JP2003197186A - Method of manufacturing for non-sintered cadmium electrode, alkaline storage battery using this electrode, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a non-sintered cadmium capable of forming crystal of dense cadmium hydroxide at a low cost without using high temperature alkaline solution and strictly conducting temperature control different from an existing method. <P>SOLUTION: An electrode core body coated with active material paste is immersed in an alkaline solution (for example NaOH solution) of relatively high viscosity (9 mPa/s) kept at 25°C, for about 20 minutes to conduct first step hydration treatment, and then immersed in an alkaline solution (for example NaOH solution) of relatively low viscosity (4 mPa/s) kept at 25°C, for about 20 minutes to conduct second step hydration treatment. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a non-sintered cadmium electrode used in an alkaline storage battery such as a nickel-cadmium (Ni-Cd) storage battery, an alkaline storage battery using this electrode, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Non-sintered cadmium electrodes used in alkaline storage batteries such as Ni-Cd storage batteries are generally manufactured by applying a paste containing cadmium oxide to a conductive core. It is required to manufacture an electrode substrate having high mechanical strength. In particular, in the step of winding the electrode, the electrode needs high mechanical strength.

Therefore, there is known a technique for securing the mechanical strength of an electrode by applying a paste containing cadmium oxide to a conductive core, and then hydrating the cadmium oxide to convert it into crystals of cadmium hydroxide. Has been.
By the way, when the hydration treatment is carried out in a low temperature alkaline solution, a reaction for an extremely long time is required, which causes problems such as production efficiency.

On the other hand, if an alkaline solution is simply heated at a high temperature in one alkaline solution tank to promote the reaction, hexagonal β-type cadmium hydroxide crystals having a small specific surface area and a large particle size are obtained. Are deposited in large numbers. In the β-type crystal formed by this method, the gap between the crystals is open, so that the filling degree of cadmium hydroxide becomes low and the strength of the electrode substrate becomes weak. Further, according to this step, since the alkaline solution rapidly permeates into the layer, it becomes difficult for gas to escape from the layer, the frequency of occurrence of blisters increases, and the electrode performance deteriorates.

From the above problems, for example, in Japanese Patent Laid-Open No. 5-217577, after coating cadmium oxide on a conductive core,
First, hydrate in an alkaline solution at 10 to 50 ° C, then
A method of hydrating in an alkaline solution at ~ 90 ° C is disclosed. According to the method of hydration treatment while controlling the temperature of the alkaline solution in this manner, crystals of γ-type cadmium hydroxide having a high specific surface area and a high density of acicular crystals are formed abundantly on the substrate surface. The mechanical strength of the electrode substrate can be increased. It is also said that it has an effect of suppressing the generation of blisters (expanded voids) caused by the active material made of a cadmium compound swelling or partial peeling from the conductive core.

[0006]

However, according to the above-mentioned prior art, in order to carry out a chemical reaction for changing cadmium oxide into cadmium hydroxide, a plurality of thermoregulators for temperature adjustment are arranged, and high temperature and different temperatures are set. A kept alkaline solution bath is required. Therefore, the size of the device becomes large, and there is a costly undesirable aspect.

As described above, there is still room for improvement in order to obtain a good non-sintered cadmium electrode. The present invention has been made in view of such problems,
The purpose is to use a high temperature alkaline solution as in the past,
It is an object of the present invention to provide a method for producing non-sintered cadmium capable of forming a dense cadmium hydroxide crystal at low cost without strict temperature control.

[0008]

In order to solve the above problems, the present invention provides a cadmium oxide layer forming step of forming a cadmium oxide layer by applying a paste containing cadmium oxide to a conductive core body, and the cadmium oxide. The conductive core having a layer formed is immersed in a first alkaline solution bath, and a first hydration treatment step of hydrating cadmium oxide and a first hydration treatment step are performed to form the cadmium oxide layer. The conductive core is immersed in a second alkaline solution tank having a lower viscosity than the first alkaline solution tank, and has a second hydration treatment step of hydrating cadmium oxide, and the first hydration treatment step And in the second hydration step,
Both the temperature of the alkaline solution in the first and second alkaline solution tanks was set to a temperature range of 10 ° C to 35 ° C.

According to this production method, first, in the first hydration treatment step, since the viscosity of the alkaline solution used is relatively high, the permeation rate into the cadmium oxide layer is small. Therefore, the cadmium oxide region near the surface of the paste applied to the conductive core changes to a hard layer (layer with high tensile strength) made of cadmium hydroxide crystals without generating blisters at this portion.

Then, in the second hydration treatment step, the alkaline solution having a relatively low viscosity permeates into the inside of the cadmium hydroxide layer through the interstices, and the crystallization is performed here as well. At this time, since the alkaline solution used has a low viscosity, the permeation rate into the cadmium oxide layer is high. Therefore, it becomes difficult for gas to escape from the cadmium oxide layer. On the surface of the layer, a layer of cadmium hydroxide having a high tensile strength formed in the first hydration treatment step has already been formed, and this layer functions to uniformly spread the reacting paste to the conductive core. Make up. This prevents the paste between the conductive core body and the cadmium hydroxide layer from swelling or floating from the conductive core body, and suppresses the occurrence of blisters.

Further, in the present invention, since the reaction temperature in the hydration reaction may be relatively low at 10 ° C. to 35 ° C., a large-scale device for maintaining the high reaction temperature by heating is required as in the prior art. There is also an effect that it can be carried out by a simple method. Furthermore, in the present invention, by changing the type of the alkaline solution used for the hydration treatment, the crystal form of cadmium hydroxide changes to β-type or γ-type. Since the formed cadmium hydroxide layer and the cadmium hydroxide crystals formed near the conductive core intermingle with each other to form a high-density crystal structure, an electrode with good mechanical strength is obtained. You can

Specifically, if a potassium hydroxide solution is used as the alkaline solution, β-type crystals are obtained, and if a sodium hydroxide solution is used, γ-type crystals are obtained. Further, the present invention is
A coating step of applying a paste containing cadmium oxide to a conductive core body, and a preliminary hydration treatment step of prehydrating cadmium oxide by immersing the conductive core body on which the cadmium oxide layer is formed in a first alkaline solution tank And, after passing through a preliminary hydration treatment step, while immersing the conductive core body on which the cadmium oxide layer is formed in a second alkaline solution tank having a lower viscosity than the first alkaline solution tank, a charge / discharge treatment for charging / discharging A hydration treatment step, and in the preliminary hydration treatment step and the charge-discharge hydration treatment step, the alkaline solution temperatures in the first and second alkaline solution tanks are both set.
A method for producing a non-sintered cadmium electrode in which the temperature range is set to 10 ° C to 35 ° C may be used. With this method, almost the same effects as the above effects can be obtained.

As the viscosity of the alkaline solution, the viscosity of the alkaline solution in the first alkaline solution tank is 9 mPa.s.
It is preferable that the viscosity of the alkaline solution in the second alkaline solution tank is 3 mPa · s or more and 6 mPa · s or less.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION 1. Embodiment 1 1-1. Configuration of Alkaline Storage Battery FIG. 1 shows a cylindrical alkaline storage battery (Ni-Cd storage battery) which is an application example of the non-sintered cadmium substrate of the present invention. FIG. The first embodiment shows an example in which the non-sintered cadmium substrate of the present invention is used for the negative electrode 2.

The alkaline storage battery has a cylindrical can 6 of AA size, and an electrode group 4 in which a positive electrode 1 and a negative electrode 2 are spirally wound around a separator 3 and an electrode group 4 concerned.
This is a configuration in which the electrolytic solution impregnated in and the like is stored. Although an alkaline solution is used as the electrolytic solution, an aqueous solution containing potassium hydroxide as a main component is used here as an example. Positive electrode
Reference numeral 1 denotes a surface obtained by sintering Ni powder on the surface of a conductive core (punching metal) made of Ni-plated Fe, which is connected to a positive electrode terminal 13 via a positive electrode current collector 7 and the sealing body 12. ing.

The negative electrode 2 is formed by forming cadmium hydroxide on the surface of a conductive core (punching metal) made of Ni-plated Fe, and is connected to the inner bottom surface of a cylindrical can 6 which also functions as a negative electrode terminal by a negative electrode current collector 5. Has been done. A sealing plate 12 is arranged in the opening at the upper end of the can 6 via a gasket 11, and a positive electrode terminal 13 is mounted so as to cover the central opening 14 of the sealing plate 12. Between the sealing plate 12 and the positive terminal 13, the valve plate is directed upward.
8, the pressing plate 9 and the coil spring 10 are placed in this order, and the valve plate 8 and the pressing plate 9 are pressed around the central opening 14 by the elastic force of the coil spring 10 to act as a safety valve. It is supposed to do.

Here, the first embodiment is characterized by the method of manufacturing the negative electrode 2. The method for manufacturing the negative electrode will be described below. 1-2. Manufacturing method of negative electrode (non-sintered cadmium electrode) 1-2-a. Cadmium oxide layer forming step 80% by mass of cadmium oxide powder and metallic cadmium powder
An active material powder consisting of 20% by mass, a methylcellulose solution and nylon fibers are kneaded to prepare an active material paste. This active material paste is applied to the surface of a conductive core (punching metal) made of Ni-plated Fe and having a thickness of about 0.08 mm.
Apply so that the thickness on one side is 30 μm. After this, 8
Dry for 15 minutes using a 0 ° C dryer.

As a result, a cadmium oxide layer is formed on the surface of the conductive core. 1-2-b. Hydration treatment step Here, the electrode core body on which the cadmium oxide layer is formed is divided into two steps for hydration treatment, and the cadmium component in the paste is chemically changed to change cadmium hydroxide. obtain. For this purpose, two kinds of alkaline solutions having different viscosities are used, and the hydration treatment is performed from the outside of the paste toward the conductive core side. This step is the most characteristic part of the first embodiment.

Here, FIGS. 2A to 2E are electrode cross-sectional views showing a process of manufacturing the negative electrode (non-sintered cadmium electrode) in the present embodiment. That is, the electrode core body coated with the above paste ((a) in the figure) is immersed in an alkaline solution (for example, NaOH solution) of relatively high viscosity (9 mPa · s) kept at 25 ° C for about 20 minutes, Perform a one-step hydration process. In the hydration treatment, the temperature of the alkaline solution is around room temperature (10
The temperature range is from ~ 35 ° C).

In this first stage hydration treatment, the alkali solution having a high viscosity to be used has a low permeation rate into the cadmium oxide layer, so that blister hardly occurs. Further, since it is not necessary to permeate into the layer so deeply, it is sufficient to permeate only into the region near the surface of the cadmium oxide layer. At this time, about 20 minutes is sufficient for the penetration time into the alkaline solution. As a result, as shown in FIG. 3D, a hard layer made of cadmium hydroxide crystals having a thickness of about 5 to 10 μm is formed on the paste surface.

Subsequently, after conducting the first stage hydration treatment as described above, the conductive core with a paste in which cadmium hydroxide was partially formed by the hydration treatment was kept at 25 ° C. Low viscosity (4mPa · s) alkaline solution (eg NaOH
Soak for about 20 minutes. The temperature of the alkaline solution at this time may also be set near room temperature (temperature range of 10 to 35 ° C.). Further, the viscosity of the alkaline solution can be adjusted by the alkaline concentration or the temperature.

In the second stage hydration treatment, the low-viscosity alkaline solution permeates between the conductive core and the cadmium hydroxide layer formed in the cadmium oxide layer side region, and the remaining paste is removed. Changes to cadmium hydroxide (Fig. (E)). At this time, the layer of the cadmium hydroxide crystals previously formed on the surface of the paste has a function of uniformly extending the paste in reaction with the alkaline solution with respect to the conductive core. This action prevents the paste in the vicinity of the conductive core from swelling or floating from the conductive core. That is, the excellent effect of suppressing the generation of blisters is exhibited.

As described above, according to the hydration treatment step of the present production method, the required time is short and the occurrence of blisters can be suppressed. In addition, in the present production method, since the hydration treatment is performed in two stages, generation of blisters is suppressed, and peeling of the active material layer from the core body is suppressed. Therefore, it is possible to manufacture an electrode having good mechanical strength. Will be realized.

Further, since the hydration treatment is carried out in two steps in this production method, the crystal arrangement of the cadmium hydroxide formed in the first step and the cadmium hydroxide formed in the second step are hydrated. Since the crystal arrangements are different and they are intricate with each other, a dense crystal structure can be obtained. This high crystal density allows the production of electrodes with good mechanical strength. In this production method, the crystal form of cadmium hydroxide can be changed to β type or γ type by changing the type of the alkaline solution used for the hydration treatment (for example,
In the NaOH solution, β-type, and in the KOH solution, γ-type), a high-density crystal structure is formed in any of these crystal forms, and thus the same effect is obtained.

Further, in the present production method, the temperature of the alkaline solution used for the hydration treatment may be relatively low as 10 ° C. to 35 ° C. (that is, the temperature is not particularly controlled, and the alkaline solution which is almost equal to the room temperature can be directly used. You may handle it). Therefore, unlike the above-mentioned conventional technology, since an alkaline solution bath whose temperature is controlled to a high temperature is not required, the cost for equipment such as a thermo controller and solution heating is fundamentally reduced, and excellent electrodes can be relatively easily prepared. It becomes possible to manufacture it.

As described above, the negative electrode 2 of the present embodiment
Will be obtained. 1-2-c. Matters concerning hydration treatment In comparison with the manufacturing method of the embodiment, the conductive core body with an active material paste shown in FIG. 2 (a) has a relatively high viscosity (9 mPa · s).
If you try to hydrate by just immersing it in the above alkaline solution (for example, NaOH solution) ((b) in the same figure), it is possible to obtain crystals of cadmium hydroxide, but a highly viscous alkaline solution Since it is difficult to penetrate into the entire paste, there is a problem that the reaction time required for the hydration treatment takes a long time (several hours), which is not desirable in practice.

Further, the conductive core body with the active material paste shown in FIG. 2 (a) is about to be hydrated just by immersing it in an alkaline solution (for example, NaOH solution) having a relatively low viscosity (3 mPa · s or less). For example, the alkaline solution immediately penetrates into the paste near the conductive core, and cadmium hydroxide is generated almost at the same time throughout the paste (Fig. (C)). At this time, the paste in the vicinity of the conductive core tends to swell in the direction away from the conductive core, which easily induces blisters, which is also undesirable.

From the above, in order to obtain the effect of this embodiment, the hydration treatment of the paste is also performed in the first step with a highly viscous alkaline solution, and a layer of cadmium hydroxide is formed on the surface of the paste. Therefore, in the second stage,
It is necessary to hydrate the remaining paste in a low viscosity alkaline solution. 1-3. Example (Hydration Treatment) Here, a non-sintered cadmium electrode was actually produced based on the method for producing a negative electrode in the first embodiment, and a performance measurement experiment was performed on the obtained electrode of the example. I do. In accordance with this, the electrode of the comparative example was also manufactured.

In the production of these electrodes, the viscosity of the alkaline solution to which the active material paste was subjected to each of the first and second hydration treatments was changed within the range of 3 mPa · s to 15 mPa · s. Moreover, the temperature of the alkaline solution was changed in the range of 5 ° C to 35 ° C. Two kinds of alkaline solutions, NaOH solution and KOH solution, were used, and the difference in the characteristics of each solution on the hydration treatment was investigated.

The results of measuring the hydration rate and the number of blisters generated for the electrodes of Examples and Comparative Examples produced under the conditions shown in Table 1 among the conditions in the above range are shown in the same table.
In the table, the alkaline solutions used for the first and second hydration treatments are referred to as the first alkaline solution and the second alkaline solution, respectively.

[0031]

【table 1】 As is clear from Table 1, the viscosity of the first alkaline solution is 9 mPa
・ S〜15mPa ・ s, the viscosity of the second alkaline solution is 3mPa ・ s〜6mP
In Examples 1 to 5 in the range of as, the hydration rate is at least
It was found that a high value of 87% or more was obtained. Also,
Regarding the number of blister generation, the example also exhibits excellent performance of being suppressed to 6 pieces / 10 cm ² or less, and it is considered that the high performance of the present invention is exhibited.

On the other hand, a comparative example shows that in Comparative Example 1, the number of blisters generated was as small as 3/10 cm ² , but the hydration rate was as low as 73%, indicating that cadmium hydroxide was sufficient. You can see that you cannot get it. That is, in Comparative Example 1,
Even if the number of blisters is small, the actual amount of active material (amount of cadmium hydroxide) is small, so it seems that the electrode performance is not very good. On the other hand, in Comparative Examples 2 and 3,
Hydration rate is 95% or more, but the number of blister is 17 / 10cm ²
The above has also occurred, and clearly does not reach the performance of the embodiment.

2. Second Embodiment 2-1. Configuration of Alkaline Storage Battery The configuration of the alkaline storage battery used in the second embodiment is the same as that of the first embodiment, but the manufacturing method of the negative electrode used in this is different. The method for manufacturing the negative electrode will be described below.

2-2. Manufacturing Method of Negative Electrode (Non-Sintered Cadmium Electrode) 2-2-a. Cadmium Oxide Layer Forming Step First, the active material paste was applied in the same manner as in Embodiment 1 above. Strip cadmium electrode of several hundred meters in length,
A strip-shaped nickel plate having the same size as the counter electrode was wound with a separator separating the electrodes interposed therebetween to form an electrode group.

2-2-b. Prehydration Treatment Step and Charge / Discharge Chemical Treatment Step Subsequently, the above electrode group was immersed in the first alkaline solution for 2 hours for prehydration treatment. Then, instead of the second hydration treatment step,
As a chemical conversion treatment, dip it in a second alkaline solution and apply 1 / 8It (I
After being charged with a current of (t: electrode plate capacity) for 10 hours, it was discharged with a current of 1/6 It to −1.0 V against the nickel plate of the counter electrode. The temperature of the second alkaline solution is controlled by a simple device.

2-3. Example (Chemical conversion treatment) Here, a non-sintered cadmium electrode was actually produced based on the method for producing the negative electrode in the above-mentioned Embodiment 2, and the performance of the electrode of the obtained example was examined. Conduct a measurement experiment. In accordance with this, the electrode of the comparative example was also manufactured. In the production of these electrodes, the viscosity of the alkaline solution was changed within the range of 3 mPa · s to 15 mPa · s as in the hydration treatment. Moreover, the temperature of the alkaline solution was changed in the range of 5 ° C to 35 ° C. Furthermore, two kinds of alkaline solutions, NaOH solution and KOH solution, were used, and the difference in the characteristics that each solution gives to the chemical conversion treatment was investigated.

Among the conditions in the above range, the results of measuring the number of blister occurrences for the electrodes of Examples and Comparative Examples produced under the conditions shown in Table 2 are shown in the same table.

[0038]

[Table 2] As can be seen from the table, the number of blisters generated in the example is suppressed lower than that in the comparative example. It can be considered that this is because the chemical conversion treatment has the same effect as the effect of the hydration treatment according to the first embodiment of the present invention. That is, in the examples, first, in a preliminary hydration treatment, a layer of strong cadmium hydroxide is formed on the paste surface by an alkaline solution having a relatively high viscosity, and the paste between this layer and the conductive core is reinforced. It becomes a structure. Then, in the subsequent chemical conversion treatment, the alkaline solution having a relatively low viscosity penetrates into the remaining paste, and cadmium hydroxide having a complicated crystal structure is formed.

As a result, the active material of cadmium hydroxide having a dense crystal structure can be obtained in the examples, and it is considered that the number of blister generation is reduced as compared with the comparative example. From the data of these Examples, it can be said that a highly viscous solution of 9 mPa · s or more and 15 mPa · s or less is desirable as the alkaline solution in the first stage hydration treatment or prehydration treatment. Also, as the alkaline solution in the second stage hydration treatment or chemical conversion treatment, 3 mPa ・ s or more and 6 mPa ・ s
The following low viscosity solutions are considered suitable.

[0040]

As is apparent from the above, the present invention provides a cadmium oxide layer forming step of forming a cadmium oxide layer by applying a paste containing cadmium oxide to a conductive core, and forming the cadmium oxide layer. The conductive core was immersed in a first alkaline solution bath, and the first hydration treatment step of hydrating the cadmium oxide layer surface side region, and after passing through the first hydration treatment step, the cadmium oxide layer was formed. The conductive core was immersed in a second alkaline solution tank having a lower viscosity than the first alkaline solution tank, and has a second hydration treatment step of hydrating the conductive core side region of the cadmium oxide layer, In the first hydration treatment step and the second hydration treatment step, a non-sintering type in which the temperature of the alkaline solution in the first and second alkaline solution tanks is both set to a temperature range of 10 ° C to 35 ° C Since it is a manufacturing method for cadmium electrodes,
In the first hydration treatment step, cadmium oxide in the vicinity of the surface of the paste applied to the conductive core reacts with the alkaline solution having a relatively high viscosity, and a layer of cadmium hydroxide is formed at this portion.

Then, in the second hydration treatment step, the alkaline solution having a relatively low viscosity penetrates into the inside of the cadmium hydroxide layer through the interstices, and finally all the paste becomes cadmium hydroxide. At this time, a layer of cadmium hydroxide has already been formed on the paste surface, and this layer functions to uniformly spread the paste during reaction with respect to the conductive core, so that the occurrence of blisters is suppressed. Is played.

Further, the reaction temperature in the hydration reaction is from 10 ° C to
Since it may be relatively low at 35 ° C., it can be carried out by a simple method without requiring a large-scale device for heating and maintaining a high reaction temperature as in the past.

[Brief description of drawings]

FIG. 1 is a sectional perspective view of a cylindrical alkaline storage battery according to a first embodiment of the present invention.

FIG. 2 is an electrode cross-sectional view showing a manufacturing process of a non-sintered cadmium substrate (negative electrode).

[Explanation of symbols]

1 Positive electrode 2 Negative electrode 3 separator 4 electrode group 6 cans

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kenji Ogasawara             2-5-3 Keihan Hondori, Moriguchi City, Osaka Prefecture             Within Yo Denki Co., Ltd. F term (reference) 5H028 AA05 BB03 BB06 BB10 BB14                       BB15 HH01 HH03 HH08                 5H050 AA19 BA13 CA03 CB14 FA18                       GA02 GA10 GA13 GA14 GA15                       GA18 GA23 GA26 GA27 HA10                       HA12 HA14 HA20

Claims (9)

[Claims] 1. A cadmium oxide layer forming step of applying a paste containing cadmium oxide to a conductive core to form a cadmium oxide layer, and immersing the conductive core having the cadmium oxide layer formed in a first alkaline solution tank. Then, a first hydration treatment step of hydrating cadmium oxide, and after passing through the first hydration treatment step, the conductive core having the cadmium oxide layer formed thereon has a viscosity lower than that of the first alkaline solution tank. A second hydration treatment step of immersing the second cadmium oxide in a second alkaline solution bath to hydrate the cadmium oxide, and a method for producing a non-sintered cadmium electrode. 2. A cadmium oxide layer forming step of forming a cadmium oxide layer by applying a paste containing cadmium oxide to a conductive core, and immersing the conductive core on which the cadmium oxide layer is formed in a first alkaline solution tank. Then, the first hydration treatment step of hydrating the cadmium oxide layer surface side region, and after passing through the first hydration treatment step, the conductive core body on which the cadmium oxide layer is formed is obtained from the first alkaline solution tank. And a second hydration treatment step of hydrating the conductive core side region of the cadmium oxide layer by immersing it in a second alkali solution tank having a low viscosity, and a method for producing a non-sintered cadmium electrode. 3. In the first hydration treatment step and the second hydration treatment step, both the temperature of the alkaline solution in the first and the second alkaline solution tank is set to a temperature range of 10 ℃ to 35 ℃. 3. The method for producing a non-sintered cadmium electrode according to claim 1 or 2. 4. The immersion time in the alkaline solution in the first hydration treatment step and the second hydration treatment step is 20 minutes or less, respectively, according to any one of claims 1 to 3. Manufacturing method of sintered cadmium electrode. 5. A cadmium oxide layer forming step of forming a cadmium oxide layer by applying a paste containing cadmium oxide to a conductive core, and immersing the conductive core having the cadmium oxide layer formed in a first alkaline solution tank. And a preliminary hydration treatment step of preliminarily hydrating cadmium oxide, and after passing through the preliminary hydration treatment step, the conductive core having the cadmium oxide layer formed thereon has a second viscosity lower than that of the first alkaline solution tank. And a charge-discharge chemical conversion treatment step of performing charge-discharge treatment while being dipped in the alkaline solution bath of 1. above, the method for producing a non-sintered cadmium electrode. 6. In the preliminary hydration treatment step and the charge-discharge chemical conversion treatment step, both of the alkali solution temperatures in the first and second alkaline solution baths are set to a temperature range of 10 ° C. to 35 ° C. 6. The method for producing a non-sintered cadmium electrode according to claim 5. 7. The viscosity of the alkaline solution in the first alkaline solution tank is 9 mPa · s or more and 15 mPa · s or less, and the viscosity of the alkaline solution in the second alkaline solution tank is 3 mPa · s or more and 6 mP.
The method for producing a non-sintered cadmium electrode according to any one of claims 1 to 5, characterized in that it is a · s or less. 8. An alkaline storage battery comprising a nickel positive electrode, a negative electrode, a separator separating these positive and negative electrodes, and an alkaline electrolyte in a can, wherein the negative electrode is any one of claims 1 to 7. An alkaline storage battery, which is the non-sintered cadmium electrode according to 1. 9. A method of manufacturing an alkaline storage battery in which a nickel positive electrode manufactured through a positive electrode manufacturing process and a negative electrode manufactured through a negative electrode manufacturing process are opposed to each other with a separator interposed between them and housed in a can together with an alkaline electrolyte. A method for producing an alkaline storage battery, characterized in that the negative electrode producing step comprises the method for producing a non-sintered cadmium electrode according to any one of claims 1 to 7.