WO2013190756A1 - コンデンサの製造方法 - Google Patents
コンデンサの製造方法 Download PDFInfo
- Publication number
- WO2013190756A1 WO2013190756A1 PCT/JP2013/002406 JP2013002406W WO2013190756A1 WO 2013190756 A1 WO2013190756 A1 WO 2013190756A1 JP 2013002406 W JP2013002406 W JP 2013002406W WO 2013190756 A1 WO2013190756 A1 WO 2013190756A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- anode body
- tungsten
- anode
- voltage
- chemical conversion
- Prior art date
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 32
- 239000010937 tungsten Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 21
- 239000012670 alkaline solution Substances 0.000 claims description 20
- 238000010304 firing Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 44
- 239000010410 layer Substances 0.000 description 37
- 238000010438 heat treatment Methods 0.000 description 23
- 239000007788 liquid Substances 0.000 description 23
- 239000000843 powder Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910001080 W alloy Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- -1 tungsten halide Chemical class 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 102100030343 Antigen peptide transporter 2 Human genes 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 101800000849 Tachykinin-associated peptide 2 Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 229910021342 tungsten silicide Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
- H01G9/0029—Processes of manufacture
- H01G9/0032—Processes of manufacture formation of the dielectric layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- 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
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
-
- 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
- H01G9/07—Dielectric layers
-
- 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
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
- H01G9/0525—Powder therefor
-
- 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
- H01G9/15—Solid electrolytic capacitors
Definitions
- the present invention relates to a method for manufacturing a capacitor. More specifically, the present invention relates to a method of manufacturing a capacitor having a tungsten anode body that has a low leakage current under high voltage conditions and a small variation in leakage current value.
- an anode body made of a tantalum sintered body or a niobium sintered body is electrolytically oxidized in an aqueous solution of phosphoric acid, and the surface layer of the sintered body is formed into a dielectric made of a metal oxide.
- Tungsten is known as a kind of valve action metal.
- the object of the present invention is to effectively remove the natural oxide film of the tungsten anode body, and to control the formation of the natural oxide film of the anode body after the chemical conversion treatment so as to be constant inside and outside the pores. It is an object of the present invention to provide a method for reducing the leakage current in the capacitor and the variation in the leakage current between capacitors.
- [1] A step of applying a voltage to the tungsten anode body in an alkaline solution using the anode body as an anode (1), a step of forming the surface of the anode body treated in the step (1) into a dielectric layer (2), And the manufacturing method of a capacitor
- the tungsten anode body is a sintered body obtained by forming a tungsten powder to obtain a formed body and firing the formed body.
- Patent Documents 1 to 4 describe similar methods such as cathodic electrolytic cleaning and alkaline solution immersion before chemical conversion treatment of a tantalum sintered body or an aluminum foil.
- leakage currents under high voltage conditions as in the present invention are described. There is no effect of stabilization. The effect of the present invention is difficult to predict from the prior art.
- the method for manufacturing a capacitor according to an embodiment of the present invention includes a step (1) of applying a voltage to a tungsten anode body using the anode body as an anode in an alkaline liquid, and the surface of the anode body treated in the step (1). It includes a step (2) for forming a dielectric layer and a step (3) for heat-treating the anode body subjected to the treatment in step (2) at a temperature of 100 ° C. or higher and 260 ° C. or lower.
- the tungsten anode body for example, a sintered body obtained by molding a tungsten powder to obtain a molded body and firing the molded body can be used.
- the tungsten powder used in the present invention may be a single tungsten metal or a tungsten alloy, or may contain other impurities as long as the characteristics of the obtained capacitor are not significantly affected. Good.
- the tungsten powder is not particularly limited and may be a commercial product. Further, the tungsten powder may be manufactured as follows. For example, the tungsten powder adjusted to a desired particle diameter can be obtained by crushing tungsten trioxide powder in a hydrogen stream.
- tungsten powder adjusted to a desired particle diameter can be obtained by reducing tungstic acid or tungsten halide using a reducing agent such as hydrogen or sodium. Furthermore, tungsten powder can be obtained from a tungsten-containing mineral through a known process.
- the tungsten anode body used in the present invention preferably has an oxygen content of 8% by mass or less, more preferably 0.05 to 8% by mass, and 0.08 to 1% by mass. Is more preferable.
- the tungsten alloy include an alloy of tungsten and a valve action metal (such as tantalum, niobium, aluminum, titanium, vanadium, zinc, molybdenum, hafnium, and zirconium).
- the tungsten anode body may be one in which at least a part of the surface thereof is silicided, borated, phosphorylated and / or carbonized, or a mixture containing at least one of them. Further, tungsten and the mixture may contain nitrogen on at least a part of the surface thereof.
- Silicided tungsten can be obtained, for example, by mixing tungsten powder with silicon powder and heating it under reduced pressure (for example, 10 2 Pa or less, 1100 to 2600 ° C.) to cause a reaction.
- reduced pressure for example, 10 2 Pa or less, 1100 to 2600 ° C.
- tungsten silicide such as W 5 Si 3 is formed in the surface layer usually within 50 nm from the tungsten particle surface.
- the tungsten containing nitrogen can be obtained, for example, by placing tungsten powder at 350 to 1500 ° C. under reduced pressure and passing nitrogen gas for several minutes to several hours. You may perform the process which contains nitrogen at the time of the temperature fall after a high temperature process when silicifying tungsten powder.
- Carbonized tungsten can be obtained, for example, by placing tungsten powder in a carbon electrode furnace at 300 to 1500 ° C. under reduced pressure for several minutes to several hours. When nitrogen is passed in a carbon electrode furnace under predetermined conditions, nitrogen absorption occurs at the same time as carbonization, and a tungsten powder having a part of the surface containing nitrogen and carbonized can be obtained.
- Boronized tungsten can be obtained, for example, by mixing a boron source such as a simple substance of boron or a compound containing boron element with tungsten powder, and heating and reacting it under reduced pressure.
- Phosphorylated tungsten can be obtained, for example, by mixing phosphorus powder with a phosphorus source such as phosphorus alone or a compound containing phosphorus element, and heating the mixture under reduced pressure for reaction.
- Tungsten powder may contain metal powder other than tungsten.
- metals include tantalum, niobium, aluminum, titanium, vanadium, zinc, molybdenum, hafnium, and zirconium.
- Content of the tungsten element in tungsten powder becomes like this. Preferably it is 50 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.
- the tungsten powder has a volume average primary particle size of preferably 0.1 to 1 ⁇ m, more preferably 0.1 to 0.7 ⁇ m, and still more preferably 0.1 to 0.3 ⁇ m.
- the tungsten powder may be a granulated powder.
- the granulated powder can be produced by sintering and pulverizing ungranulated tungsten powder or the like. Further, the granulated powder may be produced by sintering and pulverizing the granulated powder once produced.
- the 50% particle diameter of the granulated powder is preferably 20 to 170 ⁇ m, more preferably 26 to 140 ⁇ m. The 50% particle size was determined from the volume-based cumulative particle size distribution by measuring the particle size distribution with a laser diffraction scattering method using HRA 9320-X100 manufactured by Microtrack.
- the method for forming the tungsten powder is not particularly limited. For example, it can be formed by pressing and solidifying tungsten powder.
- a binder may be mixed with the raw material powder.
- Various conditions such as the amount of powder and the molding apparatus can be appropriately set so as to obtain a desired molding density and the like.
- an anode lead wire is embedded in a molded body and planted to form a terminal of the anode body.
- a metal wire such as tungsten, tantalum, or niobium can be used.
- an anode lead wire is later welded to the sintered body.
- a metal plate or metal foil may be planted or connected to the sintered body instead of the metal wire.
- Firing can be performed by a known firing furnace.
- the temperature during firing is preferably 1300 to 1700 ° C., more preferably 1400 to 1600 ° C.
- the firing time is preferably 10 to 50 minutes, more preferably 15 to 30 minutes.
- the atmosphere during firing is not particularly limited, but is preferably reduced.
- the above-mentioned silicidation, boride, phosphide or carbonization, and / or the process of containing nitrogen can also be performed.
- a sintered body in a form suitable as an anode body contains one having a shape in which one granular material and another granular material are connected to each other in a bead shape.
- the granular material is derived from tungsten powder.
- the conductivity between the granular materials is ensured by the continuous connection of the granular materials.
- a voltage is applied to the anode body in an alkaline solution using the anode body as an anode.
- the anode body is immersed in an alkaline solution to a predetermined position, and the anode body is used as an anode, and a conductor (for example, a metal bathtub) disposed in the liquid is used as a cathode to conduct electricity.
- a conductor for example, a metal bathtub
- this voltage application the natural oxide film on the surface of the anode body is removed.
- this voltage application does not form a dielectric layer on the anode body. This is presumed from the fact that there is no phenomenon peculiar to chemical formation in which the current value decreases when energized at a constant voltage.
- the alkaline solution is an aqueous solution containing a basic compound, preferably an aqueous solution containing at least one selected from the group consisting of quaternary amines such as alkali metal hydroxides, ammonia and tetramethylammonium hydroxide.
- the basic compound content, voltage application time, applied voltage value, current density, solution temperature, etc. are sufficient for the mass and size of the anode body and sufficient for removal of the natural oxide film on the anode body. Can be set as appropriate.
- the amount of the basic compound contained in the alkaline liquid is preferably 0.1 to 10% by mass.
- the current per anode body that is, the current density (number basis) is preferably 0.1 to 20 mA / piece.
- the applied voltage is preferably 0.1 to 20V.
- the voltage application time is preferably 10 minutes to 20 hours.
- the temperature of the alkaline liquid is preferably not lower than the freezing point of the alkaline liquid and not higher than 30 ° C. Within this temperature range, the dissolution rate of the anode body with respect to the alkaline liquid is slow, and it is easy to control the removal of the natural oxide film by applying a voltage. In addition, when it is just immersed in an alkaline solution without applying voltage, the leakage current characteristic is not improved because it is difficult to remove the natural oxide film formed deep in the pores of the anode body (Comparative Example). 3 and 4). After voltage application in the alkaline solution, the alkaline solution is removed by washing with pure water or the like. Next, it is naturally dried or ventilated.
- the drying temperature is preferably room temperature, specifically 10 to 40 ° C.
- the anode body surface is formed into a dielectric layer (chemical conversion treatment).
- the tungsten oxide body tends to have a non-uniform natural oxide film, so the time interval from the end of drying to the start of chemical conversion treatment is managed within a specified range. It is preferable to do.
- the time interval changes, the dielectric layer characteristics tend to vary. If possible, it is more preferable to form the dielectric layer by performing chemical conversion promptly after completion of drying.
- the chemical conversion treatment for example, the anode body is immersed in a chemical conversion solution to a predetermined position and a voltage is applied to perform electrolytic oxidation.
- a solution containing an electrolyte such as nitric acid, sulfuric acid, phosphoric acid, oxalic acid, or adipic acid, and an oxygen supplier such as hydrogen peroxide or ozone as necessary, or a manganese (VII) compound examples thereof include a solution containing an oxidizing agent composed of an oxygen-containing compound such as a chromium (VI) compound, a halogen acid compound, a persulfuric acid compound, and an organic peroxide.
- a solution containing an oxidizing agent composed of an oxygen-containing compound is preferable from the viewpoint of reducing leakage current.
- the voltage application in the chemical conversion treatment starts at a predetermined initial current density, maintains the current density value, and maintains the voltage value after reaching a predetermined voltage (chemical conversion voltage).
- the formation voltage can be appropriately set according to a desired withstand voltage.
- the voltage application time can be appropriately set according to the size of the anode body and the initial current density, but is preferably 3 to 11 hours, more preferably 5 to 10 hours, and further preferably 5 to 7 hours.
- the temperature of a chemical conversion liquid can be suitably set according to the kind of chemical conversion liquid.
- the temperature is preferably not less than the freezing point of the solution and not more than 30 ° C., more preferably 0 to 20 ° C., still more preferably 5 to 20 ° C.
- the temperature is preferably 62 ° C. or lower, more preferably 0 to 60 ° C., and further preferably 45 to 60 ° C.
- the anode body is pulled up from the chemical conversion liquid and immediately washed with pure water.
- the chemical conversion solution is removed as much as possible by this water washing.
- water that has soaked into the anode body at a temperature lower than the boiling point of water is removed.
- the removal of water can be carried out, for example, by contact with a solvent miscible with water by drying under reduced pressure so as not to bump (that is, at a temperature below the boiling point of water under the pressure during drying). .
- Preferred examples of the solvent miscible with water include at least one selected from acetic acid, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane, propanol, ethanol, methanol, and tetrahydrofuran. If drying is performed at a temperature equal to or higher than the boiling point of water without removing water, the dielectric layer may deteriorate and the capacity in the high frequency region may be lowered.
- heat treatment is performed.
- the heat treatment is performed at 100 ° C. or higher, preferably 160 ° C. or higher.
- the upper limit of the temperature during the heat treatment is preferably 260 ° C.
- More preferable heat treatment is first performed at a temperature of 105 ° C. or higher and lower than 160 ° C., and then performed at a temperature of 160 ° C. or higher and 230 ° C. or lower.
- the capacitance of the capacitor increases. Note that if the temperature at the time of heat treatment is too low, the effect of increasing the capacity may not occur, and the capacity may vary between the capacitors. If the temperature during heat treatment is too high, the leakage current may increase or the dielectric loss tangent may increase.
- the heat treatment time is not particularly limited as long as the stability of the dielectric layer can be maintained, and is preferably 10 minutes to 4 hours, more preferably 20 minutes to 2 hours.
- the chemical conversion treatment may be performed again after the heat treatment.
- the re-chemical conversion treatment can be performed under the same conditions as the first chemical conversion treatment. After the re-chemical conversion treatment, pure water cleaning, water removal, and heat treatment can be performed in the same manner as described above.
- the converted anode body that has been returned to room temperature is immediately stored in a thermo-hygrostat set to predetermined conditions, or is put into the cathode preparation process within a predetermined time.
- a member When the formed anode body (hereinafter also referred to as a member) returned to room temperature is directly put into the cathode production process, it is desirable to make the time from returning the member to room temperature to entering the cathode production process constant.
- the member stored in the constant temperature and humidity chamber is put into the cathode production step, it is desirable to make the time from taking out the member from the constant temperature and humidity chamber to entering the cathode production step constant.
- a cathode is formed on the member obtained by the above method.
- a cathode used in a conventional electrolytic capacitor can be used without limitation.
- Examples of the cathode include an electrolytic solution and an inorganic or organic semiconductive layer.
- Examples of the electrolyte for the cathode include solutions of tertiary or quaternary amine salts and sulfuric acid.
- Examples of the inorganic semiconductive layer include a manganese dioxide layer.
- the organic semiconductor layer include a layer made of polypyrrole or a derivative thereof, a layer made of polythiophene or a derivative thereof (for example, a polymer of 3,4-ethylenedioxythiophene), a layer made of polyaniline or a derivative thereof, etc.
- a conductive polymer layer such as a carbon paste layer, a silver paste layer, or a metal plating layer may be formed on the organic or inorganic semiconductive layer.
- a cathode lead is electrically connected to the cathode, and a part of the cathode lead is exposed outside the exterior of the electrolytic capacitor and becomes a cathode external terminal.
- an anode lead is electrically connected to the anode body via an anode lead wire, and a part of the anode lead is exposed outside the exterior of the electrolytic capacitor and becomes an anode external terminal.
- a normal lead frame can be used to attach the cathode lead and the anode lead. Subsequently, the exterior can be formed by sealing with resin or the like to obtain a capacitor.
- the capacitor thus produced can be subjected to an aging process as desired.
- the capacitor according to the present invention can be used by being mounted on various electric circuits or electronic circuits.
- Example 1 [Production of anode body] A tungsten powder having a 50% particle diameter (D50) of 0.5 ⁇ m was mixed with 0.3% by mass of a silicon powder having a 50% particle diameter (D50) of 1 ⁇ m, and then allowed to stand for 30 minutes under a vacuum at 1450 ° C. After returning to room temperature, the lump was crushed with a hammer mill to prepare granulated powder having a 50% particle size (D50) of 105 ⁇ m (particle size distribution range: 26 to 145 ⁇ m). A part of silicon reacted with tungsten, and an alloy of tungsten silicide was present on the tungsten surface layer. A compact was produced from this granulated powder.
- a 0.29 mm ⁇ tungsten wire (lead wire) was planted.
- the compact is put in a vacuum firing furnace and fired at 1520 ° C. for 20 minutes, and a 1.0 mm ⁇ 1.5 mm ⁇ 4.5 mm sintered body (lead wire is planted on a 1.0 mm ⁇ 1.5 mm surface) Thousands were produced.
- These produced sintered bodies with lead wires were used as anode bodies.
- the mass of the anode body excluding the lead wire was 56 mg.
- a 0.1% by mass aqueous sodium hydroxide solution was prepared as an alkaline solution.
- the anode body was immersed in a predetermined position in an alkaline solution.
- a voltage was applied for 15 minutes under the conditions of room temperature, voltage of 2.5 V, and current density of 1 mA / piece.
- a platinum plate placed in an alkaline solution was used as the cathode.
- the anode body was pulled up from the alkaline solution and washed with pure water to remove the alkaline solution.
- the anode body was immersed in an alcohol solution to remove water. It pulled up from the alcohol liquid and dried by ventilation at room temperature. Subsequently, the following chemical conversion treatment was performed promptly.
- the above alkali treatment-chemical conversion treatment-water washing-water removal-heat treatment was performed on 32 anode bodies per batch. A total of 4 batches were performed.
- the anode body having the dielectric layer subjected to the above treatment was stored in a constant temperature and humidity chamber at 23 ° C. and 30 RH% for 30 minutes.
- the 32 anode bodies were taken out from the thermo-hygrostat and the leakage current was measured. It took 1280 seconds from the completion of the first measurement to the completion of the 32nd measurement.
- the leakage current was measured under conditions of room temperature, 7 V, and 30 seconds using a 30 mass% sulfuric acid aqueous solution as an anode body, a lead wire as an anode, and a platinum blackboard placed in the liquid as a cathode. Table 1 shows the measured range of the leakage current value of the 128 anode bodies.
- an electrolytic capacitor is configured in which tungsten (anode as a capacitor) and 30% by mass sulfuric acid aqueous solution (cathode as a capacitor) are arranged with a dielectric layer interposed therebetween.
- Example 2 The dielectric layer was formed in the same manner as in Example 1 except that the chemical conversion solution was changed to a 0.5% nitric acid aqueous solution, the temperature of the chemical conversion treatment was changed to 15 ° C., and the temperature and time of the heat treatment were changed to 160 ° C. and 90 minutes.
- a leakage current was measured by the same method as in Example 1. Table 1 shows the average and dispersion of the measured leakage current of 128 anode bodies.
- Example 3 [Production of anode body] Tungsten trioxide was reduced with hydrogen to produce tungsten powder with a 50% particle size (D50) of 0.7 ⁇ m. To this, 0.5% by mass of commercially available bismuth powder having a 50% particle size (D50) of 1 ⁇ m was added and mixed. The mixed powder was left under vacuum at 300 ° C. for 30 minutes. After returning to room temperature atmosphere, it was mixed again and left under vacuum at 1360 ° C. for 30 minutes. After returning to the room temperature atmosphere, the lump was crushed with a hammer mill and classified to prepare granulated powder having a 50% particle size (D50) of 105 ⁇ m (particle size distribution range: 26 to 130 ⁇ m).
- the granulated powder was mixed with 2% by mass or more of acrylic resin, and a molded body was prepared from the mixture using a TAP2 molding machine manufactured by Seiko.
- a tantalum wire (lead wire) of 0.29 mm ⁇ was planted.
- the compact is put into a vacuum firing furnace and fired at 1420 ° C. for 30 minutes, and a 1.0 mm ⁇ 1.5 mm ⁇ 4.5 mm sintered body (1.5 mm ⁇ 1.0 mm surface with 6 mm lead wire planted) ) was produced.
- These produced sintered bodies with lead wires were used as anode bodies.
- the mass of the anode body excluding the lead wire was 56 mg.
- a 0.1% by mass aqueous potassium hydroxide solution was prepared as an alkaline solution.
- the anode body was immersed in a predetermined position in an alkaline solution.
- a voltage was applied for 15 minutes under the conditions of 15 ° C., voltage 2.5 V, and current density 2 mA / piece.
- a platinum plate placed in an alkaline solution was used as the cathode.
- the anode body was pulled up from the alkaline solution and washed with pure water to remove the alkaline solution.
- the anode body was immersed in an alcohol solution to remove water. It pulled up from the alcohol liquid and dried by ventilation at room temperature. Subsequently, the following chemical conversion treatment was performed promptly.
- the above alkali treatment-chemical conversion treatment-water washing-water removal-heat treatment was performed on 32 anode bodies per batch. A total of 4 batches were performed.
- the leakage current was measured by the same method as in Example 1. Table 1 shows the average and dispersion of the measured leakage current of 128 anode bodies.
- Example 4 The dielectric layer was changed in the same manner as in Example 3 except that the chemical conversion solution was changed to 4% potassium persulfate aqueous solution, the liquid temperature during chemical conversion treatment was changed to 25 ° C., and the temperature and time of heat treatment were changed to 230 ° C. and 120 minutes.
- a leakage current was measured by the same method as in Example 1. Table 1 shows the average and dispersion of the measured leakage current of 128 anode bodies.
- Comparative Examples 1 and 2 An anode body having a dielectric layer was manufactured by the same method as in Example 1 and Example 3 except that the alkali treatment was not performed, and the leakage current was measured by the same method as in Example 1. Table 1 shows the average and dispersion of the measured leakage current of 128 anode bodies.
- Comparative Examples 3 and 4 An anode body having a dielectric layer was produced in the same manner as in Examples 1 and 3 except that no voltage was applied in the alkali treatment, and the leakage current was measured in the same manner as in Example 1. Table 1 shows the average and dispersion of the measured leakage current of 128 anode bodies.
- Example 5 An anode body having a dielectric layer was manufactured by the same method as in Example 3 except that the heat treatment was performed at 105 ° C. for 15 minutes, and the leakage current was measured by the same method as in Example 1. Table 1 shows the average and dispersion of the measured leakage current of 128 anode bodies.
- Comparative Example 5 An anode body having a dielectric layer was produced in the same manner as in Example 5 except that the alkali treatment was not performed, and the leakage current was measured in the same manner as in Example 1. Table 1 shows the average and dispersion of the measured leakage current of 128 anode bodies.
- a voltage is applied to the anode body in an alkaline solution, the anode body surface layer is formed into a dielectric, and the anode body whose surface is formed into a dielectric is 160 ° C. or higher.
- heat treatment is performed at a temperature of 260 ° C. or less, the leakage current is reduced and the variation is reduced.
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Abstract
Description
本発明の目的は、タングステン陽極体の自然酸化被膜を効果的に除去し、且つ化成処理後の陽極体の自然酸化被膜の形成を細孔内外で一定になるように管理して、高電圧条件での漏れ電流を少なくし且つコンデンサ間の漏れ電流のバラツキを少なくする方法を提供することである。
〔2〕 タングステン陽極体が、タングステン粉を成形して成形体を得、該成形体を焼成して得た焼結体である前記〔1〕に記載の製造方法。
〔3〕 工程(1)での電圧の印加が、陽極体1個あたりの電流0.1~20mAで行なわれる前記〔1〕または〔2〕に記載の製造方法。
〔4〕 工程(1)での電圧の印加が、電圧0.1~20Vで行なわれる前記〔1〕~〔3〕のいずれかひとつに記載の製造方法。
〔5〕 アルカリ液が、アルカリ金属水酸化物、アンモニア及び4級アミンからなる群から選ばれる少なくともひとつを含有する水溶液である〔1〕~〔4〕のいずれかひとつに記載の製造方法。
〔6〕 工程(2)の後、工程(3)の前に、陽極体から水を除去する〔1〕~〔5〕のいずれかひとつに記載の製造方法。
特許文献1~4にはタンタル焼結体またはアルミニウム箔を化成処理前に陰極電解洗浄やアルカリ液浸漬するなどの類似方法が記載されているが、本発明のような高電圧条件における漏れ電流の安定化という効果を奏しない。本発明の効果は従来技術からは予測困難なものである。
本発明に使用されるタングステン粉は、タングステン金属単体であってもよいし、タングステン合金であってもよいし、得られるコンデンサの特性に大きく悪影響を及ぼさない範囲でその他の不純物を含んでいてもよい。タングステン粉は、特に制限されず、市販品であってもよい。また、タングステン粉は、次のようにして製造したものであってもよい。例えば、三酸化タングステン粉を水素気流中で解砕することによって、所望の粒子径に調整されたタングステン粉を得ることができる。また、タングステン酸やハロゲン化タングステンを水素やナトリウム等の還元剤を使用して還元することによって、所望の粒子径に調整されたタングステン粉を得ることができる。さらに、タングステン含有鉱物から公知の工程を経てタングステン粉を得ることができる。
本発明に使用されるタングステン陽極体は、酸素含有量が、8質量%以下であることが好ましく、0.05~8質量%であることがより好ましく、0.08~1質量%であることがさらに好ましい。タングステン合金としては、例えば、タングステンと弁作用金属(タンタル、ニオブ、アルミニウム、チタン、バナジウム、亜鉛、モリブデン、ハフニウム、ジルコニウムなど)との合金が挙げられる。
窒素を含有するタングステンは、例えば、タングステン粉を減圧下に350~1500℃に置き、窒素ガスを数分間から数時間通じることによって得ることができる。窒素を含有させる処理は、タングステン粉をケイ化するときの高温処理後の温度降下時に行ってもよい。
ホウ化されたタングステンは、例えば、タングステン粉にホウ素単体やホウ素元素を有する化合物などのホウ素源を混ぜ合わせ、それを減圧下で加熱して反応させることにより得ることができる。
リン化されたタングステンは、例えば、タングステン粉にリン単体やリン元素を有する化合物などのリン源を混ぜ合わせ、それを減圧下で加熱して反応させることにより得ることができる。
なお、電圧印加を行わずアルカリ液に漬けただけの場合には、陽極体の細孔深くに形成された自然酸化被膜を除去することが困難であるためか漏れ電流特性は改善されない(比較例3および4)。
アルカリ液中における電圧印加の後、純水等で洗浄しアルカリ液を除去する。次いで、自然乾燥または通風乾燥させる。該乾燥時の温度は、室温、具体的には10~40℃であることが好ましい。
化成処理では、例えば、陽極体を化成液に所定位置まで浸漬して電圧を印加して電解酸化を行う。電圧は、陽極体を陽極とし、対電極を陰極とし、これら両極間に印加する。陽極体への通電は植立させた陽極リード線を通じて行うことができる。化成液としては、硝酸、硫酸、リン酸、シュウ酸、アジピン酸などの電解質と、必要に応じて過酸化水素やオゾンなどの酸素供給剤とを含有する溶液、または、マンガン(VII)化合物、クロム(VI)化合物、ハロゲン酸化合物、過硫酸化合物、有機過酸化物などの含酸素化合物からなる酸化剤を含有する溶液が挙げられる。本発明に用いる化成液としては含酸素化合物からなる酸化剤を含有する溶液が漏れ電流を減らすという観点から好ましい。
電圧印加時間は、陽極体の大きさや初期電流密度に応じて適宜設定できるが、好ましくは3~11時間、より好ましくは5~10時間、さらに好ましくは5~7時間である。
化成液の温度は、化成液の種類に応じて適宜設定できる。例えば、電解質を含有する溶液の場合は、好ましくは該溶液の凝固点以上30℃以下、より好ましくは0~20℃、さらに好ましくは5~20℃である。含酸素化合物からなる酸化剤を含有する溶液の場合は、好ましくは62℃以下、より好ましくは0~60℃、さらに好ましくは45~60℃である。
この化成処理によって陽極体表面のタングステンが酸化されて、タングステン酸化物を含有してなる誘電体層が生成する。誘電体層は、化成電圧を調節することによって所望の厚さに調整することができる。
水との混和性を有する溶剤としては、酢酸、アセトン、アセトニトリル、ジメチルホルムアミド、ジメチルスルフォキシド、ジオキサン、プロパノール、エタノール、メタノール、およびテトラヒドロフランから選ばれる少なくとも一つが好ましいものとして挙げられる。水の除去を行わずに水の沸点以上の温度で乾燥させると誘電体層が劣化して高周波域での容量が低くなることがある。
熱処理の時間は、誘電体層の安定性が維持できる範囲であれば特に制限されず、好ましくは10分間~4時間、より好ましくは20分間~2時間である。熱処理の後に、化成処理を再度行ってもよい。再化成処理は、1回目の化成処理と同じ条件にて行うことができる。再化成処理の後は、上記と同様に、純水洗浄、水除去および熱処理を行うことができる。
〔陽極体の作製〕
50%粒子径(D50)0.5μmのタングステン粉に50%粒子径(D50)1μmの珪素粉を0.3質量%混合し、その後、1450℃の真空下に30分間放置した。室温に戻し、塊状物をハンマーミルで解砕して50%粒子径(D50)105μm(粒度分布範囲26~145μm)の造粒粉を作製した。珪素の一部はタングステンと反応し珪化タングステンの合金がタングステン表層に存在した。
この造粒粉から成形体を作製した。成形の際に0.29mmφのタングステン線(リード線)を植立した。成形体を真空焼成炉に入れ、1520℃にて20分間焼成して、1.0mm×1.5mm×4.5mmの焼結体(1.0mm×1.5mm面にリード線が植立)を千個作製した。これら作製したリード線付きの焼結体を陽極体とした。リード線を除いた陽極体の質量は56mgであった。
0.1質量%の水酸化ナトリウム水溶液をアルカリ液として用意した。陽極体をアルカリ液に所定位置まで浸漬した。陽極体を陽極として、室温、電圧2.5V、電流密度1mA/個の条件で15分間電圧を印加した。陰極としてアルカリ液中に配置した白金板を用いた。その後、アルカリ液から陽極体を引き上げ、純水で洗浄してアルカリ液を除去した。次いで、アルコール液に陽極体を浸漬して水を除去した。アルコール液から引き上げ常温にて通風乾燥させた。引き続いて速やかに以下のとおりの化成処理を行った。
i)化成処理
0.1質量%硝酸水溶液を化成液として用意した。化成液をステンレス製容器に入れた。陽極体を化成液に所定位置まで浸漬した。リード線を電源の正極に、容器を電源の負極にそれぞれ電気的に接続し、化成液の液温15℃で、初期電流密度1mA/個にて電圧印加を開始し、該電流密度値を維持し、10Vに達した時から電圧10Vに5時間維持した。
ii)水洗浄-水除去-熱処理
次いで、純水で洗浄して陽極体細孔中の化成液を除去した。その後エタノールに漬けて攪拌することにより細孔内などに付着した水のほとんどを除去した。エタノールから引き上げ、常温にて通風乾燥させた。次いで190℃にて60分間熱処理した。表面に誘電体層を有する陽極体が得られた。
漏れ電流は、陽極体を30質量%硫酸水溶液中にて、リード線を陽極に、液中に配置した白金黒板を陰極として、室温、7Vおよび30秒間の条件で測定した。該陽極体128個の漏れ電流値の測定された範囲を表1に示す。なお、この漏れ電流測定時においては、タングステン(コンデンサとしての陽極)と30質量%硫酸水溶液(コンデンサとしての陰極)とが誘電体層を挟んで配置された電解コンデンサが構成されている。
化成液を0.5%硝酸水溶液に変え、化成処理時の液温を15℃に変え、熱処理の温度および時間を160℃および90分間に変えた以外は実施例1と同じ手法で誘電体層を有する陽極体を製造し、実施例1と同じ方法で漏れ電流を測定した。該陽極体128個の漏れ電流測定値の平均及びばらつきを表1に示す。
〔陽極体の作製〕
三酸化タングステンを水素還元して50%粒子径(D50)0.7μmタングステン粉を製造した。これに市販の50%粒子径(D50)1μmのビスマス粉を0.5質量%加えて混合した。混合粉を300℃の真空下に30分間放置した。室温大気下に戻した後、再度混合し、1360℃の真空下に30分間放置した。室温大気下に戻した後に、塊状物をハンマーミルで解砕し、分級して50%粒子径(D50)105μm(粒度分布範囲26~130μm)の造粒粉を作製した。
造粒粉にアクリル樹脂2質量%以上を混合し、該混合物から精研製TAP2成形機を用いて成形体を作製した。成形の際に、0.29mmφのタンタル線(リード線)を植立した。成形体を真空焼成炉に入れ、1420℃にて30分間焼成して、1.0mm×1.5mm×4.5mmの焼結体(1.5mm×1.0mm面にリード線が6mm植立)を千個作製した。これら作製したリード線付きの焼結体を陽極体とした。リード線を除いた陽極体の質量は56mgであった。
0.1質量%の水酸化カリウム水溶液をアルカリ液として用意した。陽極体をアルカリ液に所定位置まで浸漬した。陽極体を陽極として、15℃、電圧2.5V、電流密度2mA/個の条件で15分間電圧を印加した。陰極としてアルカリ液中に配置した白金板を用いた。その後、アルカリ液から陽極体を引き上げ、純水で洗浄してアルカリ液を除去した。次いで、アルコール液に陽極体を浸漬して水を除去した。アルコール液から引き上げ常温にて通風乾燥させた。引き続いて速やかに以下のとおりの化成処理を行った。
i)化成処理
2質量%過硫酸アンモニウム水溶液を化成液として用意した。化成液をステンレス製容器に入れた。陽極体を化成液に所定位置まで浸漬した。リード線を電源の正極に、容器を電源の負極にそれぞれ電気的に接続し、化成液の液温45℃で、初期電流密度1mA/個にて電圧印加を開始し、該電流密度値を維持し、20Vに達した時から電圧20Vに7時間維持した。
ii)水洗浄-水除去-熱処理
次いで、純水で洗浄して陽極体細孔中の化成液を除去した。その後エタノールに漬けて攪拌することにより水のほとんどを除去した。エタノールから引き上げ、常温にて通風乾燥させた。次いで260℃にて30分間熱処理した。表面に誘電体層を有する陽極体が得られた。
実施例1と同じ方法で漏れ電流を測定した。該陽極体128個の漏れ電流測定値の平均及びばらつきを表1に示す。
化成液を4%過硫酸カリウム水溶液に変え、化成処理時の液温を25℃に変え、熱処理の温度および時間を230℃および120分間に変えた以外は実施例3と同じ手法で誘電体層を有する陽極体を製造し、実施例1と同じ方法で漏れ電流を測定した。該陽極体128個の漏れ電流測定値の平均及びばらつきを表1に示す。
アルカリ処理を行わなかった以外は実施例1及び実施例3と同じ手法で誘電体層を有する陽極体を製造し、実施例1と同じ方法で漏れ電流を測定した。該陽極体128個の漏れ電流測定値の平均及びばらつきを表1に示す。
アルカリ処理において電圧を印加しなかった以外は実施例1及び実施例3と同じ手法で誘電体層を有する陽極体を製造し、実施例1と同じ方法で漏れ電流を測定した。該陽極体128個の漏れ電流測定値の平均及びばらつきを表1に示す。
熱処理を105℃にて15分間行なった以外は実施例3と同じ手法で誘電体層を有する陽極体を製造し、実施例1と同じ方法で漏れ電流を測定した。該陽極体128個の漏れ電流測定値の平均及びばらつきを表1に示す。
アルカリ処理を行わなかった以外は実施例5と同じ手法で誘電体層を有する陽極体を製造し、実施例1と同じ方法で漏れ電流を測定した。該陽極体128個の漏れ電流測定値の平均及びばらつきを表1に示す。
Claims (6)
- タングステン陽極体にアルカリ液中で該陽極体を陽極として電圧を印加する工程(1)、
工程(1)の処理をした陽極体の表面を誘電体層に化成する工程(2)、および
工程(2)の処理をした陽極体を100℃以上260℃以下の温度で熱処理する工程(3)
を含むコンデンサの製造方法。 - タングステン陽極体が、タングステン粉を成形して成形体を得、該成形体を焼成して得た焼結体である請求項1に記載の製造方法。
- 工程(1)での電圧の印加が、陽極体1個あたりの電流0.1~20mAで行なわれる請求項1または2に記載の製造方法。
- 工程(1)での電圧の印加が、電圧0.1~20Vで行なわれる請求項1~3のいずれかひとつに記載の製造方法。
- アルカリ液が、アルカリ金属水酸化物、アンモニア及び4級アミンからなる群から選ばれる少なくともひとつを含有する水溶液である請求項1~4のいずれかひとつに記載の製造方法。
- 工程(2)の後、工程(3)の前に、陽極体から水を除去する請求項1~5のいずれかひとつに記載の製造方法。
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EP13807191.5A EP2866238B1 (en) | 2012-06-22 | 2013-04-09 | Capacitor production method |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5798279B1 (ja) * | 2014-05-01 | 2015-10-21 | 昭和電工株式会社 | タングステン系コンデンサ素子の製造方法 |
WO2015166670A1 (ja) * | 2014-05-01 | 2015-11-05 | 昭和電工株式会社 | タングステン系コンデンサ素子の製造方法 |
WO2020175358A1 (ja) * | 2019-02-28 | 2020-09-03 | パナソニックIpマネジメント株式会社 | 電解コンデンサ用電極箔、電解コンデンサおよびその製造方法 |
Families Citing this family (1)
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TWI577824B (zh) * | 2013-06-06 | 2017-04-11 | 應用材料股份有限公司 | 使用二氮丁二烯基前驅物沉積含錳膜之方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1079326A (ja) * | 1996-09-03 | 1998-03-24 | Matsushita Electric Ind Co Ltd | コンデンサおよびその製造方法 |
JPH10106896A (ja) | 1996-09-27 | 1998-04-24 | Matsushita Electric Ind Co Ltd | アルミ電解コンデンサ用電極箔の製造方法 |
JPH11150041A (ja) * | 1997-11-19 | 1999-06-02 | Hitachi Aic Inc | 固体電解コンデンサの製造方法 |
JP2005191421A (ja) * | 2003-12-26 | 2005-07-14 | Tdk Corp | 電解コンデンサの製造方法 |
JP2006108395A (ja) | 2004-10-06 | 2006-04-20 | Nichicon Corp | アルミニウム電解コンデンサ用電極箔の製造方法 |
JP2007123569A (ja) | 2005-10-28 | 2007-05-17 | Nichicon Corp | 電解コンデンサ用アルミニウム電極箔の製造方法およびその製造装置 |
JP2009064846A (ja) * | 2007-09-05 | 2009-03-26 | Nec Tokin Corp | 固体電解コンデンサの製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3332859A (en) * | 1963-12-27 | 1967-07-25 | Gen Electric | Process for producing tantalum foil for capacitors |
EP0714108B1 (en) * | 1994-11-25 | 1999-11-03 | Nec Corporation | Solid electrolytic capacitor having two solid electrolyte layers and method of manufacturing the same |
JP3695618B2 (ja) * | 1997-10-20 | 2005-09-14 | 富士写真フイルム株式会社 | 平版印刷版用アルミニウム支持体の製造方法 |
JP2001196274A (ja) | 2000-01-12 | 2001-07-19 | Nec Corp | 固体電解コンデンサ用陽極体の製造方法 |
JP2003272959A (ja) | 2002-03-15 | 2003-09-26 | Sanyo Electric Co Ltd | コンデンサ |
US7768773B2 (en) * | 2008-01-22 | 2010-08-03 | Avx Corporation | Sintered anode pellet etched with an organic acid for use in an electrolytic capacitor |
JPWO2011013375A1 (ja) * | 2009-07-29 | 2013-01-07 | 昭和電工株式会社 | 固体電解コンデンサの製造方法 |
JP5370188B2 (ja) * | 2010-02-04 | 2013-12-18 | 株式会社村田製作所 | 陽極酸化膜の製造方法 |
-
2013
- 2013-04-09 WO PCT/JP2013/002406 patent/WO2013190756A1/ja active Application Filing
- 2013-04-09 JP JP2014520876A patent/JP6063937B2/ja not_active Expired - Fee Related
- 2013-04-09 EP EP13807191.5A patent/EP2866238B1/en not_active Not-in-force
- 2013-04-09 US US14/409,906 patent/US9607770B2/en not_active Expired - Fee Related
-
2016
- 2016-03-15 JP JP2016050475A patent/JP6101840B2/ja not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1079326A (ja) * | 1996-09-03 | 1998-03-24 | Matsushita Electric Ind Co Ltd | コンデンサおよびその製造方法 |
JPH10106896A (ja) | 1996-09-27 | 1998-04-24 | Matsushita Electric Ind Co Ltd | アルミ電解コンデンサ用電極箔の製造方法 |
JPH11150041A (ja) * | 1997-11-19 | 1999-06-02 | Hitachi Aic Inc | 固体電解コンデンサの製造方法 |
JP2005191421A (ja) * | 2003-12-26 | 2005-07-14 | Tdk Corp | 電解コンデンサの製造方法 |
JP2006108395A (ja) | 2004-10-06 | 2006-04-20 | Nichicon Corp | アルミニウム電解コンデンサ用電極箔の製造方法 |
JP2007123569A (ja) | 2005-10-28 | 2007-05-17 | Nichicon Corp | 電解コンデンサ用アルミニウム電極箔の製造方法およびその製造装置 |
JP2009064846A (ja) * | 2007-09-05 | 2009-03-26 | Nec Tokin Corp | 固体電解コンデンサの製造方法 |
JP4863509B2 (ja) | 2007-09-05 | 2012-01-25 | Necトーキン株式会社 | 固体電解コンデンサの製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2866238A4 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5798279B1 (ja) * | 2014-05-01 | 2015-10-21 | 昭和電工株式会社 | タングステン系コンデンサ素子の製造方法 |
WO2015166670A1 (ja) * | 2014-05-01 | 2015-11-05 | 昭和電工株式会社 | タングステン系コンデンサ素子の製造方法 |
CN106463266A (zh) * | 2014-05-01 | 2017-02-22 | 昭和电工株式会社 | 钨系电容器元件的制造方法 |
US9704652B2 (en) | 2014-05-01 | 2017-07-11 | Showa Denko K.K. | Method for manufacturing tungsten-based capacitor element |
EP3139393A4 (en) * | 2014-05-01 | 2018-02-21 | Showa Denko K.K. | Method for manufacturing tungsten-based capacitor element |
WO2020175358A1 (ja) * | 2019-02-28 | 2020-09-03 | パナソニックIpマネジメント株式会社 | 電解コンデンサ用電極箔、電解コンデンサおよびその製造方法 |
CN113490768A (zh) * | 2019-02-28 | 2021-10-08 | 松下知识产权经营株式会社 | 电解电容器用电极箔、电解电容器及其制造方法 |
JP7445875B2 (ja) | 2019-02-28 | 2024-03-08 | パナソニックIpマネジメント株式会社 | 電解コンデンサ用電極箔、電解コンデンサおよびその製造方法 |
CN113490768B (zh) * | 2019-02-28 | 2024-04-30 | 松下知识产权经营株式会社 | 电解电容器用电极箔、电解电容器及其制造方法 |
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EP2866238A4 (en) | 2016-03-02 |
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US9607770B2 (en) | 2017-03-28 |
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JP6063937B2 (ja) | 2017-01-18 |
US20150340158A1 (en) | 2015-11-26 |
JP6101840B2 (ja) | 2017-03-22 |
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