WO2015016066A1 - 固体電解コンデンサ素子の陽極体及びその製造方法 - Google Patents
固体電解コンデンサ素子の陽極体及びその製造方法 Download PDFInfo
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- WO2015016066A1 WO2015016066A1 PCT/JP2014/068907 JP2014068907W WO2015016066A1 WO 2015016066 A1 WO2015016066 A1 WO 2015016066A1 JP 2014068907 W JP2014068907 W JP 2014068907W WO 2015016066 A1 WO2015016066 A1 WO 2015016066A1
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- Prior art keywords
- electrolytic capacitor
- solid electrolytic
- dielectric layer
- capacitor element
- anode body
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0032—Processes of manufacture formation of the dielectric layer
-
- 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
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/07—Dielectric layers
Definitions
- the present invention relates to an anode body of a solid electrolytic capacitor element. More specifically, the present invention relates to an anode body of a solid electrolytic capacitor element with a small capacity reduction due to excessive formation of a dielectric layer and a small leakage current, and a method for manufacturing the same.
- valve metal When the valve metal is molded and then sintered, a sintered body having appropriate pores is obtained.
- this sintered body is formed at a predetermined voltage, a dielectric layer having a uniform thickness corresponding to the applied voltage is formed.
- the semiconductor layer laminated on the dielectric layer is polymerized chemically and / or electrochemically, for example, by immersing the sintered body on which the dielectric layer is formed as an anode body in a chemical agent that becomes the semiconductor layer. Is formed.
- JP 2008-166851 A (US7349198) JP 2010-232699 A (US 7206192)
- An object of the present invention is to solve the problem of capacity reduction due to excessive formation of a dielectric layer, and to provide a solid electrolytic capacitor element with low leakage current while maintaining high capacity.
- the present inventors diligently studied to achieve the above object. As a result, the following invention has been completed. That is, the present invention relates to the following [1] to [12].
- An anode body of a solid electrolytic capacitor element having a dielectric layer on a surface layer of a sintered body, wherein at least a part of the surface of the valve metal particles constituting the sintered body is covered with the dielectric layer.
- An anode body for a solid electrolytic capacitor element wherein a part of the thickness of the dielectric layer on the surface of the particle is thicker than the other part.
- the solid electrolytic capacitor element and the capacitor manufactured based on the anode body of the present invention maintain a high capacity and have a small leakage current.
- FIG. 4 is a scanning electron micrograph of a fracture surface of an anode body having a dielectric layer on the surface obtained in Example 4.
- FIG. 4 is a scanning electron micrograph of a fracture surface of an anode body having a dielectric layer on the surface obtained in Comparative Example 3.
- FIG. 4 is a scanning electron micrograph of a fracture surface of an anode body having a dielectric layer on the surface obtained in Comparative Example 3.
- valve metal When the valve metal is molded and then sintered, the particles are bonded to each other, resulting in a sintered body having a complicated internal space that is connected and integrated in a three-dimensional bead shape.
- this sintered body When this sintered body is immersed in a chemical conversion solution and formed at a predetermined voltage, a dielectric layer having a uniform thickness corresponding to the applied voltage is formed on a particle surface layer connected in a bead shape.
- a semiconductor layer is formed on a dielectric layer, a chemical used for forming the semiconductor layer reaches through the internal space at a depth of 70 to 90% from the surface layer, and a part thereof is chemically and / or Disappears due to physical deterioration.
- the dielectric layer is likely to be deteriorated by the drug in a part where the drug easily reaches in the internal space of the dielectric layer.
- the thickness of the dielectric layer is reduced in the portion where the drug easily reaches, causing an increase in leakage current.
- the thickness of the dielectric layer where the chemical used in forming the semiconductor is likely to reach is selectively increased in advance, so that leakage is maintained while maintaining a high capacity. Suppresses current increase.
- a solid electrolytic capacitor element has at least a sintered body obtained by sintering a valve metal and a dielectric layer.
- the metal used for the sintered body examples include valve action metals such as tantalum, niobium, titanium and tungsten, alloys and compositions containing these metals as main components, and conductive oxides of these metals. Two or more kinds of these metals may be mixed and used. Further, the alloy includes a partially alloyed alloy.
- the sintered body may contain a metal other than the main component as long as it does not adversely affect the capacitor characteristics.
- the metal other than the main component include valve metals such as tantalum, niobium, aluminum, titanium, vanadium, zinc, molybdenum, hafnium, and zirconium.
- the method for producing the sintered body is not particularly limited.
- tungsten when used as the valve action metal, a raw material powder composed of tungsten powder and other metal particles is formed by pressing to form a molded body. Can be obtained by firing it.
- a binder may be mixed with the raw material powder.
- Various conditions such as the amount of powder and the molding apparatus can be appropriately set so as to obtain a desired molding density and the like.
- an anode lead wire is embedded in a molded body and planted to form a terminal of the anode body when the raw material powder is pressure-molded.
- a metal wire of each valve action metal can be used.
- an anode lead wire is later welded to the sintered body.
- a metal plate or metal foil may be planted or connected to the sintered body instead of the metal wire.
- Calcination temperature and calcination time are not particularly limited. However, if the calcination is performed at a high temperature or too long, spaces (pores) between the raw material powders are reduced, and the pore volume of the sintered body becomes too small. When firing is performed at a low temperature or for a short time, the strength is insufficient, and in some cases, the sintered body may collapse.
- the atmosphere during firing is not particularly limited, but is preferably reduced.
- the process which contains silicification, boride, or carbonization and / or nitrogen or phosphorus at the time of baking can also be performed.
- a dielectric layer thicker than the other portion is formed on a part of the particle surface layer by performing a treatment with an oxidizing agent aqueous solution.
- the chemical conversion treatment and the treatment with the oxidizing agent aqueous solution will be described below. 1.
- Chemical conversion treatment can be performed by chemical oxidation and / or electrolytic oxidation.
- the chemical conversion treatment by chemical oxidation is performed by immersing the sintered body in a solution containing the oxidizing agent. This chemical conversion treatment may be repeated a plurality of times.
- a voltage is applied in a state where the sintered body is immersed in a solution containing the oxidizing agent.
- the voltage is applied between the sintered body (anode) and the counter electrode (cathode). Energization of the sintered body can be performed through the anode lead wire.
- the voltage and voltage application time in voltage application are not particularly limited, and may be determined by an ordinary method. Moreover, the kind, concentration, etc. of the oxidizing agent to be used are not particularly limited, and may be determined according to a conventional method.
- the sintered body is washed with pure water. By this washing, the chemical conversion liquid is removed as much as possible.
- water washing it is preferable to remove water adhering to the surface or water soaked in pores of the sintered body at a temperature lower than the boiling point of water at the pressure at the time of removal. By performing this operation before the high-temperature drying process described later, deterioration of the dielectric layer can be suppressed, and the capacity in the high frequency range can be easily maintained.
- the removal of water is performed, for example, by contacting with a solvent having miscibility with water.
- a solvent having miscibility with water alcohols used in a conventional method can be used.
- the drying temperature is not particularly limited, but if the temperature is too low, the effect of increasing the capacitance in the high frequency region may not be produced, and the capacitance may vary between elements. If the temperature during drying is too high, the leakage current may increase or the dielectric loss tangent may increase.
- the drying time is not particularly limited as long as the stability of the dielectric layer can be maintained.
- the oxidizing agent used here is preferably a water-soluble oxidizing agent that is insoluble in alcohol.
- halogen acid compounds such as perchloric acid, chlorous acid, hypochlorous acid and salts thereof; organic acid peroxides such as peracetic acid, perbenzoic acid and salts and derivatives thereof; And at least one selected from the group consisting of persulfate compounds such as salts thereof.
- persulfate compounds such as ammonium persulfate, potassium persulfate, and potassium persulfate are preferred from the viewpoints of ease of handling, stability as an oxidizing agent, water solubility, and alcohol insolubility.
- These oxidizing agents can be used alone or in combination of two or more.
- the oxidizing agent is water-soluble and insoluble in alcohol
- after the treatment with the oxidizing agent aqueous solution when the sintered body is immersed in alcohol, only water in the oxidizing agent aqueous solution is removed.
- alcohol a minute amount of water that has not been removed by alcohol, and the deposited oxidant are left in the dielectric layer internal space.
- the sintered body is heated and dried, the metal in the portion where the oxidizing agent remains is oxidized, and the dielectric layer becomes thick only in that portion.
- the thickening of the dielectric layer by the above operation is a portion where the aqueous oxidizer solution easily penetrates, and this is a portion where the chemical used in forming the semiconductor layer, which is a subsequent process, is easy to penetrate, that is, the dielectric layer due to the penetration of the chemical. It is also a part that tends to deteriorate. According to the above operation, it is possible to selectively increase the thickness of the dielectric layer only in such a portion, and as a result, it is possible to form a thick dielectric layer in a portion where deterioration due to penetration of the drug is a concern. .
- the concentration of the oxidizing agent aqueous solution is preferably 0.1% by mass or more and saturated solubility or less. More preferably, it is 0.15 mass% or more and saturated solubility or less, More preferably, it is 0.2 mass% or more and saturated solubility or less.
- concentration of the oxidant is less than 0.1% by mass, it is not possible to form a dielectric layer having a sufficient thickness by only immersing it once in the oxidant aqueous solution, and LC deterioration cannot be prevented.
- the concentration of the chemical conversion solution is set in the above range and the number of immersions is set to one.
- the drying temperature of the alcohol, a small amount of water, and the oxidizing agent present in the dielectric layer internal space after immersion in alcohol is preferably 100 ° C. or higher, but can be dried at a temperature of 100 ° C. or lower under reduced pressure conditions.
- the temperature may be determined by examining the oxidation reaction temperature of the oxidizing agent used.
- the drying time can be several minutes to several tens of minutes to form a dielectric layer having a desired thickness.
- a dielectric layer in which part of the particle surface layer is thicker than the other part can be formed.
- the thickness of the dielectric layer is preferably 1.2 times or more that the thickest portion of the dielectric layer is thinner than the thinnest portion. More preferably, it is 1.2 to 3 times, and further preferably 1.5 to 3 times.
- “the thickest part of the dielectric layer” and “the thinnest part” are measured, for example, by observing the fracture surface of the sintered body on which the dielectric layer is formed, using a scanning electron microscope or the like. The thickest part and the thinnest part of the dielectric layer.
- a semiconductor layer is formed on the dielectric layer formed by the above method.
- the semiconductor layer used in the conventional solid electrolytic capacitor element can be used without limitation.
- a conductor layer such as a carbon paste layer, a silver paste layer, or a metal plating layer may be formed on the semiconductor layer.
- a cathode lead is electrically connected to the conductor layer, and a part of the cathode lead is exposed outside the exterior of the electrolytic capacitor to become a cathode external terminal.
- an anode lead is electrically connected to the anode body via an anode lead wire, and a part of the anode lead is exposed outside the exterior of the electrolytic capacitor and becomes an anode external terminal.
- a normal lead frame can be used to attach the cathode lead and the anode lead. Subsequently, the exterior can be formed by sealing with resin or the like to obtain a capacitor.
- the capacitor thus fabricated can be subjected to an aging treatment as desired.
- the capacitor according to the present invention can be used by being mounted on various electric circuits or electronic circuits.
- Examples 1-2 [Production of sintered body] Sodium fluorinated tantalate was reduced with sodium to obtain a primary powder (average particle size 0.6 ⁇ m) of tantalum (Ta), which was granulated to obtain a secondary powder (average particle size 115 ⁇ m). Form and sinter the secondary powder to sinter the sintered body (size 1.0 x 2.3 x 1.7 mm, 1.0 x 2.3 mm center of tantalum lead wire of 0.24 mm ⁇ ) Obtained.
- Example 1 Treatment with Oxidizing Aqueous Solution After washing with water, removing water, and drying, Example 1 was immersed in a saturated aqueous ammonium persulfate solution for 1 minute, and Example 2 was immersed in a 0.2% aqueous ammonium persulfate solution for 5 minutes. After the immersion in the oxidizer aqueous solution, the treated sintered body was pulled up and immediately immersed in ethanol for 10 minutes. Subsequently, it was dried at 125 ° C. for 15 minutes, washed with water to remove the oxidant solute remaining in the inner space of the dielectric layer, dried, and water was removed.
- Comparative Example 1 A solid electrolytic capacitor element was produced in the same manner as in Example 1 except that the treatment with the oxidizing agent aqueous solution was not performed. Observation with a scanning electron microscope confirmed that the dielectric layer covered the outer surface of the primary particles with a uniform thickness (about 36 to 39 nm).
- Example 3 Instead of the tantalum primary powder, a powder obtained by pulverizing hydrogen-absorbed niobium (Nb) ingot (average particle size 0.4 ⁇ m) was used as the primary powder, and granulated secondary powder having an average particle size of 100 ⁇ m A solid electrolytic capacitor element was produced in the same manner as in Example 1 except that the powder was obtained and the immersion in the oxidizer aqueous solution was performed for 5 minutes.
- the dielectric layer after the formation had a uniform thickness of 42 to 46 nm, but the dielectric layer after the treatment with the oxidant aqueous solution has a scanning type that the partial surface layer of the primary particles has a thickness of 70 nm. It confirmed with the electron microscope.
- Comparative Example 2 A solid electrolytic capacitor element was produced in the same manner as in Example 3 except that the treatment with the aqueous oxidizing agent solution was not performed. Observation with a scanning electron microscope confirmed that the dielectric layer covered the outer surface of the primary particles with a uniform thickness (about 42 to 46 nm).
- Example 4 Instead of tantalum primary powder, powder obtained by reducing hydrogen trioxide with tungsten acid (average particle size 0.5 ⁇ m) was used as the primary powder, and silicon powder (average particle size 0.7 ⁇ m) was used as the primary powder. .2% by mass mixing to form secondary powder (average particle size 85 ⁇ m), and at the time of chemical conversion, using 0.5% by mass ammonium persulfate instead of 2% by mass phosphoric acid aqueous solution, conversion at 15V A solid electrolytic capacitor element was produced in the same manner as in Example 2 except that the oxidizing agent was changed to 0.2% potassium persulfate and that the oxidizing agent was dried at 105 ° C. for 10 minutes.
- the dielectric layer after the formation had a uniform thickness of 38 to 42 nm, but the dielectric layer after the treatment with the oxidant aqueous solution has a scanning type that the surface layer of a part of the primary particles has a thickness of 90 nm. This was confirmed by electron microscope observation. The observation result (magnification ⁇ 10 5 ) by the scanning microscope is shown in FIG.
- Comparative Example 3 A solid electrolytic capacitor element was produced in the same manner as in Example 4 except that the treatment with the oxidizing agent aqueous solution was not performed. Observation with a scanning electron microscope confirmed that the dielectric layer covered the outer surface of the primary particles with a uniform thickness (about 38 to 42 nm). The observation result (magnification ⁇ 10 5 ) by the scanning microscope is shown in FIG.
- Comparative Example 4 A solid electrolytic capacitor element was produced in the same manner as in Comparative Example 3 except that the formation voltage was 25V. Observation with a scanning electron microscope confirmed that the dielectric layer covered the outer surface of the primary particles with a uniform thickness (about 48 to 52 nm).
- Table 1 shows the results of measuring the capacity and leakage current by the method described below.
- [capacity] The lead wire wired to the LCR measuring instrument (manufactured by Agilent) was applied to the conductor layer of the solid electrolytic capacitor element and the anode lead wire planted on the solid electrolytic capacitor element, and the capacity at 120 Hz was measured at a bias voltage of 4V.
- [Leak current] 4 V was applied to the solid electrolytic capacitor element at room temperature. When 30 seconds passed from the start of voltage application, the current value (leakage current) of the circuit from the positive terminal of the power source to the anode lead wire of the solid electrolytic capacitor element, the conductor layer of the solid electrolytic capacitor element, and the negative terminal of the power source was measured. .
- the solid electrolytic capacitor elements (Examples 1 to 4) according to the present invention have a capacity equal to or greater than that of the comparative solid electrolytic capacitor elements (Comparative Examples 1 to 4), and leaks. The current is low.
- the thickness of the dielectric layer is substantially uniform, whereas the solid electrolytic capacitor element according to the present invention (Example 4, FIG. 1).
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Abstract
Description
誘電体層上に積層される半導体層は、誘電体層が形成された焼結体を陽極体として、半導体層となる薬剤に浸漬する等して、化学的及び/または電気化学的に重合することにより形成される。
特開2008-166851号公報(US7349198;特許文献1)では、陽極体上に、ニオブ及び酸素を主成分とする第1誘電体層と、リンまたはイオウを含む第2誘電体層と、陰極とを順次形成してなる固体電解コンデンサについて開示している。
特開2010-232699号公報(US7206192;特許文献2)では、陽極体上に、陽極体の一部が酸化されて形成される第1誘電体層と、第1の誘電体層上に形成された第2誘電体層と、陰極とを順次形成してなる固体電解コンデンサであって、第2誘電体層中の酸素濃度が第1誘電体層側から陰極側に向かって減少している固体電解コンデンサについて開示している。
[2] 焼結体の表層上に誘電体層を有する固体電解コンデンサ素子の陽極体であって、前記焼結体を構成する少なくとも一部の弁作用金属の粒子表面が前記誘電体層で覆われ、前記誘電体層の最も厚い部分の厚さが、最も薄い部分の厚さの1.2倍以上である前項1に記載の固体電解コンデンサ素子の陽極体。
[3] 前記弁作用金属が、タンタル、ニオブ、チタン、タングステン及びこれら金属の合金の少なくとも1種である前項1または2に記載の固体電解コンデンサ素子の陽極体。
[4] 前項1~3のいずれかに記載の陽極体の上に、半導体層及び導電体層が順次形成されてなる固体電解コンデンサ素子。
[6] 前記誘電体層の最も厚い部分の厚さが、最も薄い部分の厚さの1.2倍以上である前項5に記載の固体電解コンデンサ素子の陽極体の製造方法。
[7] 前記酸化剤が、水溶性で、かつアルコールに非溶解性の酸化剤である前項5または6に記載の固体電解コンデンサ素子の陽極体の製造方法。
[8] 前記酸化剤が、過硫酸化合物である前項5~7のいずれかに記載の固体電解コンデンサ素子の陽極体の製造方法。
[9] 前記酸化剤が、ハロゲン酸化合物、及び有機過酸化物の少なくとも1種である前項5~7のいずれかに記載の固体電解コンデンサ素子の陽極体の製造方法。
[10] 前記酸化剤の濃度が、0.1質量%以上飽和溶解度以下である前項5~9のいずれかに記載の固体電解コンデンサ素子の陽極体の製造方法。
[11] 前記誘電体層を化学酸化及び/または電解酸化により形成する前項5に記載の固体電解コンデンサ素子の陽極体の製造方法。
[12] 前項5~11のいずれかに記載の製造方法により得られた陽極体の上に、半導体層及び導電体層を順次積層することを含む、固体電解コンデンサ素子の製造方法。
通常、誘電体層上に半導体層を形成するに際し、表層から70~90%の深さまでは内部空間を介して半導体層形成のために用いる薬剤が到達し、その一部は化学的及び/または物理的な劣化により消失する。この時、誘電体層の内部空間のうち、薬剤が到達しやすい部分では、誘電体層が薬剤によって劣化しやすくなると推測される。結果的に、該薬剤が到達しやすい部分においては、誘電体層の厚さが薄くなり、漏れ電流増大の原因になる。
本発明の一実施形態に係る固体電解コンデンサ素子は、弁作用金属を焼結した焼結体と誘電体層とを少なくとも有するものである。
1.化成処理
化成処理は、化学酸化及び/または電解酸化により行うことができる。
化学酸化による化成処理は、前記酸化剤を含有する溶液に焼結体を浸漬して行う。この化成処理は複数回繰り返してもよい。
電解酸化による化成処理は、前記酸化剤を含有する溶液に焼結体を浸漬した状態で、電圧を印加する。電圧は、焼結体(陽極)と対電極(陰極)との間に印加する。焼結体への通電は陽極リード線を通じて行うことができる。電圧印加における電圧や電圧印加時間は特に限定されず、定法によって決定すればよい。
また、使用する酸化剤の種類、濃度等も特に限定されず、定法に従って決定すればよい。
乾燥の時間は、誘電体層の安定性が維持できる範囲であれば特に制限されない。
上記に従って化成処理した焼結体を、酸化剤水溶液に浸漬させ、その後アルコールに浸漬する。なお、酸化剤水溶液に浸漬した後は、なるべく速やかにアルコール浸漬に移行することが好ましい。
乾燥後は焼結体を水洗して酸化剤を除去することが好ましい。
ここで、「誘電体層の最も厚い部分」及び「最も薄い部分」とは、例えば、誘電体層を形成した焼結体の破断面を、走査型電子顕微鏡等を用いて観察することによって測定される誘電体層の最も厚い部分、及び最も薄い部分である。
[焼結体の作製]
フッ化タンタル酸カリウムをナトリウム還元して、タンタル(Ta)の一次粉(平均粒径0.6μm)を得、これを造粒して二次粉(平均粒径115μm)を得た。二次粉を成形、焼結して焼結体(大きさ1.0×2.3×1.7mm、1.0×2.3mm面中央に0.24mmφのタンタルリード線を植立)を得た。
1.化成処理
焼結体を、2質量%リン酸水溶液に浸し、60℃、5時間、20Vで化成処理を行った。化成処理を行った焼結体の破断面を日本電子株式会社製走査型電子顕微鏡JSM-7500FAで確認したところ、誘電体層が、一次粒子の外表を均一な厚み(約36~39nm)で覆っていることを確認した。
2.酸化剤水溶液による処理
水洗浄、水除去、乾燥を行った後、実施例1は飽和過硫酸アンモニウム水溶液に1分間、実施例2は0.2%過硫酸アンモニウム水溶液に5分間浸漬した。酸化剤水溶液への浸漬後、処理した焼結体を引き上げて速やかにエタノールに10分間浸漬した。続いて125℃で15分乾燥した後、水洗して誘電体層内部空間に残った酸化剤の溶質を除去し、乾燥し、水を除去した。
以上の操作により誘電体層を形成した焼結体を陽極体として、定法に従って、ベンゾキノンスルフォン酸をドーパントとしてピロールを電解重合し、導電性高分子からなる半導体層を形成した。次にカーボン層、及び銀層を定法に従って順次積層して固体電解コンデンサ素子を作製した。
得られた陽極体の破断面を走査型電子顕微鏡で観察して、誘電体層の厚みが一部厚くなっていることを確認した。実施例1及び実施例2共に粒子表層の誘電体層の一部において、厚みがおおよそ80nmになっている部分が存在することを確認した。
酸化剤水溶液による処理を行わなかったこと以外は実施例1と同様にして、固体電解コンデンサ素子を作製した。走査型電子顕微鏡による観察により、誘電体層が、一次粒子の外表を均一な厚み(約36~39nm)で覆っていることを確認した。
タンタル一次粉の代わりに、水素吸収させたニオブ(Nb)インゴットを粉砕して得た粉末(平均粒径0.4μm)を一次粉として使用したこと、造粒して平均粒径100μmの二次粉を得たこと、酸化剤水溶液への浸漬を5分にしたこと以外は実施例1と同様にして固体電解コンデンサ素子を作製した。化成後の誘電体層は、42~46nmの均一な厚みを有していたが、酸化剤水溶液による処理後の誘電体層は、一次粒子の一部表層が70nmの厚みを有することを走査型電子顕微鏡により確認した。
酸化剤水溶液による処理を行わなかったこと以外は実施例3と同様にして、固体電解コンデンサ素子を作製した。走査型電子顕微鏡による観察により、誘電体層が、一次粒子の外表を均一な厚み(約42~46nm)で覆っていることを確認した。
タンタル一次粉の代わりに、三酸化タングステンを水素酸還元して得た粉末(平均粒径0.5μm)を一次粉として使用したこと、一次粉にケイ素粉(平均粒径0.7μm)を0.2質量%混合して二次粉(平均粒径85μm)を造粒したこと、化成の際、2質量%リン酸水溶液の代わりに0.5質量%の過硫酸アンモニウムを使用して15Vで化成したこと、酸化剤を0.2%過硫酸カリウムに変更したこと、酸化剤の乾燥を105℃で10分間行ったこと以外は実施例2と同様にして固体電解コンデンサ素子を作製した。化成後の誘電体層は、38~42nmの均一な厚みを有していたが、酸化剤水溶液による処理後の誘電体層は、一次粒子の一部表層が90nmの厚みを有することを走査型電子顕微鏡観察により確認した。走査型顕微鏡による観察結果(倍率×105)を図1に示す。
酸化剤水溶液による処理を行わなかったこと以外は実施例4と同様にして、固体電解コンデンサ素子を作製した。走査型電子顕微鏡による観察により、誘電体層が、一次粒子の外表を均一な厚み(約38~42nm)で覆っていることを確認した。走査型顕微鏡による観察結果(倍率×105)を図2に示す。
化成電圧を25Vとしたこと以外は比較例3と同様にして、固体電解コンデンサ素子を作製した。走査型電子顕微鏡による観察により、誘電体層が、一次粒子の外表を均一な厚み(約48~52nm)で覆っていることを確認した。
[容量]
LCR測定器(アジレント社製)に配線された導線を固体電解コンデンサ素子の導電体層と固体電解コンデンサ素子に植立した陽極リード線に当て、バイアス電圧4Vにて、120Hzにおける容量を測定した。
[漏れ電流]
固体電解コンデンサ素子に室温下で4Vを印加した。電圧印加開始から30秒経過時に、電源のプラス端子から固体電解コンデンサ素子の陽極リード線、固体電解コンデンサ素子の導電体層、さらに電源のマイナス端子に亘る回路の電流値(漏れ電流)を測定した。
酸化剤水溶液処理を行わない固体電解コンデンサ素子(比較例3、図2参照)では誘電体層の厚みがほぼ均一であるのに対し、本発明に係る固体電解コンデンサ素子(実施例4、図1参照)は、誘電体層の厚みが少ない部分と、多い部分とで1.5~3倍程度の差異が生じている。
Claims (12)
- 焼結体の表層上に誘電体層を有する固体電解コンデンサ素子の陽極体であって、前記焼結体を構成する少なくとも一部の弁作用金属の粒子表面が前記誘電体層で覆われ、前記粒子の表面上の誘電体層の厚さの一部が他部より厚くなっていることを特徴とする固体電解コンデンサ素子の陽極体。
- 焼結体の表層上に誘電体層を有する固体電解コンデンサ素子の陽極体であって、前記焼結体を構成する少なくとも一部の弁作用金属の粒子表面が前記誘電体層で覆われ、前記誘電体層の最も厚い部分の厚さが、最も薄い部分の厚さの1.2倍以上である請求項1に記載の固体電解コンデンサ素子の陽極体。
- 前記弁作用金属が、タンタル、ニオブ、チタン、タングステン及びこれら金属の合金の少なくとも1種である請求項1または2に記載の固体電解コンデンサ素子の陽極体。
- 請求項1~3のいずれかに記載の陽極体の上に、半導体層及び導電体層が順次形成されてなる固体電解コンデンサ素子。
- 弁作用金属の焼結体に化成処理を行った後、酸化剤水溶液に浸漬し、その後水溶性アルコールに浸漬し、乾燥させた後、水洗して酸化剤を除去することを含む、前記焼結体を構成する少なくとも一部の弁作用金属の粒子表面が誘電体層で覆われ、前記粒子の表面上の誘電体層の厚さの一部が他部よりも厚くなっている固体電解コンデンサ素子の陽極体の製造方法。
- 前記誘電体層の最も厚い部分の厚さが、最も薄い部分の厚さの1.2倍以上である請求項5に記載の固体電解コンデンサ素子の陽極体の製造方法。
- 前記酸化剤が、水溶性で、かつアルコールに非溶解性の酸化剤である請求項5または6に記載の固体電解コンデンサ素子の陽極体の製造方法。
- 前記酸化剤が、過硫酸化合物である請求項5~7のいずれかに記載の固体電解コンデンサ素子の陽極体の製造方法。
- 前記酸化剤が、ハロゲン酸化合物、及び有機過酸化物の少なくとも1種である請求項5~7のいずれかに記載の固体電解コンデンサ素子の陽極体の製造方法。
- 前記酸化剤の濃度が、0.1質量%以上飽和溶解度以下である請求項5~9のいずれかに記載の固体電解コンデンサ素子の陽極体の製造方法。
- 前記誘電体層を化学酸化及び/または電解酸化により形成する請求項5に記載の固体電解コンデンサ素子の陽極体の製造方法。
- 請求項5~11のいずれかに記載の製造方法により得られた陽極体の上に、半導体層及び導電体層を順次積層することを含む、固体電解コンデンサ素子の製造方法。
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CN1825509B (zh) | 2005-02-23 | 2011-04-06 | 三洋电机株式会社 | 固体电解电容器及其制造方法 |
JP4781115B2 (ja) | 2005-02-23 | 2011-09-28 | 三洋電機株式会社 | 固体電解コンデンサ及びその製造方法 |
JP4651430B2 (ja) | 2005-03-30 | 2011-03-16 | 東洋アルミニウム株式会社 | 電解コンデンサ用アルミニウム電極箔 |
US20100123993A1 (en) | 2008-02-13 | 2010-05-20 | Herzel Laor | Atomic layer deposition process for manufacture of battery electrodes, capacitors, resistors, and catalyzers |
US8681477B2 (en) * | 2011-08-30 | 2014-03-25 | Sanyo Electric Co., Ltd. | Solid electrolytic capacitor and method for manufacturing the same |
CN104081485A (zh) * | 2012-01-31 | 2014-10-01 | 三洋电机株式会社 | 固体电解电容器及其制造方法 |
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2014
- 2014-07-16 JP JP2015529508A patent/JP5940222B2/ja not_active Expired - Fee Related
- 2014-07-16 US US14/908,699 patent/US9887041B2/en not_active Expired - Fee Related
- 2014-07-16 WO PCT/JP2014/068907 patent/WO2015016066A1/ja active Application Filing
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JP2004247550A (ja) * | 2003-02-14 | 2004-09-02 | Matsushita Electric Ind Co Ltd | 固体電解コンデンサ |
JP2010034589A (ja) * | 2003-04-28 | 2010-02-12 | Showa Denko Kk | 造粒紛、固体電解コンデンサ陽極用焼結体及び固体電解コンデンサ |
WO2006038720A1 (ja) * | 2004-10-06 | 2006-04-13 | Showa Denko K.K. | ニオブ粉、ニオブ造粒物、ニオブ焼結体及びコンデンサ並びにそれらの製造方法 |
JP2012517717A (ja) * | 2009-02-12 | 2012-08-02 | ラオール・コンサルティング・エルエルシー | 焼結ナノ細孔電気キャパシタ、電気化学キャパシタおよびバッテリーならびにその製造方法 |
JP2010192502A (ja) * | 2009-02-16 | 2010-09-02 | Seiko Epson Corp | コンデンサーおよびコンデンサーの製造方法 |
Also Published As
Publication number | Publication date |
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US20160189875A1 (en) | 2016-06-30 |
JP5940222B2 (ja) | 2016-06-29 |
US9887041B2 (en) | 2018-02-06 |
JPWO2015016066A1 (ja) | 2017-03-02 |
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