JP2008226971A - Manufacturing method for solid electrolytic capacitor - Google Patents
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- JP2008226971A JP2008226971A JP2007059926A JP2007059926A JP2008226971A JP 2008226971 A JP2008226971 A JP 2008226971A JP 2007059926 A JP2007059926 A JP 2007059926A JP 2007059926 A JP2007059926 A JP 2007059926A JP 2008226971 A JP2008226971 A JP 2008226971A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
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- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000003125 aqueous solvent Substances 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000007743 anodising Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
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- 239000011260 aqueous acid Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 239000008151 electrolyte solution Substances 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
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- 238000002048 anodisation reaction Methods 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 3
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BURBNIPKSRJAIQ-UHFFFAOYSA-N 2-azaniumyl-3-[3-(trifluoromethyl)phenyl]propanoate Chemical compound OC(=O)C(N)CC1=CC=CC(C(F)(F)F)=C1 BURBNIPKSRJAIQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940063284 ammonium salicylate Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、タンタル等の弁作用金属を使用した固体電解コンデンサの製造方法に関する。 The present invention relates to a method for manufacturing a solid electrolytic capacitor using a valve action metal such as tantalum.
弁作用金属としてタンタルを用いた固体電解コンデンサにおいてはタンタル粉末を成型・焼結した多孔質の陽極体を使用している。この陽極体の表面には、陽極酸化（化成ともいう）法によりタンタルの酸化皮膜（化成皮膜ともいう）が形成され、この化成皮膜が電解コンデンサの誘電体層となる。従来、タンタルの化成皮膜を形成する際には、リン酸や硝酸、酢酸、硫酸などの水溶液が広く用いられていた。 In a solid electrolytic capacitor using tantalum as a valve metal, a porous anode body obtained by molding and sintering tantalum powder is used. A tantalum oxide film (also called a chemical film) is formed on the surface of the anode body by an anodic oxidation (also called chemical conversion) method, and this chemical film becomes a dielectric layer of the electrolytic capacitor. Conventionally, an aqueous solution of phosphoric acid, nitric acid, acetic acid, sulfuric acid or the like has been widely used for forming a tantalum chemical conversion film.
このような水溶液を用いた場合、形成される化成皮膜は緻密で均一になるが、熱による変質劣化が生じる問題がある。これは２００〜３００℃程度の熱を付加した時に、酸化皮膜内に存在する酸素原子が熱拡散するためと考えられており、この変質により漏れ電流は悪化する。 When such an aqueous solution is used, the formed chemical conversion film is dense and uniform, but there is a problem that deterioration due to heat occurs. This is considered to be because oxygen atoms existing in the oxide film thermally diffuse when heat of about 200 to 300 ° C. is applied, and this alteration deteriorates the leakage current.
一方、特許文献１では高熱安定性に優れたアルミニウムの電極配線を形成する手法として、有機酸と非水溶媒とを含む電解液中で陽極酸化する方法が提案されている。
On the other hand,
従来、固体電解コンデンサでは、高温により酸化皮膜内の酸素原子が熱拡散するため、酸化皮膜が変質し、漏れ電流が悪化する欠点があった。他方、酸化皮膜に高熱安定性を付与するために、有機酸と非水溶媒とを含む電解液中にて酸化皮膜を形成しても、電解液の電気伝導度が低いために緻密な酸化皮膜を形成することが困難であり、酸化皮膜の形成直後においても漏れ電流特性が悪いという欠点があった。 Conventionally, in a solid electrolytic capacitor, oxygen atoms in the oxide film are thermally diffused at high temperatures, so that the oxide film is altered and leakage current is deteriorated. On the other hand, in order to impart high thermal stability to the oxide film, even if the oxide film is formed in an electrolyte containing an organic acid and a non-aqueous solvent, the oxide film has a dense oxide film due to the low electrical conductivity of the electrolyte. It is difficult to form the film, and the leakage current characteristic is poor even immediately after the formation of the oxide film.
また、特許文献２においては弁作用金属の多孔質陽極体を第一の電解質で陽極酸化し、さらに第二の電解質で陽極酸化する方法が記載されている。しかしながらこの方法は多孔質陽極体の外面の陽極酸化膜を厚くし、多孔質陽極体の内部ではより薄い陽極酸化膜を形成するためのものであり熱による変質劣化に対する問題は解決できなかった。
この状況にあって、本発明の課題は酸化皮膜に高熱安定性を付与し、かつ漏れ電流特性の優れる固体電解コンデンサの製造方法を提供することにある。 In this situation, an object of the present invention is to provide a method for producing a solid electrolytic capacitor that imparts high thermal stability to an oxide film and has excellent leakage current characteristics.
本発明の固体電解コンデンサの製造方法は、弁作用金属の多孔質体からなる陽極体を有機酸と非水溶媒とを含む電解液にて陽極酸化する第一の陽極酸化工程と、前記第一の陽極酸化工程後に、前記陽極体を酸水溶液にて陽極酸化する第二の陽極酸化工程と固体電解質層を形成する工程とを含むことを特徴とする。 The method for producing a solid electrolytic capacitor according to the present invention includes a first anodizing step in which an anode body made of a porous body of a valve metal is anodized with an electrolytic solution containing an organic acid and a non-aqueous solvent; After the anodizing step, a second anodizing step of anodizing the anode body with an acid aqueous solution and a step of forming a solid electrolyte layer are included.
また、前記酸水溶液がリン酸、硝酸、酢酸、硫酸から選択される少なくとも一種の水溶液であることが好ましい。 The acid aqueous solution is preferably at least one aqueous solution selected from phosphoric acid, nitric acid, acetic acid, and sulfuric acid.
本発明によれば、有機酸と非水溶媒とを含む電解液にて陽極酸化することにより、酸化皮膜に高熱安定性を付与し、さらにリン酸等の酸水溶液にて陽極酸化を追加することにより、漏れ電流特性に優れた酸化皮膜を形成することができる。すなわち酸化皮膜に高熱安定性を付与し、かつ漏れ電流特性の優れた固体電解コンデンサの製造方法を提供することができる。 According to the present invention, anodization is performed with an electrolytic solution containing an organic acid and a non-aqueous solvent, thereby imparting high thermal stability to the oxide film, and further anodization is performed with an acid aqueous solution such as phosphoric acid Thus, an oxide film having excellent leakage current characteristics can be formed. That is, it is possible to provide a method for producing a solid electrolytic capacitor that imparts high thermal stability to an oxide film and has excellent leakage current characteristics.
次に、本発明の実施の形態について説明する。本発明の実施の形態では、弁作用金属の多孔質体からなる陽極体を有機酸と非水溶媒とを含む電解液にて陽極酸化処理を行った後、リン酸等の酸水溶液にて陽極酸化処理を行うことで、高熱安定性および漏れ電流特性に優れた固体電解コンデンサを作製する。 Next, an embodiment of the present invention will be described. In the embodiment of the present invention, an anode body made of a porous body of a valve metal is anodized with an electrolyte containing an organic acid and a non-aqueous solvent, and then an anode with an acid aqueous solution such as phosphoric acid. By performing the oxidation treatment, a solid electrolytic capacitor excellent in high thermal stability and leakage current characteristics is produced.
まず、タンタル、ニオブなどの弁作用金属からなる陽極リードが導出された多孔質体からなる陽極体を有機酸と非水溶媒とを含む電解液にて陽極酸化処理を行う。ここで用いられる電解液は有機酸として例えばサリチル酸、フタル酸、安息香酸、γ―レゾルシン酸、乳酸、リンゴ酸を、非水溶媒として例えばエチレングリコール、プロピレングリコールを使用することができる。有機酸の塩を形成するための陽イオンは、とくに限定されないが、例えばアンモニウムイオン、１、２、３または４級のアルキルアンモニウムイオンを使用することができる。なおこれらの有機酸や非水溶媒は１種を単独で用いても、２種以上を混合して用いてもよい。 First, an anode body made of a porous body from which an anode lead made of a valve action metal such as tantalum or niobium is derived is anodized with an electrolyte containing an organic acid and a non-aqueous solvent. The electrolyte used here can use, for example, salicylic acid, phthalic acid, benzoic acid, γ-resorcinic acid, lactic acid, malic acid as the organic acid, and ethylene glycol or propylene glycol as the non-aqueous solvent. The cation for forming the salt of the organic acid is not particularly limited, and for example, ammonium ion, 1, 2, 3 or quaternary alkyl ammonium ion can be used. These organic acids and non-aqueous solvents may be used alone or in combination of two or more.
次に、酸水溶液にて再度陽極酸化処理を行う。ここで用いられる酸水溶液はリン酸、硝酸、酢酸、硫酸などの水溶液を使用することができる。このとき、有機酸と非水溶媒とを含む電解液にて行う第一の陽極酸化と、酸水溶液にて行う第二の陽極酸化では、印加電圧、電流密度は同一にすることが好ましい。 Next, anodization is again performed with an acid aqueous solution. The acid aqueous solution used here can be an aqueous solution of phosphoric acid, nitric acid, acetic acid, sulfuric acid, or the like. At this time, it is preferable that the applied voltage and the current density be the same in the first anodic oxidation performed with an electrolytic solution containing an organic acid and a non-aqueous solvent and the second anodic oxidation performed with an aqueous acid solution.
上述のように陽極酸化により陽極体に酸化皮膜からなる誘電体層を形成した後、その上に二酸化マンガンまたは導電性高分子からなる固体電解質層、および陰極引き出し層としてのグラファイトペースト層を形成し、さらに銀ペースト層を形成し、固体電解コンデンサ素子を作製する。さらに例えばこの素子の陽極リード線に陽極端子を、陰極に陰極端子を接合し、外装樹脂で封止し、陽極端子および陰極端子をリードフレームから分離後、成形して固体電解コンデンサとする。 After forming a dielectric layer made of an oxide film on the anode body by anodic oxidation as described above, a solid electrolyte layer made of manganese dioxide or a conductive polymer and a graphite paste layer as a cathode lead layer are formed thereon. Further, a silver paste layer is formed to produce a solid electrolytic capacitor element. Further, for example, an anode terminal is joined to the anode lead wire of this element, and a cathode terminal is joined to the cathode, and sealed with an exterior resin, and the anode terminal and the cathode terminal are separated from the lead frame and then molded to obtain a solid electrolytic capacitor.
以下、本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically described by way of examples.
まず、陽極リード線となるタンタル線のまわりに、タンタル粉末（粉末ＣＶ値：２３，０００μＦ・Ｖ／ｇ）をプレス成型し、高真空・高温度で焼結し、寸法３．６ｍｍ×０．９ｍｍ×４．５ｍｍのコンデンサ素子を作製した。次に陽極酸化により素子表面に酸化皮膜を形成する際、酸化皮膜に高熱安定性を付与するため、有機酸と非水溶媒とを含む電解液を使用し第一の陽極酸化を、電解液として３重量％サリチル酸アンモニウムのエチレングリコール溶液（含水量１０重量％）を使用し、常温にて１０００ＣＶあたりの電流を２ｍＡ、印加電圧を２０Ｖ、処理時間を４時間で行った。さらに漏れ電流特性に優れた酸化皮膜を形成するために、リン酸水溶液を使用し第二の陽極酸化を電解液としてリン酸水溶液（電導度：９００ｍＳ／ｍ）、液温を７０℃、１０００ＣＶあたりの電流を２ｍＡ、印加電圧を２０Ｖ、処理時間を４時間で行った。 First, a tantalum powder (powder CV value: 23,000 μF · V / g) is press-molded around a tantalum wire serving as an anode lead wire, sintered at a high vacuum and at a high temperature, and a size of 3.6 mm × 0. A capacitor element of 9 mm × 4.5 mm was produced. Next, when an oxide film is formed on the element surface by anodic oxidation, in order to impart high thermal stability to the oxide film, an electrolytic solution containing an organic acid and a non-aqueous solvent is used, and the first anodic oxidation is performed as the electrolytic solution. An ethylene glycol solution of 3% by weight ammonium salicylate (water content: 10% by weight) was used. At room temperature, the current per 1000 CV was 2 mA, the applied voltage was 20 V, and the treatment time was 4 hours. Furthermore, in order to form an oxide film with excellent leakage current characteristics, a phosphoric acid aqueous solution is used and the second anodic oxidation is used as an electrolytic solution. The phosphoric acid aqueous solution (conductivity: 900 mS / m), the liquid temperature is 70 ° C. per 1000 CV The current was 2 mA, the applied voltage was 20 V, and the treatment time was 4 hours.
（比較例１）
コンデンサ素子表面に有機酸と非水溶媒とを含む電解液を使用し第一の陽極酸化を実施し、その後リン酸水溶液を使用し第二の陽極酸化を行わず固体電解質層を形成した以外は実施例と同様に、陽極酸化処理を行った。
(Comparative Example 1)
Except that the first anodic oxidation was performed using an electrolytic solution containing an organic acid and a nonaqueous solvent on the capacitor element surface, and then a solid electrolyte layer was formed without using the second anodic oxidation using a phosphoric acid aqueous solution. As in the example, anodization was performed.
（比較例２）
コンデンサ素子表面に有機酸と非水溶媒とを含む電解液を使用し第一の陽極酸化を実施せず、リン酸水溶液を使用し第二の陽極酸化のみを行なった後、固体電解質層を形成した以外は実施例と同様に、陽極酸化処理を行った。
(Comparative Example 2)
The electrolytic solution containing organic acid and non-aqueous solvent is used on the capacitor element surface and the first anodic oxidation is not performed, but the second anodic oxidation is performed using the phosphoric acid aqueous solution, and then the solid electrolyte layer is formed. Anodizing treatment was performed in the same manner as in the example except that.
上述のように陽極酸化処理を行った実施例、比較例１、比較例２のコンデンサ素子について湿式の漏れ電流およびＥＳＲを測定した。漏れ電流はリン酸水溶液（電導度：１０ｍＳ／ｍ）で１Ｖ単位で昇圧し各電圧印加時間１秒値を測定し、ＥＳＲは２５０℃、３０分の熱処理前後での酸化皮膜抵抗を６０％硫酸水溶液浸漬後５分、２０Ｈｚで測定した。図１は実施例、比較例１、２の漏れ電流を示す図であり、図２は実施例、比較例１、２の２５０℃、３０分の熱処理前後での酸化皮膜抵抗を示す図である。比較例１では、図１に示す通り漏れ電流値が大きいが、図２に示す通り酸化皮膜抵抗の高熱安定性に優れる。比較例２では、逆に図２に示す通り酸化皮膜抵抗に悪化が生じるが、漏れ電流値に優れる。一方、実施例は、図１および図２に示す通り、比較例１と比較例２のそれぞれの課題を改良した結果として漏れ電流特性および高熱安定性に優れる酸化皮膜を形成することが可能となる。 Wet leakage current and ESR were measured for the capacitor elements of Examples, Comparative Example 1, and Comparative Example 2 that were anodized as described above. Leakage current was boosted by phosphoric acid aqueous solution (conductivity: 10 mS / m) in increments of 1V, each voltage application time was measured for 1 second, ESR was 60% sulfuric acid oxide resistance before and after heat treatment at 250 ° C for 30 minutes It measured at 20 Hz for 5 minutes after immersion in aqueous solution. FIG. 1 is a diagram showing leakage currents of Examples and Comparative Examples 1 and 2, and FIG. 2 is a diagram showing oxide film resistances before and after heat treatment at 250 ° C. for 30 minutes in Examples and Comparative Examples 1 and 2. . In Comparative Example 1, the leakage current value is large as shown in FIG. 1, but the high thermal stability of the oxide film resistance is excellent as shown in FIG. In Comparative Example 2, on the contrary, the oxide film resistance deteriorates as shown in FIG. 2, but the leakage current value is excellent. On the other hand, as shown in FIGS. 1 and 2, in the example, as a result of improving the respective problems of Comparative Example 1 and Comparative Example 2, it is possible to form an oxide film having excellent leakage current characteristics and high thermal stability. .
以上、本発明の実施の形態の例を説明したが、本発明はこれに限られるものではなく、この発明の要旨を逸脱しない範囲の設計変更があっても、本発明に含まれる。すなわち、当業者であれば、なしえるであろう各種変形、修正を含むことはもちろんである。 As mentioned above, although the example of embodiment of this invention was demonstrated, this invention is not limited to this, Even if there is a design change of the range which does not deviate from the summary of this invention, it is contained in this invention. That is, it goes without saying that various modifications and corrections that can be made by those skilled in the art are included.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014531139A (en) * | 2011-10-26 | 2014-11-20 | ハー．ツェー．スタルク ゲゼルシャフト ミット ベシュレンクテル ハフツングＨ．Ｃ． Ｓｔａｒｃｋ ＧｍｂＨ | Strain-free anode stencil-printed on Ta / Nb sheets |
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| JPS63268234A (en) * | 1987-04-27 | 1988-11-04 | Matsushita Electric Ind Co Ltd | Manufacturing method of solid electrolytic capacitor |
| JP2003086593A (en) * | 2001-09-14 | 2003-03-20 | Mitsubishi Chemicals Corp | Manufacturing method of electrode wiring and its use |
| JP2003512531A (en) * | 1999-10-19 | 2003-04-02 | ケメット・エレクトロニクス・コーポレーション | Method of anodizing tantalum powder |
| JP2005252224A (en) * | 2004-02-04 | 2005-09-15 | Sanyo Electric Co Ltd | Solid electrolytic capacitor and manufacturing method thereof |
| JP2006278789A (en) * | 2005-03-29 | 2006-10-12 | Sanyo Electric Co Ltd | Solid electrolytic capacitor and its fabrication process |
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| JPS63268234A (en) * | 1987-04-27 | 1988-11-04 | Matsushita Electric Ind Co Ltd | Manufacturing method of solid electrolytic capacitor |
| JP2003512531A (en) * | 1999-10-19 | 2003-04-02 | ケメット・エレクトロニクス・コーポレーション | Method of anodizing tantalum powder |
| JP2003086593A (en) * | 2001-09-14 | 2003-03-20 | Mitsubishi Chemicals Corp | Manufacturing method of electrode wiring and its use |
| JP2005252224A (en) * | 2004-02-04 | 2005-09-15 | Sanyo Electric Co Ltd | Solid electrolytic capacitor and manufacturing method thereof |
| JP2006278789A (en) * | 2005-03-29 | 2006-10-12 | Sanyo Electric Co Ltd | Solid electrolytic capacitor and its fabrication process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014531139A (en) * | 2011-10-26 | 2014-11-20 | ハー．ツェー．スタルク ゲゼルシャフト ミット ベシュレンクテル ハフツングＨ．Ｃ． Ｓｔａｒｃｋ ＧｍｂＨ | Strain-free anode stencil-printed on Ta / Nb sheets |
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