JPH07116635B2 - Method for producing porous metal body for battery electrode plate and porous metal body for battery electrode plate produced by the method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a metal porous body having a laminated structure and a metal porous body produced by the method, and in particular, the metal porous body has a precise skeleton. The electrode plates of various batteries such as nickel-cadmium battery, lithium battery, fuel cell, etc. are uniformly filled with the active material powder so that the porosity per unit area is also held uniformly. It can be suitably used for the above, and moreover, the active material powder can be continuously filled into the porous metal body while pulling the porous metal body.

Conventional technology Conventionally, as a positive electrode plate and a negative electrode plate used for nickel cadmium battery, lithium battery, fuel cell, etc., one porous sheet made of three-dimensional reticulated foam such as polyurethane sponge, non-woven fabric, mesh net, etc. As a result, a metal porous body formed by plating is used.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Using the metal porous body described above, when manufacturing a battery electrode plate, in order to continuously fill the metal porous body with active material powder such as nickel hydroxide, The required tensile strength is required for the porous metal body. That the tensile strength is 3 kg / 2 cm or more, preferably 7 kg / 2 cm or more, that the elongation of the sheet of the metal porous body that is continuously stretched does not occur, particularly in the metal foam porous body made of polyurethane sponge or the like. It is required that the hole diameter does not change.

Conventionally, a metal porous body has a metal adhesion amount of 500 g / m ^{2 to} 600 g / m ²
If it is not above, the tensile strength does not become 3 kg / 2 cm or more, therefore, in the case of a metal foam at 500 g / m ² or less, deformation occurs by extending to the opening portion, and at 300 g / m ² or less, any Even a kind of porous metal body is in a state of being broken by handling, and it is impossible to continuously pull the sheet made of the porous metal body for filling the active material powder.

Therefore, in the plating treatment step on the porous sheet described above, in order to obtain the necessary tensile strength, 500 g / m ^{2 to} 1000 g
Since it was necessary to perform thick plating of about / m ² , the amount of plating adhered was large, which was a cost problem. Further, if the above-mentioned thick plating is applied to the porous sheet in order to obtain the required tensile strength, it is not easy to deposit the porous sheet with a uniform thickness.

And, when the metal porous body is used for a cylindrical battery electrode plate, the bending radius is very small, for example, when wound with an inner diameter of 3 mm, there is a drawback that cracks are likely to occur if thick plating is applied. is there. In particular, the metal foam made of sponge has a drawback that the holes (lattice) are likely to be cracked or damaged, the electric conductivity is deteriorated, and the battery performance is deteriorated.
At that time, when the material is wound in a spiral shape, the outer side extends from the inner side due to the plate thickness, so that cracks and damages are likely to occur particularly on the outer side. Similarly, when a metal porous body having a metal plating applied to a non-woven fabric is used, cracks and damages are likely to occur on the outer peripheral side. At that time, in particular, short fiber metal pops out, and a positive electrode plate, a negative electrode The separator that separates the plate is damaged, causing a serious defect that causes a short circuit.

Further, when only the foam sponge body sheet is continuously conveyed and plated to provide the metal foam porous body sheet, it is inevitable to apply some tension to the foam sponge body sheet in the plating process. When a tension is applied to the foamed sponge body sheet, the skeleton is easily deformed, and the hole diameter is deformed, so that the open area ratio per unit area becomes uneven. Similarly, in the case of a non-woven fabric as well, generally, short fibers are used to be produced by a dry method or a wet method, but since short fibers are used, the tensile strength is weak and deformation is likely to occur.

When the metal porous sheet obtained by metal-plating the above-mentioned foam or nonwoven fabric is used as a battery electrode plate, the porosity is non-uniform, and it becomes impossible to uniformly fill the active material powder. In the case of a secondary battery, charging and discharging are repeated hundreds of times and charged and discharged through the electrode plate (foamed metal porous sheet), so the skeleton is not uniform and the active material powder is not uniformly filled, A large difference occurs in the amount of electricity, which makes it impossible to power up the battery.

The present invention aims to solve the various problems described above, and to provide a metal porous body having a laminated structure having a required tensile strength without performing thick plating as in the conventional case, and to significantly reduce the metal adhesion amount. It is intended to reduce costs and eliminate cracks when used as a battery electrode plate. Furthermore, the porous body layer constituting the porous metal body is not easily deformed, its skeleton can be held accurately and uniformly, the porosity per unit area can be made uniform, and when used as a battery electrode plate This is to make the conductivity uniform.

Means for Solving the Problems To achieve the above object, the present invention provides a sheet having a laminated structure by stacking sheets having substantially the same shape in order to increase tensile strength, and plating the laminated sheet. The present invention provides a method for producing a sheet of a porous metal body.

That is, the present invention provides a laminate sheet having a multilayer structure in which three kinds of porous sheets, a foam sheet, a nonwoven sheet, and a mesh sheet, are laminated in advance, or a multilayer sheet composed of a foam sheet and a nonwoven sheet. A laminate sheet is provided, and a plating manufacturing method is provided while continuously conveying these laminate sheets. The foam sheet,
The non-woven fabric sheet and the mesh sheet are continuous sheets that are unwound from a coil, and these sheets are laminated on each other over substantially the entire surface to provide a continuous laminated sheet having a multilayer structure, which is continuously plated and continuous. A metal porous body is provided and wound around a coil.

Hereinafter, the foam sheet is a foam, the non-woven sheet is a non-woven fabric,
The mesh sheet may be abbreviated as foam, non-woven fabric, or mesh.

In the above-mentioned laminated body, it is preferable that the entire surface of each sheet of foam, non-woven fabric, and mesh body having substantially the same shape is integrally fixed in advance by a method such as welding or adhesion, but it is not fixed in advance by the above method. Alternatively, they may be simply laminated in an integrated state.

In addition, each of the above-described laminated bodies includes a multi-layered laminated body in which the foamed body, the non-woven fabric, and the mesh body are provided in arbitrary numbers and are laminated in a combination in an arbitrary order.

As the welding method, a method of melting and adhering the fixed side surface by a method such as heating is used, and as the adhering method, one fixing surface is coated with an adhesive, or the laminated body is adhered with an adhesive. A method of immersing and adhering in a storage tank is used.

The plating treatment for the integrated laminate sheet is carried out by continuously transporting the laminate sheet to a plating treatment step, and in the plating treatment step, transporting the laminate sheet into a vacuum container and performing vapor deposition plating in the container. A method for forming a film, or after imparting conductivity to the continuously conveyed sheet, it is carried into a plating tank, and a plating solution flow is made to strike the sheet in a direction substantially perpendicular to the sheet in the plating tank. A method of plating, and further, a method of electroless plating after performing a waveguiding property-imparting treatment by an electroless plating method, an electrolytic plating method, the above vacuum film forming method or an electroless plating method are adopted.

The present invention further comprises a metal foam layer, a metal nonwoven fabric layer, and a metal mesh body layer produced by the above-mentioned method, or a metal foam and a metal nonwoven fabric layer, which are particularly preferably used as a battery electrode plate. The present invention provides a porous metal body.

The above foam is made of polyurethane sponge,
Those having a thickness of 0.5 to 5.0 mm and a hole diameter of 50 μm to 500 μm are preferably used. Further, as the material of the non-woven fabric and the mesh body, synthetic resin such as polyester, polypropylene and polyurethane, natural fiber, crystalline material such as cellulose and paper, inorganic material such as metal, glass and carbon are used. In addition, the mesh body includes a mesh-like body in which warp yarns and weft yarns are knitted, or all knitting compositions formed by knitting one or a plurality of yarns in a fibrous form,
A 0 mesh one is preferably used. Moreover, as the mesh body and the nonwoven fabric, those having a wire diameter of 0.01 to 1.0 mm and an aperture ratio of 40 to 99% are preferably used.

The type of plating applied to the integrally laminated laminate sheet is Cu, Ni, Zn, Sn, Pd, Pb, Co, A in the above vacuum film forming method.
Any metal such as l, Mo, Ti, Fe, SUS304, SUS430, 30Cr, Bs may be used. When using electroless plating, Cu, Ni, Co, P
d, Sn, Zn are used. When using the electrolytic plating method, Cu,
Ni, Co, Pd, Sn, Zn, Pb, Fe are used.

When the above-mentioned laminated body is fixed by welding, the low melting point side is heated at the temperature of the melting point, and the fixed side surface is melted and welded. At that time, heating is performed at the following temperature depending on the material of the porous material.

Polyester 255-260 ℃ Nylon 250-260 ℃ Acrylic 210-260 ℃ Polypropylene 165-173 ℃ Polyethylene 125-230 ℃ Polyurethane 200-230 ℃ Rayon 200-260 ℃ Action As described above, in the manufacturing method according to the present invention, tension The porous body, which is liable to be deformed when loaded, is laminated and integrated to form a laminated body with increased tensile strength, and then plated to form a metallic porous body, so continuous tension is applied. It is possible to prevent the deformation of the foam and the non-woven fabric, which are likely to be deformed, even if the plating treatment is performed while applying the heat treatment. In addition, since the porous metal body having a laminated structure has an increased tensile strength as described above, the metal deposition amount is 300 g / m ²
The required tensile strength (3 kg / 2 cm or more) can also be obtained below. Therefore, it is possible to reduce the amount of metal adhered and to significantly reduce the cost, and it is possible to prevent the occurrence of cracks due to thick plating during bending.

In addition, deformation of the porous body can be prevented by increasing the tensile strength,
The skeleton can be held accurately and uniformly, and the aperture ratio per unit area can be made uniform. Therefore, when used as a battery electrode plate, the active material powder can be uniformly filled, and the amount of electricity can be made uniform,
It is possible to improve the battery performance.

Examples Hereinafter, the present invention will be described in detail with reference to Examples shown in the drawings.

1 to 5 show the first embodiment, in which three sheets, a foam sheet 1 made of polyurethane sponge, a non-woven fabric sheet 2 made of polyester and a mesh sheet 3 are integrally laminated by welding 3 After the laminated sheet 4 of layers is provided, it is continuously conveyed to a plating apparatus, and in the plating apparatus, the plating solution flow is forcibly applied so as to impinge on the laminated sheet 4 in a direction perpendicular to the laminated sheet to laminate the layers. A porous metal body having a structure is manufactured. This will be specifically described below.

FIG. 1 shows a laminated body having a three-layer structure in which the foam sheet 1, which is made of sheets having substantially the same width, the non-woven fabric sheet 2, and the mesh sheet 3 are integrally fixed to each other by welding and have the same sectional shape. The process of forming the sheet 4 will be described.

As the foam sheet 1, a sheet having a thickness of 0.5 mm to 5.0 mm and a hole diameter of 50 μm to 500 μm, preferably 200 μm to 350 μm is used. In the first embodiment, the thickness of 1.7 mm is used.

The non-woven sheet 2 has a thickness of 0.5 to 5.0 mm and a wire diameter of 0.01
~ 1.0 mm, preferably 0.05 ~ 0.1 mm, open area ratio 40 ~ 99%
What is used. In this embodiment, the one having a thickness of 2.0 mm is used.

The mesh sheet 3 has a wire diameter of 0.01 mm to 1.0 mm and 2 mesh to 200 mesh, preferably a wire diameter of 0.05 mm to 0.1 mm.
40 mesh to 120 mesh and a porosity of 40 to 99% are used. In the first embodiment, a wire having a wire diameter of 0.07 mm and 60 mesh is used.

In this embodiment, the mesh body and the non-woven fabric are formed of polyester, but not limited to polyester, synthetic resin such as nylon, acrylic, polypropylene, polyethylene, rayon, or organic material such as natural fiber, cellulose and paper, metal Inorganic substances such as glass, carbon, etc. may be used as the material. Further, in the embodiment, the mesh body has a mesh of warp and weft, but is not limited, and an appropriate knitting structure which is knitted with one or a plurality of threads in addition to the mesh It may consist of And,
The mesh line itself may be round, square or flat.

The foam sheet 1, the non-woven fabric sheet 2 and the mesh sheet 3 are coil bodies wound on a roll as illustrated.
The non-woven fabric sheet 2 and the mesh sheet 3 are laminated on the entire sides of the foam sheet 1 by continuously unwinding from the la, 2a and 3a. After heating both surfaces of the foam sheet 1 having the lower melting point among the above-mentioned sheets by the heating device 5, the above-mentioned three sheets are superposed by a pair of pressure-bonding rolls 6A and 6B, and the foam is melted by the above-mentioned heating. The nonwoven fabric sheet 2 is welded to one surface of the sheet 1 and the mesh sheet 3 is welded to the other surface. After the bonding, the cooling air is introduced into the cooling chamber 7 in which it is circulated, and while passing through the cooling chamber 7 while being supported by the metal mesh conveyor 8, the nonwoven fabric sheet 2 is sandwiched with the foam sheet 1 therebetween. The mesh sheet 3 and the mesh sheet 3 are integrally fixed and taken out as a laminate sheet 4,
It is wound around a roll to form a coil body 4a. In the figure, 9 is an expander roll for wrinkle-rolling the sheets 1, 2, and 3 unwound from the coil bodies 1a, 2a3a.

In this embodiment, as the heating device 5, an ultra-far infrared heating device is used. When both sides of the foam sheet 1 are heated by the ultra-far infrared heating device, only the both side surfaces to which a thin sheet is fixed are surely melted. It is possible and preferable.
As the heating device, a burner, a heater, hot air, etc. are also preferably used.

With the heating device 5, for example, when the surface of the urethane sponge is melted by 0.2 mm, the adhesion strength is 50 g / 25 mm, whereas when it is dissolved by 0.5 mm, the adhesion strength is 100 g / 25 mm, and the amount of dissolution is If the amount is increased, the fixing strength can be increased.

As described above, the laminate sheet 4 including the foam sheet 1, the non-woven fabric sheet 2 and the mesh sheet 3 integrally fixed by welding is then plated with Ni by the plating apparatus shown in FIGS. 2 and 3. To form a metal porous sheet composed of a metal foam, a metal nonwoven fabric and a metal mesh.

In this embodiment, as shown in FIG. 1, the laminate sheet 4 is wound into a coil, and the coiled laminate sheet 4 is unwound and conveyed to the plating apparatus. However, the laminated sheet may be directly conveyed to the plating apparatus without being wound into a coil.

In the apparatus shown in FIG. 2 and FIG. 3, the laminated sheet 4 wound around the coil body 4a is unwound, conductivity is imparted by the derivative imparting device 15, and then dried by the hot air drying device 11, and then, , Mesh net conveyor 12 and matching roller 13
Are placed on the mesh-mesh conveyer 12 in a vertically aligned manner. Since the laminate sheet 4 is provided with the mesh sheet 3, the tensile strength is high, and therefore the mesh-mesh conveyor 12 is not always necessary.

In the above state, they are successively conveyed to the first to fifth plating tanks 10 arranged in parallel, and the nickel plating treatment is performed 5 times in the five plating tanks 10 to obtain a plating thickness of 300 g / m ² .

In the plating apparatus shown in FIG. 3, the plating solution supply nozzle 20 for supplying the plating solution downward from above is installed in the plating tank 10, and the plating solution storage tank 21 is installed below the plating solution storage tank 21 and the plating solution storage tank 21. While communicating with the plating solution supply nozzle 20 via the forced feed pump 22, the porous laminate sheet 4 as the object to be plated is traversed in the plating tank 10 below the plating solution supply nozzle 20. The plating tank is configured to pass through, and is provided outside the tank on the introduction side to the plating tank 10 in contact with the laminate sheet 4 to supply electric power, and the conductor rolls 23A and 23B having the sheet 4 as a cathode are installed. Cases 25A and 25B filled with anode balls 24 (anode balls) are installed inside 10.

More specifically, the plating apparatus has a shape in which the plating tank 10 has a rectangular cross section and includes an upper portion 10a having an upper end opening and a lower portion 10c which is tapered toward the lower end center opening 10b. An object introduction hole 10d and a lead-out hole 10e are formed in both side wall portions of 10a facing each other. Conductor rolls 23A and 23B, 23C and 2 respectively arranged outside the liquid tanks of the inlet hole 10d and the outlet hole 10e.
The 3D is connected to the cathode, and the laminated sheet 4 and the supporting conveyor 12 are sandwiched between the pair of upper and lower conductor rolls to pass therethrough. 4 is the cathode.

In the plating tank 10, the laminated sheet 4 and the conveyor 12
A pair of upper and lower anode cases sandwiching the entire passage position
Installed 25A and 25B. These anode cases 25A and 2
The bottom surface of 5B has a lath mesh shape, and its outer frame portion is detachably attached to the plating tank 10. Each of the anode cases 25A and 25B is filled with a round ball 24 which is connected to the anode side and serves as an anode.

The member used as the anode is not limited to the round ball 24, and may be plate-shaped, square-shaped, or the like as long as it passes the plating liquid and hits the liquid on the laminate sheet 4 from a substantially right angle direction. Although they can act, the round drops are more preferable than the round balls, and the round balls are preferable from the viewpoint of ion supply efficiency.

In the plating tank 10, a plating solution supply nozzle 20 branched from a main supply pipe 26 arranged above the plating tank 20 is vertically provided, and the lower side portion of each of the nozzles 20 penetrates into the upper anode case 25A. The lower end injection port 20a is fitted and positioned in a hole formed in the bottom surface of the anode case. In this way, the nozzle injection port 20a is located near the surface of the laminated sheet 4, and the plating liquid is directly ejected from the injection port 20a to the laminated sheet 4 in a direction substantially perpendicular to the adjacent position. There is. A plating solution suction pipe 27 is provided at a lower position facing the plating solution supply nozzle 20 with the laminated sheet 4 interposed therebetween, which is attached to the lower anode case 25B.

Although FIG. 3 shows a state in which the plurality of nozzles 20 are installed at four intervals in the moving direction of the laminated sheet 4 to be plated, the number of the installed nozzles is not limited.
The plating solution sprayed from the nozzle 20 may be provided so as to cover the entire area of the laminate sheet 4. The nozzle 20 is supplied with a plating liquid from a plating liquid storage tank 21 through a supply pipe 28 by a forced feed pump 22, and the plating liquid injected in the plating tank 10 is collected in the plating liquid storage tank 21 from the lower end opening 10b. The plating solution is circulated in the plating tank 10 from the upper side to the lower side at a predetermined flow rate by continuous driving of the forced feed pump. The flow rate of this plating solution can be used in the range of 50 to 300 m / min, and particularly preferably 100 to 200 m / min.

Further, in the present plating apparatus, in order to prevent liquid leakage from the inlet and outlet of the sheet to be plated of the plating tank 10,
Attach liquid seals 29A and 29B to the inlet 10d and the outlet 10e,
And, the conductor roll 23 outside these liquid seals
The plating solution receivers 30A and 30B are installed below B and 23D.

In the plating apparatus having the above structure, the laminated sheet 4
Is contacted when passing between the conductor rolls 23A and 23B to be fed with electricity to serve as a cathode. In this state, the plating solution introduced into the plating tank 10 and contacting the round balls 24 of the anode collide with the laminate sheet 4 of the cathode from the direction perpendicular to the hole, and the holes of the laminate sheet 4 ( Non-woven fabric, foam,
And a hole in the mesh body) to forcefully flow at a predetermined flow rate. Therefore, the metal ions are evenly supplied to the surface layer portions and the inner layer portions on both sides of the laminate sheet 4, and are electro-folded / deposited, that is, electrodeposited uniformly on each portion. The metals that can be electrofolded are
It usually contains all metals that can be electroplated, and for example, Cu, Ni, Cr, Cd, Zn, Sn, etc. can be electrodeposited.
In this embodiment, Ni is used as described above.

In the plating step, the current efficiency is improved and the laminated sheet 4 can be plated at a high current density by increasing the flow rate. In this way, the laminate sheet 4 can be plated at a high current density from the first time, and the plating grain size (grain size of the electrodeposited metal) becomes very fine, so plating with high grain boundary strength and excellent adhesion can be performed. It can be applied from the first time. In the method of the present invention, the current density is 10 to 600 A / dm ²
Can be selected in a wide range, but 100 to 400 A / dm ² is particularly preferable.

Further, when moving in the plating tank 10, a mesh body that has a large tensile strength and does not extend easily is fixed integrally with the foam and the non-woven fabric, so that it is more stable than in the case of the foam or the non-woven fabric alone. It is possible to apply plating while moving in this state. Therefore, it is possible to suppress the change of the hole shape of the foam and the deformation of the non-woven fabric, and it is possible to prevent the formed metal porous body from waving, curving, uneven plating thickness, and the like.

As described above, when the plating method using the above-described plating apparatus is used, the laminated sheet is plated on both surface layers and the inner layer of the porous body with a uniform thickness. When the metal porous body is wound around a roll core or the like in a coil shape, no directionality occurs, and cracks do not occur even when wound with a small curvature. Moreover, since the sheet shape is maintained in a flat state without being deformed, it is possible to manufacture as a coil-wound product in terms of quality.

The required thickness (300g / m in this example)
After attaching the metal of ² ), wash with water and dry with hot air. Even at the time of washing with water, the openings are likely to be deformed in the case of only the foam and the case of only the non-woven fabric, but the deformation can be prevented because it is laminated with the mesh body.

After the above drying, 400 ° C ~ 1000 ° C with a degassing device (not shown),
Preferably, heating is performed at 700 ° C. to 800 ° C., followed by sintering and reduction at about 700 ° C. to 1100 ° C. in a reducing atmosphere. Strain removal and annealing of the electrofolding layer are also performed by the sintering process.

As described above, after plating, degassing, the metal nonwoven fabric layer produced by sintering, a metal porous body comprising a metal foam layer and a metal mesh layer, the metal adhesion amount is 300 g / m above.
^{At 2} , a tensile strength of 7.2 kg / 2 cm was obtained.

The porous metal body A manufactured by the method according to the first embodiment described above has a cross-sectional structure shown in FIG. 4, and in any portion, the metal nonwoven fabric layer B, the metal foam layer C, and the metal mesh body layer D are formed. And 3 layers. Even if tension is applied in the plating process, the porous metal body A has a laminated structure that increases the tensile strength, so that the skeleton of the foam and the nonwoven fabric is prevented from being deformed, and the skeleton is held accurately and uniformly. The porosity per unit area is kept uniform.

When the metal porous body A having the above-mentioned laminated structure is used as a battery electrode plate, it is necessary to fill 3 k in order to fill the active material powder such as nickel hydroxide.
g / 2cm or more, preferably, a tensile strength of 7kg / 2cm or more is required, but since the metal porous body has a tensile strength of 7kg / 2cm, the active material powder in a continuously pulled state Can be filled.

Further, since the metal porous body A filled with the active material powder is used as a battery electrode plate, when it is wound in a spiral as shown in FIG. Is less likely to occur. Further, since the metal mesh body D acts as a strength retainer during the bending process,
Cracks and damages are less likely to occur, and in particular, when the metal mesh body layer D is arranged on the outer peripheral side as shown in FIG. 5, cracks,
Less likely to be damaged.

In the first embodiment, the metallic nonwoven fabric layer B and the metallic foam layer C are used.
And a metal mesh body layer D, the metal nonwoven fabric layer B, the metal foam layer C, as in the second and third embodiments shown in FIGS. 6 (I) and (II). The metal mesh body layers D may be combined in any number and in any order to form one metal porous body.

The second embodiment of FIG. 6 (I) is a four-layer laminated structure in which the metal mesh layer D is arranged on both sides and the metal nonwoven fabric layer B and the metal foam layer C are sandwiched inside. 2 is a second embodiment of the present invention. The third embodiment of FIG. 6 (II) has a laminated structure of five layers with a metal mesh layer D on both sides, a metal nonwoven fabric layer B inside and a metal foam layer C in the center. 3 shows three examples.

If the thickness is wide as a multi-layer structure such as the above-mentioned five layers,
It can be suitably used as an electrode plate in a fuel cell as shown in the figure. In FIG. 7, 100 is a hydrogen electrode substrate, 101 is an air electrode substrate, 102 is a catalyst layer interposed between the hydrogen electrode substrate 100 and the air electrode substrate 101, and 103 and 104 are both outer separator plates. is there. The electrode substrate 10
Since a porous metal plate is used for 0, 101 and the catalyst layer 102, and a thick porous metal body is required for the electrode substrates 100, 101, the multi-layered porous metal body is preferably used.

FIG. 8 shows a fourth embodiment of the present invention, in which two porous sheets, a foam sheet 1 and a non-woven sheet 2, are welded and fixed integrally to form a laminated sheet 4'having a two-layer structure. .

In the fourth embodiment, as in the first embodiment, the foam sheet 1 and the nonwoven fabric sheet 2 are continuously unwound from the coil bodies 1a and 2a wound on a roll as shown in the drawing.
Among the above sheets, the foam sheet 1 on the lower melting point side,
After heating by the heating device 5 ', a pair of pressure rolls 6A,
The non-woven sheet 2 is overlaid with 6B, and the non-woven sheet 2 is welded to the surface of the foam sheet 1 melted by the above heating. After the welding, cold air is introduced into the cooling chamber 7 in which it is circulated, and while passing through the cooling chamber 7 while being supported by a metal mesh conveyor 8, the foam sheet 1 and the nonwoven fabric sheet 2 are integrated. The sheet 4'a is fixed to the sheet 4'a, taken out as a laminated sheet 4 ', and wound on a roll to form a coil body 4'a.

In the fourth embodiment, the heating device 5'is composed of a burner as shown in the figure, and heats the surface of the foam sheet 1 made of urethane sponge by directly applying a flame. Propane, butane, or any other suitable fuel is used as the fuel for the burner, and one surface of the foam sheet 1 on the fixed side is melted by the flame. At that time, the amount of dissolution is made by adjusting the height of the flame, and when the flame is low (away from the surface of the foam sheet), the amount of dissolution is small and the bonding strength with the other mesh body sheet 2 is small. Is weak, on the contrary,
When the flame is high, the amount of dissolution increases and the bonding strength increases.

FIG. 9 shows a fifth embodiment of the present invention, in which a foam sheet 1 and a non-woven fabric sheet 2 are adhered and laminated with an adhesive to form a laminate sheet 4 '. That is, before the foam sheet 1 and the non-woven fabric sheet 2 are superposed on each other by the aligning rollers 6A and 6B, the adhesive 32 is applied to the adhesive surface side of the foam sheet 1 by the application roller 31. The coating roller 31 comes into contact with the rotating roller 39 immersed in the adhesive agent storage tank 33, and the adhesive agent 32
The required amount is taken out uniformly on the surface. Therefore, when the coating roller 31 is pressed and rotated on the surface of the foam sheet 1, the adhesive 32 is uniformly applied to the surface of the foam sheet 1 on the fixed side.

In the above-described apparatus using a plurality of rotating rollers, it is possible to prevent the adhesive agent from being taken out more than necessary and to apply the adhesive agent evenly to the surface of the foam sheet 1. The foam sheet 1 and the non-woven fabric sheet 2 bonded via the adhesive 32 are subsequently introduced into the drying chamber 34. A laminated sheet 4'which is supplied with hot air from the inlet 34a into the drying chamber 34 and is conveyed while being supported by a metal mesh conveyor 35.
Is dried with hot air and exhausted from the outlet 34b.

After being dried in the drying chamber 34, it is then introduced into the cooling chamber 7 ', supported by the mesh conveyor 8', conveyed while being cooled, and the foam sheet 1 and the non-woven fabric sheet 2 are completely bonded by the adhesive 32. It adheres to and is integrated.

FIG. 10 shows a sixth embodiment and shows another method for fixing the foam sheet 1 and the nonwoven fabric sheet 2 with an adhesive. That is, the foam sheet 1 and the non-woven fabric sheet 2 are superposed on each other by the rollers 6A and 6B to be in a laminated state, guided by the roller 40 in the adhesive agent storage tank 33 'and immersed in the adhesive agent 32'. And 2 are fixed. Then, the squeezing roller 41 is used to remove unnecessary adhesive 32 '. Even when the foam sheet 1 and the non-woven fabric sheet 2 are adhered to each other via the adhesive 32 'by this method, the drying chamber 34' is similar to the above.
And then it is introduced into the cooling chamber 7'and cooled and fixed.

The fourth embodiment shown in FIG. 8 to the sixth embodiment shown in FIG. 10 are each formed by laminating two porous sheets, that is, a foam sheet 1 and a nonwoven fabric sheet 2. The number of layers to be laminated with the non-woven fabric sheet 2 and the order of combination can be changed according to the application. Various modes such as A metal porous plate composed of a large number of laminates of these foam sheets and non-woven fabric sheets can also be suitably used as an electrode plate of a fuel cell that requires a large width.

FIG. 11 shows a seventh embodiment, and in each of the above-mentioned embodiments, the laminate sheet 4 or 4'is integrally fixed in advance by a welding or an adhesive before the plating treatment. By simply stacking the sheets in close contact with each other, they are conveyed to a plating apparatus without being welded or adhered, and in the plating step, the metal is attached and the laminated sheets are integrally fixed. That is, the foam sheet 1, the non-woven fabric sheet 2 and the mesh sheet 3 are unwound from the coil body respectively, and are pressed by the pressure rollers 6A and 6B to be integrally laminated and pressure-bonded to the plating device 45, where they are plated. is doing.

FIG. 12 shows an eighth embodiment. In the eighth embodiment,
A vacuum film forming method is used as a plating method for the laminate sheets 4 and 4'having a laminated structure by any method such as welding, adhesion using an adhesive, or a state where they are simply laminated together.

The above vacuum film forming method has been conventionally developed as a thin film method, and vapor deposition plating is performed within 0.1 to 1.0 μm. In particular, for a synthetic resin sheet, when the metal is melted in a vacuum and vapor-deposited and plated, the resin is burned by the radiant heat of the metal's melting heat.
Only a thin film of ~ 1.0μ can be coated.

The vacuum film forming method of FIG. 12 described above eliminates the above-mentioned problems, and makes it possible to deposit a metal having a required thickness by a vapor deposition method.
The porous metal sheet can be easily prevented from deforming by plating the resin porous sheet with a required thickness.

In FIG. 12, 51 is a vacuum container for vapor deposition, 52 is a vacuum container for unwinding a coiled sheet, and 53 is a vacuum container for winding a coiled sheet. The vapor deposition vacuum vessel 51 and the unwinding vacuum vessel 52 communicate with each other via a sheet guide vacuum passage vessel 54, while the vapor deposition vacuum vessel 51 is a sheet cooling vacuum vessel 55.
The cooling vacuum container 55 and the winding vacuum container 53 are communicated with each other via the vacuum passage container 57.

The unwinding vacuum container 52 is formed to have a size sufficient to install the coiled laminate sheet 4a wound on a roll, and is used to guide and unwind the coiled sheet to the vacuum passage container 54. A guide roller 59 is installed, and a mechanism (not shown) for continuously feeding the sheet 4 by rotating the coiled sheet 4a in the arrow direction is provided.

In the vapor deposition vacuum container 51, the outer circumference of the container body 61 is surrounded by a cooling tank 62, and a cooling medium is supplied into the cooling tank 62. (In this embodiment, a cooling medium of -30 ° C. is supplied.) Further, in the container body 61, a guide roller 63 for guiding the sheet is provided in the vicinity of the inlet communicating with the vacuum passage container 54.
Along with the guide roller 63, guide rollers and cooling rollers 64A, 64B, 64C and 64D for refracting and guiding the laminated sheet 3 toward the outlet side are sequentially arranged. Among these rollers, in the embodiment, two rollers 64A and 64C are large-diameter rollers, and the time during which the sheet 4 contacts the rollers is lengthened to increase the cooling rate of the sheet.

In addition, the metal to be vapor-deposited inside the vapor deposition vacuum chamber body 61.
Containers 66A and 66B such as crucibles containing 65 are installed at appropriate positions with a space between them, and an electron beam generator 67 that projects an electron beam in order to melt the metal 65 in these containers.
A and 67B are installed on the outer wall surface of the container body 61. The metal 65 melted by these electron beams is evaporated in the vacuum of the container body 61, and is uniformly adhered to the laminated sheet 4 guided by the rollers 64A to 64D as a film.
The thickness of the coating film can be arbitrarily controlled according to the passage time (staying time) of the laminate sheet in the vacuum container 51.

A guide roller / cooling roller 68 is also installed in the cooling vacuum container 55 communicating with the outlet of the vapor deposition vacuum container body 61 via the vacuum passage container 56, and the metal porous taken out from the vapor deposition vacuum container 51. Before the body sheet A is wound into a coil, the temperature is lowered to an appropriate temperature. The winding vacuum container 53, which communicates with the cooling vacuum container 55 through the vacuum passage container 57, is provided with a roll for winding the porous metal sheet A conveyed therein, and the porous metal sheet A is installed.
Is wound into a coil.

In the above-described apparatus, the metal 65 is melted by the electron beam in the vapor deposition vacuum vessel 51, and vapor deposition plating of about 300 g / m ² is performed on the laminate sheet 3 at one time before exiting the outlet of the vapor deposition vacuum vessel 51. Has been given. At that time, the outer circumference of the container body 61 is surrounded by a cooling tank 62, and a cooling medium of −30 ° C. is circulated in the cooling tank 62 to lower the ambient temperature in the container body 61, so that the metal beam is generated by the electron beam. Despite heating at a high temperature to melt 65, the temperature inside the container body 61 has dropped to about 50 ° C. or lower. Moreover, the laminated sheet 4 has cooling rollers 64A-6A.
The temperature of the laminate sheet 4 is further lowered because it comes into contact with the 4D and is linearly cooled. Therefore, even if the laminate sheet 4 is made of a resin or the like that is easily deformed, the metal film can be vapor-deposited without being deformed or burned out by the heat of melting of the metal 65. Further, the staying time of the laminate sheet 4 in the vapor deposition vacuum container main body 61 hardly needs to be considered in order to prevent deformation due to heat. Therefore, it is set to an appropriate time and therefore the vapor deposition time is controlled. As a result, the thick film described above can be obtained. That is, by slowly transporting the laminate sheet 4 in the vapor deposition vacuum container 51 at a slow speed, it is possible to perform metal plating of the required thickness described above, while transporting it at a high speed as needed. thin metal plating can be subjected, metal thin film 1g / m ² ~1000g / m ² range optionally can be controlled by.

When the above-mentioned laminated sheet 4 is plated with a thickness of, for example, 300 g / m ² , since the temperature is lowered to 50 ° C. or lower as described above, the vapor-deposited metal does not have a structure, Therefore, in the next step, deoxidizing and sintering treatment is performed in a hydrogen atmosphere to form a metallographic structure and adjust strength and the like. By adjusting the strength, the extensibility can be improved. The sintering temperature is 300-1200 ℃
Is going on.

The type of plating coated by the above vapor deposition method is C
u, Ni, Zn, Sn, Pd, Pb, Co, Al, Mo, Ti, Fe, SUS304, SUS430,
Almost any metal such as 30Cr and Bs may be used. In the case of providing the two plating layers by combining the vapor deposition plating and the electrolytic plating, for example, Cu is vapor-deposited and then Ni is electrolytically plated (Cu-Ni). Similarly, Cu-Sn, Fe -Zn, Mo-
A combination of Pb and Ti-Pd is preferable.

The present invention is not limited to the above-mentioned embodiments, and is used as a method for forming a laminate by laminating three types of porous sheets of a foam, a nonwoven fabric and a mesh body, or by using two types of porous sheets of a foam and a nonwoven fabric. Regardless of whether welding, adhesion, or only laminating is used as the method for forming the laminated body to be laminated, the plating method shown in FIGS. 2 and 3 (plating solution flow) is used as the plating method for these laminated bodies. (Plating by pouring so that it hits against the sheet from a right angle method), other than by the vacuum deposition method shown in FIG. 12,
Plating may be performed by the commonly used methods listed below, that is, a vacuum film forming method by vapor deposition, ion plating, sputtering, etc., electroless plating for chemically reducing and depositing a metal on the surface of a substrate, electrolysis Plating, a method of performing electroplating after the conductivity imparting treatment by the vacuum film forming method, a method of performing electroplating after the electroconductivity imparting treatment by the electroless plating, carbon such as graphoite and carbon black, polyacetylene Conductive resin such as polyaniline, polypyrrole, polythiophene, polyparaphenylene, etc., using a conductive material made of metal powder or any mixture thereof, and applying electroconductivity by a method of coating or impregnating these, and then electroplating Method.

Further, the number of foamed bodies and mesh bodies to be laminated and the order of combination are not limited.

EFFECTS OF THE INVENTION As is apparent from the above description, according to the method for producing a porous metal body of the present invention, a laminate composed of a foam, a nonwoven fabric and a mesh body in advance, or a foam and a nonwoven fabric is formed before plating. Since a laminated body in which sheets are laminated in multiple layers is provided and the laminated body sheet having the tensile strength increased by fixing them integrally to each other is subjected to the plating treatment, a certain amount of tension is continuously applied in the plating treatment process. It is possible to prevent the porous body, especially the foamed body and the non-woven fabric, from being deformed even if the plating is performed while being conveyed.
In addition, a metal porous body obtained by laminating a metal foam layer, a metal non-woven fabric layer and a metal mesh body layer thus produced, or a metal porous body obtained by laminating a metal foam layer and a metal non-woven fabric layer is a metal foam. Since the tensile strength is large as compared with the case where only the body, the metal non-woven fabric or the metal mesh body is used, the required tensile strength can be obtained with a small amount of metal adhesion. That is, conventionally, whereas tensile that no metal adhesion amount of 500g / m ² ~600g / m ² intensity did not exceed 3 kg / 2 cm, the 3 kg / 2 cm or more metal deposition amount of 300 g / m ² The tensile strength of can be obtained.

Therefore, when the active material powder is filled into the metal porous body produced by this method to produce a battery electrode plate, while continuously pulling the metal porous body, without causing deformation in the skeleton of the metal porous body. It is possible to fill the active material powder with the porosity kept uniform. Therefore, the performance as a battery electrode plate can be improved, and since the holding strength is increased as a laminated structure, and since the metal adhesion amount is small and there is no thick plating, a cylindrical battery electrode plate, etc. Therefore, even if bending is performed with an extremely small curvature, the occurrence of cracks can be prevented. Further, since the thickness can be easily made a required thickness, it has various advantages such that it can be suitably used for an electrode plate of a fuel cell and the like.

[Brief description of drawings]

FIG. 1 is a schematic process diagram showing a method for welding a laminate sheet used in the first embodiment of the method for producing a porous metal body according to the present invention, and FIG. 2 is a schematic process showing the plating method used in the first embodiment. 3 and 4 are cross-sectional views showing the plating apparatus of FIG. 2 in detail, FIG. 4 is a cross-sectional view of the porous metal body manufactured by the first embodiment, and FIG. 5 is a cross-sectional view of the porous metal body shown in FIG. A cross-sectional view of a spirally wound coil used as a battery electrode plate, FIGS. 6 (I) and (II) show a second porous metal body formed by laminating a metal foam body, a metal nonwoven fabric and a metal mesh body. Cross-sectional views showing Examples and Third Examples, FIG. 7 is a schematic cross-sectional view of a fuel cell, and FIG. 8 shows a fourth example of the present invention showing a laminate sheet consisting of two sheets of foam and nonwoven fabric. FIG. 9 is a schematic process diagram showing a welding method, and FIG. 9 shows a fifth embodiment of the present invention when a laminated body is formed by adhesion. 10 is a schematic process drawing, FIG. 10 is a schematic process drawing in the case of forming a laminated body by another bonding method showing the sixth embodiment, and FIG. 11 is a seventh embodiment showing plating of the laminated body without pre-fixing. FIG. 12 is a schematic process diagram of the case, and FIG. 12 is a schematic diagram of a vacuum vapor deposition plating apparatus used in a plating method by vapor deposition according to the eighth embodiment. 1 ... Foam sheet, 2 ... Nonwoven sheet 3 ... Mesh sheet, 4 ... Laminate sheet, 10 ... Plating tank, 5 ... Heating device, 33 ... Adhesive storage tank, A ... Metal porous Body layer, B ... Metal nonwoven fabric layer, C ... Metal foam layer, D ... Metal mesh body layer.

Claims (15)

[Claims] 1. A laminated sheet is provided by laminating three kinds of porous sheets, a foam sheet, a non-woven sheet and a mesh sheet, in advance, and the laminated sheet is plated. A method for producing a metal porous body for a battery electrode plate having a laminated structure. 2. The foam sheet, the non-woven fabric sheet and the mesh sheet are continuous sheets, and these three types of sheets are laminated over the entire surface to provide a continuous laminated sheet having a multilayer structure, and the laminated sheet is continuously formed. The method for producing a metal porous body for a battery electrode plate according to claim 1, wherein the metal porous body having a continuous laminated structure is produced by carrying out plating while carrying the material. 3. A metal porous body for a battery electrode plate having a laminated structure, characterized in that a foam sheet and a non-woven fabric sheet are laminated in advance to provide a laminate sheet, and the laminate sheet is plated for production. Method. 4. The foam sheet and the non-woven fabric sheet are continuous sheets, and the two types of sheets are laminated over the entire surface to provide a continuous laminated sheet having a multilayer structure, and the laminated sheet is continuously conveyed. The method for producing a metal porous body for a battery electrode plate according to claim 3, wherein the metal porous body having a continuous laminated structure is produced by plating. 5. The metal porous body for a battery electrode plate according to claim 1 or 2, wherein the laminate sheet of the foam sheet, the non-woven fabric sheet and the mesh sheet comprises a plurality of layers which are laminated in a desired number in any order. Manufacturing method. 6. A laminate sheet of the foam sheet and the non-woven sheet, comprising two layers of the non-woven sheet laminated on one side of the foam sheet, non-woven sheet laminated on both sides of the foam sheet and / or on both sides of the non-woven sheet. Laminating foam sheets 3
A layer or a plurality of foam sheets and a non-woven fabric sheet, each of which comprises a plurality of layers in which the necessary number of the foam sheets and the non-woven fabric sheets are combined and laminated in any order. 4. The method for producing a metal porous body for a battery electrode plate according to 4. 7. The foam sheet 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 μm to 50.
0 μm, the non-woven fabric sheet is made of synthetic resin such as polyester, polypropylene and polyurethane, organic material such as natural fiber, cellulose and paper, inorganic material such as metal, glass and carbon, and has a wire diameter of 0.01 to 1.0 mm and open pores. The method for producing a metal porous body for a battery electrode plate according to any one of claims 1 to 6, wherein the ratio is 40 to 99%. 8. The mesh sheet, which includes a knitted structure obtained by knitting one or a plurality of threads such as a mesh and a fiber, has a mesh of 2 to 200, and a polyester,
Polypropylene, synthetic resin such as polyurethane, natural fiber, organic material such as cellulose and paper, metal, glass, inorganic material such as carbon, and wire diameter 0.01 ~ 1.0 mm,
The method for producing a metal porous body for a battery electrode plate according to any one of claims 1, 2, 5 and 6, wherein the porosity is 40 to 99%. 9. The plating of the laminate sheet, the laminate sheet is continuously moved into the plating tank after the conductivity imparting treatment, and in the plating tank, a direction substantially perpendicular to the laminate sheet. The method for producing a metal porous body for a battery electrode plate according to any one of claims 1 to 8, wherein the plating treatment is performed at a high current density by forcibly flowing the plating solution so as to hit the plating solution. . 10. A cooling roll in which the above-mentioned laminated sheet is plated, and the laminated sheet is continuously introduced into a vacuum container for vapor deposition whose outer peripheral portion is surrounded by a cooling tank, and which is installed in the vacuum container for vapor deposition. While cooling, guide and pass continuously,
The method for producing a metal porous body for a battery electrode plate according to any one of claims 1 to 8, wherein vapor deposition plating is carried out when the metal porous body for a battery electrode plate is passed through the vapor deposition vacuum container. 11. The laminate sheet is plated by a plating method such as a vacuum film forming method, an electroless plating method, and an electrolytic plating method, on the laminate sheet. 9. A method for manufacturing a metal porous body for a battery electrode plate according to any one of items 8 to 8. 12. The foam sheet, the non-woven fabric sheet and the mesh sheet are continuously unwound from the respective winding coils and laminated, and the laminated sheet is continuously plated. After the plating process is performed through the sheet, it is continuously wound on a roll or the like to form a coil.
The method for producing a metal porous body for a battery electrode plate according to any one of 1. 13. The foamed sheet and the non-woven fabric sheet are continuously unwound from the respective winding coils and laminated, and the laminated sheet is continuously passed through a plating apparatus, The battery electrode plate according to any one of claims 3, 4, 6, 7 and 9 to 11, wherein after being plated, it is continuously wound into a roll or the like to form a coil. Method for producing metal porous body. 14. A multi-layer structure in which a metal foam layer, a metal woven fabric layer, and a metal mesh layer are integrated into a single layer, and
A metal porous body for a battery electrode plate, which is produced by the method according to any one of 2, 5 and 7 to 12. 15. A multilayer structure in which a metal foam layer and a metal non-woven fabric layer are integrated, and the metal foam layer and the metal nonwoven fabric layer are integrated.
13. A metal porous body for a battery electrode plate, which is produced by the method according to any one of 12.