JP3042043B2 - Nickel positive electrode for alkaline storage battery and nickel-hydrogen storage battery using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a nickel positive electrode for an alkaline storage battery and a nickel-hydrogen storage battery using the same.
More specifically, the present invention relates to a nickel positive electrode for an alkaline storage battery in which an active material mainly composed of nickel oxide is supported by a conductive core material, and a nickel-hydrogen storage battery using the same.

[0002]

2. Description of the Related Art As a secondary battery, a nickel-cadmium storage battery (hereinafter referred to as a nickel-cadmium battery), which is a lead storage battery or an alkaline storage battery, is widely used at present. Lead-acid batteries, is inexpensive, generally energy <br/> conservation over density per unit weight (Wh / kg) is low, there is a problem in cycle life and the like, and suitable as a power supply for portable equipment compact and lightweight I can't say. On the other hand, nickel-cadmium batteries, energy density of the unit weight and volume per compared with lead-acid batteries is high and excellent reliability such as cycle life, are widely used as a power source for each of the portable apparatus.

[0003] However, in recent years, portable devices have become increasingly expensive.
Since the load on the battery with the added value is increasing, and further secondary battery of high energy density is strongly desired as a power source for portable devices.

Therefore, in the field of nickel-cadmium batteries, the capacity of conventional nickel-cadmium batteries using sintered nickel positive electrodes has been increasing, and foamed metal nickel positive electrodes having a higher capacity by 30 to 60% have been used. Nicad batteries have also been developed. Further, a nickel-hydrogen storage battery using a hydrogen storage alloy for a negative electrode having a higher capacity than a nickel-cadmium battery has been developed. This nickel-metal hydride battery has twice or more the capacity of a nickel-cadmium battery using a sintered nickel positive electrode.

[0005] These high-capacity alkaline storage battery, in order to improve the <br/> energy density of the positive electrode as a positive electrode, and Shoyuishiki nickel porous body, foamed three-dimensional having a 90% porosity A nickel porous body or a nickel fiber porous body filled with nickel hydroxide powder at a high density is used. As a result, energy of the conventional sintered nickel positive electrode
With respect to density in the range of 400~450mA h / cm ^3,
The latest sintered nickel positive electrode is 450-500mA
h / cm ³ , and that of the foamed nickel positive electrode increased to 550-650 mAh / cm ³ .

[0006] However, Shoyuishiki nickel porous body, foamed nickel porous body, the positive electrode filled at a high density nickel hydroxide to nickel fiber porous body in, energy at around room temperature
Density is high, there is a problem that energy density is lowered in high temperature atmosphere. Therefore, it is difficult to utilize the features of high <br/> energy density in a wide temperature range.

The reason for this is that, during charging in a high-temperature atmosphere, an oxygen generating reaction is likely to occur simultaneously with a charging reaction to nickel hydroxide. That is, the oxygen generation overvoltage at the positive electrode decreases, the nickel hydroxide is not sufficiently charged to the nickel oxyhydroxide, and the utilization rate of the nickel hydroxide decreases.

In order to solve this problem, Japanese Patent Laid-Open Publication No.
No. 04565 proposes a method of adding cadmium oxide powder or cadmium hydroxide powder to the positive electrode, and a method of including cadmium oxide inside nickel hydroxide powder. According to these proposals, to improve the utilization of nickel hydroxide under a high temperature atmosphere, can be suppressed to some extent the reduction in the energy density in the high temperature atmosphere.

[0009]

However, with the amount of cadmium oxide added in the above proposal, the utilization rate of nickel hydroxide in a high-temperature atmosphere is about 80%. In addition, it is necessary to increase the amount of cadmium oxide added to the inside of nickel hydroxide or the nickel positive electrode. By increasing the amount of cadmium oxide in this way, the utilization rate of nickel hydroxide in a high-temperature atmosphere can be increased to about 90%. %.

In recent years, nickel-hydrogen storage batteries that do not contain cadmium, which is a heavy metal, have attracted attention from the viewpoint of environmental issues. However, when cadmium and cadmium powder are removed from nickel hydroxide and the positive electrode, naturally, the utilization rate of nickel hydroxide in a high-temperature atmosphere becomes 50%.
There is a problem that it is reduced to about 60%.

The present invention provides a nickel positive electrode for an alkaline storage battery having an excellent nickel hydroxide utilization rate under a wide temperature atmosphere and a discharge capacity under a wide temperature atmosphere without containing heavy metals such as cadmium, with a simple structure. An object is to provide an excellent nickel-metal hydride storage battery.

[0012]

A nickel positive electrode for an alkaline storage battery according to the present invention is a nickel positive electrode comprising an active material mainly composed of nickel oxide supported by a conductive core material, wherein yttrium, indium, it is characterized in that by adding at least one of antimony Contact <br/> spare compounds of beryllium.

The above yttrium, indium, antimony
The compound of emissions Contact and _{beryllium, Y 2 O 3, Y (} O
_{H) 3, In 2 O 3} , In 2 O, In 2 O 3 · H 2 O, Sb 2 O
_{3, Sb 2 O 4, B} eO and Be (OH) ₂ is preferably used.

The above yttrium, indium, antimony
Amount of emissions Contact and compounds of beryllium is preferably 0.1 to 5 parts by weight with respect to nickel oxide 100 parts by weight.

It is desirable that at least one of cobalt and cobalt oxide and / or at least one of cadmium oxide and zinc oxide be further added to the active material.

In this case, the cobalt oxide is cobalt hydroxide and the zinc oxide is zinc oxide, and the weight ratio is nickel hydroxide: cobalt: cobalt hydroxide: zinc oxide:
(At least one of yttrium, indium, antimony Contact and compounds of beryllium) = 100: 4 to 1
The ratio is preferably from 8: 0 to 10: 0 to 10: 0.1 to 5.

Preferably, the conductive core material is a three-dimensional porous body of any one of a foamed nickel porous body, a sintered nickel porous body, and a punched metal.

Alternatively, it is preferable that the conductive core material is a flat plate, and is a nickel foil or an iron foil plated with nickel.

The foamed nickel porous body desirably has an areal density of 200 to 700 g / m ² .

The nickel oxide is spherical nickel hydroxide, or cadmium, zinc, lead, silver, indium,
At least one of yttrium, magnesium, iron, cobalt and manganese as a solid solution inside the crystal
Desirably, it is nickel hydroxide containing about 7%.

When the nickel oxide is spherical nickel hydroxide, the nickel hydroxide powder has an average particle size of 1 to 20 μm and a tap density of 1.9 g / g.
It is desirable that the particles are spherical particles of cm ³ or more. In this case, it is preferable that the BET specific surface area measured by nitrogen gas adsorption is set to 10 to 30 m ³ / g.

The active material desirably contains a powder having water repellency .

Further, the nickel-metal hydride storage battery of the present invention
A nickel positive electrode in which an active material mainly composed of nickel oxide is supported by a conductive core material; a negative electrode mainly composed of a hydrogen storage alloy capable of electrochemically storing and releasing hydrogen; and an alkaline electrolyte. a case housing the separator, these, in the nickel-metal hydride battery that includes a sealing plate having a safety valve, to the active material, yttrium, indium, that by adding at least one of antimony Contact and compounds of beryllium It is characterized by the following.

In the above nickel-hydrogen storage battery, the alkaline electrolyte is preferably composed of at least one of potassium hydroxide and sodium hydroxide and lithium hydroxide. In addition, lithium hydroxide contains 1
Desirably, the content is 0 g / l or more. Further, it is desirable that zincate ions be present in the alkaline electrolyte.

As the separator, a non-woven fabric subjected to a sulfone treatment is preferably used. The valve operating pressure of the safety valve is 5
It is preferable to set the pressure at 30 kg / cm ³ .

[0026]

[Action] With the above arrangement, i.e., in the active material of the nickel positive electrode, yttrium, indium, by adding at least one of the compounds of antimony Contact <br/> preliminary beryllium, these compounds in the active material It adsorbs on the surface of a nickel oxide and increases the overvoltage, which is a competitive reaction in charging under a high temperature atmosphere. As a result, the charging reaction of the nickel oxide, nickel hydroxide, to the nickel oxyhydroxide is sufficiently performed, and the utilization rate in a high-temperature atmosphere is improved. Further, these compounds, unlike cadmium oxide, do not affect the utilization of nickel oxide in an atmosphere at normal temperature or lower. Therefore, by including the compound in the positive electrode active material, a positive electrode having excellent active material utilization over a wide temperature range was obtained. Further, in the nickel-hydrogen storage battery from which cadmium was removed, a nickel-hydrogen storage battery having excellent discharge characteristics in a wide range of temperature atmospheres was obtained by using a positive electrode containing the above compound.

[0027]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A nickel positive electrode for an alkaline storage battery and a nickel-hydrogen storage battery using the same according to a preferred embodiment of the present invention will be described below with reference to the accompanying drawings.

( Example 1 ) First, a positive electrode was prepared as follows.

As nickel oxide as a positive electrode active material,
0.3wt each of cobalt and cadmium inside
% And 3.0% by weight of a solid nickel hydroxide solution were prepared. Carbonyl cobalt was used as the cobalt powder, and cobalt hydroxide was used as the cobalt oxide powder.

These powders, cadmium oxide powder,
Y ₂ O ₃ , In ₂ O ₃ , Sb ₂ O ₃ , Ca as additive powder
(OH) ₂ was mixed with the composition of A to J shown in Table 1 so as to have a mixing ratio (weight ratio). Water is added to the mixture thus obtained, and the mixture is mixed to form a paste. Thereafter, the mixture is filled in a foamed nickel porous body having a porosity of 95% and an areal density of 300 g / m ² , and is dried, pressurized, and dried. In order to prevent the powder from falling off the plate surface, it was immersed in an aqueous solution in which a fluororesin powder was dispersed. Then, after drying again, it was cut to a predetermined size to prepare nickel positive electrodes of Samples A to J shown in (Table 1). Samples AF are examples of the present invention, and samples GJ are comparative examples.

[0031]

[Table 1] Then, these positive electrode and a working electrode, to constitute a half cell using a nickel net as a counter electrode were tested for utilization of the nickel hydroxide as an active material. A mercury oxide electrode was used as a reference electrode.

The active material utilization was 0 ° C., 20 ° C. and 45 ° C.
In each atmosphere of ° C, the working electrode was charged at a current density equivalent to 0.1 CmA to the positive electrode capacity, that is, 150% of the theoretical capacity calculated from the nickel hydroxide active material. , A continuous discharge was performed to the mercury oxide electrode at 0.1 V at a low current density corresponding to 0.2 CmA, and the discharge was calculated using the following equation.

Active material utilization rate = (discharge capacity up to 0.1 V / theoretical nickel hydroxide capacity ) × 100 FIGS. 1 and 2 show the active material utilization rates of the positive electrodes of Samples A to F and G to J, respectively. Was. As is clear from the results of FIG. 2, when the addition amount of cadmium oxide is increased to 7 wt%, the utilization at 45 ° C. increases from 56% to 88%, but the utilization at 20 ° C. decreases to about 80%. Resulting in. On the other hand, as shown in FIG.
To F, the utilization at 45 ° C. is 82 to 93%, and the utilization at 20 ° C. is 95 to 100%.
%, The utilization rate at 0 ° C. is 97 to 105%, indicating that the utilization rate is excellent over a wide temperature range. The compound added in Examples A to F improves the utilization rate of the active material under a high-temperature atmosphere because the compound is adsorbed on the surface of nickel oxide as an active material, and is a competitive reaction of charging under a high-temperature atmosphere. This is because the charging reaction of nickel hydroxide to nickel oxyhydroxide is sufficiently performed in order to increase the overvoltage of oxygen generation. The additive used in this example has an advantage that the utilization factor at a high temperature can be improved without lowering the utilization factor at a normal temperature as compared with cadmium oxide.

In the examples, the additive amount was 3 parts by weight with respect to 100 parts by weight of nickel hydroxide.
The content is preferably in the range of 0.1 to 5 parts by weight. If it is more than 5 parts by weight, the amount of the compound as an additive on the surface of nickel hydroxide as an active material increases,
This is because the surface area of the active material that is effective for the discharge reaction is reduced, thereby lowering the discharge voltage and deteriorating the discharge characteristics. When the amount is less than 0.1 part by weight, no improvement in the utilization factor in a high-temperature atmosphere is observed. In the present embodiment,
Although oxides and hydroxides are mentioned as compounds to be added, compounds such as sulfates and chlorides may be used, and similar effects can be obtained.

In this embodiment, the support has an areal density of 300 g.
/ M ³ foamed nickel porous material, but the area density is 2
A similar effect can be obtained if the content is in the range of 00 to 700 g / m ² . Similar effects can be obtained by using a punching metal or a flat plate, which is a kind of three-dimensional porous body, in addition to the foamed nickel porous body.

In this embodiment, the amounts of cadmium and cobalt existing as solid solutions are 3.0 wt% and 0.1 wt%, respectively.
Although 3 wt% has been described as an example, the same tendency is exhibited in the range of 1 to 7 wt%. Similar effects can be obtained by using zinc, lead, silver, indium, yttrium, iron, and manganese in addition to cadmium and cobalt.

( Example 2 ) A nickel-metal hydride storage battery was produced as follows.

First, a positive electrode was prepared as follows. First, the average particle size is 12 μm, and the BET specific surface area is 22 m ^2.
/ G, a spherical nickel hydroxide powder containing 3.5 wt% of zinc and 0.3 wt% of cobalt having a tap density of 2.0 g / cm ³ as a solid solution, a cobalt powder, a cobalt hydroxide powder, and Each additive powder (yttrium oxide, indium oxide, antimony oxide, barium hydroxide, calcium hydroxide, beryllium hydroxide) was mixed at a weight ratio of 100: 7: 5: 3, and water was added thereto to knead. After mixing and forming a paste, the porosity of the support is 9
The foamed nickel porous material having a surface density of 30 g / m ^{2 and} 5% was filled, dried and pressed, and then immersed in an aqueous solution in which a fluororesin powder was dispersed in order to prevent the powder from falling off the electrode plate surface. Thereafter, it was dried again, and after this drying, it was cut into a predetermined size to prepare a cadmium-free nickel positive electrode having a capacity of 1400 mAh and containing various additives. The composition of the positive electrode is shown in (Table 2).

[0039]

[Table 2] The negative electrode was prepared as follows. The alloy composition of the negative electrode was MmNi 3.5, Co 0.7, Mn 0.4, A1
0.3 (Mm misch metal and a mixture of rare earth elements).

First, the misch metal Mm, which is a mixture of rare earth elements, and each material of Ni, Co, Mn, and Al are put in an arc furnace to make a vacuum state at 10 ^-4 to 10 ^-5 torr, and then argon gas is applied. Arc discharge was carried out under reduced pressure under an atmosphere to dissolve by heating. In order to homogenize the sample, a combustion treatment was performed at 1050 ° C. for 6 hours in a vacuum. After coarsely pulverizing the obtained alloy lump, the average particle diameter is 20 μm using a wet ball mill.
Was obtained. This powder was treated in an aqueous solution of 7.2 mol potassium hydroxide at 80 ° C. with stirring for 1 hour, washed with water to remove potassium hydroxide from the alloy powder, and dried to remove hydrogen used for the negative electrode. An occlusion alloy powder was obtained. Water and carboxymethylcellulose (CMC) are added to the hydrogen storage alloy to form a paste, which is filled into a foamed nickel porous body having a porosity of 95%, dried, pressurized, and cut into predetermined dimensions. It was created.

The purpose of the separator is to reduce self-discharge,
A sulfonated separator obtained by sulfonating a nonwoven fabric made of polypropylene and polyethylene was used .

The negative electrode 1 and the positive electrode 2 prepared as described above
Was spirally swirled through the separator 3 as shown in FIG. 3, and was inserted into the case 4 also serving as the negative electrode terminal. And, in a potassium hydroxide aqueous solution having a specific gravity of 1.30,
2.4 cm ^{3 of} an alkaline electrolyte in which LiOH.H ₂ O was dissolved at 40 g / l was injected, and finally, the case 4 was sealed with a sealing plate 7 having a safety valve 6 operating at 10 to 20 atm. Theoretical capacity of 1400 mAh with regulated battery capacity
Six kinds of 4/5 size sealed nickel-metal hydride batteries using the positive electrode having the composition shown in Table 2 above were constructed. In FIG. 3, reference numeral 8 denotes an insulating gasket, and reference numeral 9 denotes a positive electrode 2.
4 shows a positive electrode current collector that electrically connects the power supply and the sealing plate 7.

Using these batteries, a test of the active material utilization of nickel hydroxide as a positive electrode active material was conducted under the following conditions. The test conditions are shown below.

Under the respective environments of 0 ° C., 20 ° C. and 45 ° C., at a charging current of 0.1 CmA, the positive electrode capacity, that is, 150% of the theoretical capacity calculated from the nickel hydroxide active material.
Charge, pause for 3 hours, 0.2C at 20 ° C atmosphere
0.1V against mercury oxide electrode at low current density equivalent to mA
Continuous discharge was performed until the active material utilization rate was calculated using the following equation.

Active material utilization rate = (discharge capacity up to 0.1 V / theoretical nickel hydroxide capacity ) × 100 The results of these tests are shown in FIG. No. of Comparative Example.
The utilization at 20 ° C. of the battery using the positive electrode of P is as good as 97%, but the utilization under the atmosphere at 45 ° C. is 50%.
And the substantial discharge capacity decreases. On the other hand, in Example No. A battery using the positive electrodes of K to O has a capacity of 20
The utilization at 90C was 90 to 100%, and the utilization in an atmosphere at 45C was 70 to 85%, showing excellent discharge capacity in a wide temperature range. As described above, by adding the above-mentioned additives to the positive electrode, the cadmium-free nickel-metal hydride storage battery under high temperature atmosphere (45
It can be seen that the utilization rate of the active material at (° C.) can be improved and the utilization rate is excellent over a wide temperature range. This is because the added compound is adsorbed on the surface of nickel oxide, which is an active material, and increases the overvoltage of oxygen generation, which is a competitive reaction of charging in a high-humidity atmosphere. This is due to the fact that the charging reaction is sufficiently performed.

In the present embodiment, the BET specific surface area measured by the adsorption of nitrogen gas may be set in the range of 10 to 30 m ³ / g. This is because when the surface area is 10 m ³ / g or less, the reaction surface area decreases, the discharge characteristics deteriorate, and
At 0 m ³ / g, the tap density decreases and the filling property of the positive electrode decreases, so that the substantial capacity decreases.

Lithium hydroxide in the electrolytic solution is 10 g in order to improve the utilization rate of nickel hydroxide and the discharge voltage.
/ L or more is preferred.

Further, zincate ions present in the electrolytic solution can suppress the expansion of the positive electrode due to repeated discharge, and can further improve the reliability such as life characteristics.

In this embodiment, the support has an areal density of 300 g.
/ M ² foamed nickel porous material was used, but the area density was 2
The same effect is exhibited within the range of 00 to 700 g / m ² . Similar effects can be obtained by using a punching metal or a flat plate, which is a kind of three-dimensional porous body, in addition to the foamed nickel porous body.

Further, in this embodiment, the case where zinc and cobalt are contained as a solid solution in the crystal of nickel hydroxide has been described, but in addition to zinc and cobalt, lead, silver, indium, yttrium, yttrium, iron and manganese are contained. Those existing as a solid solution in the range of ７7 wt% can also be used, and these also show the same effect.

In this embodiment, an example of the nickel-metal hydride storage battery in a cylindrical shape is shown, but the same effect can be obtained in a square nickel-metal hydride storage battery.

[0052]

As described above, according to the present invention, a nickel positive electrode comprising a nickel oxide as a main component supported by a three-dimensional porous body or a flat plate imparting conductivity to the nickel oxide is provided.
By adding at least one of the compounds of yttrium, indium, antimony, barium, calcium, and beryllium, a nickel positive electrode having excellent utilization under a high-temperature atmosphere can be obtained.

A nickel positive electrode comprising a nickel oxide as a main component supported by a three-dimensional porous body or a flat plate imparting conductivity thereto, and a hydrogen storage alloy capable of electrochemically storing and releasing hydrogen. Negative electrode, an alkaline electrolyte, a separator, and a case accommodating them,
In a nickel-metal hydride battery provided with a sealing plate having a safety valve, the nickel positive electrode has a nickel hydroxide powder, at least one of cobalt oxide and zinc oxide, yttrium, indium, antimony, barium, calcium, and beryllium. By containing at least one of the above compounds, a nickel-metal hydride storage battery having excellent utilization over a wide temperature range can be obtained without containing a heavy metal such as cadmium.

[Brief description of the drawings]

FIG. 1 is a view showing the relationship between the utilization ratio of nickel hydroxide and the positive electrode composition (A to F) at each temperature of a half cell prepared in Example 1.

FIG. 2 is a diagram showing the relationship between the utilization ratio of nickel hydroxide and the positive electrode composition (G to J) at each temperature of a half cell prepared as a comparative example.

FIG. 3 is a cross-sectional view of a nickel-metal hydride storage battery prepared in Example 2.

FIG. 4 shows the utilization ratio of nickel hydroxide and the positive electrode composition (A to F) at each temperature of the nickel-metal hydride storage battery prepared in Example 2.
Diagram showing the relationship

[Explanation of symbols]

 1 negative electrode 2 positive electrode 3 separator 4 case

Continued on the front page (51) Int.Cl. ⁷ Identification code FI H01M 10/30 H01M 10/30 A (72) Inventor Hideo Kaiya 1006 Odakadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Invention Shingo Tsuda 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-63-45754 (JP, A) JP-A-62-66569 (JP, A) JP-A 63-6569 228567 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) H01M 4/52-4/62 H01M 4/32

Claims (28)

(57) [Claims] 1. A nickel positive electrode formed by supporting an active material mainly composed of nickel oxide in the conductive core member, the addition of yttrium, indium, at least one of antimony Contact and compounds of beryllium in the active material A nickel positive electrode for an alkaline storage battery. 2. A yttrium, indium, compounds of antimony Contact <br/> preliminary _{beryllium, Y 2 O 3, Y (} OH) 3, I
_{n 2 O 3, In 2 O} , In 2 O 3 · H 2 O, Sb 2 O 3, Sb 2
O _4, B eO and Be (OH) ₂ in which claim 1 an alkali nickel positive electrode for storage batteries according. Wherein yttrium, indium, amount of a compound of antimony Contact <br/> preliminary beryllium, nickel oxide 1
00 is a 0.1 to 5 parts by weight per part by weight of claim 1 Symbol
Nickel positive electrode for the mounting of an alkaline storage battery. Wherein at least one of claim 1, wherein is further added nickel positive electrode for an alkaline storage battery cobalt and cobalt oxide as the active material. 5. The active material further comprises at least one of cadmium oxide and zinc oxide.
The nickel positive electrode for an alkaline storage battery according to the above . 6. The conductive core material, foamed nickel porous body, Shoyuishiki nickel porous body and punching any of the three-dimensional porous body in which claim 1 an alkali nickel positive electrode for storage batteries according metal. 7. The conductive core material is a flat plate, and a nickel foil,
Or nickel positive electrode for an alkaline storage battery according to claim 1, wherein were subjected to nickel plating on iron foil. 8. The foamed nickel porous body has an area density of 2
00~700g / m ² and for an alkaline storage battery of nickel positive electrode according to claim 6, wherein. 9. A nickel oxide, nickel positive electrode for an alkaline storage battery according to claim 1, wherein the spherical nickel hydroxide. 10. Nickel oxide is cadmium, zinc,
Lead, silver, indium, yttrium, magnesium,
Iron, cobalt and at least one 1 to 7% content nickel hydroxide as a solid solution inside the crystal Claim 1 alkali nickel positive electrode for storage batteries according of manganese. 11. A nickel positive electrode in which an active material mainly composed of nickel oxide is supported by a conductive core material, and a negative electrode mainly composed of a hydrogen storage alloy capable of electrochemically storing and releasing hydrogen. , an alkaline electrolyte, a separator, and a case accommodating them, in the nickel-metal hydride battery that includes a sealing plate having a safety valve, to the active material, yttrium, indium, at least one of antimony Contact and compounds of beryllium A nickel-metal hydride storage battery characterized by the addition of a kind. 12. yttrium, indium, antimony
Compound of you and _{beryllium, Y 2 O 3, Y (} OH) 3,
_{In 2 O 3, In 2 O} , In 2 O 3 · H 2 O, Sb 2 O 3, Sb
12. The composition according to claim 11, which is ₂ O ₄ , BeO and Be (OH) 2.
The placing of the nickel-metal hydride battery. 13. yttrium, indium, antimony
Amount of contact and the compounds of beryllium, claim 1 is 0.1 to 5 parts by weight with respect to nickel oxide 100 parts by weight
2. The nickel-metal hydride storage battery according to 1. 14. The nickel-metal hydride storage battery according to claim 11 , wherein at least one of cobalt and cobalt oxide is further added to the active material. 15. The active material further comprises at least one of cadmium oxide and zinc oxide.
12. The nickel-metal hydride storage battery according to item 11 . 16. The nickel-metal hydride storage battery according to claim 11 , wherein at least one of cobalt and cobalt oxide and at least one of cadmium oxide and zinc oxide are further added to the active material. 17. cobalt oxide cobalt hydroxide, zinc oxide is an oxide of zinc, by weight, nickel hydroxide: cobalt: cobalt hydroxide: zinc oxide :( yttrium, indium, antimony Contact and beryllium At least one compound) = 100: 4 to 18: 0 to 1
The nickel-metal hydride storage battery according to claim 16 , wherein the ratio is 0: 0 to 10: 0.1 to 5. 18. The conductive core material is a foamed nickel porous body,
The nickel-metal hydride storage battery according to claim 11 , wherein the three-dimensional porous body is any one of a sintered nickel porous body and a punched metal. 19. The nickel-metal hydride storage battery according to claim 11 , wherein the conductive core material is a flat plate and is made of nickel foil or iron foil plated with nickel. 20. foamed nickel porous body, nickel the surface density of claim 18 wherein the 200 to 700 g / m ²
Hydrogen storage battery . 21. The nickel-metal hydride storage battery according to claim 11 , wherein the nickel oxide is a spherical nickel hydroxide powder. 22. Nickel hydroxide powder has an average particle size of 7 to 20 μm and a tap density of 1.9 g / cm.
22. The nickel-metal hydride storage battery according to claim 21, which is ^three or more spherical particles. 23. The nickel hydroxide powder has a BET specific surface area of 10 to 30 m ³ / g measured by adsorption of nitrogen gas.
22. The nickel-hydrogen storage battery according to claim 21 , wherein
Pond . 24. The nickel oxide is cadmium, zinc,
Lead, silver, indium, yttrium, magnesium,
The nickel-metal hydride storage battery according to claim 11 , wherein the nickel-hydrogen storage battery is nickel hydroxide containing at least one of iron, cobalt and manganese as a solid solution in a crystal in a content of 1 to 7%. 25. The nickel-metal hydride storage battery according to claim 11 , wherein the alkaline electrolyte comprises at least one of potassium hydroxide and sodium hydroxide and lithium hydroxide. 26. Lithium hydroxide containing 10 g / liter in the electrolyte.
12. The nickel-metal hydride storage battery according to claim 11 , wherein the nickel-hydrogen storage battery contains 1 or more. 27. The nickel-metal hydride storage battery according to claim 11 , wherein zincate ions are present in the alkaline electrolyte. 28. The valve operating pressure of the safety valve is 5 to 30 kg / cm.
The nickel-metal hydride storage battery according to claim 11 , wherein the value is set to ³ .