CN115148501B - Hot-pressed foil, preparation method thereof, electrode and capacitor - Google Patents

Hot-pressed foil, preparation method thereof, electrode and capacitor Download PDF

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Publication number
CN115148501B
CN115148501B CN202210833447.1A CN202210833447A CN115148501B CN 115148501 B CN115148501 B CN 115148501B CN 202210833447 A CN202210833447 A CN 202210833447A CN 115148501 B CN115148501 B CN 115148501B
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foil
hot
pressed
powder
treatment
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CN115148501A (en
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李新芳
游彭飞
陈锁斌
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Xinjiang Joinworld Co Ltd
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Xinjiang Joinworld Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • 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
    • H01G9/052—Sintered electrodes
    • H01G9/0525—Powder therefor

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a hot-pressed foil and a preparation method thereof, an electrode and a capacitor, wherein the preparation method of the hot-pressed foil comprises the following steps: providing powder, wherein the powder comprises aluminum powder and an organic binder in a mass ratio of 6:1-12:1; laying the powder on at least one surface of the base foil, and carrying out hot rolling treatment to prepare a hot rolled foil; degreasing the hot rolled foil in an inert atmosphere containing 0.1-5% of oxygen or water vapor by volume, and then sintering the hot rolled foil in inert gas or vacuum to prepare an unformed foil; and (3) sequentially performing water boiling treatment and formation treatment on the non-formed foil to prepare the hot-pressed foil. In the process of preparing the hot-pressed foil, oxygen or water vapor with proper volume content is introduced in the degreasing and sintering processes, so that the carbon simple substance reacts with the hot-pressed foil and is discharged in a gas form, the carbon content in the hot-pressed foil is reduced, the leakage current of the hot-pressed foil is further reduced, and the service life of a capacitor serving as an electrode is prolonged.

Description

Hot-pressed foil, preparation method thereof, electrode and capacitor
Technical Field
The invention relates to the field of capacitors, in particular to a hot-pressed foil, a preparation method thereof, an electrode and a capacitor.
Background
Aluminum electrolytic capacitors are often used to manufacture important electronic components because of their higher specific capacitance than other capacitors at the same volume. The anode foil of the traditional aluminum electrolytic capacitor is subjected to multiple electrochemical pore-forming and reaming corrosion procedures through a sulfuric acid-hydrochloric acid system and a nitric acid system, tunnel pores are formed on the surface of an electronic aluminum foil to increase the specific surface area of the aluminum foil, and finally an alumina dielectric layer is formed on the surface of the tunnel pores through formation energization to prepare the anode foil for the aluminum electrolytic capacitor. However, the conventional anode foil manufacturing process is complicated, the corrosion process is high in requirement, the utilization rate of raw materials in the electrochemical corrosion process is low, waste acid can be generated, and a large amount of electric energy loss and environmental protection pressure can be caused. Because the sintering process does not need to adopt acid liquor to corrode the pore-forming and reaming, no waste acid is produced and recovered in the preparation process, the sintering process is commonly used for preparing the capacitor electrode material.
However, the conventional sintering process has the problem of larger leakage current in the prepared capacitor electrode material, resulting in shorter service life of the capacitor.
Disclosure of Invention
Based on this, in order to make the hot-pressed foil have a small leakage current, it is necessary to provide a hot-pressed foil and a manufacturing method thereof, an electrode, and a capacitor.
The invention provides a preparation method of hot-pressed foil, which comprises the following steps:
providing powder, wherein the powder comprises aluminum powder and an organic binder in a mass ratio of 6:1-12:1;
laying the powder on at least one surface of the base foil, and carrying out hot rolling treatment to prepare a hot rolled foil;
degreasing the hot rolled foil in an inert atmosphere containing 0.1-5% of oxygen or water vapor by volume, and then sintering the hot rolled foil in inert gas or vacuum to prepare an unformed foil;
and sequentially performing water boiling treatment and formation treatment on the unformed foil to prepare the hot-pressed foil.
In one embodiment, the degreasing treatment comprises degreasing the hot rolled foil at a temperature of 200-400 ℃ for 1-6 hours.
In one embodiment, the sintering process includes sintering the hot rolled foil after the degreasing process at a temperature of 560 ℃ to 650 ℃ for 1h to 24h.
In one embodiment, the organic binder is selected from at least one of acrylic resin, ethylcellulose, polyurethane, polystyrene, and polyacrylate.
In one embodiment, the hot rolling process is performed at a pressure of 800N to 1200N and a temperature of 130 ℃ to 180 ℃.
In one embodiment, the water boiling treatment comprises immersing the non-formed foil in pure water at 90-99 ℃ for 3-30 min.
In one embodiment, the formation treatment comprises immersing a cathode and the non-formed foil subjected to the water boiling treatment as an anode in a formation liquid, and carrying out current loading to reach a preset voltage value, wherein the cathode is selected from stainless steel or graphite polar plates, so as to prepare the hot-pressed foil.
The invention also provides a hot-pressed foil, which is prepared according to the preparation method of the hot-pressed foil.
Further, the invention provides an electrode comprising the hot-pressed foil.
The invention further provides a capacitor comprising the electrode.
The leakage current of the hot-pressed foil is increased due to the fact that carbon simple substances are separated out during sintering, so that oxygen or water vapor with proper volume content is introduced during degreasing and sintering in the process of preparing the hot-pressed foil, the carbon simple substances react with the hot-pressed foil to generate carbon monoxide, carbon dioxide and hydrogen to be discharged in a gas form, the carbon content in the hot-pressed foil is reduced, the leakage current of the hot-pressed foil is further reduced, and the service life of a capacitor serving as an electrode is prolonged.
Detailed Description
The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present invention, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a preparation method of hot-pressed foil, which comprises the following steps of S10 to S40:
step S10: providing powder, wherein the powder comprises aluminum powder and an organic binder in a mass ratio of 6:1-12:1;
step S20: laying powder on at least one surface of the base foil, and carrying out hot rolling treatment to prepare hot rolled foil;
step S30: degreasing the hot rolled foil in an inert atmosphere containing 0.1-5% of oxygen or steam by volume, and then sintering the hot rolled foil under inert gas or vacuum to prepare an unformed foil;
step S40: and (3) sequentially performing water boiling treatment and formation treatment on the non-formed foil to prepare the hot-pressed foil.
In a specific example, in step S10, the mass ratio of the aluminum powder and the organic binder in the powder may be, but is not limited to, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, or 12:1.
In a specific example, the aluminum powder has an average particle diameter D 50 Is 1-8 μm.
It will be appreciated that the above-mentioned aluminum powder has an average particle diameter D 50 May be, but is not limited to, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm or 8 μm.
Further, the purity of aluminum in the aluminum powder is >99.99%.
In a specific example, the base foil is selected from aluminum alloy foils having a purity of greater than 99.7%.
Further, the thickness of the base layer foil is 10 μm to 50 μm, and specifically, the thickness of the base layer foil may be, but not limited to, selected from 10 μm, 20 μm, 30 μm, 40 μm or 50 μm.
The base foil is preferably an aluminum foil with a purity of > 99.9%.
Further, in step S20, the powder may be spread on at least one surface of the base foil by at least one of spraying, spin coating and brushing, and preferably by spraying.
In a specific example, the hot rolling treatment includes hot rolling treatment of the base foil on which the powder is laid under a pressure of 800N to 1200N and a temperature of 130 to 180 ℃.
It is understood that the pressure in the hot rolling process described above may be, but is not limited to, 800N, 850N, 900N, 950N, 1000N, 1050N, 1100N, 1150N, or 1200N. Further, the temperature in the hot rolling treatment may be, but is not limited to 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, or 180 ℃. The powder containing the mixed organic binder is hot-rolled with the base foil in a hot-rolling mode, and the binder is heated and melted and cooled and solidified after rolling, so that the powder is well combined with the base foil, and the falling phenomenon can not occur.
After the hot rolling treatment, the thickness of the powder on the surface of the base foil is 30-60 mu m.
It will be appreciated that the base layer foil has a first surface and a second surface opposite the first surface, and that the thickness of the powder is each independently selected from 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm or 60 μm when the powder is laid on the first surface and the second surface of the base layer foil.
In a specific example, in step S30, the degreasing treatment includes degreasing the hot rolled foil at a temperature of 200 to 400 ℃ for 1 to 6 hours.
Further, the degreasing treatment may be performed at a temperature of 200 ℃, 250 ℃, 300 ℃, 350 ℃ or 400 ℃ without limitation. The degreasing treatment time may be, but is not limited to, 1h, 2h, 3h, 4h, 5h, or 6h.
It will be appreciated that the degreasing treatment is to rest the hot rolled foil at the respective degreasing temperature.
In a specific example, in step S30, the inert atmosphere containing 0.1% to 5% by volume of oxygen or water vapor means that the remaining gas other than oxygen or water vapor is an inert gas.
It is understood that the inert gas may be, but is not limited to, helium or argon.
In a specific example, in step S30, the sintering treatment includes sintering the hot rolled foil after the degreasing treatment at a sintering temperature of 560 ℃ to 650 ℃ for 1h to 24h.
Further, the sintering temperature may be, but is not limited to, 560 ℃, 580 ℃, 600 ℃, 620 ℃, 640 ℃, or 650 ℃. The sintering process may be, but is not limited to, 1h, 3h, 5h, 7h, 9h, 11h, 13h, 15h, 17h, 19h, 21h, 23h, or 24h.
In a specific example, in step S40, the water boiling treatment includes immersing the non-formed foil in pure water at 90 to 99 ℃ for 3 to 30 minutes.
It is understood that the temperature of the pure water may be, but not limited to, 90 ℃, 91 ℃, 93 ℃, 95 ℃, 97 ℃ or 99 ℃ and the soaking time may be, but not limited to, 3min, 5min, 10min, 20min, 25min or 30min.
In a specific example, in step S40, the formation process includes immersing the non-formed foil subjected to the water boiling process as an anode and a cathode in a formation liquid, and loading a current to a preset voltage value to prepare a hot-pressed foil.
Further, the formation liquid is a mixed solution of 100g/L boric acid and 0.9g/L ammonium pentaborate, the cathode is selected from stainless steel or graphite polar plates as the cathode, and the formation time is 5-20 min.
Further, the formation temperature is 80 to 90 ℃, specifically, the formation temperature may be, but not limited to, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, or 90 ℃.
It is understood that the above-mentioned formation treatment is not limited to one time, and the non-formed foil subjected to the water boiling treatment after the previous formation may be treated at 400 to 600 ℃ for 1 to 5 minutes between the multiple formation treatments. The treatment method is that the mixture is put in the air.
The leakage current of the hot-pressed foil is increased due to the fact that carbon simple substances are separated out during sintering, so that oxygen or water vapor with proper volume content is introduced during degreasing and sintering in the process of preparing the hot-pressed foil, the carbon simple substances react with the hot-pressed foil to generate carbon monoxide, carbon dioxide and hydrogen to be discharged in a gas form, the carbon content in the hot-pressed foil is reduced, the leakage current of the hot-pressed foil is further reduced, and the service life of a capacitor serving as an electrode is prolonged.
The invention also provides a hot-pressed foil, which is prepared according to the preparation method of the hot-pressed foil.
Further, the invention provides an electrode comprising the hot-pressed foil.
The invention further provides a capacitor comprising the electrode.
Specific examples are provided below to illustrate the preparation method of the hot-pressed foil and the hot-pressed foil according to the present invention in further detail. The raw materials according to the following embodiments may be commercially available unless otherwise specified.
Example 1
The embodiment provides a hot-pressed foil, and the preparation method thereof specifically comprises the following steps:
uniformly mixing high-purity (> 99.99%) aluminum powder with an average particle size D50 of 3 mu m with acrylic resin according to a mass ratio of 9:1 to obtain powder;
uniformly spraying powder on a first surface of an aluminum foil with the thickness of 30 mu m and the purity of more than 99.9 percent in a spraying mode, applying 1000N pressure at the temperature of 150 ℃ in a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the first surface of the aluminum foil to be 50 mu m;
uniformly spraying powder on the second surface of the aluminum foil with the thickness of 30 mu m in sequence by a spraying mode, applying 1000N pressure at the temperature of 150 ℃ by a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the second surface of the aluminum foil to be 50 mu m to prepare a hot rolled foil;
degreasing the hot rolled foil in an argon atmosphere with the oxygen volume content of 0.1% at 200 ℃ for 6 hours and sintering the hot rolled foil in a vacuum environment at 560 ℃ for 24 hours to prepare an unformed foil;
immersing the non-formed foil in 95 ℃ pure water for 15min, taking the non-formed foil after the water boiling treatment as an anode and stainless steel as a cathode, and loading 0.5A/cm in a mixed solution containing 100g/L boric acid and 0.9g/L ammonium pentaborate at 88 DEG C 2 Carrying out electric fluidization for 20min, carrying out chemical fluidization to 520V, standing in air at 500 ℃ for 2min, and loading for 0.5A/cm 2 Performing secondary current formation for 10min until the current reaches 520V, and preparing the hot-pressed foil of the embodiment;
hot-pressed foil leakage current detection prepared through the steps: in boric acid of 70g/L at 65 ℃, a current of 4mA is used for detecting leakage current on a sample wafer of 1X 5cm, an industry universal leakage current detector is used for testing, and a leakage current result is that: 0.25mA; and (3) carbon sulfur analysis and detection: carbon residue was measured by a carbon-sulfur analyzer, 0.25%.
Example 2
The embodiment provides a hot-pressed foil, and the preparation method thereof specifically comprises the following steps:
uniformly mixing high-purity (> 99.99%) aluminum powder with an average particle size D50 of 3 mu m with acrylic resin according to a mass ratio of 9:1 to obtain powder;
uniformly spraying powder on a base foil with the thickness of 30 mu m and the first surface of an aluminum foil with the purity of more than 99.9%, applying 1000N pressure at the temperature of 150 ℃ in a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the first surface of the aluminum foil to be 50 mu m;
uniformly spraying powder on the second surface of the aluminum foil with the thickness of 30 mu m in sequence by a spraying mode, applying 1000N pressure at the temperature of 150 ℃ by a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the second surface of the aluminum foil to be 50 mu m to prepare a hot rolled foil;
degreasing the hot rolled foil in an argon atmosphere with the oxygen volume content of 5% at 400 ℃ for 1h and sintering the hot rolled foil in a vacuum environment at 650 ℃ for 1h to prepare an unformed foil;
immersing the non-formed foil in 95 ℃ pure water for 15min, taking the non-formed foil after the water boiling treatment as an anode and stainless steel as a cathode, and loading 0.5A/cm in a mixed solution containing 100g/L boric acid and 0.9g/L ammonium pentaborate at 88 DEG C 2 Carrying out electric fluidization for 20min, carrying out chemical fluidization for 520V, placing in air at 500 ℃ for 2min, and loading 0.5A/cm 2 Carrying out secondary formation on the current for 10min until the current reaches 520V, and preparing the hot-pressed foil of the embodiment;
hot-pressed foil leakage current detection prepared through the steps: in boric acid of 70g/L at 65 ℃, a current of 4mA is used for detecting leakage current on a sample wafer of 1X 5cm, an industry universal leakage current detector is used for testing, and a leakage current result is that: 0.18mA; and (3) carbon sulfur analysis and detection: carbon residue was measured by a carbon-sulfur analyzer, 0.19%.
Example 3
The embodiment provides a hot-pressed foil, and the preparation method thereof specifically comprises the following steps:
uniformly mixing high-purity (> 99.99%) aluminum powder with an average particle size D50 of 3 mu m with acrylic resin according to a mass ratio of 9:1 to obtain powder;
uniformly spraying powder on a base foil with the thickness of 30 mu m and the first surface of an aluminum foil with the purity of more than 99.9%, applying 1000N pressure at the temperature of 150 ℃ in a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the first surface of the aluminum foil to be 50 mu m;
uniformly spraying powder on the second surface of the aluminum foil with the thickness of 30 mu m in sequence by a spraying mode, applying 1000N pressure at the temperature of 150 ℃ by a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the second surface of the aluminum foil to be 50 mu m to prepare a hot rolled foil;
degreasing the hot rolled foil in an argon atmosphere with the water vapor volume content of 0.1% at 400 ℃ for 1h and sintering the hot rolled foil in an argon atmosphere at 600 ℃ for 24h to prepare an unformed foil;
immersing the non-formed foil in 95 ℃ pure water for 15min, taking the non-formed foil after the water boiling treatment as an anode and stainless steel as a cathode, and loading 0.5A/cm in a mixed solution containing 100g/L boric acid and 0.9g/L ammonium pentaborate at 88 DEG C 2 Carrying out electric fluidization for 20min, carrying out chemical fluidization for 520V, placing in air at 500 ℃ for 2min, and loading 0.5A/cm 2 Carrying out secondary formation on the current for 10min until the current reaches 520V, and preparing the hot-pressed foil of the embodiment;
hot-pressed foil leakage current detection prepared through the steps: in boric acid of 70g/L at 65 ℃, a current of 4mA is used for detecting leakage current on a sample wafer of 1X 5cm, an industry universal leakage current detector is used for testing, and a leakage current result is that: 0.26mA; and (3) carbon sulfur analysis and detection: carbon residue was measured by a carbon-sulfur analyzer, 0.28%.
Example 4
The embodiment provides a hot-pressed foil, and the preparation method thereof specifically comprises the following steps:
uniformly mixing high-purity (> 99.99%) aluminum powder with an average particle size D50 of 3 mu m with acrylic resin according to a mass ratio of 9:1 to obtain powder;
uniformly spraying powder on a base foil with the thickness of 30 mu m and the first surface of an aluminum foil with the purity of more than 99.9%, applying 1000N pressure at the temperature of 150 ℃ in a hot rolling mode to melt acrylic resin in the powder, enabling the powder to adhere to the aluminum foil, and controlling the thickness of the powder adhered to the first surface of the aluminum foil to be 50 mu m;
uniformly spraying powder on the second surface of the aluminum foil with the thickness of 30 mu m in sequence by a spraying mode, applying 1000N pressure at the temperature of 150 ℃ by a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the second surface of the aluminum foil to be 50 mu m to prepare a hot rolled foil;
degreasing the hot rolled foil in an argon atmosphere with the water vapor volume content of 5% at 300 ℃ for 3 hours and sintering the hot rolled foil in an argon atmosphere at 600 ℃ for 12 hours to prepare an unformed foil;
immersing the non-formed foil in 95 ℃ pure water for 15min, taking the non-formed foil after the water boiling treatment as an anode and stainless steel as a cathode, and loading 0.5A/cm in a mixed solution containing 100g/L boric acid and 0.9g/L ammonium pentaborate at 88 DEG C 2 Carrying out electric fluidization for 20min, carrying out chemical fluidization for 520V, placing in air at 500 ℃ for 2min, and loading 0.5A/cm 2 Carrying out secondary formation on the current for 10min until the current reaches 520V, and preparing the hot-pressed foil of the embodiment;
hot-pressed foil leakage current detection prepared through the steps: in boric acid of 70g/L at 65 ℃, a current of 4mA is used for detecting leakage current on a sample wafer of 1X 5cm, an industry universal leakage current detector is used for testing, and a leakage current result is that: 0.2mA; and (3) carbon sulfur analysis and detection: carbon residue was measured by a carbon-sulfur analyzer, 0.23%.
Comparative example 1
The comparative example provides a hot-pressed foil, the preparation method of which specifically comprises the following steps:
uniformly mixing high-purity (> 99.99%) aluminum powder with an average particle size D50 of 3 mu m with acrylic resin according to a mass ratio of 9:1 to obtain powder;
uniformly spraying powder on a base foil with the thickness of 30 mu m and the first surface of an aluminum foil with the purity of more than 99.9%, applying 1000N pressure at the temperature of 150 ℃ in a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the first surface of the aluminum foil to be 50 mu m;
uniformly spraying powder on the second surface of the aluminum foil with the thickness of 30 mu m in sequence by a spraying mode, applying 1000N pressure at the temperature of 150 ℃ by a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the second surface of the aluminum foil to be 50 mu m to prepare a hot rolled foil;
degreasing the hot rolled foil in an argon atmosphere at 400 ℃ for 1h and sintering the hot rolled foil in a vacuum environment at 650 ℃ for 24h to prepare an unformed foil;
immersing the non-formed foil in 95 ℃ pure water for 15min, taking the non-formed foil after the water boiling treatment as an anode and stainless steel as a cathode, and loading 0.5A/cm in a mixed solution containing 100g/L boric acid and 0.9g/L ammonium pentaborate at 88 DEG C 2 Carrying out electric fluidization for 20min, carrying out chemical fluidization for 520V, placing in air at 500 ℃ for 2min, and loading 0.5A/cm 2 Performing secondary formation on the current for 10min until the current reaches 520V, and preparing the hot-pressed foil of the comparative example;
hot-pressed foil leakage current detection prepared through the steps: in boric acid of 70g/L at 65 ℃, a current of 4mA is used for detecting leakage current on a sample wafer of 1X 5cm, an industry universal leakage current detector is used for testing, and a leakage current result is that: 0.29mA; and (3) carbon sulfur analysis and detection: carbon residue was measured by a carbon-sulfur analyzer, 0.3%.
Comparative example 2
The comparative example provides a hot-pressed foil, the preparation method of which specifically comprises the following steps:
uniformly mixing high-purity (> 99.99%) aluminum powder with an average particle size D50 of 3 mu m with acrylic resin according to a mass ratio of 9:1 to obtain powder;
uniformly spraying powder on a first surface of a base foil with the thickness of 30 mu m and an aluminum foil with the purity of more than 99.9% in a spraying mode, applying 1000N pressure at the temperature of 150 ℃ in a hot rolling mode to melt acrylic resin in the powder, enabling the powder to adhere to the aluminum foil, and controlling the thickness of the powder adhered to the first surface of the aluminum foil to be 50 mu m;
uniformly spraying powder on the second surface of the aluminum foil with the thickness of 30 mu m in sequence by a spraying mode, applying 1000N pressure at the temperature of 150 ℃ by a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the second surface of the aluminum foil to be 50 mu m to prepare a hot rolled foil;
degreasing the hot rolled foil in an argon atmosphere with the oxygen volume content of 6% at 400 ℃ for 1h and sintering the hot rolled foil in a vacuum environment at 660 ℃ for 24h to prepare an unformed foil;
immersing the non-formed foil in 95 ℃ pure water for 15min, taking the non-formed foil after the water boiling treatment as an anode and stainless steel as a cathode, and loading 0.5A/cm in a mixed solution containing 100g/L boric acid and 0.9g/L ammonium pentaborate at 88 DEG C 2 Carrying out electric fluidization for 20min, carrying out chemical fluidization for 520V, placing in air at 500 ℃ for 2min, and loading 0.5A/cm 2 Carrying out secondary formation on the current for 10min until the current reaches 520V, and preparing the hot-pressed foil of the comparative example;
hot-pressed foil leakage current detection prepared through the steps: in boric acid of 70g/L at 65 ℃, a current of 4mA is used for detecting leakage current on a sample wafer of 1X 5cm, an industry universal leakage current detector is used for testing, and a leakage current result is that: 0.4mA; and (3) carbon sulfur analysis and detection: carbon residue was measured by a carbon-sulfur analyzer, 0.19%.
Comparative example 3
Uniformly mixing high-purity (> 99.99%) aluminum powder with an average particle size D50 of 3 mu m with acrylic resin according to a mass ratio of 9:1 to obtain powder;
uniformly spraying powder on a base foil with the thickness of 30 mu m and the first surface of an aluminum foil with the purity of more than 99.9%, applying 1000N pressure at the temperature of 150 ℃ in a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the first surface of the aluminum foil to be 50 mu m;
uniformly spraying powder on the second surface of the aluminum foil with the thickness of 30 mu m in sequence by a spraying mode, applying 1000N pressure at the temperature of 150 ℃ by a hot rolling mode to melt acrylic resin in the powder, enabling the powder to be adhered with the aluminum foil, and controlling the thickness of the powder adhered on the second surface of the aluminum foil to be 50 mu m to prepare a hot rolled foil;
degreasing the hot rolled foil in an air atmosphere at 400 ℃ for 1h and sintering the hot rolled foil in a vacuum environment at 600 ℃ for 24h to prepare an unformed foil;
immersing the non-formed foil in 95 ℃ pure water for 15min, taking the non-formed foil after the water boiling treatment as an anode and stainless steel as a cathode, and loading 0.5A/cm in a mixed solution containing 100g/L boric acid and 0.9g/L ammonium pentaborate at 88 DEG C 2 Carrying out electric fluidization for 20min, carrying out chemical fluidization for 520V, placing in air at 500 ℃ for 2min, and loading 0.5A/cm 2 Carrying out secondary formation on the current for 10min until the current reaches 520V, and preparing the hot-pressed foil of the comparative example;
hot-pressed foil leakage current detection prepared through the steps: in boric acid of 70g/L at 65 ℃, a current of 4mA is used for detecting leakage current on a sample wafer of 1X 5cm, an industry universal leakage current detector is used for testing, and a leakage current result is that: 0.5mA; and (3) carbon sulfur analysis and detection: carbon residue was measured by a carbon-sulfur analyzer, 0.18%.
In both comparative example 2 and comparative example 3, the oxygen content was too large, although the carbon residue was effectively reduced, a thicker oxide film was formed by reaction with aluminum during degreasing, and the sintering process resulted in poor sintering, resulting in an increase in electric leakage.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that those skilled in the art, based on the technical solutions provided by the present invention, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the appended claims. The scope of the patent of the invention should therefore be determined with reference to the appended claims, which are to be construed as in accordance with the doctrines of claim interpretation.

Claims (10)

1. A method of preparing a hot-pressed foil, comprising the steps of:
providing powder, wherein the powder comprises aluminum powder and an organic binder in a mass ratio of 6:1-12:1;
laying the powder on at least one surface of the base foil, and carrying out hot rolling treatment to prepare a hot rolled foil;
degreasing the hot rolled foil in an inert atmosphere containing 0.1-5% of oxygen or water vapor by volume, and then sintering the hot rolled foil in inert gas or vacuum to prepare an unformed foil;
and sequentially performing water boiling treatment and formation treatment on the unformed foil to prepare the hot-pressed foil.
2. The method of manufacturing a hot-pressed foil according to claim 1, wherein the degreasing treatment includes degreasing the hot-rolled foil at a temperature of 200 ℃ to 400 ℃ for 1h to 6h.
3. The method of producing a hot-pressed foil according to claim 1, wherein the sintering treatment comprises sintering the hot-pressed foil after the degreasing treatment at a temperature of 560 ℃ to 650 ℃ for 1h to 24h.
4. The method of manufacturing a hot-pressed foil according to claim 1, wherein the organic binder is at least one selected from the group consisting of acrylic resin, ethylcellulose, polyurethane, polystyrene and polyacrylate.
5. The method of producing a hot-pressed foil according to any one of claims 1 to 4, wherein the hot-rolling treatment is performed at a pressure of 800N to 1200N and a temperature of 130 ℃ to 180 ℃.
6. The method of producing a hot-pressed foil according to any one of claims 1 to 4, wherein the water boiling treatment comprises immersing the non-formed foil in pure water at 90 ℃ to 99 ℃ for 3min to 30min.
7. The method of manufacturing a hot-pressed foil according to any one of claims 1 to 4, wherein the formation treatment comprises immersing a cathode selected from stainless steel or graphite plates and the non-formed foil subjected to the water boiling treatment as an anode in a formation liquid, and heating to a predetermined voltage value under a load current.
8. Hot-pressed foil, characterized in that it is produced according to the method for producing a hot-pressed foil according to any one of claims 1 to 7.
9. An electrode comprising the hot-pressed foil of claim 8.
10. A capacitor comprising the electrode of claim 9.
CN202210833447.1A 2022-07-15 2022-07-15 Hot-pressed foil, preparation method thereof, electrode and capacitor Active CN115148501B (en)

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