CN101425392B - Pre-treating process for high-voltage aluminum foil corrosion - Google Patents

Pre-treating process for high-voltage aluminum foil corrosion Download PDF

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CN101425392B
CN101425392B CN2008100298087A CN200810029808A CN101425392B CN 101425392 B CN101425392 B CN 101425392B CN 2008100298087 A CN2008100298087 A CN 2008100298087A CN 200810029808 A CN200810029808 A CN 200810029808A CN 101425392 B CN101425392 B CN 101425392B
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aluminum foil
bismuth
indium
corrosion
compound
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CN101425392A (en
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汪俊锋
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DONGGUAN DONGYANGGUANG CAPACITY Co Ltd
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DONGGUAN DONGYANGGUANG CAPACITY Co Ltd
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Abstract

The invention relates to the technical field of electrolytic capacitors, in particular to a pretreatment technology of high-voltage anode aluminum foil corrosion, which mainly comprises the following steps: 0.001-0.025 percent bismuth-containing or indium-containing compound or bismuth and indium mixture by weight is added in treatment fluid of alkali, acid, mixed alkali or mixed acid; aluminum foil is placed in pretreatment fluid and soaked for 10-200 seconds under the temperature of 30-80 DEG C; and the even pitting corrosion of the aluminum foil can happen easily when the pitting corrosion happens as the precipitation of the bismuth or the indium from the surface of the aluminum foil, thereby not only the face expansion ratio of the anode aluminum foil is improved, but also the loss of the mechanism strength can not be caused, and the specific volume of the aluminum foil is greatly improved.

Description

A kind of pre-treating technology of high-voltage aluminum foil corrosion
Technical field:
The present invention relates to technical field of electrolytic, relate in particular to a kind of pre-treating technology of high-voltage aluminum foil corrosion.
Background technology:
The anode foils of aluminium electrolytic capacitor is a high-purity aluminum foil, and the capacitance of capacitor and the real surface of capacitor electrode material are long-pending to be directly proportional, and the real surface that capacitor electrode material unit's apparent area is had is long-pending big more, and its capacitance is just big more.Amass for making anode aluminium foil have bigger real surface, dwindle the volume of capacitor, to adapt to the needs of electronic instrument complete machine miniaturization, people explore constantly always and make anode aluminium foil obtain the long-pending method of bigger real surface.
At present, electrolytic capacitor generally adopts electrochemical corrosion to handle with the high-voltage anode paper tinsel, makes its surperficial hole, tunnel that forms high density, is evenly distributed, has certain depth, and is long-pending with the real surface that increases aluminium foil, obtains high as far as possible ratio electric capacity; The etching process process generally comprises pre-treatment, sends out pitting corrosion, reaming corrosion and reprocessing.
Pre-treatment is that aluminium foil is carried out the various physics of being done before the galvanic corrosion, the processing of chemistry, main effect is greasy dirt, impurity and a natural oxide film of removing aluminium foil surface, adjust the aluminium foil institutional framework, improve its surface state, make even, the activation in its surface, form equally distributed initial voids when being beneficial to send out pitting corrosion, improve the electric corrosion performance of aluminium foil.Existing research and production reality show that all reasonably pre-treatment can improve light paper tinsel surface state effectively, enlarges the surface area of etched foil significantly, are to improve one of indispensable effective measures of etched foil static specific volume.The Chinese patent publication number is CN1458658, denomination of invention is the pre-treatment scheme that the patent application document of anode aluminum foil of electrolytic capacitor etching process has been announced a kind of aluminium foil corrosion, this patent is when doing pre-treatment or mixed acid or mixed base as pre-treatment with alkali or acid, in pre-treatment, add certain density zinc or lead, part has improved the area expanding rate and the tensile strength of aluminium foil, but specific volume is still less.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, and disclose a kind of area expanding rate that not only improves anode aluminium foil, and improved the pre-treating technology of the high-voltage aluminum foil corrosion of aluminium foil specific volume when not losing its mechanical strength greatly.
The objective of the invention is to be achieved by the following method: a kind of pre-treating technology of high-voltage aluminum foil corrosion, place the pretreatment liquid under the uniform temperature to corrode a period of time on aluminium foil, pretreatment liquid is that concentration is the mixed liquor of 1~10% NaOH, potassium hydroxide, sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, phosphoric acid and hydrofluoric acid or the mixed liquor of hydrochloric acid and hydrofluoric acid; Adding percentage by weight in the pretreatment liquid is 0.001~0.025% bismuth-containing or the compound that contains indium, or 0.001~0.025% bismuth-containing and the mixture that contains indium compound; The treatment fluid temperature is made as 30~80 ℃, and etching time is 10~200 seconds.
Wherein, adding percentage by weight in the described pretreatment liquid is 0.01~0.01% bismuth-containing or the compound that contains indium, or 0.001~0.01% bismuth-containing or contain the mixture of the compound of indium.
Described 0.001~0.01% bismuth-containing and the mixture that contains the compound of indium, mixed proportion is 1: 1.
Described bismuth-containing compound is a bismuth nitrate, and containing indium compound is indium nitrate.
Described treatment fluid temperature is made as 30~80 ℃, and etching time is 40~150 seconds.
Described treatment fluid temperature is made as 40~60 ℃, and etching time is 40~150 seconds.
The anode aluminum foil of electrolytic capacitor etching process comprises pre-treatment, sends out pitting corrosion, reaming corrosion and reprocessing, and the present invention is the pre-treating method of the electrolytic capacitor high voltage anode aluminum foil corrosion technique of uniqueness.The present invention adds bismuth-containing or the compound of indium or the mixture of bismuth and indium compound in the pretreatment liquid of present existing alkali, acid, mixed acid or mixed base, the percentage by weight of bismuth-containing or indium is 0.001~0.025% in the pretreatment liquid.Above-mentioned pretreatment liquid can be that concentration is the mixed liquor of 1~10% sodium hydroxide solution, potassium hydroxide solution, sulfuric acid solution, phosphoric acid solution, salpeter solution, hydrochloric acid solution, 1~10% phosphoric acid and 0.01~10% hydrofluoric acid, the perhaps mixed liquor of 1~10% hydrochloric acid and 0.01~1% hydrofluoric acid, but be not limited only to mixed liquor, two or more sour mixed liquor of above-mentioned alkali, acid, two or more alkali.When solution temperature is 30~80 ℃, aluminium foil soaked 10~200 seconds in above-mentioned pretreatment liquid after, carry out common send out pitting corrosion, reaming corrosion and reprocessing again.
Because the pretreatment liquid treatment temperature is lower than 25 ℃, aluminium foil surface is not reaction generation almost, the effect that does not have; And surpassing 80 ℃, undue dissolving, the effect that does not also have take place in aluminium foil surface.So the pretreatment liquid temperature ranges that the present invention suits is 30~80 ℃, specifically decide according to the composition and the concentration of pretreatment liquid.
Because the pretreatment liquid processing time is lower than 5 seconds, aluminium foil surface is not reaction generation almost, the effect that does not reach; But surpass 200 seconds, undue dissolving, the effect that does not also reach take place in aluminium foil surface.So the pretreatment liquid processing time that the present invention suits specifically decides according to the Pressure, Concentration, Temperature of pretreatment liquid for being generally 10~200 seconds.
The invention has the beneficial effects as follows that owing to added the compound of bismuth-containing or indium or the mixture of two kinds of compounds in the pretreatment liquid, when aluminium foil was carried out pre-treatment, aluminium foil surface was separated out because of bismuth or indium, help when sending out pitting corrosion the even spot corrosion of easier generation; Not only improved the corrosion area expanding rate of aluminium foil, than static capacity, and kept its excellent mechanical intensity.
Embodiment:
The invention will be further described below in conjunction with example, and the following examples can be used for making those skilled in the art more fully to understand the present invention, but do not limit the present invention in any way.
Comparative Examples is three concrete schemes of existing pre-treating technology, used pretreatment liquid all is common alkali or the acid solutions that do not add the compound of bismuth-containing or indium, when 30~80 ℃ of temperature, aluminium foil was directly soaked 40~150 seconds in pretreatment liquid, carry out common pitting corrosion, reaming corrosion and reprocessing again.
Embodiment 1 is that aluminium foil is placed temperature is that 40 ℃, concentration are 5.0% NaOH (NaOH) and 0.005% bismuth nitrate (Bi (NO 3) 3) pretreatment liquid in soaked 120 seconds, carry out common send out pitting corrosion, reaming corrosion and reprocessing again.
Embodiment 2 is that aluminium foil is placed temperature is that 80 ℃, concentration are 5.0% sulfuric acid (H 2SO 4) and 0.005% indium nitrate (In (NO 3) 3) pretreatment liquid in soaked 120 seconds, carry out common send out pitting corrosion, reaming corrosion and reprocessing again.
Embodiment 3 is that aluminium foil is placed temperature is 70 ℃, concentration 5.0% phosphoric acid (H 3PO 4) and 0.005% bismuth nitrate (Bi (NO 3) 3) pretreatment liquid in soaked 120 seconds, carry out common send out pitting corrosion, reaming corrosion and reprocessing again.
Embodiment 4 is that aluminium foil is placed temperature is that 70 ℃, concentration are 5.0% phosphoric acid (H 3PO 4) and 0.005% bismuth nitrate (Bi (NO 3) 3) and 0.005% indium nitrate (IN (NO 3) 3) pretreatment liquid in soaked 120 seconds, carry out common send out pitting corrosion, reaming corrosion and reprocessing again.
Embodiment 5 is that aluminium foil is placed temperature is 70 ℃, concentration 5.0% phosphoric acid (H 3PO 4) and 0.1% hydrofluoric acid (HF) and bismuth nitrate (Bi (NO 3) 3) pretreatment liquid in soaked 120 seconds, carry out common send out pitting corrosion, reaming corrosion and reprocessing again.
In conjunction with complete process of the present invention be: in the electrochemical corrosion of high voltage anode aluminum foil, the aluminium foil of employing be aluminium content greater than 99.99%, thickness is 110um, { 110} plane texture occupation rate is at the aluminium foil more than 95% for crystal.Send out pitting corrosion through after the pre-treatment, the etchant solution of sending out pitting corrosion is the mixed liquor of hydrochloric acid, sulfuric acid and aluminum sulfate, carries out the reaming corrosion again, and the etchant solution of reaming corrosion is a salpeter solution, and reprocessing is a salpeter solution, at last through cleaning oven dry.According to the processing of energizing of common way.
Table 1 be the preparation of Comparative Examples and method used herein and the survey static capacity of aluminium foil and tensile strength detailed numerical value relatively.
Table 1:
Figure S2008100298087D00061
Bulking value and tensile strength that data in the table 1 demonstrate among the embodiment have fully all had significant raising than Comparative Examples.

Claims (6)

1. the pre-treating technology of a high-voltage aluminum foil corrosion, place the pretreatment liquid under the uniform temperature to corrode a period of time on aluminium foil, pretreatment liquid is that concentration is the mixed liquor of 1~10% NaOH, potassium hydroxide, sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, phosphoric acid and hydrofluoric acid or the mixed liquor of hydrochloric acid and hydrofluoric acid; It is characterized in that adding percentage by weight in the pretreatment liquid is 0.001~0.025% bismuth-containing or the compound that contains indium, or 0.001~0.025% bismuth-containing and the mixture that contains indium compound; The treatment fluid temperature is made as 30~80 ℃, and etching time is 10~200 seconds.
2. the pre-treating technology of a kind of high-voltage aluminum foil corrosion according to claim 1; It is characterized in that adding percentage by weight in the described pretreatment liquid is 0.01~0.01% bismuth-containing or the compound that contains indium, or 0.001~0.01% bismuth-containing and the mixture that contains the compound of indium.
3. the pre-treating technology of a kind of high-voltage aluminum foil corrosion according to claim 2; It is characterized in that, described 0.001~0.01% bismuth-containing and the mixture that contains the compound of indium, mixed proportion is 1: 1.
4. according to the pre-treating technology of any described a kind of high-voltage aluminum foil corrosion in the claim 1,2 or 3; It is characterized in that described bismuth-containing compound is a bismuth nitrate, containing indium compound is indium nitrate.
5. according to the pre-treating technology of claim 1,2 or 3 described a kind of high-voltage aluminum foil corrosions, it is characterized in that described treatment fluid temperature is made as 30~80 ℃, etching time is 40~150 seconds.
6. according to the pre-treating technology of claim 1,2 or 3 described a kind of high-voltage aluminum foil corrosions; It is characterized in that described treatment fluid temperature is made as 40~60 ℃, etching time is 40~150 seconds.
CN2008100298087A 2008-07-29 2008-07-29 Pre-treating process for high-voltage aluminum foil corrosion Expired - Fee Related CN101425392B (en)

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CN110164696B (en) * 2019-04-12 2021-06-22 浙江丰川电子环保科技股份有限公司 Electrochemical corrosion process for producing medium-high voltage anode foil

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CN1458658A (en) * 2003-05-26 2003-11-26 深圳市东阳光化成箔股份有限公司乳源分公司 Anode aluminium foil etching process for electrolytic capacitor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1458658A (en) * 2003-05-26 2003-11-26 深圳市东阳光化成箔股份有限公司乳源分公司 Anode aluminium foil etching process for electrolytic capacitor

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