WO2014091810A1 - タングステン陽極体の製造方法 - Google Patents
タングステン陽極体の製造方法 Download PDFInfo
- Publication number
- WO2014091810A1 WO2014091810A1 PCT/JP2013/076239 JP2013076239W WO2014091810A1 WO 2014091810 A1 WO2014091810 A1 WO 2014091810A1 JP 2013076239 W JP2013076239 W JP 2013076239W WO 2014091810 A1 WO2014091810 A1 WO 2014091810A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tungsten
- powder
- silicon compound
- compound solution
- anode body
- Prior art date
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 229910052721 tungsten Inorganic materials 0.000 title claims description 37
- 239000010937 tungsten Substances 0.000 title claims description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003990 capacitor Substances 0.000 claims abstract description 42
- 239000010703 silicon Substances 0.000 claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 92
- 150000003377 silicon compounds Chemical class 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 claims description 11
- 229910021342 tungsten silicide Inorganic materials 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 8
- -1 silane compound Chemical class 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- 239000002245 particle Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 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
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000005469 ethylenyl group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
- H01G9/0525—Powder therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0078—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only silicides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- 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 tungsten anode body. More specifically, a method for efficiently producing a tungsten anode body containing tungsten silicide on at least a part of the surface, suitable for producing an electrolytic capacitor using a sintered body of tungsten powder as the anode body, It is related with the manufacturing method of the used capacitor
- an electrolytic capacitor As an electrolytic capacitor, an electrolytic capacitor has been proposed in which an anode body of a capacitor made of a sintered body of valve action metal powder such as tantalum that can be anodized is used as an anode.
- Electrolytic capacitors that use tungsten as the valve metal and have a sintered body of tungsten powder as the anode body have the same volume of anode body using tantalum powder of the same particle size, compared to electrolytic capacitors that can be obtained with the same conversion voltage.
- the leakage current (LC) is large and it has not been put to practical use as an electrolytic capacitor.
- a capacitor using an alloy of tungsten and another metal has been studied.
- the leakage current is somewhat improved, it is not sufficient (Japanese Patent Laid-Open No. 2004-349658; Patent Reference 1).
- Patent Document 2 Japanese Patent Laid-Open No. 2003-272959 discloses a capacitor using a tungsten foil electrode on which a dielectric layer selected from WO 3 , W 2 N, and WN 2 is formed. This is not a solution for the leakage current.
- Patent Document 3 International Publication No. 2004/055843 pamphlet: US Pat. No. 7,154,743 discloses an electrolytic capacitor using an anode selected from tantalum, niobium, titanium, and tungsten. There is no description of the specific examples used.
- the present inventors first mixed tungsten powder with silicon powder under reduced pressure as tungsten powder that can solve the problem of leakage current (LC) in an electrolytic capacitor having a sintered body of tungsten powder as an anode body.
- Tungsten powder in which part of the surface is tungsten silicide so that the silicon content is in a specific range (0.05 to 7% by mass) by heating and reacting, and an anode body of a capacitor formed by sintering the powder
- an electrolytic capacitor using the anode body as an electrode has been applied for a patent (International Publication No. 2012/086272 Pamphlet; Patent Document 4).
- An object of the present invention is to provide a method for producing a tungsten anode body capable of producing an electrolytic capacitor having a performance superior to that of the tungsten powder according to Patent Document 4 in which a part of the surface is tungsten silicide.
- the inventors of the present invention compared the tungsten powder obtained by the method of Patent Document 4 with a method having a step of bringing at least one of the tungsten powder and the molded body into contact with the silicon compound solution before sintering the molded body.
- the present inventors have found that tungsten powder in which tungsten silicide is uniformly dispersed is obtained, and that the performance of the tungsten anode body obtained by sintering the powder can be improved to solve the above problems.
- the present invention relates to the following [1] to [11] anode body manufacturing method, [12] capacitor manufacturing method, and [13] to [16] tungsten granulated powder manufacturing method.
- a method for producing an anode body comprising a step of bringing tungsten powder or the molded body into contact with a silicon compound solution before sintering the molded body so as to be 0.05 to 7% by mass.
- the tungsten powder separated from the solution is fired and pulverized to form a granulated powder, and the granulated powder is formed into a molded body.
- the manufacturing method of the anode body in any one of.
- the silicon compound is a compound that decomposes at a temperature lower than a sintering temperature and at least a part of the decomposition product reacts with tungsten to form tungsten silicide.
- Manufacturing method [9] The method for producing an anode body according to any one of items 1 to 8, wherein the silicon compound is a silane compound.
- a method for producing a tungsten granulated powder comprising a step of bringing a raw material tungsten powder into contact with a silicon compound solution, and a step of firing the raw material tungsten powder treated with the silicon compound solution and then crushing it.
- the method for producing tungsten granulated powder according to item 13 wherein the raw material tungsten powder is brought into contact with the silicon compound solution so that the silicon content in the granulated powder is 0.05 to 7% by mass.
- the capacity is equivalent to or better than that of the conventional tungsten sintered body, and the LC characteristics per capacity are good.
- a capacitor can be manufactured.
- a tungsten powder (unprocessed tungsten powder) that is a raw material of a tungsten powder compact is commercially available with a lower limit of the average particle size of up to about 0.5 ⁇ m. If the volume is the same, the smaller the particle size of the tungsten powder, the larger the capacity of the sintered body (anode body) can be produced, but the tungsten powder having a smaller particle size than the commercially available product is, for example, tungsten trioxide powder.
- Is pulverized in a hydrogen atmosphere, or tungstic acid or tungsten halide is obtained by using a reducing agent such as hydrogen or sodium and appropriately selecting the reducing conditions. It can also be obtained directly from the tungsten-containing mineral or by obtaining a plurality of steps and selecting reducing conditions.
- the surface of currently available tungsten powder is oxidized with an oxidizing agent (for example, hydrogen peroxide or ammonium persulfate) to form an oxide film, and the oxide film is removed with an alkaline aqueous solution.
- an oxidizing agent for example, hydrogen peroxide or ammonium persulfate
- it can be manufactured by a method or the like.
- the method for producing a tungsten anode body of the present invention includes a step in which at least one of the tungsten powder and the molded body comes into contact with the silicon compound solution before sintering.
- the tungsten powder treated with the silicon compound solution is fired under reduced pressure and then crushed.
- the silicon compound used in the present invention is soluble in organic solvents such as alcohols, esters and ethers, decomposes below the sintering temperature of tungsten powder, and at least partially reacts with tungsten to form tungsten silicide. It is preferable to use a silicon compound.
- a silane compound is preferable as the silicon compound.
- the silane compound those having a hydrolyzable group are preferable.
- Examples of such silicon compounds include silane compounds represented by the following formulas (1) to (4).
- R 1 to R 7 are each independently a hydrogen atom, an alkyl group having 6 or less carbon atoms, a mercapto group, a cyano group, an amino group, a hydroxy group, an ester, a halogen atom, An alkyl group having 6 or less carbon atoms, a phenyl group, an ethylenyl group, or an acyl group substituted with at least one of alkene, alkyne, and cycloalkane. An alkyl group having 6 or less carbon atoms and a phenyl group are preferable.
- Such compounds include the following. 1) (CH 3 ) 2 Si (OCH 3 ) 2 , ⁇ 2 Si (OCH 3 ) 2 ( ⁇ represents a phenyl group, the same applies hereinafter), (CH 3 ) 2 Si (OC 2 H 5 ) 2 , ⁇ 2 Si (OC 2 H 5 ) 2 , 2) (CH 3 ) 2 Si (OAc) 2 (Ac represents an acetyl group; hereinafter the same), and a polymer such as a silicone resin which is a single or two or more cocondensates of these compounds, 3) (CH 3 ) Si (OCH 3 ) 3 , ⁇ Si (OCH 3 ) 3 , (CH 3 ) Si (OC 2 H 5 ) 3 , ⁇ Si (OC 2 H 5 ) 3 , (CH 3 ) Si (OAc) 3 , Cl (CH 2 ) 3 Si (OCH 3 ) 3 , (OCH 3 ) 3 , HS (CH 2 ) 3 Si (CH 2
- Such a compound may be used in that state in the case of a liquid, but the amount of such a compound used is small compared to tungsten powder, as will be described later, so that dispersibility with tungsten powder is considered.
- Dissolve in alcohols such as methanol, ethanol, normal propyl alcohol and isopropanol, and esters such as butyl acetate, propyl acetate and ⁇ -butyl lactone, and ethers such as methyl ethyl ether, diethyl ether and furan. It is preferable to use it for contact with tungsten powder.
- the silicon content in the anode body to be produced is 0.05 to 7% by mass, preferably 0.1 to 5% by mass, more preferably 0.2 to 5% by mass.
- the powder may not be a powder that gives an electrolytic capacitor with good leakage current (LC) performance. If it exceeds 7% by mass, there are too many siliconized portions of the tungsten powder, and when the tungsten powder is molded to produce an anode body of an electrolytic capacitor, the dielectric layer may not be formed properly, which is not preferable.
- the silicon content in the anode body can be adjusted by a preliminary experiment, for example.
- the concentration of the silicon compound in the solution may be increased, or the amount of tungsten powder in the solution may be decreased.
- the operation reverse to that described above may be performed.
- the silicon content in an anode body can also be adjusted on the basis of silicon content in the tungsten material before sintering. For example, you may adjust similarly so that the silicon content in the granulated powder mentioned later may become the said range.
- the tungsten powder is put into the silicon compound solution and then filtered, or the silicon compound solution is applied to the tungsten powder and the tungsten powder and the silicon compound solution are mixed and then fired.
- the solvent may be removed in advance with a vacuum drying device before firing, or may be removed by evaporating or raising the temperature to the firing temperature while omitting the prior removal step.
- the temperature is returned to room temperature, and the lump is taken out and crushed to obtain silicon-containing tungsten granulated powder.
- fine powder and large particle size powder may be classified and removed to adjust to a particle size range suitable for the anode material (described later). The removed powder can be reused by firing together with other powders or independently.
- At least a part of silicon is combined with the surface layer of the sintered body to form tungsten silicide in the firing step.
- the raw material tungsten powder to be treated with the silicon compound solution in addition to the powder of tungsten alone, a powder containing nitrogen in a part of the surface of the tungsten powder, and further, carbonization, boriding, phosphation, oxidation of the tungsten powder
- one or more powders selected from tungsten powder containing at least one of nitrogen, carbon, boron, phosphorus, and oxygen in a part of the surface can be arbitrarily selected and used.
- tungsten powder As an example of a method of incorporating nitrogen into a part of the surface of tungsten powder, there is a method in which tungsten powder is placed at a temperature of 350 to 1500 ° C. under reduced pressure and nitrogen gas (usually 10 3 Pa or less) is passed for several minutes to several hours when the temperature is lowered .
- the amount of nitrogen contained in the tungsten powder is 0.5% by mass or less, and the nitrogen content in the capacitor anode body obtained by sintering the tungsten powder is preferably 0.01 to 0.5% by mass, more preferably It may be 0.05 to 0.3% by mass.
- tungsten powder As an example of a method for carbonizing a part of the surface of tungsten powder, there is a method in which tungsten powder is placed at 300 to 1500 ° C. for several minutes to several hours in a vacuum high-temperature furnace using a carbon electrode. Carbonization is preferably performed so that the carbon content is 0.001 to 0.5 mass% by selecting the temperature and time. When nitrogen is passed in a carbon electrode furnace under predetermined conditions, carbonization and nitrogen content occur at the same time, and a part of the surface is carbonized, and it is also possible to produce tungsten powder containing nitrogen on a part of the surface.
- a method for boring a part of the surface of tungsten powder there is a method of granulating by mixing boron element or a compound containing boron element as a boron source when the tungsten powder is granulated. Boriding is preferably performed so that the content is 0.001 to 0.1% by mass. Within this range, good LC characteristics can be obtained.
- nitrogen-containing powder is put into a carbon electrode furnace and a boron source is placed and granulated, nitrogen may be included in a part of the surface, and tungsten powder in which part of the surface is carbonized and borated may be produced. Is possible.
- the tungsten powder preferably has a phosphorus element content of 1 to 500 ppm by mass.
- a method for adding a phosphorus element to tungsten powder or tungsten powder containing a part of the surface that has been subjected to at least one of carbonization, boriding, and oxidation of a part of the surface each powder There is a method of preparing a powder containing phosphorus by placing phosphorus or a phosphorus compound as a phosphation source in a reduced-pressure high-temperature furnace when preparing the raw material powder or granulating powder.
- the surface of the tungsten powder or the surface of the tungsten powder in which part of the surface contains nitrogen, carbonized part of the surface, and at least one of boride was performed.
- the oxygen content of the tungsten powder is preferably 0.05 to 8% by mass, and more preferably 0.08 to 1% by mass.
- nitrogen gas containing oxygen is introduced at the time of taking out the raw material powder of each powder or taking out from the reduced-pressure high-temperature furnace at the time of producing granulated powder.
- the content of impurity elements other than silicon, nitrogen, carbon, boron, oxygen and phosphorus elements is 0 in total. It is preferable to suppress to 1% by mass or less. In order to keep these elements below the above content, the amount of impurity elements contained in raw materials, used pulverized materials, containers and the like is examined in detail.
- baking is performed by adding at least one of a boride source, a phosphide source, an oxidation source, and a nitrogen source to the silicon-containing granulated powder obtained by the method of the present invention.
- a boride source a phosphide source, an oxidation source, and a nitrogen source
- the raw material tungsten powder (unprocessed powder) is preferably processed into a granulated powder having good fluidity and easy operation such as molding. As described above, it is also possible to contact the silicon compound solution during the granulation process.
- the granulated powder may further be one in which the pore distribution is adjusted by a method similar to the method disclosed in JP-A-2003-213302 for niobium powder, for example.
- granulated powder is made by adding at least one liquid such as water or liquid resin to ungranulated tungsten powder to form granules of an appropriate size, and then heating and sintering under reduced pressure. It can also be obtained.
- Depressurized conditions for example, 1 kPa or less in a non-oxidizing gas atmosphere such as hydrogen
- high-temperature standing conditions for example, 1100 to 2600 ° C., 0.1 to 100 hours
- the granulated powder is preferably classified by sieving and adjusting the particle size distribution before being molded into a capacitor anode body material.
- the granulated powder can also be obtained by adding at least one liquid such as water or liquid resin to the raw material powder to form a granule of an appropriate size, and then heating and sintering under reduced pressure.
- the decompression condition and the heating condition can be obtained by a preliminary experiment. If there is no aggregation of the granules after sintering, there is no need for crushing.
- Such granulated powder can be classified by sieving to make the particle size uniform. If the average particle diameter is preferably in the range of 50 to 200 ⁇ m, more preferably 100 to 200 ⁇ m, it is convenient for the powder to smoothly flow from the hopper of the molding machine to the mold when molding as an anode body of an electrolytic capacitor. is there.
- the specific surface area (by the BET method) of the granulated powder is preferably 0.2 to 20 m 2 / g, more preferably 1.5 to 20 m 2 / g, the capacity of the electrolytic capacitor is increased. Is preferable.
- Such tungsten powder or granulated powder is molded and sintered to form an anode body. Sintering is performed by pressure-molding tungsten powder to obtain a compact, which is fired in a furnace.
- a binder such as an acrylic resin may be mixed with the raw material powder.
- the contact with the silicon compound solution may include the binder in the silicon compound solution, and mix the silicon compound solution containing the binder with the raw material powder. You may perform a contact with a silicon compound solution by making a molded object immerse in a silicon compound solution.
- the obtained sintered body may be used as an anode body as it is, but the sintered body may be further processed and used as an anode body.
- this processing include chemical processing operations such as including elements such as nitrogen, carbon, boron, phosphorus, and oxygen on the surface of the sintered body. This processing can be performed in the same manner as the operation for the above-described tungsten powder.
- physical processing such as connecting an anode lead wire to the obtained sintered body can be performed. Such processing can also be performed before the sintered body is produced.
- An electrolytic capacitor is formed from a capacitor anode body made of a sintered tungsten powder manufactured by the method of the present invention as one electrode and a dielectric interposed between the counter electrode (cathode).
- the dielectric is formed on the surface of the anode body (including the surface in the pores), for example, by electrolytic oxidation of the anode body.
- the counter electrode is formed, for example, by laminating a semiconductor layer such as a conductive polymer on a dielectric.
- Average particle size The particle size distribution was measured by a laser diffraction scattering method using Microtrac HRA 9320-X100. The average particle size was defined as a particle size value (D50; ⁇ m) corresponding to 50% by volume.
- the produced granulated powder was molded to produce a compact having a size of 1.0 ⁇ 1.5 ⁇ 4.5 mm.
- a tantalum wire having a diameter of 0.29 mm is planted perpendicularly to a 1.0 ⁇ 1.5 plane, embedded in the inside by 3.7 mm, and projected to the outside by 7 mm.
- This molded body was vacuum-sintered at a temperature described later for 20 minutes in a vacuum high-temperature furnace to obtain a sintered body having a mass of 60 mg.
- the element content in the anode body was determined by ICP emission analysis. Further, the amount of nitrogen element and the amount of oxygen element in the anode body were determined by a thermal conductivity method and an infrared absorption method, respectively, using an oxygen / nitrogen analyzer (TC600 manufactured by LECO).
- Capacitance and LC value of electrolytic capacitor A capacitor anode body composed of a sintered body of tungsten powder was formed in a 3% by mass ammonium persulfate aqueous solution at 9 V for 6 hours, washed with alcohol and dried at 190 ° C. to form a dielectric layer on the anode body surface.
- the anode body on which the dielectric layer was formed was dipped in a 30% by mass sulfuric acid aqueous solution using platinum black as a cathode to form an electrolytic capacitor, and the capacitance and LC value were measured.
- the capacity was measured using an Agilent LCR meter at room temperature, 120 Hz, and a bias of 2.5 V.
- the LC value is a value 30 seconds after applying 4 V at room temperature. The measurement was carried out for any 40 examples, and the average value was calculated.
- Example 1 Tungsten trioxide was reduced in a hydrogen stream to obtain tungsten powder (non-granulated powder) having an average particle size of 0.6 ⁇ m. 100 g of this powder was put into 100 mL of an ethanol solution of 0.5 mass% tetraethoxysilane and mixed well, and then put in a vacuum dryer to remove ethanol at 60 ° C. and dry. Next, it was fired at 1400 ° C. for 20 minutes under a vacuum condition of 5 ⁇ 10 ⁇ 3 Pa and returned to room temperature.
- the mixture was crushed with a hammer mill to obtain a granulated powder having an average particle size of 110 ⁇ m (particle size distribution: 26 to 180 ⁇ m) and a specific surface area of 0.3 m 2 / g and a silicon content of 0.05% by mass.
- Examples 2-5, Comparative Examples 1-3 As shown in Table 1, Examples 2 to 5 in which the concentration of the tetraethoxysilane was changed in the same manner as in Example 1 so that the silicon concentration (% by mass) in the anode body was in the range of 0 to 7.6%, and The granulated powders of Comparative Examples 1 to 3 were prepared. The granulated powder produced in each example is molded into a molded body, and the molded body is sintered into a sintered body. The results of measuring the silicon and oxygen contents in the obtained sintered body are also shown. It is shown in 1.
- the granulated powder produced in each example was molded into a molded body, and the molded body was sintered at 1550 ° C. in a vacuum high-temperature furnace to be a sintered body.
- the obtained sintered body was measured as an anode body of an electrolytic capacitor.
- the capacities and LC values measured are also shown in Table 1.
- Example 6 200 g of commercially available tungsten powder (non-granulated powder) having an average particle size of 0.5 ⁇ m was put into 400 g of water in which 10% by mass of ammonium persulfate had been dissolved, and the tungsten surface layer was oxidized by sufficiently stirring with a homogenizer. After washing with water, 500 mL of a 2N aqueous sodium hydroxide solution was added and stirred to remove the surface oxide. This series of operations of oxidation and oxide removal was repeated three times to obtain a finely divided tungsten powder having an average particle diameter of 0.3 ⁇ m.
- Examples 7 to 10, Comparative Examples 4 to 6 As shown in Table 2, by changing the concentration of the dimethyldimethoxysilane solution, the silicon concentration (mass%) in the anode body was in the range of 0 to 8.2%, and Examples 7 to 10 and Comparative Examples 4 to 6 were prepared. Granules were prepared. Table 2 shows the results of preparing sintered bodies from the granulated powder of each example and measuring the contents of silicon, oxygen, and nitrogen in the sintered bodies. The granulated powder produced in each example was molded into a molded body, the molded body was sintered at 1500 ° C. in a vacuum high-temperature furnace to be a sintered body, and the obtained sintered body was measured as an anode body of an electrolytic capacitor. The capacities and LC values measured are also shown in Table 2.
- Example 11 The same series of operations of oxidation and oxide removal as in Example 6 was repeated 6 times to obtain finely divided tungsten powder having an average particle size of 0.1 ⁇ m.
- Granulated powder having a silicon content of 0.3% by mass was prepared in the same manner as in Example 6 except that triethoxyphenylsilane was used instead of dimethyldimethoxysilane and the firing temperature was 1320 ° C. Further, 80 g of this granulated powder was added to and mixed with 200 mL of phosphoric acid aqueous solution, and then vacuum dried at 100 ° C. to remove water. Thereafter, recalcination was performed at 1320 ° C.
- the sintered body produced from this granulated powder contained 0.3 mass% silicon, 14700 mass ppm oxygen, 890 mass ppm nitrogen, and 70 mass ppm phosphorus.
- Comparative Example 7 Granulated powder was obtained in the same manner as in Example 11 except that the silicon compound (triethoxyphenylsilane) was not added in Example 11. As shown in Table 3, the sintered body produced from this granulated powder did not detect silicon, and contained 11900 mass ppm of oxygen, 850 mass ppm of nitrogen, and 70 mass ppm of phosphorus.
- Comparative Examples 8 to 10 In the same manner as in Example 3 and Example 8, a commercially available silicon powder (average particle size 1.5 ⁇ m) was added to ethanol in place of the silicon compound and stirred well to obtain a silicon powder dispersion, which was mixed with the tungsten powder. did. A granulated powder was produced in the same manner as in Example 3 (calcination temperature 1400 ° C.) and Example 8 (calcination temperature 1370 ° C.) except that the silicon compound solution was different.
- the sintered body produced from the granulated powder of Comparative Example 8 contains a silicon concentration of 1.0 mass% and an oxygen concentration of 6400 mass ppm as shown in Table 3, and the granulated powder of Comparative Example 9 has a silicon concentration of 1.5 It contained mass%, oxygen concentration 9300 mass ppm, and nitrogen 710 mass ppm.
- silicon dioxide powder having an average particle diameter of 1 ⁇ m was added to ethanol so as to be 1% by mass instead of the ethanol solution of tetraethoxysilane under the conditions of Example 3, and the silicon dioxide powder was stirred well. This was mixed with tungsten powder.
- Granulated powder was obtained in the same manner as in Example 3 except that the silicon compound was different and it was not a solution. As shown in Table 3, the granulated powder had a silicon concentration of 1.0 mass% and an oxygen concentration of 12200 mass ppm. Moreover, it was confirmed by electron microscope (SEM) observation and EDS (energy dispersive spectroscopy) analysis of this granulated powder that silicon dioxide was isolated between tungsten powders, and silicon dioxide was a crystal. This was confirmed by X-ray diffraction. In this granulated powder, a compound of tungsten and silicon was not confirmed.
- SEM electron microscope
- EDS energy dispersive spectroscopy
- Example 11 The granulated powder produced in Example 11 and Comparative Examples 7 to 10 was molded into a molded body, and the molded body was sintered in a vacuum high-temperature furnace at the temperatures shown in Table 3 to obtain a sintered body.
- the capacity and LC value measured as the anode body of the electrolytic capacitor are also shown in Table 3.
- the capacities and LC values listed in Tables 1 to 3 are average values of arbitrary 40 measurement results of each example and each comparative example, and the element content is random in each example and each comparative example. Is the average value of the two anode bodies selected. In all of the examples and comparative examples, no granulated powder in which the total amount of elements excluding tungsten, silicon, oxygen, nitrogen and phosphorus exceeded 1,000 ppm was found.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
また、特許文献3(国際公開第2004/055843号パンフレット:米国特許第7154743号)には、タンタル、ニオブ、チタン、タングステンから選択される陽極を用いた電解コンデンサを開示されているが、タングステンを用いた具体例の記載はない。
そこで、本発明者らは先に、タングステン粉の焼結体を陽極体とする電解コンデンサにおける漏れ電流(LC)の問題を解消し得るタングステン粉として、タングステン粉にケイ素粉を混合し減圧下で加熱し反応させてケイ素含有量が特定の範囲(0.05~7質量%)となるように表面の一部をケイ化タングステンとしたタングステン粉、その粉を焼結してなるコンデンサの陽極体、及びその陽極体を電極として用いた電解コンデンサについて特許出願している(国際公開第2012/086272号パンフレット;特許文献4)。
[1] タングステン粉を成形して成形体とし、その成形体を焼結して得られる焼結体を陽極体とするコンデンサ陽極体の製造方法であって、陽極体中のケイ素含有量が0.05~7質量%となるように、成形体の焼結前にタングステン粉またはその成形体をケイ素化合物溶液と接触させる工程を有することを特徴とする陽極体の製造方法。
[2] 前記ケイ素化合物溶液の溶媒とケイ素化合物との割合を調節して前記陽極体中のケイ素含有量を0.05~7質量%とする前項1に記載の陽極体の製造方法。
[3] 前記タングステン粉とケイ素化合物溶液との接触が、ケイ素化合物溶液にタングステン粉を混合することにより行われる前項1または2に記載の陽極体の製造方法。
[4] 前記成形体とケイ素化合物溶液との接触が、成形体にケイ素化合物溶液を浸み込ませることにより行われる前項1または2に記載の陽極体の製造方法。
[5] 前記タングステン粉またはそのタングステン成形体をケイ素化合物溶液と接触させる工程が、バインダーを含むケイ素化合物溶液を用いてタングステン粉を成形して成形体とする工程として行われる前項1に記載の陽極体の製造方法。
[6] 前記タングステン粉またはその成形体をケイ素化合物溶液と接触させる工程後に、前記タングステン粉またはその成形体からケイ素化合物溶液の溶媒を除去する前項1~5のいずれかに記載の陽極体の製造方法。
[7] 前記タングステン粉をケイ素化合物溶液と接触させた後、溶液から分離したタングステン粉を焼成、解砕して造粒粉とし、その造粒粉を成形して成形体とする前項1~6のいずれかに記載の陽極体の製造方法。
[8] ケイ素化合物が、焼結温度以下の温度で分解し、分解物の少なくとも一部がタングステンと反応してケイ化タングステンを形成する化合物である前項1~7のいずれかに記載の陽極体の製造方法。
[9] ケイ素化合物がシラン化合物である前項1~8のいずれかに記載の陽極体の製造方法。
[10] ケイ素化合物溶液の溶媒が、アルコール、エステル及びエーテルから選ばれる1種、または2種以上の混合溶媒である前項1~9のいずれかに記載の陽極体の製造方法。
[11] さらに、焼結体の表面の少なくとも一部に窒素、炭素、ホウ素、リン、酸素の少なくとも1つを含有させる工程を含む前項1~10のいずれかに記載の陽極体の製造方法。
[12] 前項1~11のいずれかに記載の方法により得られた陽極体を一方の電極とし、誘電体を介して対電極を設けてなるコンデンサの製造方法。
[13] 原料タングステン粉をケイ素化合物溶液と接触させる工程、及びケイ素化合物溶液で処理した原料タングステン粉を焼成した後、解砕する工程を有することを特徴とするタングステン造粒粉の製造方法。
[14] 造粒粉中のケイ素含有量が0.05~7質量%となるように原料タングステン粉をケイ素化合物溶液と接触させる前項13に記載のタングステン造粒粉の製造方法。
[15] 前記ケイ素化合物溶液の溶媒とケイ素化合物との割合を調節して前記造粒粉中のケイ素含有量を0.05~7質量%とする前項14に記載のタングステン造粒粉の製造方法。
[16] 前記タングステン粉とケイ素化合物溶液との接触が、ケイ素化合物溶液にタングステン粉を混合することにより行われる前項13~15のいずれかに記載のタングステン造粒粉の製造方法。
また、タングステン含有鉱物から直接または複数の工程を得て、還元条件を選択することによって得ることもできる。
本発明の製造方法の第一の態様では、ケイ素化合物溶液で処理したタングステン粉を減圧下で焼成した後解砕する。
1)(CH3)2Si(OCH3)2、φ2Si(OCH3)2(φはフェニル基を表わす。以下同様)、(CH3)2Si(OC2H5)2、φ2Si(OC2H5)2、
2)(CH3)2Si(OAc)2(Acはアセチル基を表わす。以下、同様)、及びにこれらの化合物の単独または2種以上の共縮合物であるシリコーン樹脂等の重合体、
3)(CH3)Si(OCH3)3、φSi(OCH3)3、(CH3)Si(OC2H5)3、φSi(OC2H5)3、(CH3)Si(OAc)3、Cl(CH2)3Si(OCH3)3、(OCH3)3、HS(CH2)3Si(OCH3)3、NC(CH2)2Si(OCH3)3、H2N(CH2)3Si(OC2H5)3の化合物ならびにこれらの化合物の単独または2種以上の共縮合物であるラダーシリコン、
4)Si(OCH3)4、Si(OC2H5)4、Si(OAc)4、(CH3)3SiOCH=CH2とその重合物、
5)(CH3)3SiO-CH=CH-CH3とその重合物、
6)CH2=CH(CH3)2SiOSi(CH3)2CH=CH2とその重合物、
7)CH2=Si(CH3)2OSi(CH3)2C=CH2とその重合物、
8)(CH3)3SiOSi(CH3)3、H(CH3)2SiOSi(CH3)2H、ClCH2(CH3)2SiOSi(CH3)2CH2Cl、HOCH2(CH3)2SiOSi(CH3)2CH2OH、H2N(CH2)3、(CH3)2SiOSi(CH3)2(CH2)3NH2、φ2Si(OH)2、(CH3)3SiOH等が挙げられる。これらの化合物は単独で、または2種以上を組み合わせて使用することもできる。
陽極体中のケイ素含有量が0.05質量%未満であると、漏れ電流(LC)性能が良好な電解コンデンサを与える粉にならない場合がある。7質量%を超えるとタングステン粉のケイ素化部分が多すぎてタングステン粉を成形して電解コンデンサの陽極体を作製して化成した場合に誘電体層がきちんと形成できないことがあり好ましくない。
陽極体中のケイ素含有量は、例えば、予備実験で調整することができる。陽極体中のケイ素含有量を増やすには、溶液中のケイ素化合物の濃度を高くしたり、溶液に対するタングステン粉の量を減らしたりすればよい。陽極体中のケイ素含有量を減らすには、前記と逆の操作をすればよい。なお、焼結をしても、タングステンに対するケイ素含有量はほとんど変わらないので、陽極体中のケイ素含有量は、焼結前のタングステン材料中のケイ素含有量を目安として調整することもできる。例えば、後述する造粒粉中のケイ素含有量が前記範囲となるように同様に調整してもよい。
タングステン粉、あるいは表面の一部に窒素を含有させた、表面の一部を炭化、ホウ化、酸化の少なくとも1つを行ったタングステン粉に、リン元素を含有させる方法の1例として、各粉の原料粉作製時や造粒粉作製時に、減圧高温炉中にリンやリン化合物をリン化源として置いてリンを含有する粉を作製する方法がある。リン化源の量を調整するなどして、前述の含有量となるようにリンを含有させると、コンデンサ陽極体を作製したときの陽極体の物理的破壊強度が増加する場合があるので好ましい。この範囲であれば、作製した電解コンデンサのLC性能がさらに良好になる。
造粒粉は、コンデンサ陽極体材料に焼成するための成形前にふるいで分級して粒径分布を調整することが好ましい。造粒粉は、原料粉に水等の液体や液状樹脂の少なくとも1種を加えて適当な大きさの顆粒状とした後に、減圧下に加熱し焼結して得ることもできる。減圧条件や加熱条件は、予備実験により求めることができる。焼結後の顆粒同士の凝集がなければ、解砕の必要はない。
造粒粉の比表面積(BET法による)は、好ましくは0.2~20m2/g、より好ましくは1.5~20m2/gになるようにすると、電解コンデンサの容量をより大きくすることができ好ましい。
焼結は、タングステン粉を加圧成形して成形体を得、それを炉において焼成することによって行う。加圧成形を容易にするために粉にアクリル樹脂等のバインダーを原料粉に混ぜてもよい。所望の成形密度等になるように粉量や成形装置などの諸条件を適宜設定することができる。
なお、ケイ素化合物溶液との接触は、ケイ素化合物溶液に前記バインダーを含ませ、バインダーを含むケイ素化合物溶液を前記原料粉に混ぜてもよい。
ケイ素化合物溶液との接触は、成形体にケイ素化合物溶液に浸み込ませることにより行なってもよい。
また、得られた焼結体に陽極リード線を接続する等の物理的な加工を施すこともできる。なお、このような加工は、焼結体作製前に行うこともできる。
なお、実施例及び比較例の造粒粉の比表面積及び平均粒径の測定、焼結体の作製、タングステン以外の元素(ケイ素、酸素、窒素及びその他の元素)の分析は以下の方法により行った。
Macsorb HM model-1208(Mountech社)を用いBET法で測定した。
マイクロトラック社製 HRA 9320-X100を用い、粒度分布をレーザー回折散乱法で測定した。その累積体積%が、50体積%に相当する粒径値(D50;μm)を平均粒径とした。
作製した造粒粉を成形して大きさ1.0×1.5×4.5mmの成形体を作製した。この成形体には、直径0.29mmのタンタル線が1.0×1.5面に垂直に植立していて、内部に3.7mm埋設され、外部に7mm出ている。この成形体を、減圧高温炉中、後述する温度で20分間真空焼結して質量60mgの焼結体を得た。
ICP発光分析によって陽極体中の元素含有量を決定した。また、酸素・窒素分析装置(LECO社製TC600)を用いて陽極体中の窒素元素量と酸素元素量をそれぞれ熱伝導度法と赤外吸収法により決定した。
タングステン粉の焼結体からなるコンデンサ陽極体を3質量%の過硫酸アンモニウム水溶液中9Vで6時間化成し、アルコール洗浄後190℃で乾燥して陽極体表面に誘電体層を形成した。誘電体層を形成した陽極体を、白金黒を陰極とした30質量%硫酸水溶液中に漬け、電解コンデンサを形成し、容量及びLC値を測定した。容量は、アジレント製LCRメーターを用い、室温、120Hz、バイアス2.5V値で測定した。LC値は、室温で4Vを印加して30秒後の数値である。測定は、各例任意の40個を行い、その平均値を算出した。
三酸化タングステンを水素気流中で還元して平均粒径0.6μmのタングステン粉(未造粒粉)を得た。この粉100gを、0.5質量%テトラエトキシシランのエタノール溶液100mLに投入して充分混合した後に、真空乾燥機に入れ60℃でエタノールを除去、乾燥した。
次に、5×10-3Paの真空条件で1400℃で20分焼成し室温に戻した。その後、ハンマーミルで解砕し、平均粒径110μm(粒径分布26~180μm)、比表面積0.3m2/gのケイ素含有量0.05質量%の造粒粉を得た。
表1に示す通り、実施例1と同様にして前記テトラエトキシシランの濃度を変えて陽極体中のケイ素濃度(質量%)が0~7.6%の範囲となる実施例2~5、及び比較例1~3の造粒粉を作製した。
各例で作製した造粒粉を成形して成形体とし、成形体を焼結して焼結体とし、得られた焼結体中のケイ素及び酸素の含有量を測定した結果を併せて表1に示す。
また、X線回析装置(X'pert PRO PANalytical社製)で造粒粉を分析したところ、反応物としてケイ化タングステンが検出され、そのほとんどはW5Si3であった。また造粒粉をスパッタリングして同様に分析したところ、反応物のケイ化タングステンは造粒粉の粒子表面から30nmまでの範囲に存在することが分かった。すなわち、ケイ素が造粒粉の表層の少なくとも一部で、ケイ化タングステンとして存在することが確認された。なお、これらは造粒粉についての分析結果であるが、陽極体に加工されたものでもほぼ同様である。
各例で作製した造粒粉を成形して成形体とし、成形体を減圧高温炉中、1550℃で焼結して焼結体とし、得られた焼結体を電解コンデンサの陽極体として測定した容量及びLC値を表1に併記した。
市販の平均粒径0.5μmのタングステン粉(未造粒粉)200gを10質量%の過硫酸アンモニウムを溶解した水400g中に投入し、ホモジナイザーで充分撹拌してタングステン表層を酸化させた。水洗後、2Nの水酸化ナトリウム水溶液500mLを加えて撹拌し、表層の酸化物を除去した。この酸化と酸化物除去の一連の操作を3回繰り返して平均粒径0.3μmの細粒化したタングステン粉を得た。この粉100gを、0.5質量%のジメチルジメトキシシランのエタノール溶液100mLに投入して充分混合した後に、真空乾燥機に入れ60℃でエタノールを除去、乾燥した。
次に5×10-3Paの真空条件で1370℃で20分焼成し室温に戻した。その後、ハンマーミルで解砕し、平均粒径105μm(粒径分布20~180μm)、比表面積2.1m2/gのケイ素含有量0.1質量%の造粒粉を得た。
表2に示す通り、前記ジメチルジメトキシシラン溶液の濃度を変えて陽極体中のケイ素濃度(質量%)が0~8.2%の範囲の実施例7~10、及び比較例4~6の造粒粉を作製した。
各例の造粒粉から焼結体を作製し、焼結体中のケイ素、酸素、窒素の含有量を測定した結果を併せて表2に示す。
各例で作製した造粒粉を成形して成形体とし、成形体を減圧高温炉中、1500℃で焼結して焼結体とし、得られた焼結体を電解コンデンサの陽極体として測定した容量及びLC値を表2に併記した。
実施例6と同じ酸化と酸化物除去の一連の操作を6回繰り返して平均粒径0.1μmの細粒化したタングステン粉を得た。ジメチルジメトキシシランの代わりにトリエトキシフェニルシランを使用し、焼成温度を1320℃にした以外は実施例6と同様にケイ素含有量0.3質量%の造粒粉を作製した。さらにこの造粒粉80gをリン酸水溶液200mLに投入して混合した後に、100℃で真空乾燥し水を除去した。その後1320℃20分の再焼成を行い、室温に戻してハンマーミルで解砕し、平均粒径93μm(粒径分布20~160μm)、比表面積10.3m2/gの造粒粉を得た。この造粒粉から作製した焼結体は表3に示す通り、ケイ素0.3質量%、酸素14700質量ppm、窒素890質量ppm、リン70質量ppmを含有していた。
実施例11でケイ素化合物(トリエトキシフェニルシラン)を加えなかった以外は実施例11と同様にして造粒粉を得た。この造粒粉から作製した焼結体は、表3に示す通り、ケイ素が検出されず、酸素11900質量ppm、窒素850質量ppm、リン70質量ppmを含有していた。
実施例3及び実施例8と同様にしてケイ素化合物の代わりに市販のケイ素粉(平均粒径1.5μm)をエタノールに加えてよく撹拌してケイ素粉の分散液とし、これをタングステン粉と混合した。ケイ素化合物溶液が異なる点以外は実施例3(焼成温度1400℃)及び実施例8(焼成温度1370℃)と同様にして造粒粉を作製した。比較例8の造粒粉から作製した焼結体は表3に示すようにケイ素濃度1.0質量%、酸素濃度6400質量ppmを含有し、比較例9の造粒粉はケイ素濃度1.5質量%、酸素濃度9300質量ppm、窒素710質量ppmを含有していた。
比較例10の造粒粉は、実施例3の条件でテトラエトキシシランのエタノール溶液の代わりに平均粒径1μmの二酸化ケイ素粉を1質量%となるようエタノールに加えてよく撹拌して二酸化ケイ素粉の分散液とし、これをタングステン粉と混合した。ケイ素化合物が異なる点及び溶液ではない点以外は実施例3と同様にして造粒粉を得た。表3に示すようにこの造粒粉のケイ素濃度は1.0質量%、酸素濃度は12200質量ppmであった。また、この造粒粉の電子顕微鏡(SEM)観察及びEDS(エネルギー分散型分光法)分析により二酸化ケイ素がタングステン粉間に孤立して存在していることを確認し、また二酸化ケイ素が結晶であることをX線回折から確認した。この造粒粉ではタングステンとケイ素の化合物は確認されなかった。
Claims (16)
- タングステン粉を成形して成形体とし、その成形体を焼結して得られる焼結体を陽極体とするコンデンサ陽極体の製造方法であって、陽極体中のケイ素含有量が0.05~7質量%となるように、成形体の焼結前にタングステン粉またはその成形体をケイ素化合物溶液と接触させる工程を有することを特徴とする陽極体の製造方法。
- 前記ケイ素化合物溶液の溶媒とケイ素化合物との割合を調節して前記陽極体中のケイ素含有量を0.05~7質量%とする請求項1に記載の陽極体の製造方法。
- 前記タングステン粉とケイ素化合物溶液との接触が、ケイ素化合物溶液にタングステン粉を混合することにより行われる請求項1または2に記載の陽極体の製造方法。
- 前記成形体とケイ素化合物溶液との接触が、成形体にケイ素化合物溶液を浸み込ませることにより行われる請求項1または2に記載の陽極体の製造方法。
- 前記タングステン粉またはそのタングステン成形体をケイ素化合物溶液と接触させる工程が、バインダーを含むケイ素化合物溶液を用いてタングステン粉を成形して成形体とする工程として行われる請求項1に記載の陽極体の製造方法。
- 前記タングステン粉またはその成形体をケイ素化合物溶液と接触させる工程後に、前記タングステン粉またはその成形体からケイ素化合物溶液の溶媒を除去する請求項1~5のいずれかに記載の陽極体の製造方法。
- 前記タングステン粉をケイ素化合物溶液と接触させた後、溶液から分離したタングステン粉を焼成、解砕して造粒粉とし、その造粒粉を成形して成形体とする請求項1~6のいずれかに記載の陽極体の製造方法。
- ケイ素化合物が、焼結温度以下の温度で分解し、分解物の少なくとも一部がタングステンと反応してケイ化タングステンを形成する化合物である請求項1~7のいずれかに記載の陽極体の製造方法。
- ケイ素化合物がシラン化合物である請求項1~8のいずれかに記載の陽極体の製造方法。
- ケイ素化合物溶液の溶媒が、アルコール、エステル及びエーテルから選ばれる1種、または2種以上の混合溶媒である請求項1~9のいずれかに記載の陽極体の製造方法。
- さらに、焼結体の表面の少なくとも一部に窒素、炭素、ホウ素、リン、酸素の少なくとも1つを含有させる工程を含む請求項1~10のいずれかに記載の陽極体の製造方法。
- 請求項1~11のいずれかに記載の方法により得られた陽極体を一方の電極とし、誘電体を介して対電極を設けてなるコンデンサの製造方法。
- 原料タングステン粉をケイ素化合物溶液と接触させる工程、及びケイ素化合物溶液で処理した原料タングステン粉を焼成した後、解砕する工程を有することを特徴とするタングステン造粒粉の製造方法。
- 造粒粉中のケイ素含有量が0.05~7質量%となるように原料タングステン粉をケイ素化合物溶液と接触させる請求項13に記載のタングステン造粒粉の製造方法。
- 前記ケイ素化合物溶液の溶媒とケイ素化合物との割合を調節して前記造粒粉中のケイ素含有量を0.05~7質量%とする請求項14に記載のタングステン造粒粉の製造方法。
- 前記タングステン粉とケイ素化合物溶液との接触が、ケイ素化合物溶液にタングステン粉を混合することにより行われる請求項13~15のいずれかに記載のタングステン造粒粉の製造方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014551918A JPWO2014091810A1 (ja) | 2012-12-13 | 2013-09-27 | タングステン陽極体の製造方法 |
US14/651,269 US9691553B2 (en) | 2012-12-13 | 2013-09-27 | Production method for tungsten anode body |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012272584 | 2012-12-13 | ||
JP2012-272584 | 2012-12-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014091810A1 true WO2014091810A1 (ja) | 2014-06-19 |
Family
ID=50934109
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/076239 WO2014091810A1 (ja) | 2012-12-13 | 2013-09-27 | タングステン陽極体の製造方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9691553B2 (ja) |
JP (2) | JPWO2014091810A1 (ja) |
WO (1) | WO2014091810A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110927089A (zh) * | 2020-01-07 | 2020-03-27 | 广东翔鹭钨业股份有限公司 | 一种钨化学分析方法中磷含量的测定方法 |
CN114535579B (zh) * | 2022-03-15 | 2023-12-05 | 崇义章源钨业股份有限公司 | 一种高纯硅钨粉的制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001026123A1 (fr) * | 1999-10-01 | 2001-04-12 | Showa Denko K.K. | Composition pour condensateur sous forme de poudre, corps fritte obtenu a partir de ladite composition et condensateur constitue du corps fritte |
WO2012086272A1 (ja) * | 2010-12-24 | 2012-06-28 | 昭和電工株式会社 | タングステン粉、コンデンサの陽極体及び電解コンデンサ |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6660057B1 (en) | 1999-10-01 | 2003-12-09 | Showa Denko K.K. | Powder composition for capacitor, sintered body using the composition and capacitor using the sintered body |
JP2003272959A (ja) | 2002-03-15 | 2003-09-26 | Sanyo Electric Co Ltd | コンデンサ |
JP4274857B2 (ja) | 2002-07-26 | 2009-06-10 | 三洋電機株式会社 | 電解コンデンサの製造方法 |
WO2004055843A1 (ja) | 2002-12-13 | 2004-07-01 | Sanyo Electric Co.,Ltd. | 固体電解コンデンサ及びその製造方法 |
-
2013
- 2013-09-27 WO PCT/JP2013/076239 patent/WO2014091810A1/ja active Application Filing
- 2013-09-27 JP JP2014551918A patent/JPWO2014091810A1/ja active Pending
- 2013-09-27 US US14/651,269 patent/US9691553B2/en not_active Expired - Fee Related
-
2017
- 2017-10-03 JP JP2017193768A patent/JP2018032867A/ja not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001026123A1 (fr) * | 1999-10-01 | 2001-04-12 | Showa Denko K.K. | Composition pour condensateur sous forme de poudre, corps fritte obtenu a partir de ladite composition et condensateur constitue du corps fritte |
WO2012086272A1 (ja) * | 2010-12-24 | 2012-06-28 | 昭和電工株式会社 | タングステン粉、コンデンサの陽極体及び電解コンデンサ |
Also Published As
Publication number | Publication date |
---|---|
US9691553B2 (en) | 2017-06-27 |
JP2018032867A (ja) | 2018-03-01 |
US20150310997A1 (en) | 2015-10-29 |
JPWO2014091810A1 (ja) | 2017-01-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5132840B2 (ja) | タングステン粉、コンデンサの陽極体及び電解コンデンサ | |
EP1405323B1 (en) | Methods of making a niobium metal oxide | |
EP1266386B1 (en) | Anode comprising niobium oxide powder and method of forming it | |
JP5779728B2 (ja) | タングステン微粉の製造方法 | |
JP2018032867A (ja) | タングステン陽極体の製造方法 | |
JP5266427B1 (ja) | コンデンサの陽極体の製造方法 | |
WO2016038959A1 (ja) | タングステンコンデンサ素子及びその製造方法 | |
WO2002004152A1 (fr) | Poudre metallique contenant de l'azote, son procede de preparation, condensateur electrolytique solide et agglomere poreux fabrique au moyen de cette poudre metallique | |
JP6412501B2 (ja) | ニオブ造粒粉末の製造方法 | |
US9865402B2 (en) | Anode body for tungsten capacitors | |
JP5750200B1 (ja) | タングステン粉、コンデンサの陽極体、及び電解コンデンサ | |
JP5613861B2 (ja) | 固体電解コンデンサの陽極体 | |
JP5613863B2 (ja) | タングステンコンデンサの陽極体及びその製造方法 | |
JP5750201B1 (ja) | タングステン粉、コンデンサの陽極体、及び電解コンデンサ | |
JP6258222B2 (ja) | ニオブコンデンサ陽極用化成体及びその製造方法 | |
JP5779741B1 (ja) | タングステンコンデンサ用陽極体の製造方法 | |
JP2019007070A (ja) | タングステン混合粉および電解コンデンサ素子の製造方法 | |
WO2015107749A1 (ja) | タングステン固体電解コンデンサ素子の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13863548 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014551918 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14651269 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13863548 Country of ref document: EP Kind code of ref document: A1 |