JPH076077B2 - 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 battery electrode produced by the method. With regard to a metal porous body used as a plate, in particular, the metal porous body is such that its skeleton is uniformly held in an accurate arrangement and at the same time the porosity per unit area is also held, so that the active material powder is It is uniformly filled and can be suitably used for electrode plates of various batteries such as nickel-cadmium battery, lithium battery and fuel cell, and moreover, the filling of the active material powder to the metal porous body is continuously performed while pulling the metal porous body. It can be carried out in a targeted manner.

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. The tensile strength is 3 kg / 2 cm or more, preferably 7 kg / 2 cm or more, so that the sheet of the continuously porous metal porous body does not extend, and the skeleton of the metal foam porous body is uniformly held as a unit. It is required in order to maintain a uniform porosity per area.

When a non-woven fabric is used to form a metal porous body, the non-woven fabric is generally made by dry or wet using short fibers, but since short fibers are used, it can be formed into a metal non-woven fabric by plating. However, when the metal adhesion amount becomes 300 g / m ² or less, the tensile strength does not become 3 kg / 2 cm or more, and the required tensile strength cannot be obtained. Therefore, in order to obtain the required tensile strength, it is necessary to perform the thickness plating of about 500g / m ² ~1000g / m ² of metal adhesion amount, the adhesion amount of plating is increased, which is a problem in cost. 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. At that time, because of the thickness of the plate, it is likely to be cracked or damaged on the outer side because the outer side is extended from the inner side. Particularly, in the case of a metal nonwoven fabric, the short fiber metal is more likely to pop out from the outer peripheral side. In a cylindrical battery, the + electrode plate and the − electrode plate are spirally wound, and the + electrode plate and the − electrode plate are separated by the separator, but if the short fiber metal pops out due to the cracks or the like, the separator is damaged. Causes a serious defect that causes a short circuit.

Further, when a single porous sheet, for example, only a nonwoven sheet is continuously conveyed and plated to provide a metallic nonwoven sheet, it is unavoidable to apply a certain amount of tension to the sheet in the plating step, Therefore, the skeleton is easily deformed, and the open area ratio per unit area becomes nonuniform. Therefore, when the porous metal sheet is used as a battery electrode plate, the active material powder cannot be uniformly filled due to the non-uniform porosity. In the case of a secondary battery, charging and discharging are repeated hundreds of times and charged and discharged through the electrode plate (metal nonwoven fabric sheet), so if the skeleton is not uniform and the active material powder is not uniformly filled, There is a big difference between the two, and this makes it impossible to power up the battery.

The present invention aims to solve the above-mentioned various problems, by providing a metal porous body having a non-woven fabric layer having a required tensile strength without performing thick plating as in the conventional case, and to reduce the metal adhesion amount. In addition to achieving a significant cost reduction, it enables continuous filling of active material powder when used as a battery electrode plate, and prevents cracks and short fiber metal protrusions when bent. is there. Further, the skeleton of the metal porous body is accurately and uniformly held, the porosity per unit area is made uniform, and the electric conductivity is made uniform when used as a battery electrode plate.

Means for Solving the Problems In order to achieve the above object, the present invention provides a porous metal body used as a battery electrode plate in which pores are filled with an active material, which is easily deformed as compared with a nonwoven fabric. The present invention provides 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 nonwoven fabric, and plating the laminated body sheet.

It is preferable that the above-mentioned laminated body of the non-woven fabric 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. Is also good.

In addition, the above-mentioned laminated body composed of a nonwoven fabric and a mesh body is provided with an arbitrary number of the nonwoven fabric and the mesh body, and is laminated in an arbitrary combination, for example, a laminated body composed of two layers of the nonwoven fabric and the mesh body. Body, a laminated body composed of three layers sandwiching the other side, four layers such as alternating layers
It includes a laminate of more than one layer.

Further, the nonwoven fabric and the mesh body, the fixing side surface is melted and welded by a method such as heating, or an adhesive is applied to one fixing surface, or the laminate is immersed in an adhesive storage tank. They are integrally fixed by a method such as adhesive bonding.

As a plating treatment for the above-mentioned integrated laminate sheet composed of a nonwoven fabric and a mesh body, the laminate sheet is continuously conveyed to a plating treatment step, and in the plating treatment step, the laminate sheet is conveyed into a vacuum container and then inside the container. In the method for forming a vacuum film by performing vapor deposition plating, or after imparting conductivity to the continuously conveyed sheet, the sheet is carried into the plating tank and the plating liquid flow is applied in a direction substantially perpendicular to the sheet in the plating tank. The method of plating by flowing so as to hit,
The electroless plating method, the electrolytic plating method, the vacuum film forming method or the electroless plating method, and the method of performing the electroplating after the conductivity imparting treatment are adopted.

The present invention further provides a porous metal body that is provided with the metal nonwoven fabric layer and the metal mesh body layer produced by the above-mentioned method and is used as a battery electrode plate.

The above-mentioned non-woven fabrics and mesh bodies each have a thickness of 0.5.
~ 5.0 mm, wire diameter 0.01 ~ 1.0 mm, preferably 0.05 ~ 0.1 m
m, the porosity of 40 to 99% is used. Further, as the material, various appropriate materials such as synthetic resins such as polyester, polypropylene and polyurethane, organic materials such as natural fiber, cellulose and paper, inorganic materials such as metal, glass and carbon can be adopted. As the mesh body, various knitted fabric bodies obtained by knitting one or a plurality of yarns such as mesh and fibrous are used. 2 mesh to 200 mesh, preferably 40 mesh to 120 mesh Used for.

The type of plating applied to the laminate sheet in which the non-woven fabric and the mesh body 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, Co, Pd, Sn, Zn, Pb, Fe are used.

When the non-woven fabric and the mesh body are fixed to each other by welding, the side having a lower melting point is heated at the temperature of the melting point to melt and weld the surface of the fixed side. At that time, it is heated at the following temperature depending on the materials of the mesh body and the nonwoven fabric.

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, deformation In the non-woven fabric which is apt to occur, a mesh body which is hard to be deformed is laminated, and a laminated body having the tensile strength increased by integrally fixing this is formed, and then the metal porous body is formed by plating. The deformation of the non-woven fabric can be prevented even when the plating treatment is performed while continuously applying tension. Further, the metal porous body composed of the metal non-woven fabric and the metal mesh body has an increased tensile strength due to the presence of the metal mesh body,
Therefore, the required tensile strength (3 kg / 2 cm or more) can be obtained even when the metal deposition amount is 300 g / m ² or less. 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. Further, by laminating with the mesh body, the deformation of the nonwoven fabric can be prevented, the skeleton can be held accurately and uniformly, and the porosity 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.

Further, in order to use the metal porous body composed of the above metal nonwoven fabric and the metal mesh body as a battery electrode plate, when the metal mesh body is arranged on the outer side when spirally wound, the short fiber metal constituting the metal nonwoven fabric pops out. Can be prevented.

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, two sheets of a nonwoven fabric sheet 1 made of polyester and a mesh body sheet 2 made of polyester are integrally laminated by welding to form a two-layer laminate sheet 3. After being provided, it is continuously conveyed to the plating tank 4, and in the plating tank 4, the plating solution flow is forcibly flowed from the direction perpendicular to the laminate sheet 3 to force the metal sheet to have a laminated structure. Are manufactured.

The first embodiment will be specifically described below.

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

As the non-woven fabric sheet 1, one having a thickness of 0.5 to 5.0 mm and a fiber diameter of 0.01 to 1.0 mm, preferably 0.05 to 0.1 mm is used. In addition, in the present embodiment, it is formed by the dry method 2.
The one with 0 mm thickness 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 40 mesh is used.

In addition, although the nonwoven fabric and the mesh body are formed of polyester in the present embodiment, the invention is not limited thereto, and synthetic resins such as nylon, acrylic, polypropylene, polyethylene, rayon, or organic materials such as natural fiber, cellulose and paper. Inorganic materials such as metal, glass, and carbon may be used as the material. Further, the mesh body may be in the form of a mesh composed of warp yarns and weft yarns, a fibrous form having a proper knitting structure by knitting one or more yarns, and the mesh wire itself may be round, square, flat, or the like. But it's okay.

The nonwoven fabric sheet 1 and the mesh body sheet 2 are continuously unwound from the coil bodies 1a and 2a wound on a roll as illustrated. Of the above-mentioned sheets, the low-melting-point nonwoven fabric sheet 1 is heated by a heating device 5, and then superposed on the mesh sheet 2 by a pair of pressure-bonding rolls 6A and 6B, and is then melted on the surface of the nonwoven fabric sheet 1 described above. The mesh sheet 2 is welded. After the welding, cool air is introduced into the cooling chamber 7 in which it is circulated, and while being supported by a mesh conveyor 8 made of metal, it is passed through the cooling chamber 7 to be cooled, and the nonwoven fabric sheet 1 and the mesh body sheet 2 are integrated. Then, the laminated body sheet 3 is adhered to 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 composed of a burner as shown in the figure, and heats the surface of the nonwoven fabric sheet 1 made of polyester 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 non-woven fabric sheet 1 on the fixed side is melted by a 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 nonwoven fabric sheet), the amount of dissolution is small and the bonding strength with the other mesh body sheet 2 is small. If the flame is weak and conversely high, the amount of dissolution increases and the bonding strength increases. For example, the surface of a nonwoven fabric sheet made of polyester is 0.007 m
When m is dissolved, the adhesive strength is 120 g / 25 mm, whereas when it is dissolved by 0.01 mm, the adhesive strength is 180 g / 25 mm.

As the above-mentioned welding method, as shown in FIG. 6, an ultra-far infrared heating device 5'is provided in place of the burner, and the heating device 5'operates the surface of the non-woven fabric sheet 1 on the fixed side in the same manner as in FIG. May be melted by heating. The ultra far infrared heating device 5 '
It is preferable to use since it is possible to surely dissolve only one surface of the thin sheet to which the 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 nonwoven fabric sheet 1 and the mesh sheet 2 that are integrally fixed by welding.
Then, as shown in FIGS. 2 and 3, Ni plating is performed by a plating device to form a metal porous body sheet composed of a metal nonwoven fabric body and a metal mesh body.

In this embodiment, as shown in FIG. 1, the laminated sheet 3 is wound into a coil shape, and the coiled laminated sheet 3 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 laminate sheet 3 wound around the coil body 3a is unwound, the conductivity is imparted by the conductivity imparting device 10, and then dried by the hot air drying device 11. Then, the mesh-ami conveyor 12 and the matching roller 13 are vertically aligned to form the mesh-ami conveyor 12
It is placed on top. 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, a plating solution supply nozzle 20 branched from a main supply pipe 26 disposed above the plating tank 20 is vertically provided, and the lower side of each nozzle 20 is penetrated 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 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 solution from a plating solution storage 21 through a supply pipe 28 by a forced feed pump 22, and the plating solution injected in the plating tank 4 is collected in the plating solution storage tank 21 from 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 forced to flow at a predetermined flow rate through the inside of the nonwoven fabric and the holes of the mesh body). 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 layer 4, is integrally fixed to the nonwoven fabric, the mesh body can be moved in a more stable state as compared with the case of the nonwoven fabric alone. Can be plated. Therefore, the change in shape of the non-woven fabric can be suppressed, and the formed metal porous body can be prevented from waviness, bending, 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 when washed with water, the shape is likely to be deformed when only the nonwoven fabric is used, but since the shape 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, the metal porous body having a metal nonwoven fabric layer and a metal mesh body layer produced by plating, desolvation, and sintering, the metal adhesion amount is 300 g / m ² , and 7.8 kg / 2 cm. Was obtained.

The porous metal body A manufactured by the method according to the first embodiment described above has a structure shown in FIG. 4, and is composed of two layers of a metal nonwoven fabric layer B and a metal plated body layer C. Since the pores of the porous metal body A having the 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 7.8 kg / 2 cm, the active material powder can be filled in a continuously pulled state.

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 C acts as a strength retainer during the bending process,
Less likely to crack or break. In particular, as shown in FIG. 5, when the metal mesh body layer C is arranged on the outer peripheral side and the metal nonwoven fabric layer B is arranged on the inner peripheral side, short fiber metal is prevented from jumping out from the outer peripheral side and damage to the separator is prevented. be able to.

In the first embodiment described above, the metal nonwoven fabric layer B and the metal mesh body layer C are composed of two layers.
As shown in (C), the metal nonwoven fabric layer B and the metal mesh body layer C may be combined in any number and in any order to form one metal porous body.

FIG. 7 (A) is a second embodiment of a three-layer structure in which metal mesh body layers C and C'are laminated on both sides of a metal nonwoven fabric layer B.
FIG. 7B shows a third embodiment having a three-layer structure in which metal nonwoven fabric layers B and B'are laminated on both sides of the metal mesh body layer C, and FIG. 7C shows metal mesh body layer C-metal nonwoven fabric from one side. It shows a fourth embodiment of a five-layer structure in which layer B-metal mesh body layer C'-metal nonwoven fabric layer B'-metal mesh body 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 nonwoven fabric layer B of the second embodiment, it has an 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 constructing the metal porous 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 nonwoven sheet 1, the mesh body Each sheet is unwound from the coil 2a 'of the sheet 2', and before the three sheets 2, 1 and 2'are integrally laminated by the laminating rollers 6A and 6B, both sides of the non-woven fabric sheet 1 placed in the middle are superposed. The far-infrared heating device 5'heats and melts, and the mesh body sheets 2 and 2'are welded to both side surfaces at the time of the above-mentioned pressure bonding.

FIG. 9 shows a fifth embodiment of the present invention, in which the nonwoven fabric sheet 1 and the mesh body 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 nonwoven fabric 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 onto the surface of the non-woven sheet 1,
The adhesive 32 is uniformly applied to the surface of the non-woven fabric sheet 1 on the fixed side.

In the above-described device 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 to the surface of the nonwoven fabric sheet 1 evenly.

The non-woven fabric sheet 1 and the mesh body 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 continuously introduced into the cooling chamber 7 ', supported by the mesh conveyor 8'and conveyed while being cooled, and the nonwoven fabric sheet 1 and the mesh body sheet 2 are completely bonded by the adhesive 32. It adheres to and is 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 non-woven fabric 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 agent storage tank 33 'and dipped in the adhesive agent 32' to form the sheet 1 2 and are fixed. Then, the squeezing roller 41 is used to remove unnecessary adhesive 32 '. Adhesive 3 by the method
Even when the non-woven sheet 1 and the mesh sheet 2 are adhered to each other via 2 ', they are dried in the drying chamber 34' and then cooled in the cooling chamber 7'to fix them, as described above.

FIG. 11 shows a seventh embodiment, and in each of the above-mentioned embodiments, the laminate sheet 3 is integrally fixed beforehand by welding or 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 sheet 2, the non-woven fabric sheet 1 and the mesh sheet 2'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 for plating. Processing. In this method, the nonwoven fabric sheet 1 is liable to be deformed when tension is applied, and the nonwoven fabric sheet 1 is stretched while being sandwiched by the mesh body sheets 2 and 2'which are less likely to be deformed. Even if it is not fixed to the sheet 2 in advance, the nonwoven fabric sheet is unlikely to be deformed when pulled.

As a method of creating a laminate of non-woven fabric and mesh,
When making a nonwoven fabric by the dry method, for example, wire diameter 70μ
2. Short fibers from both sides of the 40, 40 mesh mesh.
A non-woven fabric may be prepared by adhering with a thickness of 0 mm. As described above, when the nonwoven fabric is formed as a laminated body with the mesh body, it is possible to save the labor for preparing the laminated body again. It should be noted that 300 g is added to the laminate sheet thus created.
After plating / m ² , the tensile strength after degassing and sintering is 7.8
It was g / 2 cm.

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 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 winding 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 3a is guided to the vacuum passage container 54 and unwound. The guide roller 59 of is installed, and
The coiled sheet 3a is provided with a mechanism (not shown) for rotating the coiled sheet 3a in the direction of the arrow to continuously feed out the sheet 3.

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 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 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 3 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 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, the required metal can be attached. That is, by slowly transporting the laminate sheet 3 in the vapor deposition vacuum container 51 at a low speed, it is possible to perform the metal plating of the required height described above, while transporting it at a high speed if necessary. thin metal plating can be subjected, metal film thickness 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 this 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
Cr, Bs, etc. may be almost any metal. 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,
A Ti-Pd combination is preferred.

The present invention is not limited to the above examples, as a method for forming a laminate composed of a non-woven fabric and a mesh body, when using any method of welding, adhesion and lamination, as a plating method for these laminates, The plating method shown in FIG. 2 and FIG. 3 described above (a method of plating by flowing the plating liquid stream 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 and combination order of the nonwoven fabric and the mesh body to be laminated are not limited.

Effects of the Invention As is clear from the above description, according to the method for producing a metal porous body used as a battery electrode plate according to the present invention,
After forming a laminated sheet by integrally fixing a nonwoven fabric having low tensile strength and easily deformed with a mesh body that is not easily deformed in advance by welding or adhering with an adhesive,
Since the plating treatment is performed, the nonwoven fabric is not particularly deformed in the plating treatment process even when the plating is performed while continuously conveying the liquid under a certain tension. Further, the metal porous body used as a battery electrode plate obtained by laminating the metal nonwoven fabric layer and the metal mesh body layer produced in this manner has a large tensile strength as compared with the case where it is made of only the metal nonwoven fabric, and therefore a small amount of metal The required tensile strength can be obtained by the amount of 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, it is possible to improve the performance as a battery electrode plate, moreover, because the metal mesh body is laminated on the metal nonwoven fabric to enhance the holding strength, and since the metal adhesion amount is small and thick plating is not performed,
Since it is used for a cylindrical battery electrode plate or the like, it is possible to prevent the occurrence of cracks even when bent with an extremely small curvature. In particular, in the case of bending into a spiral shape, if the metal nonwoven fabric is on the inner peripheral side and the metal mesh body is arranged on the outer peripheral side where the extension easily occurs, cracks and damage on the outer side are prevented, and the metal nonwoven fabric is It has various advantages such as the fact that the constituent short fiber metal does not pop out and damage the separator, and the conductivity is improved.

[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 nonwoven fabric and a metal mesh body, and FIG. 8 shows three layers shown in FIG. 7 (A). FIG. 9 is a schematic process diagram for forming a laminate, FIG. 9 is a schematic process diagram for showing a fifth embodiment of the present invention and forming a laminate by adhesion, and FIG. 10 is a sixth embodiment. 11 is a schematic process drawing in the case of forming by using another bonding method, FIG. 11 is a schematic view of a seventh embodiment, and FIG. 12 is a schematic process drawing in the case of plating the laminated body without fixing it in advance. It is a schematic diagram of a vacuum evaporation plating device used for a plating method by evaporation. 1 ... Nonwoven sheet, 2 ... Mesh sheet, 3 ...
Laminated sheet, 4 ... Plating tank, 5 ... Heating device, 33 ...
… Adhesive storage tank, A… Metal porous body, B… Metal nonwoven fabric,
C: Metal mesh body.

Claims (12)

[Claims] 1. A method for producing a metal porous body having pores filled with an active material, which is used as a battery electrode plate, comprising: laminating a nonwoven fabric and a mesh body in advance to provide a laminate, A method for producing a metal porous body having a laminated structure, which comprises producing by plating. 2. A non-woven fabric and a 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 non-woven fabric and the mesh body, wherein two layers are formed by laminating the mesh body on one side of the non-woven fabric, and three layers are formed by laminating the mesh body on both sides of the non-woven fabric and / or laminating the non-woven fabric on both sides of the mesh body. Or a plurality of non-woven fabrics and a mesh body, each of which is composed of a number of layers of the non-woven fabrics and the mesh bodies, which are laminated in any order and used as a battery electrode plate.
Alternatively, the method for producing a porous metal body according to claim 2. 4. The non-woven fabric and mesh body are made of synthetic resin such as polyester, polypropylene and polyurethane, organic material such as natural fiber, cellulose and paper, and inorganic material such as metal, glass and carbon.
Used as a battery electrode plate that includes a knitting structure composed of one or more knitting yarns such as fibrous, has a mesh size of 2 to 200, a wire diameter of 0.01 to 1.0 mm, and a porosity of 40 to 99%. Claim 1
4. The method for producing a metal porous body according to any one of items 1 to 3. 5. The above-mentioned non-woven fabric and mesh body are characterized in that the fixing side surface having a lower melting point is heated and the fixing side surface is melted and welded to the other fixing side surface to be laminated. The method for producing a porous metal 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 non-woven fabric and the mesh body are fixed to each other with 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 provided. 7. The plating of a laminate sheet in which the non-woven fabric sheet and the mesh sheet are integrally fixed together is moved to a plating tank after the laminate sheet is continuously subjected to conductivity treatment, A battery electrode plate characterized by performing a plating process at a high current density by forcibly flowing a plating solution so as to hit the laminate sheet from a direction substantially perpendicular to the laminate sheet in a plating tank. 7. The method for producing a metal porous body according to any one of 1 to 6. 8. The plating of a laminate sheet in which the non-woven sheet and the mesh sheet are integrally fixed together is placed in a vacuum container for vapor deposition in which the laminate sheet is continuously surrounded by a cooling tank. Used as a battery electrode plate, characterized by being introduced, continuously guided while being cooled by a cooling roll installed in the vapor deposition vacuum vessel, and vapor-deposited when being passed through the vapor deposition vacuum vessel. The method for producing a metal porous body according to any one of claims 1 to 6, which is provided. 9. A laminate sheet obtained by integrally fixing a non-woven fabric sheet and a mesh sheet as described above is continuously plated on the laminate sheet by a vacuum film forming method, an electroless plating method and an electrolytic method. 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 such as a plating method. 10. The non-woven fabric sheet and the mesh body sheet are continuously unwound from the respective winding coils and fixed by welding or adhering means in a laminated state or laminated without adhering. Used as a battery electrode plate characterized by being integrated in a 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 claim 1. 11. A metal non-woven fabric layer and a metal mesh body layer, which are produced by the method according to any one of claims 1 to 10 and are used as a battery electrode plate in which the openings are filled with an active material. Porous metal. 12. A metal non-woven fabric layer and a metal mesh body layer, which when wound for use as a battery electrode plate,
12. The porous metal body according to claim 11, which is used as a battery electrode plate, in which the metal nonwoven fabric layer is set on the inner circumference side and the metal mesh body layer is set on the outer circumference side.