WO2021081882A1 - Solution de gravure d'alésage, processus de gravure et feuille d'électrode - Google Patents

Solution de gravure d'alésage, processus de gravure et feuille d'électrode Download PDF

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WO2021081882A1
WO2021081882A1 PCT/CN2019/114664 CN2019114664W WO2021081882A1 WO 2021081882 A1 WO2021081882 A1 WO 2021081882A1 CN 2019114664 W CN2019114664 W CN 2019114664W WO 2021081882 A1 WO2021081882 A1 WO 2021081882A1
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gallium
liquid metal
based liquid
solution
hole
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PCT/CN2019/114664
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English (en)
Chinese (zh)
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余英凤
何凤荣
邓利松
朱荣贵
向云刚
温益凡
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东莞东阳光科研发有限公司
乳源瑶族自治县东阳光化成箔有限公司
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Priority to PCT/CN2019/114664 priority Critical patent/WO2021081882A1/fr
Priority to CN201980101239.9A priority patent/CN114600210B/zh
Publication of WO2021081882A1 publication Critical patent/WO2021081882A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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

Definitions

  • the invention belongs to the technical field of electrode materials for capacitors, and specifically relates to a hole-expanding corrosion solution, a corrosion process and an electrode foil prepared by the corrosion process.
  • the anode foil for aluminum electrolytic capacitors generally generates a large number of vertical tunnel holes on its surface through electrochemical corrosion to increase its effective surface area, thereby increasing the capacity of the electrode foil; then a dense aluminum oxide film is formed on the surface of the corrosion hole through chemical conversion.
  • the voltage resistance of aluminum electrolytic capacitors is determined by the thickness of the oxide film, but its capacity, tensile strength and bending performance depend on the corrosion technology.
  • the conventional corrosion foil manufacturing process mainly includes pre-treatment, primary pore corrosion, secondary pore expansion corrosion, post-treatment and other processes.
  • the primary pores are carried out in the sulfuric acid-hydrochloric acid mixture to form high-density, uniform and small tunnel holes.
  • the secondary hole expansion is generally carried out in nitric acid solution.
  • the diameter of the small tunnel hole is enlarged to a degree larger than the thickness of the high-pressure oxide film to obtain a high specific volume. Corrosion determines the density of the tunnel hole, the uniformity of the hole distribution and The depth of the hole, etc.
  • a large number of studies have found that the tunnel hole in the aluminum foil is tapered after the hole is formed. When the hole is expanded, the tunnel hole will continue to be tapered.
  • the diameter of a part of the tunnel hole is always smaller than the thickness of the high-pressure oxide film. Blocking causes an increase in useless holes and limits the increase in capacity.
  • the hydrogen ions in the pores interact with aluminum metal to continue to consume, and a large amount of aluminum ions are enriched inside the pores, making the external hydrogen ion solution unable to enter quickly, resulting in insufficient reaming depth or horizontal branch holes. The capacity and bending performance of the corroded foil are reduced.
  • the present invention addresses the problems of insufficient reaming depth, too many branch holes or small holes in the reaming stage of the existing corrosion process, which leads to the reduction of the capacity of the corroded foil and the deterioration of the bending performance, and provides a reaming etching solution and Corrosion process.
  • the first object of the present invention is to provide a hole-reaming etching solution, the etching solution comprising a gallium-based liquid metal nanoparticle dispersion liquid, the gallium-based liquid metal nanoparticle dispersion liquid is composed of gallium-based liquid metal in polystyrene sulfonate Dispersed in a polymer solution of acid and sodium polystyrene sulfonate, wherein the mass fraction of the gallium-based liquid metal in the gallium-based liquid metal nanoparticle dispersion is 0.3-1.5%.
  • the mass ratio of the polystyrene sulfonic acid and sodium polystyrene sulfonate is 20:80-50:50.
  • the etching solution further includes a nitric acid solution with a concentration of 5-20 wt%, and the mass of the gallium-based liquid metal nanoparticle dispersion is 0.1-5% of the mass of the nitric acid solution.
  • the gallium-based liquid metal includes gallium and indium, and the mass ratio of gallium to indium is 60-75:40-25.
  • the second object of the present invention is to provide a method for preparing the above-mentioned hole expanding etching solution, which includes:
  • the gallium-based liquid metal is added dropwise to the above-mentioned polymer solution, mixed and processed to obtain a liquid metal nanoparticle dispersion, wherein the mass fraction of the gallium-based liquid metal in the gallium-based liquid metal nanoparticle dispersion is 0.3 -1.5%;
  • the above-mentioned gallium-based liquid metal nanoparticle dispersion is added dropwise to a nitric acid solution with a concentration of 5-20wt%, and mixed treatment to obtain a hole-expanding etching solution, wherein the mass of the gallium-based liquid metal nanoparticle dispersion is equal to that of the nitric acid solution. 0.1%-5%.
  • the mass ratio of the polystyrene sulfonic acid and sodium polystyrene sulfonate is 20:80-50:50.
  • the gallium-based liquid metal includes gallium and indium, and the mass ratio of gallium to indium is 60-75:40-25.
  • the gallium-based liquid metal is coated with a polymer solution first, and then mixed with a nitric acid solution.
  • a polymer protective layer is formed on the surface, and then prepared into nano particles, which can stably exist in the aqueous solution, so that it can be used in an aqueous environment, and the pore expansion corrosion is more uniform.
  • the gallium-based liquid metal is added dropwise to the above-mentioned polymer solution and mixed by stirring and ultrasonic vibration, the stirring speed is 800-2000 rpm, and the ultrasonic vibration frequency is 20-40 KHz.
  • the gallium-based liquid metal nanoparticle dispersion is added dropwise to a nitric acid solution with a concentration of 5-20 wt%, and mixed by stirring and ultrasonic vibration, the stirring speed is 2000-4000 rpm, and the ultrasonic vibration frequency is 20 -40KHz.
  • the third object of the present invention is to provide an electrode foil etching process that uses the above-mentioned hole-expanding etching solution to perform hole-expanding etching.
  • gallium-based liquid metal nanoparticles enter the corroded hole to efficiently corrode the hole wall and the aluminum matrix at the bottom of the hole. Because of its phagocytosis of aluminum, it reduces the expansion of the tapered hole and the enrichment of aluminum ions. And the consumption of hydrogen ions accelerate the rapid entry of hydrogen ions into the holes, increase the depth of the hole expansion, reduce the generation of branch holes or small holes, improve the corrosion efficiency and capacity, and improve the consistency of the corrosion foil.
  • the etching process of the electrode foil includes:
  • Drying drying the aluminum foil after the second water washing to obtain an electrode foil.
  • the temperature of washing the aluminum foil in the sodium hydroxide solution is 30-60° C., and the washing time is 15-30s; the temperature of washing in pure water is room temperature, and the time is 15-30s.
  • the conditions for the pores are: the temperature is 40-80° C., the current density is 0.5-3.0 A/cm 2 , and the time for pores is 5-20s.
  • the temperature of the one-time washing is room temperature, and the time is 15-30s.
  • the conditions for the hole expansion are: the temperature is 20-50° C., the current density is 0.1-1 A/cm 2 , and the hole expansion time is 20-50 s.
  • the temperature of the second water washing is room temperature, and the time is 15-30s.
  • the drying temperature is 100-300°C, and the time is 2-10 min.
  • the present invention provides electrode foils prepared by the etching process described in the present invention.
  • the present invention also provides an aluminum electrolytic capacitor including the above-mentioned electrode foil.
  • the present invention has the following technical effects:
  • gallium-based liquid metal is introduced in the process of hole expansion and corrosion.
  • the gallium-based liquid metal is highly corrosive to aluminum and has high corrosion efficiency.
  • gallium-based liquid metal is coated to form a polymer protective layer on its surface, and then prepared into nano-particles, which stably exist in an aqueous solution, so that they can be used in an aqueous environment and expand the hole. Corrosion is more uniform.
  • the gallium-based liquid metal nanoparticles enter the corroded hole to efficiently corrode the hole wall and the aluminum matrix at the bottom of the hole. Because of its corrosive effect on aluminum, it reduces the expansion and expansion of the tapered hole.
  • the enrichment of aluminum ions and the consumption of hydrogen ions accelerate the rapid entry of hydrogen ions into the holes, increase the depth of hole expansion, reduce the generation of branch holes or small holes, improve the corrosion efficiency and capacity, and improve the consistency of the corroded foil.
  • the electrode foil (etched foil) prepared by the etching process of the present invention has an electrostatic capacity increased by at least about 7%, bending at least increased by about 35%, and a reduction in corrosion thinning 2 ⁇ m, which improves the utilization rate of aluminum foil.
  • FIG. 1 Scanning electron microscope (SEM) morphology of the cross-section of the corroded foil prepared in Example 1 of the present invention
  • FIG. 2 Scanning electron microscope (SEM) morphology of the cross-section of the corroded foil prepared in Comparative Example 1 of the present invention.
  • the preparation of the hole reaming etching solution includes:
  • gallium-based liquid metal nanoparticle dispersion is added dropwise to a nitric acid solution with a concentration of 5-20wt%, and mixed treatment to obtain a pore-reaming etching solution, wherein the quality of the gallium-based liquid metal nanoparticle dispersion is a nitric acid solution 0.1-5% of the quality.
  • the gallium-based liquid metal includes gallium and indium, and the mass ratio of gallium to indium is 60-75:40-25.
  • Examples of the mass ratio of gallium and indium include but are not limited to: 60:40, 61:39, 62:38, 63:37, 64:36, 65:35, 66:34, 67:33, 68:32 , 69:31, 70:30, 71:39, 72:28, 73:27, 74:26, 75:25.
  • a polymer solution of polystyrene sulfonic acid and sodium polystyrene sulfonate is used to coat the gallium-based liquid metal to prepare a gallium-based liquid metal nanoparticle dispersion, and the polystyrene sulfonic acid and polystyrene are limited.
  • the mass ratio of sodium ethylene sulfonate is 20:80-50:50.
  • polystyrene sulfonic acid is easy to form a film on the surface of gallium-based liquid metal and has a slow dissolution rate in aqueous solution
  • polystyrene sulfonate has a slower film-forming ability on the surface of gallium-based liquid metal, but it is in an aqueous solution.
  • the dissolution rate is relatively fast.
  • the speed of polymer film formation on the surface of gallium-based liquid metal can be controlled by the mixing and compounding of polystyrene sulfonic acid and sodium polystyrene sulfonate, thereby regulating the size of gallium-based liquid metal nanoparticles; while ensuring gallium
  • the surface polymer film will not dissolve quickly after the liquid metal nanoparticles are added to the pore expansion corrosion. After they enter the corrosion holes, the surface polymer film can dissolve as soon as possible to release the gallium-based liquid metal nanoparticles.
  • the mass ratio of the polystyrene sulfonic acid and sodium polystyrene sulfonate is 20:80-50:50.
  • Examples of the mass ratio of polystyrene sulfonic acid and sodium polystyrene sulfonate include, but are not limited to: 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50: 50.
  • the dropping acceleration of the gallium-based liquid metal is 1-20 mL/min.
  • the dropping rate of the gallium-based liquid metal is 1-10mL/min, for example: 1mL/min, 2mL/min, 3mL/min, 4mL/min, 5mL/min, 6mL/min, 7mL/min min, 8mL/min, 9mL/min, 10mL/min.
  • the dropping rate of the gallium-based liquid metal is 10-20mL/min, for example: 10mL/min, 11mL/min, 12mL/min, 13mL/min, 14mL/min, 15mL/min, 16mL/min min, 17mL/min, 18mL/min, 19mL/min, 20mL/min.
  • the gallium-based liquid metal is added dropwise to the above-mentioned polymer solution, and mixed by stirring and ultrasonic vibration, and the stirring speed is 800-2000rpm (800rpm, 900rpm, 1000rpm, 2100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1700rpm, 1800rpm, 1900rpm, 2000rpm), the frequency of the ultrasonic oscillation is 20-40KHz (20KHz, 25KHz, 30KHz, 35KHz, 40KHz).
  • the mass fraction of the gallium-based liquid metal is 0.5-1.5%, for example: 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% , 1.1%, 1.2%, 1.3%, 1.4%, 1.5%.
  • step 3 the specific processing conditions are as follows:
  • the dropping rate is 0.1-5 mL/min.
  • the dropping rate is 0.1-0.5 mL/min, for example: 0.1 mL/min, 0.2 mL/min, 0.3 mL/min, 0.4 mL/min, 0.5 mL/min.
  • other preferred ranges of the dropping rate may include: 0.5-1.0 mL/min, 1.0-2.0 mL/min, 2.0-3.0 mL/min, 3.0-4.0 mL/min, 4.0-5.0 mL/min min.
  • the gallium-based liquid metal nanoparticle dispersion is added dropwise to a nitric acid solution with a concentration of 5-20wt%, and mixed by stirring and ultrasonic vibration, and the stirring speed is 2000-4000rpm (2000rpm, 2300rpm, 2500rpm, 2800rpm, 3000rpm, 3300rpm, 3500rpm, 3800rpm, 4000rpm), the frequency of ultrasonic vibration is 20-40KHz (20KHz, 25KHz, 30KHz, 35KHz, 40KHz).
  • the added amount of the gallium-based liquid metal nanoparticle dispersion is 0.1% to 5%, that is, preferably, in the pore expanding etching solution, the mass of the gallium-based liquid metal nanoparticle dispersion is nitric acid. 0.3%-5% of the mass of the solution.
  • the mass of the gallium-based liquid metal nanoparticle dispersion is 0.3%-1% of the mass of the nitric acid solution, for example: 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% %,1%.
  • the mass of the gallium-based liquid metal nanoparticle dispersion is 1% to 5% of the mass of the nitric acid solution, for example: 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4 %, 4.5%, 5%.
  • the concentration of the nitric acid solution may include: 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%.
  • the method for preparing the hole-reaming etching solution includes:
  • gallium-based liquid metal nanoparticle dispersion is added dropwise to a nitric acid solution with a concentration of 5-20wt% at a rate of 0.1-5mL/min, and stirring and ultrasonic vibration are applied at a flow rate of 0.1-5mL/min, stirring The speed is 2000-4000rpm, the ultrasonic oscillation frequency is 20-40KHz, and the pore expansion etching solution is obtained, wherein the mass of the gallium-based liquid metal nanoparticle dispersion liquid is 0.1-5% of the mass of the nitric acid solution.
  • the etching process of the electrode foil includes:
  • Drying drying the aluminum foil after the second water washing to obtain an electrode foil.
  • the aluminum foil Before pore corrosion, the aluminum foil generally needs to be cleaned and pre-treated, the purpose is to remove the oil stain and oxide layer on the surface of the aluminum foil.
  • the pretreatment can be carried out in an alkaline solution or/and an acid solution.
  • the pre-processing includes:
  • the aluminum foil in 1-5g/L (for example: 1g/L, 2g/L, 3g/L, 4g/L, 5g/L) sodium hydroxide solution at 30-60°C (for example: 30°C, 35 °C, 40°C, 45°C, 50°C, 55°C, 60°C) washing for 15-30s, and then placed in pure water at room temperature for 15-30s.
  • 1-5g/L for example: 1g/L, 2g/L, 3g/L, 4g/L, 5g/L
  • sodium hydroxide solution at 30-60°C (for example: 30°C, 35 °C, 40°C, 45°C, 50°C, 55°C, 60°C) washing for 15-30s, and then placed in pure water at room temperature for 15-30s.
  • the pre-treatment is: washing the aluminum foil in a 3 g/L sodium hydroxide solution at 50° C. for 15 seconds, and then washing it in pure water at room temperature for 15 seconds.
  • the pore etching solution is a mixed solution of sulfuric acid with a concentration of 20-60 wt% and hydrochloric acid with a concentration of 1-10 wt%.
  • the concentration of sulfuric acid in the mixed solution is 20-40wt%, for example: 20wt%, 23wt%, 25wt%, 28wt%, 30wt%, 33wt%, 35wt%, 38wt%, 40wt%.
  • the concentration of sulfuric acid in the mixed solution is 40-60wt%, for example: 40wt%, 43wt%, 45wt%, 48wt%, 50wt%, 53wt%, 55wt%, 58wt%, 60wt%.
  • the concentration of hydrochloric acid in the mixed solution is 1-5 wt%, for example: 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%.
  • the concentration of hydrochloric acid in the mixed solution is 5-10wt%, for example: 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%.
  • the pore etching solution is a mixed solution of sulfuric acid with a concentration of 40 wt% and hydrochloric acid with a concentration of 5 wt%.
  • the hole temperature is 40-60°C, for example: 40°C, 45°C, 50°C, 55°C, 60°C.
  • the pore temperature is 60-80°C, for example: 60°C, 65°C, 70°C, 75°C, 80°C.
  • the current density of the holes is 1-3A/cm 2 , for example: 1A/cm 2 , 1.5A/cm 2 , 1.8A/cm 2 , 2A/cm 2 , 2.5A/cm 2 , 2.8 A/cm 2 , 3A/cm 2 .
  • the time for making holes is 5-10s, for example: 5s, 6s, 7s, 8s, 9s, 10s.
  • the time for making holes is 10-20s, for example: 10s, 11s, 12s, 13s, 14s, 15s, 16s, 17s, 18s, 19s, 20s.
  • the aluminum foil after the pore treatment is placed in pure water and washed for 30 seconds at room temperature.
  • gallium-based liquid metal is used to replace part of the acid solution for corrosion to achieve the purpose of hole expansion.
  • the gallium-based liquid metal is coated, and the gallium-based liquid metal is coated with a polymer solution to obtain a gallium-based liquid metal nanoparticle dispersion. Then mix it with an acid solution to obtain a hole-expanding etching solution.
  • gallium-based liquid metal nanoparticles quickly enter the corrosion hole under the action of electric power, and efficiently corrode the hole wall and the aluminum matrix at the bottom of the hole. On the one hand, it reduces the expansion of the tapered hole and the consumption of hydrogen ions; On the one hand, unlike conventional acid corrosion, the corrosion effect of gallium-based liquid metal on aluminum is phagocytosis, which does not produce aluminum ions, reduces the concentration of aluminum ions in the solution, accelerates the rapid entry of hydrogen ions into the pores, and increases the depth of hole expansion. , Reduce the generation of branch holes or small holes, improve the corrosion efficiency and capacity, and improve the consistency of the corroded foil.
  • the pore reaming etching solution includes a gallium-based liquid metal nanoparticle dispersion
  • the gallium-based liquid metal nanoparticle dispersion is composed of a polymer of gallium-based liquid metal in polystyrene sulfonic acid and sodium polystyrene sulfonate. Dispersed in the solution, wherein the mass fraction of the gallium-based liquid metal is 0.3-1.5%.
  • the mass ratio of the polystyrene sulfonic acid and sodium polystyrene sulfonate is 20:80-50:50.
  • the gallium-based liquid metal includes gallium and indium, and the mass ratio of gallium to indium is 60-75:40-25.
  • the gallium-based liquid metal has a low melting point, has good fluidity after being in a liquid state, and has a low surface tension. It is easy to disperse in a polymer solution and facilitates the preparation of gallium-based liquid metal nanoparticles.
  • Examples of the mass ratio of gallium and indium include but are not limited to: 60:40, 61:39, 62:38, 63:37, 64:36, 65:35, 66:34, 67:33, 68:32 , 69:31, 70:30, 71:39, 72:28, 73:27, 74:26, 75:25.
  • examples of the mass ratio of polystyrene sulfonic acid and sodium polystyrene sulfonate include, but are not limited to: 20:80, 25:75, 30:70, 35:65, 40:60 , 45:55, 50:50.
  • the mass fraction of the gallium-based liquid metal is 0.5-1.5%, for example: 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% , 1.1%, 1.2%, 1.3%, 1.4%, 1.5%.
  • the acid solution may include: hydrochloric acid solution, nitric acid solution, etc., preferably nitric acid solution.
  • the concentration of the nitric acid solution is 5-20wt%, for example: 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%.
  • the mass of the gallium-based liquid metal nanoparticle dispersion is 0.1-5% of the mass of the nitric acid solution, that is, preferably, the mass of the gallium-based liquid metal nanoparticle dispersion is It is 0.3%-5% of the mass of the nitric acid solution.
  • the gallium-based liquid metal nanoparticle dispersion When the gallium-based liquid metal nanoparticle dispersion is added in a small amount, only part of the holes can be corroded, and the effect is not obvious.
  • the addition amount is too high, in addition to part of the gallium-based liquid metal nanoparticles entering the hole to corrode, some remain in the solution, corroding the hole of the hole, causing the expansion of the tapered hole and the phenomenon of merging, which will corrode the foil. The capacity is reduced.
  • the mass of the gallium-based liquid metal nanoparticle dispersion is 0.3%-1% of the mass of the nitric acid solution, for example: 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% %,1%.
  • the mass of the gallium-based liquid metal nanoparticle dispersion is 1% to 5% of the mass of the nitric acid solution, for example: 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4 %, 4.5%, 5%.
  • the conditions for the hole expansion are: the temperature is 20-50° C., the current density is 0.1-1 A/cm2, and the hole expansion time is 20-50s.
  • the expansion temperature may include: 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, and 50°C.
  • the current density of the reaming is 0.1-1A/cm 2 , for example: 0.1A/cm 2 , 0.2A/cm 2 , 0.3A/cm 2 , 0.4A/cm 2 , 0.5A/cm 2 , 0.6A/cm 2 cm 2 , 0.7A/cm 2 , 0.8A/cm 2 , 0.9A/cm 2 , 1A/cm 2 .
  • the time for the holes can be listed as: 20s, 23s, 25s, 28s, 30s, 33s, 35s, 38s, 40s, 43s, 45s, 48s, 50s.
  • the conditions for forming the holes are: a temperature of 50° C., a current density of 0.5 A/cm 2 , and a hole forming time of 30 seconds.
  • the aluminum foil after the hole expansion treatment is placed in pure water and washed for 20 seconds at room temperature.
  • the aluminum foil after the second water washing is dried at 100-300° C. for 2-10 minutes to obtain electrode foil.
  • the drying temperature may include: 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, 250°C, 280°C, and 300°C.
  • the drying time may include: 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min.
  • the etching process of the electrode foil includes:
  • Pore place the pre-treated aluminum foil in a mixed solution of 20-60wt% sulfuric acid and 1-10wt% hydrochloric acid to make holes at a temperature of 40-80°C and a current density of 0.5-3.0A /cm 2 , the time for making holes is 5-20s;
  • Drying drying the aluminum foil after the second water washing to obtain an electrode foil.
  • room temperature in the present invention refers to a temperature of 20-30°C.
  • Pre-treatment Use 3g/L sodium hydroxide solution to treat the aluminum foil to remove the oil and oxide layer on the surface. The temperature is 50°C, and the treatment time is 15s. Then the aluminum foil is cleaned in pure water at room temperature 15s.
  • Pore formation the pre-treated aluminum foil is energized in an etching bath solution, which is a mixed solution of sulfuric acid with a concentration of 40 wt% and hydrochloric acid with a concentration of 5 wt%, at a temperature of 40°C, and a current
  • the density is 1.8A/cm 2
  • the hole making time is 20s.
  • Reaming The aluminum foil washed with water is placed in the reaming etching solution prepared in step 3) and then electrified for reaming treatment.
  • the temperature is 50° C.
  • the current density is 0.5 A/cm 2
  • the reaming time is 30 seconds.
  • FIG. 1 The cross-sectional scanning electron microscope (SEM) morphology of the electrode foil (etched foil) obtained in this embodiment is shown in FIG. 1. It can be seen from the figure that the hole diameter and length of the corroded foil are relatively uniform, the thickness of the middle sandwich layer is uniform, and the hole reaming depth is consistent.
  • Pre-treatment Use 3g/L sodium hydroxide solution to treat the aluminum foil to remove the oil and oxide layer on the surface. The temperature is 50°C, and the treatment time is 15s. Then the aluminum foil is cleaned in pure water at room temperature 15s.
  • Pore formation the pre-treated aluminum foil is energized in an etching bath solution, which is a mixed solution of sulfuric acid with a concentration of 40 wt% and hydrochloric acid with a concentration of 5 wt%, at a temperature of 40°C, and a current
  • the density is 1.8A/cm 2
  • the hole making time is 20s.
  • Reaming The aluminum foil washed with water is placed in the reaming etching solution prepared in step 3) and then electrified for reaming treatment.
  • the temperature is 50° C.
  • the current density is 0.5 A/cm 2
  • the reaming time is 30 seconds.
  • Pre-treatment Use 3g/L sodium hydroxide solution to treat the aluminum foil to remove the oil and oxide layer on the surface. The temperature is 50°C, and the treatment time is 15s. Then the aluminum foil is cleaned in pure water at room temperature 15s.
  • Pore formation the pre-treated aluminum foil is energized in an etching bath solution, which is a mixed solution of sulfuric acid with a concentration of 40 wt% and hydrochloric acid with a concentration of 5 wt%, at a temperature of 40°C, and a current
  • the density is 1.8A/cm 2
  • the hole making time is 20s.
  • Reaming The aluminum foil washed with water is placed in the reaming etching solution prepared in step 3) and then electrified for reaming treatment.
  • the temperature is 50° C.
  • the current density is 0.5 A/cm 2
  • the reaming time is 30 seconds.
  • Pre-treatment Use 3g/L sodium hydroxide solution to treat the aluminum foil to remove the oil and oxide layer on the surface. The temperature is 50°C, and the treatment time is 15s. Then the aluminum foil is cleaned in pure water at room temperature 15s.
  • Pore formation the pre-treated aluminum foil is energized in an etching bath solution, which is a mixed solution of sulfuric acid with a concentration of 40 wt% and hydrochloric acid with a concentration of 5 wt%, at a temperature of 40°C, and a current
  • the density is 1.8A/cm 2
  • the hole making time is 20s.
  • Reaming The aluminum foil washed with water is placed in the reaming etching solution prepared in step 3) and then electrified for reaming treatment.
  • the temperature is 50° C.
  • the current density is 0.5 A/cm 2
  • the reaming time is 30 seconds.
  • Pre-treatment Use 3g/L sodium hydroxide solution to treat the aluminum foil to remove the oil and oxide layer on the surface. The temperature is 50°C, and the treatment time is 15s. Then the aluminum foil is cleaned in pure water at room temperature 15s.
  • Pore formation the pre-treated aluminum foil is energized in an etching bath solution, which is a mixed solution of sulfuric acid with a concentration of 40wt% and hydrochloric acid at a concentration of 5wt%, at a temperature of 40°C, and a current
  • the density is 1.8A/cm 2
  • the hole making time is 20s.
  • Reaming The aluminum foil washed with water is placed in a 6% nitric acid reaming solution and electrified for reaming treatment, the temperature is 50°C, the current density is 0.5A/cm 2 , and the reaming time is 30s.
  • FIG. 2 The cross-sectional scanning electron microscope (SEM) morphology of the electrode foil (etched foil) obtained in this embodiment is shown in FIG. 2. It can be seen from the figure that the pore size and length of the corroded foil are uneven, the thickness uniformity of the middle sandwich layer is very poor, even perforation occurs, and the consistency of the reaming depth is not good.
  • Pre-treatment Use 3g/L sodium hydroxide solution to process the aluminum foil to remove the oil stains and oxide layers on the surface.
  • the temperature is 50°C
  • the treatment time is 15s
  • the aluminum foil is cleaned in pure water at room temperature. 15s.
  • Pore formation the pre-treated aluminum foil is energized in an etching bath solution, which is a mixed solution of 40wt% sulfuric acid and 5wt% hydrochloric acid, at a temperature of 40°C, and a current
  • the density is 1.8A/cm 2
  • the hole making time is 20s.
  • One-time washing Wash the aluminum foil after pore treatment in pure water for 30s at room temperature.
  • Reaming The aluminum foil washed with water is placed in the reaming etching solution prepared in step 3) and then electrified for reaming treatment.
  • the temperature is 50° C.
  • the current density is 0.5 A/cm 2
  • the reaming time is 30 seconds.
  • Pre-treatment Use 3g/L sodium hydroxide solution to treat the aluminum foil to remove the oil and oxide layer on the surface. The temperature is 50°C, and the treatment time is 15s. Then the aluminum foil is cleaned in pure water at room temperature 15s.
  • Pore formation the pre-treated aluminum foil is energized in an etching bath solution, which is a mixed solution of sulfuric acid with a concentration of 40 wt% and hydrochloric acid with a concentration of 5 wt%, at a temperature of 40°C, and a current
  • the density is 1.8A/cm 2
  • the hole making time is 20s.
  • Reaming The aluminum foil washed with water is placed in the reaming etching solution prepared in step 3) and then electrified for reaming treatment.
  • the temperature is 50° C.
  • the current density is 0.5 A/cm 2
  • the reaming time is 30 seconds.
  • Pre-treatment Use 3g/L sodium hydroxide solution to treat the aluminum foil to remove the oil and oxide layer on the surface. The temperature is 50°C, and the treatment time is 15s. Then the aluminum foil is cleaned in pure water at room temperature 15s.
  • Pore formation the pre-treated aluminum foil is energized in an etching bath solution, which is a mixed solution of sulfuric acid with a concentration of 40 wt% and hydrochloric acid with a concentration of 5 wt%, at a temperature of 40°C, and a current
  • the density is 1.8A/cm 2
  • the hole making time is 20s.
  • Reaming The aluminum foil washed with water is placed in the reaming etching solution prepared in step 3) and then electrified for reaming treatment.
  • the temperature is 50° C.
  • the current density is 0.5 A/cm 2
  • the reaming time is 30 seconds.
  • Pre-treatment Use 3g/L sodium hydroxide solution to treat the aluminum foil to remove the oil and oxide layer on the surface. The temperature is 50°C, and the treatment time is 15s. Then the aluminum foil is cleaned in pure water at room temperature 15s.
  • Pore formation the pre-treated aluminum foil is energized in an etching bath solution, which is a mixed solution of sulfuric acid with a concentration of 40 wt% and hydrochloric acid with a concentration of 5 wt%, at a temperature of 40°C, and a current
  • the density is 1.8A/cm 2
  • the hole making time is 20s.
  • Reaming The aluminum foil washed with water is placed in the reaming etching solution prepared in step 3) and then electrified for reaming treatment.
  • the temperature is 50° C.
  • the current density is 0.5 A/cm 2
  • the reaming time is 30 seconds.
  • the corrosion foil prepared by the corrosion process of the present invention has a reduction of 2 ⁇ m in corrosion thinning compared with the existing corrosion process (Comparative Example 1), a capacity increase of at least about 7%, and a bending increase of at least about 35%, effectively reducing the generation of branch holes or small holes, improving corrosion efficiency and capacity.
  • the mass ratio of polystyrene sulfonic acid and sodium polystyrene sulfonate is 10:90.
  • the polymer film formed on the surface of the liquid metal is mainly sodium polystyrene sulfonate. After being added to the reaming solution, the polymer film on the surface of the gallium-based liquid metal nanoparticles quickly dissolves, and the gallium-based liquid metal is released. Part of the aluminum foil is corroded on the surface of the aluminum foil and the openings of the holes, resulting in an increase in the thinning of the aluminum foil, an enlarged tapered hole, and a decrease in capacity.

Abstract

La présente invention concerne une solution de gravure d'alésage, un processus de gravure et une feuille d'électrode préparée au moyen du processus de gravure dans le domaine technique des matériaux d'électrode pour condensateurs. La solution de gravure d'alésage contient une dispersion de nanoparticules de métal liquide à base de gallium, qui est obtenue par dispersion d'un métal liquide à base de gallium dans une solution polymérique d'un acide sulfonique de polystyrène et de polystyrène sulfonate de sodium, la fraction massique du métal liquide à base de gallium étant de 0,3 % à 1,5 %. La feuille d'électrode préparée par le processus de gravure pour aléser un trou au moyen d'une solution de gravure d'alésage a une profondeur de trou accrue, des trous de ramification réduits ou de petits trous, une bonne homogénéité de trou, ainsi qu'une capacité électrostatique et une résistance à la flexion plus élevées.
PCT/CN2019/114664 2019-10-31 2019-10-31 Solution de gravure d'alésage, processus de gravure et feuille d'électrode WO2021081882A1 (fr)

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CN201980101239.9A CN114600210B (zh) 2019-10-31 2019-10-31 扩孔腐蚀液、腐蚀工艺及电极箔

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