CN102426922A - Preparation method of pre-composite high dielectric constant medium film aluminum electrode foil - Google Patents
Preparation method of pre-composite high dielectric constant medium film aluminum electrode foil Download PDFInfo
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- CN102426922A CN102426922A CN2011102274337A CN201110227433A CN102426922A CN 102426922 A CN102426922 A CN 102426922A CN 2011102274337 A CN2011102274337 A CN 2011102274337A CN 201110227433 A CN201110227433 A CN 201110227433A CN 102426922 A CN102426922 A CN 102426922A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 62
- 239000011888 foil Substances 0.000 title claims abstract description 61
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 238000005516 engineering process Methods 0.000 claims abstract description 13
- 239000004411 aluminium Substances 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 15
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 238000003483 aging Methods 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 10
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001741 Ammonium adipate Substances 0.000 claims description 7
- 235000019293 ammonium adipate Nutrition 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 19
- 238000012545 processing Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000012776 electronic material Substances 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- 239000004615 ingredient Substances 0.000 abstract 1
- 235000000396 iron Nutrition 0.000 abstract 1
- 229910006587 β-Al2O3 Inorganic materials 0.000 abstract 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 16
- 229910002113 barium titanate Inorganic materials 0.000 description 16
- 230000008569 process Effects 0.000 description 13
- 239000003990 capacitor Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
A preparation method of a pre-composite high dielectric constant medium film aluminum electrode foil belongs to the electronic material technology field. In the invention, a high dielectric property of a SBA material and an Al2O3 skeleton structure are used and composite processing are performed in advance to the SBA material, the Al2O3 skeleton structure and BT so as to form a SBA (containing beta-Al2O3)/BT pre-composite structure. Then, through traditional anodic oxidation, by using a conduction effect of the Al2O3 skeleton structure in the pre-composite structure to Al and O irons, the BT material can exist in the high dielectric constant composite medium film as a 0-3 type composite form so that purposes of controlling a medium phase ingredient and a micro existence state can be reached. A technology is simple and is easy to be controlled. The method can be combined with aluminum electrode foil corrosion and a forming technology production line so as to realize the linkage production. Compared to the traditional technology, by using the technology of the invention, an aluminum forming foil specific volume in a low pressure stage has increased by 40%.
Description
Technical field
The invention belongs to technical field of electronic materials, relate to the technology of preparing of electrolytic capacitor, especially have the preparation method of high-k composite dielectric film aluminum electric pole foil with aluminum electric pole foil.
Background technology
The high speed development of microelectronic industry has been accelerated the process that the Circuits System integrated level improves; Aluminium electrolytic capacitor as in the electronic circuit must but be difficult to integrated a kind of discrete electronic device, the size of its volume has become the huge obstacle of restriction complete electronic set system miniaturization.The core component of aluminium electrolytic capacitor is an aluminum electric pole foil, its volume dwindle the raising that depends on aluminum electric pole foil specific volume level.Along with updating of aluminum electric pole foil corrosion technology, the expansion face multiplying power of aluminium etched foil is near theoretical limit, and the specific volume that improves aluminum electric pole foil through the method is very difficult.Therefore, through the dielectric constant of Composite Preparation technology raising aluminum electric pole foil deielectric-coating, becoming the important technology approach of the high specific volume aluminum electric pole foil of present acquisition, is the focus of studying in recent years and paying close attention to.
The conventional aluminum electrolytic capacitor is lower with the relative dielectric constant of anodic alumina films; Be generally 7～10; And the relative dielectric constant of valve metal (Ti, Ta, Nb, Zr etc.) oxide is higher than aluminum oxide, and the relative dielectric constant of ferroelectric material barium titanate, strontium titanates etc. more can reach hundreds of even several ten thousand.These high dielectric constant materials are incorporated in the alumilite process deielectric-coating, form the high-k composite dielectric film, can improve the aluminum electric pole foil specific volume, thereby improve the capacity of aluminium electrolytic capacitor, dwindle its volume from this technical thought.Existing patent (spy opens flat 3-131014, EP350108, spy and opens clear 55-69291, CN100463086C, CN1272815C, CN100365167C) has prepared the high-k composite dielectric film through physics or chemical method, thereby has improved the specific capacitance of aluminium electrolytic capacitor effectively.Above-mentioned technology part has obtained promotion and application in mesohigh section aluminum electric pole foil, but improves effect and not obvious at the capacity of low pressure stage, and its capacity increase rate also differs greatly apart from the compound theoretical capacity of high dielectric.
In fact, the microcosmic component of composite dielectric film and growth conditions are the key factors of decision composite dielectric film dielectric property performance.Existing compound capacity increasing technique all is through directly depositing the single phase material of high-k at aluminium foil surface, and anodic oxidation forms aluminium electrolytic capacitor and uses the high dielectric constant film then, and this high-k composite dielectric film generally is layer growth.Theoretical Calculation shows that this stratiform composite mode is unfavorable for the raising of deielectric-coating entire effective dielectric constant, and is all the more so during especially for low pressure stage deielectric-coating thinner thickness.
In recent years, conducting particles is distributed to constitutes compound system in the dielectric base body, can reach the purpose that significantly improves the dielectric film dielectric constant and the concern that enjoys the researcher.People such as Bhola N have prepared high dielectric Sodium Beta-alumina (SBA) system material (Bhola N.Pal through low temperature liquid polymerization process; Bal Mukund Dhar; Kevin C.See and Howard E.Katz.Nature Materials, 2009,8:898～903); This material has special two-dimension netted microstructure, and its skeleton structure is β-Al
2O
3, the Na ion is at Al
2O
3Have good two-dimentional conductibility between insulating barrier lattice dot matrix, under outer field action, the dielectric constant of this material can reach 170.
Technology contents
The present invention provides a kind of preparation method of preparatory composite high-dielectric constant dielectric film aluminum electrode foil electrode foil.This method is utilized the high dielectric property and the Al of SBA material
2O
3Skeleton structure is carried out Combined Processing in advance with ferroelectric barium titanate (BT) material, forms SBA and (contains β-Al
2O
3The preparatory composite construction of)/BT; Then through conventional anodization, by Al in the preparatory composite construction
2O
3Skeleton structure makes the BT material be present in the high-k composite dielectric film with 0-3 type complex form to the conduction of Al, O ion, reaches the purpose of control medium phase component and microcosmic existence.Compare with existing high-k composite dielectric film aluminum electric pole foil preparation method; This method can realize the control to complex media phase micro Distribution state; And have characteristics with low cost, simple to operate, can expand the face production line with present electrochemical corrosion and change into production line and realize interlock production.
Technic relization scheme of the present invention is following:
A kind of preparation method of preparatory composite high-dielectric constant dielectric film aluminum electrode foil electrode foil may further comprise the steps:
Step 1: aluminum nitrate and sodium hydrogensulfite are dissolved in the EGME simultaneously, stir under the room temperature and obtain solution 1, control solution 1 concentration is between 0.1～0.5mol/L, and wherein the mol ratio of aluminum nitrate and sodium hydrogensulfite is between 1: 1～40: 1.
Step 2: barium acetate is dissolved in the glacial acetic acid, obtains solution 2, control solution 2 concentration are between 0.1～1mol/L.
Step 3: butyl titanate is dissolved in the lactic acid, and 60～80 ℃ of following stirrings obtain solution 3, and control solution 3 concentration are between 0.1～1mol/L.
Step 4: step 3 gained solution 3 is slowly added in the step 2 gained solution 2, obtain solution 4, the mol ratio of control butyl titanate and barium acetate is 1: 1, and the pH value that adds glacial acetic acid adjustment solution 4 simultaneously is between 1～2.
Step 5: the solution 1 of step 1 gained is added in the solution 4 of step 4 gained, obtain solution 5, the mol ratio of control aluminum nitrate and barium acetate is between 1: 5～1: 50; Handle solution 5 ageings more than 20 hours then.
Step 6: in the solution 5 after the aluminium etched foil impregnated in the ageing of step 5 gained and handle 1～10 minute, take out then, with washed with de-ionized water and oven dry.
Step 7: will heat-treat through the aluminium etched foil that step 6 was handled, heat treatment temperature is controlled between 300～550 ℃, and heat treatment time is 2～30 minutes.Heat treatment process can directly realize in air atmosphere.In general, the control heat treatment temperature is 450～550 ℃, and heat treatment time is to be best between 10～30 minutes.
Step 8: will carry out anodized through the aluminium etched foil that step 7 was handled, and finally obtain the aluminum electric pole foil of preparatory composite high-dielectric constant deielectric-coating.
The present invention adds equally with the SBA material of organic system as the solvent preparation in the high dielectric barium titanate material organic system that adopts the sol-gel process preparation, organic system exist for barium-titanate material and the SBA material provides good combinational environment.The aluminium etched foil through impregnation process, and forms SBA on its surface and (contains β-Al in this composite system after heat treatment process
2O
3The preparatory composite construction of)/BT, the organic principle in the system is removed through pyrolysis.
Al in the SBA material
2O
3Skeleton structure and barium-titanate material compound in advance can effectively change the existence of composite dielectric film after anodic oxidation.Al
2O
3Skeleton structure can be the pathway that follow-up anode oxidation process provides Al, O ion, promotes newly-generated Al
2O
3Medium separates the BT particulate, forms the high-k composite dielectric film with body phase composite construction at aluminium etched foil spatial induction.Simultaneously, the SBA material has certain crystalline structure, helps in anode oxidation process, inducing the generation of crystal formation pellumina, and the crystal formation pellumina has promoted the raising of composite dielectric film dielectric constant to a certain extent.The aluminium anodes that utilizes the present invention to prepare changes into paper tinsel and compares with the paper tinsel of handling without the present invention that changes into, and specific volume can improve about 40% at low pressure stage; And changing into paper tinsel with respect to only carrying out the single aluminium anodes of handling mutually of high dielectric barium titanate, specific volume has 10% raising approximately at low pressure stage.
The present invention has the following advantages and effect:
1. the preparatory composite high-dielectric constant dielectric film aluminum electrode foil electrode foil of the present invention preparation, its specific volume becomes paper tinsel to improve 10% at low pressure stage than the calorize of only handling through barium titanate, and becomes paper tinsel to improve about 40% than the calorize without any processing.
2. high dielectric barium titanate material and SBA material compound in advance helps after anodic oxidation, forming the high-k composite dielectric film with body phase composite construction at surface of aluminum electrode foil.
3. the present invention is simple and convenient, is easy to realize interlock production with existing aluminum electric pole foil industrial production line.
Embodiment
Embodiment 1:
A kind of preparation method of preparatory composite high-dielectric constant dielectric film aluminum electrode foil electrode foil may further comprise the steps:
Step 1: aluminum nitrate and sodium hydrogensulfite are dissolved in the EGME simultaneously, stir under the room temperature and obtain solution 1, control solution 1 concentration is between 0.1～0.5mol/L, and wherein the mol ratio of aluminum nitrate and sodium hydrogensulfite is between 1: 1～40: 1;
Step 2: barium acetate is dissolved in the glacial acetic acid, obtains solution 2, control solution 2 concentration are between 0.1～1mol/L;
Step 3: butyl titanate is dissolved in the lactic acid, and 60～80 ℃ of following stirrings obtain solution 3, and control solution 3 concentration are between 0.1～1mol/L;
Step 4: step 3 gained solution 3 is slowly added in the step 2 gained solution 2, obtain solution 4, the mol ratio of control butyl titanate and barium acetate is 1: 1, and the pH value that adds glacial acetic acid adjustment solution 4 simultaneously is between 1～2;
Step 5: the solution 1 of step 1 gained is added in the solution 4 of step 4 gained, obtain solution 5, the mol ratio of control aluminum nitrate and barium acetate is 1: 10; Handle solution 5 ageings more than 20 hours then;
Step 6: in the solution 5 after the aluminium etched foil impregnated in the ageing of step 5 gained and handle 5 minutes, take out then, with washed with de-ionized water and oven dry;
Step 7: will place the Muffle furnace of air atmosphere to heat-treat through the aluminium etched foil that step 6 was handled, heat treatment temperature be 550 ℃, and the time is 10 minutes;
Step 8: will carry out anodized through the aluminium etched foil that step 7 was handled, and finally obtain the aluminum electric pole foil of preparatory composite high-dielectric constant deielectric-coating.Concrete anode oxidation process is: anodic oxidation electrolyte employing mass fraction is 15% ammonium adipate solution, and electrolyte temperature is controlled between 75 ± 2 ℃, and oxidation current density is 50mA/cm
2, arrive the 20V constant voltage anodic oxidation again 10 minutes of energizing behind the voltage; Through 550 ℃ of heat treatment 2min of Muffle furnace, place above-mentioned ammonium adipate solution more then, anodic oxidation is 2 minutes under identical voltage.
Adopt and obtain calorize behind the above-mentioned processing step and become paper tinsel; Test changes into the paper tinsel specific volume and can know: through the paper tinsel that changes into of PROCESS FOR TREATMENT of the present invention; Its specific volume is handled than single phase barium titanate and has been improved 9.2%, and becomes the paper tinsel specific volume to improve 38% with respect to the calorize without any Processing of Preparation.
Embodiment 2:
A kind of preparation method of preparatory composite high-dielectric constant dielectric film aluminum electrode foil electrode foil may further comprise the steps:
Step 1: aluminum nitrate and sodium hydrogensulfite are dissolved in the EGME simultaneously, stir under the room temperature and obtain solution 1, control solution 1 concentration is between 0.1～0.5mol/L, and wherein the mol ratio of aluminum nitrate and sodium hydrogensulfite is between 1: 1～40: 1;
Step 2: barium acetate is dissolved in the glacial acetic acid, obtains solution 2, control solution 2 concentration are between 0.1～1mol/L;
Step 3: butyl titanate is dissolved in the lactic acid, and 60～80 ℃ of following stirrings obtain solution 3, and control solution 3 concentration are between 0.1～1mol/L;
Step 4: step 3 gained solution 3 is slowly added in the step 2 gained solution 2, obtain solution 4, the mol ratio of control butyl titanate and barium acetate is 1: 1, and the pH value that adds glacial acetic acid adjustment solution 4 simultaneously is between 1～2;
Step 5: the solution 1 of step 1 gained is added in the solution 4 of step 4 gained, obtain solution 5, the mol ratio of control aluminum nitrate and barium acetate is 1: 5; Handle solution 5 ageings more than 20 hours then;
Step 6: in the solution 5 after the aluminium etched foil impregnated in the ageing of step 5 gained and handle 5 minutes, take out then, with washed with de-ionized water and oven dry;
Step 7: will place the Muffle furnace of air atmosphere to heat-treat through the aluminium etched foil that step 6 was handled, heat treatment temperature be 550 ℃, 10 minutes time;
Step 8: will carry out anodized through the aluminium etched foil that step 7 was handled, and finally obtain the aluminum electric pole foil of preparatory composite high-dielectric constant deielectric-coating.Concrete anode oxidation process is: anodic oxidation electrolyte employing mass fraction is 15% ammonium adipate solution, and electrolyte temperature is controlled between 75 ± 2 ℃, and oxidation current density is 50mA/cm
2, arrive the 30V constant voltage anodic oxidation again 10 minutes of energizing behind the voltage; Through 550 ℃ of heat treatment 2min of Muffle furnace, place above-mentioned ammonium adipate solution more then, anodic oxidation is 2 minutes under identical voltage.
Obtain calorize after adopting above-mentioned processing step to handle and become paper tinsel; The specific volume test result that changes into paper tinsel shows: the calorize with respect to handle gained mutually through single barium titanate becomes paper tinsel; The paper tinsel specific volume that changes into through PROCESS FOR TREATMENT gained of the present invention has improved 11.2%, and becomes the paper tinsel specific volume to improve 43% with respect to the calorize without any Processing of Preparation.
Embodiment 3:
A kind of preparation method of preparatory composite high-dielectric constant dielectric film aluminum electrode foil electrode foil may further comprise the steps:
Step 1: aluminum nitrate and sodium hydrogensulfite are dissolved in the EGME simultaneously, stir under the room temperature and obtain solution 1, control solution 1 concentration is between 0.1～0.5mol/L, and wherein the mol ratio of aluminum nitrate and sodium hydrogensulfite is between 1: 1～40: 1;
Step 2: barium acetate is dissolved in the glacial acetic acid, obtains solution 2, control solution 2 concentration are between 0.1～1mol/L;
Step 3: butyl titanate is dissolved in the lactic acid, and 60～80 ℃ of following stirrings obtain solution 3, and control solution 3 concentration are between 0.1～1mol/L;
Step 4: step 3 gained solution 3 is slowly added in the step 2 gained solution 2, obtain solution 4, the mol ratio of control butyl titanate and barium acetate is 1: 1, and the pH value that adds glacial acetic acid adjustment solution 4 simultaneously is between 1～2;
Step 5: the solution 1 of step 1 gained is added in the solution 4 of step 4 gained, obtain solution 5, the mol ratio of control aluminum nitrate and barium acetate is 1: 50; Handle solution 5 ageings more than 20 hours then;
Step 6: in the solution 5 after the aluminium etched foil impregnated in the ageing of step 5 gained and handle 5 minutes, take out then, with washed with de-ionized water and oven dry;
Step 7: will place the Muffle furnace of air atmosphere to heat-treat through the aluminium etched foil that step 6 was handled, heat treatment temperature be 550 ℃, 10 minutes time;
Step 8: will carry out anodized through the aluminium etched foil that step 7 was handled, and finally obtain the aluminum electric pole foil of preparatory composite high-dielectric constant deielectric-coating.Concrete anode oxidation process is: anodic oxidation electrolyte employing mass fraction is 15% ammonium adipate solution, and electrolyte temperature is controlled between 75 ± 2 ℃, and oxidation current density is 50mA/cm
2, arrive the 20V constant voltage anodic oxidation again 10 minutes of energizing behind the voltage; Through 550 ℃ of heat treatment 2min of Muffle furnace, place above-mentioned ammonium adipate solution more then, anodic oxidation is 2 minutes under identical voltage.
Adopt above-mentioned processing step to prepare calorize and become paper tinsel; The specific volume test result that changes into paper tinsel shows: the paper tinsel that changes into that adopts PROCESS FOR TREATMENT gained of the present invention; Its specific volume more only changes into paper tinsel through barium titanate processing gained and has improved 8.1%, and has improved 36.8% with respect to the paper tinsel that changes into without any Processing of Preparation.
Claims (3)
1. the preparation method of a preparatory composite high-dielectric constant dielectric film aluminum electrode foil electrode foil may further comprise the steps:
Step 1: aluminum nitrate and sodium hydrogensulfite are dissolved in the EGME simultaneously, stir under the room temperature and obtain solution 1, control solution 1 concentration is between 0.1～0.5mol/L, and wherein the mol ratio of aluminum nitrate and sodium hydrogensulfite is between 1: 1～40: 1;
Step 2: barium acetate is dissolved in the glacial acetic acid, obtains solution 2, control solution 2 concentration are between 0.1～1mol/L;
Step 3: butyl titanate is dissolved in the lactic acid, and 60～80 ℃ of following stirrings obtain solution 3, and control solution 3 concentration are between 0.1～1mol/L;
Step 4: step 3 gained solution 3 is slowly added in the step 2 gained solution 2, obtain solution 4, the mol ratio of control butyl titanate and barium acetate is 1: 1, and the pH value that adds glacial acetic acid adjustment solution 4 simultaneously is between 1～2;
Step 5: the solution 1 of step 1 gained is added in the step 4 gained solution 4, obtain solution 5, the mol ratio of control aluminum nitrate and barium acetate is between 1: 5～1: 50; Handle solution 5 ageings more than 20 hours then;
Step 6: in the solution 5 after the aluminium etched foil impregnated in the ageing of step 5 gained and handle 1～10 minute, take out then, with washed with de-ionized water and oven dry;
Step 7: will heat-treat through the aluminium etched foil that step 6 was handled, heat treatment temperature is controlled between 300～550 ℃, and heat treatment time is 2～30 minutes;
Step 8: will carry out anodized through the aluminium etched foil that step 7 was handled, and finally obtain the aluminum electric pole foil of preparatory composite high-dielectric constant deielectric-coating.
2. the preparation method of preparatory composite high-dielectric constant dielectric film aluminum electrode foil electrode foil according to claim 1 is characterized in that, the step 7 pair equipment that when the aluminium etched foil that step 6 was handled is heat-treated, adopts is the Muffle furnace under the air atmosphere.
3. the preparation method of preparatory composite high-dielectric constant dielectric film aluminum electrode foil electrode foil according to claim 1; It is characterized in that; The technology of anodized described in the step 8 is: anodic oxidation electrolyte employing mass fraction is 15% ammonium adipate solution; Electrolyte temperature is controlled between 75 ± 2 ℃, and oxidation current density is 50mA/cm
2, constant voltage anodic oxidation 10 minutes again behind the voltage of arrive setting of energizing.
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|---|---|---|---|
| CN 201110227433 CN102426922B (en) | 2011-08-10 | 2011-08-10 | Preparation method of pre-composite high dielectric constant medium film aluminum electrode foil |
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|---|---|---|---|
| CN 201110227433 CN102426922B (en) | 2011-08-10 | 2011-08-10 | Preparation method of pre-composite high dielectric constant medium film aluminum electrode foil |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509626A (en) * | 2011-11-21 | 2012-06-20 | 电子科技大学 | Method for preparing aluminum electrode foil with high dielectric constant composite dielectric film |
| CN108807017A (en) * | 2018-06-22 | 2018-11-13 | 宇东箔材科技南通有限公司 | The preparation method of compound dielectric film aluminum electrode foil |
| CN115172060A (en) * | 2022-08-30 | 2022-10-11 | 西安稀有金属材料研究院有限公司 | Method for preparing aluminum electrolytic capacitor anode foil based on electrophoretic deposition |
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| CN101093751A (en) * | 2006-11-17 | 2007-12-26 | 深圳清华大学研究院 | Method for preparing foil of cathode with high specific volume |
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| CN101093751A (en) * | 2006-11-17 | 2007-12-26 | 深圳清华大学研究院 | Method for preparing foil of cathode with high specific volume |
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| 《Thin Solid Films》 20080418 Xianfeng Du等 Formation of Al2O3-BaTiO3 composite thin film to increase the specific capacitance of aluminum electrolytic capacitor , * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509626A (en) * | 2011-11-21 | 2012-06-20 | 电子科技大学 | Method for preparing aluminum electrode foil with high dielectric constant composite dielectric film |
| CN108807017A (en) * | 2018-06-22 | 2018-11-13 | 宇东箔材科技南通有限公司 | The preparation method of compound dielectric film aluminum electrode foil |
| CN115172060A (en) * | 2022-08-30 | 2022-10-11 | 西安稀有金属材料研究院有限公司 | Method for preparing aluminum electrolytic capacitor anode foil based on electrophoretic deposition |
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