JPH076076B2 - Method for producing porous metal body and porous metal body produced by the method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a metal porous body having a laminated structure in which openings are filled with an active material and used as a battery electrode plate, and a metal porous body produced by the method. In particular, the porous metal body is such that the skeleton thereof is uniformly held in an accurate arrangement and also the porosity per unit area is held uniformly. It can be suitably used for electrode plates of various batteries such as cadmium battery, lithium battery, fuel cell, etc. Moreover, it is possible to continuously fill the porous metal with the active material powder while pulling the porous metal. It is what

Conventional technology Conventionally, as a positive electrode plate and a negative electrode plate used in nickel cadmium batteries, lithium batteries, fuel cells, etc., for a three-dimensional reticulated foam such as polyurethane sponge, non-woven fabric, a porous mesh sheet made of a mesh net, etc., 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. When the tensile strength is 3 kg / 2 cm or more, preferably 7 kg / 2 cm or more, the sheet of the metal porous body that is continuously stretched does not extend, and in the case of a metal foam porous body made of polyurethane sponge or the like. Is required because deformation of the hole diameter does not occur.

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 500 g / m ² or less, in the case of a metal foam, the hole extends and deforms, and at 300 g / m ² or less, any type Even with the porous metal body of
It was impossible to continuously pull a sheet made of a porous metal body to fill 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, an inner diameter of 3 m.
When wound in m, if thick plating is applied, there is a drawback that cracks easily occur. 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.

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. When the metal foam porous sheet is used as a battery electrode plate, the porosity is non-uniform, so that the active material powder cannot be uniformly filled. 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 above-mentioned various problems, and provides a metal porous body having a foam layer having a required tensile strength without performing thick plating as in the conventional case, thereby reducing a metal adhesion amount. It is intended to significantly reduce the cost and to prevent the occurrence of cracks when used as a battery electrode plate. Furthermore, the foam 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 In order to achieve the above object, the present invention is a method for producing a metal porous body which is used as a battery electrode plate in which openings are filled with an active material, and is easily deformed as compared with a foamed body. It is intended to provide a method for producing a sheet of a porous metal body by providing a sheet having a laminated structure in which a mesh body having a high tensile strength is laminated with a foam body without performing the plating, and plating the laminated body sheet.

It is preferable that the above-mentioned laminated body of the foamed body and the mesh body is integrally fixed in advance by a method such as welding or adhesion, but it is not fixed in advance by the above method, but simply laminated in an adhered state. You may stay.

In addition, the above-mentioned laminated body composed of the foamed body and the mesh body is provided with an arbitrary number of the foamed body and the mesh body, and is laminated in an arbitrary combination in order, for example, two layers of the foamed body and the mesh body. A laminated body consisting of 3 layers, a layered body consisting of 3 layers sandwiching the other side, and 4 layers such as alternately laminating
It includes a laminate of more than one layer.

Further, the foam and the mesh body are formed by a method in which the surface on the fixed side is melted and welded by a method such as heating, or one adhesive surface is coated with an adhesive, or the laminate is immersed in an adhesive storage tank. Then, they are integrally fixed by a method such as adhesion.

As a plating treatment for the above-mentioned laminated sheet composed of the foamed body and the mesh body, the laminated sheet is continuously conveyed to a plating treatment step, and in the plating treatment step, it is conveyed into a vacuum container and A method for forming a vacuum film in which vapor deposition plating is carried out, or after the sheet which is continuously conveyed is provided with conductivity and then carried into a plating tank, the plating solution is applied in a direction substantially perpendicular to the sheet in the plating tank. A method of plating by flowing so as to hit the current, and further,
The electroless plating method, the electrolytic plating method, the vacuum film forming method, the electroless plating method, or the electroless plating method may be used.

The present invention further includes a metal foam body manufactured by the above method and a metal mesh body layer, and particularly provides a metal porous body used as a battery electrode plate.

The above-mentioned foam is preferably 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. The mesh body is made of synthetic resin such as polyester, polypropylene and polyurethane, natural fiber, organic material such as cellulose and paper, metal,
Includes a knitting structure made by knitting one or more yarns, such as a mesh or a fiber, using an inorganic material such as glass or carbon, and has a 2-200 mesh and a wire diameter of 0.01-1.0 mm,
Those having a porosity of 40 to 99% are preferably used.

The type of plating applied to the laminate sheet in which the foam and the mesh are integrally laminated is Cu, Ni,
Any metal such as Zn, Sn, Pd, Pb, Co, Al, Mo, Ti, Fe, SUS304, SUS430, 30Cr, Bs may be used. Further, when the electroless plating method is used, Cu, Ni, Co, Pd, Sn and Zn are used. When electrolytic plating is used, Cu, Ni, Pd, Sn, Zn, Pb, Fe are used.

When the foamed body and the mesh body are fixed to each other by welding, the low melting point side is heated at the melting point temperature, and the fixed side surface is melted and welded. At that time, heating is carried out at the following temperature depending on the materials of the mesh body and the foam.

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 A mesh body that does not easily deform is laminated on a foam that easily deforms when a load is applied, and this is bonded together to form a laminate with increased tensile strength, and then plated to form a porous metal body. Therefore, the deformation of the foam can be prevented even when the plating treatment is performed while continuously applying tension. Further, as described above, the metal porous body composed of the metal foam body and the metal mesh body has an increased tensile strength due to the presence of the metal mesh body, and therefore the required tensile strength (3 kg / m ² even when the metal adhesion amount is 300 g / m ² or less). 2 cm or more) can be obtained. Therefore, it is possible to reduce the amount of adhered metal and to significantly reduce the cost, and it is possible to prevent the occurrence of cracks due to thick plating during bending. Further, by laminating with the mesh body, the deformation of the foam can be prevented, the skeleton can be held accurately and uniformly, and the open area ratio per unit area can be made uniform. Therefore, when it is used as a battery electrode plate, the active material powder can be uniformly filled, the amount of electricity can be made uniform, and the battery performance can be improved.

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

FIGS. 1 to 5 show the first embodiment, in which two sheets of a foam sheet 1 made of polyurethane sponge and a mesh sheet 2 made of polyester are integrally laminated by welding to form a two-layer laminated sheet. 3 is continuously conveyed to the plating tank 4, and in the plating tank 4, the plating solution flow is forcibly applied so as to impinge on the laminate sheet 3 from a direction perpendicular to the laminate sheet 3 to form a metal having a laminated structure. We manufacture porous materials. This will be specifically described below.

FIG. 1 shows a step of forming a laminate sheet 3 by integrally fixing the foam sheet 1 and the mesh sheet 2 by welding.

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 mesh body sheet 2 has a wire diameter of 0.01 mm to 1.0 mm and a mesh of 2 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 addition, although the mesh body is formed of polyester in this embodiment, it is not limited to polyester, and synthetic resins such as nylon, acrylic, polypropylene, and rayon, or organic materials such as natural fiber, cellulose and paper, metal, glass. Inorganic substances such as carbon may be used as the material.
Further, in addition to a mesh net shape in which warp yarns and weft yarns are net-like, one or a plurality of yarns may be knitted into an appropriate knitting structure, and the mesh wire itself may be round, square, flat, or the like. .

The foam sheet 1 and the mesh sheet 2 are continuously unwound from the coil bodies 1a and 2a wound on a roll as shown in the figure. Of the above-mentioned sheets, the foam sheet 1 on the lower melting point side is heated by the heating device 5 and then superposed on the mesh sheet 2 by the pair of pressure-bonding rolls 6A and 6B. The mesh sheet 2 is welded to the surface. After the welding, the 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 the metal mesh conveyor 8, the foam sheet 1 and the mesh sheet 2 are cooled. It is fixed integrally and taken out as a laminated body sheet 3 and wound on a roll to form a coil body 3a. In the figure, 9 is an expander roll for wrinkle-rolling the sheets 1 and 2 unwound from the coil bodies 1a and 2a.

In the present embodiment, the heating device 5 is made of a burner as shown in the drawing, and is a foam sheet 1 made of urethane sponge.
The surface of is heated 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. On the contrary, when the flame is high, the amount of dissolution increases and the bonding strength increases. For example, when the surface of the urethane sponge is dissolved by 0.2 mm, the adhesive strength is 50 g / 25 mm, whereas when it is dissolved by 0.5 mm, the adhesive strength is 100 g / 25 mm.

As the welding method, as shown in FIG. 6, an ultra-infrared heating device 5 ′ is provided in place of the burner, and the heating device 5 ′ is used to fix the surface of the foam sheet 1 on the fixed side as in FIG. 1. May be melted by heating. It is preferable to use the ultra-far infrared heating device 5'because it is possible to surely melt only the surface on one side to which the thin sheet is fixed. Further, as the heating device, a heater, hot air, etc. are also preferably used.

As described above, the laminate sheet 3 including the foam sheet 1 and the mesh sheet 2 which are integrally fixed by welding.
Next, as shown in FIG. 2 and FIG. 3, Ni plating is performed by a plating device to form a porous metal sheet composed of a metal foam and a metal mesh.

In this embodiment, as shown in FIG. 1, the laminated sheet 3 is wound around a coil body, and the coiled laminated sheet 3 is rewound and conveyed to a 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 3 wound around the coil body 3a is unwound, conductivity is imparted by the conductivity imparting device 10, and then dried by the hot air drying device 11, Then, the mesh-ami conveyer 12 and the aligning roller 13 are placed on the mesh-ami conveyer 12 so as to be vertically aligned. Since the laminate sheet 3 is provided with the mesh sheet 2, the tensile strength is high, and therefore the mesh-ami conveyor 12 is not always necessary.

In the above-mentioned state, they are successively conveyed to the first to fifth plating tanks 4 arranged in parallel, and the nickel plating treatment is performed 5 times in the five plating tanks 4 to obtain a plating thickness of 300 g / m ² .

In the plating apparatus shown in FIG. 3, a plating solution supply nozzle 20 for supplying the plating solution from above to below is installed in the plating tank 4, and a plating solution storage tank 21 is installed below the plating solution storage tank 21. While communicating with the plating solution supply nozzle 20 via a forced feed pump 22, a porous laminate sheet 3 as an object to be plated is traversed in the plating tank 4 below the plating solution supply nozzle 20. And the conductor sheet 23A, 23B having the sheet 3 as a cathode is installed while the laminate sheet 3 is in contact with the laminated sheet 3 to supply power to the sheet. Cases 25A and 25B filled with anode balls 24 (anode balls) are installed in the tank 4.

More specifically, the plating apparatus has a shape in which the plating tank 4 has a rectangular cross section and includes an upper portion 4a having an upper end opening and a lower portion 4c which is tapered toward the lower end center opening 4b.
Introducing hole 4d for the object to be plated and outlet hole 4e for the opposite side walls of 4a.
Has been drilled. Conductor rolls 23A and 23B, 23C and 23D respectively arranged outside the liquid tank of the introduction hole 4d and the discharge hole 4e are connected to the cathode, and the laminate sheet 3 and the conveyor 12 for supporting are provided between each pair of upper and lower conductor rolls. The laminate sheet 3 is used as a cathode by passing it with the sheet sandwiched between them and feeding power by closely contacting the upper and lower surfaces thereof.

In the plating tank 4, the laminated sheet 3 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 4. 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 3 from a substantially right angle direction. Although they can be used, they are more difficult to drop the liquid than the round balls, and the round balls are preferable from the viewpoint of ion supply efficiency.

In the plating tank 4, there are vertically provided plating solution supply nozzles 20 branched from a main supply pipe 26 disposed above the nozzles. The lower parts of the nozzles 20 penetrate into the upper anode case 25A and the lower ends thereof. The 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 3, and the plating liquid is directly ejected from the injection port 20a to the laminated sheet 3 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 laminate sheet 3 interposed therebetween, which is attached to the lower anode case 25B.

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 3 to be plated, but 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 3. 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 4 is collected in the plating liquid storage tank 21 through the lower end opening 4b. Then, by continuously driving the forced feed pump, the plating liquid is circulated in the plating tank 4 from the upper side to the lower side at a predetermined flow rate. 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 4,
Liquid seals 29A and 29B are attached to the introduction hole 4d and the lead-out portion 4e, and conductor rolls 23B and 2B outside the liquid seals are attached.
The plating solution receivers 30A and 30B are installed below the 3D.

In the plating apparatus having the above structure, the laminated sheet 3
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 4 and in contact with the round balls 24 of the anode collides with the laminate sheet 3 of the cathode from the direction perpendicular to the holes, and the holes of the laminate sheet 3 ( It is forcedly flowed at a predetermined flow velocity through the inside of the foam and mesh). Therefore, the metal ions are evenly supplied to the surface layer portions and the inner layer portions on both sides of the laminate sheet 3, and the respective portions are uniformly electrodeposited.
Deposition, that is, electrodeposition. Metals that can be electrodeposited generally include all metals that can be electroplated, such as Cu, Ni,
It is possible to electrodeposit Cr, Cd, Zn, Sn, etc. In this embodiment, Ni is used as described above.

In the above plating step, if the flow rate is increased, the current efficiency is improved and the laminate sheet 3 can be plated at a high current density. In this way, the laminate sheet 3 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. Therefore, 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.

In addition, since the mesh body, which has a large tensile strength and does not easily extend during the movement in the plating tank 4, is integrally fixed to the foam, it is more stable than the case of the foam alone. Plating can be performed while moving. Therefore, it is possible to suppress changes in the shape of the holes of the foam, and to prevent the formed metal porous body from waving, curving, and uneven plating thickness.

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 when washed with water, the hole shape is likely to be deformed when only the foam is used, but since it is laminated with the mesh body, the deformation can be prevented.

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 electrodeposited layer are also performed by the sintering process.

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

The metal porous body A used as the battery electrode plate manufactured by the method according to the first embodiment has the structure shown in FIG. 4, and is composed of two layers of the metal foam layer B and the metal plated body layer C. Even if tension is applied in the plating process, the mesh sheets are laminated, so that the skeleton of the foam is prevented from being deformed, the skeleton is held accurately and uniformly, and the opening rate per unit area is increased. Can be held uniformly.

Since the pores of the metal porous body A having the above-mentioned laminated structure are filled with active material powder such as nickel hydroxide, a tensile strength of 3 kg / 2 cm or more, preferably 7 kg / 2 cm or more is required. Since A has a tensile strength of 7 kg / 2 cm, it is possible to fill the active material powder in a continuously pulled state.

In addition, 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 C acts as a strength retainer during the bending process, cracks and damages are less likely to occur, and particularly, as shown in FIG.
When the metal mesh body layer C is arranged on the outer peripheral side and the metal foam layer B is arranged on the inner peripheral side, cracking and damage are less likely to occur.

In the first embodiment, the metal foam layer B and the metal mesh layer C are two layers, which are shown in FIG.
As shown in (C), one metal porous body may be formed by combining the metal foam layer and the metal mesh layer in any number and in any order.

FIG. 7 (A) shows a third embodiment of a three-layer structure in which metal mesh layers C and C'are laminated on both sides of a metal foam layer B.
FIG. 7B shows a third embodiment having a three-layer structure in which metal foam layers B and B ′ are laminated on both sides of the metal mesh layer C, and FIG. 7C shows the metal mesh layer C-metal from one side. The fourth embodiment has a five-layer structure in which a foam layer B, a metal mesh layer C ', a metal foam layer B', and a metal mesh layer C "are sequentially laminated.

The number of layers and the combination method described above are arbitrarily set according to the intended use. When the metal mesh layers C and C'are arranged on both outer sides of the metal foam layer B of the second embodiment, it has the advantage of good conductivity when used as a battery electrode plate.

Regarding the above-mentioned laminated sheet in which two or more sheets are laminated, as in the case of the first embodiment, among the sheets that stick to each other, the sticking side surface of the sheet with the lower melting point is heated and melted. It can be formed by press-bonding the other sheet to the formed surface and welding.

For example, in the case of manufacturing the porous metal body of the second embodiment shown in FIG. 7 (A), as shown in FIG. 8, the coil 2a of the mesh sheet 2, the coil 1a of the foam sheet 1, the mesh body The sheet 2 ′ is unwound from the coil 2a ′ of the sheet 2 ′, and the above three sheets 2 are wound by the aligning rollers 6A and 6B.
Before laminating 1, 2'integrally, both side surfaces of the foam sheet 1 located in the middle are heated and melted by the ultra far infrared heating device 5 ', and the mesh sheet 2, on both side surfaces at the time of the above pressure bonding,
2'is welded.

FIG. 9 shows a fifth embodiment of the present invention, in which a foam sheet 1 and a mesh sheet 2 are adhered and laminated with an adhesive,
The laminated sheet 3 is formed. That is, before the sheets 1 and 2 are overlapped by the alignment 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 application roller 31 comes into contact with the rotary roller 39 immersed in the adhesive agent storage tank 33, and uniformly carries out the adhesive agent 32 on the surface by a required fixed amount. Therefore, the coating roller
By pressing and rotating 31 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 mesh sheet 2 adhered via the adhesive 32 are subsequently introduced into the drying chamber 34. Hot air is supplied from the inlet 34a to the drying chamber 34, the laminated sheet 3 conveyed while being supported by the metallic 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'and conveyed while being cooled, and the foam sheet 1 and the mesh sheet 2 are bonded by the adhesive 32. It is completely fixed and integrated.

FIG. 10 shows a sixth embodiment in which sheets 1 and 2 are formed by an adhesive.
It shows another method of fixing the. That is, the foam sheet 1 and the mesh 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 storage tank 33 'and immersed in the adhesive 32', and the sheet 1 And 2 are fixed. Then, the squeezing roller 41 is used to remove unnecessary adhesive 32 '. Adhesive 3 by the method
Even when the foam sheet 1 and the mesh sheet 2 are bonded to each other via 2 ', they are dried in the drying chamber 34' and then cooled and fixed in the cooling chamber 7 ', as in the above.

FIG. 11 shows a seventh embodiment, and in each of the above-mentioned embodiments, the laminate sheet 3 is adhered or integrally fixed in advance by using an adhesive before the plating treatment. Only by stacking the sheets in a state, they are conveyed to a plating apparatus without being welded or adhered, and in the plating step, the stacked sheets are integrally fixed at the same time as the metal is attached. That is, the mesh body sheet 2, the foam body sheet 1, and the mesh body sheet 2'are unwound from the coil body, respectively, pressed by the pressure bonding rollers 6A and 6B and integrally laminated and pressure-bonded to the plating apparatus 45, It is plated. In this method, the foam sheet 1 is liable to be deformed when tension is applied, and both sides of the foam sheet 1 are stretched while being sandwiched by the mesh sheets 2 and 2'which are not easily deformed. Even if it is not fixed to the mesh sheet 2 in advance, the foam sheet is unlikely to be deformed during pulling.

FIG. 12 shows an embodiment shown in FIG. 8. In the eighth embodiment, a laminated body having a laminated structure is formed by any method such as welding, adhesion with an adhesive, or a state of only being integrally laminated. A vacuum film forming method is used as a mesh method for the sheet 3.

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 disclosed in FIG. 12 solves the above-mentioned problems and enables a metal having a required thickness to be deposited by a vapor deposition method. It is possible to prevent the metal porous body from easily deforming by plating the resin porous body 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 in a size large enough to install the coiled laminate sheet 3a wound around a roll, and the coiled sheet is guided to the vacuum passage container 54 for unwinding. A guide roller 59 is installed, and a mechanism (not shown) for continuously feeding the sheet 3 by rotating the coiled sheet 3a 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.
In addition to the guide rollers 63, guide rollers / cooling rollers 64A, 64B, 64C, 64D for refracting and guiding the laminated sheet 3 toward the outlet side are sequentially arranged following the guide roller 63. Among these rollers, in the embodiment, two rollers 64A and 64C are large diameter rollers, and the time during which the sheet 3 is in contact with the rollers is lengthened to increase the sheet cooling rate.

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 at intervals, 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 into the vacuum of the container body 61, and is uniformly deposited as a film on the entire surface of the laminated sheet 3 guided and conveyed by the rollers 64A to 64D. The thickness of the coating film can be arbitrarily controlled according to the passage time (staying time) of the laminate sheet 3 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 3 has cooling rollers 64A-6A.
The temperature of the laminate sheet 3 is further lowered because it is brought into contact with 4D and directly cooled. Therefore, even if the laminate sheet 3 is made of a resin or the like that is likely to be deformed, the metal film can be vapor-deposited without being deformed or burned out by the radiant heat of the melting heat of the metal 65. Furthermore, since it is almost unnecessary to consider the staying time of the laminated sheet 3 in the vacuum evaporation container main body 61 in order to prevent deformation due to heat, it is set to an appropriate time, and thus the evaporation time is controlled. As a result, a thick film of about 300 g / m ² can be obtained. That is, the laminated sheet 3 is placed in the vacuum container 51 for vapor deposition.
It is possible to carry out metal plating of the required height mentioned above by carrying slowly at a low speed, while it is possible to carry out thin metal plating by carrying it at a high speed, if necessary. the 1g / m ² ~1000g / m ² range optionally can be controlled by.

When the above-mentioned laminated sheet 3 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 above sintering temperature is 300-1200
It's done at ℃.

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, 30
Almost any metal such as Cr and Bs may be used. In the case of providing the two plating layers by combining the above vapor deposition plating and electrolytic plating, for example, after performing vapor deposition plating of Cu, Ni is electrolytically plated (Cu-Ni). Similarly, Cu-Sn, Fe -Zn, Mo-Pb, Ti
The combination of -Pd is preferred.

The present invention is not limited to the above-mentioned examples, and as a method for forming a laminate composed of a foam and a mesh body, any method of welding, adhesion and lamination is used as a plating method for these laminates. , The above-mentioned plating method shown in FIG. 2 and FIG. 3 (a plating method in which a plating solution flow is applied so as to hit the sheet rather than a right angle method).
In addition to the vacuum vapor deposition method shown in FIG. 12, plating may be performed by the following methods usually used.
That is, a method for forming a vacuum film by vapor deposition, ion plating, sputtering, etc., electroless plating for chemically reducing and depositing a metal on the surface of a substrate, electrolytic plating, and electrolytic plating after conducting conductivity by the above vacuum film forming method. A method of performing electroplating after conducting the conductivity imparting treatment by the above electroless plating, graphite, carbon black such as carbon black, conductive resin such as polyacetylene, polyaniline, polyprol, polythiophene, polyparaphenylene, A method of using a conductive material made of metal powder or an arbitrary mixture thereof, applying electroconductivity by a method of coating or impregnating these, and then performing electrolytic plating.

Furthermore, 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 metal porous body in which an opening is filled with an active material and used as a battery electrode plate according to the present invention, a foam that easily deforms when pulled. Since the body is integrally fixed to the mesh body which is unlikely to be deformed in advance by welding or bonding with an adhesive or the like to form a laminate sheet, the plating treatment is performed.
In the plating process, even if the plating is performed while being continuously conveyed by applying a certain amount of tension, the foam does not particularly deform. Further, the metal porous body used as a battery electrode plate by filling the active material in the opening formed by laminating the metal foam layer and the metal mesh layer produced in this manner is compared with the case where the metal porous body is composed of only the metal foam. Since the tensile strength is high, the required tensile strength can be obtained with a small amount of metal deposited. 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 moreover, since the metal mesh body is laminated on the metal foam to increase the holding strength, and since the metal adhesion amount is small, thick plating is not performed. Since it is used for a cylindrical battery electrode plate or the like, cracking can be prevented even if it is bent with an extremely small curvature.
In particular, in the case of bending into a spiral shape, when the metal foam body is on the inner peripheral side and the metal mesh body is arranged on the outer peripheral side where extension is likely to occur, cracks and damage do not occur and conductivity is improved. It has various advantages.

[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 according to 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 for a battery electrode plate, FIG. 6 is a schematic process diagram showing another welding method, and FIGS. 7 (A) and (B).
(C) is a cross-sectional view showing a second embodiment to a fourth embodiment of a metal porous body formed by laminating a metal foam and a metal mesh body, and FIG. 8 is a three-layer structure shown in FIG. 7 (A). Fig. 9 is a schematic process diagram for forming the laminated body of Fig. 9, Fig. 9 is a schematic process diagram for forming the laminated body by adhering the fifth embodiment of the present invention, and Fig. 10 is a sixth embodiment. FIG. 11 is a schematic process diagram in the case of forming the body by another bonding method, FIG. 11 is a schematic process diagram in the case where the laminated body is plated without fixing in advance, and FIG. 12 is an eighth embodiment. It is a schematic diagram of a vacuum evaporation plating device used for a plating method by vapor deposition shown. 1 ... foam sheet, 2 ... mesh sheet, 3 ...
Laminated sheet, 4 ... Plating tank, 5 ... Heating device, 33 ...
… Adhesive storage tank, A… Metal porous body, B… Metal foam,
C: Metal mesh body.

Claims (12)

[Claims] 1. A method for producing a metal porous body in which openings are filled with an active material to be used as a battery electrode plate, wherein a foamed body and a mesh body are previously laminated to provide a laminated body, and the laminated body is provided. A method for producing a metal porous body having a laminated structure, characterized by producing by plating. 2. The foamed body and the mesh body are laminated in advance,
The method for producing a metal porous body according to claim 1, which has a laminated structure used as a battery electrode plate, which is produced by integrally fixing the laminated body by welding or bonding and then plating the laminated body. 3. A laminate of the foam and the mesh, wherein two layers of the foam are laminated on one side of the foam, the mesh is laminated on both sides of the foam and / or the foam is laminated on both sides of the mesh. A battery electrode plate comprising three layers to be laminated, or a plurality of layers each having a plurality of foams and meshes and combining the foams and meshes in a desired number in any order Claim 1 used as
Alternatively, the method for producing a porous metal body according to claim 2. 4. 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.
The mesh body is made of synthetic resin such as polyester, polypropylene, polyurethane, organic material such as natural fiber, cellulose and paper, inorganic material such as metal, glass, carbon, etc. Includes a knitted structure made by knitting yarn, with a mesh size of 2 to 200 and a wire diameter of 0.01 to
The method for producing a metal porous body according to any one of claims 1 to 3, which is used as a battery electrode plate having a 1.0 mm porosity and a porosity of 40 to 99%. 5. The above-mentioned foam and mesh body are characterized in that the surface of the fixed side having a lower melting point is heated, the surface of the fixed side is melted and welded to the surface of the other fixed side to be laminated. The method for producing a metal porous body according to any one of claims 1 to 4, which is used as a battery electrode plate. 6. A battery electrode plate characterized in that the above-mentioned foam and mesh body are fixed to each other via an adhesive, and the adhesive is heated and removed by thermal decomposition in the desolvation step at the time of plating. The method for producing a metal porous body according to any one of claims 1 to 4, which is used. 7. The plating of a laminate sheet in which the foam sheet and the mesh sheet are integrally fixed to each other, and the laminate sheet is continuously moved into the plating tank after the conductivity imparting treatment, A battery electrode plate characterized by performing a plating treatment at a high current density by forcibly flowing a plating solution so as to hit the laminate sheet in a direction substantially perpendicular to the laminate sheet in the plating tank. Item 7. A method for producing a metal porous body according to any one of Items 1 to 6. 8. A vacuum container for vapor deposition in which a laminate sheet in which the foam sheet and the mesh sheet are integrally fixed is plated and the laminate sheet is continuously surrounded by a cooling tank. A battery electrode plate, which is introduced into a vacuum container for vapor deposition and is continuously guided while being cooled while being cooled by a cooling roll installed in the vacuum container for vapor deposition, and which is subjected to vapor deposition plating when passing through the vacuum container for vapor deposition. The method for producing a metal porous body according to any one of claims 1 to 6, which is used as. 9. A laminate sheet obtained by integrally fixing a foam sheet and a mesh sheet as described above, and subjecting the laminate sheet to a vacuum film forming method, an electroless plating method, an electrolytic plating method, or the like. The method for producing a metal porous body according to any one of claims 1 to 6, which is used as a battery electrode plate, which is performed by a plating method. 10. The foam sheet and the mesh sheet are continuously unwound from a coil wound around each of them and fixed in a laminated state through welding or bonding means, or without being fixed. Used as a battery electrode plate characterized by being integrated in a laminated state, continuously passing this laminated sheet through a plating device, subjected to a plating treatment, and then continuously wound into a coil to form a coil. The method for producing a porous metal body according to any one of claims 1 to 9. 11. A battery electrode plate comprising a metal foam layer and a metal mesh layer, which is manufactured by the method according to any one of claims 1 to 10 and has an opening filled with an active material. Used porous metal. 12. A metal foam layer and a metal mesh layer, which are wound for use as a battery electrode plate,
12. The metal porous body according to claim 11, which is used as a battery electrode plate, in which the metal foam layer is set on the inner side and the metal mesh layer is set on the outer side.