CN101651047B - Preparation method of Al2O3/Nb2O3 compound dielectric film aluminum electrode foil - Google Patents

Preparation method of Al2O3/Nb2O3 compound dielectric film aluminum electrode foil Download PDF

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CN101651047B
CN101651047B CN2009100600692A CN200910060069A CN101651047B CN 101651047 B CN101651047 B CN 101651047B CN 2009100600692 A CN2009100600692 A CN 2009100600692A CN 200910060069 A CN200910060069 A CN 200910060069A CN 101651047 B CN101651047 B CN 101651047B
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dielectric film
aluminum electrode
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CN101651047A (en
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冯哲圣
孙保瑞
丁甲
陈金菊
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Jiangyin Huayuan Electronic Material Co Ltd
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University of Electronic Science and Technology of China
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Abstract

The invention relates to a preparation method of an Al2O3/Nb2O3 compound dielectric film aluminum electrode foil, which belongs to the technical field of electronic materials and relates to a preparation method of a compound dielectric film aluminum electrode foil with a high specific volume. The preparation method comprises the following steps: preparing an Nb complex solution by adopting Nb(OH)5 with low price and dipping an aluminum etching foil into the Nb complex solution to ensure that complexes containing Nb are adsorbed by the surface of the aluminum etching foil; then washing and drying the aluminum etching foil the surface of which adsorbs the complexes containing Nb and carrying out high-temperature heat treatment on the aluminum etching foil to ensure that the Nb complexes aredecomposed into Nb2O5; and finally, carrying out conventional formation enabling on the Nb2O5 to ensure that the Nb2O5 on the surface of the aluminum etching foil is compounded with newly grown Al2O3to obtain the Al2O3/Nb2O5 compound dielectric film aluminum electrode foil with a high specific volume. The improvement rate of the specific volume can reach about 30 percent for the Al2O3/Nb2O5 compound dielectric film aluminum electrode foil with a high specific volume. Meanwhile, the invention has the characteristics of lower cost, energy saving, environmental protection, simple process, easy operation and convenient control.

Description

A kind of Al 2O 3/ Nb 2O 5The preparation method of compound dielectric film aluminum electrode foil
Technical field
The invention belongs to technical field of electronic materials, relate to the manufacture method of aluminum electrolysis capacitor anode foil, particularly a kind of preparation method of high specific volume compound dielectric film aluminum electrode foil electrode foil.
Background technology
In electron trade, tantalum capacitor, ceramic capacitor, aluminum capacitor, film capacitor are four main big class capacitors.Characteristics such as interim aluminium electrolytic capacitor is because of its function admirable, and is cheap, of many uses obtain broad development in the last thirty years.In the aluminum electrolysis capacitor anode material, aluminium anode oxide film Al 2O 3Dielectric constant be 8～10, this becomes the key factor that restriction aluminium electrolutic capacitor capacitance promotes.In recent years, tantalum electric capacity obtains fast development because of its good performance, but the tantalum raw material is rare, and tantalum electric capacity price is expensive.And have the physicochemical properties similar to tantalum, Ta to niobium that tantalum belongs to V family transition elements together 2O 5Dielectric constant is about 28, and Nb 2O 5Dielectric constant is then up to 41, and its reserves are relatively abundant, and China's niobium minerals product reserves are 100 times of tantalum, and the cheap cost of raw material makes it have better industrial applications prospect.If the Nb that can will have more excellent dielectric properties 2O 5Effectively compound with alumite, then may Effective Raise the specific volume of aluminum electric pole foil.
Occurred many passing through in aluminium etched foil surface pre-deposition high-k phase both at home and abroad since the eighties in 20th century, and then changed into the patent of preparation aluminum composite oxide film, they have promoted the specific volume that is anodizing to paper tinsel effectively.The metal alkoxide of dipping titanium before Japanese patent laid-open 4-42519 adopts etched foil to change into, and the special metal alkoxide of opening flat 5-315197 by dipping barium, they have all successfully made the oxide-film of high dielectric property.But the oxide-film loss that forms very high, and not obvious in the low voltage application range effect.
In the selection of high dielectric phase material system, rarely have the report of Al-Nb composite system at present, its main cause is the chemical inertness owing to niobium material, and the niobium source that causes can be used for aluminum electric pole foil deielectric-coating technology of preparing is difficult to select.If adopt the preferably prevailing price costliness such as niobium source such as ethanol niobium of dissolubility, an industrial applications prospect is not had in very easily hydrolysis and need to preserving under specific condition.The people such as Kai Kamada of Japan are at document " Anodic dissolution of tantalum and niobium in acetonesolvent with halogen additives for electrochemical synthesis of Ta 2O 5And Nb 2O 5Thin film " (Electrochimical Acta, 49 (2004): propose first 321-327) to realize Ta by electrochemical deposition technique 2O 5Or Nb 2O 5The deposition of deielectric-coating; The people such as domestic Institutes Of Technology Of Nanjing horse vertical wave have realized Al in conjunction with anode oxidation process on this basis 2O 3/ Ta 2O 5The preparation of composite dielectric film, thus prepare Al 2O 3/ Ta 2O 5Compound dielectric film aluminum electrode foil, and experimental results show that Al 2O 3/ Nb 2O 5Can utilize same method to make.But in the method, tantalum source or niobium source are that the Anodic dissolving by High-purity Tantalum or niobium metal electrode obtains, as expendable material in commercial Application, obviously will cause 1, must regular maintenance and change electrode material; 2, because High-purity Tantalum or niobium metal electrode are with high costs, so that this method is difficult to be applied in the electrolytic capacitor industry.
Summary of the invention
The invention provides a kind of Al 2O 3/ Nb 2O 5The preparation method of compound dielectric film aluminum electrode foil, and adopt first the means of complexing deposition with oxide success and the Al of Nb 2O 3Deielectric-coating carries out compound, and the method can effectively make the Fabrication of High Specific Capacitance compound dielectric film aluminum electrode foil, and has characteristics with low cost, that operation should be controlled.
Core concept of the present invention is: use the method for solution complexing to realize the stable supplying in niobium source, and the method that adopts complexing to deposit realizes the pre-deposition of high dielectric phase.Realize the effectively compound of high dielectric niobium oxide and conventional aluminum deielectric-coating by complexing deposition means in the invention, and use the lower Nb (OH) of price 5Preparation Nb complex solution is infiltrated on the aluminium etched foil in this kind complex solution, so that aluminium etched foil adsorption contains nioium complex; Then adsorption there is the aluminium etched foil that contains nioium complex after cleaning, drying, to carry out high-temperature heat treatment, so that nioium complex is decomposed into Nb 2O 5At last it is carried out formation energy-endowing in general sense, so that the Nb on aluminium etched foil surface 2O 5Al with new growth 2O 3Compound, obtain Fabrication of High Specific Capacitance Al 2O 3/ Nb 2O 5Compound dielectric film aluminum electrode foil.
For achieving the above object in the method implementation process, select the lower Nb of price (OH) for use 5Preparation Nb complex solution, the aluminium foil surface after this solution-treated deposits nioium complex.The water-soluble niobium compound treatment liquid that at first prepares finite concentration and PH, etched foil immerse a period of time in this treatment fluid under the uniform temperature, in this process aluminium etched foil surface deposition contain nioium complex [(NH 3) 4NbO] (C 2O 4) 32H 2O uses washed with de-ionized water afterwards, and is too high with local acidity in the heat treatment after preventing.Sample after the oven dry is placed in immediately and carries out high-temperature heat treatment in the heating furnace, in heating process, and [(NH 3) 4NbO] (C 2O 4) 32H 2O progressively sloughs water, ammonia etc., finally is decomposed into Nb fully 2O 5, the etched foil surface also can the Heat of Formation oxidation film layer, Nb 2O 5With Al 2O 3Carry out tentatively compound.At last, effects on surface is covered with Nb 2O 5Aluminium foil carry out anodic oxidation (namely changing into), grow the Al of high dielectric 2O 3/ Nb 2O 5Complex oxide film.
Detailed technology scheme of the present invention is as follows:
A kind of Al 2O 3/ Nb 2O 5The preparation method of compound dielectric film aluminum electrode foil as shown in Figure 1, may further comprise the steps:
Step 1: niobium hydroxide is joined in the oxalic acid aqueous solution, and 25～70 ℃ of temperature conditions stir down, niobium hydroxide are fully dissolved, the niobium oxalate solution that obtains clarifying.
During preparation niobium oxalate solution, niobium hydroxide and oxalic acid mol ratio are between 1: 2.5～4, Nb in the niobium oxalate solution that control prepares 5+Ion concentration is between 0.005～0.04mol/L.
Step 2: in the niobium oxalate solution of step 1 gained, add ammoniacal liquor, adjust between solution pH value to 1～2.
Step 3: the aluminium etched foil was infiltrated in the step 2 gained solution 2～15 minutes, takes out afterwards and clean also oven dry.
Step 4: the aluminium etched foil that high-temperature process is handled through step 3, temperature are arranged on 250～600 degree, 10 minutes～30 minutes time.
Step 5: the aluminium etched foil of processing through step 4 is carried out anodic oxidation, obtain Al 2O 3/ Nb 2O 5Compound dielectric film aluminum electrode foil.
In concrete anodic oxidation (the namely changing into) process, can adopt 15% ammonium adipate solution as electrolyte, 75 ℃ of liquid temperatures, oxidation current density are 50mA/cm 2, anodizing time is 10 minutes.
Contain the Nb complex compound and form Nb in high-temperature heat treatment 2O 5In the process, Nb 2O 5Inner micropore and the defects i.e.cracks of producing of rete, electrolyte can directly touch aluminum substrate by this kind defective in the anode oxidation process, is conducive to Nb 2O 5With Al 2O 3Compound.Effects on surface is coated with Nb 2O 5When the aluminum electric pole foil of rete carries out anodic oxidation, Al under the effect of electric field 2O 3/ Nb 2O 5Composite dielectric film can produce.
In the above-mentioned steps 1, adopt hot oxalic acid solution to Nb (OH) 5Dissolve, prepare earlier niobium oxalate solution, react as follows:
2Nb(OH) 5+5(COOH) 2＝Nb 2(C 2O 4) 5+10H 2O
Add ammoniacal liquor in the above-mentioned steps 2, can generate and contain the Nb complex compound, react as follows:
Nb 2(C 2O 4) 5+6NH 3·H 2O+(COOH) 2＝2[(NH 3) 4NbO](C 2O 4) 3·2H 2O
NH 3As ligand wherein, can with H +Ions binding and generate conjugate acid, H in complex ion solution +When ion concentration reduced, the concentration of ligand had increased, and the coordination balance is moved to the direction of producing complex compound.When solution is processed the aluminium etched foil, H +Ion has been promoted the generation of complex compound by the base aluminum metal consumption.Containing the Nb complex compound can polymerization increase to particle size of the gel, along with H +The consumption of ion when the complexing product agglomerates to critical particle diameter, namely begins to be deposited in the aluminium foil surface micropore zone.In the high-temperature process, be deposited on the [(NH on aluminium etched foil surface 3) 4NbO] (C 2O 4) 32H 2O is dehydration when surpassing 100 ℃, and deamination when surpassing 180 ℃ generates niobium pentaoxide when surpassing 250 ℃, and its reaction can be represented by the formula:
Figure GA20179783200910060069201D00031
The present invention has following characteristics:
1, the present invention can successfully make and have Al 2O 3/ Nb 2O 5The aluminum electric pole foil of composite dielectric film, prepared have an Al 2O 3/ Nb 2O 5The aluminum electric pole foil of composite dielectric film has higher specific volume than conventional aluminium corrosion Waste Acid From Hua Cheng Foil, and its specific volume gets increase rate and can reach about 30%.
2, the present invention adopts lower-cost Nb (OH) 5As the metal niobium source, effectively reduce the cost in metal niobium source; Use for reference simultaneously the thought of sol-gel process, adopt the mode that infiltrates absorption to deposit and contain niobium compound, abandoned conventional electrochemical method, can save the energy, further reduce cost.Be compared to the electrochemical method that adopts the simple metal niobium, the present invention can effectively reduce manufacturing cost.
3, the present invention prepares Al 2O 3/ Nb 2O 5In the compound dielectric film aluminum electrode foil process, because as the Nb (OH) in metal niobium source 5Can effectively use up, its waste liquid system is substantially nontoxic, and is substantially harmless to environment, is a kind of method of relative environmental protection.
4, technical process of the present invention is simple, and processing ease is convenient to control.
Description of drawings
Figure l is process flow diagram of the present invention.
Fig. 2 is at aluminium etched foil surface deposition [(NH in the step 3 of the present invention 3) 4NbO] (C 2O 4) 32H 2During O, different Nb under the identical infiltrating time 5+Ion concentration is with final Al 2O 3/ Nb 2O 5The relation curve of compound dielectric film aluminum electrode foil specific volume increase rate.
Fig. 3 is at aluminium etched foil surface deposition [(NH in the step 3 of the present invention 3) 4NbO] (C 2O 4) 32H 2During O, identical Nb 5+Infiltrating times different under the ion concentration are with final Al 2O 3/ Nb 2O 5The relation curve of compound dielectric film aluminum electrode foil specific volume increase rate.
Embodiment
On the basis of a large amount of investigative tests, with reference to the processing procedure on the existing industrial production line, designed the technological process shown in Fig. 1 (see photo): at first prepare the certain density niobium oxalate aqueous solution, add ammoniacal liquor and regulate between pH value to 1～2, obtain water-soluble niobium compound treatment liquid; Then the aluminium etched foil is immersed in the water-soluble niobium compound treatment liquid, processing a period of time at a certain temperature, in this process aluminium etched foil surface deposition contain nioium complex [(NH 3) 4NbO] (C 2O 4) 32H 2O takes out afterwards and cleans and oven dry; Sample after the oven dry is placed in immediately and carries out high-temperature heat treatment in the heating furnace, in heating process, and [(NH 3) 4NbO] (C 2O 4) 32H 2O progressively sloughs water, ammonia etc., finally is decomposed into Nb fully 2O 5, also can grow up and understand thermal oxide rete, Nb in the etched foil surface 2O 5With Al 2O 3Carry out tentatively compound; At last, effects on surface is covered with Nb 2O 5Aluminium foil carry out anodic oxidation, grow the Al of high dielectric 2O 3/ Nb 2O 5Complex oxide film.Thereby prepare Al 2O 3/ Nb 2O 5Compound dielectric film aluminum electrode foil.
Embodiment one:
Preparation niobium oxalate solution is also controlled wherein Nb 5+The concentration of ion cuts identical aluminium corrosion paillon foil and carries out the identical time infiltration experiment of (10 minutes) respectively 0.01,0.02,0.03 and 0.04mol/L.Experimental result shows Nb (OH) in obtain solution 5Concentration when surpassing 0.03mol/L, Waste Acid From Hua Cheng Foil specific volume growth rate has not had obvious raising, is deposited on the Nb on aluminium etched foil surface this moment 2O 5Rete is thicker, in anode oxidation process, can cause electrode foil surface portion micropore to seal, the effective area of surface of aluminum electrode foil is reduced, and this has just offset to a certain extent dielectric constant and has improved the specific volume growth that brings, and then causes the specific volume growth rate raising trend of Waste Acid From Hua Cheng Foil to be slowed down.Take all factors into consideration specific volume and increase effect and production cost, add Nb (OH) in the treatment fluid 5Concentration 0.03mol/L is comparatively suitable.
The solution concentration relation of specific volume growth level and Nb is seen shown in the accompanying drawing 2.
Embodiment two:
Preparation niobium oxalate solution is also controlled wherein Nb 5+The concentration of ion is 0.03mol/L, aluminium corrosion paillon foil is set respectively is infiltrated on asynchronism(-nization) in the niobium oxalate solution, is respectively 5min, 10min, 15min.
Fig. 3 changes into the specific volume growth rate of paper tinsel with soaking into the curve that the processing time changes.Soak into the processing time more in short-term, and the specific volume growth rate has a distinct increment with the increase of the time of processing, and the specific volume growth rate reaches maximum when the processing time is 10min, after this can descend with the prolongation of the time of processing again.Containing the deposition of Nb complex compound on aluminium etched foil surface increases along with the increase in processing time, the sour environment of solution also can increase the dissolving of aluminium etched foil simultaneously, so aluminium foil should not be long-time excessively through this solution-treated, otherwise its surperficial pit form will be subjected to than havoc, cause the effective area on etched foil surface to reduce, the specific volume growth rate is descended, and the meeting dissolving attenuate of aluminium foil in treatment fluid reduces the mechanical performance that changes into paper tinsel simultaneously.

Claims (2)

1. Al 2O 3/ Nb 2O 5The preparation method of compound dielectric film aluminum electrode foil may further comprise the steps:
Step 1: niobium hydroxide is joined in the oxalic acid aqueous solution, and 25～70 ℃ of temperature conditions stir down, niobium hydroxide are fully dissolved, the niobium oxalate solution that obtains clarifying; When wherein preparing niobium oxalate solution, niobium hydroxide and oxalic acid mol ratio are between 1: 2.5～4, Nb in the niobium oxalate solution for preparing 5+Ion concentration is between 0.005～0.04mol/L;
Step 2: in the niobium oxalate solution of step 1 gained, add ammoniacal liquor, adjust between solution pH value to 1～2;
Step 3: the aluminium etched foil is infiltrated in the step 2 gained solution 2-15 minute, takes out afterwards and clean also oven dry;
Step 4: the aluminium etched foil that high-temperature process is handled through step 3, temperature are arranged on 250～600 degree, 10 minutes～30 minutes time;
Step 5: the aluminium etched foil of processing through step 4 is carried out anodic oxidation, obtain Al 2O 3/ Nb 2O 5Compound dielectric film aluminum electrode foil.
2. Al according to claim 1 2O 3/ Nb 2O 5The preparation method of compound dielectric film aluminum electrode foil is characterized in that, in the concrete anode oxidation process, the ammonium adipate solution of employing 15% is as electrolyte in the step 5, and 75 ℃ of liquid temperatures, oxidation current density are 50mA/cm 2, anodizing time is 10 minutes.
CN2009100600692A 2009-07-22 2009-07-22 Preparation method of Al2O3/Nb2O3 compound dielectric film aluminum electrode foil Expired - Fee Related CN101651047B (en)

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