JPH0757717A - Metallic material plate, negative terminal plate made of the metallic material plate, and manufacture of the terminal plate - Google Patents

Abstract

PURPOSE:To prevent hydrogen gas generation without adding mercury and to increase discharge performance in a button battery. CONSTITUTION:A covered layer 5 of metal capable of alloying with zinc and heightening hydrogen overpotential of the alloy with zinc is formed on the inside, in contact with a negative active material, of a base material 2 made of steel plate, in a negative terminal plate 1 of a battery using zinc as the negative active material. The covered layer 5 of the metal having high hydrogen overpotential is formed by hot-spraying the metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal material plate used in a portion in contact with Zn, particularly a negative electrode terminal plate of a battery including a sealing plate of a button battery and a method for producing the negative electrode terminal plate. When zinc is used as the active material, mercury that has been added in the past is not required to prevent generation of hydrogen gas and passivation of zinc, thereby achieving anhydrous silver.

[0002]

2. Description of the Related Art A button battery used as a primary battery of a dry battery has a structure shown in FIG. 11, in which a case 101 serving as a positive electrode terminal plate is assembled with a sealing plate 102 serving as a negative electrode terminal plate through a gasket 103. A button battery outer plate composed of a button-shaped flat cylindrical body is formed, the inside thereof is partitioned by a separator 104, and the space sandwiched between the separator 104 and the case 101 is filled with the positive electrode active material 105, and the separator 104 and the sealing plate. The space sandwiched by 102 is filled with a negative electrode active material 106 containing zinc. In the following description, zinc is described as Zn and metals are described by chemical symbols.

The sealing plate 102 has a role of preventing leakage of the negative electrode active material 106 and the electrolytic solution and blocking of the outside air.
A base material (strip) made of iron or a stainless steel plate is provided with a Cu coating layer on the inner surface and a Ni coating layer on the outer surface by plating or clad method. The Ni coating layer is provided on the outer surface of the sealing plate 102 in order to reduce the contact electric resistance, and the Cu coating layer is provided on the inner surface.
This is because Zn as the negative electrode active material suppresses generation of hydrogen gas due to reaction with the electrolytic solution.

That is, Zn used as the negative electrode active material 106
Is very vulnerable to acids and alkalis, and if it is not subjected to anticorrosion treatment, it reacts with the alkaline component that is the electrolytic solution during storage of dry batteries, and corrodes while generating hydrogen gas. Therefore, when the Cu coating layer is provided on the inner surface of the substrate, hydrogen gas generation is more suppressed when the Cu coating layer is provided, but impurities (Fe, C, Cr, etc.) are contained in the Cu coating layer. Since the impurities are dissolved in the electrolytic solution,
It is not possible to completely prevent n from reacting to generate hydrogen gas.

Further, when Zn is used as the negative electrode active material, ZnO generated by discharge during use is passivated by covering the surface of the electrode so as to protect Zn, and Z that occurs during discharge is generated.
There is a problem that hinders the elution reaction of n. As described above, when Zn is used as the negative electrode active material, ZnO is not used during use.
It is preferable not to stay on the surface, but it is preferable that ZnO is generated and passivated during the storage of the dry battery so as not to react with the alkaline component of the electrolytic solution, and it is necessary to have the opposite characteristics.

Conventionally, the above problem has been solved by adding mercury to the negative electrode active material. That is, mercury easily forms a mercury-based alloy (amalgam) with Zn. When Zn becomes an amalgam, amalgam has a high hydrogen overvoltage, so that hydrogen gas is less likely to be generated, and therefore, a corrosion reaction of dissolution of Zn which is paired with a hydrogen gas generation reaction is prevented. The reason why the generation of hydrogen gas is suppressed when the hydrogen overvoltage is high is that metal theoretically does not generate hydrogen gas unless an overvoltage larger than the voltage generated by hydrogen gas is applied. Therefore, the higher the overvoltage on the metal surface, the more difficult it is for hydrogen gas to be generated. On the other hand, amalgam is ZnO, which has a relatively large electric resistance generated during discharge.
Has a function of making it hard to stay on the surface of Zn, and the electric resistance of amalgam is smaller than that of Zn.
The contact resistance between Zn particles can be made small, and since the contact area is increased because it is soft, the discharge characteristics can be improved. That is, mercury can satisfy both the characteristics required for Zn during storage of the battery and during use of the battery.

[0007]

However, in recent years,
As batteries are required to be made of anhydrous silver, regulations on mercury content and further prohibition of mercury use are being made.
Therefore, the present invention has the above-mentioned problems that occur when Zn is used as the negative electrode active material without adding mercury, that is, hydrogen gas generation due to the reaction between Zn and the alkaline component of the electrolyte during battery storage and Z while using battery
The purpose is to eliminate the deterioration of discharge performance due to passivation by nO.

[0008]

In order to achieve the above object, the present invention provides a metal having the same characteristics as mercury, that is, a metal which is alloyed with Zn to increase the hydrogen overvoltage of the alloy (hereinafter, referred to as a mercury substitute metal). The coating layer of (referred to) is provided on the inner surface of the base material of the negative electrode terminal plate such as a sealing plate that comes into contact with the negative electrode active material. That is, as a mercury alternative metal having the same characteristics as the above mercury, a metal with a high hydrogen overvoltage, and
Metals that are not harmful to the human body, such as mercury, but metals that are harmless to the human body, such as Pb, In, Al, Ag, Sn, M
A metal coating layer made of g, Ca, Bi or the like is provided on the inner surface of the base material. The above metals can be used alone or as a mixture. The metal material plate provided with the metal coating layer can be suitably used as a metal material plate used in a portion in contact with Zn in addition to the negative electrode terminal plate of the battery, since it has a corrosion prevention effect and the like.

The coating layer of the mercury-replacement metal is not a coating layer formed by a plating method, but a coating layer formed by forming a molten metal and then spraying the molten metal. The sprayed coating layer may be directly sprayed on the inner surface of a base material made of a stainless steel plate or the like, or C provided on the inner surface of the base material.
It may be provided by thermal spraying on the surface side (inner surface side) of the u layer. In any case, it is provided on the innermost surface side of the negative electrode active material that comes into contact with Zn. A Ni layer is provided on the outer surface side of the base material to reduce the contact electric resistance of the outer surface of the negative electrode terminal plate.

Specifically, the following aspects are included. For a plated material having a Cu plating layer on the inner surface and a Ni plating layer on the outer surface of a stainless steel plate, the surface of the Cu plating layer (inner surface) is provided with the above-mentioned spray coating layer of a mercury-replacement metal. This also includes the case where a stainless steel plate and a Cu diffusion layer or a stainless steel plate and a Ni diffusion layer are provided between the plating layer and the stainless steel plate provided on both surfaces of the stainless steel plate. For a clad material having a Cu foil on the inner surface and a Ni foil on the outer surface of a stainless steel plate, the surface of the Cu foil (inner surface) is provided with a sprayed coating layer of the above-mentioned mercury substitute metal. The inner surface of the stainless steel plate is directly provided with a thermal spray coating layer of a metal replacing mercury, and the outer surface thereof is provided with a Ni plating layer or a Ni foil layer.

The thickness of the sprayed coating layer of the above-mentioned mercury-substituting metal is preferably in the range of 0.2 μm to 15 μm. When coating via a layer, 0.2 μm to 10 μm
m, preferably 3 μm to 6 μm.

The reason why the coating layer of the alternative metal to mercury is formed by thermal spraying instead of plating as described above is as follows. That is, when the coating layer is formed by the plating method, organic substances and the like are put into the electrolytic solution tank as an additive, so that coprecipitation of organic substances occurs in the formed plated coating. Furthermore, when the base material continuously passes through the electrolytic solution bath, the components of the base material such as Fe, C, Si, Mn, and Cr are eluted,
Since it is mixed in the electrolytic solution, it is re-eutectoid in the plating film to be formed. Therefore, even if a metal plating film layer having a high hydrogen overvoltage is formed, the plating film layer contains a large amount of impurities, and the impurities are impurities (Fe, C, Cr, etc.) that lower the hydrogen overvoltage. , It becomes impossible to suppress the generation of hydrogen gas. If the amount of the impurities is 1 PPM or less, generation of hydrogen gas can be suppressed, but it is difficult to reduce the amount of the impurities to 1 PPM or less by the plating method. Further, when the coating layer is formed by plating, chemicals and the like are pumped out in each step, so a waste liquid treatment device is required from the viewpoint of preventing pollution. When the coating layer is formed by thermal spraying as compared with the above-mentioned plating method, it is possible to prevent impurities from entering during the plating process. In addition, a waste liquid treatment device is not required, and the metal coating layer forming time can be shortened to 1/5 as compared with the plating method.

For the above reasons, the present invention provides a method for producing a negative electrode terminal plate by spraying a metal (a mercury substitute metal) on the inner surface of the terminal plate, which is alloyed with Zn and has a high hydrogen overvoltage. Then, the present invention provides a manufacturing method characterized by forming a coating layer of the metal. When the mercury-replacement metal is a low-melting point metal (melting point is 500 ° C. or lower), it is preferable to use a different thermal spraying method from that of a high-melting point metal (melting point is 500 ° C. or higher). The metal used as a mercury-replacement metal in the low melting point metal is Sn (melting point 230
° C), In (melting point 156.63 ° C), Bi (melting point 271.
4 ° C.) and Pb (melting point 327.5 ° C.). The metal used as a substitute for mercury in the above-mentioned high melting point metal is M
g (melting point 651 ° C.), Al (melting point 660.4 ° C.), Ca
(Melting point 848 ° C.) and Ag (melting point 961.9 ° C.).

In the case of the low melting point metal, it is heated and melted, and the molten metal is sprayed from the spray nozzle onto the inner surface of the base material or the inner surface of the Cu layer on the inner surface of the base material to form a coating. At that time, the metal is heated and melted in a crucible, spraying from a spray nozzle is performed in a chamber, and the crucible and the chamber are filled with an atmosphere gas such as He, Ne, Ar, and N ₂ . After spraying the molten metal, it is cooled,
Then, it is calendered and then annealed in a non-oxidizing gas atmosphere.

Instead of spraying from a spray nozzle after forming the molten metal, a wire or powder made of the above metal may be provided, and the powder or wire may be sprayed by gas spraying, arc spraying, or plasma spraying. In the case of spraying with the above-mentioned spray nozzle, the distance between the nozzle tip opening and the base material is 100 mm, which is almost twice the normal distance (50 mm to 250 mm).
It is set to 500 mm. In addition, in the case of the above gas spraying, arc spraying, and plasma spraying, a distance close to double the usual one is provided.
It is set to 50 to 900 mm. The reason why the distance between the spray port and the base material is increased in this way is to prevent damage such as deformation due to spray pressure / spray heat because the base material is thin.

The pipe for supplying the metal heated and melted in the crucible to the spray nozzle has a melting point higher than that of the low melting point metal.
Preferably, by heating to 20 ° C to 50 ° C or higher than the melting point,
It prevents the molten metal from solidifying. Further, the furnace wall of the chamber that houses the crucible and the spray nozzle is made of ceramic, the crucible and the pipe are made of heat-resistant stainless steel (SUS310S), and the spray nozzle is made of Mo or the like having excellent surface properties. . Moreover, a SiC heater or an induction heater is used as a means for heating these devices.

Furthermore, when a molten metal is diffused and sprayed onto the inner surface of the base material or the inner surface of the Cu layer on the inner surface of the base material, the adhesion is improved and at the same time the base material is deformed due to a temperature difference,
In order to prevent alteration, it is preferable to heat the base material in advance to near the melting point of the low melting point metal.

When the above-mentioned high melting point metal (having a melting point of 500 ° C. or higher) is used, a pure metal or an alloy thereof is used in the form of a wire or powder, and the metal wire or metal powder is gas sprayed, plasma sprayed, arc sprayed. It is preferable that the coating layer is formed by thermal spraying on the substrate. In the case of a high melting point metal, the metal may be melted and then sprayed from a spray nozzle, but in that case, it is preferable to perform gas spraying or the like as the above-mentioned wire or powder because the cost becomes high. After spraying,
After cooling, skin pass processing is performed, and then annealing is performed in a non-oxidizing gas atmosphere. During the thermal spraying, it is preferable that a distance of 150 mm to 900 mm is provided between the thermal spraying port and the base material, and the base material is heated to near the melting point.

[0019]

In the present invention, since the negative electrode terminal plate in contact with the negative electrode active material is provided with a metal coating layer which is alloyed with Zn having the same characteristics as mercury to increase the hydrogen overvoltage of the alloy, the Zn Can be prevented or suppressed from reacting with the alkaline component of the electrolytic solution to generate hydrogen gas.
Further, as with amalgam, an alloy of Zn with a metal having a high hydrogen overvoltage coated on the inner surface of the negative electrode terminal plate is ZnO.
Has a function of making it hard to stop on the surface of Zn, can prevent passivation of Zn, and can improve discharge characteristics. Furthermore, since the metal coating layer is provided on the inner surface of the negative electrode terminal plate, impact resistance is improved.

Further, in the method for manufacturing the negative electrode terminal plate of the present invention, since the coating layer is formed by spraying a metal having a high hydrogen overvoltage provided on the inner surface of the terminal plate, the coating layer is formed by plating through the plating solution tank. It is possible to prevent the mixing of impurities that occur when forming, and it is possible to more reliably prevent the hydrogen gas generated by the mixing of the impurities.

Further, when the metal coating layer is formed by thermal spraying as compared with plating, the process can be simplified, the time for forming the metal coating layer can be shortened to about 1/5, and the waste liquid required for plating can be obtained. Processing equipment can be eliminated.

The present invention will be described in detail below with reference to the embodiments shown in the drawings. 1 to 4 show a first embodiment, and FIG.
As shown in FIG. 1, the negative electrode terminal plate 1 according to the present invention is provided with a Cu plating layer 3 on the inner surface side of a stainless steel plate 2 and a Ni plating layer 4 on the outer surface side thereof. The Sn-In sprayed coating layer 5 is provided by spraying a mixed metal obtained by melting and mixing In and In in equal amounts with a spray nozzle. A diffusion layer 6 of stainless steel and Cu is provided between the stainless steel plate 2 and the Cu plating layer 3, and a diffusion layer 7 of stainless steel and Ni is provided between the stainless steel plate 2 and the Ni plating layer 4.

The thickness of the stainless steel plate 2 and the layers laminated on the inner and outer surfaces thereof are set as follows. Stainless steel plate 2 ... 0.05 mm to 0.8 mm Cu plating layer 3 ... 2 μm to 20 μm Ni plating layer 4 ... 0.5 μm to 6.0 μm Diffusion layer 6, 7 ... 0.1 μm to 5 0.0 μm Sn-In alloy sprayed layer: 0.2 μm to 15 μm

The manufacturing method of the negative electrode terminal plate 1 is as shown in FIG. 2 until the Cu plating layer 3 is formed on the inner surface of the stainless steel plate 2 and the Ni plating layer 4 is formed on the outer surface thereof via the diffusion layers 6 and 7, respectively.
It is as shown in the flowchart described in. Figure 2 above
The steps shown in JP-A-4-52 related to the applicant's application.
The process is the same as that disclosed in No. 295, and the stainless steel plate (stainless steel base material) 2 unwound from the coil dispenser is electrolytically degreased, washed with water, and then activated. After the activation treatment, it is washed with water, then Ni strike plating is applied to the outer surface, and then C is applied to the inner surface.
u Strike plating. As described above, after performing the strike plating on each side, the outer surface is subjected to Ni main plating, and then the inner surface is subjected to Cu main plating. After the completion of the main plating, the plate is washed with water, dried, and wound into a coil with a coil winder. Then, it is unwound from a coil and conveyed to a continuous annealing furnace, heated to a heating temperature of 600 ° C. to 900 ° C. in a non-oxidizing atmosphere, and annealed for 0.5 to 15 minutes. In this annealing step, SUS- is formed between the stainless steel plate 2 and the Cu plating layer 3.
A SUS-Ni diffusion layer 7 is formed between the Cu diffusion layer 6, the stainless steel plate and the Ni plating layer 4. After the above continuous annealing, temper rolling is carried out, and then wound on a coil winder.

After the above plating process is completed, the Sn-In sprayed coating layer 5 is formed on the surface (inner surface) of the Cu plating layer 3. In order to simplify the description below, Sn-I
A state in which plating has been performed before the n sprayed coating layer 5 is formed is referred to as an adherend 8.

As shown in FIGS. 3 and 4, the apparatus for forming the Sn-In sprayed coating layer 5 has a plurality of crucibles 10A, 1A.
0B via piping 11A, 11B for storage and mixing crucible 1
2, the storage / mixing crucible 12 is extended to the inside of the chamber 14 through a pipe 13, and a plurality of spray nozzles 15 are arranged side by side at a predetermined interval at a tip portion arranged in the chamber 14. ing.

A metal inlet 21 is provided at the center of the upper surface of the crucibles 10A and 10B, and the crucibles 10A and 10B are provided.
B and 12 have inert gas inlets 16a, 17a, and 1 respectively.
8a is provided and the inert gas outlets 16b, 17b,
18b is provided, and the inside of each crucible is set to an inert gas atmosphere. He, Ne, Ar, N ₂ gas is used as the inert gas. Also, crucibles 10A, 10B, 12,
The pipes 11A, 11B and 13 are heated to the melting point of the metal used or higher, preferably 20 to 50 ° C. or higher. A SiC heater or an induction heater (not shown) is used as these heating means. The crucible and the pipe to be heated are made of heat-resistant stainless steel (SUS310S), and the spray nozzle 15 is made of Mo, which has an excellent surface property. The pipes 11A, 11B, 13
Opening / closing valves 22A, 22B, and 23 are provided in each of them, and the valves are opened at the time of thermal spraying.

An inlet / outlet (not shown) is provided in the chamber 14 so that the welded body 8 can be continuously loaded and unloaded. The welded body 8 which is continuously conveyed
A spray nozzle 15 attached to the pipe 13 is located on the upper surface of the pipe 13 at a required interval. The spray nozzle 1
The distance H from the ejection port of 5 to the welded body 8 is usually 10
It is set to 0 mm to 500 mm. A pipe 20 connected to the air compressor 19 for the inert gas is extended in the chamber 14, and the inert gas is supplied into the chamber 14 from the tip of the pipe 20 to make the chamber 14 an inert gas atmosphere. As the inert gas, the same gas as the gas supplied to the crucible is used.

The wall surface of the chamber 14 is formed of ceramics, and the lower portion thereof has a conical shape, and the recovery pipe 24 is connected to the lower end portion thereof. The recovery pipe 2
4 is provided with a recovery pump 26, and the other end is connected to a recovery metal inlet 25 provided in the storage / mixing crucible 12. The recovery pipe 24 is also made of heat-resistant stainless steel and is heated to a temperature higher than the melting point of the metal used in the pipe.

Next, the step of welding to the object to be welded 8 in the above thermal spraying device will be described. In the present embodiment, while Sn is put into the crucible 10A, In is put into the crucible 10B and is heated to a melting point or higher in the crucibles 10A and 10B to be melted, and the melted Sn and In are connected to the pipes 11A and 11 respectively.
It is supplied to the storage and mixing crucible 12 through B, and the crucible 1 is supplied.
Stirring means (not shown) provided inside No. 2 stirs and mixes. Note that Sn and In are mixed in equal amounts.

Although the molten metal as described above is affected by oxidation, it is difficult to be oxidized because the crucibles 10A, 10B, 12 and the chamber 14 to which the molten metal is sprayed are in an inert gas atmosphere. Further, since the crucible and the pipe are heated to the melting point or higher, the molten metal is not solidified and the spray nozzle 1 at the tip of the pipe 13 is not solidified.
5 can be sprayed in a molten state.

On the other hand, degreasing and acid activation treatments are performed as pretreatments on the welded body 8 having the Cu plating layer 3 and the Ni plating layer 4 on both surfaces of the stainless steel plate 2. Next, the melting point of the molten metal (the melting point of the Sn-In alloy mixed in an equal amount is about 1
The temperature is not higher than 20 ° C. and is close to the melting point, for example, is heated to 100 ° C., and is continuously conveyed to the chamber 14 in this heated state.

The welded body 8 has a Cu plating layer 3 on the upper surface on the side of the spray nozzle 15, and a molten metal mixed with Sn—In is sprayed from the spray nozzle 15 onto the upper surface of the Cu plating layer 3. Since the welded body 8 onto which the molten metal is sprayed is preheated, the heat at the time of spraying can prevent the occurrence of modification and distortion, and ensure that the sprayed and diffused molten metal is thermally fused. Adhesion can be improved.

The molten metal sprayed from the spray nozzle 15 has a uniform thickness and has the Cu plating layer 3 of the adherend 8 to be welded.
To form a Sn-In sprayed coating layer 5 on the surface of. The thickness of the Sn-In sprayed coating layer 5 is 0.2 μm to 15 μm.
It is assumed to be μm. The Sn-In sprayed coating layer 5 is Sn
Since the mixed molten metal of -In is directly sprayed on the surface of the Cu plating layer, there is no change in purity and it is possible to obtain a coating layer in which impurities are not mixed by 99.99%.

After the Sn-In sprayed coating layer 5 is formed as described above, it is cooled and subjected to skin pass processing or calendar processing. By this skin pass processing or calendar processing, the voids generated during thermal spraying are eliminated, and Sn-In
The thickness of the sprayed coating layer 5 can be set to a desired thickness. Further, thereafter, annealing is performed in a non-oxidizing gas atmosphere. By this annealing, a diffusion layer can be provided between the Sn-In sprayed coating layer 5 and the Cu plating layer 3. The negative electrode terminal plate 1 shown in FIG. 1 manufactured through the above-mentioned process is pressed by the above-mentioned FIG.
It is molded into a shape that will serve as a sealing plate for the button battery shown in FIG.

In the first embodiment, a low melting point metal having a melting point of 500 ° C. or lower is used. However, when a high melting point metal having a melting point of 500 ° C. or higher is used, the high melting point metal is formed as a wire or powder. Then, it is preferable to form the coating layer 5 by spraying the wire or powder onto the adherend by gas spraying, plasma spraying, or arc spraying.

In the second embodiment of the present invention, Al (melting point 66
0.4 ° C.) is formed on the wire rod, and the Al wire rod is sprayed on the adherend 8 by the gas spraying device 30 shown in FIG. Further, the clad material 31 shown in FIG. 6 is used as the adherend 8. For the clad material 31, a Cu foil 3 ′ is attached to the inner surface of the stainless steel plate 2, and a Ni foil 4 ′ is attached to the outer surface, and then rolling and annealing are repeatedly performed on these to press-bond them together to form the stainless steel plate 2. A Cu coating layer is obtained on the inner surface and a Ni coating layer is obtained on the outer surface.

The gas spraying device 30 has a well-known structure, and the spraying torch 31 is provided with an outer wall 32 having a conical cylindrical shape whose diameter gradually decreases toward the spraying port 31a.
An air cap 33 is attached to the tip side of the. The air cap 33 is provided with a through hole in its axial center portion, and the through hole is used as the material supply passage 34.
4, the inner peripheral side nozzle body 35 and the outer peripheral side nozzle body 36 are installed concentrically on the base side of 4, and a supply passage 37 for oxygen acetylene gas or propane gas is provided between the nozzle bodies 35 and 36, and the nozzle body 36 is provided. A compressed air passage 38 is provided between the air cap 33 and the air cap 33. The material to be welded 8 is continuously conveyed below the thermal spraying port 31a of the thermal spraying device 30 with an interval of 150 mm to 900 mm.

The thermal spray torch 31 is arranged in the chamber 14 under an inert gas atmosphere like the spray nozzle 15 of the first embodiment, and the recovery pipe is connected to the lower portion of the chamber 14. An Al wire 41 is continuously supplied to a material supply passage 34 of the thermal spray torch 31 through a pipe 40, and oxygen acetylene gas or propane gas and compressed air are piped (not shown) into the passages 37 and 38. Are supplied through.

The step of forming the Al sprayed coating layer 5 by gas spraying with the above apparatus is substantially the same as in the first embodiment. That is, the adherend 8 made of the clad material 31 is continuously conveyed into the chamber 14 with the Cu layer 3 side thereof as the upper surface,
Molten A atomized from the spray port 31a of the spray torch 31
1 is sprayed on the upper surface of the Cu layer 3 to form the Al sprayed coating layer 5. That is, the Al wire 41 supplied to the material supply passage 34 at the center of the thermal spray torch 31 is melted by the oxygen-combustion flame (acetylene flame) supplied from the outer periphery on the tip side of the passage 34, and further, Acceleration of the compressed air supplied from the outer periphery atomizes the particles to form C in the adherend 8.
It is sprayed on the surface of the u layer 3 to form a film having a required thickness.

The adherend 8 to be gas sprayed is preheated as in the first embodiment, and thus the molten Al metal is heat-sealed and adheres to the Cu coating layer 3 of the adherend 8. .
Further, a diffusion layer with the Cu coating layer 3 is formed. It should be noted that since the adherend 8 is heated to 500 ° C. or higher, distortion occurs, so that the temperature is preferably 500 ° C. or lower.

After the Al sprayed coating layer 5 is formed, it is cooled and then calendered. The calendering is performed with a weaker rolling force than the skin-passing, and is mainly performed to smooth the surface. Then, the surface layer is metallized by continuous annealing or laser in a non-oxidizing gas atmosphere, and at the same time, the Al metal layer 5 and the Cu coating layer 3 are formed.
And a diffusion layer is formed between them.

In the second embodiment, the wire is made of metal.
Although the wire is gas sprayed, the metal may be powdered and the metal powder may be gas sprayed as shown in FIG. Thermal spray torch 31 'of gas thermal spray apparatus 30' shown in FIG.
Then, the powder material feed gas is supplied to the central passage 43, and the metal powder 41 'is fed from the material feed passage 44 which merges in the middle of the central passage 43, and the metal powder 41' is sprayed by the feed gas. It leads to 31a '. Spray port 3
In 1a ′, the metal powder 41 ′ is melted by the oxygen-fuel gas ejected from the passage on the outer peripheral portion, and the adherend 8 is melted in the melted state.
Is sprayed on the surface of the Cu coating layer 3.

In the third embodiment of the present invention, as shown in FIG. 8, the Ni plating layer 4 is provided on the outer surface of the stainless steel plate 2, while the Al-Ag sprayed coating layer 5 is provided directly on the inner surface. That is, the inner surface of the stainless steel plate 2 is directly sprayed without providing the Cu coating layer. The above Al has a melting point of 660.4.
℃, Ag is a high melting point metal with a melting point of 961.9 ℃,
Al-Ag sprayed coating layer 5 using arc spraying shown in FIG.
Is provided.

The formation of the Al-Ag sprayed coating layer 5 is shown in FIG.
In the same manner as in the second embodiment shown in FIG. 7, the arc spraying torch 31 ″ is used in the chamber 14.
Are arranged. The Al and Ag are formed as wires, and the Al wire 50A is connected to the + pole and the Ag wire 50B is connected to the − pole. These wires 50
A and 50B are led out from the supply passages 52A and 52B of a nozzle 51 assembled to the tip of the thermal spray torch 31 ″ so as to come into contact with each other, and compressed air is passed through the passage 5 at the center of the contact portion.
We are supplying from 3.

The two wires 5 continuously supplied as described above.
0A and 50B are + and-electrodes,
An arc is generated at the tip of the wire, and the wires 50A and 50B are melted by the arc heat to form a mixed molten metal, which is then sprayed onto the adherend 8.

After the thermal spraying step, cooling is carried out, and then a skin pass or calendering process is carried out to obtain the above Al-Ag.
The coating layer 5 has a required thickness. In this third embodiment, since the Cu coating layer is not provided, the thickness of the Al—Ag coating layer 5 is made larger than that in the case where the Cu coating layer is provided, and the average is 10
The thickness is μm. After the above skin pass or calendering, annealing is performed in a non-oxidizing gas atmosphere.

Although gas spraying is carried out in the second embodiment and arc spraying is carried out in the third embodiment, the spraying method may be plasma spraying as shown in FIG. The plasma spraying apparatus used is well known, and a working gas filling chamber 61 surrounded by a cooling water passage 60 is provided in the spraying torch 31 ″ ′.
A working gas such as argon or helium is supplied into the chamber 1 through a passage 62. A tungsten cathode 63 is arranged inside the working gas filling chamber 61, the wall surface of the working gas filling chamber 61 is formed of copper 64, and the copper is connected to the anode. A metal powder supply passage 6 is provided at the tip of the working gas filling chamber 61.
5 is opened, and metal powder is supplied from the passage 65.

In the above plasma spraying apparatus, when a DC arc is generated by applying a voltage between a tungsten cathode and a copper nozzle anode in a working gas such as argon or helium, the working gas is dissociated and ionized to continuously generate a DC arc. A plasma arc is generated. When the plasma arc is narrowed down by a cooled nozzle, a high-speed jet having a high temperature of 15000 ° C. or higher is jetted. When metal powder is supplied to the jet, the metal powder is melted and blown off. Therefore, for example, when Al powder is supplied, the Al powder is melted by the plasma arc and forms a film on the inner surface of the adherend 8.

In each of the above embodiments, the metal material plate provided with the metal coating layer having a high hydrogen overvoltage is used as the sealing plate for the button battery. However, it is used for the portion other than the sealing plate for the button battery that comes into contact with Zn. It can be suitably used as a metal material plate for a battery or a metal material plate other than a battery.

[0051]

As is apparent from the above description, on the inner surface of the negative electrode terminal plate in contact with the negative electrode active material Zn according to the present invention,
Since a metal that is alloyed with Zn to increase the hydrogen overvoltage of the alloy is coated, generation of hydrogen gas can be prevented or suppressed due to the high hydrogen overvoltage during battery storage. In addition, ZnO is less likely to stay on the surface of Zn during use, passivation of Zn can be prevented, and discharge characteristics can be improved.

Further, since the metal coating layer is formed by a spraying method in which the metal having a high hydrogen overvoltage is sprayed in a molten state, not by a plating method, impurities are surely mixed into the metal coating layer. It can be prevented. Therefore,
It is possible to reliably prevent the generation of hydrogen gas, which increases due to the inclusion of impurities.

Furthermore, the plating method requires a waste liquid treatment facility and complicates the process. However, when the thermal spraying method is used, the waste liquid treatment facility is not required, and the process is simpler. It has various advantages such that a coating layer can be formed in about 1/5 hours.

[Brief description of drawings]

FIG. 1 is a sectional view of a negative electrode terminal plate according to a first embodiment of the present invention.

FIG. 2 is a flow chart up to the construction of the adherend of the first embodiment.

FIG. 3 is a schematic view of a spray nozzle type thermal spraying device used for thermal spraying of the first embodiment.

FIG. 4 is an enlarged view of the chamber portion shown in FIG.

FIG. 5 is a schematic view of a gas thermal spraying device used for thermal spraying of a second embodiment.

FIG. 6 is a sectional view of a negative electrode terminal plate according to a second embodiment.

FIG. 7 is a schematic view of another gas spray apparatus.

FIG. 8 is a sectional view of a negative electrode terminal plate according to a third embodiment.

FIG. 9 is a schematic view of an arc spraying device used for spraying in a third embodiment.

FIG. 10 is a schematic view of a plasma spraying apparatus used for another spraying.

FIG. 11 is a cross-sectional view showing the configuration of a button battery.

[Explanation of symbols]

102 Sealing plate 106 Negative electrode active material 1 Negative electrode terminal plate 2 Stainless steel plate 3 Cu coating layer 4 Ni coating layer 5 Thermal spray metal coating layer (Sn-In thermal spray coating layer, Al thermal spray coating layer, Al-Ag thermal spray coating layer) 8 Welding body

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[Procedure amendment]

[Submission date] November 4, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

[0022]

The present invention will be described in detail below with reference to the embodiments shown in the drawings. 1 to 4 show a first embodiment, and as shown in FIG. 1, a negative electrode terminal plate 1 according to the present invention has a Cu plating layer 3 on the inner surface side of a stainless steel plate 2 and a Ni plating layer 4 on the outer surface side thereof. The Sn-In sprayed coating layer 5 is provided on the inner surface of the Cu plating layer 3 by spraying a mixed metal obtained by melting and mixing low-melting-point metals Sn and In in equal amounts with a spray nozzle. A diffusion layer 6 of stainless steel and Cu is provided between the stainless steel plate 2 and the Cu plating layer 3, and a diffusion layer 7 of stainless steel and Ni is provided between the stainless steel plate 2 and the Ni plating layer 4.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

A metal inlet 21 is provided in the center of the upper surface of the crucibles 10A, 10B, and the crucibles 10A, 1
0B and 12 have inert gas inlets 16a and 17a,
18a is provided and the inert gas outlets 16b and 17 are provided.
b and 18b are provided, and the inside of each crucible is made an inert gas atmosphere. He, Ne, Ar, N as the inert gas
_Two gases are used. Also, crucibles 10A, 10B, 1
2. The pipes 11A, 11B and 13 are heated to the melting point of the metal used or higher, preferably 20 to 50 ° C. or higher. A SiC heater or an induction heater (not shown) is used as these heating means. Also, the crucible and piping to be heated are heat resistant stainless steel (SUS310S)
The spray nozzle 15 is formed of Mo, which has excellent surface properties. The above piping 11A, 11
Opening valves 22A, 22B, and 23 are provided on B and 13, respectively, so that the valves are opened at the time of thermal spraying.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

In each of the above embodiments, the metal material plate provided with the metal coating layer having a high hydrogen overvoltage is used as the sealing plate for the button battery. However, it is used for the portion other than the sealing plate for the button battery that comes into contact with Zn. It is also suitably used as a metal material plate for batteries or a metal material plate other than batteries.

[Procedure amendment 4]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 2

[Correction method] Change

[Correction content]

[Fig. 2]

[Procedure Amendment 5]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 7

[Correction method] Change

[Correction content]

[Figure 7]

[Procedure correction 6]

[Document name to be corrected] Drawing

[Name of item to be corrected] Fig. 10

[Correction method] Change

[Correction content]

[Figure 10]

Claims (12)

[Claims] 1. A metal material plate used in a portion in contact with Zn, wherein a steel base material is provided with a metal coating layer capable of alloying with Zn and increasing the hydrogen overvoltage of the alloy. Metal material plate to be used. 2. A negative electrode terminal plate of a battery, wherein Zn is used as a negative electrode active material, by a metal material plate provided with a metal coating layer capable of alloying with Zn on a base material made of steel and having a high hydrogen overvoltage of the alloy. A negative electrode terminal plate of a battery, which is formed and is arranged on the inner surface side in contact with the negative electrode active material. 3. The metal coating layer having a high hydrogen overvoltage comprises:
The plate according to any one of the preceding claims, comprising a coating layer formed by spraying a molten metal of the metal. 4. The metal coating layer having a high hydrogen overvoltage comprises:
The plate according to any one of the preceding claims, wherein the inner surface side of the base material is provided on the innermost surface side via a Cu layer, while the outermost surface side of the base material is provided with a Ni layer. 5. The metal forming the coating layer is S
Any one of the preceding claims, wherein n, In, Bi, Pb, Mg, Al, Ca, Ag, etc. are used alone or in combination.
The plate according to item. 6. The battery negative electrode terminal plate according to claim 2, wherein said negative electrode terminal plate is a button battery sealing plate. 7. A negative electrode terminal of a battery wherein a coating layer is formed on the inner surface side of a base material made of a steel plate in contact with the negative electrode active material by spraying a metal capable of alloying Zn and increasing the hydrogen overvoltage of the alloy. Method of manufacturing a plate. 8. The metal to be sprayed is Sn, In, Bi,
The method for producing a negative electrode terminal plate for a battery according to claim 7, which comprises Pb, Mg, Al, Ca, Ag, or the like alone or in a mixture. 9. The method for producing a negative electrode terminal plate for a battery according to claim 7, wherein the metal is heated and melted, and then the molten metal is sprayed from the spray nozzle to the steel plate side for thermal spraying. 10. A wire rod and a powder made of the above metal are provided,
9. The method for producing a negative electrode terminal plate for a battery according to claim 7, wherein the wire or powder is sprayed onto the steel plate by gas spraying, plasma spraying, or arc spraying. 11. The method according to claim 7, wherein after the metal is sprayed to form a coating layer, annealing is performed in a non-oxidizing gas atmosphere, and after cooling, skin pass processing or calendar processing is performed. The method for producing a negative electrode terminal plate according to. 12. The manufacturing method according to claim 7, wherein the negative electrode terminal plate is a sealing plate for a button battery.