KR102259542B1 - Method for manufacturing customizable aluminum polymer capacitor - Google Patents

Abstract

The present invention relates to a method for manufacturing an aluminum polymer capacitor using a polymerized conductive polymer for a solid electrolyte, wherein any one of Fe-MBS, Fe-BS, and Fe-EBS is selected as an oxidizing agent and dopant for the composition of the conductive polymer. and select any one of EDOT, ESOMT, and ESOPT as a monomer, and polymerize the selected oxidizing agent/dopant and monomer to form a solid electrolyte layer of a conductive polymer, thereby selectively controlling the characteristics of the capacitor to manufacture an aluminum polymer capacitor. can

Description

METHOD FOR MANUFACTURING CUSTOMIZABLE ALUMINUM POLYMER CAPACITOR

The present invention relates to a method for manufacturing an aluminum polymer capacitor, and more particularly, to a method for manufacturing an aluminum polymer capacitor capable of designing and controlling characteristics or performance of a capacitor according to the intended use.

The contents described below merely provide background information related to the present invention and do not constitute the prior art.

Aluminum polymer capacitors have been widely used as electrolytic capacitors due to their excellent characteristics and high reliability. Recently, with the development of digital convergence electronic devices, aluminum polymer capacitors with various characteristics are required.

For example, a capacitor with high capacitance, low dielectric loss, and relatively low equivalent series resistance is required in electronic devices that want to improve ripple characteristics. In electronic devices that want to reduce standby power, a capacitor with low leakage current is preferentially required. is required In addition, when applied to the power stage of a device, high withstand voltage performance and low leakage current will be required, heat resistance will be preferentially required in a device that generates a lot of heat, and cold resistance and long life are required when applied to outdoor facilities. will be

On the other hand, as well as various demands for the characteristics of the capacitor as described above, the demand for reduction in manufacturing cost is also increasing.

Therefore, there is a need to develop a method for manufacturing an aluminum polymer capacitor capable of selectively satisfying various characteristics of the capacitor and controlling the manufacturing cost. In other words, by selectively controlling manufacturing cost as well as capacitance, dielectric loss, equivalent series resistance (ESR), leakage current, withstand voltage, reliability, etc., which are the main characteristics of capacitors, it is possible to develop a manufacturing platform that can custom manufacture aluminum polymer capacitors. There is a need.

Korean Patent Registration No. 10-0753615 Korean Patent Registration No. 10-0417456

The present invention is to improve the problems in the manufacturing of the conventional aluminum polymer capacitor described above, and an object of the present invention is to modify the molecular weight, conductivity, and three-dimensional specificity of a material to improve resistance performance, withstand voltage performance, leakage current performance, An object of the present invention is to provide a method for manufacturing an aluminum polymer capacitor in accordance with various performance requirements of electronic devices by allowing the capacity achievement rate to be adjusted.

Specifically, by developing a suitable polymerization composition of an oxidizing agent, dopant, and monomer, the performance required for each product use of an electronic device and the corresponding price can be designed and controlled from the capacitor supplier's perspective. Conductivity for solid electrolytes of aluminum polymer capacitors This is to provide a polymer platform.

The manufacturing method of the present invention for solving the above technical problem is a manufacturing method of an aluminum polymer capacitor in which a solid electrolyte layer is formed by polymerization of a conductive polymer, and as an oxidizing agent and dopant, Fe-MBS (Fe-Methylbenzenesulfonate) and Fe- Select any one of a number of compounds in which the methyl group of MBS is substituted with a hydrogen element or an alkyl group, and also EDOT (Ethylenedioxythiophene) as a monomer, and the oxygen element of EDOT is substituted with a sulfur element, or the hydrogen element of EDOT is substituted with an alkyl group. By selecting any one of a plurality of compounds and polymerizing the selected oxidizing agent and dopant and a monomer to form a solid electrolyte layer of a conductive polymer, the characteristics of the aluminum polymer capacitor can be selectively controlled.

In the above production method, Fe-MBS as an oxidizing agent and dopant, Fe-Benzenesulfonate (Fe-BS) in which the methyl group of Fe-MBS is substituted with a hydrogen element, and Fe-EBS (Fe) in which the methyl group of Fe-MBS is substituted with an alkyl group -Ethylbenzenesulfonate), and further, as a monomer, EDOT, ESOMT in which the oxygen element of EDOT is substituted with a sulfur element, and ESOPT in which the hydrogen element of EDOT is substituted with an alkyl group is selected, and the selected oxidizing agent By polymerizing a dopant and a monomer to form a solid electrolyte layer of a conductive polymer, the characteristics of the aluminum polymer capacitor can be selectively controlled.

The characteristics of the aluminum polymer capacitor may include withstand voltage, leakage current, capacitance, and equivalent series resistance.

In the manufacturing method, Fe-BS is selected as an oxidizing agent and dopant, and any one of EDOT, ESOMT, and ESOPT is selected as a monomer, and a solid electrolyte layer of a conductive polymer is formed by polymerizing the selected oxidizing agent and dopant and a monomer. By doing so, it is possible to control the capacitance characteristics of the aluminum polymer capacitor.

In the manufacturing method, Fe-MBS is selected as an oxidizing agent and dopant, and any one of ESOMT and ESOPT is selected as a monomer, and a solid electrolyte layer of a conductive polymer is formed by polymerizing the selected oxidizing agent and dopant and a monomer. Capacitance characteristics of aluminum polymer capacitors can be adjusted.

In the manufacturing method, ESOPT is selected as a monomer, any one of Fe-BS, Fe-MBS, and Fe-EBS is selected as an oxidizing agent and dopant, and the selected oxidizing agent and dopant and a monomer are polymerized to form a conductive polymer solid electrolyte layer. By forming , it is possible to selectively control the equivalent series resistance characteristic of the aluminum polymer capacitor.

According to the method for manufacturing a customized aluminum polymer capacitor of the present invention, the following effects can be expected.

First, since the conductive polymer material can be selectively applied in the manufacture of the aluminum polymer capacitor, the overall performance of the capacitor can be improved, and the main characteristics of the capacitor can be selectively adjusted.

Second, in accordance with the various performance requirements of electronic devices, it is possible to custom manufacture an aluminum polymer capacitor with enhanced specific performance.

Third, since the conductive polymer material of the aluminum polymer capacitor can be selectively applied, an aluminum polymer capacitor having an excellent price-performance ratio can be manufactured.

1 shows chemical structures of (a) Fe-MBS, (b) Fe-BS, and (c) Fe-EBS as an oxidizing agent and dopant used in the manufacture of an aluminum polymer capacitor according to an embodiment of the present invention.
FIG. 2 shows chemical structures of (a) EDOT, (b) ESOMT, and (c) ESOPT as monomers used for manufacturing an aluminum polymer capacitor according to an embodiment of the present invention.
3 shows the chemical structure of a conductive polymer used for manufacturing an aluminum polymer capacitor.
4 shows the chemical structure of a conductive polymer in which an oxidizing agent, a dopant, and a monomer are selectively combined in the method for manufacturing an aluminum polymer capacitor according to an embodiment of the present invention.
5 is a method for manufacturing an aluminum polymer capacitor according to an embodiment of the present invention, using ESOPT as a monomer of a conductive polymer and using Fe-BS, Fe-MBS, and Fe-EBS as an oxidizing agent and dopant. represented by a graph.
6 is a flowchart illustrating a method of manufacturing an aluminum polymer capacitor according to an embodiment of the present invention.

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

The main materials of aluminum polymer capacitors are electrode foils for positive and negative electrodes, insulating paper and interior and exterior materials, and conductive polymers that form a solid electrolyte. Since the specifications of materials other than conductive polymer materials are generally fixed, the main variable influencing the characteristics and manufacturing cost of capacitors is the conductive polymer material.

Polypyrrole, polyaniline, polythiophene, etc. have been used as conductive polymers for solid electrolytes in aluminum polymer capacitors, but recently, polythiophene-based polyethylenedioxythiophene (PEDOT) is mainly used. PEDOT uses Fe-p-Toluenesulfonate (Fe-ToS) as an oxidizing agent and dopant and ethylenedioxythiophene (EDOT) as a monomer to form a solid electrolyte layer of a polymer capacitor by a chemical polymerization method.

Currently, it is known that there are few suitable capacitors in terms of stability or doping performance other than Fe-ToS as an oxidizing agent and dopant, and there are hardly any commercially available products other than EDOT as a monomer.

Since the available oxidizing agent, dopant, and monomer materials are limited, when manufacturing a capacitor using PEDOT, the characteristics and performance of the capacitor (e.g., capacitance, dielectric loss, ESR, leakage current, withstand voltage, etc.) are required. It is practically difficult to properly adjust accordingly. That is, unless the size of the capacitor is made too large to be practically used or an unrealistic manufacturing cost is invested, it is almost impossible to custom manufacture a capacitor having a specific required performance required using PEDOT.

In order to solve this problem, an oxidizing agent/dopant and a manufacturing method in which some elements of a monomer are substituted with other elements have been invented, and embodiments of the present invention will be described in detail below.

First, in Fe-ToS (Fe-Methylbenzenesulfonate: Fe-MBS), which is an oxidizing agent and dopant, an oxidizing agent and dopant in which a methyl group (CH ₃ -) is replaced with a hydrogen element or an alkyl group is synthesized. That is, Fe-BS (Fe-Benzenesulfonate) can be synthesized by substituting a methyl group with a hydrogen element, and Fe-EBS (Fe-Ethylbenzenesulfonate) can be synthesized by substituting an alkyl group, and their chemical structures are shown in FIG. It was.

Fe-BS and Fe-EBS synthesized in this way form a conductive polymer having a different structure than when Fe-MBS is used as an oxidizing agent and dopant, and accordingly, the molecular weight, conductivity, withstand voltage, capacitance, It causes differences in characteristics such as ESR.

Next, ESOMT may be synthesized by substituting a sulfur element for the oxygen element of EDOT as a monomer, and ESOPT may be synthesized by substituting a hydrogen element with an alkyl group. Their chemical structures are shown in FIG. 2 . ESOMT and ESOPT synthesized in this way form a conductive polymer having a different structure than when EDOT is used as a monomer, thereby causing differences in characteristics such as molecular weight, conductivity, withstand voltage, capacitance, and ESR of polymer capacitors. do.

That is, by substituting the oxidizing agent-dopant and monomer for synthesis as described above, various properties can be controlled by utilizing the steric hindrance of the conductive polymer. Hereinafter, when EDOT is used as a monomer, the conductive polymer is denoted as PEDOT, when ESOMT is used, the conductive polymer is denoted as PESOMT, and when ESOPT is used, the conductive polymer is denoted as PESOPT.

As described above, according to the present invention, by selectively combining three kinds of Fe-MBS, Fe-BS, and Fe-EBS as an oxidizing agent and dopant and three kinds of EDOT, ESOMT and ESOPT as monomers, a conductive polymer having a different structure is formed can do.

3 shows the structure of a conventional conductive polymer, and FIG. 4 shows the structure of a conductive polymer in which an oxidizing agent and a dopant and a monomer are selectively combined according to an embodiment of the present invention.

In addition, in FIG. 5, chemical properties (Intensity, Transmittance, Weight Fraction) in the case of using ESOPT as a monomer of the conductive polymer and Fe-BS, Fe-MBS and Fe-EBS as an oxidizing agent and dopant were compared with each other. . 5 (a) is X-ray photoelectron spectroscopy (XPS), (b) is FT-IR (Fourier-transform infrared spectroscopy), (c) is TG/DSC (Glass transition temperature/Differential Scanning Calorimetry) indicated.

As shown in FIG. 4, the conductive polymer can be polymerized using Fe-EBS as an oxidizing agent and dopant and three types of EDOT, ESOMT, and ESOPT as monomers, respectively, using ESOPT as a monomer and Fe as an oxidizing agent and dopant. -BS, Fe-MBS and Fe-EBS can be used to polymerize the conductive polymer, respectively.

Hereinafter, a method for selectively combining conductive polymer materials and manufacturing an aluminum polymer capacitor using the materials will be described.

A method of manufacturing an aluminum polymer capacitor according to an embodiment of the present invention includes etching, forming, slitting, winding, welding, carbonization, and re- It is carried out including the manufacturing process of general aluminum polymer capacitors such as forming, polymerization, assembling, and aging. Some of these processes may be omitted, and other special processes may be added as necessary.

As an example, as shown in FIG. 6 , after forming a dielectric oxide film on the surface of the anode aluminum foil, insulating paper is inserted and wound between the anode aluminum foil and the cathode aluminum foil to form a winding element (step 100). ). That is, step 100 is a step of forming a winding device through general etching, chemical conversion, cutting and winding processes.

Next, a welding process (step 200), a carbonization process (step 300), and a recharging process (step 400) are performed. The welding process is a process of resistance welding and fixing a number of unit elements to an iron rod for mass production, and the carbonization process prevents the concentration of the polymer solution on the insulating paper 30 by burning the fibrous tissue of the insulating paper 30 . The re-oxidation process is to perform anodization again to repair the damaged dielectric oxide film.

Next, in order to form a solid electrolyte layer, a conductive polymer solution is injected into the winding element and polymerized (step 500).

The polymerization process may use integral polymerization or separate polymerization. In the integral polymerization, an oxidizing agent/dopant and a monomer are mixed in an alcohol solvent in an appropriate ratio, the mixed solution is quickly injected into the winding element, and then the conductive polymer is polymerized through high temperature drying to form a solid electrolyte layer. In the separation-type polymerization, an oxidizing agent and dopant solution is injected into the winding element, the solvent is removed through drying, and then the monomer solution is injected into the winding element, and then the conductive polymer is polymerized through drying to form a solid electrolyte layer.

In this case, the conductive polymer is polymerized by selectively combining a plurality of oxidizing agents and dopants and a plurality of monomers described above. That is, the conductive polymer is polymerized by appropriately combining an oxidizing agent, a dopant, and a monomer so that the capacitor can have customized characteristics.

After the polymerization process (step 500), an assembling process of sealing the device to the case (step 600), an aging process of electrically aging the assembled device (step 700), and the like may be performed.

Hereinafter, three types of Fe-MBS, Fe-BS, and Fe-EBS as oxidizing agents and dopants and three types of EDOT, ESOMT and ESOPT as monomers are selectively combined to polymerize conductive polymers having different structures. Explain. Through these experiments, it is possible to derive a method of combining the oxidizing agent and dopant and the monomer in order to improve specific characteristics of the capacitor.

<Experimental Example 1: Product 16V/100㎌, average of 100 samples each>

- Conventional example: oxidizing agent and dopant Fe-MBS, monomer EDOT

- Invention Example 1: Oxidizing agent and dopant Fe-BS, monomer EDOT

- Invention Example 2: Oxidizing agent and dopant Fe-EBS, monomer EDOT

division Capacity (㎌) Loss (%) ESR (mΩ) LC yield
≤0.2CV (320㎂) prior art 98.6 1.5 10.6 73% Example 1 108.3 1.1 9.7 69% Example 2 93.1 1.6 11.7 88%

<Experimental Example 2: Product 16V/100㎌, average of 100 samples each>

- Conventional example: oxidizing agent and dopant Fe-MBS, monomer EDOT

- Invention Example 1: Oxidizing agent and dopant Fe-MBS, monomer ESOMT

- Invention Example 2: Oxidizing agent and dopant Fe-MBS, monomer ESOPT

division Capacity (㎌) Loss (%) ESR (mΩ) LC yield
≤0.2CV (320㎂) prior art 98.6 1.5 10.6 73% Example 1 91.5 1.8 10.0 84% Example 2 84.4 2.1 8.9 90%

<Experimental Example 3: Product 16V/100㎌, average of 100 samples each>

- Conventional example: oxidizing agent and dopant Fe-BS, monomer EDOT

- Invention Example 1: Oxidizing agent and dopant Fe-BS, monomer ESOMT

- Invention Example 2: Oxidizing agent and dopant Fe-BS, monomer ESOPT

division Capacity (㎌) Loss (%) ESR (mΩ) LC yield
≤0.2CV (320㎂) prior art 108.3 1.1 9.7 69% Example 1 93.9 1.6 9.6 79% Example 2 86.8 1.9 9.1 85%

<Experimental Example 4: Product 16V/100㎌, average of 100 samples each>

- Conventional example: oxidizing agent and dopant Fe-EBS, monomer EDOT

- Invention Example 1: Oxidizing agent and dopant Fe-EBS, monomer ESOMT

- Invention Example 2: Oxidizing agent and dopant Fe-EBS, monomer ESOPT

division Capacity (㎌) Loss (%) ESR (mΩ) LC yield
≤0.2CV (320㎂) prior art 95.1 1.6 11.7 88% Example 1 88.7 1.9 7.2 93% Example 2 82.6 2.3 6.9 99%

<Experimental Example 5: Product 16V/100㎌, average of 50 samples each>

- Invention Example 1: Oxidizing agent and dopant Fe-BS, monomer ESOPT

- Invention Example 2: Oxidizing agent and dopant Fe-MBS, monomer ESOPT

- Invention Example 3: Oxidizing agent and dopant Fe-EBS, monomer ESOPT

division Capacity (㎌) Loss (%) ESR (mΩ) LC yield
≤0.2CV (320㎂) Example 1 86.8 1.9 9.1 85% Example 2 84.4 2.1 8.9 90% Example 3 82.6 2.3 6.9 99%

<Experimental Example 6: Product 7.5V/500㎌, average of 50 samples each>

- Conventional example: oxidizing agent and dopant Fe-MBS, monomer EDOT

- Invention Example 1: Oxidizing agent and dopant Fe-BS, monomer EDOT

- Invention Example 2: Oxidizing agent and dopant Fe-EBS, monomer EDOT

division Capacity (㎌) Loss (%) ESR (mΩ) LC yield
≤0.2CV (320㎂) prior art 493.5 1.5 8.3 95% Example 1 503.4 1.1 7.7 94% Example 2 482.9 1.9 8.8 97%

<Experimental Example 7: Product 25V/47㎌, average of 50 samples each>

- Conventional example: oxidizing agent and dopant Fe-EBS, monomer EDOT

- Invention Example 1: Oxidizing agent and dopant Fe-EBS, monomer ESOMT

- Invention Example 2: Oxidizing agent and dopant Fe-EBS, monomer ESOPT

division Capacity (㎌) Loss (%) ESR (mΩ) LC yield
≤0.2CV(320㎂) prior art 46.2 2.1 14.4 51% Example 1 43.6 1.1 11.2 93% Example 2 41.8 1.9 10.1 98%

From the above experimental results, it can be seen that the specific characteristics of the capacitor can be improved according to the selection of the oxidizing agent, dopant, and monomer to compose the conductive polymer.

The relationship between the characteristics of a capacitor having a rated voltage of 16V or higher and the oxidizer, dopant, and monomer is as follows.

1) Capacitance improvement effect (Fe-BS application standard): EDOT ＜ ESOMT ＜ ESOPT

2) ESR improvement effect (ESOPT application standard): Fe-BS ＜ Fe-MBS ＜ Fe-EBS

3) Withstanding voltage and leakage current improvement effect: EDOT < ESOMT < ESOPT

4) Material price: EDOT ＜ ESOMT ＜ ESOPT, Fe-BS ＜ Fe-MBS ＜ Fe-EBS

From the above, it is preferable to use Fe-BS rather than Fe-MBS as an oxidizing agent and dopant to improve capacitance, and to improve ESR, it is preferable to use ESOMT and ESOPT rather than EDOT as a monomer, and to improve withstand voltage and leakage current. For this purpose, it can be seen that it is preferable to use ESOMT and ESOPT rather than EDOT as a monomer.

The capacitor manufacturing method of the present invention described above may be optimally applied to the field of aluminum polymer capacitors, and may also be suitably applied to the manufacture of other capacitors or electronic components.

Although the present invention has been described with reference to the above-described preferred embodiments and the accompanying drawings, different embodiments may be configured within the spirit and scope of the present invention. Accordingly, the scope of the present invention is defined by the appended claims, and should not be construed as limited by the specific embodiments described herein.

Claims (6)

An aluminum polymer capacitor that forms a solid electrolyte layer by polymerization of a conductive polymer
In the manufacturing method of the sheeter,
As an oxidizing agent and dopant, any one of Fe-BS or Fe-EBS is selected, and
As a monomer, any one of ESOMT and ESOPT is selected,
A method of manufacturing an aluminum polymer capacitor, characterized in that selectively controlling the characteristics of the aluminum polymer capacitor by forming a solid electrolyte layer of a conductive polymer by polymerizing the selected oxidizing agent and dopant and a monomer. The method of claim 1,
As an oxidizing agent and dopant, Fe-EBS is selected,
A method of manufacturing an aluminum polymer capacitor, characterized in that by polymerizing the selected oxidizing agent and dopant and a monomer to form a solid electrolyte layer of a conductive polymer, the capacitance characteristics of the aluminum polymer capacitor are adjusted. The method of claim 1,
Characteristics of the aluminum polymer capacitor include withstand voltage, leakage current, capacitance, and equivalent series resistance. The method of claim 1,
ESOMT is selected as the monomer,
A method of manufacturing an aluminum polymer capacitor, characterized in that by polymerizing the selected oxidizing agent and dopant and a monomer to form a solid electrolyte layer of a conductive polymer, the capacitance characteristics of the aluminum polymer capacitor are adjusted. The method of claim 1,
ESOPT is selected as the monomer,
A method of manufacturing an aluminum polymer capacitor, characterized in that by polymerizing the selected oxidizing agent and dopant and a monomer to form a solid electrolyte layer of a conductive polymer, the capacitance characteristics of the aluminum polymer capacitor are adjusted. The method of claim 1,
Select ESOPT as the monomer, and also
Fe-EBS is selected as an oxidizing agent and dopant,
A method of manufacturing an aluminum polymer capacitor, characterized in that selectively controlling the equivalent series resistance characteristic of the aluminum polymer capacitor by forming a solid electrolyte layer of a conductive polymer by polymerizing the selected oxidizing agent and dopant and a monomer.

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