2 to about 8 times, about 2 to about 7 times. about 2 to about 6 times, about 3 to about 8 times, about 3 to about 7 times, about 3 to about 6 times, about 4 to about 8 times, about 4 to about 7 times, or It may be performed about 4 times to about 6 times.

In one embodiment of the present application, in the method of manufacturing the hybrid structure of the present application, the conductive polymer may be nano-dispersed by stirring the conductive polymer structure and the first reducing agent through a microfluidizer, and the conductive polymer may be nano-dispersed through the microfluidizer. When the polymer structure is nano-dispersed, there is an effect of realizing excellent uniformity of the conductive polymer and the metal particles in the prepared hybrid structure.

In one embodiment of the present application, by using a microfluidic device in which optimal conditions are set, the yield of the hybrid structure manufactured by improving the synthesis method is improved, and energy can be saved by lowering the sintering temperature.

In one embodiment of the present application, in step (b), a surfactant may be additionally used. Specifically, the surfactant may be polyvinyl alcohol (PVA), polyivnylpyrrolidone (PVP), polyethylene imine (PEI), gelatin, dextrin, or albumin, but is not limited thereto.

In one embodiment of the present application, the second reducing agent used in step (c) is aqueous ammonia, sodium hydroxide, sodium hypophosphite (NaH ₂ PO) used as dedoping agents of the conductive polymer. ₂ ), sodium borohydride, hydrazine, and combinations thereof may be included.

In one embodiment of the present application, the second reducing agent may be hydrazine, and the hydrazine is hydrazine monohydrate, 1,1-dimethylhydrazine, monomethylhydrazine, or 1,2-bis(3,5-di- tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine (1,2-bis(3,5-di-tert-butyl-4-hydroxylhydrocinnamoyl)hydrzine), but is not limited thereto. Specifically, the hydrazine may be hydrazine monohydrate, and the hydrazine monohydrate serves to secondary-reduce copper ions.

In one embodiment of the present application, unlike the prior art, there is an effect of improving the yield of the hybrid structure in which the metal thin film is uniformly coated on the surface of the conductive polymer structure by secondary reduction of the metal precursor using a second reducing agent. there is.

In one embodiment of the present application, the metal thin film layer may be coated on a part or the entire surface of the conductive polymer structure, but is not limited thereto. For example, the metal thin film layer is about 10% to about 100%, about 20% to about 100%, about 30% to about 100%, about 40% to about 100%, about 50% of the surface of the conductive polymer structure. to about 100%, or from about 60% to about 100% may be coated, but is not limited thereto.

In one embodiment of the present application, the step of sintering after the step (c) may be further included.

In one embodiment of the present application, the sintering may be performed at a temperature of about 100 ℃ to about 400 ℃. For example, the sintering may be from about 100 °C to about 400 °C, from about 100 °C to about 380 °C, from about 100 °C to about 360 °C, from about 100 °C to about 340 °C, from about 100 °C to about 320 °C, about 140 °C to about 400 °C, about 140 °C to about 380 °C, about 140 °C to about 360 °C, about 140 °C to about 340 °C, about 140 °C to about 320 °C, about 140 °C to about 400 °C, about 140 °C to about 380 °C, about 140 °C to about 360 °C, about 140 °C to about 340 °C, about 140 °C to about 320 °C, about 160 °C to about 320 °C, about 180 °C to about 320 °C, about 200 °C to about 320 °C , from about 220 °C to about 320 °C, from about 260 °C to about 320 °C, from about 200 °C to about 300 °C, from about 220 °C to about 300 °C, or from about 260 °C to about 300 °C. The sintering is performed after coating a metal on the surface of the conductive polymer structure, and the method for manufacturing a hybrid structure according to the present invention has the advantage of being able to manufacture a hybrid structure having a low surface resistance value by identifying an optimal sintering temperature. there is.

In one embodiment of the present application, the sintering may be performed for about 5 minutes to 3 hours. Specifically, the sintering is about 5 minutes to 3 hours, about 5 minutes to 2 hours, about 10 minutes to 3 hours, about 10 minutes to 2 hours, about 30 minutes to 3 hours, about 30 minutes to 2 hours, or about 30 minutes. It may be performed in minutes to 1 hour. If the sintering time is longer than 3 hours or less than 5 minutes and is too long or short, the surface resistance may increase.

In one embodiment of the present application, in step (c), the sum of the conductive polymer structure and the metal precursor: the content ratio of the second reducing agent may be about 1 mol: about 0.5 mol to about 12 mol. Specifically, the sum of the conductive polymer structure and the metal precursor: the content ratio of the second reducing agent is about 1 mol: 0.5 mol to 12 mol, about 1 mol: 0.5 mol to 10 mol, about 1 mol: 0.5 mol to 8 mole, about 1 mole: 0.5 moles to 6 moles, about 1 mole: 0.5 moles to 4 moles, about 1 mole: 0.5 moles to 2 moles, or about 1 mole: 1 mole to 2 moles. When the content of the second reducing agent is larger than the above range, the reduction proceeds excessively, and the properties of the conductive polymer in the hybrid structure become insignificant. can The first reducing agent and the second reducing agent of the present application are sequentially administered in steps (b) and (c), respectively, and it is very important to control the content ratio of each, and the content of one reducing agent is too much compared to the other reducing agent or In a small case, there is a problem that the desired effect cannot be achieved.

A second aspect of the present application provides a hybrid structure manufactured by the method for manufacturing the hybrid structure according to the first aspect.

Accordingly, although detailed descriptions of parts overlapping with the first aspect of the present application are omitted, the contents described with respect to the first aspect of the present application may be equally applied even if the description thereof is omitted in the second aspect of the present application.

In one embodiment of the present application, the metal thin film layer may include a metal selected from Fe compounds, Cu compounds, Ag compounds, Cr compounds, Mn compounds, Co compounds, Ni compounds, Ga compounds, and combinations thereof. , but is not limited thereto.

In one embodiment of the present application, the metal thin film layer may be coated on a part or the entire surface of the conductive polymer structure, but is not limited thereto. For example, the metal thin film layer is about 10% to about 100%, about 20% to about 100%, about 30% to about 100%, about 40% to about 100%, about 50% of the surface of the conductive polymer structure. to about 100%, or from about 60% to about 100% may be coated, but is not limited thereto.

In one embodiment of the present application, the thickness of the metal thin film layer may be about 1 nm to about 300 nm. For example, the thickness of the metal thin film layer is about 1 nm to about 300 nm, about 10 nm to about 300 nm, about 20 nm to about 300 nm, about 40 nm to about 300 nm, about 60 nm to about 300 nm , about 80 nm to about 300 nm, about 100 nm to about 300 nm, about 120 nm to about 300 nm, about 140 nm to about 300 nm, about 160 nm to about 300 nm, about 180 nm to about 300 nm, about 200 nm to about 300 nm, about 220 nm to about 300 nm, about 240 nm to about 300 nm, about 260 nm to about 300 nm, or about 280 nm to about 300 nm.

In one embodiment of the present application, the metal thin film layer has oxidation resistance at a high temperature of about 100° C. or higher. For example, the metal thin film layer may have oxidation resistance at a high temperature of about 100° C. or more, about 150° C. or more, about 200° C. or more, about 250° C. or more, or about 300° C. or more, but is not limited thereto.

In one embodiment of the present application, the hybrid structure (EB-copper composite) may be included in a conductive ink filler, an electromagnetic wave shielding agent, a fuel cell separator, an electrode or a flexible electrode, a touch panel, a solar cell, etc., but is limited thereto not.

In one embodiment of the present application, the hybrid structure comprising a metal thin film layer coated on the surface of the conductive polymer structure is manufactured using a method of coating a metal on the surface of the conductive polymer structure by inhibiting further oxidation of the metal There is an effect that the oxidation resistance of the conductive polymer is improved.

Hereinafter, the present application will be described in more detail with reference to Examples, but the present application is not limited thereto.

[Example]

Example 1: Preparation of Polyaniline Emeraldine Base (EB; Emeraldine Base)

1) Reaction at 10°C

A cooling circulator was installed in a 1 L double jacketed reactor, 60 mL of a 1 M hydrochloric acid solution was put into the reactor, 0.025 mol (4 mL) of an aniline monomer was added thereto, and the mixture was stirred at 10° C. for 1 hour. To this, 300 mL of chloroform was added and dispersed. At this time, the aniline monomer-hydrochloride acted as a surfactant to obtain a stable first solution. As the second solution, 5.7 g (0.025 mol) of ammonium persulfate (APS) as an initiator was dissolved in 125 mL of a 1 M HCl solution and stirred for 1 hour. This was added dropwise to the first solution for 1 hour while stirring at 300 rpm. After all of the second solution was added dropwise, the reaction was allowed to proceed for an additional hour, and then the reaction was terminated and filtered through a 2 μm filter paper. The resulting polyaniline particles were washed 3 times with 1 M hydrochloric acid solution and then washed with methanol and water until the color no longer appeared, and this was stirred in 150 mL of 1 M aqueous ammonia solution for 24 hours to obtain EB (emeraldine base). , Emeraldine Base) was converted to the state. The EB was filtered and dried in a vacuum oven at 50° C. for at least 24 hours to obtain polyaniline EB.

2) Reaction at -10°C

A cooling circulator was installed in a 1 L double jacketed reactor, 60 mL of a 1 M hydrochloric acid solution was put into the reactor, 0.025 mol (4 mL) of an aniline monomer was added thereto, and then stirred at -10°C for 1 hour. Polyaniline EB was obtained in the same manner as in 1) except for stirring at -10°C.

Example 2: Metal film coating, polyol method

1.5% of the polyaniline EB particles prepared in Example 1 were added dropwise to ethylene glycol and then sonicated for two hours and stirred. Then, the stirred solution was nano-dispersed using a microfluidizer (MF, microfluidizer).

1 shows polyaniline after no treatment, 5 times treatment, and 10 times treatment using MF, respectively. As can be seen from FIG. 1a , polyaniline without MF treatment before dispersion is clustered like a bunch of grapes, but in FIG. 1b it can be seen that polyaniline treated with MF 5 times is nano-dispersed, FIG. 1c is polyaniline treated with MF 10 times It can be seen that the polyaniline is re-agglomerated like a bunch of grapes. Referring to this, it can be seen that it is most ideal for nano-dispersion of polyaniline to process the sonicated solution at 15,000 psi, 5 times using the MF.

The dispersed polyaniline/ethylene glycol solution and H ₂ 0 were stirred at a weight ratio of 1:1. During the stirring, the reaction temperature was raised to 60°C and 80°C, respectively. When copper (±) nitrate trihydrate was added to the solution and completely dissolved, PVP (MW 40,000) was added and stirred for 30 minutes for good dispersion. The copper (±) nitrate trihydrate was added so that the weight ratio of polyaniline:copper was 70:30 when compared to the polyaniline. Then, while maintaining the reaction temperature, hydrazine monohydrate was added dropwise for one hour. The solution was stirred for one hour after the dropwise addition. After completion of the reaction, the mixture was stirred at 5,000 rpm in a centrifuge for 10 minutes, and then washed three times with methanol. Thereafter, it was dried at 50° C. to obtain a copper-aniline (Cu-Aniline=Copper PANI) composite powder. At this time, the yield was 50% to 60%.

2 is a photograph before (left) adding hydrazine monohydrate dropwise, and after adding dropwise (right) of the hydrazine monohydrate (Hydrazine monohydrate).

Example 3: SEM and TEM analysis (particle size analysis)

FE-SEM analysis was performed for the analysis of the copper-aniline (Cu-Aniline=Copper PANI) complex synthesized using copper (±) nitrate trihydrate. 3a is an FE-SEM image of a Copper PANI composite synthesized at 60° C. (70 parts by weight of a PANi structure and 30 parts by weight of copper, polymerization of EB at 10° C.), and FIG. 3b is a Copper PANI composite synthesized at 80° C. FE-SEM image of (70 parts by weight of PANi structure and 30 parts by weight of copper, polymerization of EB at -10°C). Referring to FIG. 3 , it can be seen that the copper PANI composite surface obtained after synthesizing at 60° C. and 80° C., respectively, has a particle size of 1 μm or less and is well dispersed.

FE-TEM analysis was performed for the analysis of the copper-aniline (Cu-Aniline=Copper PANI) complex synthesized using copper (±) nitrate trihydrate. Figure 4a is a FE-TEM image of a Copper PANI composite synthesized at 60 ° C (70 parts by weight of a PANi structure and 30 parts by weight of copper, polymerization of EB at 10 ° C), Figure 4b is a Copper PANI composite synthesized at 80 ° C. FE-TEM image of (70 parts by weight of PANi structure and 30 parts by weight of copper, polymerization of EB at -10°C). Here, the copper-coated ones appearing as dark black and those with only PANI particles are faintly visible. That is, it can be confirmed that copper is well coated on the surface of the PANI through the FE-TEM image.

Example 4: Analysis of Oxidation and Oxidation Resistance

XRD was used to measure the oxidation properties of Copper PANI composites. 5 shows the XRD of the Copper PANI composite powder, and an oxidation peak such as copper oxide was not observed in the XRD. This means that after synthesis, the complex is not oxidized and is stable.

In order to measure the oxidation resistance of the Copper PANI composite, it was confirmed whether an oxidation peak was observed by measuring XRD after reacting at 85° C. for 16 hours using KS C 0221. FIG. 6A is an XRD of Copper PANI composite powder before heat treatment, and FIG. 6B is an XRD of Copper PANI composite powder after heat treatment. No oxidation peaks such as copper oxide were observed in the XRD of FIG. 6 , indicating improved oxidation resistance.

Example 5: Sintering Experiment

1 g of Copper PANI composite powder was pelletized at 15,000 pounds, 1 minute, and sintering was performed. The data obtained by sintering the pellets by temperature (150° C. to 300° C.) are shown in [Table 1].

[Table 1]

Referring to Table 1, it can be seen that the powder synthesized at 80°C using EB polymerized at -10°C among the Copper PANI composites shows the lowest surface resistance value. The higher the temperature, the lower the surface resistance value.

Figure 7a shows EB polymerized at 10 °C (using a wet reduction method at 60 °C to obtain a Cu-EB mixture of 70 parts by weight of a PANi structure and 30 parts by weight of copper) by temperature (250 °C, 280 °C, 300 °C, 320 °C) ), and FIG. 7b shows EB polymerized at 10° C. (using a wet reduction method at 80° C., to obtain a Cu-EB mixture of 70 parts by weight of a PANi structure and 30 parts by weight of copper) by temperature (250° C., 280 ℃, 300 ℃, 320 ℃) is an image of pellet molding. In addition, Figure 7c shows EB polymerized at 10 ° C (using a wet reduction method at 60 ° C to obtain a Cu-EB mixture of 70 parts by weight of a PANi structure and 30 parts by weight of copper) by temperature (250 ° C, 280 ° C, 300 ° C, 320 ° C.), and Figure 7d shows EB polymerized at -10 ° C (using a wet reduction method at 80 ° C, to obtain a Cu-EB mixture of 70 parts by weight of PANi structure and 30 parts by weight of copper) by temperature ( 250℃, 280℃, 300℃, 320℃) is an image of pellet molding.

8A is an XRD image of the Copper PANI composite pellets before sintering, and FIG. 8B is an XRD image of the Copper PANI composite pellets after sintering. As can be seen from FIG. 8b , it appears that a small amount of copper oxide is contained in XRD after sintering at 280° C. for 1 hour, which can be recognized as improved oxidation resistance.

9 is an SEM image of a pellet surface and a pellet cross section before and after sintering. As can be seen from FIG. 9 , in the pellet before SEM sintering, the Copper PANI particles are agglomerated but not connected.

The data obtained by sintering the pellets at each temperature (150° C. to 300° C.) and time (5 minutes to 2 hours) are shown in [Table 2].

[Table 2]

Table 2 shows the surface resistance according to the sintering conditions for each temperature (150° C. to 300° C.), and for each time (5 minutes, 10 minutes, 30 minutes, 1 hour, 2 hours). It can be seen that the surface resistance value decreases as the sintering temperature increases, and it can be confirmed that the effect is most excellent at around 280 °C. In addition, judging by the sintering time, it can be confirmed that the surface resistance value is rather increased when the sintering is performed indefinitely, so it can be confirmed that the optimal sintering time is about 1 hour.

The foregoing description of the present application is for illustration, and those of ordinary skill in the art to which the present application pertains will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and likewise components described as distributed may also be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims, and their equivalent concepts should be construed as being included in the scope of the present application. .

Claims (18)

(a) forming a conductive polymer structure;
(b) primary reduction of the metal precursor by stirring a solution containing the conductive polymer structure, the metal precursor, a first reducing agent, and a dispersion solvent;
(c) a hybrid structure comprising a metal thin film layer coated on the surface of the conductive polymer structure by coating the metal on the surface of the conductive polymer structure by secondary reduction of the firstly reduced metal precursor using a second reducing agent to obtain
A method for producing a hybrid structure comprising:
The first reducing agent is ethylene glycol, diethylene glycol, propylene glycol, butanediol or polyhydric alcohol including pentanediol, ascorbic acid, glycine, di-malic acid, sodium tartrate , to include those selected from ammonium acetate and combinations thereof,
The second reducing agent is selected from aqueous ammonia, sodium hydroxide, sodium hypophosphite (NaH ₂ PO ₂ ), sodium borohydride, hydrazine, and combinations thereof used as dedoping agents of the conductive polymer A method for producing a hybrid structure comprising being
The method of claim 1,
In the step (a), the conductive polymer structure comprises an emeraldine base (Emeraldine Base), the method for producing a hybrid structure.
delete The method of claim 1,
The method for producing a hybrid structure, wherein the ultrasonic treatment is performed in step (b).
The method of claim 1,
In the step (b), the sum of the conductive polymer structure and the metal precursor: the content ratio of the first reducing agent is 1 mol: 0.5 mol to 12 mol, the method for producing a hybrid structure.
The method of claim 1,
In the step (b), the conductive polymer structure and the first reducing agent are stirred through a microfluidizer, and then the metal precursor and the dispersion solvent are added, a method for producing a hybrid structure.
7. The method of claim 6,
The method for producing a hybrid structure, wherein the microfluidic device is performed at a pressure of 10,000 psi to 20,000 psi.
7. The method of claim 6,
Stirring in the microfluidic device will be performed 1 to 8 times, the method for producing a hybrid structure.
delete The method of claim 1,
The method for producing a hybrid structure, further comprising the step of sintering after step (c).
11. The method of claim 10,
The sintering is to be performed at a temperature of 100 ℃ to 400 ℃, the manufacturing method of the hybrid structure.
11. The method of claim 10,
Wherein the sintering is performed for 5 minutes to 3 hours, the method of manufacturing a hybrid structure.
The method of claim 1,
In step (c), the sum of the conductive polymer structure and the metal precursor: the content ratio of the second reducing agent is 1 mol: 0.5 mol to 12 mol, the method for producing a hybrid structure.
The method of claim 1,
The method for producing a hybrid structure, wherein the conductive polymer structure comprises a conductive polymer selected from polyaniline, polypyrrole, polythiophene, poly(3,4-ethylene dioxythiophene), polyacetylene, and combinations thereof.
The method of claim 1,
The metal precursor is a Fe compound, a Cu compound, an Ag compound, a Cr compound, a Mn compound, a Co compound, a Ni compound, a Ga compound, and a method for producing a hybrid structure comprising one selected from a combination thereof.
The method of claim 1,
Wherein the metal thin film layer is coated on a part or the entire surface of the conductive polymer structure, the hybrid structure manufacturing method.
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