JP4797754B2 - Electrode capacitor electrode material - Google Patents
Electrode capacitor electrode material Download PDFInfo
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- JP4797754B2 JP4797754B2 JP2006101099A JP2006101099A JP4797754B2 JP 4797754 B2 JP4797754 B2 JP 4797754B2 JP 2006101099 A JP2006101099 A JP 2006101099A JP 2006101099 A JP2006101099 A JP 2006101099A JP 4797754 B2 JP4797754 B2 JP 4797754B2
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- 239000007772 electrode material Substances 0.000 title claims description 63
- 239000003990 capacitor Substances 0.000 title claims description 51
- 239000002923 metal particle Substances 0.000 claims description 61
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002048 anodisation reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010407 anodic oxide Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000011888 foil Substances 0.000 description 27
- 238000005530 etching Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 5
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000001741 Ammonium adipate Substances 0.000 description 3
- 235000019293 ammonium adipate Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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Description
本発明は、電解コンデンサ用電極材に関し、さらに詳しくは従来にない高静電容量特性を有する電解コンデンサ用電極材に関する。 The present invention relates to an electrode material for an electrolytic capacitor, and more particularly to an electrode material for an electrolytic capacitor having unprecedented high capacitance characteristics.
近年、電子機器の小型化、高信頼性化に伴い、電解コンデンサに対する小型化、高容量化が強く要望されている。 In recent years, with the miniaturization and high reliability of electronic devices, there has been a strong demand for miniaturization and high capacity of electrolytic capacitors.
電解コンデンサは、一般的には帯状の高純度のアルミニウム箔に、化学的あるいは電気化学的にエッチング処理を施して、アルミニウム箔表面を拡大させるとともに、このアルミニウム箔をアジピン酸アンモニウム水溶液等の化成液中にて化成処理して表面に酸化皮膜層を形成させた陽極電極箔と、エッチング処理のみを施した高純度のアルミニウム箔からなる陰極電極箔とを、マニラ紙等からなるセパレータを介して巻回してコンデンサ素子を形成する。そして、このコンデンサ素子は、電解コンデンサ駆動用の電解液を含浸した後、アルミニウム等からなる有底筒状の外装ケースに収納する。外装ケースの開口部には弾性ゴムからなる封口体を装着し、絞り加工により外装ケースを密封している。 An electrolytic capacitor is generally a strip-like high-purity aluminum foil that is chemically or electrochemically etched to enlarge the surface of the aluminum foil, and this aluminum foil is converted into a chemical conversion solution such as an aqueous solution of ammonium adipate. Anode electrode foil formed by chemical conversion treatment inside to form an oxide film layer on the surface, and a cathode electrode foil made of high-purity aluminum foil subjected only to etching treatment are wound through a separator made of manila paper or the like. Turn to form a capacitor element. The capacitor element is impregnated with an electrolytic solution for driving an electrolytic capacitor, and then stored in a bottomed cylindrical outer case made of aluminum or the like. A sealing body made of elastic rubber is attached to the opening of the outer case, and the outer case is sealed by drawing.
このようなアルミ電解コンデンサにおいて、その静電容量を高めるためには、エッチング箔の実効表面積を拡大し単位面積当たりの静電容量の向上を図っており、エッチング箔の実効表面積を拡大させるエッチング技術の開発が行われている。このようなエッチング技術としては、エッチング液の組成やエッチング時に印加する電流波形の開発が行われている。 In such an aluminum electrolytic capacitor, in order to increase its capacitance, the effective surface area of the etching foil is increased to improve the capacitance per unit area, and the etching technology that increases the effective surface area of the etching foil. Development is underway. As such an etching technique, the composition of an etching solution and the development of a current waveform applied during etching have been performed.
ところで、近年、電子情報機器のデジタル化が進むのに伴い、このような電極箔を用いる電解コンデンサには小型で大容量かつ高周波領域でのインピーダンスの低いものが求められるようになってきている。特に、パーソナルコンピュータや携帯電話等の通信機器においては、搭載されるＣＰＵの演算速度の増大に伴い、コンデンサの静電容量をさらに増大させることが強く求められている。 By the way, in recent years, with the progress of digitalization of electronic information equipment, electrolytic capacitors using such electrode foils are required to be small, have a large capacity and have a low impedance in a high frequency region. In particular, in communication devices such as personal computers and mobile phones, there is a strong demand for further increasing the capacitance of the capacitor as the calculation speed of the mounted CPU increases.
従来、通信機器に用いられるコンデンサとしては、小型化の要求に応えるために、積層セラミックコンデンサ等が広く用いられてきた。しかしながら、これらのコンデンサでは近年の大容量化の要求に応えることはできない。そこで、低い等価直列抵抗値（ＥＳＲ値）を有し、かつ大きな静電容量を有すると共に十分に小型化できるコンデンサとして、電解コンデンサが用いられるようになっている。 Conventionally, multilayer ceramic capacitors and the like have been widely used as capacitors used in communication devices in order to meet the demand for miniaturization. However, these capacitors cannot meet the demand for larger capacity in recent years. Therefore, electrolytic capacitors have been used as capacitors having a low equivalent series resistance value (ESR value), a large capacitance, and a sufficiently small size.
そして、電解コンデンサ用電極箔として、電極箔のエッチングされていない部分、すなわち残芯部を厚くしてさらにＥＳＲを低減する試みがある（特許文献１、２）が、大容量化の要求は高く、従来の電極箔ではこの要求に答えることができない。
そこで、本発明は従来のエッチング箔では達成することのできない静電容量が大きく、かつＥＳＲの低い電解コンデンサ用電極材を提供することをその目的とする。 Accordingly, an object of the present invention is to provide an electrode material for an electrolytic capacitor that has a large capacitance that cannot be achieved by a conventional etching foil and that has a low ESR.
本発明の第一の電解コンデンサ用電極材は、表面に酸化皮膜を有する弁金属粒子層が、基材の表面に形成された電解コンデンサ用電極材において、前記弁金属粒子層を構成する弁金属粒子が、その粒子径を少なくとも0.005〜0.1μmの範囲で小さな弁金属粒子と大きな弁金属粒子のそれぞれを多く含む分布であって、前記弁金属粒子層が、その空隙率20〜60％、比表面積30×103〜400×103cm2／cm3 であり、前記弁金属粒子層が、厚みが50〜200μmの基材の表面に形成されていることを特徴とし、従来の電極箔の数倍の静電容量を有し、電極材の抵抗も低い。 The first electrode material for an electrolytic capacitor of the present invention is the valve metal constituting the valve metal particle layer in the electrode material for an electrolytic capacitor in which the valve metal particle layer having an oxide film on the surface is formed on the surface of the substrate. The particles have a distribution containing a large amount of small valve metal particles and large valve metal particles in a particle diameter range of at least 0.005 to 0.1 μm, and the valve metal particle layer has a porosity of 20 to 60% and a ratio of the surface area 30 × 10 3 ~400 × 10 3 cm 2 / cm 3, wherein the valve metal particle layer, the thickness is characterized by being formed on a surface of a substrate of 50 to 200 [mu] m, the conventional electrode foil It has several times the capacitance, and the resistance of the electrode material is low.
本発明の第二の電解コンデンサ用電極材は、表面に酸化皮膜を有する弁金属粒子層が、基材の表面に形成された電解コンデンサ用電極材において、前記弁金属粒子層を構成する弁金属粒子が、その粒子径を少なくとも0.005〜0.1μmの範囲で小さな弁金属粒子と大きな弁金属粒子のそれぞれを多く含む分布であって、前記弁金属粒子層が、その空隙率20〜60％、比表面積30×103〜400×103cm2／cm3 であり、前記弁金属粒子層が、前記弁金属と異なる金属からなる基材の表面に形成されていることを特徴とし従来の電極箔の数倍の静電容量を有し、電極材の抵抗も低い。 The second electrode material for an electrolytic capacitor of the present invention is the valve metal constituting the valve metal particle layer in the electrode material for an electrolytic capacitor in which the valve metal particle layer having an oxide film on the surface is formed on the surface of the substrate. The particles have a distribution containing a large amount of small valve metal particles and large valve metal particles in a particle diameter range of at least 0.005 to 0.1 μm, and the valve metal particle layer has a porosity of 20 to 60% and a ratio of the surface area 30 × 10 3 ~400 × 10 3 cm 2 / cm 3, wherein the valve metal particle layer, characterized in that it is formed on the surface of the substrate made of the valve metal and the different metals conventional electrode foil The resistance of the electrode material is low.
さらに、以上の電極材は、前記弁金属粒子の一次粒子が、その粒子径を少なくとも0.005〜0.1μmの範囲で所定の分布をもって混在している。粒径の小さい粒子によって静電容量は高くなり、粒径の大きい粒子によって空隙が確保できるので電解コンデンサを作成した後電解液との反応で生成される酸化皮膜による目詰まりを抑制することができる。 Further, in the above electrode material, the primary particles of the valve metal particles are mixed with a predetermined distribution in a particle diameter range of at least 0.005 to 0.1 μm. Capacitance is increased by particles having a small particle size, and voids can be secured by particles having a large particle size, so that clogging due to an oxide film generated by reaction with an electrolytic solution can be suppressed after an electrolytic capacitor is created. .
また、本発明の電解コンデンサ用電極材は、弁金属がアルミニウムであり、表面に酸化皮膜を有する弁金属粒子層のAｌ／O組成比が2.0〜5.5であるので、静電容量の安定性を有することができ、さらにこの組成比の酸素の含有率によって弁金属粒子同士の接合性が向上する。 Moreover, the electrode material for electrolytic capacitors of the present invention has a valve metal made of aluminum, and a valve metal particle layer having an oxide film on the surface has an Al / O composition ratio of 2.0 to 5.5. Furthermore, the bonding property between the valve metal particles is improved by the oxygen content of this composition ratio.
本発明の第三の電解コンデンサ用電極材は、表面に酸化皮膜を有する弁金属粒子層が、空隙率20〜60％、比表面積20×103〜70×103 cm2／cm3とし、前記弁金属粒子が、陽極化成により陽極酸化皮膜を形成したときに、当該陽極酸化皮膜により空隙が埋まらないように粒子径0.2μm以上のものを含み、前記弁金属粒子層が、厚みが50〜200μmの基材の表面に形成されていることを特徴とし、従来の電極箔では実現できない静電容量を有し、電極材の抵抗も低い。 In the third electrolytic capacitor electrode material of the present invention, the valve metal particle layer having an oxide film on the surface has a porosity of 20 to 60%, a specific surface area of 20 × 10 3 to 70 × 10 3 cm 2 / cm 3 , the valve metal particles, when forming an anodic oxide film by anodization, see contains more than a particle size of 0.2μm so as voids not filled by the anodic oxidation coating, the valve metal particle layer, the thickness 50 It is characterized by being formed on the surface of a substrate of ˜200 μm, has a capacitance that cannot be realized with a conventional electrode foil, and has a low resistance of the electrode material.
本発明の第四の電解コンデンサ用電極材は、表面に酸化皮膜を有する弁金属粒子層が、空隙率20〜60％、比表面積20×103〜70×103 cm2／cm3とし、前記弁金属粒子が、陽極化成により陽極酸化皮膜を形成したときに、当該陽極酸化皮膜により空隙が埋まらないように粒子径0.2μm以上のものを含み、前記弁金属粒子層が、前記弁金属と異なる金属からなる基材の表面に形成されていることを特徴とし、従来の電極箔では実現できない静電容量を有し、電極材の抵抗も低い。 The electrode material for a fourth electrolytic capacitor of the present invention has a valve metal particle layer having an oxide film on the surface , a porosity of 20 to 60%, a specific surface area of 20 × 10 3 to 70 × 10 3 cm 2 / cm 3 , the valve metal particles, when forming an anodic oxide film by anodization, see contains more than a particle size of 0.2μm so as voids not filled by the anodic oxidation coating, the valve metal particle layer, said valve metal It is formed on the surface of a base material made of a different metal, has a capacitance that cannot be realized by a conventional electrode foil, and has a low resistance of the electrode material.
さらに、以上の電極材は、弁金属粒子層に粒子径が0.2μm以上の表面に酸化皮膜を有する弁金属粒子を含んでいるので、弁金属粒子間に大きな空隙を設けることができる。したがって、陽極化成によって陽極酸化皮膜を形成した際に、酸化皮膜によって空隙が埋まってしまうというようなことが抑制され、高い静電容量を得ることができる。 Furthermore, since the above electrode material contains valve metal particles having an oxide film on the surface having a particle diameter of 0.2 μm or more in the valve metal particle layer, a large gap can be provided between the valve metal particles. Therefore, when an anodic oxide film is formed by anodization, it is suppressed that the void is filled with the oxide film, and a high capacitance can be obtained.
また、本発明の電解コンデンサ用電極材は、弁金属がアルミニウムであり、表面に酸化皮膜を有する弁金属粒子層のAｌ／O組成比が2.0〜125であるので、静電容量の安定性を有することができ、さらにこの組成比の酸素の含有率によって弁金属粒子同士の接合性が向上する。 In the electrode material for electrolytic capacitors of the present invention, the valve metal is aluminum, and the Al / O composition ratio of the valve metal particle layer having an oxide film on the surface is 2.0 to 125. Furthermore, the bonding property between the valve metal particles is improved by the oxygen content of this composition ratio.
本発明の第二、第四の電極材においては、基材として前記弁金属と異なる金属を用いるが、この金属として銅又は銀を用いると電極材の抵抗が低減し、本電極材を用いた電解コンデンサのＥＳＲは低減する。 In the second and fourth electrode materials of the present invention, a metal different from the valve metal is used as a base material. However, when copper or silver is used as the metal, the resistance of the electrode material is reduced, and this electrode material is used. The ESR of the electrolytic capacitor is reduced.
本発明の電極材は、エッチング技術による電極箔では実現できない静電容量特性を有し、基材が厚くまたエッチング箔の残芯に比べて平坦なので電極材の抵抗も低い。 The electrode material of the present invention has a capacitance characteristic that cannot be realized by an electrode foil obtained by an etching technique, and the resistance of the electrode material is low because the substrate is thick and flat compared to the remaining core of the etching foil.
以上のように、本発明の電解コンデンサ用電極材は、高い静電容量を有し、電極材の抵抗も低いので、この電解コンデンサ用電極材を陰極に、またはこの電解コンデンサ用電極材を陽極酸化して陽極に用いることによって、従来にない高い静電容量と低ＥＳＲ特性を有する電解コンデンサを実現することができる。 As described above, the electrode material for an electrolytic capacitor of the present invention has a high capacitance and the resistance of the electrode material is low. Therefore, the electrode material for an electrolytic capacitor is used as a cathode, or the electrode material for an electrolytic capacitor is used as an anode. By oxidizing and using it for the anode, an electrolytic capacitor having unprecedented high capacitance and low ESR characteristics can be realized.
本発明の第一、第二の電解コンデンサ用電極材は、表面に酸化皮膜を有する弁金属粒子層を有する電極材であって、弁金属粒子層の空隙率は、20〜60％、好ましくは25〜55％、さらに好ましくは30〜50％である。そして、比表面積は、30×103〜400×103cm2／cm3、好ましくは70×103〜400×103cm2／cm3、さらに好ましくは90×103〜400×103cm2／cm3である。 The first and second electrode materials for electrolytic capacitors of the present invention are electrode materials having a valve metal particle layer having an oxide film on the surface, and the porosity of the valve metal particle layer is 20 to 60%, preferably It is 25 to 55%, more preferably 30 to 50%. The specific surface area is 30 × 10 3 to 400 × 10 3 cm 2 / cm 3 , preferably 70 × 10 3 to 400 × 10 3 cm 2 / cm 3 , more preferably 90 × 10 3 to 400 × 10 3. cm 2 / cm 3 .
比表面積は本発明の電極材に静電容量を有する皮膜を形成し、同様の皮膜を形成したプレーン箔の静電容量と面積から算出する。また、空隙率は水銀圧入法で測定することができる。 The specific surface area is calculated from the capacitance and area of a plain foil on which a film having capacitance is formed on the electrode material of the present invention, and a similar film is formed. The porosity can be measured by a mercury intrusion method.
また、前記電極材は、前記弁金属粒子の一次粒子が、その粒子径を少なくとも0.005〜0.1μmの範囲で所定の分布をもって混在している。このような小さな粒子によって高い静電容量が得られ、大きな粒子によって空隙が確保できるので電解コンデンサを作成した後電解液との反応で生成される酸化皮膜による目詰まりを抑制することができる。したがって、粒径の小さい粒子の数を多くすることによって、静電容量の大きな電極材が得られ、粒径の大きい粒子の数を多くすることによって静電容量の安定性を高めることができる。 In the electrode material, primary particles of the valve metal particles are mixed with a predetermined distribution within a particle diameter range of at least 0.005 to 0.1 μm. High capacitance can be obtained by such small particles, and voids can be secured by the large particles, so that clogging due to an oxide film generated by reaction with the electrolytic solution after the electrolytic capacitor is formed can be suppressed. Therefore, an electrode material having a large capacitance can be obtained by increasing the number of particles having a small particle diameter, and the stability of the capacitance can be increased by increasing the number of particles having a large particle diameter.
また、前記電極材は、弁金属がアルミニウムであり、表面に酸化皮膜を有する弁金属粒子層のAｌ／O組成比が2.0〜5.5である。Aｌ／O組成比は、ＧＤＳ分析によって測定、算出することができる。 In the electrode material, the valve metal is aluminum, and the Al / O composition ratio of the valve metal particle layer having an oxide film on the surface is 2.0 to 5.5. The Al / O composition ratio can be measured and calculated by GDS analysis.
前記電極材は、陰極として用いると好適であるが、陰極化成を施してもよい。さらに極低圧の陽極化成を施すことによって電解コンデンサ用陽極材として用いることもできる。化成方法は通常電解コンデンサ用アルミニウム箔の化成方法と同様の化成方法を用いることができる。 The electrode material is preferably used as a cathode, but may be subjected to cathodic conversion. Furthermore, it can also be used as an anode material for electrolytic capacitors by performing anodization at an extremely low pressure. As a chemical conversion method, a chemical conversion method similar to that of an aluminum foil for electrolytic capacitors can be used.
本発明の第三、第四の電解コンデンサ用電極材は、表面に酸化皮膜を有する弁金属粒子層を有する電極材であって、弁金属粒子層の空隙率は、20〜60％、好ましくは22〜58％、さらに好ましくは25〜55％である。そして、比表面積は、20×103〜70×103cm2／cm3、好ましくは30×103〜60×103cm2／cm3、さらに好ましくは35×103〜55×103cm2／cm3である。 The third and fourth electrode materials for electrolytic capacitors of the present invention are electrode materials having a valve metal particle layer having an oxide film on the surface, and the porosity of the valve metal particle layer is 20 to 60%, preferably It is 22 to 58%, more preferably 25 to 55%. The specific surface area is 20 × 10 3 to 70 × 10 3 cm 2 / cm 3 , preferably 30 × 10 3 to 60 × 10 3 cm 2 / cm 3 , more preferably 35 × 10 3 to 55 × 10 3. cm 2 / cm 3 .
また、前記電極材は、弁金属粒子層に粒子径が0.2μm以上の表面に酸化皮膜を有する弁金属粒子を含んでいるので、弁金属粒子間に大きな空隙を設けることができる。したがって、陽極化成によって陽極酸化皮膜を形成した際に、酸化皮膜によって空隙が埋まってしまうというようなことが抑制され、高い静電容量を得ることができる。 Further, since the electrode material includes valve metal particles having an oxide film on the surface having a particle diameter of 0.2 μm or more in the valve metal particle layer, a large gap can be provided between the valve metal particles. Therefore, when an anodic oxide film is formed by anodization, it is suppressed that the void is filled with the oxide film, and a high capacitance can be obtained.
また、前記電極材は、弁金属がアルミニウムであり、表面に酸化皮膜を有する弁金属粒子層のAｌ／O組成比が2.0〜125であるので、静電容量の安定性を有することができ、さらにこの組成比の酸素の含有率によって弁金属粒子同士の接合性が向上する。 In addition, the electrode material, the valve metal is aluminum, and the Al / O composition ratio of the valve metal particle layer having an oxide film on the surface is 2.0 to 125, so that the capacitance can be stable, Furthermore, the bondability between the valve metal particles is improved by the oxygen content of this composition ratio.
前記電極材は、陽極化成を施すことによって電解コンデンサ用陽極材として用いると好適である。化成方法は通常電解コンデンサ用アルミニウム箔の化成方法と同様の化成方法を用いることができる。 The electrode material is preferably used as an anode material for electrolytic capacitors by anodizing. As a chemical conversion method, a chemical conversion method similar to that of an aluminum foil for electrolytic capacitors can be used.
本発明の第１、第３の電極材においては、厚みが５０〜２００μｍの基材を用いるが、好ましくは５０〜１７０μｍ、さらに好ましくは６０〜１５０μｍである。基材は、種々の金属を用いることができるがアルミニウムが好ましい。アルミニウムの純度は９９ｗｔ％から９９．９９９ｗｔ％が好ましい。 In the first and third electrode materials of the present invention, a base material having a thickness of 50 to 200 μm is used, preferably 50 to 170 μm, more preferably 60 to 150 μm. As the base material, various metals can be used, but aluminum is preferable. The purity of aluminum is preferably 99 wt% to 99.999 wt%.
本発明の第２、第４の電極材においては、基材として前記弁金属と異なる金属を用いるが、この金属として銅又は銀を用いると電極材の抵抗が低減し、本電極材を用いた電解コンデンサのＥＳＲは低減する。 In the second and fourth electrode materials of the present invention, a metal different from the valve metal is used as a base material. However, when copper or silver is used as the metal, the resistance of the electrode material is reduced, and this electrode material is used. The ESR of the electrolytic capacitor is reduced.
以上のような電極材は、通常の蒸着法によって得ることができる。表面に酸化皮膜を有する弁金属粒子層を形成するには、酸素を含む不活性ガス雰囲気内で蒸着を行う。不活性ガスとしては、アルゴン、窒素等を用いることができる。不活性ガスの圧力は０．０５〜０．８Ｐａ、酸素分圧は不活性ガスの圧力の１／１０以下が好ましい。 The electrode material as described above can be obtained by a normal vapor deposition method. In order to form a valve metal particle layer having an oxide film on the surface, vapor deposition is performed in an inert gas atmosphere containing oxygen. Argon, nitrogen, etc. can be used as the inert gas. The pressure of the inert gas is preferably 0.05 to 0.8 Pa, and the oxygen partial pressure is preferably 1/10 or less of the pressure of the inert gas.
以下に実施例により本発明をさらに具体的に説明する。
（実施例１−１） ０．１Ｐａの圧力の窒素と窒素の圧力の１／１０以下の圧力の酸素雰囲気内で、１０２μｍの９９．９ｗｔ％のアルミニウムシートにアルミニウムを蒸着して、本発明の電極材を作成した。
（実施例１−２） ０．３Ｐａの圧力の窒素と窒素の圧力の１／１０以下の圧力の酸素雰囲気内で、１００μｍの９９．９ｗｔ％のアルミニウムシートにアルミニウムを蒸着して本発明の電極材を作成した。その後、アジピン酸アンモニウム水溶液中で２０Ｖ電圧印加によって陽極化成を行った。
（実施例２−１） ０．１Ｐａの圧力の窒素と窒素の圧力の１／１０以下の圧力の酸素雰囲気内で、６１μｍの９９．９ｗｔ％の銅からなるシートにアルミニウムを蒸着して、本発明の電極材を作成した。
（実施例２−２） ０．３Ｐａの圧力の窒素と窒素の圧力の１／１０以下の圧力の酸素雰囲気内で、６０μｍの９９．９ｗｔ％の銅からなるシートにアルミニウムを蒸着して本発明の電極材を作成した。その後、アジピン酸アンモニウム水溶液中で２０Ｖ電圧印加によって陽極化成を行った。
（比較例１）塩酸、硫酸、硝酸の混合液を電解液に用い、周波数５０Ｈｚ以下、電流密度を１Ａ／ｃｍ2以下の交流電流を９９．９ｗｔ％のアルミニウムシートに印加して芯厚が３０μｍとなるようにエッチング処理を行いエッチング箔を作成した。
The present invention will be described more specifically with reference to the following examples.
(Example 1-1) Aluminum was vapor-deposited on a 99.9 wt% aluminum sheet of 102 μm in an oxygen atmosphere at a pressure of 1/10 or less of the pressure of nitrogen of 0.1 Pa and the pressure of nitrogen. An electrode material was prepared.
Example 1-2 Electrode of the present invention by depositing aluminum on a 99.9 wt% aluminum sheet of 100 μm in an oxygen atmosphere at a pressure of 1/10 or less of nitrogen at a pressure of 0.3 Pa and nitrogen Made the material. Thereafter, anodization was performed by applying a voltage of 20 V in an aqueous solution of ammonium adipate.
(Example 2-1) In a nitrogen atmosphere of 0.1 Pa and in an oxygen atmosphere of 1/10 or less of the pressure of nitrogen, aluminum was vapor-deposited on a sheet made of 99.9 wt% copper of 61 μm, and this An electrode material of the invention was prepared.
(Example 2-2) In the present invention, aluminum was vapor-deposited on a sheet made of 99.9 wt% of copper of 60 μm in an oxygen atmosphere at a pressure of 1/10 or less of the pressure of nitrogen of 0.3 Pa and the pressure of nitrogen. An electrode material was prepared. Thereafter, anodization was performed by applying a voltage of 20 V in an aqueous solution of ammonium adipate.
(Comparative Example 1) A mixed liquid of hydrochloric acid, sulfuric acid, and nitric acid was used as an electrolyte, an alternating current having a frequency of 50 Hz or less and a current density of 1 A / cm 2 or less was applied to a 99.9 wt% aluminum sheet, and the core thickness was 30 μm. Etching treatment was performed so as to obtain an etching foil.
（比較例２）塩酸、硫酸、硝酸の混合液を電解液に用い、周波数２０Ｈｚ以下、電流密度を１Ａ／ｃｍ2以下の交流電流を９９．９ｗｔ％のアルミニウムシートに印加して芯厚が３０μｍとなるようにエッチング処理を行い、エッチング箔を作成した。その後、実施例と同様にして陽極化成を行った。 (Comparative Example 2) A mixed liquid of hydrochloric acid, sulfuric acid, and nitric acid was used as an electrolyte, an alternating current having a frequency of 20 Hz or less and a current density of 1 A / cm 2 or less was applied to a 99.9 wt% aluminum sheet, and the core thickness was 30 μm. Etching treatment was performed to obtain an etching foil. Thereafter, anodization was performed in the same manner as in the example.
これらの電極材、エッチング箔の金属粒子層またはエッチング層の空隙率、比表面積、静電容量、及び抵抗を（表１）に示す。なお、抵抗は電極材の単位面積当たりの抵抗値、つまり正四角形の電極材の端面間の抵抗値を測定した。 (Table 1) shows the porosity, specific surface area, capacitance, and resistance of these electrode materials, metal particle layers of the etching foil, or etching layers. In addition, resistance measured the resistance value per unit area of an electrode material, ie, the resistance value between the end surfaces of a square electrode material.
以上のように、本発明の電極材および化成した電極材である実施例１−１〜２−２の静電容量は、従来のエッチング箔、および化成箔である比較例１、２より、２〜７倍の静電容量を有しており、抵抗も低く、高周波領域で用いるコンデンサに適した従来にない電解コンデンサ用電極材であるということが分かる。
As described above, the capacitances of Examples 1-1 to 2-2, which are the electrode material of the present invention and the formed electrode material, are 2 from Comparative Examples 1 and 2 which are conventional etching foils and chemical conversion foils. It can be seen that this is an unprecedented electrode material for electrolytic capacitors suitable for capacitors used in the high-frequency region, having a capacitance of ˜7 times and low resistance.
Claims (8)
前記弁金属粒子層を構成する弁金属粒子が、その粒子径を少なくとも0.005〜0.1μmの範囲で小さな弁金属粒子と大きな弁金属粒子のそれぞれを多く含む分布であって、
前記弁金属粒子層が、その空隙率20〜60％、比表面積30×103〜400×103cm2／cm3 であり、
前記弁金属粒子層が、厚みが50〜200μmの基材の表面に形成されていることを特徴とする電解コンデンサ用電極材。 In the electrode material for electrolytic capacitors in which the valve metal particle layer having an oxide film on the surface is formed on the surface of the base material,
The valve metal particles constituting the valve metal particle layer have a distribution containing a large amount of small valve metal particles and large valve metal particles in a particle diameter range of at least 0.005 to 0.1 μm ,
The valve metal particle layer, the porosity of 20% to 60%, a specific surface area 30 × 10 3 ~400 × 10 3 cm 2 / cm 3,
The electrode material for an electrolytic capacitor, wherein the valve metal particle layer is formed on a surface of a substrate having a thickness of 50 to 200 μm.
前記弁金属粒子層を構成する弁金属粒子が、その粒子径を少なくとも0.005〜0.1μmの範囲で小さな弁金属粒子と大きな弁金属粒子のそれぞれを多く含む分布であって、
前記弁金属粒子層が、その空隙率20〜60％、比表面積30×103〜400×103cm2／cm3 であり、
前記弁金属粒子層が、前記弁金属と異なる金属からなる基材の表面に形成されていることを特徴とする電解コンデンサ用電極材。 In the electrode material for electrolytic capacitors in which the valve metal particle layer having an oxide film on the surface is formed on the surface of the base material,
The valve metal particles constituting the valve metal particle layer have a distribution containing a large amount of small valve metal particles and large valve metal particles in a particle diameter range of at least 0.005 to 0.1 μm ,
The valve metal particle layer, the porosity of 20% to 60%, a specific surface area 30 × 10 3 ~400 × 10 3 cm 2 / cm 3,
The electrode material for an electrolytic capacitor, wherein the valve metal particle layer is formed on a surface of a base material made of a metal different from the valve metal.
前記弁金属粒子層が、厚みが50〜200μmの基材の表面に形成されていることを特徴とする電解コンデンサ用電極材。 The valve metal particle layer having an oxide film on the surface has a porosity of 20 to 60% and a specific surface area of 20 × 10 3 to 70 × 10 3 cm 2 / cm 3 , and the valve metal particle has an anodized film formed by anodization. at the time of forming, viewed contains more than a particle size of 0.2μm so as voids not filled by the anodic oxide film,
The electrode material for an electrolytic capacitor, wherein the valve metal particle layer is formed on a surface of a substrate having a thickness of 50 to 200 μm.
前記弁金属粒子層が、前記弁金属と異なる金属からなる基材の表面に形成されていることを特徴とする電解コンデンサ用電極材。 The valve metal particle layer having an oxide film on the surface has a porosity of 20 to 60% and a specific surface area of 20 × 10 3 to 70 × 10 3 cm 2 / cm 3 , and the valve metal particle has an anodized film formed by anodization. at the time of forming, viewed contains more than a particle size of 0.2μm so as voids not filled by the anodic oxide film,
The electrode material for an electrolytic capacitor, wherein the valve metal particle layer is formed on a surface of a base material made of a metal different from the valve metal.
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