CN114411232A - Preparation method of soft low-pressure corrosion foil - Google Patents
Preparation method of soft low-pressure corrosion foil Download PDFInfo
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- CN114411232A CN114411232A CN202210086922.3A CN202210086922A CN114411232A CN 114411232 A CN114411232 A CN 114411232A CN 202210086922 A CN202210086922 A CN 202210086922A CN 114411232 A CN114411232 A CN 114411232A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/04—Etching of light metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a soft low-pressure corrosion foil. The deep corrosion of the preparation method of the soft-state low-voltage corrosion foil is alternating current corrosion, the alternating current waveform comprises a positive half cycle and a negative half cycle which are distributed in a mirror image mode, the positive half cycle and the negative half cycle are composed of two or more first half waves (1) with the same waveform, amplitude and application time, interval time exists between the two first half waves (1), the interval time period of the positive half cycle is composed of a second half wave (2) which is smaller than the half wave in amplitude and smaller than the half wave in application time and passes through an abscissa and is positioned in a corresponding half cycle of the positive half cycle, and the interval time period of the negative half cycle is composed of a third half wave (3) which is smaller than the half wave in amplitude and smaller than the half wave in application time and passes through the abscissa and is positioned in a corresponding half cycle of the positive half cycle. The soft low-pressure corrosion foil prepared by the invention has the advantages of high capacity, uniform corrosion hole layer, flat sandwich layer and excellent bending performance.
Description
Technical Field
The invention relates to the technical field of aluminum electrolytic capacitors, in particular to a preparation method of a soft low-voltage corrosion foil.
Background
In recent years, as electronic devices are becoming lighter, thinner and miniaturized, aluminum electrolytic capacitors are becoming more and more important as one of the important electronic components, and the demands for miniaturization and high capacity are also increasing. The corrosion foil is used as a component which has the greatest influence on capacitance in the aluminum electrolytic capacitor, and the specific volume of the corrosion foil is improved by increasing the specific surface area per unit, so that the corrosion foil becomes one of key technologies in the production of the corrosion foil.
In the conventional corrosion foil for a low-voltage aluminum electrolytic capacitor, the surface area of the aluminum foil is generally enlarged by electrochemically etching the aluminum foil in an electrolyte solution containing hydrochloric acid as a main component. The prior art discloses a method for corroding an anode foil for a low-voltage aluminum electrolytic capacitor, wherein a corrosive foil with higher capacitance is prepared by applying alternating current to an aluminum foil, and the waveform of the alternating current is mainly sine wave, triangular wave and square wave. Different alternating current waveforms can form different numbers and shapes of corrosion holes, thereby affecting the performance of the corrosion foil. Conventional etching is shown in FIG. 1 with an alternating current waveform in which the positive half cycle is used for etch hole formation and the negative half cycle is passivated. Only one half-wave exists in each half-cycle, which reflects that only one corrosion hole can be formed in the corrosion pit in the period of the positive half-cycle of the waveform in the corrosion process, and the corrosion hole is passivated immediately, so that the corrosion efficiency is low; in addition, the mode of single-hole growth easily causes the corrosion hole to be repeatedly formed at a certain position where the hole is easy to form, so that the corrosion hole layer of the corrosion foil is not uniform, the sandwich layer of the corrosion foil is not flat and the like, and the mechanical strength and the performance of the corrosion foil are influenced; on the other hand, in the conventional corrosion alternating current waveform, more corrosion products are generated during corrosion of the aluminum foil in the positive half period, the corrosion products are concentrated, but no mass transfer method is used for exchanging the corrosion products with external electrolyte, when corrosion is carried out to a certain depth, the corrosion products cannot be timely transmitted to the outside, corrosion holes can be blocked, the corrosion holes cannot continue to grow to the deep part, and when power is continuously applied, current can be caused to corrode the existing corrosion holes and the surface of the corrosion foil, so that the phenomena of hole merging, blackening and powder falling of the corrosion foil are caused.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings that an alternating current waveform in the existing corrosion foil treatment process easily causes uneven corrosion hole layer, uneven corrosion foil sandwich layer, non-deep corrosion hole and lower specific volume of the corrosion foil, and provides a preparation method of a soft-state low-voltage corrosion foil.
The above purpose of the invention is realized by the following technical scheme:
a method for preparing a soft low-pressure corrosion foil comprises the following steps:
1) pre-treating;
2) cloth hole corrosion;
3) performing intermediate treatment;
4) deep corrosion;
5) post-treatment;
the deep corrosion is alternating current corrosion, the alternating current waveform comprises a positive half period and a negative half period which are distributed in a mirror image mode,
the positive half-cycle and the negative half-cycle are composed of two or more first half-waves (1) with the same waveform, amplitude and application time, and an interval time exists between the two first half-waves (1),
the interval period of the positive half-cycle is constituted by a second half-cycle (2) having an amplitude less than a half-cycle and an application time less than a half-cycle, crossing the abscissa, located in the corresponding half-cycle of the positive half-cycle,
the interval time period of the negative half cycle is composed of a third half cycle (3) which has an amplitude smaller than the half cycle and an application time smaller than the half cycle, crosses the abscissa, and is located in the corresponding half cycle of the positive half cycle.
The alternating current waveform adopted by the preparation method of the soft-state low-voltage corrosion foil is divided into a positive half cycle and a negative half cycle, and is distributed in a mirror image mode, wherein the positive half cycle or the negative half cycle is composed of two or more half cycles with the same waveform, amplitude and application time, an interval exists between every two half cycles, the waveform in the interval time period is composed of one of sine waves, triangular waves, rectangular waves or deformation forms of the sine waves, the triangular waves, the rectangular waves or the deformation forms of the sine waves, the rectangular waves and the deformation forms of the triangular waves, the amplitude of the waveform penetrates through the abscissa, the waveform is positioned in the corresponding half cycle of the main half cycle, and the amplitude of the waveform is smaller and the time is shorter.
Wherein:
the positive half cycle or the negative half cycle of the alternating current waveform is composed of two or more than two half waves with the same waveform, amplitude and application time, wherein in the same half cycle, on the basis of the first half wave generating hole, the second half wave and the following half waves can easily continue to be long holes without puncturing a thicker protective film formed in the negative half cycle again, and in the same half cycle, a plurality of corrosion holes can be generated in an etching pit, so that the generation probability of transverse branch holes is increased, and the corrosion efficiency is improved.
In the same half period, an interval exists between every two half waves, and the waveform design can form a thin protective film on the surface of the sent corrosion hole in the interval period, so that the sent corrosion hole is protected from being corroded again when the next half wave is corroded, the phenomenon of hole combination is avoided, and the problem of non-uniform corrosion hole layers is solved.
The waveform in the interval time period is composed of one of sine waves, triangular waves, square waves or deformation forms of the sine waves, the triangular waves and the square waves, and the purpose is to control the state of the protective film through the waveform, so that the appearance, the number and the growth positions of new corrosion holes are controlled when the next half wave occurs, the number and the position distribution of the corrosion holes in the aluminum foil in unit thickness are optimal, the corrosion layer in unit thickness obtains higher capacitance, the corrosion foil sandwich layer is ensured to have certain thickness, and the mechanical strength of the corrosion foil is improved.
The waveform in the half-wave interval time period passes through the abscissa and is positioned in the corresponding half cycle, the amplitude is small, and the time is short. The method aims to add a small section of anisotropic current, strengthen the material exchange between the corrosion hole and the external corrosion tank liquid, bring the corrosion product out of the corrosion hole, bring the fresh corrosion tank liquid into the corrosion hole, and lay a foundation for the next half-wave perforation.
The preparation method of the low-voltage corrosion foil solves the problems encountered in the corrosion process of the traditional corrosion alternating current waveform, obtains the corrosion foil with high specific volume, uniform corrosion hole layer, flat sandwich layer and good mechanical strength, and plays an important role in improving the performance of the low-voltage aluminum electrolytic capacitor.
Preferably, the amplitude of the second half-wave (2) and the third half-wave (3) is 2-10% of the first half-wave (1) and the application time is 5-20% of the first half-wave (1).
In the invention, the second half-wave (2) and the third half-wave (3) generate an interval between every two first half-waves (1) of the vent hole and a section of heterogeneous current is added, the purpose is to form a layer of protective film on the surface of the vent hole in the interval period, the amplitude and the application time of the second half-wave (2) and the third half-wave (3) can influence the thickness and the state of the protective film, the amplitude is small, the application time is short, the thickness of the formed protective film is insufficient, and holes are easily formed in the subsequent first half-wave (1) slot hole process; the amplitude is too large, the application time is long, and the formed protective film is too thick, so that the continuous long hole of the subsequent first half-wave (1) is not facilitated.
In addition, the existence of the heterogeneous current is also beneficial to bringing out corrosion products from the corrosion holes, increasing the material exchange between the corrosion holes and the corrosion tank liquid and improving the corrosion efficiency. If the application time is short, the material exchange is insufficient, which is not beneficial to the growth of the subsequent holes; if the application time is long, the production efficiency is affected.
Preferably, the positive half-cycle and the negative half-cycle are composed of 2 to 7 first half-cycles (1) having the same waveform, amplitude and application time.
In the whole half period, the number of the half waves is preferably less than or equal to 7, because in the whole half period, the etching holes generated by the first half wave (1) basically continuously grow, on the basis of the etching holes generated by the initial first half wave (1), the etching holes generated by the subsequent first half wave (1) comprise transverse and longitudinal equal branch holes, each etching hole is only protected by a weak protective film provided in the interval time period of the second half wave (2) or the third half wave (3), if the number of the half waves is more, the branch holes are generated, the weak protective film is easily corroded, and therefore the hole merging phenomenon is generated, and the corrosion foil performance is influenced.
Preferably, the waveform of the first half wave (1) is one or more of sine wave, triangular wave, square wave or deformation form thereof.
Further preferably, the waveform of the first half wave (1) is a square wave.
The pretreatment process in the step 1) comprises the following steps:
washing the aluminum foil with water to remove impurities such as dust on the surface of the aluminum foil; then the aluminum foil is put into pretreatment tank liquid for pretreatment to remove oil stains and oxidation films on the surface of the aluminum foil and form a uniform phosphide film; after the pretreatment is finished, taking out the aluminum foil and performing water washing treatment;
the pretreatment conditions are as follows: the water washing time is 10-20 s, the pretreatment tank liquid is phosphoric acid water solution with the mass content of 1-10%, the temperature of the pretreatment tank liquid is 60-80 ℃, and the pretreatment time is 60-120 s.
The hole distribution corrosion process in the step 2) comprises the following steps:
placing the aluminum foil treated in the step 1) in corrosion bath solution, controlling corrosion time, and adding alternating current to carry out hole distribution corrosion so as to distribute holes on the surface of the aluminum foil; taking out the aluminum foil after hole distribution and carrying out water washing treatment;
the hole distribution corrosion conditions are as follows: the corrosion tank solution consists of 5-15% by mass of hydrochloric acid, 0.01-0.1% by mass of sulfuric acid and 0.5-1.5% by mass of aluminum trichloride, the temperature of the corrosion tank solution is 15-60 ℃, and the current density is 0.2-0.8A/cm2The etching frequency is 10-60 Hz, and the etching time is 20-70 s.
The processing process in the step 3) is as follows:
placing the aluminum foil treated in the step 2) in a middle treatment bath for middle treatment, so as to form a protective layer on the surface of the corrosion hole and protect the existing corrosion hole from being damaged in subsequent corrosion; after the middle treatment is finished, taking out the aluminum foil and carrying out water washing treatment;
the medium treatment conditions are as follows: the medium treatment bath solution is 1-10% of hydrogen phosphate and/or dihydrogen phosphate aqueous solution by mass, the temperature of the medium treatment bath solution is 50-90 ℃, and the medium treatment time is 60-120 s.
The step 4) deep etching process comprises the following steps:
placing the aluminum foil treated in the step 3) in corrosion bath solution, controlling corrosion time, and adding alternating current for deep corrosion, wherein the purpose is to continue long holes on the basis of existing corrosion holes; after the corrosion is finished, taking out the aluminum foil and carrying out water washing treatment;
the deep corrosion conditions are as follows: the corrosion tank solution consists of 5-15% by mass of hydrochloric acid, 0.01-0.1% by mass of sulfuric acid and 0.5-1.5% by mass of aluminum trichloride, the temperature of the corrosion tank solution is 15-60 ℃, and the current density is 0.2-0.8A/cm2The etching frequency is 10-60 Hz, and the etching time is 60-150 s.
The post-treatment process of the step 5) comprises the following steps:
placing the aluminum foil treated in the step 4) in a primary post-treatment tank solution for primary post-treatment, and washing after the primary post-treatment; then placing the aluminum foil in a secondary post-treatment tank liquor for secondary post-treatment, and washing after the secondary post-treatment;
the conditions of the post-treatment are as follows: the primary post-treatment tank liquid is a sulfuric acid water solution with the mass content of 5-20%, the temperature of the primary post-treatment tank liquid is 40-70 ℃, and the primary post-treatment time is 60-120 s; the secondary post-treatment tank liquor is a triethanolamine aqueous solution with the mass content of 1-5%, the temperature of the secondary post-treatment tank liquor is 40-70 ℃, and the secondary post-treatment time is 60-120 s.
Repeating the step 3) and the step 4) for a plurality of times, wherein the repetition times are determined according to the thickness of the aluminum foil and the corrosion time in the step 4), and are generally 4-8 times;
drying the aluminum foil after the post-treatment in the step 5), wherein the drying conditions are as follows: the drying temperature is 200-400 ℃, and the drying time is 2-10 min.
And (3) the water washing treatment in the steps 1) to 5) aims at removing residual corrosion bath solution or treatment bath solution on the aluminum foil, and pure water or tap water is used, and the water washing time is 20-60 s.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the soft low-pressure corrosion foil solves the problem of low efficiency of the traditional waveform corrosion, improves the corrosion efficiency, and improves the specific volume of the corrosion foil by increasing the specific surface area of the corrosion foil.
The preparation method of the soft low-pressure corrosion foil solves the problems of uneven corrosion hole layer, uneven sandwich layer and poor mechanical strength of the corrosion foil.
The preparation method of the soft low-pressure corrosion foil solves the problems that the corrosion hole of the corrosion foil cannot be deeply processed, the hole is merged in the corrosion process of the corrosion foil, and the surface of the corrosion foil is blackened and powdered.
According to the invention, by regulating and controlling the corrosion current waveform, on the basis of the first half-wave hole, the second and the following half-waves can easily continue to form a long hole in the same half period, and a thicker protective film formed in the negative half period does not need to be punctured again, and in the same half period, a plurality of corrosion holes can be generated in one corrosion pit, so that the generation probability of transverse branch holes is increased, and further the corrosion efficiency and the capacity of the corrosion foil are improved.
Drawings
FIG. 1 is a standard sine wave used in a conventional etching process;
FIG. 2 is a waveform of an etching AC power used in example 1 of the present invention;
FIG. 3 is a waveform of an etching AC power used in example 2 of the present invention;
FIG. 4 is a waveform of an etching AC power used in example 3 of the present invention;
FIG. 5 is a cross-sectional view of a corrosion foil produced in comparative example 1 of the present invention;
FIG. 6 is a cross-sectional view of a corrosion foil produced in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A preparation method of a soft low-voltage corrosion foil for an aluminum electrolytic capacitor comprises the following steps:
s1, pretreatment: washing aluminum foil with tap water for 10s, pre-treating in 70 deg.C phosphoric acid water solution containing 5 wt% of phosphoric acid for 60s, taking out, and washing with pure water for 30 s;
s2, hole distribution corrosion: placing the aluminum foil processed in the step S1 into corrosion tank liquor containing 12 wt% hydrochloric acid, 0.03 wt% sulfuric acid and 0.9 wt% aluminum trichloride at 40 ℃ for hole distribution corrosion, wherein the corrosion current waveform is sine wave, and the corrosion current density is 0.5A/cm2The corrosion frequency is 50Hz, the corrosion time is 30s, and the product is taken out and washed by pure water for 30 s;
s3, performing intermediate treatment: soaking the aluminum foil processed in the step S2 in a medium processing bath solution containing 5 wt% of ammonium dihydrogen phosphate at 70 ℃ for medium processing for 60S, taking out, and washing with pure water for 30S;
s4, deep corrosion: the aluminum foil processed in the step S3 is put into a corrosion tank solution containing 12 wt% hydrochloric acid, 0.03 wt% sulfuric acid and 0.9 wt% aluminum trichloride at 25 ℃ for deep corrosion, the corrosion current waveform is shown in figure 2, and the corrosion current density is 0.3A/cm2Corrosion frequency ofAt 25Hz, the etching time was 120 seconds, and the sample was washed with pure water for 30 seconds after being taken out.
S5, repeating the steps S3 and S4 four times;
s6, post-processing: placing the aluminum foil treated in the step S5 into an aqueous solution containing 10 wt% of sulfuric acid at 60 ℃ for primary post-treatment for 60S, taking out after the treatment, and washing with pure water for 30S; then the aluminum foil is put into an aqueous solution containing 3 wt% of triethanolamine at 60 ℃ for secondary post-treatment, the treatment time is 60s, and after the treatment is finished, the aluminum foil is taken out and washed by pure water for 30 s.
S7, drying: the aluminum foil treated in step S6 was dried in a 400 ℃ muffle furnace for 120 seconds.
Wherein, the deep corrosion in S4 is ac corrosion, as shown in fig. 2, the ac waveform includes a positive half cycle and a negative half cycle which are mirror-distributed, the positive half cycle and the negative half cycle are composed of two first half waves (1) having the same waveform, amplitude and application time, and there is an interval time between the two first half waves (1), the interval time of the positive half cycle is composed of a second half wave (2) having an amplitude smaller than that of the half wave and having an application time smaller than that of the half wave, crossing the abscissa, and located in a corresponding half cycle of the positive half cycle, and the interval time of the negative half cycle is composed of a third half wave (3) having an amplitude smaller than that of the half wave and having an application time smaller than that of the half wave, crossing the abscissa, and located in a corresponding half cycle of the positive half cycle; the amplitude of the second half-wave (2) and the third half-wave (3) is 5% of the first half-wave (1) and the application time is 10% of the first half-wave (1); the positive and negative half-cycles are constituted by 2 first half-waves (1) having the same waveform, amplitude and application time.
The waveform of the first half wave (1) is a sine wave.
Example 2
A method for producing a soft low-voltage etched foil for an aluminum electrolytic capacitor, comprising substantially the same steps as in example 1, except that the etching current waveform in step S4 is as shown in fig. 3.
The deep corrosion in the S4 is alternating current corrosion, the alternating current waveform comprises a positive half cycle and a negative half cycle which are in mirror image distribution, the positive half cycle and the negative half cycle are composed of two first half waves (1) with the same waveform, amplitude and application time, an interval time exists between the two first half waves (1), the interval time period of the positive half cycle is composed of a second half wave (2) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa, and the interval time period of the negative half cycle is composed of a third half wave (3) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa and has the application time smaller than that of the half wave and has the abscissa; the amplitude of the second half-wave (2) and the third half-wave (3) is 5% of the first half-wave (1) and the application time is 10% of the first half-wave (1); the positive and negative half-cycles are constituted by 2 first half-waves (1) having the same waveform, amplitude and application time.
The waveform of the first half wave (1) is a triangular wave.
Example 3
A method for producing a soft low-voltage etched foil for an aluminum electrolytic capacitor, comprising substantially the same steps as in example 1, except that the etching current waveform in step S4 is as shown in fig. 4.
The deep corrosion in the S4 is alternating current corrosion, the alternating current waveform comprises a positive half cycle and a negative half cycle which are in mirror image distribution, the positive half cycle and the negative half cycle are composed of two first half waves (1) with the same waveform, amplitude and application time, an interval time exists between the two first half waves (1), the interval time period of the positive half cycle is composed of a second half wave (2) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa, and the interval time period of the negative half cycle is composed of a third half wave (3) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa and has the application time smaller than that of the half wave and has the abscissa; the amplitude of the second half-wave (2) and the third half-wave (3) is 5% of the first half-wave (1) and the application time is 10% of the first half-wave (1); the positive and negative half-cycles are constituted by 2 first half-waves (1) having the same waveform, amplitude and application time.
The waveform of the first half wave (1) is a square wave.
Example 4
A method for producing a soft low-voltage etched foil for an aluminum electrolytic capacitor, comprising substantially the same steps as in example 1, except that the etching current waveform in step S4 is as shown in fig. 4.
The deep corrosion in the S4 is alternating current corrosion, the alternating current waveform comprises a positive half cycle and a negative half cycle which are in mirror image distribution, the positive half cycle and the negative half cycle are composed of two first half waves (1) with the same waveform, amplitude and application time, an interval time exists between the two first half waves (1), the interval time period of the positive half cycle is composed of a second half wave (2) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa, and the interval time period of the negative half cycle is composed of a third half wave (3) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa and has the application time smaller than that of the half wave and has the abscissa; the amplitude of the second half-wave (2) and the third half-wave (3) is 2% of the first half-wave (1) and the application time is 5% of the first half-wave (1); the positive and negative half-cycles are constituted by 2 first half-waves (1) having the same waveform, amplitude and application time.
The waveform of the first half wave (1) is a square wave.
Example 5
A method for producing a soft low-voltage etched foil for an aluminum electrolytic capacitor, comprising substantially the same steps as in example 1, except that the etching current waveform in step S4 is as shown in fig. 4.
The deep corrosion in the S4 is alternating current corrosion, the alternating current waveform comprises a positive half cycle and a negative half cycle which are in mirror image distribution, the positive half cycle and the negative half cycle are composed of two first half waves (1) with the same waveform, amplitude and application time, an interval time exists between the two first half waves (1), the interval time period of the positive half cycle is composed of a second half wave (2) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa, and the interval time period of the negative half cycle is composed of a third half wave (3) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa and has the application time smaller than that of the half wave and has the abscissa; the amplitude of the second half-wave (2) and the third half-wave (3) is 10% of the first half-wave (1) and the application time is 20% of the first half-wave (1); the positive and negative half-cycles are constituted by 2 first half-waves (1) having the same waveform, amplitude and application time.
The waveform of the first half wave (1) is a square wave.
Example 6
A method for producing a soft low-voltage etched foil for an aluminum electrolytic capacitor, comprising substantially the same steps as in example 1, except that the etching current waveform in step S4 is as shown in fig. 4.
The deep corrosion in the S4 is alternating current corrosion, the alternating current waveform comprises a positive half cycle and a negative half cycle which are in mirror image distribution, the positive half cycle and the negative half cycle are composed of two first half waves (1) with the same waveform, amplitude and application time, an interval time exists between the two first half waves (1), the interval time period of the positive half cycle is composed of a second half wave (2) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa, and the interval time period of the negative half cycle is composed of a third half wave (3) which has the amplitude smaller than that of the half wave and has the application time smaller than that of the half wave and passes through the abscissa and has the application time smaller than that of the half wave and has the abscissa; the amplitude of the second half-wave (2) and the third half-wave (3) is 5% of the first half-wave (1) and the application time is 10% of the first half-wave (1); the positive and negative half-cycles consist of 7 first half-waves (1) with the same waveform, amplitude and application time.
The waveform of the first half wave (1) is a square wave.
Comparative example 1
A method for producing a soft low-voltage etched foil for an aluminum electrolytic capacitor, comprising substantially the same steps as in example 1, except that the etching current waveform in step S4 is a standard sine wave as shown in fig. 1.
Result detection
(1) Scanning electron microscope test
FIG. 6 is a sectional view of a soft low-voltage etched foil for an aluminum electrolytic capacitor in example 1, FIG. 5 is a sectional view of a soft low-voltage etched foil for an aluminum electrolytic capacitor in comparative example 1, and it can be seen from FIG. 5 that the etched layer of the soft low-voltage etched foil for an aluminum electrolytic capacitor in comparative example 1 has a saw-tooth shape, the thickness distribution of the etched layer is not uniform, and is between 27 and 34 μm, and some black clusters exist in the etched layer, indicating that there is a certain aggregation and pitting phenomenon in the etched holes; as can be seen from FIG. 6, the soft low-voltage etched foil for aluminum electrolytic capacitors in example 1 had a smooth etched layer with uniform thickness distribution of 29-30 μm, uniform color and uniform hole distribution, and no holes or clusters.
(2) Flexural strength test: bending strength was obtained by using an MIT bending machine of Toyo Seiki, Japan, and a collet of R1.0.
(2) And (3) capacity testing: the corrosion foils prepared in the examples and the comparative examples are formed under the following conditions: 15% ammonium adipate solution at 85 deg.C and current density of 5A/dm2Vfe ═ 21V; then, the formed foil after formation was detected, and the detection results are shown in table 1.
Table 1 results of performance testing
| Numbering | 21Vf capacity (%) | Bending Strength (Hui) |
| Example 1 | 103.4 | 89 |
| Example 2 | 105.8 | 87 |
| Example 3 | 106.3 | 84 |
| Example 4 | 103.7 | 87 |
| Example 5 | 105.6 | 83 |
| Example 6 | 107.9 | 81 |
| Comparative example 1 | 100 | 80 |
As can be seen from Table 1, the corrosion foils obtained by the treatments of examples 1 to 6 all have better performance than that of comparative example 1, and the results show that the corrosion foils with better performance, higher specific capacity and stronger mechanical performance can be prepared by treating the aluminum foils with the alternating current waveforms (shown in FIGS. 2, 3 and 4) of the invention.
In examples 1-3, the etched foil obtained in example 3 had a specific volume better than that of examples 1 and 2, which indicates that the aluminum foil treated using the AC waveform of example 3 (FIG. 4) had better results than the AC waveform of examples 1 and 2 (FIGS. 2 and 3). The waveform used in example 3 (fig. 4) is taken as a preferred waveform.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (12)
1. A method for preparing a soft low-pressure corrosion foil comprises the following steps:
1) pre-treating;
2) cloth hole corrosion;
3) performing intermediate treatment;
4) deep corrosion;
5) post-treatment;
the deep corrosion is alternating current corrosion, the alternating current waveform comprises a positive half period and a negative half period which are distributed in a mirror image manner,
the positive half-cycle and the negative half-cycle are composed of two or more first half-waves (1) with the same waveform, amplitude and application time, and an interval time exists between the two first half-waves (1),
the interval period of the positive half-cycle is constituted by a second half-cycle (2) having an amplitude less than a half-cycle and an application time less than a half-cycle, crossing the abscissa, located in the corresponding half-cycle of the positive half-cycle,
the interval time period of the negative half cycle is composed of a third half cycle (3) which has an amplitude smaller than the half cycle and an application time smaller than the half cycle, crosses the abscissa, and is located in the corresponding half cycle of the positive half cycle.
2. The method for preparing a soft low-pressure etched foil according to claim 1, wherein the second half-wave (2) and the third half-wave (3) have an amplitude of 2-10% of the first half-wave (1) and an application time of 5-20% of the first half-wave (1).
3. Method for the production of a soft low-pressure etched foil according to claim 1, wherein the positive and negative half cycles consist of 2 to 7 first half waves (1) with the same waveform, amplitude and application time.
4. The method for preparing a soft low-pressure etched foil according to claim 1, wherein the waveform of the first half-wave (1) is one or more of a sine wave, a triangular wave, a square wave or a modified form thereof.
5. The method for preparing a soft low-pressure etched foil according to claim 1, wherein the pretreatment in step 1) comprises:
washing the aluminum foil with water to remove impurities such as dust on the surface of the aluminum foil, then placing the aluminum foil in pretreatment tank liquid for pretreatment, taking out the aluminum foil after the pretreatment is finished, and washing the aluminum foil with water;
the pretreatment conditions are as follows: the water washing time is 10-20 s, the pretreatment tank liquid is phosphoric acid water solution with the mass content of 1-10%, the temperature of the pretreatment tank liquid is 60-80 ℃, and the pretreatment time is 60-120 s.
6. The method for preparing a soft low-pressure etched foil according to claim 1, wherein the step 2) of hole-distribution etching comprises the following steps:
placing the aluminum foil treated in the step 1) in corrosion bath solution, controlling corrosion time, adding alternating current to carry out hole distribution corrosion, taking out the aluminum foil after the corrosion is finished, and carrying out water washing treatment;
the hole distribution corrosion conditions are as follows: the corrosion tank solution consists of 5-15% by mass of hydrochloric acid, 0.01-0.1% by mass of sulfuric acid and 0.5-1.5% by mass of aluminum trichloride, the temperature of the corrosion tank solution is 15-60 ℃, and the current density is 0.2-0.8A/cm2The etching frequency is 10-60 Hz, and the etching time is 20-70 s.
7. The method for preparing a soft low pressure etched foil according to claim 1, wherein the step 3) comprises the steps of:
placing the aluminum foil treated in the step 2) in a middle treatment tank solution for middle treatment, and taking out the aluminum foil after the middle treatment and carrying out water washing treatment;
the medium treatment conditions are as follows: the medium treatment bath solution is 1-10% of hydrogen phosphate and/or dihydrogen phosphate aqueous solution by mass, the temperature of the medium treatment bath solution is 50-90 ℃, and the medium treatment time is 60-120 s.
8. The method for preparing a soft low pressure etched foil according to claim 1 wherein the deep etching of step 4) is performed by:
placing the aluminum foil treated in the step 3) in corrosion bath solution, controlling corrosion time, adding alternating current for deep corrosion, taking out the aluminum foil after corrosion and performing water washing treatment;
the deep corrosion conditions are as follows: the corrosion tank solution consists of 5-15% by mass of hydrochloric acid, 0.01-0.1% by mass of sulfuric acid and 0.5-1.5% by mass of aluminum trichloride, the temperature of the corrosion tank solution is 15-60 ℃, and the current density is 0.2-0.8A/cm2The etching frequency is 10-60 Hz, and the etching time is 60-150 s.
9. The method for preparing a soft low pressure etched foil according to claim 1 wherein the step 5) post-treatment comprises:
placing the aluminum foil treated in the step 4) in a primary post-treatment tank solution for primary post-treatment, and washing after the primary post-treatment; then placing the aluminum foil in a secondary post-treatment tank liquor for secondary post-treatment, and washing after the secondary post-treatment;
the conditions of the post-treatment are as follows: the primary post-treatment tank liquid is a sulfuric acid water solution with the mass content of 5-20%, the temperature of the primary post-treatment tank liquid is 40-70 ℃, and the primary post-treatment time is 60-120 s; the secondary post-treatment tank liquor is a triethanolamine aqueous solution with the mass content of 1-5%, the temperature of the secondary post-treatment tank liquor is 40-70 ℃, and the secondary post-treatment time is 60-120 s.
10. Method for the production of a soft low pressure etched foil according to any of claims 1 to 9, wherein steps 3) and 4) are repeated several times.
11. The method for preparing a soft low-pressure etched foil according to any one of claims 1 to 9, wherein the aluminum foil after the post-treatment in step 5) is dried under the following conditions: the drying temperature is 200-400 ℃, and the drying time is 2-10 min.
12. The method for preparing the soft low-pressure etched foil according to any one of claims 1 to 9, wherein pure water or tap water is used for the water washing treatment in the steps 1) to 5), and the water washing time is 20 to 60 seconds.
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| CN1111028A (en) * | 1993-12-28 | 1995-11-01 | 日本蓄电器工业株式会社 | Method of etching aluminum foil for electrolytic condenser |
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| CN1111028A (en) * | 1993-12-28 | 1995-11-01 | 日本蓄电器工业株式会社 | Method of etching aluminum foil for electrolytic condenser |
| CN105006367A (en) * | 2015-05-25 | 2015-10-28 | 厦门大学 | Stepped non-sinusoidal waveform frequency conversion corrosion method for low-voltage anode aluminum foil used for electrolytic capacitor |
| CN110085455A (en) * | 2019-03-20 | 2019-08-02 | 东莞东阳光科研发有限公司 | The method for promoting low pressure corrosive aluminum foil specific volume |
| CN112080787A (en) * | 2020-08-14 | 2020-12-15 | 东莞东阳光科研发有限公司 | Corrosion foil for aluminum electrolytic capacitor and preparation method thereof |
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