JPH07138609A - Metallic porous body and its production - Google Patents

Abstract

PURPOSE:To form a metallic porous body by allowing a metallic layer to adhere to a porous body sheet without applying electroplating. CONSTITUTION:A slurry of adhesive and metallic fine-grain powder is applied, by impregnation, to a base material of porous body consisting of formed body, nonwoven fabric, mesh body, and laminated body of them to provide a conductive metallic layer. Thereafter the conductive metallic layer is burned by means of soot removal and sintering, if necessary to produce the metallic porous body. Moreover, the base material can be allowed to remain without performing soot removal.

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 an organic substance such as paper and an inorganic substance such as glass, electroconductivity is given before the electroplating treatment, and after the electroconductivity imparting treatment, approximately 100% of the required basis weight is attached by electroplating. .

Further, as the conductivity imparting treatment performed before the electroplating step, conventionally, carbon is applied to the surface of a base material made of a porous material, or a conductive material such as metal is chemically plated or vapor-deposited on the surface of the porous material. Is used.

[0005]

When 100% of the required basis weight is deposited by electroplating as described above, in particular,
In the case of thickening, there is a problem that a large amount of electricity is consumed and cost is increased, a long plating time is required, and productivity is lowered.

Further, even in the electroconductivity imparting treatment required in the pre-process of electroplating, the above-mentioned conventional methods 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. There is also 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. As described above, all of the three conventional methods for imparting conductivity have problems, but since the cost is low, the method for imparting 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 the line speed must be reduced, and there is a drawback that improvement in productivity cannot be expected.

The present invention has been made in view of the above conventional problems, and provides a novel method for producing a porous metal body which is completely different from the conventional method, and a porous metal body produced by the method. It is an object.

[0008]

That is, according to the present invention, a required basis weight of 100 is achieved by applying fine metal powder using an adhesive, not by attaching metal by electroplating.
% Of metal is coated on the surface of a substrate made of a porous sheet.

More specifically, the present invention provides the foam, the non-woven fabric or the mesh alone as claimed in claim 8 or 2 thereof.
A conductive metal layer is formed by impregnating and 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 made of a laminated body in which at least one kind is laminated, After that, the present invention provides a method for producing a porous metal body, characterized by performing soot removal and sintering. After forming the conductive metal layer,
The base material may be left without removing the soot from the base material. (Claim 7) Further, after the conductive metal layer is formed, it may be soot-removed, then immersed in a solution containing metal ions to adsorb the metal ions, and then sintered. (Claim 9) Alternatively, after the conductive metal layer is formed, it may be soaked in a liquid containing metal ions to adsorb the metal ions without being soot-removed, and thereafter, soot-removed and sintered. (Claim 10)

The fine metal particles forming the conductive metal layer are provided with conductivity by subjecting the porous body to activation and / or substitution treatment before coating. 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 12) Furthermore, before being applied to the porous body, it is a conductive metal that is hard to oxidize and is soft, such as Au,
A metal powder made of Ag, Cu, In or the like is put into a ball mill together with the metal fine particle powder and stirred, whereby the metal powder is pressure-contacted on the surface of the metal fine particle powder to enhance conductivity. 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.

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 the soot and sintering are performed on the downstream side.
(Claim 13) 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, an organic adhesive is applied to the porous body in advance, and then fine metal powder is applied. (Claim 14) Alternatively, a slurry is prepared by mixing fine metal particles and an organic adhesive, and the slurry is formed by impregnating and coating the entire surface including the surface of the porous body and the inner peripheral surface of the pores. . (Claim 15) Furthermore,
A mixture of fine metal powder, an organic adhesive and an ion-adsorbing resin may be used as the slurry. (Claim 16) When using the slurry,
Slurry is applied by spray, applied by a roll immersed in a slurry tank, or applied by roll coating through a roll applying slurry, and the slurry supplied inside the roll is impregnated and applied through a screen on the outer circumference of the roll. I can do things. (Claim 17) Further, it is preferable to impregnate and apply the slurry from both surfaces of the porous body. (Claim 18)

The present invention provides a porous metal body produced by the above method as described in claims 1 to 6. That is, the present invention provides, in claim 1, a porous metal body in which a three-dimensional net-like skeleton is constituted only by a conductive metal layer made of fine metal powder. The conductive metal layer is made by sintering fine metal powder. (Claim 2)

According to the first aspect of the present invention, the porous metal body as a base material is burnt off to form only the conductive metal layer. There is also provided a porous metal body having a conductive metal layer made of fine metal powder on the surface of the skeleton of the porous body, which is not burnt out of a three-dimensional net-like porous body composed of a laminate of one or more kinds of layers. (Claim 3)

The fine metal particles forming the conductive metal layer are Ni, NiO, Cu, Ag, Al, Fe, Zn, Sn,
It is composed of at least one of Au, In, P and Cr or a mixture of two or more thereof. (Claim 4) Further, the conductive metal layer made of the fine metal powder may have metal ions attached to the surface or penetrated into the inside. (Claim 5) In that case, the metal ions are Ni, Cu, Ag,
It consists of Fe, Zn, Sn, In and Au. (Claim 6)

Of the three-dimensional mesh-like porous material 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.

[0017]

When the fine metal powder is applied by the method according to the present invention to provide the metal layer, the electroplating, which has been necessary until now, becomes unnecessary. 100% of the required basis weight can be deposited. As described above, by omitting the electroplating step, it is possible to significantly reduce the cost and dramatically improve the productivity. In particular, when the metal porous body is used as a battery electrode plate, it is desired to increase the volume of the pores and increase the filling amount of the active material powder to fill the pores, and as a result, It is required to reduce the amount of metal weight. Therefore, in the porous metal body, the weight per unit area of the metal is conventionally 600 g / m ² , but is changing to 420 g / m ² . In that case, a sufficient required basis weight can be provided only by applying the fine metal powder.

[0018]

Embodiments of the present invention will now be described in detail with reference to the drawings. In the first embodiment, as shown in the flowchart of FIG. 1 and the schematic process diagram of FIG. 2, a three-dimensional net-like porous body made of a foam, a nonwoven fabric, or a mesh body or a laminate of two or more kinds of these bodies is used. It is used as a base material, and the porous body 1 is continuously conveyed in the form of a continuous sheet. In the carrying process, first, step # 1 in FIG.
As shown in FIG. 5, the slurry 40 of the organic adhesive 2 and the fine metal particles 4 is conveyed to the adhesive tank 11 that stores the same, and the upper and lower surfaces of the porous body 1 and the inner peripheral surface of the pores are formed in a mode described later. The slurry 40 is impregnated and applied. The fine metal powder 4 used is at least 5.0 μm or less, preferably 1.0 μm.
m or less is preferable, and as the metal fine powder, Ni, Ni
O, Cu, Ag, Al, Fe, Zn, Sn, Au, I
One or a mixture of two or more of n, P and Cr is preferably used. An organic adhesive is used as the adhesive, and a mixture of an acrylic or epoxy resin with water, alcohol, or a solvent is preferably used.

If the slurry 40 in which the organic adhesive 2 and the fine metal powder 4 are mixed has a high viscosity, the coated surface of the porous body will be rough. 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 viscosity of the slurry 40 is 2000 cp
It is preferably s or more and 15,000 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, although it is possible to set the required basis weight only by applying the slurry 40 once, when the thickness of the conductive metal layer is increased, the surface can be obtained by applying the slurry only once. Since it becomes rough and variations in the basis weight are likely to occur, it is preferable to divide into small amounts and perform several times.

Various methods can be used for impregnating / applying the slurry 40 to the porous body 1. In the roll coater type apparatus shown in FIG. 2, the pickup roll 22 is placed in the liquid tank 11 storing the slurry 40.
The coating roll 23 is arranged above the pickup roll 22.
A service roll 24 is arranged above the coating roll 23 so as to sandwich the porous body 1. In this apparatus, the slurry 40 is picked up by the pickup roll 22, transferred to the coating roll 23, and the coating roll 2
3, the slurry 40 is impregnated and applied while the porous body 1 is pressed against the service roll 24.

At this time, the amount of application to the porous body 1 can be adjusted by adjusting the gap between the pickup roll 23 and the service roll 24. In this embodiment, the gap between the rolls is adjusted to about 1/3 of the thickness of the porous body 1,
The slurry 40 is surely impregnated into the inside of the porous body 1.

In the above apparatus, the coating roll 2
Since the lower surface of the porous body in contact with No. 3 has a larger coating amount of the slurry 40 than the upper surface in contact with the service roll 24, as shown in FIG.
It is preferable that the porous body 1 is turned upside down by the same apparatus as shown in FIG. 1 and then the slurry 40 is applied to the upper surface side of the porous body by the coating roll 23. In this case, the slurry 40 is evenly applied from both surfaces of the porous body 1.

The apparatus shown in FIGS. 3 (A) and 3 (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 the above device, the side plates 45 on both sides are
A cylindrical peripheral wall portion in which a screen 46 made of a wire mesh is stretched is provided between the holes, and a hole 45 is formed at the center of the side plate 45.
a is formed, the both sides of the slurry supply pipe 47 are inserted into the hole 45a, and the slurry supply pipe 47 is disposed along the axis of rotation 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. 4A and 4B is also a rotary type.
It is a screen type, and as in FIG. 3, a pair of upper and lower coating rolls 50 are arranged so as to sandwich the conveyance path of the porous body 1, and like the coating roll 48, the outer peripheral surfaces of these coating rolls 50 are separated from the wire mesh. It is surrounded by a screen 51. A cage 52 is arranged inside the coating roll 50, and the foamed slurry 40 is supplied to the cage 52 from a tube (not shown) arranged at the core of the roll rotation shaft at a pressure of 2 to 3 atmospheres. There is.

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. 2, 3 and 4, the gap between the coating rolls is made smaller than the thickness of the porous body, and the slurry 40 is applied while being pressed by the coating rolls on both sides when passing through the rolls. It is preferable to push the slurry 40 in the thickness direction of the porous body with a pressing force so that the slurry permeates. 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 onto the surface of the porous body 1 may be used. Furthermore, using the doctor knife 35 shown in FIG. 6, the slurry 40 is first supplied to the surface of the porous body, and the slurry is evenly spread and distributed by the doctor knife 35 and impregnated in the thickness direction of the porous body. Can also be adopted.

In step # 1, the slurry 40 is applied to and impregnated into the porous body 1 by the various methods described above, and then the slurry 40 applied with the air knife 14 in step # 2 is applied in the thickness direction as shown in FIG. Through the eyes, the slurry 40 clogged in the pores of the porous body 1 is blown off, and the slurry 40 is applied 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. It should be noted that biflation may be applied instead of the air knife, or the air knife and biflation may be used in combination.

After step # 2, dry and step # 3
In step # 4, the metal fine powder is activated, and in step # 4, the replacement process is performed. The activation and replacement treatment of the fine metal powder may be performed before mixing with the organic adhesive to form a slurry. That is, when the fine metal powder 4 is a fine metal powder other than Cu or Ag whose surface is susceptible to oxidation, step #
In order to perform the activation treatment of the fine metal powder 4 of No. 3, it is immersed in the activation liquid tank 15. Next, in step # 4, when the specific resistance value of the fine metal powder 4 is high, the porous body 1 is immersed in the replacement liquid tank 16 for replacement.

Then, after the drying in step # 5,
Heat at the required temperature for the required time with the heating device 19 and step #
The soot removal of No. 6 was performed, and when the porous body was made of a material other than metal, the base material was burned off. Then, as shown in step # 7, 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 # 8, the skin pass roll 21
Adjust the required plate thickness through.

By going through the above steps # 1 to # 8, the skeleton surrounding the pores as shown in FIG.
The metal porous body 8 having a three-dimensional network skeleton composed of the conductive metal layer 5 is manufactured.

[0035]

[Experimental Example 1] 140 parts of acrylic adhesive (30% acrylic, 70% water content), 400 parts Ni fine powder, 680 water
Parts, dispersant 2 parts, and 5% MC solution 40 parts were put into a high-speed rotary stirrer and stirred to form a slurry 40. The cup viscosity of the slurry 40 was 6200 cps. A foam made of a 1.7 mm thick ester polyurethane sponge is used as a porous body, and 0.5 between a pair of upper and lower coating rolls 23 and circle rolls 24 shown in FIG.
The slurry 40 was applied to the surface of the porous body 1 from the coating roll 23 through a gap of mm. Since the slurry 40 is applied while reducing the gap between the coating roll 23 and the sir roll 24 and pressing the foam between the rolls, the slurry 40 applied from the lower surface side is impregnated in the thickness direction and is sufficiently applied to the upper surface side. Was impregnated and applied.

After that, the product is perforated with an air knife and set to 150
It was dried at ℃ for 1 minute. In this state, the basis weight of the formed conductive metal layer 5 was measured and found to be 125 g / m ² . The weight includes the organic adhesive 2, and the substantial metal weight of the fine metal powder 4 alone is 112.5 g / m ² . (The above-mentioned substantial metal weight was measured after sintering to burn off the organic adhesive.)

Similarly, the slurry 40 was applied for the second time. In this second coating, the lower surface that was the lower side in the first coating was made the upper surface in the second coating, and it was turned upside down and coating was performed in the tank 11 shown in FIG. The second coating of the slurry 40 gave a basis weight of 266 g / m ² . Similarly, 3
With the second slurry application, a coating weight of 480 g / m ² could be obtained. When converted to a substantial metal content, 432 g / m ² was obtained. Therefore, the required final basis weight of this type of porous metal is 4
20 g / m ² could be obtained without electroplating.

The metal porous body 8 was heated at 800 ° C. for 3 minutes,
Soot was removed by heating. Then 100 in a reducing atmosphere
Sintering was performed by heating at 0 ° C. for 30 minutes. Then, it was passed through a skin pass roll having a gap of 1.5 mm to obtain a porous metal body 8 having a thickness of 1.55 mm.

The width of the porous metal body is 20 before the sintering.
Although it was 0 mm, it contracted to 180 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%.

[0040]

[Experimental Example 2] 110 parts of acrylic adhesive (30% acrylic content, 70% water content), 800 parts Ni fine powder, 680 water
Parts and 1 part of the dispersant were put into a high-speed rotary stirrer and stirred to prepare a slurry 40. The cup viscosity of the slurry 40 was 3600 cps. A non-woven fabric made of polyester resin having a thickness of 2.2 mm was used as a porous body, and the dipping device shown in FIG.
0, and so as to be immersed in the slurry 40, a pair of upper and lower coating rolls 56A and 5A having an outer diameter of 80 mm.
6B installed in 2 places, each upper and lower coating roll 56A
And the gap of 56B was 2.0 mm. Further, the gap between the squeezing rolls 57A and 57B rising from the tank was set to 1.9 mm.

In the dipping device, the non-woven fabric was passed between the coating rolls 56A and 56B at two places, and passed between the squeezing rolls 57A and 57B at the rising of the tank. Then, look through with an air knife, then at 200 ℃ 1.
It was dried by heating for 2 minutes. The above steps were repeated 3 times to obtain a total Ni content of 426 g / m ² .

In the above apparatus, the gap between the coating rolls 56A and 56B in the second step is 1.9 mm.
Then, the gap between the squeezing rolls 57A and 57B is set to 1.8 mm, and the coating roll 56A for the third step is further used.
And 56B with a gap of 1.8 mm, squeeze rolls 57A and 57
Finish the gap of B with 1.7 mm, remove soot at 800 ° C for 3 minutes,
Sintering was performed at 1000 ° C. for 30 minutes in a reducing atmosphere. Then, the plate thickness was set to 1.4 mm through a skin pass roll.

In the metal porous body 8 manufactured from the above-mentioned nonwoven fabric, the contraction of the plate width was about 7%, which was smaller than that when the foam was used as the base material. The tension was 2.1 kg / 20 mm, which was sufficient to withstand continuous transport while applying tension to the porous metal body 8. Further, in the bending test, it was confirmed that there was no crack on the curved surface even when it was bent at 360 °, and there was no problem in using it as a battery electrode plate.

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 called pills, and there is a gap called scaly, so that 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.

[0045]

[Experimental Example 3] 200 parts of acrylic adhesive (30% acrylic, 70% water content), 1000 parts Ni fine powder, 680 water
Parts, dispersant 3 parts, and 5% MC solution 40 parts were put into a high-speed rotary stirrer and stirred to prepare a slurry 40. The cup viscosity of the slurry 40 was 9000 cps. A 90-mesh polyester resin mesh body was used as the porous body, and the dipping device shown in FIG. 5 was used.
In the same manner as in Experimental Example 3, the slurry 40 was applied to the mesh body, and then, it was perforated with an air knife, and then 150
It was dried by heating at 0 ° C. for 1 minute, and a Ni adhesion amount of 253 g / m ² was obtained. Then, soot removal was performed at 800 ° C. for 1 minute and sintering was performed at 900 ° C. for 30 minutes.

The metal porous body produced by using the above mesh body had a tension of 4.8 kg / 20 mm, and cracks did not occur even when it was bent by 360 ° in the bending test.

FIG. 8 shows a flow chart of the second embodiment. In the first embodiment, the porous body is impregnated with a slurry in which an adhesive and a fine metal powder are mixed, but in the second embodiment,
An adhesive is applied to the porous body in step # 1, and then fine metal powder is sprinkled in step # 2. Then, in Step # 3, while vibrating,
In step # 4, the fine metal powder sprinkled on the surface is permeated into the inside of the porous body through the air knife. Next, in step # 5, the fine metal powder is activated and then dried in step # 6. Then step #
The soot is removed in step 7, sintering is performed in step # 8, and rolling is performed in step # 9.

FIG. 9 shows a flow chart of the third embodiment. In the first and second embodiments, soot and sintering are carried out to burn off the porous body which is the base material, and the electroconductivity of fine metal particles is used. Although a metal porous body consisting of only a metal layer is formed,
In the third embodiment, the porous metal body which is the base material is not burned out, and the porous metal body which is the base material is finally manufactured by laminating the conductive metal layer made of fine metal particles on the surface of the porous body. . That is, in step # 1, a slurry in which an adhesive and metal fine particles are mixed is applied to the porous body 1 made of a continuous sheet, the slurry is perforated with an air knife in step # 2, and the fine metal particles are activated in step # 3. In step # 4, the fine metal powder is replaced, and in step # 5, it is dried, and in the final step # 6.
It is rolled in.

FIG. 10 shows a flow chart of the fourth embodiment. In the fourth embodiment, metal ions are attached to or penetrate into the conductive metal layer. That is, step # 1
Then, a slurry in which fine metal powder, an organic adhesive and an ion-adsorbing resin are mixed is provided, and the slurry is applied to the porous body 1,
A conductive metal layer is formed. Next, in step # 2, the same metal ion containing liquid as the metal fine particle powder is immersed to adsorb the ions. Then, soot removal in step # 3, step #
Sintered in 4 and rolled in step # 5.

FIG. 11 shows a flow chart of the fifth embodiment. In the fourth embodiment, a slurry prepared by mixing fine metal powder, an organic adhesive and an ion-adsorbing resin is provided in step # 1.
The slurry is applied to the porous body 1 to form a conductive metal layer. Then, the soot is removed in step # 2. After that, in step # 3, it is immersed in the same liquid containing metal ions as the fine metal particles to adsorb the ions. Then, it is sintered in step # 4 and rolled in step # 5.

The same metal ions as the fine metal particles forming the conductive metal layer are used as the metal ions attached to or penetrated into the conductive metal layer. The metal ions may be Ni, Cu, Ag. , Fe, Zn, Sn, Au,
In is preferably used. In addition, the fourth embodiment and the fifth embodiment described above.
It is properly used depending on the type of metal used and the like.

In the above-mentioned embodiments of the present invention, a single body of a foam, a nonwoven fabric, and a mesh body was used as the porous body serving as the base material. However, two or more kinds of these are laminated to form, for example, a foam body and a mesh body. It is also preferable to use as a base material a laminate or a laminate in which a nonwoven fabric is sandwiched between mesh bodies.
In the case of this laminated body, the porous body sheets to be laminated may be fixed to each other in advance, or they may be conveyed simply in an overlapped state and simultaneously integrated when the slurry containing the adhesive is impregnated. .

[0053]

As is apparent from the above description, according to the present invention, the fine metal powder is applied to the upper and lower surfaces of the porous sheet as the base material and the inner peripheral surface of the pores by using the adhesive. Since it is possible to obtain the required amount of metal deposition by itself, the metal porous body can be manufactured without using electroplating. Therefore, a large amount of electricity required for electroplating is not required, and a large cost reduction can be achieved. In addition, although electroplating has conventionally required a long time, the electroplating step is not required, so that the metal porous body can be manufactured in a short time, and the productivity can be dramatically improved.

Further, the type of the base material of the porous body is a foam,
When a nonwoven fabric, a mesh body, or a laminate of these is selected, the slurry viscosity of the fine metal powder and the adhesive is adjusted according to the selected base material, so that the upper and lower surfaces of the porous body and the empty space can be reliably ensured. A conductive metal layer can be formed on the entire inner peripheral surface of the hole.

In addition, although carbon remains as an impurity in the conventional coating of carbon which has been generally used for imparting conductivity, no impurities remain in the present invention. Therefore, the quality of the metal porous body manufactured 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 drawing of the above embodiment.

3A and 3B show a slurry coating apparatus used in the above-mentioned examples, FIG. 3A is a schematic side view, and FIG. 3B is a schematic front view.

4A and 4B show another slurry coating apparatus, FIG. 4A is a schematic side view, and FIG. 4B is a partially enlarged view of FIG.

FIG. 5 is a schematic view of another slurry coating device.

FIG. 6 is a schematic view of another slurry coating device.

FIG. 7 is a partially enlarged cross-sectional view of the porous metal body of the present invention.

FIG. 8 is a flowchart of a second embodiment of the present invention.

FIG. 9 is a flowchart of the third embodiment of the present invention.

FIG. 10 is a flow chart of a fourth embodiment of the present invention.

FIG. 11 is a flowchart of a fifth embodiment of the present invention.

[Explanation of symbols]

 1 Porous Body 2 Organic Adhesive 4 Metallic Fine Particles 5 Conductive Metal Layer 8 Metallic Porous Body 40 Slurry 14 Air Knife 23, 48, 50, 56, 56B Coating Roll 35 Doctor Knife

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location H01M 4/80 AC

Claims (18)

[Claims] 1. A metal porous body having a three-dimensional network skeleton composed of a conductive metal layer made of fine metal powder. 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 powder is provided on the surface of a skeleton of a three-dimensional net-like porous body made of a foam, a nonwoven fabric, a mesh body alone or a laminated body in which two or more kinds of these are laminated. A porous metal body. 4. The fine metal particles forming the conductive metal layer are Ni, NiO, Cu, Ag, Al, Fe, Zn, S.
Any one of the preceding claims comprising at least one of n, Au, In, P and Cr 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 metallic porous body according to claim 5, comprising Fe, Zn, Sn, In, and Au. 7. 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 mesh-like porous body. Method for producing metal porous body. 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, after which soot removal and baking are performed. A method for producing a porous metal body, which comprises binding. 9. A conductive metal layer is formed by applying a fine metal powder to the entire surface including the inner peripheral surface of the pores of a three-dimensional mesh-like porous body using an adhesive, and then removing soot, Next, a method for producing a porous metal body, which comprises impregnating a liquid containing metal ions to adsorb the metal ions, and then sintering. 10. 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 mesh-like porous body, and then containing a metal ion. Method for producing a porous metal body, which is characterized by impregnating the solution with a solution for adsorbing metal ions, and then removing soot and sintering. 11. The method according to claim 7, 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. 12. The metal according to any one of claims 7 to 11, 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. 13. The porous body according to any one of claims 7 to 12, wherein the porous body is continuously conveyed as a sheet, and the conductive metal layer is formed in the conveying process.
The method for producing a porous metal body according to item. 14. An organic adhesive is applied to the porous body in advance, and then fine metal powder is applied to form the conductive metal layer.
The method for producing a porous metal body according to item. 15. 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 7 to 13, which is formed. 16. 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 porous metal body according to any one of claims 7 to 13, wherein a porous metal layer is formed. 17. The porous body is spray-coated with the slurry, roll-coated with a roll immersed in a slurry tank, roll-coated with the slurry coating the surface, or supplied inside the roll. The method for producing a metal porous body according to claim 15 or 16, wherein the slurry is impregnated and applied through a screen on the outer peripheral surface of the roll. 18. The method for producing a metal porous body according to claim 15, wherein the mixed slurry is impregnated and applied from both side surfaces of the porous body.