JP4711250B2 - Nickel electrode for secondary battery and its manufacturing method - Google Patents

Description

  The present invention relates to a nickel electrode for a secondary battery and a method for producing the same.

  In recent years, various secondary batteries have been used in many applications such as portable devices and mobile devices. For example, nickel-hydrogen batteries have been used as secondary batteries for small devices such as mobile phones and personal computers, and the use of lithium-ion batteries is also expanding. Also, nickel-cadmium batteries, nickel-hydrogen batteries, and the like are used as large-capacity power supplies used for electric tools, shavers, remote control toys, vacuum cleaners, and the like.

  On the other hand, in recent years, hybrid vehicles driven by engines and batteries have been attracting attention as having energy-saving properties and low pollution, and automakers have become active in commercialization, and widespread use in the future is expected. ing.

  As a power source for hybrid vehicles, high output characteristics are important. Cylindrical and prismatic nickel-hydrogen batteries have been put into practical use and their fuel efficiency has been proven. For such secondary batteries, in addition to high output characteristics, various performances such as low price, long life, low pollution, and reliability are required. In addition to nickel-hydrogen batteries, lithium ion batteries and lead storage batteries are also required. Is being developed and put into practical use, but at present it is being put into practical use as a nickel-hydrogen battery is the most suitable battery based on a comprehensive judgment.

  A nickel-hydrogen battery is a battery that uses a nickel electrode as a positive electrode and a hydrogen electrode filled with an alloy capable of occluding and releasing hydrogen as a negative electrode. Usually, a negative electrode is mainly composed of a core material made of punching metal. An electrode obtained by applying and pressing a paste containing an alloy powder is used.

  On the other hand, the nickel electrode of the positive electrode has been improved by coating nickel hydroxide, which is an active material, with a cobalt compound to improve conductivity, but it is still more conductive than the metal, which is the active material of the negative electrode. Is inferior. For this reason, in the nickel electrode, the performance is improved by adopting a three-dimensional structure in which a sintered body or a foamed porous body is filled with an active material. Various improvements have been made (see, for example, Patent Documents 1, 2, and 3 below).

  However, when the nickel electrode has such a three-dimensional structure, the substrate itself used for the sintered nickel electrode and the foamed nickel electrode is expensive, and the filling process of the active material becomes complicated. For this reason, the nickel electrode is more expensive than a paste electrode having a punching metal substrate as used in the negative electrode, and occupies a considerable part of the battery price.

  As long as the battery is the power source of the equipment, it is required to reduce the price for all applications. In particular, it requires a large capacity battery such as a battery for electric vehicles, a battery for hybrid vehicles, a stationary battery, and many batteries. In such applications, the demand for lower prices for batteries has become more severe.

  Under such circumstances, many proposals have been made for improving the structure and the active material filling method of the nickel electrode that causes the cost increase of the secondary battery using the nickel electrode such as a nickel-hydrogen battery.

  For example, if a base material having a two-dimensional structure, such as a punching metal, is used as the base material for the nickel electrode, it is possible to reduce the price of the nickel electrode (for example, see Patent Document 4 below). In this case, if an extremely thin electrode is used, the distance between the active material and the substrate is shortened, and the decrease in utilization rate and output is reduced. However, since there is a limit to thinning, an excellent conductive agent is necessary to improve the utilization rate, and an excellent binder is necessary for extending the life, and a two-dimensional structure is required. A nickel electrode using a substrate has not yet exhibited sufficient performance.

  By the way, paste-type electrodes such as cadmium electrodes of nickel-cadmium batteries and alloy negative electrodes of nickel-hydrogen batteries are usually used as a base material having a two-dimensional structure such as punching metal and screen, and an active material paste. In the state which applied, it passes between the slits which have a fixed space | interval, and the surface of a paste is smooth | blunted, Then, it dries and pressurizes and is manufactured.

  In this case, since it is necessary to pass the base material to which the paste is applied, the slit interval is about 0.3 mm when a punching metal having a thickness of about 50 μm is used as the base material. An interval is set, and after passing through this interval, pressure is applied to adjust the thickness of the electrode to form an electrode having a desired thickness.

  Thus, in the conventional method for manufacturing a paste-type electrode, a method of passing between slits having an interval larger than the thickness of the base material is common. For this reason, there is a problem in the effect of the moisture of the paste and the accuracy of smoothness due to the slits, and in mass production, variations occur between the electrodes, which often causes non-uniformity in capacity and output.

In addition, when a nickel electrode is produced by such a method, if an active material having poor conductivity such as nickel hydroxide is used, the active material layer in a part away from the substrate existing on the surface part of the nickel electrode is used. There is a disadvantage that the utilization rate is low, and there is also a problem that the active material is likely to fall off during charging and discharging, and the electrode life is shortened.
JP-A-5-62686 Japanese Patent Laid-Open No. 11-176450 Japanese Patent Laid-Open No. 11-176451 JP-A-7-94181

  The present invention has been made in view of the problems of the prior art as described above, and its main purpose is that there are few variations in capacity, output, etc., excellent output characteristics, low cost and long life. It is a nickel electrode for batteries, and in particular, to provide a nickel electrode capable of high output.

The inventor has intensively studied to achieve the above-described object. As a result, a punching metal having an opening degree of 5 to 20% and a thickness of 20 to 50 μm in which uneven portions were formed by embossing was used as an electrode substrate, and most of the active material for nickel electrode in the recesses of the substrate. The convex portion of the substrate, that is, the surface of the substrate has a high output and a high utilization rate by being substantially exposed or having a very small amount of active material attached, and It has been found that a long-life nickel electrode can be obtained. And as a manufacturing method of the nickel electrode having such a structure, in particular, after applying the active material paste for nickel electrode to the embossed punching metal base material, the slit having substantially the same interval as the thickness of the base material It has been found that a nickel electrode having the above-described structure can be manufactured relatively efficiently when a method of passing the substrate through the gap and then pressurizing is employed. The present invention has been completed based on such findings.

That is, the present invention provides the following nickel electrode for a secondary battery and a method for producing the same.
1. A nickel electrode for a secondary battery comprising an electrode base material and an electrode active material made of a punching metal having a porosity of 5 to 20% and a thickness of 20 to 50 μm , wherein the irregularities are formed by embossing, A nickel electrode for a secondary battery, wherein a concave portion of the material is filled with an active material, and the convex portion of the base material is in a state where a surface is exposed or an active material is attached.
2. Item 2. The nickel electrode for a secondary battery according to Item 1, wherein the amount of the active material adhering to the convex portion of the substrate is 10% by weight or less of the total amount of the active material.
3. Item 3. The nickel for a secondary battery according to Item 1 or 2, wherein the surface of the convex portion of the substrate is exposed, which is obtained by removing the active material attached to the substrate surface after filling the substrate with the active material. very.
4). Item 4. The nickel electrode for a secondary battery according to any one of Items 1 to 3, wherein the electrode substrate is mechanically embossed and has a concavo-convex portion formed on a punching metal.
5. Item 5. The nickel electrode for a secondary battery according to any one of Items 1 to 4, wherein the punching metal has a porosity of 5 to 15%.
6). The apparent thickness of the punching metal of d Nbosu processed by uneven portion formed electrode substrate 0.2 to 0.5 mm, the weight per unit area of substrate ranges from 200-500 g / ^{m 2} The nickel electrode for secondary batteries in any one of claim | item 1 -5.
7). Item 7. The nickel electrode for secondary battery according to any one of Items 1 to 6, wherein the electrode active material is spherical nickel hydroxide whose surface is coated with a cobalt compound.
8). A paste containing an electrode active material is applied to an electrode substrate made of a punching metal having a porosity of 5 to 20% and a thickness of 20 to 50 μm where uneven portions are formed by embossing, and then passes through the substrate. A method for producing a nickel electrode for a secondary battery, wherein the substrate is passed between slits having substantially the same spacing as the apparent thickness of the substrate and then pressurized.
9. When passing the substrate, the method of passing the substrate between the slits that are substantially the same as the apparent thickness of the substrate is the same interval as the thickness of the substrate or an interval narrower than the thickness of the substrate. Item 9. The method for producing a nickel electrode according to Item 8, wherein the substrate is passed between slits formed by a slit forming member that is set and elastically biased in the direction of narrowing the slit interval.
10. A slit formed by an elastically biased slit forming member, a slit formed by an elastic material, a slit formed by a member that can be pressed in the direction of narrowing the slit interval using a spring Item 10. The method for producing a nickel electrode according to Item 8 or 9, wherein the nickel electrode is a slit formed by a cylindrical member having both ends fixed by an elastic body.

In the present invention, a punching metal having an opening degree of 5 to 20% and a thickness of 20 to 50 μm in which uneven portions are formed by embossing is used as the electrode substrate for the nickel electrode.

  The method for producing such an electrode substrate is not particularly limited, for example, using a thin metal material, using a mold for punching metal processing and a mold for forming an embossed structure, It is preferable to manufacture by mechanical processing. When performing punching metalization and embossing by mechanical processing, it can be processed with high precision, and the thickness and recess of the base material can be easily and uniformly manufactured. The variation is greatly reduced, and a high-performance electrode can be obtained.

The material of the electrode substrate is not particularly limited, and for example, a metal plate such as a nickel plate or a nickel-plated iron plate can be used.
For punching the thickness of the metal for forming the electrode base material may be any thickness that can perform machine械的machining easily may be set to 2 0~50μm.

In the present invention, the opening degree of from 5 to 20% extent as punching metal, preferably used of about 5-15%. Conventionally used general-purpose punching metal has an opening degree of about 40 to 60%. The opening degree is increased, and the active material layers on both sides of the base material are bonded at the hole portions. Increases adhesion to the substrate. In the present invention, by forming embossed portions on the punching metal by embossing and filling most of the active material into the recesses, the contact area between the active material and the base material is increased, whereby the active material becomes a base material. The adhesion force of can be improved. As a result, even when using a punching metal with a low porosity of 5 to 20% , a sufficient bonding force can be obtained, the contact area between the base material and the active material is increased, the utilization rate and The potential can be improved.

  Although there is no limitation in particular about the hole diameter of a punching metal, Usually, it may be about 0.1-1 mm, and it is preferable to set it as about 0.3-0.8 mm.

  There is no particular limitation on the size of the concavo-convex portions formed by embossing, and it is only necessary that the concavo-convex portions that can be filled with the active material are alternately formed. For example, the distance between the recesses, that is, the width of the recesses may be about 0.5 to 1.5 mm.

Although there is no limitation in particular about the apparent thickness of the base material after embossing to a punching metal base material, it should just be about 0.2-0.5 mm, for example. In addition, the weight per unit area of the substrate is usually about 200 to 500 g / m ² .

  The base material should just be planar as a whole, and can be made into planar shape or curved surface shape according to the usage form of an electrode.

  In the nickel electrode of the present invention, the concave portion of the base material having the structure described above is filled with an active material for nickel, and the convex portion of the base material is in a state where the surface is exposed or an active material is attached.

  In order to manufacture a nickel electrode having such a structure, first, a paste containing an active material for nickel is sufficiently applied to the whole of the electrode substrate including the recesses.

  As the paste itself containing the active material, the same paste as that conventionally used for electrodes formed by applying paste, so-called paste type electrodes, can be used.

  For example, nickel hydroxide can be used as the active material. In particular, spherical nickel hydroxide having a surface coated with a cobalt compound such as cobalt oxyhydroxide is preferable because of its excellent utilization rate and discharge rate.

A known binder can also be used as a binder for the nickel electrode. For example, polyolefin is preferable because it is excellent in both performance and life. The polyolefin may be used alone or in combination with a fluororesin.

  The method for applying the paste containing the active material to the electrode substrate is not particularly limited, and may be the same as the normal paste application method. The simplest method includes a method of passing a substrate through the paste. In addition, a method such as a method of spraying the paste from both sides may be applied as appropriate to apply the paste to the entire substrate including the recesses.

  In the present invention, after applying the paste containing the active material to the base material having the concavo-convex structure in this way, the concave portion of the base material is filled with the active material, and the convex portion of the base material has the surface of the base material. The exposed state or the active material is attached.

  By having such a filling state, most of the active material is uniformly filled into the concave portion of the base material, and the convex portion of the base material, that is, the surface of the base material has a small amount of active material attached, Partial variation can be greatly reduced, and the electrode can have stable performance, and further, it is possible to suppress a decrease in the utilization rate and dropout of the active material.

  About the adhesion amount of the active material in the convex part of a base material, it is preferable to set it as about 10 weight% or less of the total filling amount of an active material, and it is more preferable to set it as about 5 weight% or less. In this way, most of the active material is filled in the concave portions of the base material, and the amount of the active material attached to the convex portions is very small, so that the obtained nickel electrode has particularly high output and high utilization rate. It has a long life.

  In particular, when the active material adhering to the convex portion of the base material is almost completely removed and the surface of the base material is exposed, the ratio of the base material to the active material increases, so the capacity decreases. The output nickel electrode can be used.

  The method of filling the active material described above is not particularly limited. For example, after the active material paste is applied to the base material, the active material paste is dried and adhered to the convex portions of the base material. It is possible to adopt a method of removing the surface with a sharp blade.

  Also, after the paste containing the active material is applied to the base material, when the base material is passed, the base material is passed through a slit that is substantially the same as the apparent thickness of the base material. According to this, the above-described filling state can be achieved very efficiently.

  As a method for this, using a slit forming member elastically biased in the direction of narrowing the slit interval, the slit interval is set to be the same as the thickness of the base material, or slightly narrower than the thickness of the base material, What is necessary is just to let a base material pass between these slits. The elastically formed slit forming member includes a material having elasticity such as rubber, a member that can be pressed in the direction of narrowing the slit interval using a spring, etc., and a circle having both ends fixed by an elastic body. A columnar member or the like can be used. In such a slit forming member, by appropriately setting the strength of elasticity, when the base material passes between the slits, the interval between the slits can be made substantially the same as the thickness of the base material. For example, when a rubber slit forming member is used, the member is deformed in the direction of travel of the base material so that the slit forming member is in close contact with the base material, and the slit interval is substantially equal to the thickness of the base material. The same thickness can be used. In addition, in a slit in which a cylindrical member whose both ends are fixed by an elastic body is a slit forming member, when the base material passes between the slits, the interval between the cylindrical members spreads to substantially the same thickness as the base material. Thus, the columnar member is in close contact with the substrate.

  In particular, when a cylindrical member is used as the slit forming member, passage of the base material between the slits can be made smoother than when a slit forming member having a sharp cross section is used.

  By filling the concave portion of the base material with the active material by the above-described method, a nickel electrode for a secondary battery can be obtained according to a conventional method. For example, the base material filled with the active material may be dried and subjected to pressure processing by a flat plate pressure, a roller press or the like so as to have a predetermined thickness. The thickness of the nickel electrode after pressurization is not particularly limited, but is preferably about 0.4 mm or less in consideration of high output characteristics and active material utilization, and about 0.2 to 0.35 mm. It is more preferable that

  According to the above method, the concave portion of the base material is uniformly filled with the active material, so that the partial variation can be greatly reduced, and the electrode has stable performance. In addition, most of the active material is filled in the recesses of the base material, and the convex part of the base material has a small amount of active material on the surface and the surface of the base material is exposed or a small amount of active material is attached. It becomes. By adopting such a structure, it is possible to suppress a decrease in the utilization rate and dropout of the active material.

  The nickel electrode thus obtained is useful as an electrode for a secondary battery, and can be effectively used as an electrode for a nickel-hydrogen secondary battery.

In the nickel electrode obtained by the present invention, the concave portion of the base material is sufficiently filled with the active material, and the active material is less adhered to the convex portion of the base material. For this reason, there is little dispersion | variation in a capacity | capacitance, it becomes what was excellent in the output characteristic, and it becomes a long-life nickel electrode by little dropping of an active material. Further, since the punching metal having a small opening of 5 to 20% is used as the base material, the ratio of the active material in contact with the base material is increased, and a nickel electrode having a high output and a high utilization factor can be obtained.

  Moreover, since the base material used by this invention can be obtained by machining, it can be produced very cheaply compared with the base material used for a sintered nickel electrode or a foamed nickel electrode. Moreover, the active material can be filled by a simple coating method. Therefore, by using such a base material, it is possible to obtain a nickel electrode having a very high industrial value with low cost and high performance.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  Using a steel thin plate (thickness 30 μm) on which a nickel plating film having an average thickness of 2.5 μm was formed, a punching metal having a hole diameter of 0.5 mm and a degree of opening of 10% was prepared.

This punching metal was embossed to form an uneven portion to obtain an electrode substrate. In the substrate, the distance between the recesses was 0.8 mm, the apparent thickness of the substrate was 0.42 mm, and the weight per unit was 280 g / m ² .

  A plan view and a sectional view of the substrate are shown in FIG. In FIG. 1, 1 is a punching metal portion, 2 is a hole portion, 3 is a concave portion of embossed punching metal, and 4 is a convex portion.

  Nickel hydroxide powder whose surface was coated with 4% by weight of cobalt oxyhydroxide was used as an active material, and 92% by weight of nickel hydroxide and 4 parts by weight of cobalt hydroxide were further added to make 1% paste. A 2% fluororesin suspension and 2% polyethylene emulsion were added as binders to obtain a paste containing an active material.

  The paste obtained in this manner was passed through the substrate obtained by embossing, and the paste containing the active material was sufficiently applied to the substrate.

  On the other hand, two stainless steel cylinders with a diameter of 20 mm, which are fixed by soft rubber members at both ends, are installed in such a way that the outer peripheral surfaces face each other, and the slits are set so that the interval between the cylinders is substantially zero. The base material formed and coated with the active material paste by the above-described method was passed through the slits formed by the two cylinders so as to smooth the surface of the base material. The appearance of the cross-sectional view of the substrate in this state is shown in FIG. As shown in FIG. 2, an active material was filled in the concave portion, and a nickel electrode with less active material coating was obtained in the convex portion.

  Subsequently, after drying, it was pressed with a roller press to obtain an average thickness of 0.27 mm, and dried to obtain a paste-type nickel electrode. The nickel electrode thus obtained is defined as a nickel electrode a.

  In addition, after filling the base material with the active material in the same manner as described above, the active material layer adhering to the convex portion was removed, and the weight was determined to be 3.5% by weight of the total active material filling amount. there were.

  For comparison, an active material paste similar to that described above was applied to a punching metal made of a nickel-plated iron plate having a thickness of 0.04 mm and a porosity of 50%, and formed of a steel member. The paste was smoothed by passing between slits with a spacing of 0.38 mm. Subsequently, after drying, it was pressed with a roller press to obtain a nickel electrode having an average thickness of 0.27 mm. The nickel electrode thus obtained is referred to as a nickel electrode b.

  Further, a general-purpose foamed nickel electrode having a thickness of 0.27 mm obtained by filling the active material after adjusting the thickness was used as a nickel electrode c.

  Using the nickel electrodes a to c as positive electrodes, a battery having the following structure was produced.

  First, a 1% carboxymethylcellulose aqueous solution is added to an MmNiCoAlMn alloy, which is a known ternary hydrogen storage alloy obtained by adding Al, Mn, and Co to an MmNi alloy, to form a paste, which has a thickness of 50 μm and an opening degree of 50 % Perforated metal. This was passed between slits made of steel members set at an interval of 0.22 mm, dried, and then pressed with a roller press to obtain a negative electrode having a thickness of 0.18 mm. The actual capacity of this negative electrode was set to 17.0% with respect to the positive electrode capacity.

  As a separator, a polypropylene non-woven fabric having a thickness of 0.13 mm was used, and the electrode group was wound and inserted into a known SubC battery case. Further, as an electrolytic solution, an aqueous solution in which 25 g / liter of lithium hydroxide was dissolved in a 30% aqueous potassium hydroxide solution was added. After sealing, a battery was produced by a known tabless method.

  The battery obtained using the nickel electrode a by the above method is referred to as battery A, the battery obtained using the nickel electrode b as battery B, and the battery obtained using the nickel electrode c as battery C. All the batteries had a capacity of 2.82 Ah at 0.1 C discharge in a full charge.

  The batteries A, B, and C thus obtained were formed by repeating twice charging to 150% of the capacity at 0.1 C and discharging to 0.1 V at the final voltage of 0.1 C, and examining the discharge capacity. The charge was 120% of the discharge capacity, the ambient temperature was 30 ° C., and the measurement was performed in the vicinity of 40 cycles. Table 1 below shows the discharge current and discharge capacity values performed at an ambient temperature of 30 ° C. The final voltage was 0.9V for discharge currents up to 5A, and 0.7V for discharge currents higher than that.

  As is clear from Table 1, the battery A using the nickel electrode a had the same discharge characteristics as the battery C using the foamed nickel electrode c, and exhibited an excellent utilization rate. Regarding battery B, the capacity greatly decreases with the increase of the discharge current, the discharge capacity at 30 A discharge becomes less than half of 0.5 C discharge, and it can be said that the discharge is almost impossible.

  Next, for batteries A, B, and C, the relationship between the discharge current and the discharge average voltage (intermediate value) was determined. The results are shown in Table 2 below. In this case as well, charging was performed at 120% of the discharge capacity, the ambient temperature was 30 ° C., and the measurement was performed in the vicinity of 80 cycles.

  As shown in Table 2, the battery A had a higher output than the battery B. This is presumably due to the fact that in the nickel electrode a used in the battery A, the surface of the convex part of the base material has little active material and the concave part is filled with most of the active material.

  Thus, in a thin electrode with an emphasis on output characteristics, the nickel electrode a obtained by the method of the present invention exhibits the same characteristics as the conventional foamed nickel electrode c. In addition, it can be seen that the utilization rate and voltage drop at a large current are less than that of the nickel electrode b using a conventional punching metal base material, and the high discharge characteristics are excellent.

  Next, the lifetimes of the batteries A and B were confirmed. As conditions, charging and discharging were repeated at an ambient temperature of 25 ° C. under conditions of 110% charge of discharge capacity at 0.5 C and a terminal voltage of 0.9 V at 1 C. Table 3 below shows the relationship between the number of cycles and the capacity retention ratio when the capacity at 25 cycles is 100.

  As is clear from the above results, the battery A using the nickel electrode a has a much longer life than the battery B, and is about the same as the battery C using the expensive foamed nickel electrode c.

  This is because the nickel electrode b having a two-dimensional structure of punching metal as a base material has a concavo-convex structure obtained by embossing, whereas the distance between the base material and the active material layer is large and easily falls off. The nickel electrode a using a small amount of active material on the surface of the convex part and a large part of the active material filled in the concave part has a high degree of contact between the base material skeleton and the active material, This is thought to be due to the suppression of dropout.

  Using an iron thin plate (thickness 30 μm) plated with nickel with an average thickness of 2.5 μm, five types of punching metals with a hole diameter of 0.5 mm and a degree of opening of 0, 5, 15, 25 and 30% were produced.

  Using these punching metals, a nickel electrode was produced in the same manner as the nickel electrode a in Example 1. These nickel electrodes are respectively a nickel electrode d (opening degree 0%), a nickel electrode e (opening degree 5%), a nickel electrode f (opening degree 15%), and a nickel electrode g (opening degree 25%). Nickel electrode h (opening degree 30%).

  Next, a battery having the same configuration as the battery A of Example 1 was produced using these nickel electrodes. Assume that batteries D, E, F, G, and H respectively.

  For each of these batteries and the battery A obtained in Example 1, the discharge capacity and discharge average voltage (intermediate value) at 30 A discharge and the discharge capacity after 1000 cycles are shown in Table 4 below.

  As is clear from Table 4, the batteries A, D, and E using the base material with a porosity of 10% or less had a discharge average voltage higher than 1 V, and higher output than the batteries F, G, and H. . Further, the discharge capacity rapidly decreased when the degree of opening of the base material was 25% or more.

  From these results, it can be seen that the active material is more effectively used as the porosity of the base material becomes lower.

  Further, the cycle characteristics are almost the same as the trends of the discharge capacity and the average discharge voltage, but the characteristics are low in the battery D in which the opening degree of the base material is 0%. This is considered to be due to the fact that the active material retention characteristics are greatly reduced if there is no opening.

  From the above results, it is considered that the range of the porosity of the base material is preferably about 5 to 15%.

  Five types of punched metal with a hole diameter of 0.5 mm and an opening degree of 10% were used using five types of nickel-plated iron plates with a thickness of 20 μm, 25 μm, 40 μm, 50 μm and 60 μm, which were plated with an average thickness of 2.5 μm. Produced.

  Using these punching metals, a nickel electrode was produced in the same manner as the nickel electrode a in Example 1. These nickel electrodes are respectively a nickel electrode i (thickness 20 μm), a nickel electrode j (thickness 25 μm), a nickel electrode k (thickness 40 μm), a nickel electrode l (thickness 50 μm), and a nickel electrode m (thickness 60 μm). ).

  A battery having the same configuration as that of the battery A of Example 1 was produced using each of these nickel electrodes. Assume that batteries I, J, K, L, and M, respectively.

  Table 5 shows the discharge capacity and discharge average voltage (intermediate value) at the time of 30 A discharge and the discharge capacity after 1000 cycles for each of these batteries and the battery A obtained in Example 1.

  From Table 5, it can be seen that the discharge capacity and the discharge average voltage increase as the substrate thickness increases and increase in output, but decrease when the substrate thickness exceeds 50 μm. This is because when the substrate thickness is increased, the electrical resistance of the substrate is reduced and the voltage drop during high output discharge is reduced. However, if the substrate is too thick, the volume of the substrate is increased and the porosity of the electrode is reduced. This is considered to be due to the deterioration of the high rate discharge characteristics.

  In addition, the cycle characteristics were greatly reduced when the substrate thickness exceeded 50 μm.

  From the above results, it is considered that the base material thickness is preferably about 20 to 50 μm.

The top view and sectional drawing of the base material for electrodes used in Example 1. FIG. Sectional drawing of the base material of the state filled with the active material.

Explanation of symbols

1 Punching metal 2 Hole part 3 Concave part 4 Convex part

Claims (10)

A nickel electrode for a secondary battery comprising an electrode base material and an electrode active material made of a punching metal having a porosity of 5 to 20% and a thickness of 20 to 50 μm , wherein the irregularities are formed by embossing, A nickel electrode for a secondary battery, wherein a concave portion of the material is filled with an active material, and the convex portion of the base material is in a state where a surface is exposed or an active material is attached. 2. The nickel electrode for a secondary battery according to claim 1, wherein the amount of the active material adhering to the convex portion of the base material is 10 wt% or less of the total amount of the active material. The nickel for secondary batteries according to claim 1 or 2, wherein the surface of the convex portion of the base material, which is obtained by filling the base material with the active material and then removing the active material attached to the base material surface, is exposed. very. The nickel electrode for a secondary battery according to any one of claims 1 to 3, wherein the electrode base material is mechanically embossed to form an uneven portion on the punching metal. The nickel electrode for a secondary battery according to any one of claims 1 to 4, wherein the punching metal has a porosity of 5 to 15%. Billing apparent thickness of the punching metal of d Nbosu processed by uneven portion formed electrode substrate 0.2 to 0.5 mm, the weight per unit area of substrate ranges from 200-500 g / ^{m 2} The nickel electrode for secondary batteries in any one of claim | item 1 -5. The nickel electrode for a secondary battery according to any one of claims 1 to 6, wherein the electrode active material is spherical nickel hydroxide whose surface is coated with a cobalt compound. A paste containing an electrode active material is applied to an electrode substrate made of a punching metal having a porosity of 5 to 20% and a thickness of 20 to 50 μm where uneven portions are formed by embossing, and then passes through the substrate. A method for producing a nickel electrode for a secondary battery, wherein the substrate is passed between slits having substantially the same spacing as the apparent thickness of the substrate and then pressurized. When passing the substrate, the method of passing the substrate between the slits that are substantially the same as the apparent thickness of the substrate is the same interval as the thickness of the substrate or an interval narrower than the thickness of the substrate. The method for producing a nickel electrode according to claim 8, wherein the substrate is passed between slits formed by slit forming members that are set and elastically biased in the direction of narrowing the slit interval. A slit formed by an elastically biased slit forming member, a slit formed by an elastic material, a slit formed by a member that can be pressed in the direction of narrowing the slit interval using a spring The method for producing a nickel electrode according to claim 8 or 9, wherein the nickel electrode is a slit formed by a cylindrical member having both ends fixed by an elastic body.

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