JP3386805B2 - Method of manufacturing porous metal body with tab and metal porous body with tab manufactured by the method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a tabbed metal porous body and a tabbed metal porous body produced by the method, and more specifically,
It is preferably used as a spirally wound electrode body for a battery. It is a spirally wound body obtained by filling an active material into a laminated body of porous sheets made of foam sponge, non-woven fabric, mesh or the like or a metal porous body formed by plating a single body. To be used as an electrode body,
It is configured such that a tab made of a continuous solid metal portion serving as a current collecting element is provided along the peripheral edge portion on the end face side of the spiral body.

2. Description of the Related Art Conventionally, in a cylindrical battery provided with a spirally wound electrode body, a metal porous core material is used as a core material of the electrode body for both the positive electrode and the negative electrode. That is, as shown in FIG. 34, in a typical sealed cylindrical nickel-cadmium battery, a punched nickel-plated perforated steel sheet (metal porous core material)
In addition, the strip-shaped positive electrode body 1 and the negative electrode body 2 which are formed by filling the active material are spirally wound with the separator 3 interposed therebetween.

As shown in the same figure, as a method of collecting the battery of the above-mentioned spiral electrode body, one end of each of the collecting leads 4 and 5 is spot-welded to the positive electrode body 1 and the negative electrode body 2, respectively, and the positive electrode side collection is performed. The other end of the electric lead 4 is welded to a sealing portion 7 having a cap 6 which also serves as a positive electrode terminal, and the negative electrode side current collecting terminal 5
The other end of is welded to the inner bottom surface of the metallic case 8.

In addition to the method of spot-welding and attaching the current collecting leads 4 and 5 described above, a method of exposing a part of the metal porous core material upward or downward and welding it to the sealing portion 7 or the case 8 provided with the cap 6 Is also provided.

As mentioned above, the nickel-cadmium battery is widely used as a portable power source for electric and electronic devices.
For example, when it is used for an electric power tool or the like, it is required to have excellent strong discharge characteristics. That is, it is required that the discharge voltage drop during strong discharge is as small as possible, and for this purpose, it is essential to minimize the internal resistance of the battery.

However, in the method shown in FIGS. 34 and 35, in which the current collecting leads 4 and 5 are attached to the electrode plates 1 and 2 at one location, the current collecting leads 4 and 5 are collected in order to collect the current generated in the electrode plates 1 and 2. The distance to reach 5 becomes long, and the collected current can flow only through one current collecting lead. Therefore, there is a drawback that the internal resistance of the battery increases.

As a solution to the above drawbacks, as shown in FIG. 36, the positive electrode plate 1 ′ and the negative electrode plate 2 ′ are wound in a spiral shape with a separator 3 ′ interposed between them and slightly displaced in the vertical direction. The metal porous core materials 9 and 10 disposed in the plates 1'and 2'are vertically projected, and the exposed metal core materials 9 and 10 have a metal lath plate, a net, and a current collector 11 composed of a plate. , 12 are placed and the current collector 11 and the electrode plates 1 ′, 12 and 2 ′ are connected by welding, and a multi-point current collecting system generally called a tabless system is provided.

The above-mentioned multi-point current collection method has the advantage that the internal resistance of the battery can be reduced because the distance from the generated current to the current collector is shortened because the current is collected from many locations on one electrode plate. However, the strong discharge characteristics are excellent.

However, in the tabless method using the above metal porous core material, as shown in FIG. 37, an electrode structure in which the metal porous core materials 9 and 10 are arranged inside and the active material 13 is held in the sintered metal powder. In the above, although the metal porous core materials 9 and 10 are partially exposed, the exposed core material parts 9a and 10a generally consist of parts that have not been punched (solid parts),
A width A of 0.5 to 2.0 mm is required for welding with the current collectors 11 and 12, but the exposed portions of the core material 9a and 10a are not filled with an active material and become portions not directly involved in the battery reaction. . Therefore, the core material exposed portions (solid portions) 9a, 10a that are not directly involved in the battery reaction are located above or below the electrodes, or both. Therefore, in the battery in which the width B of the electrode plate is set to be short, the occupancy rate of the exposed portion of the core material (solid portion) that is not directly involved in the battery reaction is increased and decreased, and the battery capacity must be reduced accordingly. It has drawbacks that cannot be obtained.

When using the above metal porous core material as the electrode plate, the porosity that can be filled with the active material is about 60%, but in order to increase the filling rate of the active material, a foam that can have a porosity of 90% or more,
The applicant of the present invention has proposed a technique in which a laminated body of porous sheets such as a nonwoven fabric and a mesh or a metal porous body formed by plating a single body is used as a core material of an electrode plate.
(Japanese Patent Application Nos. 1-270034, 1-270035, 1-270036, etc.) Problems to be Solved by the Invention Laminated porous sheets made of fibrous resin such as foam resin, non-woven fabric and mesh When a metal porous body formed by plating a single body or a single body is used as the core material of the electrode body, unlike the case of the metal porous core material, a tab made of only metal (solid portion) is formed on the peripheral edge portion that is the end face of the spiral. ) Was not possible. Therefore, in general, the 34th
As with the case shown in Fig. 35 and Fig. 35, using a current collecting lead,
One end of the current collecting lead is spot-welded to the positive electrode plate and the negative electrode plate, and the other end of the current collecting lead is welded to the cap also serving as the positive electrode terminal, the sealing portion having electrical continuity, and the inner bottom surface of the metal case. There is.

However, when using the current collecting lead, as described above, current is taken out from one position of the electrode plate through one current collecting lead, so that the internal resistance is large and the voltage drop during strong discharge is large. There is a drawback that the output of the battery decreases.

Furthermore, when the current collector leads are attached by spot welding, if the entire surface of the metal porous body is filled with the active material, it is difficult to perform spot welding because the electric conductivity of the active material itself is poor. Spot welding is not possible in the process. Therefore, before filling with the active material, the foam,
It is necessary to mask in advance the spot welded connection part of porous metal such as non-woven fabric so that the active material does not adhere to only the masking part when filling the active material, which is a very poor workability. There is.

And, when welding the current collecting lead to the portion where the active material does not adhere to the masking, the thickness of the metal porous body itself is usually 1.0 to 2.0 mm, and since the open area ratio is 63 to 98%, When pressure is applied in the thickness direction during or before spot welding, the thickness becomes as thin as 0.02 to 0.14 mm. Therefore, the strength of the welded portion is very weak.

Furthermore, the metal adhesion of the metal porous body plated on this foam or nonwoven fabric laminate was generally around 600 g / m ² , but due to recent technological innovation, conductivity addition in the active material is added. located less tends and 200g / m ² ~300g / m ² as development progresses agent, correspondingly, by increasing the amount of active material, although it is possible to keep a large battery capacity, the porous metal body It also has the drawback of weakening strength retention.

The present invention has the above-mentioned problems that occur when an active material is filled into a metal porous body formed by plating a laminate or a single body of a porous sheet such as the above-mentioned foam, non-woven fabric or mesh, and used as an electrode body. For the purpose of solving the problem, a method for producing a metal porous body having a connection portion with a highly reliable electrode terminal excellent in strength and electrical properties, that is, a tab, and a tabbed metal porous body produced by the method It is intended to provide the body.

Means for Solving the Problems In order to achieve the above object, the present invention is formed by plating a laminate or a single body of a porous sheet made of a fibrous resin or the like such as a foam resin, a non-woven fabric or a mesh body. A metal porous body is used as a core material, and the metal porous body core material is filled with an active material and used as a spiral electrode plate.
When wound in a spiral shape, at least on the peripheral portion on the one end face side,
Provided is a method for producing a tabbed metal porous body in which tabs made of continuous solid metal portions are integrally formed when the porous sheet is plated, and a tabbed metal porous body produced by the method. It is a thing.

More specifically, the present invention relates to a laminated body or a single body of a porous sheet made of a fibrous resin such as a foam resin, a mesh body or a non-woven fabric, at least one surface side of which is continuous with plating during plating. A metal foam body, a metal mesh body, and a metal non-woven fabric are provided by providing a base material integrally laminated with tab-forming sheets configured to have tabs made of solid metal, and plating the base material with a predetermined thickness. Provided is a method for producing a porous metal body with a tab, which comprises forming a tab made of a continuous solid metal portion on at least one surface of a porous metal body made of, for example.

The tab forming sheet has a continuous tape-like tab forming portion having a predetermined width with a constant interval,
A metal foil sheet, a resin sheet, or the like having a structure having a porous portion by performing lath, expanded, punching, or netting between the tab forming portions, or a metal foil tape, a resin coating or a metal forming the tab forming portions. A water-soluble film having a tab forming portion printed with powder is used, and a mesh body having a stitch having a porosity of 40 to 99% is used between the tab forming portion and the tab forming portion. In order to form the tabs by plating, a masking sheet to which plating is not attached is attached to the surface of the metal porous body formed by the primary plating except the tab forming portion, and the secondary plating is thickened. Can also be used.

Furthermore, the present invention is such that at least one side surface of a porous metal sheet made by plating a laminated body or a simple substance of a porous sheet made of resin such as foam, mesh, nonwoven fabric, etc. is plated at the time of the plating. The present invention provides a porous metal body with a tab, which is integrally provided with a tab made of a solid metal part formed by adhesion.

The tab provided on at least one surface side of the porous metal body is characterized in that it is provided with a predetermined width at a predetermined interval in the width direction and is continuous in the length direction.

The tabbed metal porous body cuts the metal porous body sheet along the length direction at the tab portion, and opens the metal porous body sheet at a predetermined length in a direction orthogonal to the length direction. The tabs are set so as to be positioned along the peripheral edges of both ends when the cut pieces divided by the cutting are wound in a spiral shape, or the tab portions and the tabs. And a portion between the two, while cutting in the length direction of the porous metal sheet, cut in the direction orthogonal to the length direction, when the cut pieces divided by the cutting are spirally wound, one end thereof It is characterized in that the tabs are set to be located along the peripheral edge.

Action of the invention As described above, a continuous sheet required when a porous sheet made of a fibrous resin such as a foam resin, a mesh body or a non-woven fabric is plated to form a metal porous body as a spiral electrode body. The tab made of the solid metal part is integrally formed at the time of plating the porous sheet, and the tabbed metal porous body can be manufactured very easily.

Moreover, it is necessary to adjust the position, width, etc. of the tab depending on the model of the battery. However, since it is easy to position and set the width of the tab forming portion of the tab forming sheet, it is extremely difficult to adjust the position and width of the tab. It can be done easily.

Further, since the tab made of the continuous solid metal portion is integrally provided with the porous metal body, the strength of the porous metal body itself can be increased. When the portion is provided, the porous portion also becomes a metal porous portion, so that the strength is further increased.

Further, when the tab is arranged only on the one surface side of the porous metal body, the active material can be filled in the position on the back surface side of the tab,
Providing the tab has various functions such as preventing a problem that the active material filling amount is reduced.

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

In the first embodiment of the tabbed metal porous body according to the present invention, as shown in FIG. 1, the mesh body 21 is laminated on the entire surface on one surface side of the foam 20, and the entire surface on the other surface side of the foam 20 is formed. A base material 23 made of a long body having a predetermined width W, which is obtained by laminating a metal foil sheet 22 as a tab forming sheet and integrally fixing the same, is provided, and the base material 23 is plated with a predetermined thickness and removed. The metal porous body 25 with tabs shown in FIG. 2 was prepared through a medium and a sintering process. The tabbed metal porous body 25 is composed of a metal mesh body 21 ', a metal foam body 20', and a metal foil porous body 22 'which are synergistic metal porous bodies, and the metal foil porous body 22' is shown in FIG. As described above, the tab 22'a made of a solid metal portion is provided on one surface side in the width direction at regular intervals in the width direction and is continuous in the length direction.

That is, as shown in FIG. 1, the metal foil sheet 22 which becomes the metal foil porous body 22 'is provided with tab forming tape portions 22a having a predetermined width S shorter than one end in the width direction at predetermined intervals L. At the same time, the gap L between the tape portions 22a is provided with a porous portion 22b having a porosity of 80 to 97% by performing lath, expanded, punching, reticulation and the like. Therefore,
By plating the metal foil sheet 22 integrally with the foam body 20 and the mesh body 21, one side surface of the metal porous body 25 has a structure in which the plating is adhered to the tape portion 22a with a predetermined thickness in the length direction. A continuous solid tab 22'a of metal is formed, and a porous metal foil portion 22'b is formed between the tabs 22'a.

The metal foil sheet 22 has a thickness of 0.005 mm to 0.1 mm.
In this embodiment, the width L of the porous portion 22b is set so that L + S is substantially the same as the height of the electrode plate of the battery used. As the metal foil sheet 22, Cu, Ni, Zn, Sn, Pd, Pb,
Co, Al, Mo, Ti, Fe, SUS304, SUS430, 30Cr, BS, etc. are used.

The foam 20 is made of polyurethane sponge,
A sheet having a thickness of 0.5 to 5.0 mm and a hole diameter of 50 to 500 μm, preferably 200 to 350 μm is used.

The mesh body 21 has a wire diameter of 0.01 to 1.0 mm and 2 to 200 mesh, preferably a wire diameter of 0.05 to 0.1 mm and 40 to 120 mesh, and an opening ratio of 40 to 99% is preferably used. . The material of the mesh body 21 may be any of synthetic resins such as polyester, nylon, acrylic, polypropylene, polyethylene and rayon, organic materials such as natural fibers, cellulose and paper, and inorganic materials such as metal, glass and carbon.
In addition, the mesh body includes a knitted shape in which warp threads and weft threads are knitted, or all knitted structures formed by knitting one or a plurality of threads into a fibrous shape. Moreover, the mesh line itself may be round, square, flat, or the like.

Foam 20, mesh 21 and metal foil sheet described above
22 is integrally fixed by a method described below to form a base material 23, and the base material 23 is plated to form a tabbed metal porous body 25 shown in FIG. 2 and FIG. A plurality of porous bodies 25 within the predetermined width W (eight in this embodiment)
The tab 22'a is provided with the porous portion 22'b interposed therebetween.

Before describing the method for producing the tabbed metal porous body 25 in detail, first, a case where the tabbed metal porous body 25 is used as a material for a spiral battery electrode plate will be described below.

First, while supplying the tabbed metal porous body 25 continuously, the active material is filled in the openings. At the time of the filling, the active material is filled in the openings of the laminated metal mesh body 21 ', the metal foam body 20' and the metal foil porous body portion 22'b, but the tab 22b
Since there are no holes in the active material, and when the active material is filled and applied from the side of the metal mesh body 21 ', the tab 22'a
The active material does not adhere to the surface side of, and the continuous metal surface is exposed.

The metal porous body 25 filled with the above active material has the center portion of the tab 22'a indicated by the alternate long and short dash line C ₁ in FIG. 3 and the cutting line in the direction orthogonal to the lengthwise direction indicated by the alternate long and two short dashes line C _2. Along the slitter, a slitter is used to cut, and as shown in FIG. 4, an electrode plate 26 composed of cut pieces divided by the above cutting is formed. In the electrode plate 26, the length L of the porous portion and the length of the tab 22'a are set to correspond to the height B of the electrode plate, and the length between the cutting lines C ₂ is set. It is set according to the length of the electrode plate. On one surface of the electrode plate 26, the tabs 22'a are arranged at both upper and lower ends in the height direction.

When the electrode plate 26 shown in FIG. 4 is wound into a spiral shape,
The tab 22'a will be located continuously on the edge portion, and the tab 22'a will be the whole current collecting element.

The tabbed metal porous body 25 'shown in FIG. 5 has a wide interval L'between the tabs 22'a, while the centerline C ₁ of the tab 22'a and the centerline C _{3 of the} porous portion 22'b are set. Is cut along. The C _1, so that the electrode body 26 was cut at C ₃ consists cut pieces obtained by dividing the created 'is shown in Figure 6, the length the height of the electrode body between the cut lines C ₁ and C ₃ In the electrode body 26 ', a tab is provided only at one end (upper end in the illustrated embodiment) in the vertical direction.
22'a is located. Therefore, on the positive electrode body side, the one having the tab 22'a only on the peripheral edge of ethane is used, and on the non-electrode body side, the one having the tab 22'a only on the lower end peripheral edge is used.

When the positive electrode body and the non-electrode body having the tabs 22'a shown in FIGS. 4 and 6 are used as the spiral electrode body,
Similar to the case of using the nickel-plated metal porous core material shown in FIGS. 36 and 27, the positive electrode plate and the non-electrode plate are wound in a spiral shape with a separator interposed therebetween and each being slightly offset in the vertical direction. The tab 22'a is disposed so as to be exposed vertically at one end. A metal current collector made of a lath plate, a steel plate or the like is placed on the exposed tab 22'a, and the current collector and the tab 22'a are connected by welding.

When the multi-point current collecting method is used, as described above, unlike the method in which the current collecting terminal is attached to one place of the electrode plate and the current generated inside the electrode plate is collected to one place, one electrode is used. The current can be collected from multiple locations on the plate electrode plate. Therefore, the internal resistance of the battery can be reduced and the strong discharge characteristics are excellent.

Further, as shown in FIG. 6 (C), a porous metal body with tabs
When 25 'is filled with the active material 13 as shown by the dashed-dotted cross-section line to form an electrode plate, the metal foam 2 on the back surface side of the tab 22'a is formed.
Since the active material 13 can be filled also in the openings of 0'a and the metal mesh body 21'a, it is possible to maximize the battery capacity.

Next, a method for manufacturing the tabbed metal porous body will be described in detail.

In the manufacturing process of the tabbed metal porous body 25 formed of a laminate of the foam body 20, the mesh body 21, and the tab-forming sheet metal foil sheet 22 shown in the first embodiment, first, the sheet-shaped foam body 20, the mesh The body 21 and the metal foil sheet 22 are the seventh
As shown in the figure, the coil body 200, 21 wound into a roll shape
0 and 220 are continuously unwound, and the mesh body 21 and the metal foil sheet 22 are laminated on both sides of the foam body 20 with an adhesive. That is, the adhesive 32 is applied to one surface of the foam 20 by the application roller 31 before the foam 20 and the mesh 21 are superposed on each other by the rollers 30A and 30B. The coating roller 31 comes into contact with the rotating roller 34 immersed in the adhesive agent tank 33 to uniformly carry out the adhesive agent 32 on the surface by a required fixed amount. Therefore, the application roller 31 is pressed against the surface of the foam body 20 to rotate, so that the adhesive 32 is evenly applied to the surface of the side where the mesh body 21 is fixed to the foam body 20 and the mesh body 21.
And are fixed together. These foam 20 and mesh 21
The metal foil sheet 22 is integrally fixed to the surface of the foamed body 20 with respect to the laminated body via an adhesive 32 ′. Since the method of supplying the adhesive 32 'is the same as the method of supplying the adhesive 32 to the foam, the same reference numeral is given with (') and its description is omitted. The metal foil sheet 22 is integrally fixed to the laminated body of the foam body 20 and the mesh body 21 by the adhesive 32 '. The laminated body integrally fixed by the adhesives 32, 32 'in this manner is then introduced into the hot air drying chamber 34 to be dried with hot air, and then introduced into the cooling material 35 to form the adhesive 32. , 32 'completely integrates the mesh body 21, the foam body 20, and the metal foil sheet 22. The base material 23 composed of the integrated laminated body is continuously wound as a coil body 230.

FIG. 8 shows a modified example of the fixing method using an adhesive, which is unwound from the coil bodies 210, 200 and 220, and the mesh body 21 and the foam 2 which are unwound from the coil bodies 210, 200 and 220.
0, the metal foil sheet 22 is superposed by the superposing rollers 30A, 30B in a laminated state, guided by the roller 36 in the adhesive tank 33 and immersed in the adhesive 32, the mesh body 21, the foam 20,
And the metal foil sheet 22 is integrally fixed. Then,
After the unnecessary amount of the adhesive 32 is removed by the squeezing roller 37, the adhesive 32 is introduced into the hot air drying chamber 34 and the cooling chamber 35 as in the embodiment shown in FIG.

Further, as a method of fixing and integrating the laminate of the mesh 21, the foam 20, and the metal foil sheet 22, the metal foil sheet 22 is previously bonded to the foam 20 through an adhesive, It is also possible to use a method of welding the contact surfaces of the foam 20 and the mesh 21. That is, as shown in FIG.
After the mesh body 21 is heated by the heating device 38, the pair of pressure-bonding rolls 39A and 39B are overlapped, and the foam 20 is welded to one surface of the mesh body 21 melted by the above heating. After the welding, cold air is introduced into the cooling chamber 35 in which the cold air is circulated, and the mesh body 21, the foam 20, and the metal foil sheet 22 are integrally fixed. A super far infrared heating device is preferably used as the heating device 38, but a burner, a heater, hot air, or the like is also used.

Further, as shown in FIG. 10, while the foam 20 is heated by the heating device 38, the adhesive 32 is applied to the metal foil sheet, and the mesh body 21 and the foam 20 are overlapped with the overlapping rolls 30A and 30B. And the metal foil sheet 22.
And may be fixed via the adhesive 32.

As described above, the base material 23 consisting of the mesh body 21, the foamed body 20, and the metal foil sheet 22 integrally fixed to each other via an adhesive or by welding is then plated with a plating device to form a metal mesh. The metal porous body 25 including the body 21 ′, the metal foam body 20 ′, and the metal foil porous body 22 ′ is manufactured.

In this embodiment, the base material 23 is wound up as the coil body 230, and the coil body 230 is unwound and conveyed to the plating apparatus. However, the coil body 230 may be directly conveyed to the plating apparatus without being wound onto the coil body. You may

In addition, the mesh body 21, the foam body 20, the metal foil sheet 22.
The base material 23 may be formed by simply laminating and integrating with each other without fixing by adhesive or welding.

As the plating method applied to the base material 23, the plating method disclosed in the prior application of the present applicant (see Japanese Patent Application No. 1-270034) is preferably used. That is, a vacuum imitation method of transferring into a vacuum container and performing vapor deposition plating in the container, transferring conductivity to the base material 23, and then transferring to a plating tank, and with respect to the base material 23 without the plating tank. And plating by flowing the plating solution in such a manner as to hit the plating solution from a substantially right angle direction, and further electroless plating after electroconductivity imparting treatment by electroless plating, electroplating, the above vacuum imitation method or electroless plating. A method can be adopted.

Specifically, in the method of plating by hitting the plating solution flow in a direction substantially perpendicular to the base material in the plating tank, as shown in FIG. 11, the base material wound on the coil body 230 is used. After unwinding 23 and imparting conductivity with the conductivity imparting device 40, it is dried by the hot air drying device 41. Then, it is sequentially transferred to the first to fifth plating baths 42, and nickel plating is performed 5 times in the five plating baths 42 to obtain a plating thickness of a required thickness (300 g / m ² in this embodiment). I am trying.

In each of the plating layers 42, as shown in FIG. 12, a plating solution supply nozzle 44 branched from a supply pipe 43 for supplying the plating solution downward is installed, and a plating solution storage tank 5 is installed below. , The plating solution storage tank 45 and the plating solution supply nozzle 44 are communicated with each other through a forced feed pump 46, and the base material 23 as the object to be plated is traversed in the plating tank 42 at one position below the plating solution supply nozzle 44. The conductor roll 47 outside the introduction side tank to the plating tank 43.
And the base material 23 in contact is used as the cathode, while the plating bath
The anode balls 9 are installed by being housed in a mesh case 48 inside 42.

In the above plating apparatus, the base material 23 comes into contact when passing through the conductor roll 47 and is supplied with electricity to become a cathode, and the plating liquid which comes into contact with the anode ball 49 in the plating tank 42 serves as a cathode base material.
It collides with the base material 23 in a direction perpendicular to the base material 23, penetrates through the holes (the foam body, the mesh body, the metal foil) of the base material 23 and is forced to flow at a predetermined flow velocity. Therefore, the metal ions are uniformly supplied to the both surface layers and the inner layer of the base material 23 made of the laminated sheet, and each portion is electrodeposited uniformly.

When the vapor deposition plating method is adopted, the vapor deposition plating apparatus 50 shown in FIG. 13 is preferably used because the plating thickness can be easily controlled to a predetermined thickness.

In FIG. 13, reference numeral 51 denotes a vapor deposition vacuum container, which includes a take-out vacuum container 52 for setting the coil body 230 of the base material 23, and a take-up vacuum container 53 for taking up after vapor deposition plating and a vacuum passage container 54. , Through 55. Vacuum container 51 for vapor deposition
Inside, a container 57 containing a metal 56 to be vapor-deposited is installed.
The electron beam generator 58 melts 56 and evaporates it into a vacuum, and it uniformly adheres to the base material 23 which is guided by the guide roller 59 and passes through the inside of the vacuum container 51.
Since the outer circumference of the vacuum container 51 is surrounded by the cooling tank 60 to lower the atmospheric temperature inside the container, the temperature inside the container is kept high even though it is heated at a high temperature in order to melt the metal with the electron beam. It is possible to prevent the substrate from being deformed or burned by the radiation heat of the metal. Therefore, the time for the base material 23 to pass through the inside of the container 51 (that is, the thickness of the deposited plating) can be set appropriately.

As the plating method for the base material 23 made of a laminate, the methods listed below can be appropriately adopted in addition to the above methods.

Vacuum film formation method by vapor deposition, ion plating, sputtering, etc., electroless plating for chemically reducing and depositing metal on the surface of the base material, electrolytic plating, and electrolytic plating after conducting conductivity imparting treatment by the above vacuum film formation method Method, a method of performing electroplating after imparting conductivity by the above electroless plating, graphite, carbon such as carbon black, conductive resin such as polyacetylene, polyanine, polyprol, polythiophene, polyparaphenylene, metal powder Alternatively, a method is used in which a conductive material made of an arbitrary mixture of these is used, and conductivity is imparted by a method of coating or impregnating these materials, and then electrolytic plating is performed.

The type of plating applied to the base material 23 by the above-mentioned plating method is Cu, Ni, Zn, Sn, in the above vacuum film forming method.
Pd, Pb, Co, Al, Mo, Ti, Fe, SUS304, SUS430, 30Cr, B
Any metal such as s may be used. When the electroless plating method is used, Cu, Ni, Co, Pd, Sn, Zn or the like is used. When using electroplating, Cu, Ni, Pd, Sn, Z
n, Pb, Fe, etc. are used.

As shown in FIGS. 2 and 3, the base material 23 made of a laminate is plated by the above-described method, and then, a desolvation and sintering process is performed, so that one side surface side is formed. The metal porous body 25 having the tabs 22'a formed from the solid metal portion is formed at a predetermined interval.

In the metal porous body 25, the metal foil sheet 22 that is laminated at the same time in the step of forming a metal porous body by plating a laminated body including a foam body and a mesh body is integrally fixed to the metal foam body and the metal mesh body. Thus, the porous metal body having the tabs provided at the required positions can be produced very easily.

In addition, since the metal foil sheets are laminated, the strength and the holding power can be increased as compared with the case of the laminated body including only the foam and the mesh. That is, in the case of a laminate of only the foam and the mesh, after plating the laminate,
Since the resin part is removed by performing the desolvation sintering and the center part of the plating becomes hollow, there is a problem that the strength is weak. On the other hand, a solid metal part (tab) with the above-mentioned interval
When laminating a metal foil sheet having lath, expanded, punched, net-processed, or other metal foil porous portion between the solid metal portions, the thickness of the metal foil is added to the plating thickness. The strength is improved. As a result, the amount of metal deposited per square meter can be set to 200 g / m ² . It is possible to provide an inexpensive and economical porous metal body with a tab by reducing the amount of the adhered metal.

Further, when the tab is provided only on one surface side of the porous metal body, the metal mesh body and the metal foam body are donated to the back surface of the tab as described with reference to FIG. 6 (C). Because of the openings, when used as an electrode body, the active material can be filled in all the openings of the porous metal body including the back surface position of the tab.

<< Experimental Example 1 >> A metal foil sheet of 50 g / m ² that has been subjected to a net-like processing with a porosity of 88% while leaving a 5 mm tab forming portion on a 30 μ iron foil is used.
1.5 mm thick by stacking on a 40-mesh mesh body and a foam sponge with a thickness of 1.37 mm and an average hole diameter of 320 μm.
Was provided. The substrate was plated with 250 g / m ² of nickel, and a porous metal body was prepared through the steps of removing the medium and sintering.
The weight of the metal porous body was 300 g / m ² , and the thickness of the tab was iron foil 30.
μ and plating thickness of 20μ gave a total of 50μ. With this porous metal body, a tensile tension of 12.1 kg per 0 mm width was obtained.

<< Experimental Example 2 >> In order to compare with Experimental Example 1 described above, metal foils were not laminated,
Instead of the metal foil, a metal porous body was prepared by laminating mesh bodies on both sides of the foam. That is, a 25-mesh mesh body with a wire diameter of 0.1 mm was attached to both sides of a foam sponge having the same 1.37 mm thickness as in Experimental Example 1 and an average hole diameter of 320 μm, and 320 g of nickel plating was applied to this laminated body. After performing the above, degassing and sintering were performed. The tension of the porous metal body thus produced was 2.2 kg per 20 mm.

From the results of Example 1 and Experimental Example 2 described above, it was confirmed that the tensile strength can be increased in the porous metal body to which the metal foil sheet made of the iron foil is attached, although the nickel deposition amount is small. Further, by bonding the metal foil sheets, the metal net-like metal porous portion is provided on one surface, and the thickness is increased by plating, which is very effective in terms of conductivity. In particular, when the above-mentioned porous metal body is used for the positive electrode body and the negative electrode body of the spirally wound electrode body, iron has an advantage that the tab cross section is more weldable than nickel when welding the current collector.

The tabbed metal porous body according to the present invention is not limited to the above-mentioned examples, and can be variously modified as listed below in the material of the porous sheet to be laminated, the laminating mode, the method of forming the tab, and the like. Is.

First, FIG. 14 shows a comparison of the foam with the first embodiment.
The modification of the first embodiment in which the stacking order of the mesh body and the metal foil sheet is changed is shown.
The metal foil sheet 22 is bonded to the other surface of the mesh body 21 while the metal foil sheet 21 is bonded.

FIG. 15 also shows a modified example of the first embodiment, in which the mesh bodies 21 and 21 are attached to both side surfaces of the foam body 20 to form one mesh body.
A metal foil sheet 22 is attached to the surface of 21.

In the modification shown in FIG. 14 and FIG. 15 above, the foam, mesh and metal foil sheet are integrally fixed by various methods in the same manner as in the first embodiment to prepare a base material composed of a laminated body. Then, the base material is plated by the above-described various plating methods to form a tabbed metal porous body.

Further, although not shown, by forming a base material in which the metal foil sheets 22 are laminated on both sides of the foam body 20 or both outer side surfaces of the laminated body of the foam body 20 and the mesh 21, and plating the base material. It is also possible to prepare a metal porous body with a tab by providing a tab made of a solid metal portion and a metal foil porous portion on both surfaces of the metal foam body 20 'or a laminated body of the metal foam body 20' and the metal mesh body 21 '. . When the tabbed metal porous body 25 is used as an electrode body, tabs are provided on both side surfaces in the thickness direction along the periphery of the spirally wound electrode body, which facilitates welding and improves strength, etc. There are advantages.

Incidentally, also in the examples described below, various methods can be adopted as a fixing method and a plating method, and a base material composed of an integrated laminated body is fixed and plated, and the base material is plated to form a tabbed metal. Since the point that the porous body is formed is the same, the description regarding this point is omitted.

FIG. 16 shows a non-woven fabric 70 instead of foam as a porous sheet.
A modification of the first embodiment using is shown. A metal foil sheet 22 that is a tab forming sheet is laminated on one surface of the non-woven fabric 70 to form a base material.
23 are created. The nonwoven fabric 70 has a thickness of 0.5 to
5.0mm, wire diameter 0.01-1.0mm, preferably 0.05-0.1m
Those having m and a porosity of 40 to 99% are preferably used. Like the mesh body, the material of the non-woven fabric may be synthetic resin such as polyester, nylon, acryl, polypropylene, polyethylene, rayon, organic material such as natural fiber, cellulose and paper, inorganic material such as metal, glass and carbon. .

FIG. 17 shows a modification of the first embodiment in which a laminated body of porous sheets is used as a base material. The mesh body 21 is attached to one surface of the nonwoven fabric 70 and the metal foil sheet 22 is attached to the other surface of the nonwoven fabric 70. The base material is also created.

FIG. 18 shows a laminated body in which a metal foil sheet 22 for tab formation is attached to the outer surface of a foam body 20 of a three-layer porous body sheet in which a mesh body 21, a non-woven fabric 70 and a foam body 20 are sequentially laminated. It shows a modification of the first embodiment for producing a base material.

Furthermore, a plurality of meshes may be laminated, and a metal foil sheet may be attached to one surface or both surfaces of the mesh, and the porous body sheets may be appropriately combined and laminated, or may be a single body or the same kind. A plurality of sheets may be laminated.

FIGS. 19 and 20 show a second embodiment of the present invention, in which a resin film 75 is used as a tab forming sheet instead of the metal foil sheet used in the first embodiment. Similar to the metal foil sheet 22, the resin film 75 has tab forming portions 75a made of a solid resin portion arranged side by side at a predetermined interval as shown in FIG. 20, while lath, expanded, punching, Porosity 80 to 97% by applying mesh processing etc.
The porous portion 75b is provided. The resin film 75 has a thickness
0.005-0.1mm, material is vinyl chloride, polyethylene,
Polyester and polyole are preferably used.

The resin film 75 is fixed to the outer surface of the foam body 20 of the laminated body of the mesh body 21 and the foam body 20 as in the first embodiment, and is formed as a base material. The base material is plated with a predetermined thickness, and a porous metal body is prepared through a desolvation and sintering process. In the metal porous body, the solid portion of the resin film is plated to become a solid metal foil and tabs are formed during the plating process.

21 to 23 show a third embodiment of the present invention. In the first embodiment described above, the metal foil sheet 2 having the perforated portion 22b between the tab portions 22a, which is subjected to the net-like processing, etc.
Although 2 is used, in the third embodiment, the narrow metal foil tape 80 forming only the tab portion is used as the tab-forming sheet, and one side surface of the porous sheet such as foam, nonwoven fabric and mesh body is used. On the side, a predetermined distance (a distance corresponding to the height of the electrode plate) is provided and the layers are attached in parallel. The width of the metal foil tape 80 is 2 to 20 mm, preferably 2 to 5 mm. In the third embodiment, the metal foil tape 80 is laminated on the surface of the foam body 20 laminated with the mesh body 21 and integrally fixed to form the base material 23. Similarly, a plate having a predetermined thickness is plated, and a metal porous body with a tab is prepared through a degassing and sintering process. In this case, since the metal foil tape 80 is plated, the plating thickness is added to the thickness of the metal foil tape 80, and a tabbed metal porous body having high strength and holding power is produced.

When affixing the thin metal foil tape 80 forming the tab, the width of the tape is so narrow that the dimensional intersection between the tabs is required to be ± 0.5 mm. The dimensions of the metal foil tape 80 need to be set wide. FIG. 23 shows an example in which the metal foil tape 80 has a wide width, and the tab is cut along the cutting line C ₁ which is close to both ends. Therefore, the portions X ₁ and X sandwiched by the cutting line C ₁ are formed. ₂ , X ₃ is discarded as a loss.

24 and 25 show a reference example of the present invention, in which a resin-printed or metal-powder-printed water-soluble film (PVA) 85 is used as a tab-forming sheet, and a foam, mesh, non-woven fabric, or other simple substance is used. Alternatively, it is attached to the laminate. That is, the water-soluble film 85 is preliminarily printed with a water-insoluble resin paint or a metal powder paint on one surface of the water-soluble film 85 at predetermined intervals to form the tab forming parts 85a. The water-soluble film 85 preferably has a thickness of 0.005 to 0.05 mm.

A base material 23 made of a laminated body in which the water-soluble film 85 is fixed to the foam body 20 is prepared, and before the base material 23 is plated, it is immersed in a bath at a temperature of 50 ° C. ± 10 ° C. for about 4 to 5 seconds. , Dissolve the water-soluble film 85. As a result of the preceding step, as shown in FIG. 25, only the tab forming portion 85a printed with the paint remains on the surface of the foam 20. The base material is plated with a required thickness in a plating process, and a porous metal body is prepared through a desolvation and sintering process. In this case, the printed portion is continuously plated to form a metal foil and tabs are formed.

FIG. 26 shows that the mesh body 21 is laminated on the back surface side of the foam body 20,
Water-soluble film 85 on the laminate of foam 20 and mesh 21
It shows a modified example of the above-mentioned reference example in which the.

By performing mesh-like printing between the tab forming portions 85a, it is possible to form a metal foil porous portion between the tabs and improve the strength.

27 and 28 show a fourth embodiment of the present invention. In the fifth embodiment, the mesh body 90 is used as a tab-forming sheet, and the mesh body 90 is woven by weaving a woven fabric at a predetermined interval without any gaps and providing a tab-forming portion 90a. 40 to 99% between the tab forming portions 90a
Is knitted so as to form a porous portion 90b having a porosity of. The mesh body 90 is attached to one surface of the foam body 20 to form the base material 23 made of a laminated body. This base material 23 is plated with a predetermined thickness, and a porous metal body is created through a desolvation and sintering process. In this case, the tab forming portion 90a in which the woven fabric is packed and knitted is in the shape of a metal foil, and the tab is formed.

FIG. 29 shows a modification of the fourth embodiment, in which a mesh body 21 having a normal porosity of 40 to 99% is laminated on the other surface of the foam body 20. With this deformation, the mesh body is attached to both surfaces of the foam body 20, and the strength is improved.

30 to 32 show another reference embodiment of the present invention. In the other reference examples, first, as shown in FIG. 30, a base material 23 made of a laminate of a foam body 20 and a mesh body 21 is prepared. The base material 23 is subjected to primary plating with a required thickness to form a metal porous body including a metal foam body 20 'and a metal mesh body 21'. Then, a resin sheet 95 for masking is attached to the entire one surface side (the mesh surface side in this embodiment) of the metal porous body while the metal porous body 25
On the other surface side, that is, on the foam surface side, a resin tape 100 for masking is attached to a portion other than where the tab is formed. The second plating is performed in this state. The secondary plating is performed so as to have a plating thickness which is 2-3 times as large as that of the primary plating. Resin sheet for masking by the secondary plating
Only the tab forming portion 105 to which the 95 and the masking resin tape 100 are not attached is plated. After the secondary plating described above, the metal porous body 25 with tabs is created through desolvation and sintering. A state in which the masking resin sheet 95 and the resin tape 100 are removed after the secondary plating is shown in FIG. 32, and the tab forming portion 105 is adhered with a predetermined 2-3 times plating, When making a plate, the metal porous body is filled with an active material and then rolled to about 1/2 of the thickness of the metal porous body, so that the tab forming portion 105 is rolled to form a metal foil to form a tab 106. It

FIG. 33 shows a modified example of another reference example, in which the mesh bodies 21, 21 are donated on both sides of the foam body 20 to create the base material 21,
Primary plating is applied to the base material. Secondary plating is applied to the base material by attaching resin sheets 95, 95 for masking to the portions on both outer surfaces of the base material, except for forming tabs. In this modification, tabs are formed on both side surfaces of a metal porous body composed of a laminated body of a metal foam body and a metal mesh body.

EFFECTS OF THE INVENTION As is apparent from the above description, according to the present invention, a solid metal portion which is extremely easily continuous with a metal porous body formed by plating a single body or a laminated body such as a foam, a nonwoven fabric, and a mesh body. Tabs can be formed. Further, the position and width of the tab can be easily set, and the type of battery can be easily supported. And when the metal porous body provided with the tab is used as a battery electrode plate, the variation of the storage battery is corrected, the stability of the performance,
It is possible to provide an excellent battery which can improve reliability and can be charged and discharged rapidly with high efficiency.
Further, since the tabbed metal porous body can be continuously produced in a wide width, it can be supplied at a low cost, and further, it can be wound into a coil and supplied as a coil body, so that it can be easily transported and complemented and has a wide range of applications. It has various advantages such as.

[Brief description of drawings]

FIG. 1 is a sectional view of a base material according to the first embodiment of the present invention, FIG. 2 is a sectional view of a porous metal body with tabs according to the first embodiment, and FIG.
FIG. 4 is a front view of FIG. 4, FIG. 4 is a front view of an electrode body material cut and divided from the tabbed metal porous body of the first embodiment, and FIG. 5 is a front view similar to FIG. 3 showing a modification of the cutting line. Figure, Figure 6 (A)
FIG. 6B is a front view and a side view of the electrode body material which is cut along the cutting line of FIG. 5 and divided, and FIG. 6C is a magnified view showing a state in which the electrode body material is filled with an active material. Sectional views, FIGS. 7 to 10 are schematic views showing a method of fixing and laminating a porous sheet and a metal foil sheet for forming a tab, FIG. 11 is a schematic diagram of a plating process, and FIG. 12 is FIG. Sectional view of the plating apparatus used in the plating step of FIG. 13, FIG. 13 is a schematic view of the plating apparatus used in vapor deposition plating, and FIGS. 14 to 18 are schematic sectional views showing a modification of the first embodiment. FIG. 21 is a schematic sectional view showing a second embodiment of the present invention, FIG. 20 is a front view of FIG. 19, FIG. 21 is a schematic sectional view of a third embodiment, and FIG. 22 is a front view of FIG. FIG. 23 is a drawing showing the cutting method in the case of the tabbed metal porous body of the third embodiment, and FIGS. 24 and 25 are schematic cross-sectional views showing the reference embodiment, and FIG. 26. Is a schematic sectional view showing a modified example of the fourth embodiment, FIG. 27 is a schematic sectional view showing the fourth embodiment, FIG. 28 is a front view of FIG. 27, and FIG. 29 is a schematic sectional view showing a reference embodiment. FIGS. 30 to 32 are schematic sectional views showing the fifth embodiment, FIG. 33 is a schematic sectional view showing a modification of the fifth embodiment, and FIG. 34 is a conventional spiral electrode plate current collecting mechanism. FIG. 35 is a partial cross-sectional perspective view showing another conventional current collecting mechanism, FIG. 35 is a development view of an electrode body used in the current collecting mechanism of FIG. 34, and FIG. FIGS. (A) and (B) are a developed view and a sectional view of an electrode body used in the current collecting mechanism of FIG. 20 …… foam, 20 '…… metal foam, 21 …… mesh, 21' …… metal mesh, 22 …… metal foil sheet, 22a …… tape part, 22'a …… tab, 22 ' b …… Metal foil porous part, 23 …… Base material, 25 …… Metal porous body, 26 …… Electrode plate, 70 …… Nonwoven fabric, 75 …… Resin film, 80 …… Metal foil tape, 85 …… Water soluble Film, 90 …… Mesh body, 95 …… Resin sheet for masking, 100 …… Resin tape for masking.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) H01M 2/26 H01M 4/04 H01M 4/80

Claims (11)

(57) [Claims] 1. A laminate for use as an electrode body of a battery, comprising a foam sheet, a mesh body, and / or a porous sheet made of a non-woven fabric, or a single body, and at least one surface side thereof has a tab At least one of a metal foam body, a metal mesh body, a metal porous body made of a metal non-woven fabric, or a laminate body thereof is provided by providing a base material in which the forming sheets are integrally laminated and plating the base material with a predetermined thickness. A method for producing a porous metal body with a tab, comprising forming a tab made of a continuous solid metal portion on a side surface. 2. The tabbed metal according to claim 1, wherein the tab-forming sheet is a tab composed of a continuous solid metal portion to which plating is adhered when laminated with the porous sheet and plated. Method for manufacturing porous body. 3. The tab forming sheet has a continuous tape-like tab forming portion having a predetermined width at a constant interval, and laths, expanded, punching or netting are provided between the tab forming portions. It is made of a metal foil sheet and a resin sheet having a structure having other holes by applying it, and the tab-forming sheet is integrally laminated with the porous sheet made of resin, and the base material is plated with a predetermined thickness. ,
After that, through a desolvation and sintering process, the tape-shaped tap forming portion of the tab forming sheet becomes a tab made of a continuous solid metal portion, and the plated porous portion of the tab is a metal porous body. The method for producing a tabbed metal porous body according to claim 1 or 2, which is attached to the surface of a sheet. 4. The tab-forming sheet is made of a narrow metal foil tape, and a base material is provided, in which the metal foil tape is laminated on at least one surface side of the porous sheet at a predetermined interval, and the base is formed. The material is plated with a predetermined thickness, and a tab having a plating thickness added to the thickness of the metal foil tape is provided on at least one surface side of the porous metal body. The method for producing a metal porous body with a tab according to item 4. 5. The tap forming sheet is made of a mesh body, and the mesh body has a tap forming portion formed by knitting and weaving a weave with a constant width at a predetermined interval, and is open to the tab forming portion. A porous material having a porosity of 40 to 99% is provided, the mesh body is laminated with the porous sheet to provide a base material, and the base material is plated to close the texture. The method for producing a porous metal body with a tab according to claim 1, wherein plating is attached to the knitted tab forming portion to form a solid metal portion and the tab is provided. 6. A tabbed metal porous body, which is produced by the method according to claim 1 and is used as an electrode body of a battery. 7. A metal tab made of a metal foam, a metal mesh, or a metal nonwoven fabric, or a plated tab made of a solid metal portion adhered to at least one surface of a laminate of the metal is the metal porous body. A metal porous body with a tab, characterized in that it is integrated with. 8. The tab provided on at least one surface side of the porous metal body is provided with a predetermined width at a predetermined interval in the width direction and is continuous in the length direction. The metal porous body with a tab according to claim 6 or 7. 9. A porous metal sheet is cut along the lengthwise direction of the tab portion, and the porous metal sheet is cut at a predetermined length in a direction orthogonal to the lengthwise direction. 8. When the cut pieces divided by the cutting are wound in a spiral shape, the tabs are set so as to be positioned along the peripheral edges of both ends of the cut pieces. Metal porous body with tab. 10. A porous metal sheet is cut in the lengthwise direction at a portion of the tab and a portion between the taps, and is cut in a direction orthogonal to the lengthwise direction and divided by the cutting. The tapped metal porous body according to claim 6 or 7, wherein when the cut piece is wound in a spiral shape, the tab is positioned along the peripheral edge of one end thereof. 11. The porous electrode body is filled with an active material for use as a spiral electrode body.
11. The tabbed metal porous body according to claim 10.