KR20160127370A - Method of manufacturing a secondary battery adhesion utilizing inverse opal structure - Google Patents

Abstract

The present invention relates to an assembly for a secondary battery using an inverse opal structure and a manufacturing method thereof. The method includes: a step of forming an opal structure by applying spherical particles onto the surface of a metal specimen; a step of plating the opal structure to form a dented part with a height greater than the radius of the spherical particles and an open part smaller than the diameter of the spherical particles; a step of forming an inverse opal structure including the dented part and the open part by removing the spherical particles; and a step of jetting polymers to the inverse opal structure through the open part. By doing so, the present invention can form the inverse opal structure onto the surface of the metal specimen, increase the boding force between the metal and the polymers by injecting the polymers into the inverse opal structure, and accordingly prevent leak of an electrolyte in a secondary battery and improve the sealing performance.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a secondary battery using a reverse opal structure,

The present invention relates to a junction body for a secondary battery using an inverse opal structure, and more particularly, to an inverse opal structure formed on a surface of a metal specimen, and a polymer is injected into the inverse opal structure to increase a bonding force between the metal and the polymer. To a junction body for a secondary battery using a reverse opal structure for improving the leakage prevention and sealing function of an electrolyte in a secondary battery, and a manufacturing method thereof.

With the aim of miniaturization of portable electronic devices and continuous use for a long time in line with the improvement of industrial development and living standards, there is a need for a high performance energy storage device capable of realizing small size and high capacity in addition to research for lightening of parts and strategy for low consumption. In recent years, secondary batteries have been used as small-sized, high-performance energy sources such as large-capacity power storage batteries for electric vehicles, battery power storage systems, and portable electronic devices such as mobile phones, camcorders, and notebook computers. Secondary cells have the advantages of high energy density, large capacity per area, low self-discharge rate and long life. Also, since there is no memory effect, it is convenient for user to use, and has a characteristic of long life.

Currently, the cell of a rechargeable battery for an electric vehicle includes a pouch type in which a pouch of a film material is enclosed and a can type in which a metal material such as aluminum encloses an inner material such as a cathode active material, an anode active material, Are being developed. From the viewpoints of sealing properties, corrosion resistance, and stability of the battery due to external impact, which are required for electric vehicles, it is considered that a metal can type secondary battery case is more suitable than a pouch type. Polyethylene sulfide, which is an industrial polymer resin, is generally used as a material for sealing the can type secondary battery at the anode terminal of aluminum, the anode terminal of copper, and the material sealing between the terminal and the can case.

Polyphenylenesulfide (PPS) is one of the most thermostable plastics with dimensional stability and can maintain its strength in high temperature and corrosive environments. Also, it is widely used as a precision instrument parts such as a chemical plant, a medicine, and a semiconductor manufacturing process, which have excellent chemical resistance and heat resistance and are required to have high temperature chemical resistance. However, the polyphenylene sulfide has a remarkably low adhesive force with copper, so that the sealing property of the battery cell can not be guaranteed only by a combination component manufactured by a general injection molding method. In particular, unlike aluminum, copper has very limited surface structure control, such as anodic oxidation, and is relatively inferior to related technologies.

In the prior art 'Korean Patent Registration No. 10-1450260', in order to improve the bonding force of polyphenylene sulfide, which is a substance sealing the gap between copper and the can case which is an anode terminal, a rough surface is formed by chemical etching on the copper surface step; Forming a polyphenylene sulfide thin film on copper having a rough surface; Subjecting the polyphenylene sulfide thin film to plasma treatment; And injecting a polyphenylene sulfide resin into the plasma-treated copper plate. If the polyphenylene sulfide is injected after the chemical etching as described above, polyphenylene sulfide can not be easily injected to the inner end of the etched copper, so that copper and polyphenylene sulfide can not be firmly coupled.

Korean Intellectual Property Office Registration No. 10-1450260 Korea Patent Office Registration No. 10-2084033 Korea Patent Office Registration No. 10-0670515

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide an inverse opal structure in which an inverse opal structure is formed on a surface of a metal specimen and a polymer is injected into the inverse opal structure to increase the bonding force between the metal and the polymer, Structure and a method for manufacturing the same.

The above-described object is achieved by a method of manufacturing a metal object, comprising: forming spherical particles on a surface of a metal specimen to form an opal structure; Plating on the opal structure such that a depression having a height greater than a radius of the spherical particle and an opening smaller than a diameter of the spherical particle are formed; Removing the spherical particles to form an inverse opal structure including the depressions and the openings; And injecting the polymer into the inverse opal structure through the opening. The method for manufacturing a junction body for a secondary battery using the inverse opal structure is also provided.

Prior to the step of forming the opal structure, further comprising the step of surface modifying the surface of the metallic specimen groups hydrophilic function, the method comprising: surface modifying groups of the hydrophilic function, the oxygen (O ₂₎ as a reactant gas, argon ( Ar) is used as a base gas and processed through a plasma system.

Here, the forming of the opal structure may be performed by applying the spherical particles to the surface of the metal specimen using spin coating or dip coating, and the spin coating is performed at a speed of 1000 to 2000 rpm Coating the spherical particles on the metal specimen rotated by a predetermined angle; Further comprising the step of heat treating the metal specimen coated with the spherical particles at a temperature of 90 to 120 DEG C, wherein the dip coating is performed by applying the metal specimen lifted at a speed of 10 to 100 mu m / s to a solution containing spherical particles Dip coating; And heat treating the metal to be bonded coated with the spherical particles at 90 to 120 ° C.

Also, after the step of forming the opal structure, the method includes: surface modification of the opal structure with a hydrophilic functional group; Further comprising applying spherical particles to the top of the opaque structure to form a laminated multi-layer opal structure, wherein forming the inverse opal structure comprises: And immersing the specimen to dissolve the spherical particles.

Wherein the spherical particles are at least one of polystyrene particles and silica particles having a diameter of 80 to 2000 nm and the diameter of the inverse opal structure is 80 to 2000 nm, 0.6 to 0.9 times, and the opening is preferably 0.1 to 0.7 times the diameter of the inverse opal structure.

Preferably, the polymer is poly phenylene sulfide (PPS), and the metal specimen is in a curved or plate shape.

The above-described object is also achieved by a method of manufacturing a semiconductor device comprising: a metal specimen including an inverse opal structure having a diameter larger than an opening portion exposed on a surface; And a polymer layer injected into the inverse opal structure of the metal specimen.

Here, the diameter of the inverse opal structure is 80 to 2000 nm, and the size of the open portion is 0.1 to 0.7 times the diameter of the inverse opal structure, and the inverse opal structure has a height of 400 to 1500 nm.

In addition, it is preferable that the inverse opal structure comprises a multi-layer inverted opal structure laminated on the metal specimen.

According to the configuration of the present invention described above, the inverse opal structure is formed on the surface of the metal specimen, and the polymer is injected into the inverse opal structure to increase the bonding force between the metal and the polymer, thereby improving the leakage prevention and sealing function of the electrolyte in the secondary battery. Effect can be obtained.

1 is a flowchart of a method of manufacturing a bonded body for a secondary battery using an inverse opal structure according to an embodiment of the present invention,
2 is a sectional view showing an opal structure and an inverse opal structure,
3 is a cross-sectional view showing a bent metal specimen,
4 is a cross-sectional view showing a multilayer opal structure and a multilayer inverse opal structure,
5A and 5B are cross-sectional views showing the inverse opal structure and the semicircular structure and the polymer bonded,
6 is a perspective view showing a metal specimen and a polymer conjugate.

Hereinafter, a junction body for a secondary battery using a reverse opal structure and a manufacturing method thereof according to an embodiment of the present invention will be described with reference to the drawings.

As shown in FIG. 1, first, the surface of the metal specimen 100 is surface-modified (S1).

As shown in FIG. 2, a metal specimen 100, which is the same material as the material used for a part where the inter-metal bonding of the secondary battery is required, such as a can type secondary battery, is prepared and the surface of the metal specimen 100 is made hydrophilic Surface modification with functional group (Hydrophilic functional group). When the surface of the metal specimen 100 is hydrophilic rather than hydrophilic, spherical particles 210 having hydrophobic properties are coated on the metal specimen 100 in a subsequent step, so that the metal specimen 100 is aggregated with the metal specimen 100, The surface of the metal specimen 100 is surface-modified with a hydrophilic functional group so that the spherical particles 210 can be widely and evenly spread. Here, the metal specimen 100 is preferably made of a material such as copper (Cu), nickel (Ni), aluminum (Al), and platinum (Pt), which are mainly used for a secondary battery. Other metal materials may be used . The metal specimen 100 may be either bent or plate-shaped as shown in Fig.

Plasma system is mainly used for surface modification of the metal specimen 100 with a hydrophilic functional group. Plasma processing is performed using argon (Ar) as a base gas and oxygen (O ₂ ) as a reaction gas. Here, the plasma system uses any one of an RF & MF (Atmospheric Pressure) discharge system, a DBD (Dielectric barrier discharge) discharge system, a Capillary discharge, a microwave discharge system, an Induction & DC Torch system, .

The opal structure 200 is formed on the surface of the metal specimen 100 (S2).

Spherical particles 210 are applied to the surface of a metal specimen 100 surface-modified with a hydrophilic functional group to form an opal structure 200. Since the metal specimen 100 is a hydrophilic functional group, when the spherical particles 210 having hydrophobicity are applied to the metal specimen 100, the opal structure 200 having a uniform shape spreads evenly without being aggregated. Here, the opal structure 200 refers to a structure similar to an opal gem. The opal structure 200 has a high surface area per unit volume because the spherical particles 210 are regularly packed and stacked. That is, the opaque structure 200 is formed by applying the spherical particles 210 on the surface of the metal specimen 100 so as to be uniformly densely packed.

Here, the spherical particles 210 are preferably at least one of polystyrene particles and silica particles having a diameter of 80 to 2000 nm, and it is preferable that the spherical particles 210 are subjected to a simple dissolution process The spherical particles 210 can be easily removed. If the diameter of the spherical particle 210 is less than 80 nm, the diameter of the inverse opal structure 300 is too small to easily make the inverse opal structure 300, and if the diameter exceeds 2000 nm, .

Spin coating or dip coating may be used as a method of applying the spherical particles 210 to the metal specimen 100. In the case of spin coating, the spherical particles 210 are coated on the metal specimen 100 rotating at a speed of 1000 to 2000 rpm. The dip coating is a method of lifting the metal specimen 100 lifted at a speed of 10 to 100 탆 / Is coated by immersing it in a solution containing the particles (210). After the spherical particles 210 are coated, the metal specimen 100 may be thermally treated at 90 to 120 ° C. In the case of the heat treatment, in order to remove the solvent required in the coating process, when the heat treatment temperature is less than 90 ° C, the solvent can not be completely removed, and when the temperature exceeds 120 ° C, the shape of the spherical particles 100 may be changed. In some cases, it is not necessary to follow Step S1 when dip coating is performed.

After the step of forming the opal structure 200 as occasion demands, a multi-layered opal structure 200a stacked on the opal structure 200 may be formed (S1 ').

A secondary battery may be formed using the opal structure 200 formed of one layer, but a multi-layered opal structure 200a may be formed as shown in FIG. 4 to form a more rigid bonded body. As a method of forming the multilayer opal structure 200a, the opal structure 200 formed in the step S2 is surface-modified with a hydrophilic functional group in the same manner as in the step S1, and the spherical particles 210 are applied thereto as in the step S2 Thereby forming a multilayer opal structure 200a. The reason why the surface is modified with the hydrophilic functional group is that the opal structure 200 stacked on the top is uniformly distributed as in the step S1. When the multilayered opal structure 200a is formed as described above, it is easy to control the thickness of the structure and a more rigid bonded body can be obtained.

Plating is performed on the opal structure 200 (S3).

Plating is performed on a region of the opaque structure 200 including the spherical particles 210 except for the spherical particles 210 in the metal specimen 100. At this time, the plating is performed to form a depression 310 having a height that is longer than the radius of the spherical particles 210 and a thickness of the spherical particles 210 that are thicker than the radius of the spherical particles 210 so as to form an opening 330 smaller than the diameter of the spherical particles 210 A plating layer 350 is formed. When the plating is performed to the upper part so that the spherical particles 210 are completely covered without forming the openings 330, the plating is performed to a thickness at which the openings 330 are formed since the polymer 400 can not be injected later . In addition, when the plating layer 350 having a thickness smaller than the radius of the spherical particles 210 is formed, the semicircular openings 330 are formed. When the plating is performed in such a shape, 400 and the plating layer 350 can be easily separated from each other. It is preferable that the plating layer 350 having a thickness larger than the radius of the spherical particles 210 is formed so that the depressions 310 and the openings 330 are formed in a jar shape instead of a semicircle.

The spherical particles 210 are removed to form the inverse opal structure 300 (S4).

Only the spherical particles 210 are removed from the spherical particles 210 and the plated layer 350 formed on the metal specimen 100 so that the plated layer 350 becomes the inverse opal structure 300. As a method of removing the spherical particles 210, it is preferable to prepare a solvent capable of dissolving the spherical particles 210, immerse the metal specimen 100 in the solvent, and dissolve the spherical particles in the solvent to remove Do.

When the spherical particles 210 are removed, a hollow space is formed in the place where the spherical particles are present. The hollow space is a narrow jar shape having a depression 310 having a height longer than the radius of the spherical particle 210, And an opening 330 having a diameter smaller than the diameter of the spherical particles 210. The plating layer 350 plated by the electroplating method has a plating surface 351 whose surface is not smooth. The bonding force with the polymer 400 injected by the plating surface 351 becomes stronger.

Here, the diameter of the inverse opal structure 300 is 80 to 2000 nm, which is the same as the diameter of the spherical particle 210, and the depression 310 is 0.6 to 0.9 times the diameter of the spherical particle 210 or the inverse opal structure 300 And the opening 330 is preferably 0.1 to 0.7 times the diameter of the spherical particle 210 or the inverse opal structure 300. When the dimple 310 is less than 0.6 times, the semicircular shape is close to the inverse opal structure. If the dimple 310 is more than 0.9 times, the polymer 400 is not easily injected into the inverse opal structure 300. If the open portion 330 is less than 0.1 times the diameter of the spherical particles 210 or the inverse opal structure 300 it is too narrow to permit the injection of the polymer 400 and if it exceeds 0.7 times the open portion 330 Separation may occur between the polymer 400 and the inverse opal structure 300 that are too wide to be injected.

The inverse opal structure 300 preferably has a thickness of 400 to 2000 nm, and may be formed of a stacked multilayer inverse opal structure 300a as occasion demands.

The polymer 400 is injected into the inverse opal structure 300 (S5).

The polymer 400 is injection molded into the inverse opal structure 300 through the opening 330 to finally form the junction body for the secondary battery composed of the metal specimen 100 and the polymer 400. In this case, it is most preferable to use poly phenylene sulfide (PPS), which is mainly used in a secondary battery, because the polymer 400 is excellent in stability and adhesion, and other polymers may be used. 5A shows the polymer 400 injected into the inverse opal structure 300a. When the polymer 400 is injected into the structure 400, the polymer 400 and the inverse opal structure 300a are firmly coupled to each other The problem does not occur. In contrast, FIG. 5B shows a structure in which a semicircle is formed rather than an inverse opal structure. When the polymer 400 is injected into the structure as described above, separation easily occurs and it is not firmly coupled.

Hereinafter, embodiments according to the present invention will be described in more detail.

<Examples>

A copper (Cu) specimen having a thickness of 3 mm on a 10 × 20 mm 2 area was prepared, mechanically polished, and then the surface was washed with ethanol to remove impurities. Next, the surface of the copper specimen was subjected to shower type RF atmospheric pressure plasma treatment. Argon (Ar) was used as the base gas of the plasma, and oxygen (O ₂ ) was used as the reactive gas. The flow rate of argon, which is the base gas introduced into the atmospheric plasma treatment, was 4.0 LPM (Liters Per Minute), and the flow rate of oxygen as reactive gas was 50 SCCM (Standard Cubic Centimeter per minute).

In order to form the opal structure by spin coating on the surface-modified copper specimen, the copper specimen was first fixed to the spin-coating equipment. Thereafter, it was rotated at a rotation speed of 1500 rpm for 1 minute. At this time, 0.1 ml of a spherical polystyrene particle solution having a concentration of 8 wt% and a diameter of 600 nm is applied to the surface of the copper specimen rotating within 10 seconds. After the spin coating, the copper specimen was heat-treated in an electric heating furnace at a temperature of 95 캜 for 3 hours. The heat-treated specimen is immersed in a Ni-sulfamate solution to form an inverse opal structure of nickel material through electrodeposition.

The inverse opal structure is obtained by first dipping a specimen formed with an opal structure into a nickel-sulfamate solution and applying a current of 0.3 mA / cm 2 for 2 hours to form an inverse opal structure. Thereafter, the polystyrene particles remaining in the specimen are immersed in a tetrahydrofuran solution for 3 hours, and the copper specimen is transferred to a heating furnace and heat-treated at 450 ° C. for 1 hour. The heat treatment was performed in a mixed gas atmosphere in which argon / hydrogen (Ar / H ₂ ) was mixed at a ratio of 90: 1. Thus, the specimen of Example 1 in which the inverse opal structure was formed was obtained.

&Lt; Comparative Example 1 &

Copper specimens of the same size as in Example 1 having a thickness of 3 mm on a 10 x 20 mm2 area were prepared and washed with ethanol after passing through only mechanical polishing. Thus, a copper specimen of Comparative Example 1 in which no separate shape was formed on the surface was obtained.

&Lt; Comparative Example 2 &

Nickel (Ni) was deposited on the surface of the copper specimen obtained through the same polishing and cleaning processes as in Comparative Example 1 by electroplating for 2 hours. Thus, a copper specimen of Comparative Example 2 in which nickel was deposited on the surface was obtained.

&Lt; Comparative Example 3 &

Copper specimens obtained through the same polishing and cleaning processes as in Comparative Example 1 were further washed with 15% nitric acid (HNO ₃ ) for 30 seconds for chemical etching. Then, it was immersed in a solution of 99% acetic acid (CH ₃ COOH), 85% phosphoric acid (CH ₃ PO ₄ ) and 70% nitric acid (HNO ₃ ) in a weight ratio of 70: 26: 4 for 2 minutes. Then, 1 L of water at 65 to 70 캜 was immersed in a solution obtained by mixing 60 g of sodium hydroxide (NaOH) and 16 g of potassium persulfate (K ₂ S ₂ O ₈ ) for 4 minutes. After that, it was washed with water, transferred to a heating furnace, and heat treated at 250 ° C for 1 minute. As a result, a sample of Comparative Example 3 was obtained through chemical etching.

Experiments were conducted to measure the tensile strength of the copper samples of Example 1 and Comparative Examples 1 to 3 prepared by the above method by applying bulk polyphenylene sulfide (PPS) to the copper surface.

The measurement of the tensile strength was carried out using the superposition model shown in Fig. Each of the specimens of the Examples and Comparative Examples was heated to about 250 DEG C, and a bulk PPS (1000) was applied on the specimen in a thickness of 0.5 mm, and the other specimen was placed on the bulk PPS to form a model Completed. Then, both ends of the copper specimen were pulled to measure the tensile strength by dividing the force until the separation of the bulk PPS and the copper specimen was divided by the bonding cross-sectional area. This was measured at a rate of 0.1 mm / min at a temperature of 25 ° C.

Tensile force / area (MPa) Deviation Example 1 26.1 5.2 Comparative Example 1 0.5 0.5 Comparative Example 2 0.4 0.3 Comparative Example 3 15.3 5.1

Referring to Table 1, which is an experimental result of the tensile strength, the tensile strength of Example 1 was superior to that of Comparative Examples 1 to 3. It is thus confirmed that the inverse opal structure according to the present invention has a considerable effect on the improvement of the tensile force and the bonding force of the copper-PPS junction. Particularly, in the case of Example 1, it was confirmed that the maximum tensile strength was 31 MPa.

In the case of forming the junction body for a secondary battery by using the inverse opal structure of the present invention, a stronger bond is formed through the inverted opal structure having a narrow opening shape than the existing metal specimen and the polymer, And the sealing function can be improved.

100: metal specimen
200, 200a: opal structure
210: spherical particles
300, 300a: inverted opal structure
310: depression
330:
350: plated layer
351: Plated surface
400: polymer

Claims (16)

A method of manufacturing a bonded body for a secondary battery using an inverse opal structure,
Applying spherical particles to the surface of the metal specimen to form an opal structure;
Plating on the opal structure such that a depression having a height greater than a radius of the spherical particle and an opening smaller than a diameter of the spherical particle are formed;
Removing the spherical particles to form an inverse opal structure including the depressions and the openings;
And inserting the polymer into the inverse opal structure through the opening to inject the polymer into the inverse opal structure. The method according to claim 1,
Prior to forming the opal structure,
Further comprising the step of surface-modifying the surface of the metal specimen with a hydrophilic functional group. 3. The method of claim 2,
The step of modifying the surface with the hydrophilic functional group comprises:
Wherein the plasma is processed through a plasma system using oxygen (O ₂ ) as a reaction gas and argon (Ar) as a base gas. The method according to claim 1,
Wherein forming the opal structure comprises:
Wherein the spherical particles are applied to the surface of the metal specimen by spin coating or dip coating. &Lt; RTI ID = 0.0 &gt; 18. &lt; / RTI &gt; 5. The method of claim 4,
The spin-
Coating the spherical particles on the metal specimen rotating at a speed of 1000 to 2000 rpm;
Further comprising the step of heat treating the metal specimen coated with the spherical particles at 90 to 120 ° C. 5. The method of claim 4,
The dip-
Dipping the metal specimen lifting at a speed of 10 to 100 占 퐉 / s in a solution containing spherical particles and coating;
Further comprising the step of heat treating the metal to be bonded coated with the spherical particles at a temperature of 90 to 120 占 폚. The method according to claim 1,
After the step of forming the opal structure,
Modifying the opal structure with a hydrophilic functional group;
Further comprising coating spherical particles on top of the opaque structure to form a laminated multilayer opal structure. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt; The method according to claim 1,
Wherein forming the inverse opal structure comprises:
And dipping the metal specimen in a solvent capable of dissolving the spherical particles to dissolve the spherical particles. The method according to claim 1,
Wherein the spherical particles are at least one of polystyrene particles and silica particles having a diameter of 80 to 2000 nm. The method according to claim 1,
The diameter of the inverse opal structure is 80 to 2000 nm,
The depression is 0.6 to 0.9 times the diameter of the inverse opal structure,
Wherein the opening is 0.1 to 0.7 times the diameter of the inverse opal structure. The method according to claim 1,
Wherein the polymer is polyphenylene sulfide (PPS). &Lt; RTI ID = 0.0 &gt; 15. &lt; / RTI &gt; The method according to claim 1,
Wherein the metal specimen has a curved shape or a plate shape. In a junction body for a secondary battery using an inverse opal structure,
A metal specimen including an inverse opal structure having a diameter larger than an opening portion exposed on a surface;
And a polymer layer injected into the inverse opal structure of the metal specimen. 14. The method of claim 13,
The diameter of the inverse opal structure is 80 to 2000 nm,
Wherein the opening is 0.1 to 0.7 times the diameter of the inverse opal structure. 14. The method of claim 13,
Wherein the inverse opal structure has a height of 400 to 1500 nm. 14. The method of claim 13,
Wherein the inverse opal structure comprises a multi-layer inverted opal structure laminated on the metallic specimen.

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