CN107316745B - Electrode structural body and aluminium electrolutic capacitor for aluminium electrolutic capacitor - Google Patents
Electrode structural body and aluminium electrolutic capacitor for aluminium electrolutic capacitor Download PDFInfo
- Publication number
- CN107316745B CN107316745B CN201710587393.4A CN201710587393A CN107316745B CN 107316745 B CN107316745 B CN 107316745B CN 201710587393 A CN201710587393 A CN 201710587393A CN 107316745 B CN107316745 B CN 107316745B
- Authority
- CN
- China
- Prior art keywords
- aluminium
- engineering
- structural body
- electrode structural
- coating
- 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.)
- Active
Links
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 93
- 239000004411 aluminium Substances 0.000 title claims abstract description 88
- 239000003990 capacitor Substances 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000005030 aluminium foil Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 239000011888 foil Substances 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 239000000758 substrate Substances 0.000 abstract description 17
- 238000001035 drying Methods 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- 210000000981 epithelium Anatomy 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 3
- 239000001741 Ammonium adipate Substances 0.000 description 3
- 235000019293 ammonium adipate Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- -1 aluminium Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- YQXQWFASZYSARF-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC YQXQWFASZYSARF-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention provides a kind of aluminium electrolutic capacitor electrode structural body and its manufacturing method containing high capacity.After coating comprising organic oxide (aluminium powder and Al alloy powder and valve metal are constituted), organic bond and organic solvent is formed on aluminum substrates, sinter layer is generated through drying, heat-agglomerating engineering, restore again heating engineering, later, positive oxidation is carried out again, can produce the electrode structural body that can be adapted for aluminium electrolutic capacitor high capacity anode and negative foil in this way.
Description
Technical field
The manufacturing method of the electrode structural body used the present invention relates to the electrode material of aluminium electrolutic capacitor, electrode structure
Body and the aluminium electrolutic capacitor for having this electrode structural body.
Technical background
There are two electrodes, that is, anode and cathode for capacitor.The positive electrode of capacitor is can be in Surface Creation
The valve metals such as aluminium, the tantalum of dielectric oxide film.Herein, so-called valve metal aoxidizes by anode, is oxidized the gold of epithelium covering
Belong to, such as: there are aluminium, tantalum, niobium, titanium, hafnium etc..
Negative electrode material is electrolyte, inorganic semiconductor, organic conductive substance or metallic film etc.Cathode material
The case where material is the occasion of electrolyte, and negative terminal is using the aluminium foil for being extended surface area is more.
In order to increase the static capacity of capacitor, it also proposed several methods in the past.Such as Japan Patent P2004-
It is recorded in 259932A (patent document 1), as the method for expanding anode and negative terminal surface product: by the crystallinity containing Pb
Oxide is formed in the uniform distribution of aluminium foil surface, by inhibiting surface when corroding to dissolve, has been extended after corrosion
Surface area.
Also, it is recorded in Japanese Patent Laid-Open 11-317331 bulletin (Patent Document 2), is electric as electrolysis is expanded
The method of the surface area of container electrode foil: base is configured in the not active atmosphere under about 10-3torr~about 10-2torr pressure
Then, in order to make substrate have surface structure body material allows substrate to steam valve metal in not active gases.But implementing to pass through
When steaming the method that lures electrics layer of the formation containing valve metal, high vacuum is not only kept, industrialized generation homogeneous thickness is also wanted
Lure electrics layer, this is difficult.
But it if using sol-gel method, is compared with the method for steaming, generates and lure electrics layer to be easy containing valve metal, it can industry
The generation homogeneous thickness of change lures electrics layer.But, electrics layer is lured to lure electric body predecessor in heating by what sol-gel method obtained
Matter, generation lure in the engineering of electrics layer because situations such as being easy to produce rift defect, weaker with the adherence of substrate aluminium, and
And lure between electrics layer and aluminium base formed lure electric body epithelium aluminium oxide can make capacity decline, with substrate peeling etc. ask
Topic.
In order to solve problem above, it is proposed in Japanese Patent International Publication WO02/062569 (patent document 3), content
Described is the manufacturing method that the tectosome of oxycompound layer is generated on matrix.This method has following engineering: allotment
The coating of oxide skin(coating) coating modulates engineering；Pre-treatment is done to substrate surface, obtains the substrate surface of treated substrate
Pretreatment Engineering；To Jing Guo pre-treatment substrate daub, obtain the coating engineering of coated substrates；Coated substrates are sintered,
The sintering engineering of oxide skin(coating) is formed on matrix.Matrix surface Pretreatment Engineering is that have stereo structure structure in matrix surface generation
Face, containing first processing method.
But, even by this method, it is desirable to obtain that adherence is excellent and the electrode structural body of high capacity, still very
It is difficult.
Therefore, in order to improve substrate aluminium and lure the adherence between electrics layer, luring containing valve metal is formed on aluminium base surface
After electric body precursor, electrics layer is lured containing valve metal by heating in carbon oxide gas, being formed on aluminium base surface, and
It aluminium base and lures and forms Jie containing aluminium and carbon between electrics layer in layer, aluminium base and lure the adherence of electrics layer to improve,
In method record and Japan Patent International Publication WO2007/055121 (patent document 4).
The formation recorded in Japan Patent International Publication WO2007/055121 (Patent Document 4) lures electrics layer method suggestion
Using colloid, gel method.But, wanted if thickening the thickness for luring electrics layer in order to improve static capacity, crack can be generated
The defects of, it aluminium base and lures adherence between electrics layer or lures the adherence sharp fall between electrics layer.Therefore, on
It states and says that the possible thickness generated is conditional on aluminum substrates in method, it is also limitary for as a result obtaining capability value.And
Apply alive occasion by this method, because can substrate aluminium and luring generate between electrics layer lure electric body epithelium, due to cause to occur
Peeling phenomenon is only used as the use of conducting polymer solid-state aluminum electrolytic capacitor cathode so being defined.Therefore, the purpose of the present invention
It is exactly to solve the above-mentioned problems, to provide the electrode structural body and its manufacturing method that can be obtained than former higher capacity, even if increasing
Thickness lures electrics layer, substrate aluminium and lures adherence between electrics layer and lures the adherence between electrics layer also good.
[advanced technical literature]
[Patent Document]
[Patent Document 1] Japanese Patent P2004-259932
[Patent Document 2] Japanese Patent Japanese Laid-Open Patent Publication 11-317331
[Patent Document 3] Japanese Patent International Publication WO 02/062569
[Patent Document 4] Japanese Patent International Publication WO 2007/055121
Summary of the invention
The present invention is in order to solve all the time points, the result of study discovery summed up: aluminium foil (by
What aluminium powder crossed that Al metal alloy powder and organic valve metal compound and organic bond constitute lures electric body covering layer) with specific
Condition heat-agglomerating reaches above-mentioned purpose by restoring heating, may can develop desired electrode structural body.
According to electrode structural body (electrode foil) manufacturing method in the present invention: coating (is closed by aluminium powder or aluminum metal
Bronze end and organic valve metal compound and organic bond are constituted) smear dry (being coated with dry engineering) aluminium base (such as
Aluminium foil) surface form coating, then, the aluminium base that forms coating heats in vacuum environment or not active gases atmosphere and (adds
Thermal sintering engineering), it is heated in reproducibility atmosphere later, again.
Middle manufacturing method according to the present invention: vacuum is that 1torr or less is relatively good.Active gases is not nitrogen, argon gas
It is relatively good.Reproducibility atmosphere is that the atmosphere of hydrogen is relatively good.
There are also, according to the present invention in manufacturing method: suggest that the vacuum environment needed in engineering or non-active gas environment are warm
Degree is between 450 DEG C~640 DEG C.
The heating condition suggestion of reducibility gas is set between 550 DEG C~640 DEG C.
Middle manufacturing method according to the present invention: aoxidizing aluminium base anode after reduction heating engineering, carries out anode oxidation engineering.
Be arranged within 5V it is recommended that doing the occasion anode oxidation voltage that cathode uses, do occasion voltage setting that anode uses 5V with
Above, it can arbitrarily be set in the range of using voltage.
Electrode structural body in the present invention is that aluminium powder and Al metal alloy powder (generate on aluminium base and substrate surface
Contain valve metal) sintered body.
Electrode structural body in the present invention: aluminium foil surface will be that (or aluminum metal is closed for aluminium base and aluminium powder at least partially
Bronze end) it is sintered, the adherence of aluminium base and covering layer is good.
And by reduction heating engineering, the electric conductivity of sintered body layer and aluminium base can be promoted, formation is extended surface area
Tectosome.
Anode oxidation engineering is carried out after reduction heating engineering, may can be generated the aluminium oxide containing valve metal oxides and be lured electric body
Epithelium, because the rising of surface area and dielectric constant can produce the aluminium electrolutic capacitor electrode structural body of high capacity.
Valve metal in the present invention in electrode structural body is examined from dielectric constant, the materials of valve metal organic compound etc.
Consider, it is proposed that selection titanium.
Middle manufacturing method through the invention, the available electrode structural body for having high capacity.And because having carried out positive oxygen
Chemical industry journey makes it have the construction of proof voltage, so may all use as aluminium electrolutic capacitor anode, cathode.
Specific implementation method
The manufacturing method of electrode structural body
For example following engineering of the manufacturing method of the present invention: by coating (by aluminium powder or Al metal alloy powder and organic valve
Metallic compound and organic bond are constituted) it smears, is dry in the surface of aluminium base formation coating (generating coating engineering), so
Afterwards, the aluminium foil for forming coating heats (heat-agglomerating engineering) in vacuum environment or not active gases atmosphere, is restoring later, again
It is heated in property atmosphere.
Here is illustrating for the manufacturing method of the present invention.
Form coating engineering
The manufacturing method of the present invention is: first by coating medium (by aluminium powder or Al metal alloy powder and organic valve gold
Belong to compound and organic bond constituted) it smears, is dry, coating (generating coating engineering) is formed on aluminum substrates.
Aluminium foil is aluminium base, smeared on aluminium foil surface mixing coating fluid (by aluminium powder or Al metal alloy powder and
Organic valve metal compound and organic bond are constituted) re-dry, the method that forms coating are not particularly limited, but aluminium powder
Titanium series alkyl oxide or titanium series chelating can be used in last Al metal alloy powder and organic valve metal compound
Compound.Such as: tetraisopropyl titanate (CAS:564-68-9), butyl titanate (CAS:5593-70-4), four (ethyl -1 2-,
3- hexylene glycol) titanium (CAS:5575-43-9), methanol titanium (CAS:992-92-7), four (2,4- pentanediones) close titanium (IV) (CAS:
It can 17501-79-0) etc. select.Also there is no limit can choose polyvinyl acetate resin, propylene tree to organic bond
The merchandisings such as rouge, polyester based resin, polyurethane series resin.
Ethyl alcohol class, ketone, esters, carbonized hydrogen type, the merchandisings such as di-alcohols can be put into these materials and solvent
Any one or a variety of mixed solvents, recycle dispersion machine to break up and coating be made, then be put on aluminium foil surface, after formation
Engineering is dried.Dry engineering is evaporated the solvent in 100 DEG C or more of temperature or environment.Wish two-sided all to be formed
Occasion will climb over again the process before another side repeats after one side coating, drying.Also unicoater can be used, it can
With two-sided disposable generation coating.The coating suggestion of generation is compressed it using jigs such as idler wheels, and compressed thickness is unsatisfactory for
It is required that when, the amount of sizing object can be increased by the above process of repetitive operation, or in coating to adjust.
If about the formula of coating, for the occasion of negative foil or the low positive foil of formation voltage, it is proposed that reduce aluminium powder (or
Al alloy powder) and organic bond additive amount, promoted organic titanic compound ratio.Also, aluminium powder and aluminium alloy
The average grain diameter of powder more dot is relatively good.The coating constructed like this can be adapted for Gao Rong because of the promotion of Ti content ratio
Measure the negative foil of aluminium electrolutic capacitor and the low positive foil of formation voltage.When having again, wishing the positive foil of available higher formation voltage,
It is recommended that promoting the formula ratio of aluminium powder (or Al alloy powder) and organic bond.The coating capacity constructed in this way it is low but
It is to obtain satisfied pressure resistance to also ensure that capacity perhaps by thickening the thickness of coating.
In generation coating engineering manufacturing method of the invention, it is proposed that dispersion aluminium powder and Al alloy powder and organic knot is added
The engineering of mixture and solvent.Generate includes that substance very uneven inside dispersion engineering can be eliminated is (such as mixed in the engineering of coating
Close powder, particle or the bonding agent in object).Later, generated coating can be made to uniform by being coated with, heating engineering.
In this way, while further increasing adherence between coating and aluminium foil, similar powder, interparticle adherence are contained in coating
It may also improve, as a result, the thickness of coating can also thicken.
Because aluminium powder available on the market or Al alloy powder surface have firm oxidation film, so sintering test is very
It is difficult.For this purpose, when being dispersed, needing to destroy the oxide scale film of aluminium or Al alloy powder surface, it is proposed that use high shear dispersion
Machine.Dispersion machine can select abrading-ball dispersion machine, the ultrasonic dispersion machine etc. having in the market.
Then, aluminium powder or Al alloy powder can be selected available on the market is made of aluminium powder or Al alloy powder
Aluminium cream (aluminium paste).
It is recommended that the purity of aluminium powder or Al alloy powder, in 99.5wt% or more, 99.7wt% or more is more preferable.Aluminium powder
Shape is not particularly limited, and spherical or sheet etc. can be used.It is recommended that its average grain diameter is between 1um~10um.
Heat-agglomerating engineering
Later, it is heated in vacuum environment or not active gases, carries out the decomposition and sintering of organic bond.If knot
Mixture volatilizees completely decompose if, it may occur that apply interlayer and generate crack or gap, cause aluminium foil and coating adherence or
It is worse that the adherence of aluminium powder and Al alloy powder ratio does not use the case where bonding agent.But it is tried with 550 DEG C or more of heating condition
The occasion tested, aluminium foil (aluminium foil that aluminium powder and aluminium alloy are aluminium base) and similar aluminium powder attracts each other and the conjunction of valve metal titanizing
The sintering such as object, generates a part of sintered body, promotes adherence.This when, it is proposed that when compression coating, synchronize and be sintered.
Vacuum environment is air pressure 1torr state below or active gases is not that nitrogen, argon gas etc. are relatively good.Heating
Temperature is relatively good if being appropriately arranged with according to the composition, the composition of covering layer, thickness etc. of heating target aluminium foil, if temperature is 450
DEG C~640 DEG C between, the time is again within 1~10H.In order to avoid bonding agent sharply decomposes, ensures homogeneity, it is proposed that not set
Disposable temperature, segmentation gradually heat relatively good.In order to produce ideal sintering state, it is proposed that temperature be 550 DEG C~
640 DEG C, the time be 30 minutes or more under conditions of be compared.
Reduction heating engineering
It after heat-agglomerating engineering, heated in reducibility gas, carry out heating reduction engineering.
Reducibility gas is not particularly limited, such as hydrogen is cheaply easy to use.Can also mix with not active gases makes
With.Heating temperature is relatively good if being appropriately arranged with according to the composition, composition, thickness etc. of heating target aluminium foil, usually suggests temperature
Degree is 550 DEG C~640 DEG C, and the time is 1~10h.It is heated in reducibility gas, some aluminium powder is at least wanted in coating
(or Al alloy powder) and the valve metal titanium compound in addition to aluminium powder are reduced.Because of aluminium powder and Al alloy powder and valve metal
Titanium compound will become if being reduced a part conductive materials, so with no conductive materials there are the case where compared with, draw
The area of capacity is extended, obtains high capacity out.
Anode oxidation engineering
After aforementioned reduction heating engineering, by the oxidation of obtained electrode structural body anode, anode oxidation engineering is carried out.
By implementing this anode oxidation engineering, the aluminium and aluminium alloy and titanium compound being reduced make with anode oxidation engineering
Electrolyte solution contacts are oxidized, and generate titaniferous lures electrics layer.Anode oxidation engineering is not particularly limited, such as:
In the aqueous solutions such as ammonium adipate, boric acid, ammonium phosphate, applies 0.5V~5V voltage using the occasion that negative foil is tested, use positive foil
Occasion applies the free voltage within the scope of 5V~700V.
Also, the electrode foil that middle manufacturing method obtains through the invention is because carrying out this anode oxidation engineering, so not
It can be only applicable in the negative foil with aluminium electrolutic capacitor, positive foil can also be applied.
Aluminium used in the manufacturing method of the present invention has been done as described below.
Aluminium base
One of embodiment in the present invention: the aluminium foil selected as aluminium base is not particularly limited, and can select pure
Aluminium foil.This aluminium foil suggests that aluminium purity is 99.5wt% or more, and 99.9wt% or more is more preferable.It can prevent as alminium electrolytic condenser
Occurrence features deterioration, the situation that leakage current is big, short-circuit when device uses.The thickness of aluminium foil does not specially require, it is proposed that thickness exists
Within 15um~40um.It is difficult to be utilized below this thickness range, fracture may occur in manufacturing engineering, crumple
The phenomenon that.Then, the area that more than this thickness range, can be accommodated capacitor reduces, and loses high capacity electrolysis electricity
The advantage of container, Yu Chengben are also unfavorable.
Above-mentioned aluminium foil can be made up of common manufacturing method.It can also be by the methods of making annealing treatment, being heat-treated
It is quenched at soft foil, or it is not quenched at hard foil.
Then, about aluminium foil, it can also be initially formed covering layer, then implement washing process or make rough surface engineering.It closes
Chemical attack, the electrochemically communal techniques such as burn into grinding can be used in roughening method.
The present invention combines following specific embodiment and comparative example further elucidated above to the present invention.
Embodiment 1
Average grain diameter is 20 weight of aluminium powder of 1.5um, 5 weight of organic bond polyester based resin, organic valve metal
Close object tetraisopropyl titanate (CAS:546-68-9) 10 weight, 10 weight of 10 weight of solvent toluene and methyl ethyl ketone, by these
It mixes and is stirred 20 minutes with ball mill.By obtained coating material on the aluminium foil that 30um is thick, aluminium purity is 99.9%, apply
The final thickness of cloth film is 5um, dries 30 minutes in 120 DEG C of drying oven that later, turn over another side also same step process
Form coated film.
Later, after compressing the aluminium foil for forming coated film with idler wheel, the heat treatment of 1H is carried out in 450 DEG C of nitrogen.So
Afterwards the temperature setting of heat treatment to 630 DEG C, the heat treatment of 3 hours of progress in nitrogen environment.Subsequently, at 630 DEG C
The reductive heat treatment of 5 hours is carried out in hydrogen environment.The electrode structural body of reductive heat treatment has been carried out again in ammonium adipate 15
Positive oxidation processes are done in quality %, 85 DEG C of temperature of aqueous solution, lead to DC current, voltage liter with the current density of 25mA/cm2
Fix application 10 minutes after to 2V.
About the static capacity after test clean dry, sample making and test capacity and the method for epithelium pressure resistance can be by
Hold according to aluminum electrolytic capacitor electrode foil specified in Japan Electronics intelligence technology industry association (JEITA) standard EIAJ-2364A
Weight testing method is tested.
Comparative example 1
The aluminium foil of thick 40um aluminium purity 99.0wt% etchant solution (hydrochloric acid, 2wt% aluminium chloride containing 5wt%,
The phosphoric acid of 0.5wt%) in lead to the alternating current of 60Hz, the current density of 300mA/cm2 applies 4 minutes, corrosion temperature is 40 DEG C.
Corrosion is washed again, is dried later, carries out positive oxidation with the same condition of embodiment 1 again later.
Embodiment 2
Average particle is 40 weight of aluminium powder of 5um, 5 weight of organic bond polyester resin, organic valve metal compound
5 weight of isopropyl titanate (CAS:546-68-9), solvent are 10 weight of 10 weight of toluene and methyl ethyl ketone, and the above substance is mixed
Share ball grinding stirring 20 minutes.By obtained coating material on the aluminium foil that 30um is thick, purity is 99.9%, applied using coating machine
Final thickness is the film of 20um thickness out, after 30 minutes dry in 120 DEG C of drying ovens, reverse side is also carried out similarly to handle shape
At coated film.Later, such as embodiment 1, the same heat-agglomerating engineering of progress and reduction heating engineering.Then, 85 DEG C of temperature,
Energization current density is the DC current of 25mA/cm2 in the ammonium adipate aqueous solution of 15wt%, and voltage is raised to after 20V the holding that fixes
10 minutes.Test experiments that are the same manner as in Example 1 after washing and drying, doing sample making and capacity and epithelium pressure resistance.
Comparative example 2
70um thickness available on the market is not melted into etched foil and carries out positive oxidation, washing according to the experimental condition of embodiment 2
After drying as embodiment 1, do the test of sample making and capacity and epithelium pressure resistance.
By these results, epithelium pressure resistance, capacity this be counted as CV value, as shown in table 1.
Table 1
| Epithelium proof voltage (V) | Capacity (μ F) | CV value | |
| Embodiment 1 | 1.9 | 420 | 798 |
| Comparative example 1 | 2.1 | 140 | 294 |
| Embodiment 2 | 20.5 | 106 | 2173 |
| Comparative example 2 | 21.0 | 87 | 1827 |
It is higher than the CV value of comparative example to can be seen that embodiment 1,2 from this result.Therefore, whether it is used for alminium electrolytic condenser
The cathode or anode of device may all use.Offer is made that aluminium electrolutic capacitor is small-sized, electrode structural body of high capacity product.
A possibility that being utilized in industry
Manufacturing method according to the invention, as high capacity, electrode foil for aluminum electrolytic capacitors in use, can be made small
The product of type, high capacity.Because electrode foil is free of corrosion engineering thus, so not needing generate because of corrosion engineering yet
Drainage sunk well.Furthermore because the electrode foil in the present invention can be used as positive use, cathode use can also be used as, so using
Rate is high.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective
In the case where can make changes, modifications, alterations, and variations to the above described embodiments within the scope of the invention.
Claims (9)
1. a kind of preparation method of aluminium electrolutic capacitor electrode structural body, comprising:
It forms coating engineering: will be made of aluminium powder or Al metal alloy powder and organic valve metal compound and organic bond
Coating material on the surface of aluminium base, and be dried to form coating；
Heat-agglomerating engineering: and then heat the aluminium base for forming coating in vacuum environment or not active gases atmosphere；
Reduction heating engineering: and then again heat the aluminium base after heat-agglomerating engineering in reproducibility atmosphere；
Anode oxidation engineering: and then reduction is heated to the aluminium base anode oxidation after engineering again,
To obtain the electrode structural body.
2. aluminium electrolutic capacitor electrode structural body made from a kind of preparation method according to claim 1, comprising: aluminium base
With the coating for being coated with formation on aluminium base surface, which is characterized in that aluminium base is aluminium foil, the surface of the aluminium foil at least one
Part is to be sintered by aluminium base and aluminium powder or Al metal alloy powder by heat-agglomerating engineering.
3. electrode structural body as claimed in claim 2, it is characterised in that: also contain valve metal titanium in coating in addition to aluminium.
4. the electrode structural body as described in any one of claim 2-3, it is characterised in that: by there are also valve metals in addition to aluminum
What titanium was constituted.
5. electrode structural body as claimed in claim 2, it is characterised in that: temperature used in heat-agglomerating engineering is 450 DEG C
It~640 DEG C, is reacted in active gases in a vacuum or not.
6. electrode structural body as claimed in claim 2, it is characterised in that: restored after sintering engineering used in heating engineering
Temperature is 550 DEG C~640 DEG C, is reacted in hydrogen.
7. the electrode structural body as described in any one of claim 2,5 or 6, it is characterised in that: after reduction heating engineering
Also implement positive oxidation processes.
8. electrode structural body as claimed in claim 2, it is characterised in that: the average grain diameter of aluminium and Al alloy powder is 1um
~10um.
9. a kind of aluminium electrolutic capacitor, which is characterized in that the aluminium electrolutic capacitor includes any described by claim 2-8
Electrode structural body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710587393.4A CN107316745B (en) | 2017-07-18 | 2017-07-18 | Electrode structural body and aluminium electrolutic capacitor for aluminium electrolutic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710587393.4A CN107316745B (en) | 2017-07-18 | 2017-07-18 | Electrode structural body and aluminium electrolutic capacitor for aluminium electrolutic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107316745A CN107316745A (en) | 2017-11-03 |
| CN107316745B true CN107316745B (en) | 2019-05-07 |
Family
ID=60179161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710587393.4A Active CN107316745B (en) | 2017-07-18 | 2017-07-18 | Electrode structural body and aluminium electrolutic capacitor for aluminium electrolutic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107316745B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108666139A (en) * | 2018-03-30 | 2018-10-16 | 益阳艾华富贤电子有限公司 | Anode foils and aluminium electrolutic capacitor production method |
| CN113178335B (en) * | 2019-03-20 | 2023-01-06 | 安徽纳诺箔材有限公司 | High specific volume negative electrode foil and liquid aluminum electrolytic capacitor |
| CN109830374B (en) * | 2019-03-20 | 2021-04-20 | 安徽纳诺箔材有限公司 | Production process of negative electrode foil, negative electrode foil and polymer solid-state aluminum electrolytic capacitor |
| CN110648849B (en) * | 2019-09-26 | 2021-12-14 | 宇启材料科技南通有限公司 | Valve metal porous body coating electrode foil, manufacturing method and electrolytic capacitor |
| CN111364016B (en) * | 2020-04-10 | 2021-05-28 | 西安交通大学 | Method for preparing porous anode aluminum foil by aid of ALD (atomic layer deposition) assisted nitrogen-doped micro-nano aluminum powder |
| CN114551105B (en) * | 2020-11-25 | 2023-10-20 | 丰宾电子科技股份有限公司 | Manufacturing method of negative foil for aluminum electrolytic capacitor |
| CN113611537A (en) * | 2021-08-17 | 2021-11-05 | 深圳江浩电子有限公司 | Aluminum electrolytic capacitor and manufacturing method thereof |
| CN113745006B (en) * | 2021-08-17 | 2024-01-16 | 深圳江浩电子有限公司 | Organic powder mixed casting type aluminum electrode positive electrode manufacturing method |
| CN114267542B (en) * | 2021-12-31 | 2023-11-14 | 丰宾电子科技股份有限公司 | Method for manufacturing positive electrode structure of high-capacity aluminum electrolytic capacitor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102362324A (en) * | 2009-03-23 | 2012-02-22 | 东洋铝株式会社 | Electrode structure, capacitor, battery, and method for producing electrode structure |
| CN103688327A (en) * | 2011-07-15 | 2014-03-26 | 东洋铝株式会社 | Electrode material for aluminum electrolytic capacitor, and method for producing same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007055121A1 (en) * | 2005-11-10 | 2007-05-18 | Toyo Aluminium Kabushiki Kaisha | Electrode structure, capacitor and method for producing electrode structure |
-
2017
- 2017-07-18 CN CN201710587393.4A patent/CN107316745B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102362324A (en) * | 2009-03-23 | 2012-02-22 | 东洋铝株式会社 | Electrode structure, capacitor, battery, and method for producing electrode structure |
| CN103688327A (en) * | 2011-07-15 | 2014-03-26 | 东洋铝株式会社 | Electrode material for aluminum electrolytic capacitor, and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107316745A (en) | 2017-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107316745B (en) | Electrode structural body and aluminium electrolutic capacitor for aluminium electrolutic capacitor | |
| US5600535A (en) | Amorphous thin film electrode materials from hydrous metal oxides | |
| JP2007243202A (en) | Wet electrolytic capacitor having cathode film | |
| DE102007011358A1 (en) | Wet electrolytic capacitor | |
| KR101809189B1 (en) | Metal foil, metal foil manufacturing method and electrode manufacturing method using the same | |
| WO2010050558A1 (en) | Method for manufacturing capacitor element | |
| CN107354498B (en) | A kind of manufacturing method of the electrode foil for aluminum electrolytic capacitors of high pressure high capacity | |
| EP3090079B1 (en) | Composition and method for inhibiting corrosion of an anodized material | |
| TW201135770A (en) | Electrode material for aluminum electrolytic capacitor and production method therefor | |
| CN111364016B (en) | Method for preparing porous anode aluminum foil by aid of ALD (atomic layer deposition) assisted nitrogen-doped micro-nano aluminum powder | |
| WO2014034201A1 (en) | Method for manufacturing solid electrolytic capacitor, and solid electrolytic capacitor | |
| CN101425395B (en) | Manufacturing method for low-voltage high-dielectric formed foil of aluminum electrolysis capacitor | |
| CN114843108A (en) | Electrode foil and preparation method and application thereof | |
| CN101101817B (en) | Electrolytic capacitor pure aluminium cathode foil anode oxidation production method | |
| CN116288636B (en) | High-pressure-resistant ordered porous tantalum foil and preparation method and application thereof | |
| CN101578673B (en) | Capacitor material, method for manufacturing the capacitor material, capacitor containing the capacitor material, wiring board and electronic device | |
| CN114267542B (en) | Method for manufacturing positive electrode structure of high-capacity aluminum electrolytic capacitor | |
| CN112011814B (en) | Graphene heat dissipation film, and preparation method and application thereof | |
| CN112840422B (en) | Method for producing electrode material for aluminum electrolytic capacitor | |
| CN102113074B (en) | Method for manufacturing niobium solid electrolytic capacitor | |
| JP2011228129A (en) | Aluminum material for dye-sensitized solar cell electrode, and dye-sensitized solar cell | |
| JP3195871B2 (en) | Method for manufacturing solid electrolytic capacitor | |
| JPH1174158A (en) | Solid electrolyte forming paste composition, solid electrolytic capacitor provided therewith, and manufacture thereof | |
| CN114551105B (en) | Manufacturing method of negative foil for aluminum electrolytic capacitor | |
| Berndt et al. | Anodization of Aluminum in Highly Viscous Phosphoric Acid. PART 2: Investigation of Anodic Oxide Formation and Dissolution Rates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 518000 Tangwei Industrial Zone, Tangwei Village, Gongming Town, Guangming New District, Shenzhen City, Guangdong Province Patentee after: Fengbin Electronic Technology Co.,Ltd. Address before: 518000 Tangwei Industrial Zone, Tangwei Village, Gongming Town, Guangming New District, Shenzhen City, Guangdong Province Patentee before: CAPXON ELECTRONIC (SHEN ZHEN) Co.,Ltd. |