WO2004055843A1 - 固体電解コンデンサ及びその製造方法 - Google Patents
固体電解コンデンサ及びその製造方法 Download PDFInfo
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- WO2004055843A1 WO2004055843A1 PCT/JP2003/015501 JP0315501W WO2004055843A1 WO 2004055843 A1 WO2004055843 A1 WO 2004055843A1 JP 0315501 W JP0315501 W JP 0315501W WO 2004055843 A1 WO2004055843 A1 WO 2004055843A1
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- solid electrolytic
- electrolytic capacitor
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- silver particles
- layer
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- 239000003990 capacitor Substances 0.000 title claims abstract description 149
- 239000007787 solid Substances 0.000 title claims abstract description 148
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 5
- 239000002245 particle Substances 0.000 claims abstract description 209
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 139
- 229910052709 silver Inorganic materials 0.000 claims abstract description 139
- 239000004332 silver Substances 0.000 claims abstract description 139
- 239000000463 material Substances 0.000 claims abstract description 122
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 239000011230 binding agent Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 239000010955 niobium Substances 0.000 claims abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 39
- 229910001923 silver oxide Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 5
- 239000009719 polyimide resin Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 35
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 18
- 239000006230 acetylene black Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 10
- 239000004962 Polyamide-imide Substances 0.000 description 9
- 229920002312 polyamide-imide Polymers 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
Definitions
- the present invention relates to a solid electrolytic capacitor and a method for manufacturing the same.
- the present invention relates to a solid electrolytic capacitor and a method for manufacturing the same, and in particular, a dielectric layer is formed on an anode made of at least one metal selected from tantalum, niobium, titanium, and tungsten.
- a dielectric layer is formed on an anode made of at least one metal selected from tantalum, niobium, titanium, and tungsten.
- the above-mentioned solid electrolytic capacitor generally has a structure in which a dielectric layer made of an oxide thereof is formed on an anode made of a metal such as tantalum, and an electrolyte layer and a cathode are laminated on this dielectric layer. Is used.
- a cathode of the solid electrolytic capacitor generally, a laminate in which two layers of a carbon layer and a silver layer are laminated on the above-mentioned electrolyte layer is used.
- An object of the present invention is to solve the above-described problems in a solid electrolytic capacitor, and to reduce a contact resistance and the like in the solid electrolytic capacitor to obtain a solid electrolytic capacitor having a small equivalent series resistance in a high frequency region.
- the purpose is to be able to
- the solid electrolytic capacitor in which a dielectric layer, an electrolyte layer, and a cathode are stacked on an anode made of at least one metal selected from tantalum, niobium, titanium, and tungsten
- the above-mentioned cathode is composed of a first material composed of silver particles having an average particle diameter (median diameter) of 2 / zm or more, conductive carbon particles and Z or an average particle diameter (median diameter) of 1 im or less. It has a mixed layer containing a second material made of silver particles and a binder.
- a first material composed of silver particles having a median diameter of 2 m or more, conductive carbon particles and / or silver having a median diameter of 1 m or less as a cathode on the electrolyte layer When a mixed layer containing a second material composed of particles and a binder is provided, conductive carbon particles and a median diameter between the first material composed of silver particles having a median diameter of 2 m or more are provided in the mixed layer.
- a second material composed of silver particles having a particle diameter of 1 m or less enters, and the conductivity in the mixed layer is improved, and the adhesion between the mixed layer and the electrolyte layer is also improved, and the contact resistance is also improved.
- a carbon layer may be provided between the above-mentioned electrolyte layer and the above-mentioned mixed layer in the above-mentioned cathode.
- a carbon layer is formed on the electrolyte layer as described above, and a first material composed of silver particles having a median diameter of 2 im or more, conductive carbon particles and / or a median diameter is formed on the carbon layer.
- a mixed layer containing a second material made of silver particles having a median diameter of 1 im or less and a binder is provided, the first material made of silver particles having a median diameter of 2 tm or more in the mixed layer as described above.
- a second material composed of conductive carbon particles and silver particles having a median diameter of 1 m or less enters, and the conductivity in the mixed layer is improved. As a result, the contact resistance is reduced, and the equivalent series resistance in the high-frequency region is greatly reduced.
- the amount of the conductive carbon particles or the second material composed of silver particles having a median diameter of l ⁇ m or less when the amount of the conductive carbon particles or the second material composed of silver particles having a median diameter of l ⁇ m or less is small in the mixed layer, silver having a median diameter of 2 m or more is used.
- the second material made of silver particles having a median diameter of 1 ⁇ or less between the conductive carbon particles and the first material made of particles does not sufficiently enter, and the above-described effects cannot be sufficiently obtained.
- the amount of the second material is too large, the amount of the first material having a large particle diameter becomes small, so that electricity passes through many contact portions while flowing, and the amount of particles between the particles increases. As the contact resistance increases, the equivalent series resistance increases.
- the amount of the second material with respect to the total amount of the first material and the second material is preferably in the range of 0.5 to 40 wt%, more preferably 3 to 40 wt%. Range.
- the mixed layer is made to contain silver oxide particles having a median diameter of 1 im or less, and the silver oxide particles are reduced. I do.
- the contact area between the silver particles of the first material and the silver particles of the second material is increased to increase the conductivity in the mixed layer and reduce the equivalent series resistance. It is preferable to use, as the silver particles of the first material and / or the silver particles of the second material, scaly particles having a very small thickness with respect to the length.
- the median of the maximum length should be less than 1 m.
- the maximum length of these silver particles is the maximum length of a line drawn between two points on the outer periphery of the particle.
- the median of the maximum length is the length when the cumulative value of these particles in the cumulative distribution curve of the maximum length reaches 50%.
- the ratio (L / d) of the maximum length L to the thickness d of each of the flaky silver particles is small, the contact area between the silver particles of the first material and the silver particles of the second material is increased.
- the above ratio (LZ d) is too large, the amount of the binder covering the surface of these silver particles increases, and the equivalent series resistance decreases. Since it is difficult to reduce the thickness, it is preferable to use flaky silver particles having a ratio (L / d) of the maximum length L to the thickness d in the range of 4 to 100.
- the first material a flaky silver particle having a median maximum length of 2 / m or more is used, or as a second material, the median maximum length is 1 / m or less.
- the second material is interposed between the first materials. If the material does not penetrate sufficiently, the above effects cannot be sufficiently obtained.
- the amount of the second material is too large, the amount of the first material is small. As a result, electricity passes through many contact points while flowing, and the contact resistance between particles increases, so the equivalent series resistance increases.
- the amount of the second material with respect to the total amount of the first material and the second material is in the range of 0.5 to 40 wt%, more preferably 3 to 4.0 wt%. Be within the range of%.
- scale-like silver particles having a median of the maximum length of 1 m or less are difficult to obtain with a powder frame like silver particles having a median diameter of 1 or less.
- reduce flaky silver oxide particles with a median maximum length of 1 or less Is preferred.
- a mixed layer with a median maximum length of 1 m or less in the mixed layer Of silver oxide particles In order to obtain a mixed layer containing flaky silver oxide particles with a median maximum length of 1 m or less, a mixed layer with a median maximum length of 1 m or less in the mixed layer Of silver oxide particles, and the silver oxide particles are reduced.
- the silver oxide particles in order to reduce the silver oxide particles by including flaky silver oxide particles having a median maximum length of 1 m or less in the mixed layer, for example, at 160 ° C. or more It is desirable to heat-treat at a temperature of.
- conductive carbon particles used for the second material for example, force pump racks and graphite can be used, but it is particularly preferable to use a mixture of carbon black and graphite.
- the binder used for the above-mentioned mixed layer a conventionally known binder generally used can be used, and at least one selected from polyimide resin, epoxy resin, and polyester resin can be used. Preferably, it is used.
- the first solid electrolytic capacitor described above has the above-described one-component layer and mixed layer.
- the adhesion between the electrolyte layer and the mixed layer is further improved, and the equivalent series resistance in a high-frequency region is further reduced.
- FIG. 1 is an explanatory sectional view of a solid electrolytic capacitor according to Embodiment 1 of the present invention.
- FIG. 2 is an explanatory sectional view of a solid electrolytic capacitor according to Embodiment 2 of the present invention.
- FIG. 3 is an explanatory cross-sectional view of the solid electrolytic capacitor manufactured in Comparative Example 1.
- FIG. 4 is an explanatory cross-sectional view of the solid electrolytic capacitor manufactured in Comparative Example 2.
- the solid electrolytic capacitor of Embodiment 1 has an anode 1 made of at least one metal selected from the group consisting of nanta, niobium, titanium, and tungsten.
- a dielectric layer 2 made of an oxide is formed.
- An electrolyte layer 3 using a conductive polymer, manganese dioxide, or the like is formed on the dielectric layer 2, and a cathode 4 is formed on the electrolyte layer 3. The structure has been.
- a carbon layer 4a is formed on the electrolyte layer 3 and a median diameter is formed on the carbon layer 4a.
- first material composed of silver particles having a median diameter of 2 m or more
- scale-like silver particles having a median maximum length of 2 or more may be used as the first material
- second material made of silver particles having a median diameter of 1 m or less
- flaky silver particles having a median maximum length of 1 m or less may be used as the second material. it can.
- anode 1 made of at least one metal selected from niobium, titanium, and tungsten is anodized to form a dielectric layer 2 made of an oxide on the surface of the anode 1.
- An electrolyte layer 3 made of a conductive polymer, manganese dioxide, or the like is formed thereon, and a cathode 4 is formed on the electrolyte layer 3.
- the cathode 4 is formed from silver particles having a median diameter of 2 / im or more without forming the carbon layer 4 a on the electrolyte layer 3. Only a mixed layer 4b containing a first material, a second material made of conductive carbon particles and / or silver particles having a median diameter of 1 ⁇ or less, and a binder is formed.
- the median of the maximum length was 2 m or more as the first material instead of the above-mentioned first material made of silver particles having a median diameter of 2 m or more.
- the median maximum length as a second material became 1 im or less.
- Scaly silver particles can be used.
- the solid electrolytic capacitor according to the embodiment of the present invention and the method of manufacturing the same will be specifically described, and the solid electrolytic capacitor according to the embodiment of the present invention will show that the equivalent series resistance in a high frequency region is significantly reduced. This will be clarified by giving a comparative example.
- the solid electrolytic capacitor and the method of manufacturing the same according to the present invention are not limited to those described in the following embodiments, but can be implemented with appropriate changes without departing from the scope of the invention.
- the solid electrolytic capacitor of Example A1 has the configuration of the solid electrolytic capacitor shown in the first embodiment.
- a tantalum sintered body is used for the anode 1.
- the anode 1 is anodized to form a dielectric layer 2 made of an oxide film on the surface thereof.
- an electrolyte layer 3 made of conductive polymer polypyrrole obtained by electrolytic polymerization or the like was formed, and a cathode 4 was formed on the electrolyte layer 3.
- the above-mentioned paste for the mixed layer is applied on the above-mentioned carbon layer 4a, and dried at 160 ° C. for 30 minutes, and the above-mentioned silver oxide (I) Ag 2 O particles are reduced.
- the silver oxide (I) Ag 2 having a median diameter of 0.5 m was used in the solid electrolytic capacitor of Example A2.
- silver oxide (II) AgO particles having a substantially spherical shape and a median diameter of 0.5 ⁇ m were used in place of the 0 particles. Otherwise, the median diameter was 3 in the same manner as in Example A1 above.
- a mixed layer 4b containing silver particles having a median diameter of 0.5 and silver particles having a median diameter of 0.5 was bound by polyamideimide.
- Example A3 In the solid electrolytic capacitor of Example A3, in the production of the mixed layer base in the solid electrolytic capacitor of Example A1, the median diameter was 0.5. Instead of! im Ag 2 O particles, acetylene black with a median diameter of 0.05 m, which is a kind of force pump rack, was used, and the other conditions were the same as in Example A 1 above. Thus, a mixed layer 4b containing silver particles having a median diameter of 3 and acetylene black having a median diameter of 0.05 / zm and bound by polyamideimide was formed.
- Example A4 in the preparation of the mixed layer paste in the solid electrolytic capacitor of Example A1 described above, the substantially spherical silver particles having a median diameter of 3 m and the substantially spherical median diameters of 3 m were used.
- silver particles having a median diameter of 3 im, silver particles having a median diameter of 0.5 / zm, and acetylene black having a median diameter of 0.05 tm were obtained.
- a mixed layer 4b contained and bound by polyamideimide was formed.
- the solid electrolytic capacitor of Example B1 has the configuration of the solid electrolytic capacitor described in the second embodiment.
- the carbon layer 4 a is not provided, and otherwise, in the same manner as in Example A 1 above, a silver particle having a median diameter of 3 m and a median diameter of 0.5 m are formed on the electrolyte layer 3.
- the equivalent series resistance (ESR) at a frequency of 100 kHz was used.
- the equivalent series resistance (ESR) of each solid electrolytic capacitor was measured using an index with the equivalent series resistance (ESR) of the solid electrolytic capacitor of Example A1 set to 100. Shown in 1.
- Example A3 using only acetylene black as conductive carbon particles as the second material were compared.
- the ESR of the solid electrolytic capacitor using the second material containing silver particles with a median diameter of 1 m or less is lower than that of silver particles with a median diameter of 1 m or less.
- ESR was further reduced in the solid electrolytic capacitor of Example A4 using both of the solid electrolytic capacitor and acetylene black as conductive carbon particles.
- Example A5 and A6 in the solid electrolytic capacitor of Example A3, the type of the conductive carbon particles contained in the mixed layer 4b was changed. In the same manner as in the case of 3, the solid electrolytic capacitors of Examples A5 and A6 were produced.
- Example A5 graphite having a median diameter of 5 zm was used in Example A5
- acetylene black having a median diameter of 0.05 m was used in Example A6.
- acetylene black was also used in the solid electrolytic capacitors of Examples A5 and A6 in which the conductive carbon particles contained in the mixed layer 4b were mixed with graphite or acetylene black and graphite.
- the ESR was significantly reduced as compared with the solid electrolytic capacitors of Comparative Examples 1 and 2.
- the ESR was further reduced, and in particular, the solid electrolytic capacitor of Example A6 using a mixture of acetylene black having a small particle size and graphite having a large particle size further reduced the ESR.
- Example A 7 A 8 and Comparative Example 3, 4, in the solid electrolytic capacitor of Example A 1 described above, by changing the median diameter of A g 2 0 particles to be added to the mixed layer paste described above, In the above mixed layer 4b, the median diameter of the small silver particles mixed with the silver particles having a median diameter of 3 m was changed, and the other conditions were the same as in the case of Example A1 above. Thus, the solid electrolytic capacitors of Examples A7 and A8 and Comparative Examples 3 and 4 were produced.
- the A g 2 ⁇ particle median diameter of 0. 1 m in Example A 7 the median size in the real ⁇ A 8 is viii ⁇ 2 0 particles 1.0 111 Comparative Example 3 Odor median size viii 8 2 0 particle median diameter of 1.5 111, in Comparative example 4 Te There were used A g 2 0 particles 2. 0 m. Then, the above manner 1 6 Ot: in dried between 3 0 minutes, if these A g 2 0 particles are reduced to silver particles, silver particles was the same median diameter as before the reduction, respectively is contained It became so.
- the solid electrolytic capacitors of Examples A1, A7, and A8 in which the median diameter of small silver particles mixed with silver particles having a median diameter of 3 was 1 m or less were obtained.
- the ESR was significantly reduced as compared with the solid electrolytic capacitors of Comparative Examples 3 and 4 in which the small silver particles mixed with silver particles having a median diameter of 3 ⁇ m had a median diameter of more than 1 in Comparative Examples 3 and 4.
- Example A9 to A18 when the mixed layer 4b was provided, similarly to the solid electrolytic capacitor in Example A4 above, a silver particle having a median diameter of 3 ⁇ and a median diameter of 0.5 111
- the 2 % particles were mixed with acetylene black having a median diameter of 0.05 ⁇ , and the weight ratio thereof was changed.
- Example A9 it becomes 99.7: 0.1.25: 0.125, and in Example A10, it becomes 99.5: 0.25: 0.25, and Example All 99: 0.5: 0.5, Example A12: 98: 1: 1, Example A13: 97: 1: 2, Example A14: 90: 5: 5
- the ratio is 80: 15: 5, in the embodiment A16, 60: 35: 5, in the embodiment A17, 55: 40: 5, and in the embodiment A18.
- the solid electrolytic capacitors of Examples A9 to A18 were produced in the same manner as in Example A4, except that the ratio was set to 50: 45: 5.
- Example 18 0.25 wt% in Example A9, 0.5 wt% in Example A10, 1 wt% in Example A11, 2 wt% in Example A12, Example A1 3 wt% in Example 3, 10 wt% in Example A14, 20 wt% in Example A15, 40 wt% in Example A16, 45 wt% in Example A17, Example A In Example 18, the content was 50 wt%, and in Example A4, the content was 5 wt%.
- ESR equivalent series resistance
- Table 4 shows the equivalent series resistance (ESR) of each of these solid electrolytic capacitors as an index with the equivalent series resistance (ESR) of the solid electrolytic capacitor of Example A4 set to 100.
- the weight ratio of the second material to the total amount of the first material composed of silver particles having a median diameter of 3 and the second material composed of silver particles having a median diameter of 0.5 ⁇ and acetylene black was used.
- the weight ratio W was 0.25 wt%.
- Example The ESR is significantly reduced as compared with the solid electrolytic capacitor of Example A9 and the solid electrolytic capacitors of Examples A17 and A18 in which the weight ratio W exceeds 40 wt%.
- the ESR was further reduced.
- Examples A 19, A 20 and Comparative Example 5 In Examples A19, A20 and Comparative Example 5, in the production of the solid electrolytic capacitor in Example A1 above, only the drying temperature was used to dry the mixed layer paste. The temperature was changed to 170 ° C in Example A19, 180 ° C in Example A20, and 150 ° C in Comparative Example 5, and otherwise the same as in Example A1 above. Similarly, the solid electrolytic capacitors of Examples A 19 and A 20 and Comparative Example 5 were produced. When the drying temperature of the mixed layer paste was set to 150 ° C. as in Comparative Example 5, the Ag 20 particles in the mixed layer paste were sufficiently reduced to silver particles. Was not done.
- the solid electrolytic capacitors of Examples A19, A20 and Comparative Example 5 fabricated in this manner also have an equivalent series resistance (ESR) at a frequency of 100 kHz in the same manner as described above.
- ESR equivalent series resistance
- Table 5 below shows the equivalent series resistance (ESR) of each of these solid electrolytic capacitors as an index with the equivalent series resistance (ESR) of the solid electrolytic capacitor of Example A1 as 100. Indicated.
- Example A la, A lb, Eighteenth and Comparative Example 13, lb, 1 c In Example A la, A lb, A le, in the production of the solid electrolytic capacitor in Example A 1 above. The kind of the binder used for producing the mixed layer paste was changed.
- Example Ala an epoxy resin was used as a binder and diethylene dalicol monobutyl ether was used as a solvent.
- Example A1b a polyester resin was used as a binder and cyclohexane was used as a solvent. Hexanone was used, and in Example Ale, phenol resin was used as the binder and propylene dalicol was used as the solvent, and the other conditions were the same as in Example A1 above.
- Example Ala an epoxy resin was used as a binder and diethylene dalicol monobutyl ether was used as a solvent.
- Example A1b a polyester resin was used as a binder and cyclohexane was used as a solvent. Hexanone was used, and in Example Ale, phenol resin was used as the binder and propylene dalicol was used as the solvent, and the other conditions were the same as in Example A1 above.
- the solid electrolytic capacitors of Examples A la, A lb, and A le were produced.
- Comparative Examples la, lb, and 1c the type of the binder used for the mixed layer paste was changed in the production of the solid electrolytic capacitor in Comparative Example 1 described above.
- Comparative Example la an epoxy resin was used as a binder and diethylene dalicol monobutyl ether was used as a solvent.
- Comparative Example 1b a polyester resin was used as a binder and a solvent was used as a solvent. Cyclohexanone was used, and in Comparative Example lc, a phenol resin was used as the binder and propylene glycol was used as the solvent, and otherwise the same as in Comparative Example 1 above.
- solid electrolytic capacitors of Comparative Examples 1a, lb, and 1c were produced.
- Example C1 to C3 the first material and the substantially spherical median which are included in the mixed layer 4b of the solid electrolytic capacitor in the above-described Example A4 and are composed of substantially spherical silver particles having a median diameter of 3 are used.
- the second material made of silver particles having a diameter of 0.5 m was changed.Otherwise, the solid electrolytic capacitors of Examples C1 to C3 were changed in the same manner as in Example A4 above. Produced.
- Example C1 flaky silver particles having a median of the maximum length L of 3 m and a ratio (LZd) of the maximum length L to the thickness d of 20 were added to the first material.
- flaky silver particles having a median of the maximum length L of 0.5 zm and a ratio (L / d) of the maximum length L to the thickness d (L / d) of 20 are used. .
- Example C2 flaky silver particles having a median of the maximum length L of 3 ⁇ and a ratio (LZd) of the maximum length L to the thickness d (LZd) of 20 were used as the first material.
- the second material silver particles having the same substantially spherical shape and a median diameter of 0.5 m as in Example A4 were used.
- Example C3 silver particles having the same substantially spherical shape and a median diameter of 3 zm as in Example A4 were used as the first material, and the median of the maximum length L was changed to the second material.
- the equivalent series resistance (ESR) at a frequency of 100 kHz was measured in the same manner as in the above case.
- the equivalent series resistance (ESR) of each of these solid electrolytic capacitors is shown in Table 7 below as an index with the equivalent series resistance (ESR) of the solid electrolytic capacitor of Example A4 set to 100.
- each of the solid electrolytic capacitors of Examples C1 to C3 using scale-like silver particles for at least one of the first material and the second material has substantially spherical silver particles for the first material and the second material.
- the ESR was reduced as compared with the solid electrolytic capacitor of Example A4 using flakes, and in particular, Example C1 using scale-like silver particles for both the first material and the second material was used. In the solid electrolytic capacitor of No. 1, the ESR was greatly reduced.
- the first material uses flaky silver particles having a median of the maximum length L of 3 ⁇
- flaky silver particles having a median of the maximum length L of 0.5 m are used, while the maximum for the thickness d of the first and second flaky silver particles is used.
- the solid electrolytic capacitors of Examples C4 to C4 were produced in the same manner as in Example C1 except that the ratio of length L (LZd) was changed.
- Example C4 the first and second flaky silver particles in which the ratio (L / d) of the maximum length L to the thickness d was 4 were obtained.
- the ratio (LZd) of the maximum length L to the thickness d was reduced in the first and second flaky silver particles in which the ratio (L / d) of the maximum length L to d was 50.
- the first and second flaky silver particles having a thickness of 100 were converted to the first and second silver particles having a maximum length L with respect to the thickness d (LZd) of 120.
- the scale-like silver particles were used.
- the equivalent series resistance (ESR) at a frequency of 100 kHz was measured in the same manner as described above.
- the equivalent series resistance (ESR) of each of these solid electrolytic capacitors is shown in Table 8 below as an index with the equivalent series resistance (ESR) of the solid electrolytic capacitor of Example A4 set to 100.
- Examples C1 and C4 to C4 using the first and second flaky silver particles having a ratio (L / d) of the maximum length L to the thickness d in the range of 4 to 100 were obtained.
- the ESR was greatly reduced.
- the first material made of silver particles having a median diameter of 2 / im or more, the conductive carbon particles and the Z
- the second layer composed of silver particles having a median diameter of 2 / m or more in this mixed layer is provided.
- a second material composed of conductive carbon particles and silver particles having a median diameter of 1 or less enters between the materials, improving the conductivity in the mixed layer and the adhesion between the mixed layer and the electrolyte layer. The contact resistance has also been reduced, and the equivalent series resistance in the high-frequency region has been greatly reduced.
- the adhesion between the mixed layer and the carbon layer is improved, The contact resistance has also been reduced, and the equivalent series resistance in the high-frequency range has been further reduced.
- the scale particles having a very small thickness with respect to the length are used for the silver particles used for the first material and the second material in the mixed layer, the silver particles of the first material are used. Also, the contact area of silver particles of the second material was increased, and the equivalent series resistance in the high-frequency region was further reduced.
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Abstract
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JP2005502484A JP4368349B2 (ja) | 2002-12-13 | 2003-12-03 | 固体電解コンデンサ及びその製造方法 |
US10/537,813 US7154743B2 (en) | 2002-12-13 | 2003-12-03 | Solid electrolytic capacitor and method for manufacturing same |
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Cited By (13)
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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 |
WO2013058018A1 (ja) | 2011-10-18 | 2013-04-25 | 昭和電工株式会社 | コンデンサの陽極体の製造方法 |
WO2013073253A1 (ja) | 2011-11-15 | 2013-05-23 | 昭和電工株式会社 | タングステン細粉の製造方法 |
WO2013080617A1 (ja) | 2011-11-29 | 2013-06-06 | 昭和電工株式会社 | タングステン細粉の製造方法 |
WO2013094252A1 (ja) | 2011-12-19 | 2013-06-27 | 昭和電工株式会社 | タングステンコンデンサの陽極及びその製造方法 |
WO2013172453A1 (ja) | 2012-05-18 | 2013-11-21 | 昭和電工株式会社 | コンデンサ素子の製造方法 |
WO2013190886A1 (ja) | 2012-06-22 | 2013-12-27 | 昭和電工株式会社 | コンデンサの陽極体 |
WO2013190885A1 (ja) | 2012-06-22 | 2013-12-27 | 昭和電工株式会社 | 固体電解コンデンサの陽極体 |
WO2014097698A1 (ja) | 2012-12-17 | 2014-06-26 | 昭和電工株式会社 | タングステン微粉の製造方法 |
US9530569B2 (en) | 2012-05-29 | 2016-12-27 | Showa Denko K.K. | Method for manufacturing solid electrolytic capacitor element |
US9691553B2 (en) | 2012-12-13 | 2017-06-27 | Showa Denko K.K. | Production method for tungsten anode body |
US9812624B2 (en) | 2008-01-17 | 2017-11-07 | Nichia Corporation | Method for producing conductive material, conductive material obtained by the method, electronic device containing the conductive material, light-emitting device, and method for producing light-emitting device |
WO2024116649A1 (ja) * | 2022-11-28 | 2024-06-06 | パナソニックIpマネジメント株式会社 | 固体電解コンデンサ |
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US20080232038A1 (en) * | 2005-09-04 | 2008-09-25 | Cerel (Ceramic Technologies) Ltd. | Method For Electrophoretic Deposition Of Conductive Polymer Into Porous Solid Anodes For Electrolyte Capacitor |
WO2012017618A1 (ja) | 2010-08-02 | 2012-02-09 | パナソニック株式会社 | 固体電解コンデンサ |
JPWO2021172272A1 (ja) * | 2020-02-28 | 2021-09-02 |
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JP3482983B2 (ja) | 1997-02-28 | 2004-01-06 | エルナー株式会社 | タンタル固体電解コンデンサ素子およびタンタル固体電解コンデンサ |
US6381121B1 (en) * | 1999-05-24 | 2002-04-30 | Showa Denko Kabushiki Kaisha | Solid electrolytic capacitor |
-
2003
- 2003-12-03 WO PCT/JP2003/015501 patent/WO2004055843A1/ja active Application Filing
- 2003-12-03 JP JP2005502484A patent/JP4368349B2/ja not_active Expired - Lifetime
- 2003-12-03 US US10/537,813 patent/US7154743B2/en not_active Expired - Lifetime
- 2003-12-08 TW TW092134518A patent/TWI231512B/zh not_active IP Right Cessation
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JPS5783022A (en) * | 1980-11-11 | 1982-05-24 | Matsushita Electric Ind Co Ltd | Solid electrolytic condenser |
JPS58161315A (ja) * | 1982-03-18 | 1983-09-24 | 日本電気ホームエレクトロニクス株式会社 | 電子部品 |
JPH0256915A (ja) * | 1988-08-22 | 1990-02-26 | Nec Corp | 固体電解コンデンサ |
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US9053860B2 (en) | 2010-12-24 | 2015-06-09 | Showa Denko K.K. | Tungsten powder, anode body for capacitors, and electrolytic capacitor |
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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 |
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WO2013172453A1 (ja) | 2012-05-18 | 2013-11-21 | 昭和電工株式会社 | コンデンサ素子の製造方法 |
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WO2024116649A1 (ja) * | 2022-11-28 | 2024-06-06 | パナソニックIpマネジメント株式会社 | 固体電解コンデンサ |
Also Published As
Publication number | Publication date |
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US7154743B2 (en) | 2006-12-26 |
TW200414248A (en) | 2004-08-01 |
JP4368349B2 (ja) | 2009-11-18 |
US20060114645A1 (en) | 2006-06-01 |
TWI231512B (en) | 2005-04-21 |
JPWO2004055843A1 (ja) | 2006-04-20 |
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