KR20070036292A - Etching method of cathode foil for aluminum electrolytic capacitor - Google Patents
Etching method of cathode foil for aluminum electrolytic capacitor Download PDFInfo
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- KR20070036292A KR20070036292A KR1020050091165A KR20050091165A KR20070036292A KR 20070036292 A KR20070036292 A KR 20070036292A KR 1020050091165 A KR1020050091165 A KR 1020050091165A KR 20050091165 A KR20050091165 A KR 20050091165A KR 20070036292 A KR20070036292 A KR 20070036292A
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- 239000011888 foil Substances 0.000 title claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000005530 etching Methods 0.000 title claims abstract description 28
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000866 electrolytic etching Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- -1 chlorine ions Chemical class 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/06—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00 with provision for removing metal surfaces
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
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- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
본 발명은 알루미늄 전해 커패시터용 음극 박의 에칭 효율을 향상시키는 방법에 관한 것으로서, 더욱 상세하게는 알루미늄 박에 염소 이온을 포함한 전해액에서 교류전류를 인가하여 에칭을 실시할 때 염산을 주성분으로 하는 전해액에서 0.1 ~ 0.5N의 황산을 첨가하여 전류밀도, 온도, 주파수에 따른 전해 에칭을 실시함으로써, 알루미늄 박의 표면 적을 증가시켜 정전용량을 증가시키는 알루미늄 전해 커패시터용 음극 박의 제조방법을 제공한다.The present invention relates to a method for improving the etching efficiency of an anode foil for an aluminum electrolytic capacitor, and more particularly, in an electrolyte solution containing hydrochloric acid as a main component when applying an alternating current in an electrolyte solution containing chlorine ions to an aluminum foil. The present invention provides a method for producing a cathode foil for an aluminum electrolytic capacitor, by adding sulfuric acid of 0.1 to 0.5N and performing electrolytic etching according to current density, temperature, and frequency, thereby increasing the surface area of the aluminum foil and increasing capacitance.
알루미늄 전해 커패시터, 교류, 에칭, 음극 박, 염산, 표면적, 정전용량 Aluminum Electrolytic Capacitors, Alternating Current, Etching, Cathode Foil, Hydrochloric Acid, Surface Area, Capacitance
Description
제 1도는 본 발명에 따른 에칭방법의 장치를 도시한 장치개략도1 is a device schematic showing an apparatus of an etching method according to the present invention.
제 2도는 본 발명에 따른 전해 에칭 후의 표면 이미지 사진.2 is a surface image photograph after the electrolytic etching according to the present invention.
본 발명은 알루미늄 전해 커패시터용 음극박의 에칭 효율을 향상 시킨 방법에 관한 것으로서, 더욱 상세하게는 알루미늄박에 염소이온을 포함한 전해액에서 교류전류를 인가하여 에칭을 실시할 때 염산을 주성분으로 하는 전해액에서 0.1 ~ 0.5 N 의 황산을 첨가하여 전류밀도, 온도, 주파수에 따른 전해 에칭을 실시함으로써, 알루미늄박의 표면적을 증가시켜 정전용량을 증가시키는 알루미늄 전해 커패시터용 음극박의 제조방법을 제공한다The present invention relates to a method for improving the etching efficiency of a cathode foil for an aluminum electrolytic capacitor, and more particularly, in an electrolytic solution containing hydrochloric acid as the main component when an alternating current is applied to an aluminum foil in an electrolyte solution containing chlorine ions. The present invention provides a method for producing a cathode foil for an aluminum electrolytic capacitor, in which electrolytic etching is performed according to current density, temperature, and frequency by adding 0.1 to 0.5 N sulfuric acid to increase the surface area of the aluminum foil.
알루미늄 전해 커패시터는 고출력과 더불어 높은 용량을 요구하고 있으며 이러한 용량을 향상시키는 일반적인 방법으로 알루미늄 전해 커패시터는 고순도 알 루미늄 박을 염화물 수용액 중에서 직류, 교류 또는 직류, 교류를 중첩하여 전기 화학적으로 에칭하여 표면적을 확대하고 있다. 저전압용 양극 화성 박은 교류 전해를 주로 하는 에칭을, 중·고압용 박은 직류 전해를 주로 하는 에칭을 실시하여 표면적을 확대하고 있으며 음극 박은 교류 에칭을 주로 하여 에칭을 실시, 표면적을 확대하고 있다.Aluminum electrolytic capacitors require high capacity as well as high capacity.As a general method of improving such capacity, aluminum electrolytic capacitors are electrochemically etched by superimposing direct-current, alternating current, direct current or alternating current in an aqueous solution of high-purity aluminum foil in chloride solution. It is expanding. Low voltage anodic foils are used for etching mainly for alternating current electrolysis, while medium and high pressure foils are used for etching mainly for direct current electrolysis.
본 발명은 고용량의 알루미늄 전해 커패시터용 음극 박을 제조하는데 교류 전해 에칭시 여러 가지 공정변수들(전류밀도, 전해액, 온도, 교류주파수)은 정전용량에 큰 영향을 미치며 이러한 변수들에 의해 에치피트의 크기, 밀도를 좌우하므로 이러한 어려움을 해결하면서 용량 및 성능을 향상시킬 수 있는 새로운 방법을 제공하는데 있다.According to the present invention, various process variables (current density, electrolyte, temperature, and alternating frequency) have a great effect on the capacitance during alternating electrolytic etching. Its size and density are used to address these challenges and provide new ways to improve capacity and performance.
상기한 목적을 달성하기 위해 본 발명에서는 In the present invention to achieve the above object
알루미늄 박에 염소 이온을 포함한 전해액에서 교류전류를 인가하여 에칭을 실시할 때 염산을 주성분으로 하는 전해액에서 0.1 ~ 0.5 N의 황산을 첨가하여 전류밀도, 온도, 주파수에 따른 전해 에칭을 실시함으로서, 알루미늄 박의 표면적을 증가시켜 정전용량을 증가시키는 알루미늄 전해 커패시터용 음극 박의 제조방법을 주요 구성으로 한다.When etching by applying an alternating current to an aluminum foil in an electrolyte solution containing chlorine ions, electrolytic etching is performed according to the current density, temperature, and frequency by adding sulfuric acid of 0.1 to 0.5 N in an electrolyte solution containing hydrochloric acid as the main component. The manufacturing method of the cathode foil for aluminum electrolytic capacitor which increases a surface area of foil and increases a capacitance is made into a main structure.
교류전원을 이용하여 전해에칭을 실시한 알루미늄 전해커패시터용 음극박의 제조는, 교류전원을 이용한 전해에칭의 경우 생성되는 에치피트의 분포와 형상에 미치는 제 변수로는 전해액의 농도 및 온도, 전류밀도 및 주파수 등의 영향에 따라서 에칭박의 정전용량값 및 에칭양상도 서로 다르다. The production of the negative electrode foil for aluminum electrolytic capacitors subjected to electrolytic etching using an alternating current power source includes the concentration, temperature, current density, and concentration of the electrolyte solution. The capacitance value and etching pattern of the etching foil are also different depending on the influence of the frequency and the like.
전자기기 등의 소형화가 이루어지면서 알루미늄 전해커패시터의 성능도 소형화 및 고용량을 요구하고 있다. 종래에도 더욱 콘덴서의 소형화의 요청은 높아져 있었고, 에칭된 박의 용량은 더욱 요구되어 왔으며, 더욱이 다른 첨가물 없이 전해에칭을 실시하여 표면적을 증대시키는 것은 기업에서도 요구하는 기술로서, 본 발명에서는 에칭된 박의 기계적 강도를 저하시키지 않고 에칭효율을 향상시켜서 표면적을 확대하고 정전용량을 높일 수 있는 에칭방법을 제공하고자 하는 것이다.As miniaturization of electronic devices, etc., the performance of aluminum electrolytic capacitors also demands miniaturization and high capacity. Conventionally, there has been a high demand for miniaturization of capacitors, and the capacity of the etched foil has been further demanded. Furthermore, increasing the surface area by performing electroetching without other additives is a technology required by the enterprise. It is to provide an etching method that can increase the surface area and increase the capacitance by improving the etching efficiency without lowering the mechanical strength of the.
상기 구성에 따른 상세한 설명은 다음과 같다. Detailed description of the configuration is as follows.
알루미늄 박을 25 ~ 35℃의 5%인산에서 30초 ~ 3분간 전처리한 후 염산에서 30초 ~ 3분간 전처리하여 에칭 피트가 형성될 수 있는 최적의 표면상태를 만드는 단계;Pretreating the aluminum foil in 5% phosphoric acid at 25-35 ° C. for 30 seconds to 3 minutes and then pretreating in hydrochloric acid for 30 seconds to 3 minutes to create an optimal surface condition where etching pits can be formed;
염산을 포함한 전해액에서 에칭을 하되, 전해액의 농도는 0.1 ~ 0.5N의 황산을 첨가하여, 전류밀도, 전해액의 온도, 전해액에 포함되는 Cu 함량, Si 함량, Fe 함량 조절하여 에칭하는 단계를 거쳐 알루미늄 전해커패시터용 음극박의 에칭방법이 구성되며,Etch in an electrolyte solution containing hydrochloric acid, but the concentration of the electrolyte solution is 0.1 ~ 0.5N sulfuric acid, aluminum current through the step of etching by adjusting the current density, temperature of the electrolyte solution, Cu content, Si content, Fe content contained in the electrolyte solution Etching method of the cathode foil for electrolytic capacitors is configured,
이때 알루미늄 박은 순도가 99.00 ~ 99.99%이고, 두께가 0.010 ~ 0.030mm이며, 바람직하게는 순도 99.97%, 두께 0.020mm인 것을 사용한다.At this time, aluminum foil has a purity of 99.00 to 99.99%, a thickness of 0.010 to 0.030mm, preferably a purity of 99.97% and a thickness of 0.020mm.
상기 전해 에칭시 전류밀도는 0.1 ~ 0.2 A/㎠에서 주파수는 0.1 Hz ~ 100 Hz로 사용하고, 전해액의 온도는 35 ~ 95℃이며, 전해액에 포함되는 Cu, Si 및 Fe의 함량은 Cu 1 ~ 20ppm, Si 1 ~ 60ppm 및 Fe 1 ~ 65ppm으로 사용하며, 바람직하게는 전해 에칭시 전류밀도를 0.1 또는 0.2 A/㎠에서 주파수를 0.1 ~ 100㎐로 하고, 전해액의 온도는 40, 60, 90℃ 중 선택되는 한 온도로 설정하여 사용한다.In the electrolytic etching, the current density is 0.1 to 0.2 A / cm 2, the frequency is 0.1 Hz to 100 Hz, the temperature of the electrolyte is 35 to 95 ° C., and the content of Cu, Si, and Fe contained in the electrolyte is Cu 1 ~. 20ppm, Si 1 ~ 60ppm and Fe 1 ~ 65ppm, preferably in the electrolytic etching current density of 0.1 or 0.2 A / ㎠ at a frequency of 0.1 ~ 100kHz, the temperature of the electrolyte solution 40, 60, 90 ℃ Set the temperature as long as it is selected.
전류 밀도는 0.1 ~ 0.2A/㎠의 범위로 조절하게 되는데, 0.2 A/㎠ 보다 큰 전류밀도로 사용하게 되면, 급격한 산화반응이 일어나 비 표면적이 오히려 감소하게 된다.The current density is controlled in the range of 0.1 ~ 0.2A / ㎠, when used with a current density greater than 0.2 A / ㎠, the rapid oxidation occurs to reduce the specific surface area rather.
주파수는 0.1 ~ 100㎐의 범위로 사용하며, 주파수가 0.1 ㎐ 보다 낮아질 경우, 파형이 직류와 거의 같아져서 교류 에칭이 이루어지지 않으며 고주파수 즉 100 Hz 이상에서는 파형으로 인하여 비 표면적이 증가하다가 감소하는 현상이 일어난다.The frequency is used in the range of 0.1 to 100 Hz. If the frequency is lower than 0.1 Hz, the waveform is almost the same as the direct current so that no AC etching occurs. At high frequencies, that is, the specific surface area increases and decreases due to the waveform. This happens.
전해액의 온도는 35 ~ 65℃의 범위로 사용하며, 온도가 높아질수록 급격히 반응이 진행되어 산화반응이 일어나는 시간이 극히 짧고 빨라 에칭을 하기에 부적합하다는 단점을 갖는다.The temperature of the electrolyte is used in the range of 35 ~ 65 ℃, has a disadvantage that the reaction proceeds rapidly as the temperature increases so that the time of the oxidation reaction is extremely short and fast to be inadequate for etching.
또한, 전해 에칭시 전해액에 포함되어 있는 금속의 양은 매우 중요한 것으로, 포함되어 있는 금속의 농도에 따라서 에칭 표면이 많이 달라지는데 구리의 양이 적당량 이상으로 함유되어 에칭시에 갈바닉 전위(galvanic electric potential)를 형성하여 전기적인 에칭 이외에 화학적 에칭도 동시에 이루어진다.In addition, the amount of metal contained in the electrolyte during the electrolytic etching is very important. The etching surface varies considerably according to the concentration of the contained metal, and the amount of copper is contained in an appropriate amount or more, so that the galvanic electric potential during etching is increased. In addition to electrical etching, chemical etching is also performed simultaneously.
따라서 금속의 농도가 진해질 경우 표면에 급격히 반응이 일어나 부식 속도가 급격히 증가하고 비 표면적도 감소한다. 특히 음극박의 경우 두께가 얇기 때문에 Cu 1 ~ 20ppm, Si 1 ~ 60ppm 및 Fe 1 ~ 65ppm의 범위로 사용한다.Therefore, when the concentration of metal increases, the reaction occurs rapidly on the surface, and the corrosion rate increases rapidly and the specific surface area decreases. In particular, since the thickness of the cathode foil is thin, it is used in the range of Cu 1 ~ 20ppm, Si 1 ~ 60ppm and Fe 1 ~ 65ppm.
이하, 본 발명에 따른 구성을 실시 예를 통해 보다 구체적으로 살펴보도록 한다.Hereinafter, the configuration according to the present invention will be described in more detail with reference to the following examples.
실시 예Example
순도 99.97%의, 두께 0.020 ㎜의 고순도 알루미늄 박을 30℃의 5% 인산에서 1분간 전처리를 한 후, 염산에서 1분간 전처리를 행하였다.High purity aluminum foil having a purity of 99.97% and a thickness of 0.020 mm was pretreated with 5% phosphoric acid at 30 ° C. for 1 minute, followed by pretreatment with hydrochloric acid for 1 minute.
도 1에 의해 에칭을 실시하는 장비를 도식화하였다. 본 발명에 따른 염산을 포함한 전해액에서 에칭을 실시하며, 전해액의 농도는 0.5 N의 황산을 첨가하여 에칭을 실시하였다. 에칭시 전류밀도는 0.1 A/㎠, 0.2 A/㎠에서 주파수는 100 Hz, 전해액의 온도는 40, 60, 90℃이며 전해액에 포함되는 Cu의 함량은 20ppm 이하, Si의 함량은 60ppm 이하, Fe의 함량은 65ppm 이하를 유지한다. 상기와 같이하여 에칭된 알루미늄 박의 표면을 도 2에 나타내었다.The equipment for etching is shown by FIG. Etching was performed in an electrolyte solution containing hydrochloric acid according to the present invention, and the concentration of the electrolyte solution was etched by adding 0.5 N sulfuric acid. At the time of etching, the current density is 0.1 A / cm 2, 0.2 A / cm 2, the frequency is 100 Hz, the temperature of the electrolyte is 40, 60, 90 ° C. The Cu content in the electrolyte is 20ppm or less, Si content is 60ppm or less, Fe The content of is maintained below 65ppm. The surface of the aluminum foil etched as described above is shown in FIG. 2.
본 발명에 따른 알루미늄 전해커패시터용 음극 박의 에칭방법은 알루미늄 전해커패시터용 음극 박을 비교적 간단한 방법을 사용하여 제조할 수 있으며, 고용량의 음극 박 제조를 가능하게 한다.The etching method of the negative electrode foil for aluminum electrolytic capacitors according to the present invention can be produced using a relatively simple method for the negative electrode foil for aluminum electrolytic capacitors, it is possible to manufacture a high capacity negative electrode foil.
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