KR102604581B1 - 3- dimensional polypyrrole film on metal surface and the method of synthesizing thereof - Google Patents

Abstract

One embodiment of the present invention involves an ion generation step of generating nitrosonium ions (NO ⁺ ) by supporting a metal material in an acid solution, and mixing a solution containing the generated nitrosonium ions and pyrrole monomer to carry out a polymer reaction. A method for manufacturing a polypyrrole film with a three-dimensional structure is provided, which includes a polymer reaction step.
According to one embodiment of the present invention, it is possible to manufacture a three-dimensional polypyrrole film on the surface of a target metal material in a short time without providing additional energy from outside the reaction system.

Description

Polypyrrole film with three-dimensional structure on a metal surface and its manufacturing method {3- DIMENSIONAL POLYPYRROLE FILM ON METAL SURFACE AND THE METHOD OF SYNTHESIZING THEREOF}

The present invention relates to a polypyrrole film with a three-dimensional structure on a metal surface and a method for manufacturing the same. More specifically, the present invention relates to a polypyrrole film with a three-dimensional structure using nitrosonium ions formed by the reaction of a metal material and dilute nitric acid and its production. It's about method.

In the field of energy production, as a solution to the depletion of fossil fuels and environmental problems, rechargeable batteries are presented as an alternative, either renewable energy or sustainable energy. Experiments were conducted on various metal materials as electrodes for these rechargeable batteries, but metal materials had disadvantages such as heat generation problems and electrochemical limitations.

Various attempts have been made to overcome this, but stacking functional layers on the surface of the metal electrode has been presented as the most promising strategy for reasons such as economic efficiency and diverse functions.

Polypyrrole is a material for which application development has been promoted since the 1980s, and is receiving great attention because it has superior conductivity performance (more than 1,000 S/cm) compared to polyaniline or polythiophene. It is a metal surface of pure polypyrrole. Phase deposition can maximize the properties of polypyrrole, so it is used in various fields such as energy, bio, and environment.

Conventionally, in order to deposit a polypyrrole film on a metal surface, a physical coating that mixes a polymer binder and polypyrrole, or a chemical method of electropolymerizing pyrrole by applying voltage or current and depositing it on the metal surface, is typically used. It has been done.

However, the above prior art had the disadvantage that a complex system had to be prepared in order to deposit impurities (polymer binder, etc.) or to apply voltage or current. Therefore, the simple method of deposition without special equipment increases industrial process efficiency. Improvements can be made and such methods are required.

Republic of Korea Patent Publication No. 2015-0059615

The technical problem to be achieved by the present invention is to provide a manufacturing method for forming a three-dimensional polypyrrole directly on a metal surface through a simple method without an energy source outside the reaction system, such as heat, electricity, or radioactive materials.

The technical problem to be achieved by the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned can be clearly understood by those skilled in the art from the description below. There will be.

In order to achieve the above technical problem, an embodiment of the present invention includes an ion generation step of generating nitrosonium ions (NO ⁺ ) by supporting a metal material in an acid solution; and a polymer reaction step of performing a polymer reaction by mixing a solution containing the generated nitrosonium ions and pyrrole monomer.

In an embodiment of the present invention, the metal material may be a method of manufacturing a polypyrrole film with a three-dimensional structure, characterized in that it contains a metal with a lower (negative) reduction potential than the standard reduction potential of cadmium.

At this time, the metal material may be a method of manufacturing a polypyrrole film with a three-dimensional structure, characterized in that it contains one or more of Zn, Fe, Cr, Mn, V, and Mg.

Additionally, in an embodiment of the present invention, the acid solution may be a method of producing a three-dimensional polypyrrole film, characterized in that it contains dilute nitric acid.

In addition, in an embodiment of the present invention, the solution containing the pyrrole monomer may be a method of producing a polypyrrole film with a three-dimensional structure, characterized in that it has a concentration of 0.3M to 0.7M.

In addition, in an embodiment of the present invention, in the ion generation step, the production of a three-dimensional polypyrrole film is characterized in that it does not include the step of adding energy from outside the reaction system to generate the nitrosonium ions. It could be a way.

In order to achieve the above technical problem, another embodiment of the present invention provides a polypyrrole film with a three-dimensional structure manufactured by an embodiment of the present invention.

In order to achieve the above technical problem, another embodiment of the present invention provides an electrode material including the polypyrrole film of the three-dimensional structure.

In order to achieve the above technical problem, another embodiment of the present invention provides a secondary battery including the electrode material.

According to an embodiment of the present invention, it is possible to manufacture polypyrrole with a three-dimensional structure on a metal surface simply and quickly, and it is possible to produce polypyrrole with a pure composition and large-area polypyrrole.

In addition, according to the present invention, the reaction can proceed within a short time of less than 3 minutes, and unlike other conventional techniques, it can have the effect of not requiring energy for the formation of polypyrrole.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

Figure 1 is a schematic diagram of a method for manufacturing a polypyrrole film with a three-dimensional structure, according to an embodiment of the present invention.
Figure 2 is a diagram illustrating a method for manufacturing a polypyrrole film with a three-dimensional structure according to an embodiment of the present invention.
Figure 3 is a diagram showing photographs taken in chronological order of the experimental process used in one embodiment of the present invention.
Figure 4 is a diagram showing a photograph taken by SEM of a polypyrrole film with a three-dimensional structure formed by varying the concentration of pyrrole monomer in Preparation Example 2 to 0.05M, 0.2M, 0.4M, 0.8M, and 1.0M.
Figure 5 is a photograph showing the experimental results of the comparative experiment of Comparative Example 1.
Figure 6 shows the results of FT-IR, XRD, and XPS analysis in Experimental Example 1.
Figure 7 is a diagram showing the results of SEM EDS analysis of a polypyrrole film with a three-dimensional structure manufactured according to an embodiment of the present invention.
Figure 8 is a picture showing an example when magnesium film and iron film were used as target metal materials, and a picture showing the results taken by SEM.
Figure 9 is a diagram showing the results of Experimental Example 3.

Hereinafter, the present invention will be described with reference to the attached drawings. However, the present invention may be implemented in various different forms and, therefore, is not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts that are not related to the description are omitted, and similar parts are given similar reference numerals throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, combined)" with another part, this means not only "directly connected" but also "indirectly connected" with another member in between. "Includes cases where it is. In addition, when a part is said to “include” a certain component, this does not mean that other components are excluded, but that other components can be added, unless specifically stated to the contrary.

The terms used herein are only used to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. As used herein, “comprises.” Or “to have.” Terms such as are intended to designate the presence of features, numbers, steps, operations, components, parts, or a combination thereof described in the specification, but are intended to indicate the presence of one or more other features, numbers, steps, operations, components, parts, or It should be understood that the existence or addition possibility of combinations of these is not excluded in advance.

Polypyrrole has excellent conductive performance (more than 1,000 S/cm) and is the most widely used conductive polymer. Deposition of pure polypyrrole on a metal surface can maximize the properties of polypyrrole and is used in various fields.

Conventionally, techniques for depositing a polypyrrole film on a metal surface had the disadvantage of requiring impurities to be deposited together or other complex systems to be prepared, so a simple method of deposition without special equipment is required.

Figure 1 is a schematic diagram of a method for manufacturing a three-dimensional polypyrrole film according to an embodiment of the present invention.

Figure 2 is a diagram illustrating a method for manufacturing a three-dimensional polypyrrole film according to an embodiment of the present invention. Below, an embodiment of the present invention will be described with reference to FIGS. 1 and 2.

The present invention provides a method for producing a three-dimensional polypyrrole film located on a metal surface, comprising the following three reaction steps.

At this time, the above three reaction steps are a method of depositing a polypyrrole film with a three-dimensional structure on a metal surface. The target metal material (M) to be laminated is supported in dilute nitric acid to generate nitrosonium ions ( A nitrosonium ion forming step (S100) to form ^NO It may include a polymerization reaction step (S300) of forming polypyrrole through a polymerization reaction with pyrrole monomer.

At this time, the reaction step can be performed through a one-step process. That is, the three reaction steps may proceed through a single process step of supporting the target metal material in a mixed solution of nitric acid and pyrrole monomer.

It is generally known that nitrosonium ions can induce the polymerization reaction of polypyrrole. The nitrosonium ions formed during the above process are generated on the surface of the target metal material by the reaction between the target metal material and nitric acid, ultimately The polypyrrole film with the three-dimensional structure can also be manufactured on the surface of the target metal material.

The nitrosonium ion forming step (S100) includes the step of reacting the target metal material (M) with dilute nitric acid to form hydrogen gas and nitrosonium ions, and the reaction formula is as shown in Reaction Formula 1 below.

[Reaction Formula 1]

1) M + 2HNO ₃ → M ²⁺ +2NO ₃ ^- +H ₂ ↑+2e ^-

2) NO ₃ ^- +3H ⁺ +2e ^- → HNO ₂ +H ₂ O

3) HNO ₂ +H ⁺ ↔ H ₂ NO ₂ ⁺ ↔ NO ⁺ +H ₂ O

In Scheme 1, a possible candidate metal material as the target metal material (M) is cadmium, which is a metal that can react with dilute nitric acid to form hydrogen gas (H ₂ ), considering the standard reduction potential. Metal materials such as Zn, Fe, Cr, Mn, V, Mg, etc., which have a lower reduction potential (negative) than (Cd), can be considered.

In addition, the concentration of the dilute nitric acid may range from 0.4M to 1.0M, and preferably, the formation of radical cations can easily occur at a concentration of 0.8M.

If the concentration of dilute nitric acid is less than 0.4M, the reaction does not start because sufficient acid is not provided, and if the concentration of dilute nitric acid exceeds 1.0M, NO ₂ rather than H ₂ gas is produced in the reaction with the metal. Alternatively, there is a problem that the initiator (NO ⁺ ) decreases due to the reaction of NO gas.

After the nitrosonium ion formation step (S100), the initiation step of the polypyrrole polymerization reaction (S200) and the polypyrrole formation step (S300) can be expressed as shown in Scheme 2 below, which is based on a radical polymerization reaction.

[Scheme 2]

1) Py + NO ⁺ → Py ^{+ .} +NO

2) Py ^{+ .} +Py ^{+ .} → Py-Py

3) Py-Py + NO ⁺ → Py-Py ^{+ .} +NO

4) Py ^{+ .} + Py-Py ^{+ .} → Py-Py-Py → … … → PPy

In addition, in the initiation step (S200), a method of reacting the pyrrole monomer with NO ⁺ may include a method of stirring a solution containing the pyrrole monomer and NO ⁺ . In this case, the solution containing the pyrrole monomer By controlling the concentration of pyrrole monomer in solution, the structure of polypyrrole can ultimately be controlled.

The reaction of the three-dimensional polypyrrole film manufacturing method is a manufacturing method using a radical polymerization reaction, and the entire reaction of the present invention can be completed within a short time of minutes or less, and unlike other technologies, the formation of polypyrrole requires no outside reaction system. No energy is required.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. However, the present invention is not limited to the following examples and experimental examples.

Manufacturing Example 1

In this Preparation Example 1, a polypyrrole film with a three-dimensional structure was manufactured using zinc (Zn), and a polypyrrole film with a three-dimensional structure was manufactured on the metal surface of zinc.

Figure 3 is a diagram showing photographs taken in chronological order of the experimental process used in one embodiment of the present invention. Hereinafter, Manufacturing Example 1 will be described with reference to FIG. 3.

In this Preparation Example 1, the prepared zinc (S10) was supported in a mixed solution of nitric acid and pyrrole monomers having a ratio of 0.8M (S20) to form nitrosonium ions, and the formed nitrosonium ions were present near the zinc surface. Let the pyrrole monomer become a radical cation. Accordingly, the radical cation undergoes a polymerization reaction with the nearby pyrrole monomer (S30), and the color of the solution changes as an oligomeric is formed. Finally, a three-dimensional polypyrrole film is formed on the zinc surface through a polymerization reaction (S50, S60) (S70).

Manufacturing example 2

In this Preparation Example 2, the concentration of dilute nitric acid was prepared at 0.8M, and the concentration of pyrrole monomer was adjusted to 0.05M to 1M to examine changes according to concentration.

Figure 4 is a diagram showing a photograph taken by SEM of a polypyrrole film with a three-dimensional structure formed by varying the concentration of pyrrole monomer in Preparation Example 2 to 0.05M, 0.2M, 0.4M, 0.8M, and 1.0M. Hereinafter, it will be described with reference to FIG. 4.

As can be seen from Figure 4, it can be seen that the structures of the three-dimensional polypyrrole film change as the concentration of pyrrole monomer is changed from 0.05M to 1.0M, and when 0.05M and 0.2M of pyrrole monomer are used, Although a polypyrrole film with a three-dimensional structure is not formed, it can be seen that a polypyrrole film with a three-dimensional structure is formed at 0.4M.

In addition, it can be seen that when 0.8M pyrrole monomer and 1.0M pyrrole monomer were used, a polypyrrole film was formed, but a polypyrrole film with a three-dimensional structure was not formed.

Comparative Example 1

In this Comparative Example 1, a comparative experiment was conducted to see whether a polypyrrole film with a three-dimensional structure is formed when either nitric acid, sulfuric acid, or hydrochloric acid is used as the acid solution in the method for producing a polypyrrole film with a three-dimensional structure of the present invention. proceeded.

Figure 5 is a photograph showing the experimental results of the comparative experiment of Comparative Example 1.

As can be seen from the results of experiments #1 and #2 in Figure 5, no polypyrrole film was found on the zinc surface when sulfuric acid or hydrochloric acid was used as the acid. On the other hand, as can be seen from the results of experiment #3 in Figure 5, a polypyrrole film with a three-dimensional structure was found on the zinc surface.

Experimental Example 1

In this Experimental Example 1, a three-dimensional polypyrrole film manufactured under the conditions of 0.8M dilute nitric acid, Zn metal foil, and 0.4M pyrrole monomer was chemically confirmed through FT-IR, XRD, and XPS analysis methods.

Figure 6 shows the results of FT-IR, XRD, and XPS analysis in Experimental Example 1, which will be described below with reference to Figure 6.

As can be seen from Figure 6, the polypyrrole film with a three-dimensional structure manufactured by an embodiment of the present invention has FT-IR results of 3422 cm ^-1 (-NH stretching), 1636 cm ^-1 , which confirms the formation of polypyrrole. 1542cm ^-1 (-CC and CC stretching in the Pyrrole ring), 1290cm ^-1 (CH and CN in-plane deformation), 1037cm ^-1 (CH and NH deformation), 1182cm ^-1 & 892cm ^-1 (doping states of PPy ) can be seen.

In the XRD analysis results, the formation of polypyrrole can be confirmed through a characteristic peak at 2θ of 24.3 degrees.

Through XPS analysis, it can be confirmed that polypyrrole on Zn metal has been well formed.

Experimental Example 2

In this Experimental Example 2, the cross-section of the polypyrrole film with a three-dimensional structure manufactured according to an example of the present invention was confirmed using SEM analysis equipment, and the elements of the polypyrrole film with a three-dimensional structure were analyzed through EDS.

Figure 7 is a diagram showing the results of SEM EDS analysis of a polypyrrole film with a three-dimensional structure manufactured according to an embodiment of the present invention. Hereinafter, description will be made with reference to FIG. 7.

As can be seen in Figure 7, it can be confirmed that the polypyrrole film with a three-dimensional structure prepared in Experimental Example 2 has a three-dimensional porous structure and was well formed on the Zn cathode.

Manufacturing example 3

In this Preparation Example 3, in an embodiment of the present invention, when not only zinc but also magnesium (Mg) and iron (Fe) were used as the target metal material, it was tested whether a polypyrrole film with a three-dimensional structure could be formed. .

Figure 8 is a picture showing an example when magnesium film and iron film were used as target metal materials, and a picture showing the results taken by SEM. Hereinafter, it will be described with reference to FIG. 8.

According to this manufacturing method 3, it was found that a polypyrrole film with a three-dimensional structure was manufactured on the metal surface even when magnesium and iron were used as the target metal materials. Through this Preparation Example 3, it can be seen that metals with a lower (negative) reduction potential than cadmium can be used to form a polypyrrole film with a three-dimensional structure.

Experimental Example 3

In this Experimental Example 3, a zinc metal material formed with a three-dimensional polypyrrole film manufactured in an example of the present invention was applied as an electrode of an aqueous zinc ion battery as a next-generation energy storage device, and a symmetric cell was manufactured to perform electrochemical analysis. Stability was confirmed using this method.

Figure 9 is a diagram showing the results of Experimental Example 3. Hereinafter, it will be described with reference to FIG. 9.

As can be seen from Figure 9, the polypyrrole film with a three-dimensional structure manufactured according to an embodiment of the present invention shows stable cycling despite repeated stripping/plating of Zn ions, thereby forming the corresponding Zn cathode. Even when applied as a battery, it can be seen that in addition to electrochemical stability, short-circuiting of the battery can be prevented by suppressing the formation of Zn dendrites on the cathode, ultimately confirming the stability of the battery.

The description of the present invention described above is for illustrative purposes, and those skilled in the art will understand that the present invention can be easily modified into other specific forms without changing the technical idea or essential features of the present invention. will be. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the patent claims described below, and all changes or modified forms 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 invention.

Claims (9)

An ion generation step of generating nitrosonium ions (NO ⁺ ) by supporting a metal material in an acid solution; and
A polymer reaction step of performing a polymer reaction by mixing a solution containing the generated nitrosonium ions and pyrrole monomer;
Characterized by including,
The metal material is characterized in that it contains a metal with a lower (negative) reduction potential than the standard reduction potential of cadmium,
The acid solution is characterized in that it contains dilute nitric acid,
A method of producing a polypyrrole film with a three-dimensional structure, characterized in that the solution containing the pyrrole monomer has a concentration of 0.3M to 0.7M. delete According to paragraph 1,
A method of manufacturing a polypyrrole film with a three-dimensional structure, wherein the metal material contains one or more of Zn, Fe, V, and Mg. delete delete According to paragraph 1,
In the ion generation step, a method of producing a three-dimensional polypyrrole film, characterized in that it does not include the step of adding energy from outside the reaction system to generate the nitrosonium ions. A polypyrrole film with a three-dimensional structure manufactured by the method of claim 1. An electrode comprising the polypyrrole film of claim 7 with a three-dimensional structure. A secondary battery comprising the electrode of claim 8.