JPH05190399A - High capacitance electrolytic capacitor electrode material and its manufacturing method - Google Patents

Abstract

(57) [Abstract] [Objective] In an electrode foil for an electrolytic capacitor in which a metal thin film made of a Ti alloy is formed on a substrate, it is possible to obtain a high capacitance while making the electrode foil thinner, and Stabilize. [Structure] An electrode foil for an electrolytic capacitor in which a Ti alloy metal thin film made of a column structure aggregate having a special structure is formed while blowing an inert gas onto a substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode material for electrolytic capacitors and a method for producing the same. More specifically, the present invention relates to an electrode material that contributes to miniaturization and high capacity of a high capacity electrolytic capacitor and stabilization of electrostatic capacity, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In order to reduce the size and capacity of a capacitor, it is necessary to increase the dielectric constant of the dielectric layer, reduce the thickness of the dielectric layer, or increase the surface area of the counter electrode. However, in the current aluminum electrolytic capacitor, generally, aluminum foil is etched to form a large number of bores, the surface area is enlarged, and then a dielectric layer of Al ₂ O ₃ is formed by anodic oxidation. Is increasing. However, the increase in surface area of the aluminum foil due to etching is accompanied by a decrease in the strength of the aluminum foil, and is close to the limit of reducing the thickness of the aluminum electrode material after etching.

On the other hand, in Japanese Unexamined Patent Publication No. 56-29669, a porous metal film is formed by injecting a vapor of a valve metal such as aluminum or tantalum into a substrate at an incident angle of 30 degrees or more, preferably 80 to 85 degrees. Has been proposed to obtain an electrode foil for an electrolytic capacitor having an increased surface area. Further, in Japanese Patent Laid-Open No. 59-167090, the conductivity of aluminum, tantalum, titanium, niobium, zirconium, etc. is set on a substrate such as aluminum foil in an inert gas atmosphere of 1 × 10 ^{−4 to} 1 Torr such as argon. A metal is vapor-deposited to form a porous metal film having a film thickness of 1 to 20 microns,
It has been proposed to increase the surface area of the dielectric layer and increase the dielectric constant. Further, according to Japanese Patent Publication No. 3-37293, titanium having a thickness of 0.2 to 5.0 microns, which is made of titanium fine particles having an average grain size of 0.02 to 1.0 micron, is formed on the surface of an aluminum foil roughened by etching. A cathode material for electrolytic capacitors, which is coated with a vapor-deposited coating, has been proposed.

[0004]

However, these techniques still have the following problems. (1) In order to obtain a sufficient surface area expansion effect, it is necessary to increase the thickness of the conductive metal film to 1 to 20 microns,
There is a problem in terms of productivity such as repeatedly forming a vapor deposition layer. In addition, since conductive metals other than aluminum are high melting point materials, when attempting to form such a thick film as described above, there is a problem that the substrate is damaged by heat during vapor deposition, causing many wrinkles or cutting. It was (2) When vapor-deposited on a substrate that has been etched and has irregularities, the rupture strength and tear strength of the etched substrate are inferior, and the problem of frequent fracture during vapor deposition is encountered. (3) In the method of vapor-depositing a conductive metal in an inert gas, a higher surface pressure, that is, a larger capacitance can be obtained by increasing the pressure in the vacuum layer, but the pressure in the vacuum layer is increased by increasing the pressure in the vacuum layer. Then, there is a problem that the film deposition rate decreases. Particularly in a large-scale production machine, the film deposition rate is remarkably reduced with the increase in pressure in the vacuum layer, resulting in a significant decrease in productivity. (4) 0.1-500,000 for aluminum electrolytic capacitors
Although it is used in a wide capacitance range of microfarads, when it is used in a high capacitance range of 1,000 microfarads or more, it is necessary to increase the thickness of the electrolytic capacitor foil in the conventionally known technique. However, there is a drawback that the capacity change rate during high temperature storage after impregnation with the electrolytic solution is large.

The present invention was devised in view of the above-mentioned drawbacks of the prior art.
An extremely thin vapor-deposited layer made of an alloy, which is extremely effective in increasing capacitance and has excellent productivity during manufacturing. The vapor-deposited layer has an ultrafine column structure, and the column structure is uniform and has a column gap. The object of the present invention is to provide an electrode material for a high-capacity electrolytic capacitor, which is excellent in electrolytic solution impregnation property and has stable electric characteristics, and a manufacturing method thereof.

[0006]

The first object of the present invention is, firstly, an electrode material for an electrolytic capacitor comprising a substrate and an extremely thin metal thin film formed on at least one surface of the substrate, wherein the metal thin film is , Ti alloys, ie Zn, Mg, C
a, Sr, Ba, Al, Sn, Mn, V, Cr, Ni,
It is made of a Ti alloy containing a metal selected from Fe, Zr, B, Sb and Pd, and the number of columns is 5 × 10 ⁸ to 1
10 to ^{12 12} pieces / cm ² , column gap 50 to 5000
This can be achieved by an electrode material for a high-capacity electrolytic capacitor, which is characterized in that it is in the form of an independent column having an angstrom, a thickness of 100 to 5000 angstrom, and a surface expansion ratio of 50 to 1000 times.

Secondly, the object of the present invention is to add Ti to the substrate.
Evaporating a metal thin film made of an alloy from a gas inlet having one or more outlets while inflowing at least 0.03 liter / min or more of an inert gas, nitrogen gas or / and an inert gas containing nitrogen gas. It is achieved by a method for producing the electrode material, which comprises:

The substrate constituting the electrode foil of the present invention includes:
In addition to aluminum foil, you can choose from a wide range of aluminum alloy foil, non-aluminum metal foil, plastic film, etc., but aluminum foil, aluminum alloy foil because of its low leakage current, high mechanical strength, and high heat resistance. Alternatively, it is preferable to use a plastic film. The metal foil or the plastic film as the substrate is preferably a thin and substantially smooth substrate in order to downsize the electrolytic capacitor and stabilize the electric characteristics. In addition, the thickness of the metal foil is preferably in the range of 6 to 100 μm in view of the relationship between mechanical strength and occupied volume, and 10 to 30 μm.
The micron range is more preferred.

When a plastic film is used as the substrate, specific examples of the resin constituting the film include polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, polyolefins such as polypropylene, polyphenylene sulfides and polyether ethers. Examples thereof include polyethers such as ketones, aromatic polyamides, polycarbonates, and the like, and polyethylene terephthalate, polypropylene, and polyphenylene sulfide are preferable in terms of electric characteristics and price. It is preferable that these plastic films are biaxially stretched to form a film from the viewpoint of mechanical strength and stability. The thickness of the plastic film is preferably in the range of 0.5 to 50 μm from the viewpoint of mechanical strength and occupied volume, and
The range of 5 to 15 microns is more preferable.

It is preferable that the surface of the substrate is substantially smooth, and it is preferable that there is no large unevenness or bore due to etching or the like. Specifically, the average surface roughness is 50
It is preferably ˜5000 Å. 5
When the thickness is less than 0 angstrom, the slipperiness is poor and the workability is deteriorated. When it exceeds 5000 angstroms, the metal layer of the column structure formed on the surface becomes non-uniform, and the change rate of the electrostatic capacitance becomes large in the long-term heat resistance test, resulting in a defect of electric characteristics.

The metal thin film in the present invention is a Ti alloy, that is, Zn, Mg, Ca, Sr, Ba, Al, Sn, Mn,
It is made of a Ti alloy containing a metal selected from V, Cr, Ni, Fe, Zr, B, Sb and Pd. Z
n, Mg, Ca, Sr, Ba, Al, Sn, Mn, V,
A Ti alloy containing a metal selected from Cr, Ni, Fe, Zr, B, Sb and Pd has effects such as an effect of increasing electrostatic capacity, less heat loss, and improvement of vapor deposition productivity. There are advantages to occur.

The metal thin film of the present invention is characterized in that the number of columns is 5 × 10 ⁸ to 1 × 10 ¹² pieces / cm ² , the column gap is 50 to 5000 Å, and the thickness is 100 to 50.
It is composed of an aggregate of columns of 00 angstrom, and as a result, the surface expansion rate is increased by 50 to 1000 times. In order to further improve the electrostatic capacity, it is preferable that the surface expansion rate is large, a large number of fine columns are formed, and the thickness thereof is also preferably thick. Therefore, if the number of columns is less than 5 × 10 ⁸ , the improvement in capacitance is insufficient, and if the thickness is less than 100 Å, the surface expansion rate is small and the improvement in capacitance is insufficient. On the other hand, the column gap affects the impregnation property of the electrolytic solution, and it is difficult to improve the electrostatic capacity with an electrolytic solution having poor wettability, and the electrostatic capacity changes during high temperature storage. Therefore, the number of columns is 1 × 10 ^12.
If the number / cm ² or more, the column gap becomes too small,
The column gap is preferably 50 to 5000 angstroms. When the column aggregate has a thickness of 5000 angstroms or more, the productivity of vapor deposition is poor and the cost is high. The theoretical value of the conventionally used etched aluminum foil is calculated to be 60 to 300 times the surface expansion rate, but the surface expansion rate is usually 30 to 100 times. Is 50 to 1000 times larger, and an electrolytic capacitor having a larger capacitance can be obtained.

In the present invention, when a non-conductive substrate such as a plastic film is used, it is preferable that the surface on which the metal thin film is formed is metallized in advance in order to reduce the dielectric loss. Further, pretreatment such as easy adhesion treatment may be performed prior to the metallization.

FIG. 1 shows a column structure in the present invention, and FIG. 2 shows a structure of an etching foil conventionally used for comparison. Although the etching foil has concave bores (pits) formed on a smooth surface, it is non-uniform and needs to be deep in order to increase the surface expansion rate. The diameter of the pit is 0.1 to 1.5 microns (1000 to 1500
0 angstrom), the number of pits is 5 × 10 ^{7 to} 3
Since it was × 10 ⁸ pieces / cm ² , there was a limit to the technique for controlling the surface expansion rate. On the other hand, FIG. 1 schematically shows a column structure of the present invention and an aggregate thereof.
It is an aggregate of columnar particles grown in the thickness direction of the metal thin film. In order to increase the surface expansion rate, along with the column structure,
The column gap is important, and it is preferable that each column has a separate structure in order to improve the electrostatic capacity, but it is not limited to these structures.
Due to the impregnation property of the electrolytic solution, when the column is perpendicular to the surface of the substrate, when it is inclined, when the shape of the column is narrow at the base, or when it is tapered on the surface side The magnitude may vary or the rate of change in capacitance may vary, but the invention is not limited thereto.

The number of columns in the present invention is a scanning electron micrograph of the surface of the thin film.
It is measured by cutting a sample into an ultrathin section and observing a cross section of a metal thin film, that is, an aggregate of columns with a transmission electron microscope. The surface expansion rate can be obtained by measuring the surface area by the BET method by gas adsorption.

In the present invention, the manufacturing method for forming the metal thin film on the substrate is a vacuum such as resistance heating vacuum deposition, induction heating vacuum deposition, electron beam heating vacuum deposition, laser heating vacuum deposition, sputtering or ion plating. Although the vapor deposition method is adopted, the substrate is preheated or heated with a heating roll in a temperature range of from room temperature to 350 ° C. or subjected to an electric discharge treatment, and then the metal thin film is blown with one or more layers. At least 0.0 from a nitrogen gas inlet with an outlet
A method of vapor deposition is used in which 3 l / min or more of an inert gas, a nitrogen gas or a nitrogen gas containing an inert gas is introduced. In order to form a column structure aggregate including a column gap and to greatly improve the surface expansion rate, an inert gas, a nitrogen gas, or a nitrogen gas containing an inert gas is positively blown into the high vacuum system to further improve the surface expansion rate. Preferably, it can be achieved by directly blowing an inert gas, a nitrogen gas or a nitrogen gas containing an inert gas into the vapor gas from the outlets of the multiple holes. The static gas replacement does not improve the surface expansion rate and is non-uniform. Therefore, it is necessary that at least 0.03 liters / minute or more of inert gas, nitrogen gas, or nitrogen gas containing an inert gas is introduced as a gas flow rate. The column shape becomes larger and the column gap becomes larger as the flow rate increases, but the flow rate can be appropriately determined depending on the size of the vacuum chamber, the number of outlets, and the like.

Further, in the present invention, the number of columns and the column gap can be controlled in addition to improving the adhesion of the metal thin film by preheating or heating the substrate with a heating roll or performing various discharge treatments. The impregnating property of can be improved, and the rate of change in capacitance can be suppressed at any time. When a plastic film is used as the base material, the upper limit of the temperature is limited due to the heat resistance limit. Ti in the present invention
In order to evaporate a refractory metal such as an alloy, it is preferable to adopt an electron beam heating method. It is permissible to perform ion plating by radiating high frequency power between these evaporation sources and the substrate.

As the inert gas, a rare gas such as helium, neon, argon, krypton or xenon can be adopted, but argon is preferable. In the present invention, nitrogen gas or nitrogen gas containing an inert gas is also used, but a rare gas such as helium, neon, argon, krypton, or xenon can be adopted as the inert gas mixed in the nitrogen gas. Of these, the use of argon is preferable because it is easy to handle and inexpensive. Further, it is preferable to introduce the nitrogen gas and the inert gas from separate outlets because they have the effects of controlling the column structure of the metal thin film and increasing the capacitance. Further, it is preferable to add a small amount of oxygen to the inert gas because it has the effect of making the fine structure of the thin film fine and increasing the capacitance.

The formation of the metal thin film of the present invention by the vacuum deposition method will be described with reference to FIG. FIG. 3 schematically shows a preferred example of a vacuum vapor deposition apparatus used in the present invention, which is equipped with a long substrate unwinding and winding traveling system. In the vacuum chamber 16, a long substrate traveling system including a winding shaft 2, a winding shaft 3, and cylindrical cooling drums 4 and 5 is installed. A predetermined long substrate 1 is installed in the substrate traveling system. The vacuum chamber 16 includes an upper chamber 17 in which the unwinding shaft 2 and the winding shaft 3 are housed, and evaporation sources 6 and 7.
Is separated from the lower chamber 18 in which is separated by isolations 8 and 8'and a mask, and vacuum exhaust is performed from exhaust ports 19 and 20, respectively. The mask regulates the amount of vapor reaching the substrate from the evaporation sources 6 and 7. 5 × 10 ⁻⁵ T in the lower chamber 18
After exhausting to orr or lower, the valves 9 and 10 are opened, inert gas is blown to the drum surfaces 4 and 5 through the nozzles 11 and / or 12, and the pressure in the lower chamber 18 is set to 2 × 10 ^−4.
Adjust to a predetermined pressure in the range of ˜1 × 10 ⁻² Torr. The evaporation sources 6 and 7 are, for example, electron beam heaters 13 and 14
Is heated in. While the substrate 1 is running, the evaporation source is melted and evaporated to deposit a metal thin film having a predetermined thickness on the substrate on the drum 4 surface. By the same operation, the metal thin film is attached to the surface of the drum surface 5 on the back side of the substrate.

The present invention is particularly preferable as an aluminum electrolytic capacitor having an extremely high capacitance, that is, a capacitor element comprising an aluminum foil for an anode, an aluminum foil for a cathode, a separator and an impregnated electrolytic solution, particularly as an aluminum foil for a high capacitance cathode. used.

As the electrolytic solution used in the present invention, any organic polar solvent usually used for electrolytic capacitors can be used. Amides, lactones, glycols, sulfur compounds, ketones and ethers can be used as preferable solvents. As the solute of the electrolytic solution used in the present invention, any solute used in the electrolytic capacitor can be used. Preferably ammonium salts of aromatic carboxylic acids or unsaturated dicarboxylic acids, first to
Examples thereof include tertiary amine salts and quaternary ammonium salts. Also, water can be added to enhance conductivity.

[0022]

[Characteristic measuring method, evaluation method]

(1) Capacitance measuring method A sample in which a metal thin film is formed on both surfaces of a substrate is cut out, and 2
The sample is sandwiched and fixed by two holders each having an opening of 0 mm × 20 mm. A sample fixed to the holder is prepared and fixed in parallel in an electrolytic solution of a 10% ammonium borate aqueous solution. LC using two samples as electrodes
1 with R meter (AG-4311 manufactured by Ando Electric Co., Ltd.)
The capacitance at 20 Hz was measured. One half of the measured value was taken as the capacitance per unit volume. (2) Thickness of metal thin film, number of columns, and column gap A sample was cut into an ultrathin section, and the surface and cross section of the metal thin film were examined with a transmission electron microscope (JEM-120 manufactured by JEOL Ltd.).
0EX) 400,000 times or field emission type electron microscope (S-800 manufactured by Hitachi, Ltd.) 50,000 times to observe 10 base lines vertically and horizontally and measure at least 10 parts each And averaged. (3) Measurement of Surface Expansion Ratio A sample was cut into an ultrathin section and measured by the BET method by a gas adsorption method. (4) Average Surface Roughness (Centerline Average Roughness: Ra (Converts μm Measurement to Angstrom) Measured value by a stylus surface roughness meter (cutoff value of 0.
25 mm, measuring length 4 mm. However, JIS-B-0601
by).

[0023]

EXAMPLES The present invention will be described in detail with reference to examples below, but the present invention is not limited thereto. Example 1 A long-sided aluminum foil base having a thickness of 12 μm was mounted on a double-sided continuous electron beam heating vacuum deposition apparatus equipped with the long web running system shown in FIG. The aluminum foil has a flat surface (average surface roughness of 400 angstroms) without a bore on both sides, and is inserted into a vapor deposition drum through an argon plasma treatment process. After filling the electron beam heater with the titanium alloy ingot containing 5% of antimony, the inside of the vacuum chamber was evacuated from the exhaust port, and the pressure in the lower chamber cut off by the isolation, mask, and vapor deposition drum was 5 × 10 5. ^-5 Tor
It was set to r or less. Next, when nitrogen gas was introduced at a rate of 0.7 liter / min toward the vapor of the titanium alloy through a porous nozzle installed in a circular shape above the electron beam heater, the pressure in the lower tank was 8 × 10 ^−4. It became Torr. While running the aluminum foil base, adjust the EB gun output and melt and evaporate the titanium alloy ingot to deposit a flat surface of aluminum foil with a deposition rate of 3.0 m /
A titanium alloy columnar vapor-deposited film having a thickness of 0.1 micron was formed by a minute. When forming a titanium alloy film, the vapor deposition drum-
Adjusted to 20 degrees. Further, a titanium metal columnar vapor deposition film having the same thickness was formed on the front and back surfaces by the same operation on the back surface.

The electrode foil for electrolytic capacitors thus obtained was not deformed by heat damage during vapor deposition and had good flatness. The vapor-deposited metal thin film is composed of an aggregate of column structures, the titanium alloy thin film layer has a thickness of about 1200 angstroms, and the number of columns is 220 × 10 ⁸ pieces / cm ² .
The average column gap was about 300 Å and the surface expansion ratio was about 200 times. When the capacitance of the electrode foil for electrolytic capacitors was measured using a 10% ammonium borate aqueous solution as an electrolytic solution, the capacitance was 360 microfarads / cm ^2.
And a big value was obtained. With only smooth aluminum foil, the capacitance was 4 microfarads / cm ² .

Using this as a cathode foil, it was wound together with a 90 μm anode foil having an anodized film through a separator to produce a capacitor element, and the capacitor element was made to have a moisture content of 1% by weight and γ-butyrolactone of 74% by weight. , O
-Impregnated with a driving electrolytic solution consisting of 25% by weight of tetraethylammonium phthalate, rated at 25V / 3300μ.
An F electrolytic capacitor was manufactured. The capacitance of the electrolytic capacitor was measured to find out the manifestation of the capacitance, and it was 3360 μF. When the durability of this electrolytic capacitor was examined, the rate of change in capacitance after 110 hours and 5000 hours was within ± 5%.

Example 2 As in Example 1, a double-sided continuous electron beam heating vacuum deposition apparatus equipped with the long web traveling system shown in FIG. 3 was equipped with a long aluminum foil base having a thickness of 20 μm. The aluminum foil has a flat surface (average surface roughness of 400 angstroms) without a bore on both sides, and is inserted into a vapor deposition drum through an argon plasma treatment process. After filling the electron beam heater with a titanium alloy ingot containing 5% tin, the inside of the vacuum tank was evacuated from the exhaust port to isolate it, and the pressure in the lower tank, which was cut off by the mask and vapor deposition drum, was set to 5 × 1.
0 ^-5 Torr was below. Next, when nitrogen gas was flowed into the titanium alloy vapor at a rate of 0.5 liter / min through a porous nozzle installed in a circular shape above the electron beam heater, the pressure in the lower tank was 8 × 10 ^{−. 4} T
became orr. While running the aluminum foil base, adjust the EB gun output, melt and evaporate the titanium alloy ingot, and deposit 2.0 m /
A titanium alloy column-shaped vapor deposition film having a thickness of 0.2 μm was formed in a minute. When forming a titanium alloy film, the vapor deposition drum-
Adjusted to 20 degrees. Further, an alloy column-shaped vapor deposition film having the same thickness was formed on the front and back surfaces by the same operation on the back surface.

The electrode foil for an electrolytic capacitor thus obtained had no deformation due to heat damage during vapor deposition and had good flatness. The vapor-deposited metal thin film is composed of an aggregate of column structures, the titanium alloy thin film tank has a thickness of about 1800 angstroms, and the number of columns is 130 × 10 ⁸ pieces / cm ² .
The average column gap was about 400 Å and the surface expansion ratio was about 280 times. When the capacitance of the electrode foil for an electrolytic capacitor was measured using a 10% ammonium borate aqueous solution as an electrolytic solution, the capacitance was measured to be 510 microfarads / cm ^2.
And a big value was obtained.

Comparative Example 1 As in Example 1, a double-sided continuous electron beam heating vacuum deposition apparatus equipped with the long web traveling system shown in FIG. 3 was equipped with a long aluminum foil base having a thickness of 20 μm. The aluminum foil is flat and smooth (mean surface roughness 400 angstroms) on both sides and has no bore, and is inserted into the vapor deposition drum. After filling the electron beam heater with a titanium ingot, the inside of the vacuum chamber was evacuated from the exhaust port, and the pressure in the lower chamber, which was separated by the isolation, mask, and vapor deposition drum, was set to 5 × 1.
0 ^-5 Torr was below. Next, when nitrogen gas was introduced at a rate of 0.02 liter / minute toward the vapor of the titanium alloy through a porous nozzle installed in a circular shape above the electron beam heater, the pressure in the lower tank was 8 × 10 ^−4. T
became orr. While running the aluminum foil base, adjust the EB gun output, melt and evaporate the titanium ingot, and deposit it on a flat smooth foil at a deposition rate of 0.3 m / min and a thickness of 0.6 microns (6000 angstroms). ), 1.0 micron (10,000 angstroms)
An attempt was made to form a titanium columnar vapor-deposited film. But,
The latter was cut by heat loss, and the electrode foil for electrolytic capacitors obtained from the former was significantly deformed due to expansion due to heat during vapor deposition, and it was difficult to wind it into a capacitor shape.

[0029]

The electrode material according to the present invention can be formed by a dry method as compared with a conventional etching foil by a wet method, and since the surface area can be increased with an extremely thin film, the productivity is good, there is no pollution problem, and the cost is low. Moreover, the capacitance per unit volume can be increased, and as a result, it can be extremely effective for downsizing, high performance, and cost reduction of the high capacitance electrolytic capacitor. Furthermore, since a fine and uniform column structure and a column gap having a good impregnation property can be formed, an electrolytic capacitor having stable electric characteristics such as capacitance can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a schematic view of an electrode foil of the present invention.

FIG. 2 is a diagram showing an example of a schematic diagram of a conventional etching electrode foil.

FIG. 3 is an example of a vacuum vapor deposition apparatus for producing the electrode foil for electrolytic capacitors of the present invention.

[Explanation of symbols]

 a substrate b b vapor-deposited metal thin film having a column structure c substrate smooth surface d bore by etching e Al foil substrate 1 long substrate 2 unwinding shaft 3 winding shaft 4,5 cooling drum 6,7 evaporation source 8,8 'isolation 9, 10 valve 11,12 nozzle 13,14 electron beam 16 vacuum chamber 17 upper chamber 18 lower chamber 19,20 exhaust port 21,22 preheater

Claims (2)

[Claims] 1. An electrode material for an electrolytic capacitor comprising a substrate and a metal thin film formed on at least one surface of the substrate, wherein the metal thin film is Zn, Mg, Ca, Sr, Ba, A.
1, Sn, Mn, V, Cr, Ni, Fe, Zr, B, S
It is made of a Ti alloy containing a metal selected from b and Pd, and the number of columns is 5 × 10 ^{8 to} 1 to 10 ¹² number /
An electrode material for a high-capacity electrolytic capacitor, characterized in that it has an independent columnar shape with a cm ² column gap of 50 to 5000 angstroms, a thickness of 100 to 5000 angstroms, and a surface expansion ratio of 50 to 1000 times. 2. An inert gas containing at least 0.03 liters / minute or more of an inert gas, a nitrogen gas, and / or a nitrogen gas from the gas inlet having one or more outlets, the metal thin film on the substrate. The method for producing an electrode material for a high-capacity electrolytic capacitor according to claim 1, wherein vapor deposition is performed while gas is introduced.