CN85101034A - The two-step electrochemical of high voltage aluminium anode foil and chemical method for etching - Google Patents
The two-step electrochemical of high voltage aluminium anode foil and chemical method for etching Download PDFInfo
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- CN85101034A CN85101034A CN85101034.2A CN85101034A CN85101034A CN 85101034 A CN85101034 A CN 85101034A CN 85101034 A CN85101034 A CN 85101034A CN 85101034 A CN85101034 A CN 85101034A
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Abstract
Aluminum electrolysis capacitor anode foil with high cubic structure carries out etching with two-step approach.At first, under 75 ℃ of temperature and direct current effect, handle aluminium foil with the electrolyte bath that contains 3% hydrochloric acid and 1% aluminium (with the aluminum chloride form), use the water-bath that contains that contains 8% nitric acid and 2.6% aluminium (with the aluminum nitrate form) in second step then, under 85 ℃ of temperature, the aluminium foil after the said etching was handled 5-7 minute.The aluminium foil that obtains after the etching in this way is owing to the raceway groove with higher gully density, elongation be intact linear pattern channel structure and have much higher capacitance.
Description
Background technology of the present invention
The invention from technical field
The invention relates to and make two-step etching method, use direct current during the first step etching and contain hydrochloric acid and the etch bath of aluminum chloride, when second step etching, use nitric acid bath then with high capacitance and high cubic structure aluminium electrolutic capacitor usefulness aluminium foil.
The introduction of prior art
In the typical engraving method of aluminium foil for electrolytic capacitor,, use always and contain sodium-chlor or basic electrolytical electrolytic baths such as other salt and vitriol as the etch bath that the first step etching is used.The pH value of this solution is being neutral in typical case.After the first step etching, usually use the nitric acid bath etching.But the ratio capacitance of the aluminium foil of producing does not reach such height that the inventive method can reach at all.In the time of 260 volts, typical C V value be not higher than 200 volts/microfarad/centimetre
2
US Patent No 4,213 discloses a kind of electrograving in 835 through the method for crystalline aluminium foil again, and to make certain aluminium foil, the channel shape of this aluminium foil all is single cylindrical or cube, and gully density is higher than 10
7/ centimetre
2The paper tinsel surface.This method has adopted the constant voltage etching technique.But the problem of this method is it is unsuitable for producing by batch on a large scale etched foil.
US Patent No 4,420 discloses the method for a kind of etching electrolytic condenser with the recrystallization aluminium foil in 367, and this method is to carry out the electrolysis trench etch process in first etch phase, and this method is general in this technical field.The improvements of this patent are to adopt non-electrolysis process to expand the continuous etching of raceway groove, have also adopted one or several chemical milling stages simultaneously.In the first step recrystallization aluminium foil electrolysis raceway groove is shaped, to make the channel structure of this aluminium foil; In subordinate phase, make the aluminium foil of making by first etch phase with channel structure, at least again through non-electrolytically etching process once, make formed raceway groove expansion by chemical method for etching.
In order to produce the high specific capacitance aluminium foil, also adopted other processing method.The present invention seeks to significantly to increase the ratio electric capacity of high-pressure aluminium foil.
Main points of the present invention
Feature of the present invention is that etching has high cubic structure aluminum capacitor anode paper tinsel, compares so that produce with the product that this existing method is made, and has the etched surfaces of homogeneous more and the aluminium foil of high capacitance more.
Several Factors is necessary for the ratio electric capacity that increases the aluminium electrolutic capacitor paper tinsel.A factor is significantly to improve gully density and channel structure.The raceway groove that stretch on straight edge provides the most surface-area that is caused by etching in fact.Along with the increase of gully density, the increase that produces surface-area will be accompanied by.The another one principal element of control ratio electric capacity is to use the type of aluminium foil.As everyone knows, the raceway groove that is etched in the anode foils of under being suitable for high pressure, using, major part is in (100) direction.Therefore can close hand logically supposes to have the paper tinsel of more (100) crystalline orientation, promptly has the paper tinsel of more cubic structures, will produce higher gully density.Up to now, be used for etched aluminium foil and have at random cubic structure.This paper tinsel can be referred to as " non-cubic " paper tinsel, and cubic structure wherein is less than 25%.When the cubic structure amount surpasses 50%, this aluminium foil will be included into the row of high cubic structure.The preferential aluminium foil that adopts of the present invention with high cubic structure, its cubic structure is far longer than 50%, and does not use the aluminium foil of low cubic structure, because it is found that the former through after the etching, channel structure homogeneous, elongation, so gully density can increase.Another principal element that control ratio electric capacity increases is an etching process procedure, and it is controlling the generation of raceway groove and the degree of depth and the brightness of etched raceway groove.Just as the table I show like that, suitably select desire to it etched aluminium foil and etch process method, will cause forming the more raceway groove of homogeneous, thereby obtain much higher capacitance is arranged than the aluminium foil that makes in the past.
The table I
CV value V μ F/cm under 260 volts of the types of aluminium foil type process method
2
The non-traditional processing method 200 of standard
Cubic structure
The processing method 210 non-of the present invention of standard
Cubic structure
Novel height write a biography the system processing method 210
Square structure
Novel height founds processing method 360 of the present invention
Square structure
Electrolytical chemical constitution of the etching of using in the first step of the present invention and chemical property are principal elements of control high pressure (for example being higher than 200 volts) the etched etching characteristic of anode foils direct current.Used hydrochloric acid rather than other muriate in this application, because this can be avoided generating aluminum hydroxide precipitation, this precipitation can be blocked in the elongate channels that stretches in the technological process of the present invention.If allow to produce such precipitation, it will influence the height cube performance of aluminium foil so, thereby can not make full use of in following benefit that can access of the situation that suitably is used high cubic structure aluminium foil and etch process method.Can be about this point by the third line digital proof in the table I, this data declaration be to adopt resulting result under the condition of high cubicity aluminium foil and traditional technology method, the capacitance that is presented is very low.The temperature of the first step etching process remains on 85 ℃ or be lower than 85 ℃, so that reduce vaporization losses, makes this process more economical, easier control.In the first step etching process, aluminium foil is in containing the electrolytic bath that is in aluminium under the aluminum chloride form of 1.5-7% hydrochloric acid, 0-2%, and is etched in addition under 70-85 ℃ and direct current effect.
And the second step etching process is in the water-bath that contains 2-11% nitric acid, 0-3.5% aluminum nitrate shape aluminium, under 80-95 ℃ of temperature aluminium foil is handled 3-12 minute.The long-pending value of CV that mass production goes out aluminium foil up to 360 volts of microfarads/centimetre
2Laboratory experiment shows that higher CV is long-pending also can be reached.
Processing method of the present invention is efficient and economic two step etching method.Needn't do at existing installation under the condition of bigger change, the aluminium foil that this method is produced, its capacitance can reach with market on can buy best aluminium foil capacitance equate or higher.The advantage of the inventive method is, can obtain its road ditch density greater than 10
7/ centimetre
2The etch channels structure of aluminium foil surface, and etched raceway groove is evenly distributed on the aluminium foil.Utilize the inventive method under the condition of aluminium etching extent minimum, to obtain surface expansion maximum under possible condition and electric capacity gain, also keep aluminium foil that enough intensity is arranged simultaneously.
The simple declaration of accompanying drawing
Fig. 1 is description electron microscope (SEM) photo of a slice aluminum electrolysis capacitor anode foil cross section made from traditional engraving method, shows the channel structure that this method obtains.
Fig. 2 a and 2b are two SEM photos of a slice aluminum electrolysis capacitor anode foil made from the inventive method, Fig. 2 a is that Fig. 2 b is the channel structure through the straight relatively extension that is obtained behind the inventive method second step etching through after the etching of the inventive method the first step.
Fig. 3 shows that etching period in nitric acid is to the figure that influences of electric capacity.
The description of preferred embodiment
In preferred embodiments, the first step is the 70-100 micron, has an aluminum electrolysis capacitor anode foil of high cubic texture (preferentially selecting for use cubic texture to be higher than 70%) thickness, under 75 ℃ of temperature and under the direct current effect with in addition etching of the etch electrolyte bath that contains 3% hydrochloric acid and 1% aluminium (with chloride form).Current density be the 0.40-0.45 ampere/centimetre
2, the etching electric weight be the 9-15 coulomb/centimetre
2Second step of preferential selecting method is to contain the aluminium foil of handling the first step etching in the water-bath that contains of 8% nitric acid, 2.6% aluminium (with the aluminum nitrate form), and solution temperature remains on 85 ℃.Using the etched purpose of this solution is the raceway groove that expansion occurs when the first step etching.Etching period in nitric acid is 4-7 minute.Along with the variation of this etching period, the result of appearance is also different, i.e. the paper tinsel of under 260 volts, making, the minimum capacitance voltage product value be 285 volts of microfarads/centimetre
2, maximum for be not higher than 360 volts of microfarads/centimetre
2The paper tinsel of under 465 volts, making, the long-pending value of CV be in 243-321 lie prostrate microfarad/centimetre
2Between.
When the top condition of preferred this processing method, consider that three key factors (physical strength of aluminium foil, high capacitance and production cost are low) adopt following each value.In the first step, current density remains on 0.40 ampere/centimetre
2, the etching electric weight is 9.In second step, the etching period in solution is 6 minutes.The long-pending value of the best CV of Huo Deing in this way, for 260 volts and 465 volts times aluminium foils of making be respectively 355 volts of microfarads/centimetre
2With 320 volts of microfarads/centimetre
2This two step process methods can form the sort of etch channels structure shown in the SEM photo among a kind of image pattern 2a and the 2b, and Fig. 2 a is that the first step is taken afterwards, and Fig. 2 b took after second step.
These figure demonstrate the channel structure of etched foil cross section.Linearly the light grey structure of shape is the etch channels of aluminium foil, and the boundary surface of aluminium foil can be differentiated slightly in the upper and lower of the raceway groove relative with the edge material.Compare with the prior art of Fig. 1 explanation, in Fig. 2 a and Fig. 2 b SEM photo, in vertical plane, demonstrate the channel structure that extends along more straight direction significantly.The light gray areas that these channel structures demonstrate further is full of aluminium foil.These raceway grooves seem to have the pattern of comparison rule, and channel structure density is also of the prior art the sort of much higher than what presented among Fig. 1.The fact that has crucial meaning in these photos is that a lot of raceway grooves are interpenetration not, makes it to lose this channel structure.
As mentioned above, the inventive method is used the aluminium foil with high cubic texture, and its cubic texture is 75%, and the aluminium amount that dissolve this moment is approximately 6.5 ± 0.5 milligrams/centimetre
2What following table illustrated is when forming anodic oxide under 260 volts and 465 volts, the ratio electric capacity of resultant aluminium foil.Wherein CV is the product of electric capacity and voltage, and CV/mg is that electric capacity multiply by voltage and dissolves the aluminium amount of getting off divided by every square centimeter of aluminium foil again, and these data are measuring of etching process relative efficiency.
The parameter that the present invention uses allows following variation.Employed aluminium foil is the aluminium foil with very high cubic texture, this means that the many particles in this aluminium foil are orientated by (100) direction.
The table II
260 volts 465 volts of the aluminium amounts of dissolving
(mg/cm
2) CV value CV/mg value CV value CV/mg value
5.1 304 59 284 55
6.3 338 53 320 50
7.35 374 50 338 46
With regard to the inventive method purpose, have been found that the aluminium foil that has at least 70% particle to be orientated according to (100) direction is enough to reach the desired result who obtains.On market, this aluminium foil can have been bought the branch of clear and aluminium company (Showa Aluminum Company), half aluminium company (Toyo Aluminum Company) and SCAL(Bai Qini aluminium company, a Division of Pechiney Aluminum Company) product.Use the aluminium foil of high cubic texture can etch very straight raceway groove, the surf zone that keeps etching thus simultaneously and produced.The raceway groove that produces is tending towards more uniformity, so gully density can increase.The cubicity of aluminium foil is high more, and this electric capacity is just big more.Yet, by experiment confirm, for produce going up, use have 70% or the aluminium foil of higher cubicity can satisfy the demand enough.
The value of other parameter also can have certain limit in the method for the present invention.The first step will satisfy conditions such as a large amount of muriates existence and acidic medium are arranged with the chemical constitution and the chemical property of electrolyte bath.Occur the shortcoming of aluminum hydroxide precipitation during for fear of use sodium-chlor, preferentially select hydrochloric acid for use.In electrolyte bath, add aluminium and will make electrolyte bath so not expensive, and can reduce electrolytical replacing in the technological process.The first step is as follows with the scope of parameters in the electrolyte bath.The concentration of hydrochloric acid that can exist is 1.5-7.0%, and the aluminium that can exist (with the aluminum chloride form) amount is 0-2%.Operable temperature range is 70-85 ℃ during the first step etching.Operable current density value be the 0.25-0.60 ampere/centimetre
2Operable etching electric weight be the 6-25 coulomb/centimetre
2These parameter range that are used for the mass production high-pressure aluminium foil are determined by experiment.Use the parameter value in institute's proposition scope, can under the condition of the complex control system that does not use these parameters of monitoring, produce aluminium foil in a large number and apace, thereby make the used equipment of processing method of the present invention more cheap.With regard to temperature range, when being higher than 85 ℃, evaporation just becomes a significant factor.If temperature is lower than 70 ℃, etching process or can not carry out then perhaps carries out very slowly so that can not produce the etch channels of sufficient amount.With regard to current density, if be lower than the lower limit of this span, then the raceway groove number of Chan Shenging is less, thereby gully density is reduced.If current density is higher than said scope, then trench size differs, and this is to cause owing to the raceway groove that occurred of coexistence simultaneously produces such two kinds of processes to depth expansion and new raceway groove.Uneven raceway groove should be avoided, and this point is not always the case in any etching process because when the anode foils moulding, a lot of raceway grooves under high pressure in fact oxide stop up.
The span that second step of present method is adopted is as follows.Use in the etch bath in second step, concentration of nitric acid can be 2-11%, and aluminium (with the aluminum nitrate form) concentration can be 0-3.5%.Temperature range can be 80-95 ℃, and as the said mistake in front, the etch time in this is bathed can be 3-12 minute.
The soak time of the curve shows that provides among Fig. 3 in nitric acid is to making the influence of aluminium foil electric capacity.
Find out obviously that by these examples the aluminium foil that obtains according to the inventive method etching can be used for high-voltage electrolysis capacitor, and compare with the aluminium foil that makes in the past, can produce much higher ratio electric capacity (by centimetre
2Calculate).Therefore, obtain given capacitance, the volume of electrical condenser can be done forr a short time, is perhaps having under the condition of equal volume, and the electrical condenser of making has higher capacitance.Though also can be changed by prior art various secondary causes as can be known, be should be understood that I wish the variation range of the secondary cause that puts forward is here generally fitted within the scope of this patent with suitably and rational subordinate claim form.
Errata
Claims (11)
1, the two-stage process of etching aluminum electrolysis capacitor anode foil, wherein this aluminium foil has high cubic structure, cubic structure comprises greater than 70%: the first step:
Under 70-85 ℃ of temperature and dc electrolysis effect, handle said aluminium foil with the electrolyte bath that contains 1.5-7.0% hydrochloric acid and 0-2% aluminium (with chloride form); And when said aluminium foil is immersed said hydrochloric acid bath, by said aluminium foil with the 6-25 coulomb electric charge, current density be controlled at the 0.25-0.6 ampere/centimetre
2Between; And
In second step, to bathe with the moisture etch that contains 2-11% nitric acid and 0-3.5% aluminium (with the aluminum nitrate form), the said aluminium foil that will take out from said first bath was handled 3-12 minute, and bath temperature is 80-95 ℃.
2, in accordance with the method for claim 1, wherein said aluminium foil cube be 70% or higher.
3,, be 3% with the hydrochloric acid percentage concentration in the electrolyte bath wherein in the said the first step according to the said aluminium foil of claim 1.
4, in accordance with the method for claim 1, the aluminium percentage concentration that wherein exists with chloride form in said electrolyte bath in the said the first step is 1%.
5, in accordance with the method for claim 1, wherein the temperature in the said the first step is 75 ℃.
6, in accordance with the method for claim 1, wherein the current density in the said the first step is 0.40 ampere/centimetre
2
7, in accordance with the method for claim 1, wherein the etching electric weight is 9 coulombs/centimetre
2
8, in accordance with the method for claim 1, wherein the said etch bath in said second step contains 8% nitric acid.
9, in accordance with the method for claim 1, wherein said second the step in said etch bath, containing to some extent, the aluminium amount of aluminum nitrate form is 2.6%.
10, according to the said method of claim 1, the temperature of wherein said second bath is 85 ℃.
11, according to the said method of claim 1, wherein said paper tinsel was handled 6 minutes with said bath in said second step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101034.2A CN1006001B (en) | 1984-07-16 | 1985-04-01 | Two-step electrochemical and chemical etching method of hish voltage aluminium anode foil |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/631,667 US4525249A (en) | 1984-07-16 | 1984-07-16 | Two step electro chemical and chemical etch process for high volt aluminum anode foil |
| CN85101034.2A CN1006001B (en) | 1984-07-16 | 1985-04-01 | Two-step electrochemical and chemical etching method of hish voltage aluminium anode foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101034A true CN85101034A (en) | 1987-01-10 |
| CN1006001B CN1006001B (en) | 1989-12-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85101034.2A Expired CN1006001B (en) | 1984-07-16 | 1985-04-01 | Two-step electrochemical and chemical etching method of hish voltage aluminium anode foil |
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| Country | Link |
|---|---|
| CN (1) | CN1006001B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371500C (en) * | 2005-09-28 | 2008-02-27 | 重庆钢铁(集团)有限责任公司 | Aviation pipe internal surface chemical corrosion method |
| CN101029413B (en) * | 2006-12-19 | 2010-05-12 | 东莞市东阳光电容器有限公司 | Production of medium-high voltage anode corrosive foil |
| CN101880881A (en) * | 2010-06-13 | 2010-11-10 | 西南大学 | High aluminum zinc alloy etching agent and use method thereof |
| CN101210341B (en) * | 2006-12-30 | 2010-12-29 | 新疆众和股份有限公司 | Method for producing reaming electrolyte and high specific surface area aluminum electrolytic capacitor electrode foil |
| CN106981367A (en) * | 2017-04-18 | 2017-07-25 | 扬州宏远电子有限公司 | The follow-on solid-state capacitor electrode aluminium foil processing method of one kind post processing |
| CN107130245A (en) * | 2017-03-21 | 2017-09-05 | 广东宇彤创业投资有限公司 | A kind of preparation method of perforated foil |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100338703C (en) * | 2002-07-24 | 2007-09-19 | 扬州宏远电子有限公司 | Process for preparing 35Vw and 50Vw anode foil with high specific capacity and low contact resistance |
-
1985
- 1985-04-01 CN CN85101034.2A patent/CN1006001B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371500C (en) * | 2005-09-28 | 2008-02-27 | 重庆钢铁(集团)有限责任公司 | Aviation pipe internal surface chemical corrosion method |
| CN101029413B (en) * | 2006-12-19 | 2010-05-12 | 东莞市东阳光电容器有限公司 | Production of medium-high voltage anode corrosive foil |
| CN101210341B (en) * | 2006-12-30 | 2010-12-29 | 新疆众和股份有限公司 | Method for producing reaming electrolyte and high specific surface area aluminum electrolytic capacitor electrode foil |
| CN101880881A (en) * | 2010-06-13 | 2010-11-10 | 西南大学 | High aluminum zinc alloy etching agent and use method thereof |
| CN107130245A (en) * | 2017-03-21 | 2017-09-05 | 广东宇彤创业投资有限公司 | A kind of preparation method of perforated foil |
| CN106981367A (en) * | 2017-04-18 | 2017-07-25 | 扬州宏远电子有限公司 | The follow-on solid-state capacitor electrode aluminium foil processing method of one kind post processing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1006001B (en) | 1989-12-06 |
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