JPH07138792A - Metallic porous body and production of metallic porous body - Google Patents

Abstract

PURPOSE:To execute a conductivity imparting process before an electroplating process with excellent workability, to reduce the electric resistance of the conductive layer, and to decrease the coating weight in the electroplating process. CONSTITUTION:A conductive metallic layer is formed by applying a metallic particulate powder 4 with an adhesive on a three dimensional net like porous body sheet 1 composed of a foamed body, a non-woven fiber, a mesh body and these laminated body. An electroplated layer is provided on the surface of the conductive metallic layer. The conductive metallic layer is remained at the time of desooting and sintering and the metallic layer is composed of a laminated body of the conductive metallic layer and the electroplated layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous metal body and a method for producing the porous metal body, and more specifically to a three-dimensional reticulated porous body made of a foam, a non-woven fabric, a mesh or a laminate of these. A porous metal body is formed by using the same, and by filling the pores of the porous metal body with an active material powder, electrode plates of various batteries such as nickel-cadmium battery, nickel-hydrogen battery, lithium battery and fuel cell, automobile It can be suitably used as an electrode plate of a battery for automobiles.

[0002]

2. Description of the Related Art The applicant of the present invention has previously proposed, as the metal porous body used in the above-mentioned battery electrode plate, a single body such as a foam, a nonwoven fabric, a mesh body, or a laminated body in which two or more kinds of these are laminated, A variety of metal plated porous bodies are provided. (JP-A-1-290792 and JP-A-3-290792)
130393 etc.)

Foams, non-woven fabrics, meshes, etc., which are the base materials of the above-mentioned porous metal, are synthetic resins, natural fibers, cellulose,
In the case of organic materials such as paper and inorganic materials such as glass, it is necessary to give conductivity before performing electroplating treatment.
Even when the base material is made of metal, it is preferable to apply the conductivity imparting treatment. As the above-mentioned conductivity imparting treatment, conventionally, there has been used a method of coating carbon on the surface of a substrate made of a porous material or coating a conductive material such as metal on the surface of the porous material by chemical plating or vapor deposition.

[0004]

The above-mentioned conventional processes for imparting conductivity have the following problems. a) Vapor deposition method It is necessary to perform vapor deposition in a vacuum apparatus. However, when the substrate is continuously processed, it is not easy to deposit the vapor through the vacuum apparatus in the vacuum apparatus, and air leakage occurs at the inlet and outlet of the substrate. Occurs and is not easy to maintain in a vacuum state. In addition, there is a drawback that the equipment becomes large, and that the cost is very high and the time is long. b) Chemical plating method When chemical plating is performed, the number of steps is large, and it is necessary to manage a large number of chemical liquids. In particular, it is necessary to pay attention to waste liquid treatment. In addition, there is a drawback that the cost of chemicals is high. c) Carbon coating method Although the cost is lower than that of the above vapor deposition or chemical plating, there is a drawback that a large amount of carbon remains as impurities. In addition, the resistance value after applying carbon is 100 to 2
Since it is as high as 00 Ω / cm, it is difficult to generate a high current in the electroplating in the next step. When trying to output a high current, the base material burns out, so the speed of the line for conveying the base material must be slowed down. For example, the speed becomes 0.1 to 0.5 m / min, resulting in poor productivity. Has become.

All of the above-mentioned three conventional methods have problems, but since the cost is low, the method of applying conductivity by applying carbon is generally used. However, in the case of the carbon coating method as described above, the resistance value becomes high, so that the line speed must be reduced. Therefore, it is required to reduce the resistance value of the conductive treatment layer to 30 Ω / cm or less so that a high current can be generated in the electroplating in the next step, and to increase the line speed and enhance the productivity.

Further, there is a problem that the carbon applied for imparting the above-mentioned conductivity is not completely burned out in the soot-removing and sintering steps after electroplating, and a small amount of carbon remains as impurities. Further, conventionally, when a metal porous body is formed by using a base material made of a resin sheet of a porous body or the like, the required metal deposition amount is almost 100% deposited by electroplating, resulting in high electricity consumption and high cost. In addition, there is a problem that it takes a long time for plating and it is difficult to improve productivity.

The present invention has been made in view of the above-mentioned problems of the conventional conductivity imparting treatment method, and uses a novel conductivity imparting treatment method and a novel conductivity imparting treatment method which are completely different from the conventional methods. The object is to provide a metal porous body produced by the method.

That is, the present invention provides a method for imparting conductivity, in which the formed conductive metal layer has a low electric resistance value and a high current can be generated in the subsequent electroplating step, and
Not burnt out in the soot removal step after electroplating, leaving the conductive metal layer as a constituent material of the skeleton of the metal porous body,
The thickness of the metal layer formed by electroplating in the subsequent step can be reduced by that amount, and a conductivity imparting treatment method in which carbon does not remain like the carbon coating method is adopted.

[0009]

The present invention firstly provides a method according to any one of claims 8 to 24 as a method for producing a metal porous body. Based on the method according to claim 8, the inner peripheral surface of the pores of a three-dimensional net-like porous body composed of a single body of a foam, a nonwoven fabric or a mesh body or a laminated body in which two or more kinds of these are laminated. To form a conductive metal layer by applying fine metal powder to the entire surface including using an adhesive,
Then, the surface of the conductive metal layer is electroplated to form a metal plating layer to form a porous metal body.

As a method for producing a metal porous body, it is preferable to remove soot and sinter after forming the metal plating layer. (Claim 9) Further, electroplating may be performed again after the soot removal and sintering. (Claim 10) Alternatively, after the metal plating layer is formed, the base material may be left without removing the soot from the base material.

Further, after the conductive metal layer is formed by the fine metal powder, it is soot-removed, and then impregnated with a solution containing metal ions to adsorb the metal ions, and then electroplating is performed to perform metal plating. The layers may be formed and then sintered. (Claim 11) Further, after forming a conductive metal layer of fine metal particles, the metal ions are adsorbed without performing soot removal, and then electroplating is performed, and thereafter, soot removal and sintering are performed. You can go. (Claim 12)

The fine metal powder is activated and / or replaced before being applied to the porous body to impart conductivity. Alternatively, the fine metal powder may be applied to the porous body, and then the fine metal powder may be activated and / or substituted to impart conductivity. (Claim 14) Also, before being applied to the porous body, it is a conductive metal that is hard to oxidize and is soft, such as Au, Ag, Cu, In.
A method may be used in which a metal powder composed of the above is charged into a ball mill together with the metal fine particle powder and stirred to press-coat the metal powder on the surface of the metal fine particle powder. The activation and / or substitution treatment of the fine metal powder is not necessarily performed when the fine metal powder is Cu or Ag having high conductivity. Further, before applying the electroplating, a thin adhesive is applied to the surface of the conductive metal layer formed of a coating layer of fine metal powder. (Claim 15)

The porous body is continuously conveyed in the form of a sheet, the conductive metal layer is formed on the upstream side of the conveying process, and then electroplating is performed, and thereafter, the soot-removing / soot-forming material is formed on the downstream side. It is sintering. (Claim 16) Incidentally, when the porous sheet is made of metal, the soot removing step is omitted, and also when the porous sheet is left, the soot removing and sintering steps are omitted.

In the step of forming the conductive metal layer, it is possible to use a method in which an organic adhesive is applied to the porous body in advance and then fine metal particles are applied. (Claim 17) In that case, the above-mentioned organic adhesive is applied by spraying, dipping in a liquid tank of the organic adhesive, applying by roll coating with a roll applying the organic adhesive on the surface, or An organic adhesive can be supplied to the inside of the roll and impregnated and applied through a screen on the outer periphery of the roll. (Claim 18) After applying the organic adhesive to the porous body in the above-mentioned mode, sprinkling fine metal powder on the surface of the organic adhesive, and then permeating through the porous body in the thickness direction with a vibration and / or an air knife. Thus, the fine metal powder is uniformly attached to the entire surface of the porous body including the surface of the porous body and the inner peripheral surface of the pores.
(Claim 19) Alternatively, the fine metal powder is supplied to the surface of the organic adhesive, and then distributed by a doctor knife, and then penetrated in the thickness direction of the porous body with a vibration and / or an air knife to obtain the surface of the porous body. It may also be uniformly attached to the entire surface of the porous body including the inner peripheral surface of the pores. (Claim 20)

As an alternative to the method of applying the fine metal powder after applying the organic adhesive, a slurry in which the fine metal powder and the organic adhesive are mixed is provided, and the slurry is provided on the surface of the porous body and in the pores. Apply to all surfaces including the peripheral surface,
You may form the said conductive metal layer. (Claim 21) Alternatively, a slurry in which the fine metal particle powder, an organic adhesive, and an ion-adsorbing resin are mixed is provided, and the slurry is applied to the entire surface including the surface of the porous body and the inner peripheral surface of the pores,
You may form the said conductive metal layer. (Claim 22) In that case, the slurry is applied to the porous body by spraying, is applied by a roll immersed in a slurry tank, or is applied by roll coating via a roll applying the slurry. The slurry supplied inside can be impregnated and applied through a screen on the outer periphery of the roll. (Claim 23) It is preferable that the slurry is impregnated and applied from both surfaces of the porous body. (Claim 24)

The present invention provides a porous metal body produced by the above method according to any one of claims 1 to 7. That is, the present invention provides a porous metal body having a three-dimensional network skeleton composed of a conductive metal layer made of fine metal powder and a metal layer formed by electroplating on the surface of the conductive metal layer. To do. (Claim 1) The conductive metal layer is formed by sintering fine metal powder. (Claim 2)

Further, the present invention provides a porous metal body in which the three-dimensional mesh-like porous body is left without being burnt out and the conductive metal layer and the metal plating layer are provided on the surface of the three-dimensional mesh-like porous body. providing. (Claim 3)

The fine metal particles forming the conductive metal layer include Ni, NiO, Cu, Ag, Al, Au and F.
e, Zn, Sn, P, Cr, In, Pb at least one kind or a mixture of two or more kinds Ni, Cu, Ag,
Fine particles of Al, Fe and Zn are preferably used. (Claim 4) Further, the conductive metal layer made of the fine metal powder has metal ions attached to the surface or permeated into the inside. (Claim 5) The metal ions include Ni, Cu, Ag, Fe and Z.
n, Sn, Au or In is preferably used. (Claim 6) Further, as the metal of the metal layer formed by the electroplating, Ni, Cu, Ag, Fe, Zn, Sn, Au,
In is preferably used. (Claim 7)

Of the three-dimensional reticulated porous materials used in the present invention, the foam is made of polyurethane sponge or the like, and has a thickness of 0.5 to 5.0 mm and a hole diameter of 50 to 500 μm.
Those having m and porosity of 50 to 99% are preferably used. Among the three-dimensional mesh-like porous bodies, the materials for the non-woven fabrics and mesh bodies are synthetic resins such as polyester, polypropylene and polyurethane, organic materials such as natural fibers, cellulose and paper, inorganic materials such as metals, glass and carbon. What is used. Further, the mesh body includes a knitted warp yarn and a weft yarn, or a knitted fabric having all knitting structures formed by knitting one or a plurality of yarns into a fibrous shape.
Those having a mesh size of up to 200 mesh are preferably used. Moreover, as the mesh body and the non-woven fabric, the wire diameter is 0.01 mm to
Those having a thickness of 1.0 mm and an aperture ratio of 40 to 99% are preferably used.

[0020]

When a fine metal powder is applied by the method according to the present invention to provide a conductive metal layer, the conductive metal layer has an electric resistance value of 8 Ω of 30 Ω / cm or less.
/ Cm to 1 Ω / cm.
Therefore, the electroplating in the next step can be performed at a high current, and when the electroplating having a predetermined thickness is applied, the plating process can be performed at a high speed, and the productivity can be significantly improved. it can.

In addition, since the conductive metal layer is not burnt out in the soot removal / sintering step and can be left as a constituent material of the skeleton of the metal porous body to be produced, the thickness of the metal layer formed by electroplating in the next step. Can be reduced by that amount. Particularly, in the case of a metal porous body, it is desired to increase the volume of the pores to increase the filling amount of the active material powder filling the pores, and as a result, the metal deposition amount by electroplating can be reduced. Is required. In the porous metal body, the weight per unit area of the metal was 600 g / m ² in the past, but is changing to 420 g / m ² . In that case, when the conductive metal layer is 100 g / m ² , the basis weight of the electroplating is 320 g / m ² . Therefore, the conventional unit weight of electroplating was 600 g / m ²
It can be halved to about 0 g / m ² .

[0022]

Embodiments of the present invention will now be described in detail with reference to the drawings. In the first embodiment, as shown in the flow chart of FIG. 1 and the schematic process diagram of FIG. 2, a single body made of foam, a nonwoven fabric, a mesh body, or a three-dimensional net-like porous body made of a laminate of two or more kinds of these is used as a base material. The porous body 1 is continuously conveyed in the form of a continuous sheet. In the transportation process, first, as shown in step # 1 in FIG. 1, the organic adhesive 2 is transported to the adhesive tank 11 and the upper and lower surfaces of the porous body 1 and pores are formed in a manner described later. The organic adhesive 2 is applied to the inner peripheral surface of the part.

Then, as shown in Step # 2, at least 5.0 μm or less, preferably 1.0 μm or less of the metal fine powder 4 is jetted from the powder jetting device 12 arranged along the porous body conveying path, Sprinkle on the surface of the organic adhesive 2. At that time, as shown in FIG. 2, the porous body 1 is turned upside down, and the fine metal particles 4 are sprinkled on both upper and lower surfaces. Examples of the fine metal particles include Ni, NiO, Cu, Ag, and A.
A mixed powder of at least one or two or more of 1, Fe, Zn, Sn, Au, In, P and Cr, and an alloy powder of Cr and Fe are preferably used. Since the fine metal particles 4 may not be evenly distributed and may not be distributed to the surface of the inner hole portion 1c just by sprinkling the powder sprayer 12, as shown in step # 3, vibration may occur. Vibration is applied to the porous body 1 by the generator 13 to uniformly distribute the fine metal particles 4 on the surface of the porous body 1, and
Excessive fine metal powder is removed. Then, step # 4
As shown in, when the fine metal powder 4 is penetrated in the thickness direction of the porous body 1 by the air knife 14 and the fine metal powder is clogged in the pores of the porous body, the clogged metal fine powder is dropped. Let In this way, the fine metal powder 4 is surely adhered to the surface of the adhesive 2 applied to the inner peripheral surface of the hole with a uniform thickness to form the conductive metal layer 5.

The above steps # 2 to # 4 are performed once to three times as needed, and the weight per unit area (adhesion amount) of the conductive metal layer 5 becomes about 1/2 of the final metal weight. I am trying. The basis weight is not limited to 1/2, but is 1/2 in this embodiment. Next, when the fine metal powder 4 is a fine metal powder other than Cu and Ag whose surface is easily oxidized, the fine metal powder 4 is activated as shown in step # 5. The porous body 1 provided with the conductive metal layer 5 is immersed in 15. Then, as shown in step # 6, when the specific resistance value of the fine metal particles 4 is high, the porous body 1 is immersed in the replacement liquid tank 16 for replacement.

After the drying shown in step # 7, the organic adhesive 6 is applied to the surface of the conductive metal layer 5 as shown in step # 8. The application of the organic adhesive 6 is carried to the adhesive tank 17 in the same manner as the application of the organic adhesive 2. After applying the organic adhesive 6 above, step #
As shown in FIG. 9, the electroplating device 18 performs electroplating similar to the conventional one to form the electroplated metal layer 7.
The basis weight of the electroplated metal layer 7 may be the required basis weight minus the basis weight of the conductive metal layer 5. The metal used for the electroplating is Ni, Cu, A
g, Fe, Zn, Sn, In, etc. are used.

After the electroplating, the heating device 19 is heated at a required temperature for a required time, and as shown in step # 10,
When soot is removed and the base material made of a porous material is made of a material other than metal, the base material is burnt out. Then, as shown in step # 11, in the heating device 20, sintering is performed by heating at a required temperature for a required time in a reducing atmosphere. Finally, as shown in step # 12, the required thickness adjustment is performed through the skin pass roll 21.

Steps # 1 to # 12 described above
Through the above process, a porous metal body 8 having a skeleton surrounding the pores, which is composed of a laminated body of the conductive metal layer 5 and the electroplated metal layer 7, as shown in FIG. 3, is manufactured.

As an apparatus for applying the adhesive 2 in the above step # 1, as shown in FIG. 2, an organic adhesive 2 such as an acrylic adhesive is stored in an adhesive tank 11 and adhered in the adhesive tank 11. The pick-up roll 22 is installed so as to come into contact with the agent 2, and the coating roll 23 is arranged so that the surface is in contact with the upper part of the pick-up roll 22. The coating roll 23 and the porous body 1 are sandwiched and service is performed relative to each other. A roll 24 is arranged. In the above device, the adhesive tank 1
The adhesive 2 in 1 is pulled up by the pickup roll 22, and the coating roll 23 serves as the service roll 24.
The porous body 1 is impregnated and coated with the adhesive 2 in a state where the porous body 1 is pressed between, and, that is, by the roll coater method.

Instead of the apparatus shown in FIG. 2, as shown in FIG. 4, a plurality of rolls 25A and 25B are arranged in the adhesive tank 11 so as to come into contact with the adhesive 2, and these rolls 25 are arranged.
Porous body 1 so as to be immersed in adhesive 2 along A and 25B
Even if the adhesive 2 is applied to the porous body 1 by a dipping method in which the excess adhesive 2 is squeezed through the space between the pair of squeezing rolls 26A and 26B provided above the exit portion. Good.

In each of the methods for applying the adhesive 2 shown in FIGS. 2 and 4, the porous body 1 is passed between the rolls so that the porous body 1
Therefore, when the porous body 1 is a foam, the porous body 1 elastically returns to the original state after passing through the rolls and recovers the initial thickness, which can be adopted without any problem. However, when the porous body 1 is a non-woven fabric, it does not return to the initial thickness after passing through the roll. Therefore, the method of applying the adhesive by spraying is preferable to the above method. In the case of this spray method, the adhesive 2 is sprayed in a mist form and sprayed, and in order to make the amount of the sprayed adhesive 2 uniform, a vacuum is applied to absorb the excess adhesive 2. ing. still,
In the case of a mesh body, there is no problem with any of the above methods.

The sprinkling of the fine metal powder 4 in step # 2 is carried out by using two powder jetting machines 12 as shown in FIG. 2 and the porous body 1 is turned upside down to sprinkle the fine metal powder on both upper and lower surfaces. ing. As shown in FIGS. 5 and 6, the powder sprayer 12 is disposed above the porous body 1 that is continuously conveyed in the horizontal direction, and the fine metal powder 4 is sprinkled from the upper side to the lower side of the porous body 1. There is. The powder jet machine 12 is
The lower end outlet portion 27a of the powder hopper 27 into which the fine metal powder 4 is charged is opened between the rotor hole 28a of the casing 28 and the outer peripheral surface of the fixed amount rotor 29 rotatably arranged in the rotor hole 28a. . The quantitative rotor 29 is shown in FIG.
As shown in FIG. 5, slanted blade portions 29a are provided on the outer peripheral surface at a predetermined pitch, and the fine metal particles 4 falling from the outlet portion 27a are scooped between the blade portions 29a, and adjacent blade portions 29a. It rotates while holding a fixed amount of the fine metal powder 4 between them.

On the side of the casing 28 facing the outlet 27a of the powder hopper 27, a vertical injection passage 30 communicating with the outer peripheral surface of the metering rotor 29 is formed, and the pressure is higher than the upper end of the injection passage 30. Supplying N ₂ gas.
The blade portion 29a of the metering rotor 29 faces downward in a portion communicating with the injection passage 30, and the fine metal particles 4 held between the blade portions 29a fall, and the fine metal powder 4 is supplied from above N ₂ Gas is ejected downward. The porous body 1 is conveyed below the casing 29 and sprinkled with the fine metal powder 4. In FIG. 5, reference numeral 32 is a vibrator.

While the fine metal powder 4 is sprinkled from the upper surface side of the porous body 1 by the powder sprayer 12 shown in FIGS.
As shown in FIG. 2, the porous body 1 is turned upside down along the transport path, and the lower surface side of the porous body 1 is also sprinkled with the fine metal powder by the powder sprayer 12 arranged in the lower stage.

When the fine metal powder 4 is sprinkled on the porous body 1 with the powder jet machine 12, the fine metal powder 4 may not be uniformly distributed, and the fine metal powder 4 may be distributed inside the pores of the porous body 1. It may get stuck. Therefore, after sprinkling the fine metal powder 4 on the porous body 1, vibration is applied to the porous body 1 from the lower surface of the porous body 1 to disperse the hardened fine metal powder 4 and the excess pores clogging the pores. The fine metal powder 4 is blown off, and the fine metal powder 4 is uniformly applied to the adhesive 2 applied to the surface of the porous body 1 and the inner peripheral surface of the pores.
Attach. The fine metal powder that has been sprayed from the powder sprayer 12 and has not adhered to the adhesive 2 and the fine metal powder 4 that has been blown away by vibration are collected and reused. Therefore, the powder ejector 12 and the vibration generator 13 are provided in a closed casing so that the fine metal powder 4 blown off and dropped can be collected in the casing.

After the vibration is applied, as described above, high-pressure air is blown by the air knife 14 so that the fine metal particles 4 on the surface of the porous body 1 are perforated in the thickness direction, and the inner peripheral surface of the pores is covered. The fine metal powder 4 is surely covered, and the fine metal powder clogged in the pores is blown off.

The steps of sprinkling the fine metal powder, vibration, and perforation with an air knife may be repeated. Further, when the porous body is thin, the fine metal powder may be sprinkled only from one side of the porous body.

After the conductive metal layer 5 is formed by the steps up to the above step # 4, activation and substitution treatments are performed in the next steps # 5 and # 6. , Ag, which are electrically conductive, do not necessarily have to be formed. However, in the case of a metal whose surface is easily oxidized, the conductivity cannot be obtained. Therefore, the activation treatment is performed in step # 5, and if the specific resistance of the metal is high, the resistance value is lowered. And the electric resistance value is reduced to 30 Ω / cm or less.

In the activation and replacement treatments in steps # 5 and # 6, the fine metal particles are sequentially immersed in the activation liquid and the replacement liquid in advance before the fine metal particles 4 are attached to the porous body 1. The activated fine metal powder 4 may be sprayed from the powder sprayer 12 and sprinkled on the porous body 1. Furthermore, before being immersed in the activation liquid and the replacement liquid, or instead of being immersed in the activation liquid and the replacement liquid, a conductive metal that is better in conductivity than the fine metal powder and has a low hardness and softness and is hard to be oxidized. For example, a method in which a metal powder made of Au, Ag, Cu, In or the like is put into a ball mill together with the metal fine particle powder and stirred to press-coat the metal powder on the surface of the metal fine particle powder. The conductivity of the powder is improved.

Specifically, the ball mill 100 shown in FIG.
Zirconia balls 101 are previously put inside the ball mill 100, and
First, the fine metal powder 4 made of fine Ni powder or the like is charged, and the inner cylinder 100a and the outer cylinder 100b of the ball mill 100 are required for a required time.
Rotate and to loosen the fine metal powder. Next, the metal powder 102 made of Ag or the like is put into the ball mill 100, and is rotated together with the metal fine particle powder 4 for a required time and stirred. By this agitation, the metal powder 102 such as soft Ag is pressed onto the surface of the fine metal particle powder 4 to form a film.

[0040]

[Experimental Example 1] An acrylic adhesive (45% acrylic resin, 55% water, alcohol or solvent) was placed in the adhesive tank 11.
%) And the porous body 1 made of a non-woven fabric is conveyed while being immersed in the adhesive 2 in the adhesive tank 11 by the method shown in FIG. The excess adhesive 2 was sucked off with a vacuum at the position where it exited the adhesive tank 11. Then, from the powder sprayer 12, 1.
After sprinkling Ni fine powder of 0 μm or less and applying vibration, look through with an air knife and then 150 ° C.
And dried for 1 minute. The fine Ni powder was sprinkled once on each of the upper and lower surfaces as shown in FIG. When the weight of the conductive metal layer 5 attached in the above step was measured, 130 g / m ² of the fine metal powder 4 was attached.

Next, the porous body 1 provided with the conductive metal layer 5 was immersed in a 2N nitric acid solution at room temperature for 1 minute to carry out an activation treatment. The electric resistance value at this time was 4800 Ω / cm. As shown in FIG. 8, this measurement is performed on the conductive metal layer 5
A pair of testers 33 is attached to the surface of the porous body 1 on which the
The lead wire connected to the tester 33 was connected to the measuring instrument 34 for measurement.

After the above activation treatment, an Ag replacement solution (silver nitrate 5
A reducing agent such as ammonia, aldehyde, and sodium hypophosphite was mixed in g / liter to 10 g / liter), and the solution was immersed for 30 seconds in a substitution solution having a pH of 4 to 5 at room temperature.
After the replacement treatment, the electric resistance was measured and found to be 8.0 Ω /
cm, 30Ω / required before entering electroplating
It was lower than cm. Incidentally, instead of the above Ag substitution liquid,
When immersed in a chemical Ni (reaction) liquid and plated with 22 g / m ² , the electric resistance value was 6.0 Ω / cm.

After the replacement treatment, an organic adhesive 6 similar to the organic adhesive contained in the adhesive tank 11 was sprayed on the entire surface of the conductive metal 5, and then electroplated. The plating solution for electroplating was a mixed bath of Ni sulfate 360 g / liter, Ni chloride 60 g / liter, and shelf acid 42 g / liter, and the solution temperature was set to 65 ° C. A Ni-plated layer was deposited on the surface of the conductive metal layer 5 in a state of being laminated by the electroplating. The basis weight of the electroplating is 290 g /
m ² and the conductive metal layer 5, the final weight is 42
It was set to 0 g / m ² . After the electroplating, heating was performed at 800 ° C. for 3 minutes to remove soot, and thereafter, heating was performed at 1000 ° C. for 10 minutes in an ammonia decomposition gas atmosphere to perform sintering.

In the first embodiment, the fine metal powder 4 is used.
9 is sprinkled on the porous body 1 from the powder jetting machine 12. Instead of the sprinkling method, as shown in FIG. 9, the fine metal powder 4 is supplied to the surface of the porous body 1, and the fine metal powder 4 is doctored. It may be spread with a knife 35 so as to be distributed over the entire surface with a predetermined thickness. After being distributed over the whole area by the doctor knife 35, it is vibrated in the same manner as in the first embodiment, and the interior is perforated with an air knife.

FIG. 10 is a flow chart showing a second embodiment of the present invention. The difference from the first embodiment is that the adhesive 2 is used instead of the steps # 1 to # 3 of the first embodiment.
The point is that the slurry in which the metal fine particles 4 and the metal fine particles 4 are mixed in advance is applied to the porous body 1 of the base material as the step # 1 ′, and the step # 10 subsequent to the step # 1 ′ is the first embodiment. Steps # 4 to # 12 are the same.

In the second embodiment, in step # 1 ′, as described above, the slurry 40 in which the organic adhesive 2 and the fine metal powder 4 are mixed is provided in advance, and the slurry 40 is added to the porous body 1.
The entire surface including the inner peripheral surface of the hole is impregnated and applied. As a method of impregnating / applying the slurry 40,
A roll coater method is preferable, but application by spraying, application by a roll immersed in the slurry 40, or impregnation / application by screen coating can also be performed.

In the roll coater type apparatus shown in FIG.
A pickup roll 42 is arranged in a liquid tank 41 storing the slurry 40 in a state where the lower portion is immersed in the slurry 40, and a coating roll 43 is arranged above the pickup roll 42. A service roll 44 is arranged above the coating roll 43 so as to sandwich the porous body 1. In the apparatus, the slurry 40 is picked up by a pickup roll 42, transferred to a coating roll 43, and the service roll 4 is transferred by the coating roll 43.
The slurry 40 is impregnated and applied while the porous body 1 is pressed between the two. At that time, the pickup roll 43
The coating amount on the porous body 1 can be adjusted by adjusting the gap between the service rolls 44 and 44. In this embodiment, the gap between the rolls is adjusted to about ⅓ of the thickness of the porous body 1 so that the slurry 40 is surely impregnated into the inside of the porous body 1.

In the above apparatus, the coating roll 4
Since the lower surface of the porous body in contact with 3 has a larger coating amount of the slurry 40 than the upper surface in contact with the service roll 44, the porous body 1 is turned upside down in the same apparatus as that shown in FIG. Coating roll 43 on the top side of
It is preferable to apply the slurry 40 in Step 1. in this case,
The slurry 40 is evenly applied from both surfaces of the porous body 1.

The apparatus shown in FIGS. 12 (A) and 12 (B) is a rotary screen system, in which the slurry is supplied to the inside of the roll and the slurry is applied through a screen constituting the outer peripheral wall of the roll. In this apparatus, a cylindrical peripheral wall portion in which a screen 46 made of a wire mesh is stretched is provided between the side surface plates 45 on both sides, and a hole 45a is formed at the center of the side surface plate 45.
Both sides of the slurry supply pipe 47 are inserted into the hole 45a, and the slurry supply pipe 47 is arranged along the axis of the rotary shaft of the cylindrical screen 46. The formed coating roll 48 is provided, and the coating roll 48 is arranged on both upper and lower sides of the porous body 1. In the coating roll 48, the slurry 40 is supplied to the slurry supply pipe 47 inside the coating roll 48, the slurry 40 is jetted from the slurry jet port 47 a, and the surface of the porous body 1 is impregnated and applied through the screen 46. When the slurry 40 passes through the screen 46, the amount of jetting is uniform, and the slurry 40 is impregnated and applied with a uniform thickness.

The apparatus shown in FIGS. 13 (A) and 13 (B) is also of the rotary screen type, and similarly to FIG. 12, a pair of upper and lower coating rolls 50 are arranged with the conveying path of the porous body 1 interposed therebetween, and Similar to the roll 48, the outer peripheral surfaces of these coating rolls 50 are surrounded by a screen 51 made of a wire mesh. The coating roll 50
A cage 52 is disposed inside the container, and the foamed slurry 40 is supplied to the cage 52 from a tube (not shown) arranged at the roll shaft core portion at a pressure of 2 to 3 atmospheres.

The cage 5 to which the foamed slurry is supplied.
2 has a discharge port 52a on the contact side with the porous body, contacts the atmosphere when being supplied to the porous body through the screen 51 from the discharge port 52a, and the foamed slurry bursts due to the pressure difference with the atmosphere, Return to normal paste. Since the porous body 1 is coated when the foamed slurry bursts, a uniform film can be obtained.

In the apparatus shown in FIGS. 11, 12 and 13, the gap between the coating rolls is set to be smaller than the thickness of the porous body, and the slurry 40 is applied while being pressed by both rolls when passing through the rolls, and the slurry is pressed by the pressing force of the rolls. 40 is pushed in the thickness direction of the porous body to permeate it. At that time, when the porous body 1 is a foam, there is no problem because it elastically returns to the original thickness after passing through the roll. Also, there is no problem when the porous body is a mesh body. However,
When the porous body 1 is a nonwoven fabric, there is a problem that it is difficult to return to the original thickness after passing through the roll.

Therefore, in the case of a non-woven fabric, it is preferable to apply it by immersing it in the slurry 40 as shown in FIG.
That is, in the dipping device, a plurality of pairs of upper and lower coating rolls 56A and 56B are arranged in parallel in a liquid tank 55 storing the slurry 40, and a pair of squeezing rolls 57A and 57B are arranged at the tank rising position. There is. The coating rolls 56A and 56B are immersed in the slurry 40. The porous body 1 is continuously inserted into the gap between the coating rolls 56A and 56B, and the porous body 1 is immersed in the slurry 40 to be applied. By immersing the porous body 1 in the slurry 40 in this way, the slurry 40 can be sufficiently permeated in the thickness direction of the porous body. However,
Since the extra slurry 40 is attached, the porous body 1 is lightly squeezed through the squeezing rolls 57A and 57B at the position of rising the tank to return the extra slurry 40 to the liquid tank 55.

Further, a method of spraying the slurry 40 on the surface of the porous body 1 can be used. Furthermore, a method is used in which the slurry is first supplied to the surface of the porous body using the doctor knife shown in FIG. 9, and the slurry is uniformly spread and distributed by the doctor knife and impregnated in the thickness direction of the porous body. it can.

In step # 1 ', the porous body 1 is coated with and impregnated with the slurry 40 by the various methods described above, and then the slurry 40 coated with the air knife 14 in step # 2 is thickened in the same manner as in the first embodiment. The slurry 40, which is clogged in the pores of the porous body, is blown off in the direction, so that the slurry 40 adheres to the entire surface including the inner peripheral surface of the pores and the upper and lower surfaces of the porous body with a uniform thickness. . In addition, vibration may be applied instead of the air knife, or
You may use an air knife and vibration together.

After step # 2, it is dried, and in the same manner as in the first embodiment, the activation process of the fine metal powder is performed in step # 3, and the substitution process is performed in step # 4. The activation and replacement treatment of the fine metal powder may be performed before mixing with the organic adhesive to form a slurry. Since the activation and replacement process is the same as that of the first embodiment, the description is omitted. Also, since steps # 5 to # 9 are the same as those in the first embodiment, the description thereof will be omitted.

When the method of providing the slurry 40 in which the organic adhesive and the fine metal powder are mixed and applying the slurry 40 to the porous body 1 is used, if the viscosity of the slurry 40 is high, the coating surface of the porous body becomes rough. Occurs. That is, when the viscosity is high, the slurry adheres in a ball shape, so that the surface of the porous body becomes non-smooth and the surface becomes uneven. On the other hand, if the amount of water is increased in order to reduce the viscosity, the drying time after applying the slurry becomes longer. Therefore, the cup viscosity of the slurry 40 is preferably 2000 cps or more and 15000 cps or less.

As for the mixing ratio of the organic adhesive 2 mixed to form the slurry 40, the smaller the organic adhesive 2, the lower the electric resistance value, and the larger the mixing ratio, the higher the electric resistance value. Therefore, the smaller the proportion of the adhesive 2, the better, but at least the amount of the fine metal particles 4 that can adhere to the porous body is required. Therefore, the mixing ratio of the adhesive 2 is 4
It is preferable to set it in the range of 3 to 20% by weight.

Further, the ratio of the conductive metal layer 5 formed by applying the slurry 40 to the metal layer formed by electroplating in the subsequent step is 50 to 95% of the final basis weight of the conductive metal layer 5, It is preferable to use 5 to 50% of the plated metal layer. In addition, the conductive metal layer 5 can be formed by applying the slurry 40 once, but the conductive metal layer 5 can be formed.
When the thickness is large, if the coating is performed only once, the surface becomes rough and variation in the basis weight is likely to occur. Therefore, it is preferable to divide the coating into small portions and perform the coating several times. In that case, the smaller the amount of the adhesive in the slurry to be applied finally, the lower the electric resistance value, and it becomes possible to perform the electroplating in the subsequent step at a high current.

[0060]

[Experimental Example 2] 90 parts of epoxy adhesive (10% of epoxy, 90% of water content), 600 parts of Ni fine powder, 480 parts of water,
1 part of the dispersant was put into a high-speed rotary stirrer and stirred to prepare a slurry 40. The cup viscosity of the slurry 40 was 4200 cps. A pair of upper and lower coating rolls 48 shown in FIG. 12 are used as a porous body, which is a foam made of an Ertel polyurethane sponge having a thickness of 1.6 mm.
The slurry 40 is passed through a gap of 0.2 mm between the upper and lower coating rolls 48, 48 and the porous body 1
It was impregnated and applied on both upper and lower sides. Then, it was perforated with an air knife and dried at 150 ° C. for 1 minute. In this state,
When the adhesion amount of the formed conductive metal layer 5 is measured, it is 85
It was g / m ² . The weight includes the organic adhesive 2, and the substantial metal weight of the fine metal powder 4 alone is 76.5 g / m ² . (The above-mentioned substantial metal weight was measured after sintering to burn off the organic adhesive.) Further, when the electrical resistance value was measured after applying the slurry 40 and drying it, it was 97,000.
It was very high at 0 Ω / cm. Then, when the electric resistance value was measured after the activation treatment, it was lowered to 850 Ω / cm. Next, we plan to activate it by chemical reaction treatment of silver,
When the electric resistance value was measured, it fell to 7.5 Ω / cm.

[0061]

[Experimental example 3] Acrylic adhesive 140 parts, Ni fine powder 4
00 parts, 680 parts of water, 2 parts of dispersant, and 40 parts of 5% MC solution were put into a high-speed rotary stirrer and stirred to prepare slurry 40
It was created. The cup viscosity of the slurry 40 is 6200c
It was ps. A foam made of polyurethane sponge having a thickness of 1.7 mm is used as a porous body, and 0.2 mm between the pair of upper and lower coating rolls 50, 50 shown in FIG.
The slurry 40 was applied to the upper and lower surfaces of the foam by the upper and lower coating rolls 50 and 50.
After that, look through with an air knife and at 150 ° C for 1 minute,
Dried. In this state, the adhesion amount of the formed conductive metal layer 5 was measured and found to be 125 g / m ² . The substantial metal weight was 112.5 g / m ² . Then, when the slurry 40 is applied for the second time in the same manner, the adhesion amount is 250 in total.
g / m ² , and when the slurry 40 was applied a third time, the total amount of adhesion was 375 g / m ² .

Thereafter, after drying, activation treatment was performed with 2N nitric acid for 30 seconds, and further silver substitution was performed to reduce the electric resistance value to 7 Ω / cm. Then, electroplating 50
It was applied at A / dm ² for 35 seconds to deposit 45 g / m ² .
Then, it is heated at 800 ° C. for 3 minutes to remove soot, and then heated at 1000 ° C. for 30 minutes in a reducing atmosphere to sinter, and then passed through a 1.5 mm gap of a skin pass roll to obtain 1.55 mm. A porous metal body 8 was obtained.

The width of the porous metal body is 20 before the sintering.
Although it was 0 mm, it contracted to 194 mm after sintering. The thickness was also contracted. The above shrinkage is slurry 4
This is because the adhesive contained in No. 0 burned at the time of sintering and contracted at the time of forming a metallographic structure at the time of sintering. Therefore, the size of the voids (cells) of the metal porous body to be manufactured also shrinks and becomes small. When the pores become small, when the porous material is used as an electrode plate for a battery and the pores are filled with an active material, the filling amount becomes small.
Therefore, it has been found that it is preferable to make the size of the pores larger than the conventional one, for example, when the diameter of the conventional pores is 200 to 500 μφ, it is increased by about 10%.

[0064]

[Experimental Example 4] 37 parts of acrylic adhesive, 50 fine Ni powder
0 part, 550 parts of water, 1 part of a dispersant, and 25 parts of a 5% MC solution were put into a high-speed rotary stirrer and stirred to form a slurry 40.
It was created. The cup viscosity of the slurry 40 is 3800c
It was ps. A non-woven fabric made of polyester resin having a thickness of 2.5 mm is used as a porous body, and the slurry 40 is placed in a liquid tank using the dipping device shown in FIG. A pair of upper and lower coating rolls 56A and 56B were installed at three places, and the gap between the upper and lower coating rolls 56A and 56B was set to 2.3 mm. In addition, the squeezing roll 57A rising from the tank
And the gap between 57B and 57B was 2.0 mm.

In the dipping device, the non-woven fabric was passed between the coating rolls 56A and 56B at three locations, and was passed between the squeezing rolls 57A and 57B at the rising of the tank. Then, it was perforated with an air knife, and then heat-dried at 150 ° C. for 1 minute to finish to a plate thickness of 2 mm.

[0066] adhesion amount of the slurry 40 conductive metal layer 5 formed by coating a is 54 g / m ^2, substantially metal weight was 48.6 g / m ^2. The electric resistance value of the conductive metal layer 5 was 900,000 Ω / cm. Then, when the conductive metal layer 5 was activated, the electric resistance value was lowered to 820 Ω / cm. Furthermore, when activated by a chemical reaction treatment of silver, the electric resistance value was lowered to 8.6 Ω / cm. The subsequent electroplating and soot-removing sintering steps were the same as in Experimental Example 1.

When the above non-woven fabric is used, since it is formed of short fibers, the fiber density is not evenly distributed. Therefore, short fibers are concentrated in a part as called pills,
Since there is a gap called a scale, it is difficult to uniformly impregnate the slurry. Therefore, compared with the foam, the mixing ratio of the fine metal powder is reduced by about 20%, and the slurry viscosity is reduced to about 3000 to 4000 cps to soften the slurry so that the slurry easily impregnates the nonwoven fabric. did.

[0068]

[Experimental Example 5] Acrylic adhesive 75 parts, Ni fine powder 50
0 parts, 360 parts of water, 1 part of dispersant, and 25 parts of 5% MC solution were put into a high-speed rotary stirrer and stirred to form a slurry 40.
It was created. The cup viscosity of the slurry 40 is 9000c
It was ps. A 90-mesh polyester resin mesh body was used as the porous body, and the dipping device shown in FIG. 14 was used. In the same manner as in Experimental Example 4, the slurry 40 was applied to the mesh body, then perforated with an air knife, and then dried by heating at 150 ° C. for 1 minute.

The conductive metal layer 5 formed by applying the slurry 40 had an adhesion amount of 32 g / m ² and a substantial metal weight of 18 g / m ² . In addition, the conductive metal layer 5
Had an electric resistance value of 97,000 Ω / cm. Then,
When the conductive metal layer 5 was activated, the electric resistance value decreased to 520 Ω / cm. Furthermore, when activated by a chemical reaction treatment of silver, the electric resistance value was lowered to 6.2 Ω / cm.

When the mesh body is used as the porous body as described above, after the slurry 40 is applied, the excess slurry is blown off with an air knife. At that time, the cup viscosity is adjusted so that the entire slurry is not blown off. Thus, it is preferable to have a high viscosity of 9000 cps to 7000 cps.

FIG. 15 shows a flow chart of the third embodiment of the present invention, which is different from the second embodiment in that the soot removal in step # 8 is not performed. That is, the foam, the non-woven fabric, and the mesh body made of polyurethane sponge or the like as the base material are left without being burnt off. The same steps as those in the first embodiment are performed when the soot removal in step # 10 of the first embodiment is not performed. In particular, when the mesh body is formed by knitting a metal wire, it is not necessary to remove soot and burn it off.

FIG. 16 shows a flowchart of the fourth embodiment of the present invention. First, in step # 1, a slurry prepared by mixing an organic adhesive, fine metal particles and an ion-adsorbing resin is applied to a substrate. A conductive metal layer made of fine metal powder is formed. Then, in step # 2, the base material is immersed in a containing liquid containing the same metal ions as the fine metal particles to allow the metal ions in the containing liquid to adhere to or penetrate into the surface of the conductive metal layer. Then, in step # 3, the base material is burned off to remove soot. Then, in step # 4, the surface of the conductive metal layer is electroplated to form an electroplating layer. afterwards,
It is sintered in step # 5 and rolled in step # 6.
The metal ions include Ni, Cu, Ag, Fe and Z.
n, Sn and In are preferably used.

FIG. 17 shows a flow chart of the fifth embodiment of the present invention. The difference from the fourth embodiment is that step # 3 is performed without impregnating soot after impregnation with metal ions in step # 2. The point is that electroplating is performed to form an electroplating layer, and then soot is removed in step # 4 and sintering is performed in step # 5. The difference between the steps of the fourth embodiment and the fifth embodiment is properly used according to the type of metal used and the like.

In each of the above-mentioned first to fifth examples, the porous body as the base material is made of foam, nonwoven fabric or mesh, but two or more of these are laminated,
For example, a laminated body in which a foam body and a mesh body are laminated, or a laminated body in which a nonwoven fabric is sandwiched between mesh bodies can be used as a base material. In the case of this laminated body, the porous bodies to be laminated may be fixed to each other in advance, or they may be conveyed simply in an overlapped state and similarly fixed together when the adhesive is applied and impregnated. good.

[0075]

As is apparent from the above description, according to the present invention, as a conductivity imparting treatment required for applying electroplating, fine metal powder is applied to a porous body using an adhesive, Since the conductive metal layer is formed by impregnation, the electric resistance value of the conductive metal layer is 30 Ω / c required.
It can be easily reduced to about 8 Ω / cm to 6 Ω / cm or less. Therefore, the electroplating in the next step can be performed at a high current, and when the electroplating having a predetermined thickness is applied, the plating process can be performed at a high speed, and the productivity can be significantly improved. it can.

In the case where the conventional conductive carbon is applied or the conductive agent is applied by vapor deposition to impart the conductivity, it is burned off in the soot-removing / sintering step after the electroplating and required. It was necessary to apply 100% of the basis weight by electroplating. On the other hand, in the present invention, the conductive metal layer provided for imparting the conductivity is not burnt off in the soot-sintering step and remains as it is as a three-dimensional network skeleton of the metal porous body. Therefore, the required basis weight by electroplating is the amount obtained by subtracting the basis weight of the conductive metal layer. As a result, the amount of electricity during electroplating can be reduced, the time required for electroplating can be shortened, and productivity can be improved and production cost can be reduced.

Further, when the kind of the base material of the porous body, that is, the foam, the non-woven fabric, the mesh body and the laminated body thereof is changed, the kind of the base material to be used is changed, the fine metal powder is applied according to the base material. When the impregnation method is selected, and when it is applied as a slurry, the conductive metal layer is surely formed on the entire surface including the upper and lower surfaces of the porous sheet and the inner peripheral surface of the pores by adjusting the viscosity thereof. Can be formed.

Further, in the application of carbon which has been generally used for imparting conductivity, carbon remains as an impurity even after soot removal and sintering, but in the present invention, this impurity does not remain. Therefore, the quality of the porous metal body produced by the method of the present invention is improved, and when it is used as a battery electrode plate, it is possible to supply a high quality battery with few impurities.

[Brief description of drawings]

FIG. 1 is a flow chart showing a manufacturing process of a first embodiment of the present invention.

FIG. 2 is a schematic process diagram of the first embodiment.

FIG. 3 is a partially enlarged cross-sectional view of a metal porous body manufactured by the above manufacturing method.

FIG. 4 is a schematic view of an adhesive application device in the first embodiment.

FIG. 5 is a schematic view of a sprinkling device for fine metal powder in the first embodiment.

6 is a partially enlarged view of FIG.

FIG. 7 is a schematic cross-sectional view of a device for imparting electrical conductivity to fine metal particles.

FIG. 8 is a schematic diagram showing a method for measuring an electric resistance value of a conductive metal layer.

FIG. 9 is a schematic view showing another example of sprinkling fine metal powder.

FIG. 10 is a flowchart showing a manufacturing process of the second embodiment of the present invention.

FIG. 11 is a schematic view showing a slurry coating apparatus of the second embodiment.

12A and 12B show another slurry coating device, wherein FIG. 12A is a schematic side view and FIG. 12B is a schematic front view.

13A and 13B show another slurry coating device, FIG. 13A is a schematic side view, and FIG. 13B is a partially enlarged view.

FIG. 14 is a schematic view of another slurry coating device.

FIG. 15 is a flowchart of the third embodiment of the present invention.

FIG. 16 is a flow chart of a fourth embodiment of the present invention.

FIG. 17 is a flowchart of the fifth embodiment of the present invention.

[Explanation of symbols]

 1 Porous Body 2, 6 Organic Adhesive 4 Metallic Fine Particles 5 Conductive Metal Layer 7 Electroplating Layer 8 Metallic Porous Body 12 Powder Injector 13 Vibration Generator 14 Air Knife 23, 43, 48, 50 Coating Roll

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location H01M 4/80 A // H01M 4/04 Z

Claims (24)

[Claims] 1. A porous metal body having a three-dimensional net-like skeleton composed of a conductive metal layer made of fine metal powder and a metal layer formed by electroplating on the surface of the conductive metal layer. 2. The porous metal body according to claim 1, wherein the conductive metal layer is formed by sintering fine metal particles. 3. A conductive metal layer made of fine metal particles on the surface of a skeleton of a three-dimensional net-like porous body made of a foam, a non-woven fabric, a mesh body alone or a laminated body in which two or more kinds thereof are laminated, A porous metal body, comprising a metal layer formed by electroplating on the surface of a conductive metal layer. 4. The fine metal particles constituting the conductive metal layer are Ni, NiO, Cu, Ag, Al, Au, Fe, Z.
Any one of the preceding claims comprising at least one of n, Sn, P, Cr and In or a mixture of two or more thereof.
The metallic porous body according to the item. 5. The porous metal body according to claim 1, wherein the conductive metal layer made of the fine metal powder has metal ions attached to the surface or penetrated into the inside. 6. The metal ions are Ni, Cu, Ag,
The metal porous body according to claim 5, comprising Fe, Zn, Sn, Au, and In. 7. The metal of the metal layer formed by the electroplating is Ni, Cu, Ag, Fe, Zn, Sn, Au,
The porous metal body according to claim 1, wherein the porous metal body is composed of In. 8. A conductive metal layer is formed by coating fine metal powder with an adhesive on the entire surface including the inner peripheral surface of the pores of a three-dimensional net-like porous body, and then the conductive metal is formed. A method for producing a porous metal body, characterized in that the surface of the layer is electroplated to form a metal plating layer. 9. A conductive metal layer is formed by coating fine metal particles with an adhesive on the entire surface including the inner peripheral surface of the pores of a three-dimensional mesh-like porous body, and then the conductive metal is formed. A method for producing a metal porous body, which comprises electroplating a surface of a layer to form a metal plating layer, and then performing soot removal and sintering. 10. A conductive metal layer is formed by coating fine metal particles with an adhesive on the entire surface including the inner peripheral surface of the pores of a three-dimensional mesh-like porous body, and then the conductive metal is formed. The surface of the layer is electroplated to form a metal plating layer, which is then subjected to soot removal and sintering, and then the surface of the metal plating layer is electroplated again, followed by sintering. A method for producing a porous metal body. 11. A conductive metal layer is formed by coating fine metal powder with an adhesive on the entire surface including the inner peripheral surface of the pores of a three-dimensional net-like porous body, and then removing soot, Next, a liquid containing metal ions is impregnated to adsorb the metal ions, and then the surface of the conductive metal layer is electroplated to form a metal plating layer, which is then sintered. A method for producing a porous metal body. 12. A conductive metal layer is formed by coating fine metal powder with an adhesive on the entire surface including the inner peripheral surface of the pores of a three-dimensional net-like porous body, and then containing a metal ion. Liquid is impregnated with the solution to adsorb metal ions, and then the surface of the above-mentioned conductive metal layer is electroplated to form a metal plating layer, which is then subjected to soot removal and sintering. Body manufacturing method. 13. The method according to claim 8, wherein the three-dimensional mesh-like porous body is a foam, a nonwoven fabric or a mesh body alone or a laminated body in which two or more kinds thereof are laminated. The method for producing a porous metal body described. 14. The metal according to any one of claims 8 to 13, wherein an activation treatment and / or a substitution treatment is performed before or after the fine metal powder is applied to the porous body. Method for manufacturing porous body. 15. The method for producing a metal porous body according to any one of claims 8 to 14, wherein an adhesive is applied to the surface of the conductive metal layer before the electroplating. 16. The porous body as a continuous sheet, which is continuously conveyed, the conductive metal layer is formed on the upstream side of the conveying process, and then electroplating is performed. The method for producing a porous metal body according to claim 15. 17. The electroconductive metal layer is formed by applying an organic adhesive to the porous body in advance, and then applying fine metal particles to the conductive metal layer.
The method for producing a porous metal body according to item. 18. The organic adhesive is applied by spraying, dipped in a liquid tank of the organic adhesive to be applied, and the organic adhesive is applied by roll coating through a roll attached to the surface,
18. The method for producing a porous metal body according to claim 17, wherein the organic adhesive supplied to the inside of the roll is impregnated and applied through a screen on the outer peripheral surface of the roll. 19. The fine metal powder is sprinkled on the surface of the organic adhesive applied to the porous body, and then penetrated through the inside of the porous body in the thickness direction with a vibration and / or an air knife to form a porous body. The method for producing a porous metal body according to claim 17 or 18, wherein the fine metal powder is uniformly attached to the entire surface including the surface and the inner peripheral surface of the pores. 20. The fine metal powder is supplied onto the surface of the organic adhesive applied to the porous body, and then uniformly distributed by a doctor knife, and then the direction of thickness of the porous body is measured by vibration and / or air knife. The method for producing a metal porous body according to claim 17 or 18, wherein the fine metal powder is adhered uniformly to the entire surface including the surface of the porous body and the inner peripheral surface of the pores so as to penetrate the inside. 21. A slurry in which the fine metal powder is mixed with an organic adhesive is provided, and the slurry is applied to the entire surface including the surface of the porous body and the inner peripheral surface of the pores to form the conductive metal layer. The method for producing a metal porous body according to any one of claims 8 to 16, which is formed. 22. A slurry in which the fine metal powder, an organic adhesive and an ion-adsorbing resin are mixed is provided, and the slurry is applied to the entire surface including the surface of the porous body and the inner peripheral surface of the pores to obtain the conductivity. The method for producing a metal porous body according to any one of claims 8 to 16, wherein a porous metal layer is formed. 23. The slurry is applied to the porous body by spraying, roll coating is performed by a roll immersed in a slurry tank, roll coating is performed by a roll coating the slurry on the surface, or the slurry is supplied into the inside of the roll. The method for producing a metal porous body according to claim 21 or 22, wherein the slurry is impregnated and applied through a screen on the outer peripheral surface of the roll. 24. The method for producing a metal porous body according to any one of claims 21 to 23, wherein the slurry is impregnated and applied from both side surfaces of the porous body.