CN1027718C - Aluminum foil as electrolytic condenser electrodes - Google Patents
Aluminum foil as electrolytic condenser electrodes Download PDFInfo
- Publication number
- CN1027718C CN1027718C CN 91112795 CN91112795A CN1027718C CN 1027718 C CN1027718 C CN 1027718C CN 91112795 CN91112795 CN 91112795 CN 91112795 A CN91112795 A CN 91112795A CN 1027718 C CN1027718 C CN 1027718C
- Authority
- CN
- China
- Prior art keywords
- paper tinsel
- concentration
- aluminium foil
- elements
- auxiliary element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Abstract
An aluminum foil for use as the electrolytic condenser electrodes is composed of 99.9 % or more of aluminum. The fil also contains given amounts of one or more auxiliary elements selected from a group consisting of Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, Pb, In and rare-earth elements, with the auxiliary elements being contained either in a boundary region disposed between a foil body and an oxide layer thereon, or in surface portion of the oxide layer, at a concentrated state such that an ion strength ratio of the concentration of the auxiliary elements in the region or the portion to their concentration in the foil body is from 1.2 : 1 to 30 : 1. Alternatively, the foil may contain given amounts of one or more auxiliary elements selected from a group consisting of Fe, Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, B, Mg, Pb, In, Bi and rare-earth elements, with the auxiliary elements being contained not only in the boundary region but also in the surface portion at the same concentrated state as described above.
Description
The present invention relates to a kind of aluminium foil, particularly relate to aluminium foil as the anode in the medium-pressure or high pressure electrolytic capacitor as electrolytic capacitor.
In order to increase the density of etch pit, a large amount of research work have been carried out, wherein be used as the aluminium foil surface of electrolytic capacitor with galvano-cautery or electrochemical erosion method etching, form etch pit, thereby the effective surface area of aluminium foil is increased, and the capacitance of unit are is increased, in nearest this research work, JP-A-63-288088 discloses a kind of aluminium foil, and it comprises from its outer surface thickness is the superficial layer of 0.1 μ m and the Pb that contains 10-100ppm.Yet the superficial layer that contains the Pb element does not equably improve corrosion property, and has caused the etch pit density of difference.So, can not obtain big active surface, and therefore can not guarantee higher capacitance.
What the research work of carrying out according to the technology of latest developments according to the inventor proposed the objective of the invention is, a kind of aluminium foil as electrolytic capacitor is provided, the superficial layer that this aluminium foil has then has effective surface area to greatest extent if contain the best distribution and the concentration of these required metallic elements.
For realizing purpose of the present invention, in the part that the only auxiliary element selected is needed most in aluminium foil by specific enrichment CONCENTRATION DISTRIBUTION.
By first kind of pattern of the present invention, the objective of the invention is such realization, comprise the 99.9wt%(percentage by weight as the aluminium foil of electrolytic capacitor) or more aluminium and be selected from one or more auxiliary elements in the auxiliary element group that following element forms, the unit that the auxiliary element group is comprised have: Cu(copper), Si(silicon), Zn(zinc), Mn(manganese), the Ga(gallium), P(phosphorus), the V(vanadium), the Ti(titanium), Cr(chromium), Ni(nickel), the Ta(tantalum), the Zr(zirconium), C(carbon), the Be(beryllium), Pb(lead), the In(indium) and rare earth (that is group of the lanthanides) element.Have bigger concentration in the boundary zone between the oxide layer that these auxiliary elements form on paper tinsel body and paper tinsel body, the ion concentration of the interior auxiliary element content of auxiliary element content and paper tinsel body is 1.2: 1 to 30: 1 in the boundary zone.
By second kind of pattern of the present invention, the objective of the invention is such realization, contain 99.9wt% or more aluminium and be selected from one or more auxiliary elements in the auxiliary element group that following element forms as the Aluminium Foil Package of electrolytic capacitor, the unit that constitutes the auxiliary element group have: Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, Pb, In and rare earth element.Bigger concentration is arranged in the surface portion of the oxide layer that these auxiliary elements form on the paper tinsel body, and the ion concentration of the auxiliary element content in auxiliary element content in the surface portion and the paper tinsel body is 1.2: 1 to 30: 1.
By the third pattern of the present invention, the object of the present invention is achieved like this, comprise 99.9wt% or more aluminium and be selected from one or more auxiliary elements in the auxiliary element group that following element forms as the aluminium foil of electrolytic capacitor, the unit that forms the auxiliary element group have: Fe(iron), Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, B(boron), Mg(magnesium), Pb, In, Bi(bismuth) and rare earth element.Have bigger concentration in the surface portion of the oxide layer that these auxiliary elements not only form on the paper tinsel body, also have bigger concentration in the boundary zone between paper tinsel body and oxide layer.The ion concentration of the auxiliary element content that auxiliary element content in the surface portion and the boundary zone and paper tinsel body are interior is 1.2: 1 to 30: 1.
Other purpose of the present invention, feature and advantage will become cheer and bright from the explanation of doing below in conjunction with accompanying drawing.
Fig. 1 is the detected ion concentration data and curves of the aluminium foil surface part figure as electrolytic capacitor from providing by first kind of pattern of the present invention;
Fig. 2 is another curve chart from the detected in the same manner ion concentration data of another kind of aluminium foil surface part that are used as electrolytic capacitor that provide by second kind of pattern of the present invention;
Fig. 3 is the another curve chart from the detected ion concentration data of another aluminium foil surface part that are used as electrolytic capacitor that provide by the third pattern of the present invention.
First kind of pattern of the present invention
In first kind of pattern of the present invention, in the boundary zone between the oxide layer that selecteed enrichment of element forms on aluminium foil body and paper tinsel body.
The purity of aluminium must be 99.9wt% or higher in whole raw material paper tinsel, because purity is when low, and the impurity content height, this can hinder etch pit evenly to grow into dark tunnel type hole, and electrolytic corrosion process just can't make the capacitance increase.Therefore, wish to adopt the raw material paper tinsel that contains 99.98wt% or more aluminium.
As shown in Figure 1, the boundary zone between the oxide layer that forms on paper tinsel body and the paper tinsel body contains one or more elements of the high concentration that forms the corrosion nucleus.This is the key factor that improves the aluminium foil capacitance.Because these elements that are enriched in the boundary zone can play the effect of corroding nucleus, to produce the etch pit of sufficient amount, the thin tunnel hole of etch pit president plutonic for stretching into to aluminium foil inside.Consequently can obtain bigger effective surface area.
Ion concentration in the boundary zone between the concentration of the interior selected element of the concentration of selected element and paper tinsel body is 1.2: 1 to 30: 1.When being lower than down, concentration prescribes a time limit, given etch pit density deficiency, so effective surface area can not increase to enough degree.On the other hand, concentration is higher than in limited time, and the resistance to corrosion on paper tinsel surface is obviously descended.This also will cause very high etch pit density, make adjacent hole be merged into macropore, so that the whole surface dissolution of paper tinsel is gone in the etching tank basically, therefore effective surface area undesirable obvious reduction can occur.Therefore, Zui Jia ion concentration is 3: 1 to 25: 1.Measure ion concentration and can adopt following condition: use Ar
+(argon ion) makes basic ion; Beam diameter is 500 microns; Accelerating voltage is 10 kilovolts; Electric current is 0.3 microampere.For example, the available Hitachi, Ltd IMA-S type instrument of producing is measured ion concentration.
Corrosion nucleus forming element, promptly auxiliary element is selected from the element set that Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, Pb, In and rare earth element are formed.Here rare earth element is meant 17 kinds of elements, comprises that atomic number is 15 kinds of elements (being La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Im, Yb and Lu) and the Y(yttrium of 57-71) and the Sc(scandium).In first kind of pattern of the present invention, these elements are equivalent with regard to their function, promptly improve the effect of surface area-enhancing etching process.Any selected element needn't be used separately, two or more elements can be used simultaneously.With regard to rare earth element, can use so-called " mischmetal(l) (M.M) ".It is to make with the muriatic mixture electrolysis of two or more rare earth elements.Under actual conditions, preferably use any type of compound of one or more elements of Y, La, Ce, Pr, Nd, Sm and mischmetal(l), because they prepare easily than other compound.
Adopting under the situation of Cu, Si, Zn, Mn and/or Ga, except that thickness is 0.1 micron outermost layer, wishing that the concentration at inner contained these elements of paper tinsel is 3-60ppm.Under the another kind of situation of using P, V, Ti, Cr, Ni, Ta, Zr, C and/or Be, wish that concentration is 1-40ppm.And under the situation of using Pb, In and/or any or multiple rare earth element, concentration is set at 0.01-3ppm.Under any circumstance, concentration is lower than down in limited time, will cause etch pit to form deficiency; And concentration is higher than in limited time, can cause excessive corrosion.
For Cu, Si, Zn, Mn and/or Ga, concentration is about 10-30ppm preferably; For P.V.Ti, Cr, Ni, Ta, Zr, C and/or Be, concentration is about 5-25ppm preferably; For Pb, In and/or rare earth element, concentration is about 0.2-1.5ppm preferably.
When making this aluminium foil that is enriched with the corrosion nucleus forming element of described distributions, one or more corrosion nucleus forming elements of scheduled volume are added in aluminium ingots, mould is injected in aluminium ingot fusing back.Subsequently, with the thick plate hot rolling that pours into, the interline of going forward side by side if desired annealing is rerolled and is made the raw material paper tinsel.Then this raw material paper tinsel is done final annealing and handled, for example under 450-550 ℃ of temperature, annealed 1-30 hour in a vacuum, preferably under 470-520 ℃ of temperature, annealed 3-10 hour.At last, carry out " ion implantation technology ", the above-mentioned element of scheduled volume is injected in the boundary zone between paper tinsel body and the oxide layer.The nucleus forming element that has added aluminium ingot or be injected in the paper tinsel optionally is diffused in the boundary zone, will occur the special enrichment state by said element of the present invention like this in this district.
The aluminium foil that first kind of pattern provides has good etching characteristic as electrolytic capacitor, makes that its effective surface area obviously increases in etching process.If carried out suitable preliminary treatment before etching process, corrosiveness can obviously be improved so, and can not cause the uniform dissolution that may occur on paper tinsel outermost top layer.
Therefore, the aluminium foil after the corrosion can provide sufficiently high capacitance, excellent electric characteristics and high mechanical strength.
Second kind of pattern of the present invention
In second kind of pattern of the present invention, in the outermost portion of the oxide layer that selected enrichment of element forms on the paper tinsel body.
The purity of aluminium must be 99.9wt% or higher in whole raw material paper tinsel, because identical with first kind of pattern, when purity was low, impurity content was higher, this can hinder etch pit evenly to grow into dark tunnel type hole, and electrolytic corrosion process just can not increase capacitance.Thereby, wish with the raw material paper tinsel that contains 99.98wt% or more aluminium.
As shown in Figure 2, one or more selected elements that form the corrosion nucleus have high concentration in the outermost portion of oxide layer.Identical with first kind of pattern, this is the key factor that increases the aluminium foil capacitance.Because the effect of a large amount of thin faults is played by the most external branch of the oxide layer that these enrichment of element form on the paper tinsel body.In the starting stage of etching process, can produce a large amount of etch pits from thin fault, and long successively plutonic is the hole, thin tunnel towards aluminium foil inside.Consequently, on aluminium foil, obtain bigger effective surface area.
Ion concentration in the concentration of the selected element in the oxide layer outermost portion and the paper tinsel body between the concentration of selected element should be 1.2: 1 to 30: 1.Concentration is lower than down in limited time, can make etch pit density deficiency, thereby effective surface area can not increase to enough degree.On the other hand, concentration is higher than in limited time, and the resistance to corrosion on paper tinsel surface obviously reduces.This also can produce extra high etch pit density, makes adjacent hole be merged into macropore, and like this, the whole surface of paper tinsel can be dissolved in etching tank basically, and undesirable reducing can appear in effective surface area.Therefore, comparatively suitable ion concentration is 3: 1 to 25: 1.
Corrosion nucleus forming element, promptly auxiliary element is selected from and first kind of element set that pattern is identical, and the unit of component group have: Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, Pb, In and rare earth element.In second kind of pattern of the present invention, these elements are equivalent with regard to their function, promptly improve the effect of surface area-enhancing etching process, and are identical with first kind of pattern, needn't can use two or more elements simultaneously only with selected any element.
Using under the situation of Cu, Si, Zn, Mn and/or Ga, except that thickness is 0.1 micron outermost layer, wishing that the concentration of these elements in paper tinsel is 3-60ppm.Under the another kind of situation of using P, V, Ti, Cr, Ni, Ta, Zr, C and/or Be, wish that concentration is 1-40ppm.And under the situation of using Pb, In and/or any or multiple rare earth element, concentration is set at 0.01-3ppm.In any case, concentration is lower than lower limit and can causes etch pit to form deficiency, can cause excessive corrosion and concentration is higher than the upper limit.
When using Cu, Si, Zn, Mn and/or Ga, concentration is about 10-30ppm preferably; When using P, V, Ti, Cr, Ni, Ta, Zr, C and/or Be, concentration is about 5-25ppm preferably; When using Pb, In and/or rare earth element, concentration is about 0.2-1.5ppm preferably.
When making this aluminium foil that is enriched with the corrosion nucleus forming element of described distributions, one or more corrosion nucleus forming elements of scheduled volume are added in the aluminium ingot, and with aluminium ingot fusing injection mould, and then, with the thick plate hot rolling that pours into, the interline of going forward side by side if desired annealing, and be rolled into the raw material paper tinsel once more, clean the raw material paper tinsel then.This raw material paper tinsel is carried out annealing in process thereafter, for example, be preferably in 470-520 ℃ of following annealing in process 3-10 hour in a vacuum at 450-550 ℃ of following annealing in process 1-30 hour.At last, carry out " sputter ", " wet plating " or " ion implantation technology ", so that the element of scheduled volume is added to the outer surface of paper tinsel.The heat treatment once more of this paper tinsel, for example under vacuum at 300-550 ℃ of heat treatment 0.2-10 hour, be preferably in 400-500 ℃ of heat treatment 1-3 hour.Because heat treatment once more, make to be added in the aluminium ingot or to be added to the lip-deep nucleus forming element of paper tinsel enrichment (enrichment) optionally in the outermost portion of oxide layer, therefore, the special enrichment state by said element of the present invention can appear in this section.
The aluminium foil that provides in second kind of pattern has good etching characteristic as electrolytic capacitor, makes that its effective surface area obviously increases in etching process.Particularly, carried out any preliminary treatment before etching process, corrosive effect all has more obvious improvement, and can not cause the uniform dissolution that may occur on paper tinsel outermost top layer.
Therefore, the aluminium foil after the corrosion can provide sufficiently high capacitance, excellent electric characteristics and high mechanical strength.
The third pattern of the present invention
In the third pattern of the present invention, selected element not only is enriched in the boundary zone between paper tinsel body and the oxide layer; Also be enriched in the outermost portion of oxide layer.
The purity of aluminium must be 99.9wt% or higher in whole raw material paper tinsel, because, the same with situation in first kind and the second kind of pattern, when purity is low, impurity content is higher, and this can hinder etch pit evenly to grow into dark tunnel type hole, and electrolytic corrosion process just can not improve capacitance.Therefore, wish to use and to contain 99.98% or the raw material paper tinsel of more aluminium.
As shown in Figure 3, one or more selected elements that form the corrosion nucleus have high concentration in oxide layer.Identical with first and second kinds of patterns, this is the key factor that improves the aluminium foil capacitance.Because, in the boundary zone and these elements that are formed on enrichment in the oxide layer outermost portion on the paper tinsel body will play the effects of a large amount of thin faults.In the starting stage of etching process, these thin fault places can form the macro-corrosion hole, grow up to the hole, thin tunnel in paper tinsel subsequently.When these holes, thin tunnel reached boundary zone between oxide layer and the paper tinsel body, the element of enrichment also can play the effect of corrosion nucleus in this district, and therefore, etch pit can look darker towards paper tinsel body inside.Thereby can obtain very big effective surface area.
Ion concentration between the concentration of the selected element that comprises in the concentration of the selected element that boundary zone and oxide layer outermost portion comprise and the paper tinsel body is 1.2: 1-30: 1.Concentration is lower than lower limit can make etch pit density deficiency, and effective surface area can not increase to enough degree.On the other hand, concentration is higher than the obviously resistance to corrosion on reduction paper tinsel surface of the upper limit.This can cause that also etch pit density is too high, makes adjacent holes be merged into macropore, makes basically that the whole surface of paper tinsel is dissolved in etching tank, and undesirable reducing can appear in effective surface area.Therefore, ion concentration is 3: 1 to 25: 1 preferably.
Corrosion nucleus forming element, promptly auxiliary element is selected from the element set of being made up of Fe, Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, B, Mg, Pb, In, Bi and rare earth element.
In three-mode of the present invention, these elements are equivalent with regard to their function, promptly improve the effect of surface area-enhancing etching process.Identical with first and second kinds of patterns, needn't only use any selected element, can use two or more elements simultaneously.
When using Fe, Cu, Si, Zn, Mn and/or Ga, except that thickness is 0.1 micron outermost layer, wish that the concentration of these contained elements is 3-60ppm in paper tinsel.When using P, V, Ti, Cr, Ni, Ta, Zr, C, Be, B and/or Mg, wish that concentration is 1-40ppm.When using Pb, In, Bi and/or any or multiple rare earth element, wish that concentration is 0.01-3ppm.Under any circumstance, concentration is lower than lower limit, and can to cause etch pit to form insufficient, can cause excessive corrosion and concentration is higher than the upper limit.
For Fe, Cu, Si, Zn, Mn and/or Ga, concentration is about 10-30ppm preferably; For P, V, Ti, Cr, Ni, Ta, Zr, C, Be, B and/or Mg, concentration is about 5-25ppm preferably; For Pb, In, Bi and/or rare earth element, concentration is about 0.2-1.5ppm preferably.
When making this aluminium foil that is enriched with the corrosion nucleus forming element of described distributions, one or more nucleus forming elements of scheduled volume are joined in the aluminium ingot, the aluminium ingot fusing is poured in the mould, subsequently, the thick sheet material that pours into is through hot rolling, the interline of going forward side by side if desired annealing, the rolling once more raw material paper tinsel of making.Then, with these raw material paper tinsel annealing in process, for example in a vacuum at 450-550 ℃ of following annealing in process 1-30 hour.Preferably at 470-520 ℃ of annealing in process 3-10 hour.Then, through in " ion implantation technology " selected element adding aluminium foil paper tinsel body and the boundary zone between paper tinsel body and the oxide layer with scheduled volume.Element with scheduled volume before " sputter " or " wet plating " finished adds the paper tinsel outer surface.At last, this paper tinsel is done final heat treatment, for example under vacuum at 200-550 ℃ of heat treatment 0.2-10 hour, be preferably under the vacuum at 300-500 ℃ of heat treatment 1-3 hour.Because final heat treatment, make and add aluminium ingot or add corrosion nucleus forming element in aluminium foil enrichment (enrichment) optionally in the boundary zone, and the said element that joins the paper tinsel surface successively is at the outermost portion of oxide layer also enrichment, therefore, the state that the special enrichment of said element of the present invention in these zones and part, occurred.
The aluminium foil that provides in the third pattern has good etching characteristic as electrolytic capacitor, makes that its effective surface area obviously increases in etching process.Because selected enrichment of element in two zones or part, so obviously improvement of corrosive effect, and can not cause the uniform dissolution that its outermost top layer may occur.Aluminium foil can preliminary treatment before etching process, also can not preliminary treatment.
Therefore, the aluminium foil after the corrosion provides sufficiently high capacitance, good electrical characteristic and high mechanical strength.
First embodiment
With purity be 99.99% and the aluminium ingot that contains the Fe of 0.002% Si and 0.002% make raw material.From the element set of forming by Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, Pb, In and rare earth element, select one or more elements, as shown in table 1.Behind every kind of selected element adding aluminium ingot with scheduled volume, sheet material is made in aluminium ingot fusing and cast that each sample is used.Then with plate hot rolling, intermediate annealing, be rolled into paper tinsel, cleaning, and under vacuum under 490 ℃ of temperature annealing in process 4 hours.The aluminum foil thickness of making thus is 0.1 millimeter, and this aluminium foil will pass through ion implantation technology, so that the above-mentioned selected element of scheduled volume injects wherein.Ion concentration to its boundary zone of sample in measurement (between the oxide layer that forms on paper tinsel body and the paper tinsel body) of making and paper tinsel body inside (i.e. inside 0.1 micron or depths more from the surface).The condition of the IMA-S type apparatus measures ion concentration of producing with Hitachi, Ltd is: Ar
+Make basic ion; Beam diameter is 500 microns; Accelerating voltage is 10 kilovolts; Electric current is 0.3 microampere.Test result is shown in Table 1.These raw material paper tinsels will be through excessive erosion before being used as electrolytic capacitor.
Etching process is as follows, and the raw material paper tinsel is at the NaOH(NaOH that contains 1%) temperature is to soak for two seconds in 50 ℃ the etching tank, after the immersion, the raw material paper tinsel is at 5% HCl(hydrochloric acid) and 15% H
2SO
4Be direct current 20 peace/decimetres 85 ℃ and current density in the etchant solution that (sulfuric acid) is mixed with
2Condition under carry out the first time corrosion in 60 seconds.Then, the aluminium foil that corroded is carried out the corrosion second time again, etching condition is: in the another kind of etchant solution that HCl 5% and 0.1% ethanedioic acid are mixed with, be 5 amperes/decimeter of direct currents at 85 ℃ with current density
2The time, corroded 8 minutes.
The what is called of the aluminium foil that these corroded " processing of energizing (forming treatment) " is carried out under 380 volts of voltages.Capacitance to aluminium foil is measured, and measured result is listed in the table 1.Capacity with No. 24 reference samples is the capacitance percent value of 100% each sample of expression.
As shown in table 1, capacitances that various electrode foil had that the boundary zone between the oxide layer on paper tinsel body and the paper tinsel body contains one or more corrosion nucleus forming elements of normal concentration of the present invention all include the capacitance of the reference sample of excessive said element above the boundary zone.
(table 1 is seen the literary composition back)
Second embodiment
With purity be 99.99% and the aluminium ingot that contains the Fe of 0.002% Si and 0.002% be raw material.From the element set of forming by Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, Pb, In and rare earth element, select one or more elements, as shown in table 2.Behind the scheduled volume adding aluminium ingot of selected element, melt the used aluminium ingot of each sample, and cast becomes sheet material by every kind of element.Then, plate hot rolling, intermediate annealing and the system of rerolling being formed thickness is 0.1 millimeter raw material paper tinsel.These raw material paper tinsels are cleaned and annealing in process 4 hours under 490 ℃ of temperature in a vacuum, subsequently, these aluminium foils are carried out ion sputtering handle, make selected element predetermined amounts be added to the paper tinsel surface, and under 400 ℃ of temperature, carry out heat treatment in 1 hour again.Ion concentration to (i.e. inside 0.1 micron or depths more from the surface) in its oxide layer surface portion of sample in measurement and paper tinsel body of making.With the IMA-S type apparatus measures ion concentration that Hitachi, Ltd produces, condition is: Ar
+Make basic ion; Beam diameter is 500 microns; Accelerating voltage is 10 kilovolts; Electric current is 0.3 microampere.The results are shown in Table 2.These raw material paper tinsels will corrode as before the electrolytic capacitor.
Etching process is as follows, and the raw material paper tinsel is at 5% HCl and 15% H
2SO
4In the etchant solution that is mixed with, be 20 amperes/decimeter of direct currents with current density at 85 ℃
2Condition under, through corrosion first time in 60 seconds, then, aluminium foil is 5 amperes/decimeter of direct currents 85 ℃ and current density again in the another kind of etchant solution that the ethanedioic acid of 0.5% HCl and 0.1% is mixed with
2Condition under, through corrosion second time of 8 minutes.
These aluminium foils through excessive erosion carry out so-called " processing of energizing " with 380 volts of voltages.Measure the capacitance of aluminium foil.Measurement result is listed in the table 2, is 100% to represent the capacitance percent value of each sample with the capacitance of No. 53 reference samples.
As shown in table 2, the oxide layer surface portion contains capacitance that every kind of electrode foils of one or more corrosion nucleus forming elements of normal concentration of the present invention have all above the capacitance of any reference sample of the selected element that contains excess on the paper tinsel body.
(table 2 is seen the literary composition back)
The 3rd embodiment
With purity be 99.99% and the aluminium ingot that contains the Fe of 0.002% Si and 0.002% make raw material.From the element set of forming by Fe, Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, B, Mg, Pb, In, Bi and rare earth element, select one or more elements, as shown in table 3.After every kind of selected element of scheduled volume joined aluminium ingot, the aluminium ingot fusing and the cast that will be used for each sample form sheet material, then, sheet material through hot rolling, intermediate annealing, to be rolled into thickness be 0.1 millimeter raw material aluminium foil, these raw material aluminium foils are carried out annealing in process, for example annealing in process 4 hours under 490 ℃ of temperature in a vacuum.The aluminium foil of so making makes the selected element of scheduled volume inject the paper tinsel body of every aluminium foil and the boundary zone between the oxide layer through ion implantation technology.Further, with the ion sputtering method the selected element of other scheduled volume is added to the surface of every aluminium foil.Then with the heat treatment 1 hour under 400 ℃ of temperature in a vacuum again of these aluminium foils.The ion concentration of (i.e. inside 0.1 micron or depths more from the surface) in the boundary zone (between paper tinsel body and the oxide layer on it) of measuring the aluminium foil of these samples then and the paper tinsel body.With the IMA-S type apparatus measures ion concentration that Hitachi, Ltd makes, measuring condition is: Ar
+Make basic ion; Beam diameter is 500 microns; Accelerating voltage is 10 kilovolts; Electric current is 0.3 microampere.Measurement result is listed among the table J, and these aluminium foils will be through excessive erosion before being used as electrolytic capacitor.
Etching process is as follows, and aluminium foil is at 5% HCl and 15% H
2SO
4In the etchant solution that is mixed with, be direct current 20 peace/decimetres with current density at 85 ℃
2Condition under, through corrosion first time in 60 seconds.Then, these aluminium foils are direct current 5 peace/decimetres 85 ℃ and current density again in second kind of etchant solution that the ethanedioic acid with 5% HCl and 0.1% is mixed with
2Condition under, experience 8 minutes second time corrosion.
Aluminium foil after these corrosion carries out so-called " processing of energizing " with 380 volts of voltages.Capacitance to these aluminium foils is measured, and the results are shown in Table 3, is the capacitance percent value of 100% each sample of expression with the capacitance of No. 87 reference samples.
Just as seen in Table 3, not only in the boundary zone between the oxide layer on paper tinsel body and paper tinsel body, and in the surface portion of oxide layer, contain capacitance that every paper tinsels of one or more corrosion nucleus forming elements of normal concentration of the present invention have all above the capacitance of any reference sample of the selected element that contains excess.
Table 1
Sample and constituent content boundary zone and capacitance
In the selected element of reference sample (ppm) paper tinsel from (%)
Sub-concentration ratio
Sample
1 Cu 19 14 109
2 Si 39 16 104
3 Zn 47 27 104
4 Mn 39 25 103
5 Ga 23 13 106
6 Cu 15 12 104
With Si 20 8.3
7 P 17 6.2 109
8 V 23 8.1 107
9 Cr 11 17 105
10 Ti 14 6.1 106
11 Ni 13 7.2 108
12 Ta 15 7.2 106
13 Zr 12 9.1 105
14 C 19 8.8 104
15 Be 11 5.8 104
16 P 10 7.2 104
With V 15 8.8
17 P 0.3 16 105
18 In 0.7 22 106
19 Y 0.2 8.8 104
20 La 0.5 13 104
21 Ce 0.4 19 103
22 Pr 0.3 8.2 104
With M.M 0.5 5.5
Reference sample
23 Cu 15 38 98
24 In 0.7 44 100
25 Ni 13 48 92
Annotate: " M.M " represents mischmetal(l).
Table 2
Sample and constituent content oxide layer are " with capacitance
In the selected element of reference sample (ppm) paper tinsel from (%)
Sub-concentration ratio
Sample
31 Cu 22 12 106
32 Si 39 14 103
33 Zn 48 29 102
34 Mn 41 21 101
35 Ga 24 23 104
36 Cu 25 13 103
With Si 30 12
37 P 14 18 105
38 V 22 22 103
39 Cr 13 4.2 102
40 Ti 14 3.7 106
41 Ni 11 8.4 107
42 Ta 15 7.2 105
43 Zr 21 8.3 104
44 C 19 9.9 103
45 Be 13 11.5 103
46 P 12 7.2 105
With V 15 5.8
47 Pb 0.3 16 104
48 In 0.7 4.4 107
Sample
49 Y 0.4 15 106
50 La 0.5 13 102
51 Ce 0.6 8.8 104
52 Pr 0.3 5.3 105
With M.M. 0.5 8.1
Reference sample
53 Cu 18 36 100
54 In 25 48 93
55 Ni 20 38 96
Annotate: " M.M " represents mischmetal(l), and * represents outermost portion.
Table 3
Sample and selected constituent content ion concentration specific capacitance
Reference element (ppm)
*A/
*C
*B/
*(%)
Sample C
Sample
61 Fe 15 16 17 106
62 Cu 20 13 15 107
63 Si 39 15 16 103
64 Zn 48 27 24 102
65 Mn 40 21 27 102
66 Ga 23 23 14 105
67 Si 10 5.5 4.1 104
With Mn 30 6.2 7.2
68 P 16 19 6.4 104
69 V 24 21 8.7 105
70 Cr 12 3.6 19 102
71 Ti 15 2.8 6.4 106
72 Ni 12 8.6 7.7 109
73 Ta 15 6.5 6.8 107
74 Zr 10 7.2 7.8 106
75 C 24 11 9.5 104
76 Be 15 13 11.5 104
77 B 15 18 19 103
78 Mg 20 23 25 107
Sample
79 P 12 6.7 6.5 106
With V 15 4.1 3.7
80 Pb 0.3 16 19 108
81 In 0.3 11 9.8 103
82 Bi 0.5 27 25 102
83 Y 0.5 21 13 106
84 La 0.4 15 16 104
85 Ce 0.3 15 13 104
86 Pr 0.3 5.1 5.8 103
With M.M. 0.5 4.6 4.6
Reference
Sample
87 Cu 20 38 19 100
88 V 25 51 27 91
89 In 0.7 29 46 94
Annotate: " M.M " represents mischmetal(l).
*A/
*C represents the ion concentration in oxide layer surface portion and the paper tinsel body.
*B/
*C represent in (between oxide layer and paper tinsel body) boundary zone with the paper tinsel body in ion concentration.
Claims (12)
1, a kind of aluminium foil as electrolytic capacitor, it comprises 99.9% or more aluminium and one or more auxiliary elements of selecting from the element set that Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, Pb, In and rare earth element are formed, it is characterized in that auxiliary element is enriched in the boundary zone between the oxide layer on paper tinsel body and the paper tinsel body, make that auxiliary element concentration in the boundary zone and the ion concentration between the auxiliary element concentration in the paper tinsel body are 1.2: 1 to 30: 1.
2, according to the aluminium foil of claim 1, it is characterized in that auxiliary element is one or more elements of selecting from the element set that Cu, Si, Zn, Mn and Ga form, wherein except that thickness was 0.1 micron superficial layer, the paper tinsel body included selected auxiliary element 3-60ppm.
3, according to the aluminium foil of claim 1, it is characterized in that auxiliary element is one or more elements of selecting from the element set that P, V, Ti, Cr, Ni, Ta, Zr, C and Be form, wherein except that thickness was 0.1 micron superficial layer, the paper tinsel body included selected auxiliary element 1-40ppm.
4, according to the aluminium foil of claim 1, it is characterized in that auxiliary element is one or more elements of selecting from the element set that Pb, In and rare earth element are formed, wherein except that thickness was 0.1 micron superficial layer, the paper tinsel body included selected auxiliary element 0.01-3ppm.
5, a kind of aluminium foil as electrolytic capacitor, it comprises 99.9% or more aluminium and one or more auxiliary elements of selecting from the element set that Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, Pb, In and rare earth element are formed, it is characterized in that auxiliary element is enriched in the surface portion of the oxide layer that forms on the aluminium foil paper tinsel body, make that the auxiliary element concentration of surface portion and the ion concentration between the auxiliary element concentration in the paper tinsel body are 1.2: 1 to 30: 1.
6, according to the aluminium foil of claim 5, it is characterized in that auxiliary element is one or more elements of selecting from the element set that Cu, Si, Zn, Mn and Ga form, wherein except that thickness was 0.1 micron superficial layer, the paper tinsel body included selected auxiliary element 3-60ppm.
7, according to the aluminium foil of claim 5, it is characterized in that auxiliary element is one or more elements of selecting from the element set that P, V, Ti, Cr, Ni, Ta, Zr, C and Be form, wherein except that thickness was 0.1 micron superficial layer, the paper tinsel body included selected auxiliary element 1-40ppm.
8, according to the aluminium foil of claim 5, it is characterized in that auxiliary element is one or more elements of selecting from the element set that Pb, In and rare earth element are formed, wherein except that thickness was 0.1 micron surface, the paper tinsel body included selected auxiliary element 0.01-3ppm.
9, a kind of aluminium foil as electrolytic capacitor, it comprises 99.9% or more aluminium and one or more auxiliary elements of selecting from the element set that Fe, Cu, Si, Zn, Mn, Ga, P, V, Ti, Cr, Ni, Ta, Zr, C, Be, B, Mg, Bi, Pb, In and rare earth element are formed.It is characterized in that auxiliary element not only is enriched in the boundary zone between the oxide layer that forms on paper tinsel body and the paper tinsel body, also be enriched in the surface portion of oxide layer, make that auxiliary element concentration in boundary zone and surface portion and the ion concentration between the auxiliary element concentration in the paper tinsel body are 1.2: 1 to 30: 1, wherein the auxiliary element concentration in the part except that boundary zone and surface portion is lower than the auxiliary element concentration in boundary zone and the surface portion.
10, according to the aluminium foil of claim 9, it is characterized in that auxiliary element is one kind of multiple elements of selecting from the element set that Fe, Cu, Si, Zn, Mn and Ga form, wherein except that thickness was 0.1 micron superficial layer, the paper tinsel body included selected auxiliary element 3-60ppm.
11, according to the aluminium foil of claim 9, it is characterized in that auxiliary element be one or more elements of from the element set that P, V, Ti, Cr, Ni, Ta, Zr, C, Be, B and Mg form, selecting wherein except that thickness is 0.1 micron superficial layer, the paper tinsel body includes selected auxiliary element 1-40ppm.
12, according to the aluminium foil of claim 9, it is characterized in that auxiliary element is one or more elements of selecting from the element set that Pb, In, Bi and rare earth element are formed, wherein except that thickness was 0.1 micron superficial layer, the paper tinsel body included selected auxiliary element 0.01-3ppm.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02401401A JP3130056B2 (en) | 1990-12-11 | 1990-12-11 | Aluminum foil for electrolytic capacitor electrodes |
| JP401401/90 | 1990-12-11 | ||
| JP401399/90 | 1990-12-11 | ||
| JP02401397A JP3130054B2 (en) | 1990-12-11 | 1990-12-11 | Aluminum foil for electrolytic capacitor electrodes |
| JP401397/90 | 1990-12-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063178A CN1063178A (en) | 1992-07-29 |
| CN1027718C true CN1027718C (en) | 1995-02-22 |
Family
ID=26582885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91112795 Expired - Lifetime CN1027718C (en) | 1990-12-11 | 1991-12-11 | Aluminum foil as electrolytic condenser electrodes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1027718C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333415C (en) * | 2003-05-26 | 2007-08-22 | 乳源瑶族自治县东阳光化成箔有限公司 | Anode aluminium foil etching process for electrolytic capacitor |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500904C (en) * | 2007-08-03 | 2009-06-17 | 乳源东阳光精箔有限公司 | Aluminum foil used for heat exchanger and manufacturing method thereof |
| CN101877278B (en) * | 2009-12-17 | 2011-09-28 | 北京中拓机械有限责任公司 | Aluminum foil for medium-voltage electrolytic capacitor anode and method for producing same |
| CN102095939A (en) * | 2010-12-07 | 2011-06-15 | 胡冠奇 | Method for measuring specific capacitance of 3003 cathode electronic aluminum foil |
| CN104178662A (en) * | 2013-05-21 | 2014-12-03 | 界首市枫慧金属有限公司 | Aluminum alloy sheet material |
| CN104616897B (en) * | 2013-11-05 | 2017-10-17 | 昭和电工株式会社 | Electrolytic capacitor aluminium alloy material and its manufacture method |
| CN103915648A (en) * | 2014-03-31 | 2014-07-09 | 上虞安卡拖车配件有限公司 | High-power large-capacity long-service-life flexibly-packaged lithium ion battery |
| CN107805744B (en) * | 2014-05-30 | 2019-10-11 | 东洋铝株式会社 | The manufacturing method of aluminium foil, the electronic component circuit board for having used it and aluminium foil |
| CN104124064B (en) * | 2014-06-10 | 2017-12-26 | 新疆众和股份有限公司 | Produce high-purity aluminum-sheet ingot and anode aluminium foil, the electrolytic capacitor of anode aluminum foil of electrolytic capacitor |
| CN112646990A (en) * | 2019-10-09 | 2021-04-13 | 昭和电工株式会社 | Rolled aluminum material for anode of low-voltage electrolytic capacitor and method for producing same |
| CN115194105B (en) * | 2022-07-07 | 2023-10-24 | 江苏鼎胜新能源材料股份有限公司 | System for reducing aluminum foil trimming amount for new energy power battery |
-
1991
- 1991-12-11 CN CN 91112795 patent/CN1027718C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333415C (en) * | 2003-05-26 | 2007-08-22 | 乳源瑶族自治县东阳光化成箔有限公司 | Anode aluminium foil etching process for electrolytic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1063178A (en) | 1992-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1027718C (en) | Aluminum foil as electrolytic condenser electrodes | |
| CN1841570A (en) | Thermal resistant tinned Cu-Ni-Si-Zn-Sn sieries alloy bar with excellent stripping character and tinned bar | |
| CN100350064C (en) | Cu-Ni-Si-Mg series copper alloy strip | |
| JP4061211B2 (en) | Titanium alloy used for cathode electrode for producing electrolytic copper foil and method for producing the same | |
| CN1879239A (en) | Negative electrode active material for battery, anode can for battery, zinc negative plate for battery, manganese dry battery and method for manufacturing same | |
| CN85108620A (en) | Be suitable for the cold-rolled steel sheet and the manufacture method of enamel coating | |
| CN1667148A (en) | 6063 aluminium alloy made by fine grained aluminium ingot and preparation method thereof | |
| JP2009084593A (en) | Cu-Cr-Si-BASED ALLOY FOIL | |
| CN1696320A (en) | Cu-Ni-Si-Mg seris copper alloy strip | |
| CN1921042A (en) | Aluminum foil for the electrolytic capacitor and etching method for forming etching pits | |
| JPH1143734A (en) | Aluminum alloy for semiconductor producing device excellent in formability of alumite coating excellent in gas corrosion resistance and plasma corrosion resistance and heat resistance and material for semiconductor producing device | |
| CN1128085A (en) | Negative electrode zinc-can for dry cell, its manufacture, and manganese dry cell using it | |
| CN101045969A (en) | Copper alloy with excellent hot working property and manufacturing method thereof | |
| JP2009299131A (en) | Aluminum foil for electrolytic capacitor and method for producing the same | |
| JP3797645B2 (en) | Method for producing aluminum foil for electrolytic capacitor electrode | |
| JP2007169690A (en) | Aluminum foil for electrolytic capacitor | |
| CN1178841A (en) | Method for producing zinc-titanium alloy and manganese dry battery | |
| JP2007131922A (en) | Aluminum foil for electrolytic capacitor | |
| JP6210573B1 (en) | Copper alloy wire rod and method for producing the same | |
| JP5094025B2 (en) | Aluminum foil for electrolytic capacitor electrode | |
| JP2007113085A (en) | Aluminum foil for electrolytic capacitor | |
| JP2578521B2 (en) | Aluminum foil for electrolytic capacitor electrodes | |
| JP4582627B2 (en) | Aluminum alloy foil for electrolytic capacitor cathode | |
| JP3985130B2 (en) | High purity Ni alloy anode material for electrolytic Ni plating showing high plating yield | |
| JP4958464B2 (en) | Aluminum foil for electrolytic capacitor electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHOWA DENKO K. K. Free format text: FORMER NAME OR ADDRESS: SHOWA ALUMINIUM CORP. |
|
| CP01 | Change in the name or title of a patent holder |
Patentee after: Showa Denko K. K. Patentee before: Showa Aluminum Corp. |
|
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Expiration termination date: 20111211 Granted publication date: 19950222 |