KR102326739B1 - Flexible aluminum electrode based on textile materials and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a fabric-based flexible aluminum electrode and a method for manufacturing the same, and the fabric-based flexible aluminum electrode according to an embodiment of the present invention includes a porous substrate 10 formed by crossing a plurality of fibers 11; a bonding layer 20 formed on the surface of the fiber 11; A base comprising a nanoparticle layer 31 comprising metal nanoparticles and formed on the bonding layer 20, and a monomolecular layer 33 comprising a monomolecular material containing an _{amine group (NH 2 ) and formed on the nanoparticle layer 31} layer 30; and a plating layer 40 formed by electroplating aluminum (Al) on the base layer 30 .

Description

Fabric material-based flexible aluminum electrode and manufacturing method thereof

To a flexible aluminum electrode based on a textile material and a method for manufacturing the same, and more particularly, to a flexible electrode having excellent electrical and mechanical properties and workability by coating aluminum on a textile substrate, which is an insulator, and a method for manufacturing the same.

As interest in electronic devices that are portable and that can be worn directly on the body increases, the need for development of highly flexible electrodes having light and flexible mechanical properties is also increasing. In particular, such a highly flexible electrode must be able to maintain electrical conductivity even under various mechanical stresses (bending, stretching, twisting), and a long lifespan without degradation of performance is required even in various environments. In addition, the portable electrode should be lightweight while implementing high electrical conductivity, and furthermore, when applied as an electrode of an energy storage device, it should be able to implement a high ion flux in order to exhibit high performance.

A general flexible electrode is manufactured by forming an electrode material having high electrical conductivity on a substrate, and as an electrode material currently in the spotlight, graphene, carbon nanotube, There are carbon materials such as CNT), metal wires, and conductive polymers. Such an electrode material may secure high electrical conductivity per area due to a structural feature having a large area, and may have mechanical flexibility. However, in order to reduce the loss of electrical conductivity, synthesis at a high temperature is required, and the process is complicated, takes a long time, and requires a chemical reduction reaction for additional strong bonding, and has disadvantages in terms of cost.

Therefore, there is a demand for the development of electrodes that can expect high electrical properties through a simple and fast process while maintaining flexible mechanical properties.

US 10-2012-0042777 A

The present invention is to solve the problems of the prior art described above, and one aspect of the present invention is a fabric material-based flexible aluminum electrode in which aluminum is uniformly coated with high packing density by employing an electroplating method on a porous insulating fabric material substrate. and to provide a method for manufacturing the same.

A fabric-based flexible aluminum electrode according to an embodiment of the present invention includes: a porous substrate formed by crossing a plurality of fibers with each other; a bonding layer formed on the surface of the fiber; a base layer comprising a nanoparticle layer comprising metal nanoparticles and formed on the bonding layer, and a monomolecular layer comprising a monomolecular material containing an _{amine group (NH 2 ) and formed on the nanoparticle layer;} and a plating layer formed by electroplating aluminum (Al) on the base layer.

In addition, in the fabric-based flexible aluminum electrode according to an embodiment of the present invention, the fibers may include any one or more selected from the group consisting of polyester, nylon and acrylic fibers.

In addition, in the fabric-based flexible aluminum electrode according to an embodiment of the present invention, the bonding layer may include an amine group (NH ₂ )-containing polymer material.

In addition, in the flexible aluminum electrode based on a fabric material according to an embodiment of the present invention, the polymer material may include any one or more selected from the group consisting of polyethylenimine (PEI), and poly(allylamine)hydrochloride (PAH). have.

In addition, in the fabric-based flexible aluminum electrode according to an embodiment of the present invention, the metal nanoparticles may include any one or more selected from the group consisting of Au, Ag, Al, Cu, and Pt.

In addition, in the flexible aluminum electrode based on a fabric material according to an embodiment of the present invention, the monomolecular material is tris(2-aminoethyl)amine (TREN), propane-1,2,3-triamine, diehthylenetriamine (DETA), It may include any one or more selected from the group consisting of tetrakis (aminomethyl) methane, and methanetetramine.

In addition, in the fabric-based flexible aluminum electrode according to an embodiment of the present invention, a plurality of the base layer may be sequentially stacked.

In addition, in the fabric-based flexible aluminum electrode according to an embodiment of the present invention, the base layer may have a sheet resistance of 10 ⁰ to 10 ⁴ Ω/sq.

In addition, in the flexible aluminum electrode based on a fabric material according to an embodiment of the present invention, at least two or more of the plurality of base layers may be made of a material different from each other at least one or more of the nanoparticle layer and the monomolecular layer. .

On the other hand, in the method for manufacturing a fabric material-based flexible aluminum electrode according to an embodiment of the present invention, (a) a porous substrate formed by crossing a plurality of fibers with each other is immersed in a first dispersion in which a polymer material is dispersed, forming a bonding layer on the surface; (b) forming a nanoparticle layer by immersing the substrate on which the bonding layer is formed in a second dispersion in which the metal nanoparticles are dispersed; (c) immersing the substrate on which the nanoparticle layer is formed in a third dispersion in which an amine group-containing monomolecular material is dispersed to form a monomolecular layer; and (d) electroplating aluminum (Al) to form a plating layer on the monomolecular layer.

In addition, in the method for manufacturing a fabric-based flexible aluminum electrode according to an embodiment of the present invention, before the step (d), the steps (b) and (c) are sequentially repeated at least a plurality of times, the nano A plurality of conductive layers in which the monomolecular layer is laminated may be laminated on the particle layer.

The features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings.

Prior to this, the terms or words used in the present specification and claims should not be construed in a conventional and dictionary meaning, and the inventor may properly define the concept of the term to describe his invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

According to the present invention, a lightweight and human-friendly flexible electrode is realized by simply and quickly coating aluminum on an insulator substrate made of a textile material having high flexibility by means of an electroplating method, and at the same time, it is possible to improve the electrical conductivity, mechanical strength, and workability of the electrode. can

In addition, since the electrode manufactured according to the present invention has high bonding force between particles and at the same time has numerous pores inherent to the fabric material, high ion mobility and driving stability can be secured when used as a current collector for an energy storage device. Aluminum has superior electrical conductivity compared to other metals in terms of price and mass, and has excellent stability at high voltage, so it can be applied to the positive electrode current collector of a battery.

Furthermore, the electrode manufactured according to the present invention can be applied not only to an energy storage device, but also to various electrical devices that require light weight and high flexibility. does not

1 to 2 are perspective views schematically showing a fabric-based flexible aluminum electrode according to an embodiment of the present invention.
3 is a cross-sectional view taken along line A-A' of FIG. 2 of a fabric-based flexible aluminum electrode according to another embodiment of the present invention.
4 is a process diagram of a method for manufacturing a fabric-based flexible aluminum electrode according to an embodiment of the present invention.
5 is a process diagram of a method for manufacturing a fabric-based flexible aluminum electrode according to another embodiment of the present invention.
6A is an SEM image of an electrode manufactured according to an embodiment of the present invention.
6B is an EDS mapping image of an electrode manufactured according to an embodiment of the present invention.
7 is a graph showing a change in sheet resistance of an electrode manufactured according to an embodiment of the present invention.
8A to 8B are mechanical stability test results of electrodes manufactured according to an embodiment of the present invention.
9A to 9B are graphs of electrochemical characteristics evaluation results of an energy storage element (battery) to which an electrode manufactured according to an embodiment of the present invention is applied.

The objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings and preferred embodiments. In the present specification, in adding reference numbers to the components of each drawing, it should be noted that only the same components are given the same number as possible even though they are indicated on different drawings. Also, terms such as “first” and “second” are used to distinguish one component from another, and the component is not limited by the terms. Hereinafter, in describing the present invention, detailed descriptions of related known technologies that may unnecessarily obscure the gist of the present invention will be omitted.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 to 2 are perspective views schematically showing a fabric-based flexible aluminum electrode according to an embodiment of the present invention.

1 to 2, the fabric-based flexible aluminum electrode according to an embodiment of the present invention includes a porous substrate 10 in which a plurality of fibers 11 are crossed with each other; a bonding layer 20 formed on the surface of the fiber 11; A base comprising a nanoparticle layer 31 comprising metal nanoparticles and formed on the bonding layer 20, and a monomolecular layer 33 comprising a monomolecular material containing an _{amine group (NH 2 ) and formed on the nanoparticle layer 31} layer 30; and a plating layer 40 formed by electroplating aluminum (Al) on the base layer 30 .

The present invention relates to a flexible electrode. Recently, as wearable electronic devices that can be directly worn on the body are developed, the need for highly flexible electrodes is increasing. . In addition, a long lifespan without degradation of performance is required in various environments, and in order to be used as an electrode of a high-performance energy storage device, a high ion flux must be realized. Accordingly, as a result of the development of an electrode capable of satisfying the above requirements, a fabric-based flexible aluminum electrode according to the present invention was devised.

Specifically, the fabric-based flexible aluminum electrode according to the present invention includes a porous substrate 10 , a bonding layer 20 , a base layer 30 , and a plating layer 40 .

Here, the substrate 10 is a woven substrate in which a plurality of fibers 11 are intersected with each other, and has a plurality of pores formed while the fibers 11 intersect each other. The fiber 11 constituting the material of the substrate 10 is a long, thin, and softly bendable linear object, and may include both natural and synthetic fibers. Accordingly, the substrate 10 has flexibility by woven with natural fibers or synthetic fibers alone, or by mixing these fibers 11 with each other. The fibers 11 constituting the flexible substrate 10 may be made of at least one of polyester, nylon, and acrylic fibers. However, the fibers 11 are not necessarily limited thereto, and as long as the flexible substrate 10 having a predetermined shape while crossing each other can be formed, the type thereof is not particularly limited.

On the other hand, there is a weaving method as a representative method of manufacturing the substrate 10 using a plurality of fibers 11. In the present invention, the scope of rights should not be limited by the method, and two-dimensional to three-dimensional As long as the substrate 10 can be formed in a predetermined shape, such as, it may be manufactured in any manner. The flexible substrate 10 manufactured by the fiber 11 in this way has a number of fine-sized pores, which are connected from the outer surface to the inside of the substrate 10 . In addition, the substrate 10 may have electrical insulation according to the type of the fibers 11 . The substrate 10 supports the base layer 30 and the plating layer 40 , wherein the base layer 30 is coupled to the substrate 10 via the bonding layer 20 .

The bonding layer 20 is a layer formed by adsorbing a polymer material to the flexible porous substrate 10 . Here, the polymer material allows metal nanoparticles to be described later to be coated on the substrate 10 to form the nanoparticle layer 31 . On the other hand, the polymer material penetrates into the surface of the substrate 10, that is, through the pores of the substrate 10 as well as the outer fibers 11 exposed to the outside, and is adsorbed to the outer surface of each of the inner fibers 11. can In this case, the polymer material may be adsorbed in a form surrounding the outer surface of the fiber 11 . _{Such a polymer material may contain an amine group (NH 2} ) having a strong affinity with the metal nanoparticles, and one or more selected from the group consisting of polyethylenimine (PEI), and poly(allylamine) hydrochloride (PAH) as an example can be used by However, the polymer material is not necessarily limited to the polymer, and there is no particular limitation as long as it is a material capable of fixing the metal nanoparticles to the surface of the fiber 11 .

The base layer 30 is a double layer in which the monomolecular layer 33 is laminated on the nanoparticle layer 31 formed on the bonding layer 20 . Here, the nanoparticle layer 31 is a layer formed by metal nanoparticles on the bonding layer 20 , and is fixed to the substrate 10 by the bonding layer 20 as described above, the outer side of the substrate 10 . And is formed on each of the fibers 11 on the inside, in this case may be formed in a form surrounding the outer surface of the bonding layer (20). Meanwhile, the metal nanoparticles may include any one or more selected from the group consisting of Au, Ag, Al, Cu, and Pt, but the material is not necessarily limited thereto.

The monomolecular layer 33 is a layer formed by coating a monomolecular material on the nanoparticle layer 31 . Here, the monomolecular substance is an amine group (NH ₂ )-containing monomolecular substance, tris(2-aminoethyl)amine(TREN), propane-1,2,3-triamine, diehthylenetriamine(DETA), tetrakis(aminomethyl)methane, And it may include any one or more selected from the group consisting of methanetetramine. However, the monomolecular material is not necessarily limited thereto, and there is no particular limitation as long as it is a monomolecular material containing an amine group. The monomolecular material fixes the metal nanoparticles together with the above-described polymer material, and imparts electrical conductivity to the nanoparticle layer 31 . In the case of a thin film made of metal particles, insulating properties are shown because the constituent particles are surrounded by long organic ligands. Therefore, in the present invention, the amine group-containing polymer material (binding layer 20) and the amine group-containing monomolecular material (monomolecule layer 33) replace the insulating organic ligand to improve the bonding force between the metal nanoparticles, Electrical conductivity is imparted to the particle layer 31 .

The base layer 30 thus formed may be formed to have the minimum electrical conductivity capable of electroplating in order to form the plating layer 40 by an electroplating method. In this case, the base layer 30 may have ^{a sheet resistance of 10 0} to 10 ⁴ Ω/sq, and electroplating may be effectively performed within that range. However, the sheet resistance of the base layer 30 is not necessarily limited within the above range, and may be determined differently depending on the types of metal nanoparticles and monomolecular materials, the number of layers of the base layer 30 to be described later, and the like.

The plating layer 40 is a layer formed by electroplating aluminum (Al) on the base layer 30 . Aluminum is an economical electrode material because its electrical conductivity compared to other metals is far superior to that of other metals, and its wearability and portability are excellent because of its high electrical conductivity compared to its mass. In addition, since it has excellent stability at high voltage, it can be used as a material for a positive electrode of a battery. This aluminum is coated with an electroplating method, and can be coated with a high packing density. At this time, since the porosity of the substrate 10 is maintained as it is, the aluminum is adsorbed very uniformly and disposed on the outside and inside of the substrate 10 . The plating layer 40 may be evenly formed on each of the fibers 11 . Furthermore, since the electroplating is performed in a short time in a simple manner, the time taken to form the electrode can be shortened, the manufacturing cost can be lowered, and the size or shape of the electrode can be selected according to the purpose of use, so that various designs are possible.

Overall, according to the present invention, the electrical conductivity, mechanical strength, and workability of the flexible electrode can be improved by simply and quickly coating aluminum on an insulator substrate made of a textile material having high flexibility by an electroplating method.

In addition, since the fabric-based flexible aluminum electrode according to the present invention has a high bonding force between particles and at the same time contains numerous pores inherent to the fabric material, when applied to the current collector of an energy storage device, it not only facilitates the inflow of the electrolyte, Compared to a flat plate having no pores, the number of particles introduced per unit area can be maximized with a relatively large surface area. That is, high ion mobility and driving stability can be secured.

Furthermore, since aluminum has excellent electrical conductivity compared to other metals in price and mass, and excellent stability at high voltage, the electrode according to the present invention can be applied to the positive electrode current collector of a battery, and not only has a high It can be applied to various electrical devices that require flexibility, and since simple electroplating is applied, there is no restriction on the size and shape of the electrode to be manufactured.

3 is a cross-sectional view taken along line A-A' of FIG. 2 of a fabric-based flexible aluminum electrode according to another embodiment of the present invention.

Referring to FIG. 3 , in another embodiment of the present invention, the base layer 30 may be formed in a structure in which a plurality of pieces are sequentially stacked. That is, the second base layer 30b may be stacked on the first base layer 30a, or another base layer 30 may be stacked thereon. At this time, the nanoparticle layer 31 and the monomolecular layer 33 constituting each base layer 30 may be made of the same material, but may be made of different materials. For example, the nanoparticles of the nanoparticle layer 31a constituting the first base layer 30a use Au, the monomolecular material of the monomolecular layer 33a uses DETA, and the nanoparticles constituting the second base layer 30b By using Ag as the nanoparticles of the particle layer 31b and TREN as the monomolecular material of the monomolecular layer 33b, the double base layer 30 having a (Au/DETA)/(Ag/TREN) structure may be configured. Here, the number of layers of the base layer 30 and the types of metal nanoparticles and monomolecules may be determined according to securing minimum electrical conductivity for aluminum electroplating.

Overall, according to the present invention, the electrical conductivity, mechanical strength, and workability of the flexible electrode can be improved by simply and quickly coating aluminum on an insulator substrate made of a textile material having high flexibility by an electroplating method.

In addition, since the fabric-based flexible aluminum electrode according to the present invention has a high bonding force between particles and at the same time contains numerous pores inherent to the fabric material, when applied to the current collector of an energy storage device, it not only facilitates the inflow of the electrolyte, Compared to a flat plate having no pores, the number of particles introduced per unit area can be maximized with a relatively large surface area. That is, high ion mobility and driving stability can be secured.

Furthermore, since aluminum has excellent electrical conductivity compared to other metals in price and mass, and excellent stability at high voltage, the electrode according to the present invention can be applied to the positive electrode current collector of a battery, and not only has a high It can be applied to various electrical devices that require flexibility, and since simple electroplating is applied, there is no restriction on the size and shape of the electrode to be manufactured.

Hereinafter, a method for manufacturing a fabric-based flexible aluminum electrode according to an embodiment of the present invention will be described. As described above for the fabric-based flexible aluminum electrode according to the present invention, the detailed description of the overlapping matters will be omitted or only briefly described.

4 is a process diagram of a method for manufacturing a fabric-based flexible aluminum electrode according to an embodiment of the present invention.

As shown in FIG. 4, the method for manufacturing a fabric material-based flexible aluminum electrode according to an embodiment of the present invention includes (a) immersing a porous substrate formed by crossing a plurality of fibers in a first dispersion in which a polymer material is dispersed. , forming a bonding layer on the surface of the fiber (S100); (b) forming a nanoparticle layer by immersing the substrate on which the bonding layer is formed in the second dispersion in which the metal nanoparticles are dispersed (S200); (c) immersing the substrate on which the nanoparticle layer is formed in the third dispersion in which the amine group-containing monomolecular material is dispersed to form a monomolecular layer (S300); and (d) electroplating aluminum (Al) to form a plating layer on the monolayer (S400).

The fabric material-based porous water decomposition catalyst manufacturing method according to the present invention may include a bonding layer forming step (S100), a nanoparticle layer forming step (S200), a monomolecular layer forming step (S300), and a plating layer forming step (S400).

The bonding layer forming step (S100) is a process of forming a bonding layer on the surface of the fibers constituting the porous flexible substrate. Here, a first dispersion in which the polymer material is dispersed is prepared, and the substrate is immersed in the first dispersion. At this time, since the substrate is a porous flexible substrate formed by intersecting a plurality of fibers, the first dispersion is permeated along the pores of the substrate, and the polymer material is adsorbed to the surface of the fibers inside as well as outside. Here, the fiber may include any one or more selected from the group consisting of polyester, nylon and acrylic fiber, and the polymer material is a polymer containing an amine group, such as polyethylenimine (PEI), and poly(allylamine)hydrochloride (PAH). It may include any one or more selected from the group consisting of. However, fibers and polymer materials are not necessarily limited to the above materials. In addition, the first dispersion liquid may use, for example, ethanol as a solvent, as long as it is a solvent capable of dispersing a polymer material to form a bonding layer on the fiber surface, and there is no particular limitation.

The nanoparticle layer forming step (S200) is a process of coating metal nanoparticles on the bonding layer, and the substrate on which the bonding layer is formed is immersed in a second dispersion in which the metal nanoparticles are dispersed to form a nanoparticle layer. At this time, since the pores of the substrate are not closed by the bonding layer, the second dispersion is penetrated through the pores and coated on the bonding layer adsorbed on the inner fiber surface. Here, the metal nanoparticles may include any one or more selected from the group consisting of Au, Ag, Al, Cu, and Pt, and disperse them in toluene or the like to prepare a second dispersion. However, the metal nanoparticles and the solvent are not necessarily limited thereto.

The monomolecular layer forming step ( S300 ) is a process of forming a thin film on the nanoparticle layer using an amine group-containing monomolecular material. Here, a third dispersion is prepared by dispersing an amine group-containing monomolecular substance in ethanol or the like, and the substrate is immersed. At this time, since the third dispersion also penetrates to the inside through the pores of the substrate, the nanoparticle layer formed on the outer and inner fiber surfaces is coated with a monomolecular material to form a monomolecular layer. Here, the monomolecular substance is any one or more selected from the group consisting of tris (2-aminoethyl) amine (TREN), propane-1,2,3-triamine, diehthylenetriamine (DETA), tetrakis (aminomethyl) methane, and methanetetramine. may be included, but is not necessarily limited thereto. By stacking the monomolecular layer on the nanoparticle layer in this way, the base layer is formed.

The base layer thus formed may be formed to have the minimum electrical conductivity capable of electroplating in order to form a plating layer by an electroplating method. Accordingly, the sheet resistance of the base layer is preferably in the range ^{of 10 0} to 10 ^{4 Ω/sq.} To this end, the type of metal nanoparticles may be appropriately selected or the base layer may be formed in a multi-layered structure, which will be described later.

The plating layer forming step ( S400 ) is a process of electroplating aluminum on the base layer. The substrate may be used as a cathode and aluminum metal as an anode, each of which is immersed in an electrolyte solution, and a power supply is connected to the cathode and anode to supply electricity. Thereby, an aluminum plating layer is formed in the base layer.

On the other hand, when the bonding layer, the base layer, and the plating layer are sequentially laminated on the fiber, the substrate is cleaned using a cleaning solution such as distilled water, and after the cleaning is completed, the substrate can be dried using an inert gas such as nitrogen. have.

5 is a process diagram of a method for manufacturing a fabric-based flexible aluminum electrode according to another embodiment of the present invention.

Referring to FIG. 5, the base layer of the multi-layer structure is formed by a layer-by-Layer assembly by sequentially repeating the metal nanoparticle layer forming step (S200) and the monomolecular layer forming step (S300) several times. can In this case, the metal nanoparticles and the monomolecular material constituting each base layer may be the same as each other, or at least one of them may be selected as a different material.

Hereinafter, the present invention will be described in more detail through specific examples and evaluation examples.

Example: Fabrication of flexible aluminum electrode based on fabric material

A first dispersion is prepared by dispersing PEI, which is a polymer having an amine group, at 2 mg/mL in ethanol, and then, a porous fabric substrate made of a polyester material is supported for 3 hours. After the process of washing the supported fabric substrate with ethanol twice, the fabric substrate is dried using a dryer. After synthesizing the hydrophobically stabilized Au nanoparticles as TOABr (tetraoctylammonium bromide), and dispersing them in toluene to prepare a second dispersion, the fabric substrate is supported for 1 hour. After washing twice with toluene, the fabric substrate is dried using a dryer, and 2 mg/mL of DETA (diehthylenetriamine), a single molecule having an amine group, is dispersed in an ethanol solution (third dispersion) for 30 minutes. Similarly, wash twice with ethanol and dry the fabric substrate. By sequentially supporting the second and third dispersions above, Au nanoparticles and DETA monomolecules are stacked by a layered assembly method (TOABr-Au NP/DETA) to form a sheet resistance of 10 ⁰ ~ 10 ⁴ Ω/ By cross-stacking Au nanoparticles and DETA monomolecules until sq, the base layer is generated (Polyester/PEI/(TOABr-Au/DETA) _n ).

Then, electroplating is performed with an ionic liquid aluminum plating solution (1-ethyl-3-methylimidazolium chloride - aluminum chloride) (performed for 15 minutes at ^{8 mA/cm 2 based on polyester substrate).} At this time, the plating is carried out in a three-electrode system, and the polyester substrate to be plated is used as a working electrode, the metal to be used for plating is used as a counter electrode, and a platinum electrode (pt coil) is used as a reference electrode. ) is placed. After these electrodes are immersed in an electrolyte solution, an aluminum plating layer is formed on the base layer when a power supply is connected to supply electricity. Here, the above plating process may be performed in an argon (or nitrogen) atmosphere to prevent oxidation of the ionic liquid, or may be performed after pouring decane, a protective layer, on the ionic liquid in order to perform an experiment in air. The aluminum-plated substrate is washed twice with DI (deionized water), and dried in a vacuum oven at 100° C. under vacuum for 1 hour.

Through this process, Polyester/PEI/(TOABr-Au/DETA) ₄ /Al samples were prepared.

Evaluation Example 1: Structural Analysis of Fabric-Based Flexible Aluminum Electrodes

6A is an SEM image of an electrode manufactured according to an embodiment of the present invention, and FIG. 6B is an EDS mapping image of an electrode manufactured according to an embodiment of the present invention.

Figure 6a shows the bare textile used in the example and the flexible aluminum electrode manufactured in the example through a scanning electron microscope (SEM), and Figure 6b shows energy dispersive spectroscopy (Energy Dispersive X) As a result of observing the flexible aluminum electrode prepared in Example with -ray spectroscope, EDS), it was confirmed that the aluminum was evenly coated to the inside without any influence on the internal structure and shape of the porous substrate in which the fibers cross each other as a reference. Based on these results, it can be seen that there is no change in the mechanical properties of the fabric-based flexible aluminum electrode.

Evaluation Example 2: Analysis of sheet resistance of fabric-based flexible aluminum electrodes

7 is a graph showing a change in sheet resistance of an electrode manufactured according to an embodiment of the present invention.

The polyester substrate of Example, Polyester/PEI/(TOABr-Au/DETA) _n , Polyester/PEI/(TOABr-Au/DETA) ₄ /Al The sheet resistance was measured for each sample. As a result, the polyester substrate showed insulation, but as the base layer was formed, Polyester/PEI/(TOABr-Au/DETA) _n had electrical conductivity, and the sheet resistance decreased as the number of laminated layers (n) of the base layer increased. did. When the four base layers were laminated, ^{the sheet resistance was 3.2 × 10 2} Ω/sq, where the sheet resistance of the aluminum-plated Polyester/PEI/(TOABr-Au/DETA) ₄ /Al sample was 1.8 × 10 ^{− It} was measured to have 2 Ω/sq, and it was confirmed that the electrical conductivity was improved through aluminum plating. Taken together, it can be seen that the flexible aluminum electrode manufactured according to the embodiment of the present invention has conductivity close to the metal within a very short time through electroplating.

Evaluation Example 4: Evaluation of Mechanical Stability of Fabric-Based Flexible Aluminum Electrodes

8A to 8B are mechanical stability test results of electrodes manufactured according to an embodiment of the present invention.

In FIG. 8a, a test was conducted to turn on the LED light by connecting the flexible aluminum electrode manufactured according to the embodiment with a conducting wire and flowing a current. As a result, it can be seen that the flexible aluminum electrode according to the present invention maintains excellent conductivity even when mechanical deformation is applied.

In Figure 8b, an aluminum electrode was manufactured using electroless plating instead of electroplating in the above example, and the conductivity (σ) was measured _{for the initial conductivity (σ 0 ) during 5000 crumpling cycles,} As a result, it was confirmed that the mechanical stability of the flexible aluminum electrode fabricated by electroplating according to this embodiment was superior to that of the aluminum electrode fabricated by electroless plating.

Evaluation Example 5: Evaluation of the electrochemical properties of an energy storage device to which a fabric-based flexible aluminum electrode is applied

9A to 9B are graphs of electrochemical characteristics evaluation results of an energy storage element (battery) to which an electrode manufactured according to an embodiment of the present invention is applied.

_{Lithium iron phosphate (LiFePO 4} ) nanoparticles, which are battery positive nanoparticles, were laminated on the flexible aluminum electrode manufactured according to the embodiment using a layered self-assembly method, and this was used as a working electrode and a counter electrode. A coin cell was manufactured using lithium foil, and CV (Cyclic Voltammetry) and GCD (Gavanostatic Charge/Discharge) were measured, and the results are shown in FIGS. 9a to 9b. In addition, instead of the flexible aluminum electrode according to the embodiment, the above experiment was repeated by manufacturing the electrode using a nonporous aluminum plate, and the results are also shown in FIGS. 9A to 9B .

Referring to FIGS. 9a to 9b, _{the peak of LiFePO 4} was confirmed at around 3.5 V, and in particular, a large capacity difference appeared when compared with an electrode made of a non-porous aluminum plate. A porous fabric substrate according to the present invention It can be confirmed that the flexible aluminum electrode plated with aluminum can be applied to the energy storage device.

Although the present invention has been described in detail through specific examples, this is intended to describe the present invention in detail, and the present invention is not limited thereto, and by those of ordinary skill in the art within the technical spirit of the present invention. It is clear that the modification or improvement is possible.

All simple modifications and variations of the present invention belong to the scope of the present invention, and the specific scope of protection of the present invention will be made clear by the appended claims.

10: substrate 11: fiber
20: bonding layer 30: base layer
31: nanoparticle layer 33: monolayer
40: plating layer

Claims (11)

a porous substrate formed by crossing a plurality of fibers;
a bonding layer formed on the surface of the fiber;
a base layer comprising a nanoparticle layer comprising metal nanoparticles and _{a monomolecular layer comprising a monomolecular material containing an amine group (NH 2} ), wherein the nanoparticle layer and the monomolecular layer are sequentially stacked on the bonding layer; and
a plating layer formed by electroplating aluminum (Al) on the base layer;
The metal nanoparticles are gold (TOABr-Au) nanoparticles stabilized with TOABr (tetraoctylammonium bromide),
The monomolecular substance is DETA (diehthylenetriamine),
The base layer, respectively, n (n = 4) of the nanoparticle layer and the monolayer are sequentially stacked, the sheet resistance is 3.0 × 10 ² ~ 3.5 × 10 ² Ω / sq,
The plated layer is formed on the base layer, the sheet resistance is 1.5 × 10 ^-2 ~ 2.0 × 10 ^-2 Ω / sq of a fabric-based flexible aluminum electrode.
The method according to claim 1,
The fiber is
A fabric-based flexible aluminum electrode comprising at least one selected from the group consisting of polyester, nylon and acrylic fibers.
The method according to claim 1,
The bonding layer is
A flexible aluminum electrode based on a textile material containing an amine group (NH _{2 )-containing polymer material.}
4. The method according to claim 3,
The polymer material is
A fabric-based flexible aluminum electrode comprising at least one selected from the group consisting of polyethylenimine (PEI), and poly(allylamine)hydrochloride (PAH).
delete delete delete delete delete (a) immersing a porous substrate formed by crossing a plurality of fibers in a first dispersion in which a polymer material is dispersed, thereby forming a bonding layer on the surface of the fibers;
(b) forming a nanoparticle layer by immersing the substrate on which the bonding layer is formed in a second dispersion in which the metal nanoparticles are dispersed;
(c) immersing the substrate on which the nanoparticle layer is formed in a third dispersion in which an amine group-containing monomolecular material is dispersed to form a monomolecular layer; and
(d) electroplating aluminum (Al) to form a plating layer on the monomolecular layer;
The metal nanoparticles are gold (TOABr-Au) nanoparticles stabilized with TOABr (tetraoctylammonium bromide),
The monomolecular substance is DETA (diehthylenetriamine),
Before step (d), steps (b) and (c) are sequentially repeated n (n = 4) times, respectively, n (n = 4) of the nanoparticle layer and the monolayer are sequentially stacked to form a base layer,
The sheet resistance of the base layer is 3.0 × 10 ² ~ 3.5 × 10 ² Ω / sq,
The plating layer is formed on the base layer, the sheet resistance is 1.5 × 10 ^-2 ~ 2.0 × 10 ^-2 Ω / sq of a fabric material-based flexible aluminum electrode manufacturing method.
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