CN101093751B - Method for preparing cathode foil with high specific volume - Google Patents
Method for preparing cathode foil with high specific volume Download PDFInfo
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- CN101093751B CN101093751B CN 200610156891 CN200610156891A CN101093751B CN 101093751 B CN101093751 B CN 101093751B CN 200610156891 CN200610156891 CN 200610156891 CN 200610156891 A CN200610156891 A CN 200610156891A CN 101093751 B CN101093751 B CN 101093751B
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- 239000011888 foil Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 41
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000012545 processing Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005030 aluminium foil Substances 0.000 claims description 58
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000280 densification Methods 0.000 claims description 4
- 238000001311 chemical methods and process Methods 0.000 claims description 3
- 238000002848 electrochemical method Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000007787 solid Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003763 carbonization Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 150000004767 nitrides Chemical class 0.000 abstract 1
- 238000009834 vaporization Methods 0.000 abstract 1
- 230000008016 vaporization Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 description 21
- 230000008020 evaporation Effects 0.000 description 21
- 239000004411 aluminium Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000007747 plating Methods 0.000 description 9
- 239000007784 solid electrolyte Substances 0.000 description 8
- 238000006056 electrooxidation reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 6
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 5
- 239000001741 Ammonium adipate Substances 0.000 description 5
- 235000019293 ammonium adipate Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009798 acute exacerbation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021324 titanium aluminide Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Abstract
Characters of the preparation method are that raw foil is selected as basis material; formation process on surface is adopted so as to form a layer of compact, even, alumina layer (AL) with unilateral conductivity on surface of aluminum foil (AF); then forming a layer of titanium (Ti) film on surface of AF by using magnetron sputtering (MS) method; after process of coating by vaporization on surface of AF, high temperature processing is carried on Ti so as to form a passive film. Since anodic oxidation is carried out in advance, thus, stable AL is contacted to coated metal directly. AL has no influence on adhesive force of the metal. Carbonization is carried out in air. Impedance and capacity are not affected on product so as to simplify difficulty for preparing solid capacitor with high specific volume. In MS process, adjusting concentration of nitrogen gas makes Ti on surface of AF gradient descent, and Ti nitride gradient ascent so as to raise stability of sputtered layer.
Description
[technical field]
The present invention relates to a kind of aluminium electrolytic capacitor, relate in particular to a kind of cathode with high specific volume manufacturing aluminum foil that can be applicable to solid electrolyte capacitor.
[background technology]
Aluminium electrolytic capacitor becomes a kind of important foundation components and parts that are widely used in all kinds of electronic system products, high speed development along with information industry, complete electronic set is swift and violent to thin, light, little direction growth momentum, as in circuit, acting on the aluminium electrolytic capacitor of still not replacing, its volume limiting factor that become bigger than normal, demand exploring new technical cue urgently and increase substantially the ratio electric capacity of capacitor and other every electrical property, to adapt to the requirement of electronic device long lifetime.In general, be formed on anode oxide film on the aluminum electric pole foil by anodic oxidation, as the dielectric layer of aluminium electrolytic capacitor, its physics and chemical property have determined the performance of aluminium electrolytic capacitor.In the prior art, the dielectric layer of aluminum electrolysis capacitor anode foil obtains by chemical synthesis technology, described chemical synthesis technology is utilized electrochemical principle exactly, aluminium foil is carried out anodized, oxygen atom in the solution is combined with the aluminium atom, form the oxide film dielectric layer that one deck has certain dielectric constant and ability specific voltage at aluminium foil surface.
Raising aluminium electrolytic capacitor aluminium foil than the approach of electric capacity is: the long-pending S of real surface that 1. increases aluminium foil; 2. improve the relative dielectric constant ε r of dielectric layer; 3. reduce the thickness d of dielectric layer.Adopting chemistry or electrochemical etching method to enlarge aluminium foil surface long-pending is to improve the effective way of aluminium foil than electric capacity, at present in the technology, the etch factor of aluminium foil promptly expands face multiplying power G (forming the effective area of capacity and the ratio of geometric area), the target paper tinsel can reach 200, low blocking is 100, high blocking is 30, though its technology is still in continuous development, but demonstrated sign near the limit, this is because will enlarge G again, the hole that has only further refinement corrosion to form, and this will cause Working electrolyte to enter the hole difficulty, with deielectric-coating surface loose contact, loss, impedance, deteriorations such as frequency characteristic.Because under specific withstand voltage, the thickness d of dielectric layer and relative dielectric constant ε r are that the structure of matter by dielectric layer is determined, therefore might improve by the structure of matter that changes dielectric layer and compare electric capacity.At present, by changing the structure of matter of dielectric layer, form the complex oxide film of high-k, the ratio electric capacity that improves aluminium foil has become a focus of capacitor material research.
[summary of the invention]
For solving the problems of the technologies described above, the invention provides a kind of cathode with high specific volume manufacturing aluminum foil that can be applicable to solid electrolyte capacitor, it can introduce one deck high-k, high-specific surface area plated film at aluminium foil surface, makes it have very high specific capacity and chemical substance and air are at high temperature had good stable.
For achieving the above object, technical scheme proposed by the invention is:
A kind of preparation method of foil of cathode with high specific volume, it is characterized in that: select aluminium foil as base material, adopt on its surface earlier and change into processing, make it to form one deck densification, uniform, as to have unilateral conduction alumina layer, and then adopt magnetically controlled sputter method to form one deck titanium metal film, titanium nitride film, nitrogen calorize titanium film or titanium carbonitride film on its surface at aluminium foil surface; The described time 5min～30min that changes into processing, 50 ℃～80 ℃ of temperature, voltage is between 1.0～3.0 volts.
Described aluminium foil surface carries out high-temperature process after handling through magnetron sputtering again, makes surface of metal titanium form one deck passivating film;
In the described magnetron sputtering step, adopt the concentration style that improves nitrogen continuously, the composition of Titanium is descended in gradient, the composition of titanium nitride increases in gradient;
The thicknesses of layers of described titanium metal film, titanium nitride film, nitrogen calorize titanium film or titanium carbonitride film is between 1～3 μ m;
Described aluminium foil adopts mechanical means to brush out ditch earlier on its surface earlier and returns before changing into treatment step;
Perhaps, described aluminium foil adopts chemistry or electrochemical method that aluminium foil surface is slightly corroded earlier before changing into treatment step, and its corrosion multiplying power is 1～10.
The temperature that described magnetron sputtering is handled the back high-temperature process of doing is 300～500 ℃, and the time is 20～60 minutes.
The invention has the beneficial effects as follows: by before the aluminium foil evaporation, forming one deck densification, uniform, as to have unilateral conduction alumina layer on its surface, can carry out anodic oxidation to the aluminium surface in advance, air is directly contacted with alumina layer, thereby improved the adhesive force of titanium film to evaporation metal, even if in air, carry out high temperature carbonization, also can not influence the impedance and the capacity of product, simplify the preparation difficulty of high specific volume solid electric capacity greatly.In addition, aluminium foil behind the evaporation is carried out high-temperature process again, make surface of metal titanium form one deck passivating film, can make its capacity stable, and because the iris action of passivating film, can avoid changing into liquid and highly acid electrolyte corrosiveness, improve the stability of final products solid electrolyte capacitors titanium.
[embodiment]
At present, in the aluminium electrolytic capacitor field, the specific volume of aluminum electric pole foil is proportional to the relative dielectric constant of oxide-film.Aluminium anode oxide film Al
20
3Dielectric constant be generally 8～10, and Detitanium-ore-type TiO
2Dielectric constant be 48, rutile TiO
2Dielectric constant be 110～117.In the prior art field, will have ceramic oxide such as high-k valve metal oxides and be incorporated into through the method on the aluminium foil of expansion face and can adopt physical method or chemical method.
Physical method normally will have high-k valve metal or its oxide, adopt the way of magnetron sputtering, electron beam heating equal vacuum evaporation, make it form the coating of micron thickness at aluminium foil surface; Chemical method then is that the aluminium foil that will be coated with metal alkoxide carries out elevated temperature heat and decomposes or hydrolysis, prepares ultra micro (nanoscale) metal oxide powder and is deposited on method on the aluminium foil.Two kinds of methods are compared, and adopt the aluminium foil specific capacity of vacuum deposition method gained higher, and impedance is lower.
For the conductive solid polymer electrochemical capacitor, its capacity is closely related with tightness degree and the contact area that aluminium foil contacts with solid electrolyte with impedance, and solid electrolyte adheres to tight more on Cathode Foil and anode foils, and contact area is big more, it is big more that it draws capacity, and impedance is more little.Compare with liquid electrolytic electric capacity, because solid electrolyte and the contacted area of aluminium foil and level of intimate can not show a candle to the exposure level of liquid electrolyte and aluminium foil after all in the solid electrolytic capacitor, so in wet-electrolytic capacitor, show and the problem of inapparent capacity extraction rate, it is most important just to seem in solid electrolytic capacitor.For the fuse of same size, solid electric capacity will seek out the capacity close with liquid electrolytic electric capacity, is a very thing of difficulty.
Usually, the total capacity of capacitor is closely related by the actual capacity of drawing of its Cathode Foil and anode foils, has following relation.
C＝Ca×Cc/(Ca+Cc)
Wherein: C is the capacitor total capacity, and Ca is the anode foils specific volume, and Cc is the Cathode Foil specific volume.
By above-mentioned formula as can be seen, improve the specific volume of Cathode Foil, can make high the drawing of trying one's best of the capacity of anode foils.As want to draw the capacity of anode foils 80%, and the capacity that then needs Cathode Foil is 4 times of anode foils, wants to draw the capacity of anode foils 90%, the capacity that then needs Cathode Foil is 9 times of anode foils.For low pressure large bulk capacitance series, usually adopt the aluminium foil of low pressure high power capacity as anode foils, the high capacity of drawing anode foils of trying one's best, thereby the size of reduction capacitor, need adopt the very Cathode Foil of high power capacity, yet be difficult to reach so high capacity by the prepared conventional cathode paper tinsel of electrochemical corrosion.
At corrosive aluminum foil or light paper tinsel surperficial mode evaporation one deck titanium, titanium nitride or nitrogen titanium aluminide, titanium carbonitride by magnetron sputtering or other vacuum evaporations, greatly improved the specific area of aluminium foil, to compare with former paper tinsel surface, its specific capacity is several times and increases.With its negative electrode, can improve the capacity extraction rate greatly, and reduce the impedance and the DF value of electric capacity as solid electric capacity.
Because capacitor core before the impregnation polymerization generates solid electrolyte, need be handled through high temperature carbonization after a while usually, this just requires through the foil of cathode with high specific volume of special processing at high temperature in the air atmosphere, advantages of higher stability is arranged.On light paper tinsel or etched foil surface, the method by magnetron sputtering plates one deck titanium or titanium nitride, can make the very big raising of capacity of aluminium foil, uses it for the negative paper tinsel of coiling type solid electric capacity, can obtain desirable capacity extraction rate.But the applicant finds that high-temperature process will be found the big high attenuation of its capacity after a period of time in air, and impedance also improves a lot, for the Cathode Foil of using it for solid electric capacity has caused very big difficulty.If the high temperature carbonization process is carried out under nitrogen protection; these problems can be avoided; capacity and impedance nearly all do not have any change; but because high temperature processing step needs nitrogen protection; for production brings very big inconvenience; and under nitrogen atmosphere, obtain sufficient charing, need the long time.
By the Cathode Foil surface of the high specific volume of this class is analyzed, find at high temperature, above-mentioned defective mainly is that airborne oxygen can be to the binding site generation oxidation of aluminium and titanium, make the surface oxidation of aluminium, generate oxide layer, cause the script close attachment to descend to some extent, thereby cause its capacity and impedance operator acute exacerbation in the Titanium on aluminium surface and the combination degree between the base material.
Selective light paper tinsel of the present invention is as base material, earlier carry out anodized on its surface, its formation voltage is between 1.0～3.0 volts, change into 50 ℃～80 ℃ of temperature, change into time 5min～30min, make it form one deck densification, uniform, as to have unilateral conduction alumina layer, and then the mode of employing magnetron sputtering is at its surperficial evaporation one deck titanium, titanium nitride, nitrogen titanium aluminide or titanium carbonitride at aluminium foil surface, to improve the specific area of its aluminium foil, increase specific capacity.Owing in advance anodic oxidation is carried out on the aluminium surface, what directly contact with evaporation metal during magnetron sputtering is exactly alumina layer, and aluminium oxide is highly stable under oxidizing atmosphere, can not change, thus to the adhesive force of evaporation metal less than influencing.Thereby, even if in air, carry out high temperature carbonization, the final impedance and the capacity that also can not influence product, simplified the preparation difficulty of high specific volume solid electric capacity greatly, when simultaneously also having solved high-temperature process, airborne oxygen causes the problem of its capacity and impedance operator acute exacerbation to the binding site generation oxidation of aluminium and titanium.
Light paper tinsel as base material, can adopt the means of mechanical expansion face, adopting metallic brush to brush out ditch earlier on its surface returns, to increase its surface area, also can adopt chemistry or electrochemical means,, its surface slightly be corroded as adopting hydrochloric acid and sulfuric acid as corrosive liquid, suitably increase the surface, its corrosion multiplying power is defined as 1～10.This is because when Cathode Foil corrosion multiplying power is too high, can cause the impedance of Cathode Foil to increase.
In the magnetron sputtering process, by improving the concentration of nitrogen continuously, from aluminium foil surface, the composition of Titanium descends in gradient with acquisition, and the composition of titanium nitride increases in gradient.Because titanium nitride is at high temperature more stable to air than titanium, thereby further improve the stability of sputtering layer.Thickness of coating is lower than 1 μ m between 1～3 μ m, or is higher than 3 μ m, and the aluminium foil capacity is all not enough.
Behind the aluminium foil surface process magnetron sputtering layer of metal titanium, again 300～500 ℃ of following high-temperature process 20～60 minutes, (it is identical to carry out high temperature carbonization in high-temperature process herein and the air, be in high temperature furnace, to handle) make surface of metal titanium form one deck passivating film, can make capacity stable, and because the iris action of passivating film, can avoid changing into liquid and highly acid electrolyte corrosiveness, thereby improve the stability of final products solid electrolyte capacitor titanium.
Embodiment below by contrast illustrates characteristics of the present invention.
Contrast test one:
(1) Comparative Examples:
At pressure is 7 * 10
-3In the vacuum chamber of Pa, be provided with and put paper tinsel, receive two beaming rollers of paper tinsel, the thick smooth paper tinsel of 50 μ m, through the means of mechanical expansion face, adopt the hard metal brush to brush out ditch and return on its surface, the degree of depth is about 1 μ m, to increase the processing on its surface, can pass through a cylindric drum cooler by continuous reeling.Then with Titanium as the target source, adopt the mode of magnetron sputtering, adding man-hour its evaporation rate is 0.5 μ m/min, continuous evaporating-plating 3 minutes, the thick 1.5 μ m of coating.Recording than electric capacity is 2100 μ F/cm
2, then aluminium foil is placed air, 300 ℃ were heated 1 hour down, and recording its capacity is 520 μ F/cm
2
(2) test example:
Do base material with the thick smooth paper tinsel of 50 μ m, handle by the identical processing mode in early stage of Comparative Examples earlier, and then change into processing, wherein with 15% ammonium adipate solution as changing into liquid, formation voltage is 1.8 volts, the time of changing into is half an hour, changes into 80 ℃ of temperature, does vacuum evaporation then and handles, during evaporation with Titanium as the target source, adopt the mode of magnetron sputtering, adding man-hour its evaporation rate is 0.5 μ m/min, continuous evaporating-plating 3 minutes, the thick 1.5 μ m of coating, and in evaporate process, increase continuously the concentration of nitrogen, make that the composition of titanium nitride increases in gradient in the plated film.Recording than electric capacity is 2000 μ F/cm
2, again aluminium foil is placed air, 300 ℃ were heated 1 hour down, and recording its capacity is 1780 μ F/cm
2
Contrast test two:
(1) Comparative Examples:
Not pass through the thick smooth paper tinsel of 50 μ m that changes into processing, other are identical with embodiment one Comparative Examples, and thickness of coating is 3 μ m.Recording than electric capacity is 1900 μ F/cm
2, aluminium foil places air, and 500 ℃ were heated 30 minutes down, and recording its capacity is 480 μ F/cm
2
(2) test example:
Do base material with the thick smooth paper tinsel of 50 μ m, handle earlier, and then change into processing by the identical processing mode in early stage of Comparative Examples, wherein with ammonium adipate solution as changing into liquid, formation voltage is 2.5v, the time of changing into is 25min, and changing into temperature is 70 ℃, carries out vapor deposition treatment then, adding man-hour its evaporation rate is 1 μ m/min, continuous evaporating-plating 3 minutes, the thick 3 μ m of coating, the method and apparatus of its evaporation is identical with Comparative Examples.Recording than electric capacity is 2000 μ F/cm
2, again aluminium foil is placed air, 500 ℃ were heated 30 minutes down, and recording its capacity is 1850 μ F/cm
2
Contrast test three:
(1) Comparative Examples:
With not through changing into the electrochemical corrosion aluminium foil instead of optical paper tinsel of processing, its corrosion multiplying power is 6, then with Titanium as the target source, adopt the mode of magnetron sputtering, adding man-hour its evaporation rate is 0.5 μ m/min, continuous evaporating-plating 4 minutes, thickness of coating is 2 μ m.Recording than electric capacity is 1200 μ F/cm
2, aluminium foil places air, and 400 ℃ were heated 45 minutes down, and recording its capacity is 490 μ F/cm
2
(2) test example:
With electrochemical corrosion aluminium foil instead of optical paper tinsel, its corrosion multiplying power is 6, change into processing then, wherein with 15% ammonium adipate solution as changing into liquid, formation voltage is 2 volts, the time of changing into is 20 minutes, changes into 60 ℃ of temperature, carries out vacuum evaporation again and handles, during evaporation with Titanium as the target source, adopt the mode of magnetron sputtering, adding man-hour its evaporation rate is 0.5 μ m/min, continuous evaporating-plating 4 minutes, the thick 2 μ m of coating, and in evaporate process, increase continuously the concentration of nitrogen, make that the composition of titanium nitride increases in gradient in the plated film.Recording than electric capacity is 1300 μ F/cm
2, again aluminium foil is placed air, 400 ℃ were heated 45 minutes down, and recording its capacity is 900 μ F/cm
2
Contrast test four:
(1) Comparative Examples:
With not through changing into the electrochemical corrosion aluminium foil instead of optical paper tinsel of processing, its corrosion multiplying power is 2, then with Titanium as the target source, adopt the mode of magnetron sputtering, adding man-hour its evaporation rate is 0.5 μ m/min, continuous evaporating-plating 3 minutes, thickness of coating is 1 μ m.Recording than electric capacity is 1100 μ F/cm
2, aluminium foil places air, and 350 ℃ were heated 20 minutes down, and recording its capacity is 350 μ F/cm
2
(2) test example:
With electrochemical corrosion aluminium foil instead of optical paper tinsel, its corrosion multiplying power is 2, change into processing then, wherein with 15% ammonium adipate solution as changing into liquid, formation voltage is 1 volt, and the time of changing into is 10 minutes, changes into 50 ℃ of temperature, carrying out vacuum evaporation again handles, during evaporation with Titanium as the target source, adopt the mode of magnetron sputtering, adding man-hour its evaporation rate is 0.5 μ m/min, continuous evaporating-plating 3 minutes, the thick 1 μ m of coating, and in evaporate process, increase continuously the concentration of nitrogen, make that the composition of titanium nitride increases in gradient in the plated film, recording than electric capacity is 1150 μ F/cm
2, again aluminium foil is placed air, 350 ℃ were heated 20 minutes down, and recording its capacity is 860 μ F/cm
2
Contrast test five:
(1) Comparative Examples:
With not through changing into the electrochemical corrosion aluminium foil instead of optical paper tinsel of processing, its corrosion multiplying power is 10, then with Titanium as the target source, adopt the mode of magnetron sputtering, adding man-hour its evaporation rate is 0.5 μ m/min, continuous evaporating-plating 3 minutes, thickness of coating is 1.5 μ m.Recording than electric capacity is 1100 μ F/cm
2, aluminium foil places air, and 450 ℃ were heated 50 minutes down, and recording its capacity is 400 μ F/cm
2
(2) test example:
With electrochemical corrosion aluminium foil instead of optical paper tinsel, its corrosion multiplying power is 10, change into processing then, wherein with 15% ammonium adipate solution as changing into liquid, formation voltage is 3 volts, and the time of changing into is 15 minutes, changes into 80 ℃ of temperature, carrying out vacuum evaporation again handles, during evaporation with Titanium as the target source, adopt the mode of magnetron sputtering, adding man-hour its evaporation rate is 0.5 μ m/min, continuous evaporating-plating 3 minutes, the thick 1.5 μ m of coating, and in evaporate process, increase continuously the concentration of nitrogen, make that the composition of titanium nitride increases in gradient in the plated film, recording than electric capacity is 1170 μ F/cm
2, again aluminium foil is placed air, 450 ℃ were heated 50 minutes down, and recording its capacity is 920 μ F/cm
2
By above comparative example as can be known, the base material that changed into through low pressure has better high-temperature stability, and as base material, the light paper tinsel has bigger advantage than etched foil.
Claims (9)
1. the preparation method of a foil of cathode with high specific volume, it is characterized in that: select aluminium foil as base material, adopt on its surface earlier and change into processing, make it to form one deck densification, uniform, as to have unilateral conduction alumina layer, and then adopt magnetically controlled sputter method to form one deck titanium metal film, titanium nitride film, nitrogen calorize titanium film or titanium carbonitride film on its surface at aluminium foil surface; The described processing time 5～30min that changes into, 50～80 ℃ of temperature, voltage is between 1.0～3.0 volts.
2. the preparation method of foil of cathode with high specific volume according to claim 1 is characterized in that: after described aluminium foil surface process magnetron sputtering is handled, carry out high-temperature process again, make surface of metal titanium form one deck passivating film.
3. the preparation method of foil of cathode with high specific volume according to claim 1 and 2 is characterized in that: in the described magnetron sputtering step, adopt the concentration style of regulating nitrogen continuously, the composition of Titanium is descended in gradient, the composition of titanium nitride increases in gradient.
4. the preparation method of foil of cathode with high specific volume according to claim 1, it is characterized in that: the thicknesses of layers of described titanium metal film, titanium nitride film, nitrogen calorize titanium film or titanium carbonitride film is between 1～3 μ m.
5. according to the preparation method of claim 1 or 2 or 4 each described foil of cathode with high specific volume, it is characterized in that: described aluminium foil adopts mechanical means to brush out ditch earlier on its surface earlier and returns before changing into treatment step.
6. the preparation method of foil of cathode with high specific volume according to claim 3 is characterized in that: described aluminium foil adopts mechanical means to brush out ditch earlier on its surface earlier and returns before changing into treatment step.
7. according to the preparation method of claim 1 or 2 or 4 each described foil of cathode with high specific volume, it is characterized in that: described aluminium foil adopts chemistry or electrochemical method that aluminium foil surface is slightly corroded earlier before changing into treatment step, and its corrosion multiplying power is 1～10.
8. the preparation method of foil of cathode with high specific volume according to claim 3 is characterized in that: described aluminium foil adopts chemistry or electrochemical method that aluminium foil surface is slightly corroded earlier before changing into treatment step, and its corrosion multiplying power is 1～10.
9. the preparation method of foil of cathode with high specific volume according to claim 2 is characterized in that: the temperature that described magnetron sputtering is handled the back high-temperature process of doing is 300～500 ℃, and the time is 20～60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610156891 CN101093751B (en) | 2006-11-17 | 2006-11-17 | Method for preparing cathode foil with high specific volume |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610156891 CN101093751B (en) | 2006-11-17 | 2006-11-17 | Method for preparing cathode foil with high specific volume |
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| Publication Number | Publication Date |
|---|---|
| CN101093751A CN101093751A (en) | 2007-12-26 |
| CN101093751B true CN101093751B (en) | 2010-05-19 |
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| CN102061472A (en) * | 2011-01-26 | 2011-05-18 | 巨科集团有限公司 | Surface oxidizing and film coating method for mirror finish aluminum |
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| CN107731530A (en) * | 2017-08-29 | 2018-02-23 | 浙江长兴鑫启元电子科技有限公司 | A kind of electric aluminum foil complex media production technology |
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| CN112435856A (en) * | 2020-11-05 | 2021-03-02 | 肇庆绿宝石电子科技股份有限公司 | Aluminum electrolytic capacitor and manufacturing method and application thereof |
| CN114703526B (en) * | 2022-06-07 | 2022-11-01 | 南通海星电子股份有限公司 | Preparation method of high specific volume low-voltage electrode foil for automotive electronics |
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