JPH08295970A - Hydrogen storage alloy and hidrogen storage alloy electrode - Google Patents

Abstract

PURPOSE: To produce a hydrogen storage alloy maintaining high amt. of occlud ed hydrogen and furthermore excellent in initial activity and low temp. high rate discharging characteristics. CONSTITUTION: This hydrogen storage alloy is the one shown by the general formula of ZrMna Vb Moc Crd Coe Nif (0.4<=a<=0.8, 0<=b<0.3, 0<c<=0.3, 0<d<=0.3, 0<e<=0.1, 1.0<=f<=1.5, 0.1<=b+c<=0.3 and 2.0<=a+b+c+d+e+f<=2.4 are satisfied) or Zr1-x Tix Mna Vb Moc Crd Coe Nif (0<x<=0.5, 0.4<=a<=0.8, 0<=b<0.3, 0<c<=0.3, 0<d<=0.3, 0<e<=0.1, 1.0<=f<=1.5, 0.1<=b+c<=0.3, x<=b+c+d+e and 7<=a+b+c+d+e+f<=2.2 are satisfied) and in which the main compoent of the alloy phase is constituted of a C15(MgCu2 ) type Laves phase.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage alloy capable of reversibly electrochemically storing and releasing hydrogen, and a hydrogen storage alloy electrode using the same.

[0002]

2. Description of the Related Art A hydrogen storage alloy electrode using a hydrogen storage alloy capable of reversibly absorbing and releasing hydrogen has a theoretical capacity density higher than that of a cadmium electrode, and does not cause deformation such as a zinc electrode or formation of dendrites. Therefore, it is expected as a negative electrode for an alkaline storage battery that has a long life, is pollution-free, and has a high energy density. The alloy used for such a hydrogen storage alloy electrode is usually produced by an arc melting method, a high frequency induction heating melting method, or the like. Generally, a Ti-Ni-based and La (or Mm) -Ni-based multi-component alloy is used. well known. The Ti-Ni-based multi-component alloy is classified as an AB type (A: an element having a high affinity for hydrogen such as La, Zr, and Ti, and B: a transition element such as Ni, Mn, and Cr). This type of alloy exhibits a relatively large discharge capacity at the beginning of the charge / discharge cycle, but there is a problem that it is difficult to maintain the capacity for a long time when the charge / discharge is repeated. Also, AB ₅ type La (or Mm) -N
Many developments of i-type multi-component alloys have been advanced in recent years as electrode materials, and in particular, Mm-Ni-based multi-component alloys have already been put to practical use. This type of alloy has also reached its capacity limit, and a new hydrogen storage alloy material having a large discharge capacity is desired.

On the other hand, the AB ₂ type Laves phase alloy has a relatively high hydrogen storage capacity and is promising as an electrode having a high capacity and a long life. Regarding this alloy system, for example, ZrαVβNiγMδ system alloy (JP-A-64-60961), AxByNiz system alloy (JP-A-1-102855), ZrαMnβVγ.
CrδNiε alloy _{(JP-A-3-289041), ZrMn x V y Ni} z alloy (JP-A-4-3010
No. 45) has been proposed.

However, when an AB ₂ type Larvus phase alloy is used for the electrode, Ti--Ni system or La (or M
m) -Ni-based multi-component alloy has a higher discharge capacity and a longer life, but further improvement in performance is desired. Then, the alloy system is Zr-Mn-V-Cr-N.
0.34 Ah by limiting the composition to i type and adjusting the composition
A hydrogen storage alloy electrode having a discharge capacity of / g or more has been obtained (JP-A-3-290441, etc.). Also, Z
r-Mn-VM-Ni system (M is one or more elements selected from Fe or Co) or Zr-Mn-VN
By adjusting the composition in the i-system, the initial discharge characteristics are improved while maintaining a high capacity (Japanese Patent Laid-Open No. 4-3010).
45, Japanese Patent Application No. 4-70704).

[0005]

However, as a result of making and testing a nickel-hydrogen storage battery using such a hydrogen storage alloy electrode, it was found that the high rate discharge characteristics were inferior especially at low temperatures. In view of the above, it is an object of the present invention to provide a hydrogen storage alloy that improves high rate discharge characteristics at low temperatures and provides an electrode having a high hydrogen storage capacity and initial discharge characteristics.

[0006]

The hydrogen storage alloy of the present invention According to an aspect of the general formula _{ZrMn a V b Mo c Cr d} Co e Ni f (0.4
≦ a ≦ 0.8, 0 ≦ b <0.3, 0 <c ≦ 0.3, 0 <
d ≦ 0.3, 0 <e ≦ 0.1, 1.0 ≦ f ≦ 1.5,
0.1 ≦ b + c ≦ 0.3 and 2.0 ≦ a + b + c + d
+ E + f ≦ 2.4) and the main component of the alloy phase is C15.
It is a (MgCu ₂ ) type Larvus phase. The hydrogen storage alloy of the present invention have the general formula _{Zr 1-x Ti x Mn a} V b Mo c Cr d
_{Co e Ni f (0 <x} ≦ 0.5,0.4 ≦ a ≦ 0.8,0
≦ b <0.3, 0 <c ≦ 0.3, 0 <d ≦ 0.3, 0 <
e ≦ 0.1, 1.0 ≦ f ≦ 1.5, 0.1 ≦ b + c ≦
0.3, x ≦ b + c + d + e, and 1.7 ≦ a + b + c
+ D + e + f ≦ 2.2) and the main component of the alloy phase is C
It is a 15 (MgCu ₂ ) type Larvus phase. Furthermore, the present invention provides a hydrogen storage alloy in which there are at least two phases, a phase having a larger amount of Mo and a phase having a smaller amount of Mo than the charged composition. Here, the alloy is 1000 to 1300 after fabrication.
It is preferable that the homogenization heat treatment is performed in a vacuum at 0 ° C. or in an inert gas atmosphere. The hydrogen storage alloy electrode of the present invention comprises the above hydrogen storage alloy or a hydride thereof.

[0007]

In the past, as a method for improving the high rate discharge characteristics, there have been methods such as providing a catalyst layer of Ni or the like on the surface, plating, controlling the particle size, and the like. Aiming to improve this in terms of alloy composition,
As a result of repeated studies, the present invention has been completed. That is, by improving the composition of the hydrogen storage alloy, we succeeded in obtaining a hydrogen storage alloy that improves the high rate discharge characteristics at low temperatures and maintains a high hydrogen storage amount and initial discharge characteristics. The hydrogen storage alloy of the present invention is a conventional Zr-
Mn-V-Cr-Co-Ni alloy, Zr-Mn-Cr
-Co-Ni-based alloys, or improved hydrogen storage alloys in which Zr in these alloys is replaced by Ti, and improved high-rate discharge characteristics at low temperatures by adding Mo to the conventional alloy composition. is there. Since Mo has a large atomic radius, the addition of Mo increases the crystal lattice constant of the alloy and increases the hydrogen storage amount. This is the same effect as V, but in the case of V, since hydrogen has a strong affinity with hydrogen, hydrogen in the lattice is stabilized, and there is a drawback that it becomes difficult to discharge particularly in high-rate discharge. However, in the case of Mo,
Since the affinity with hydrogen is weaker than V, the high rate discharge ability can be improved without lowering the hydrogen storage ability. Therefore, by adding Mo to the alloy not containing V or substituting V for Mo, it is possible to achieve both high capacity and high rate discharge capability.

Next, the composition range of each element is determined from the viewpoint of ensuring hydrogen storage capacity and electrode characteristics. First, the general formula _{ZrMn a V b Mo c Cr d} Co e alloy represented by Ni _f will be described. As described above, Mo improves the hydrogen storage amount and the low temperature high rate discharge characteristics. When the amount exceeds 0.3 in the atomic ratio c of Mo to Zr, the lattice constant becomes too large and the crystal structure collapses, so that the homogeneity of the alloy deteriorates significantly. Therefore, the hydrogen storage amount becomes small. Therefore, the appropriate amount of Mo to be added is c ≦ 0.3.
V contributes to an increase in the amount of hydrogen storage-release, but when the atomic ratio b of V to Zr exceeds 0.3, the homogeneity of the alloy becomes very poor as in the case of Mo, and conversely hydrogen storage- The amount released is reduced. b ≦ 0.3 is suitable. Further, since V and Mo have similar effects on the crystal structure, the total amount of V and Mo, that is, (b + c) must also be 0.3 or less.

Ni is an essential element for the alloy to occlude and release hydrogen electrochemically, and the minimum atomic number ratio f of Ni to Zr is 1.0. If the amount of Ni is less than this, the electrochemical discharge capacity decreases. On the other hand, Ni
Causes the hydrogen equilibrium pressure of the hydrogen storage alloy to rise, so that if the addition ratio is too large, the hydrogen storage amount decreases. When the Ni content f exceeds 1.5, the discharge capacity starts to decrease substantially. Therefore, it is suitable that the amount of Ni is 1.0 ≦ f ≦ 1.5. Co also contributes to the further improvement of the activity for electrochemical storage and release of hydrogen. Furthermore, when a small amount of Co is added, the alloy crystals tend to be uniform and the amount of occlusion increases. However, Co also raises the hydrogen equilibrium pressure similarly to Ni, and therefore, if added excessively, the hydrogen storage amount decreases. Z
When the atomic ratio e of Co to r is 0.1 or less, the characteristics can be sufficiently improved. Therefore, the Co content is preferably 0 <e ≦ 0.1.

Mn affects the flatness of the hydrogen equilibrium pressure in the PCT curve, and the atomic ratio of Mn to Zr a
Is 0.4 or more, the flatness is improved and the discharge capacity is increased. However, when the Mn amount a exceeds 0.8, Mn is liable to be eluted into the electrolytic solution and the cycle life characteristics deteriorate.
Therefore, it is appropriate that the amount of Mn be 0.4 ≦ a ≦ 0.8. Cr forms a passive film on the alloy surface and imparts corrosion resistance to the alloy. Therefore, it is effective to add Cr in order to improve the life characteristics and the high temperature storage characteristics of the battery. However, if added excessively, the coating becomes too strong and also impedes hydrogen permeation, making activation difficult. If the atomic ratio d of Cr to Zr exceeds 0.3, charging and discharging must be repeated for 10 cycles or more for activation, which is not practical. Therefore, the Cr amount d is 0 <d
≦ 0.3 is suitable. The ratio of the number of B-site atoms to the number of A-site atoms (a + b + c + d + e + f) is 2.0.
When it becomes above, the homogeneity of the alloy is improved and the hydrogen storage amount is increased. However, when it is larger than 2.4, the hydrogen equilibrium pressure rises because the crystal lattice constant becomes very small,
Hydrogen storage capacity decreases. Therefore, 2.0 ≦ a + b +
It is appropriate that c + d + e + f ≦ 2.4.

[0011] Next, the general formula _{Zr 1-x Ti x Mn a} V b Mo c
Explained cr _d Co _e alloy represented by Ni _f. In this alloy, Ti is an element that occupies the A site like Zr. And since Ti has a small atomic radius,
When the substitution amount increases, the lattice constant decreases and the hydrogen storage amount decreases. If the amount of Ti is smaller than the amount of Zr, there is no large capacity decrease. Further, when the amount of Ti is increased, the alloy phase is changed to C
It tends to be difficult to maintain the 15-type Laves phase, but Ti is more than the sum of the amounts of V, Mo, Cr, and Co at the B site.
If the amount is small, no major disorder in the crystal structure is observed. Therefore, it is desirable that x ≦ b + c + d + e.
Other elements are the same as in the case of the Zr-based alloy described above. The value of (a + b + c + d + e + f) is preferably 2.2 or less because the crystal lattice constant decreases when the value exceeds 2.2 because it contains Ti. Even if the lower limit is lowered to 1.7, the homogeneity of the alloy is not deteriorated.
Therefore, 1.7 ≦ a + b + c + d + e + f ≦ 2.2
Is appropriate. From the above, excellent initial discharge characteristics,
It can be seen that it is important to satisfy the conditions of the alloy composition of the present invention in order to obtain a hydrogen storage alloy electrode having a high capacity and capable of low temperature and high rate discharge.

[0012]

EXAMPLES The present invention will be described in more detail below by way of its examples. [Example 1] Commercially available Zr, Mn, V, Mo, Cr, C
Alloys having compositions shown in Tables 1 and 2 were prepared by melting and melting O and Ni metal as raw materials in a high-frequency induction heating furnace. Then, in vacuum, 1100 ° C
Was heat-treated for 12 hours to prepare an alloy sample.

[0013]

[Table 1]

[0014]

[Table 2]

A part of this alloy sample is used for alloy analysis such as X-ray diffraction and hydrogen absorption-desorption amount measurement (normal P (hydrogen pressure) -C (composition) -T (temperature) measurement) in a hydrogen gas atmosphere. The rest was used for electrode characteristic evaluation. Sample N
o. Sample Nos. 1 to 10 are comparative examples having different constituent elements or composition ratios from the present invention. 10 to 18 are some examples of the hydrogen storage alloy of the present invention. First, X-ray diffraction measurement was performed on each alloy sample. As a result, in any of the alloy samples, the main component of the alloy phase was the C15 type Lavas phase (MgCu ₂ type face centered cubic structure (fc
c)) was confirmed. Then, the sample No. 8
In Nos. 9 and 9, a large amount of C14 type Lavas phase (MgZn ₂ type hexagonal structure) was mixed, and it was found that the homogeneity of the alloy was low. Also, after the vacuum heat treatment, the peak of fcc was larger and sharper than that before the heat treatment, so the heat treatment increased the proportion of the C15 type Larvus phase and improved the homogeneity and crystallinity of the alloy. I understood. In addition, from the result of PCT measurement, No. with a large amount of Co and Ni. In 4 and 7, the hydrogen equilibrium pressure is high,
It was confirmed that the occlusion amount was small, and that the lattice constant increased and the equilibrium pressure decreased with the addition of Mo or V.

Sample No. The alloys 1 to 18 were subjected to a single cell test in order to evaluate electrode characteristics as a negative electrode for an alkaline storage battery by electrochemical charge / discharge reaction, particularly initial discharge characteristics and maximum discharge capacity. Sample N
o. 1-18 alloys are mechanically crushed to 38 μm or less,
A 3 wt% aqueous solution of polyvinyl alcohol was added to form a paste. Then, this paste was filled in a foamed nickel plate having a porosity of 95% and a thickness of 0.8 mm and pressed. The thus obtained hydrogen storage alloy negative electrode and a counter electrode composed of a nickel oxide electrode having an excessive electric capacity were immersed in an electrolytic solution composed of an aqueous solution of potassium hydroxide having a specific gravity of 1.30, and under a condition rich in the electrolytic solution. Charging and discharging were performed in an open system whose capacity was regulated by the hydrogen storage alloy negative electrode. Charging is 100 mA / g of hydrogen storage alloy for 5.5 hours, discharging is alloy 1
The terminal voltage was set to 0.8 V at 50 mA per gram.

The first cycle discharge capacity and the maximum discharge capacity of each electrode are shown in FIG. The discharge capacity of the first cycle is Cr
No. with a large amount No. 6, which does not include Co and Mo. Two, one
No. 0 and No. 2 with a small Mn amount. It became a low value such as 5. In addition, No. The samples Nos. 1 and 3 showed high initial activity, but the elution of Mn and the like was severe, so that the capacity deterioration was large and the maximum capacity was small. The electrodes according to the present invention all show a discharge capacity of 200 mAh / g or more from the first cycle, high initial activity is obtained, and the maximum discharge capacity is 350 to 400.
It showed mAh / g and was found to have a high capacity.

Next, the results of comparing the characteristics of a sealed battery constructed by using these electrodes will be described. The above electrodes were adjusted to have a width of 3.5 cm, a length of 14.5 cm and a thickness of 0.50 mm. Then, the positive electrode and the separator were combined to form a spiral electrode group, which was then housed in a 4/5 A size battery case. The positive electrode was a well-known foamed nickel electrode having a width of 3.5 cm and a length of 11 cm. A lead plate was attached to the positive electrode, and this was welded to the positive electrode terminal. As the separator, a polypropylene non-woven fabric having hydrophilicity was used. Specific gravity of the electrolyte is 1.3
0 g of potassium hydroxide aqueous solution containing 30 g of lithium hydroxide /
1 The dissolved product was used. After injecting the electrolytic solution, the battery case was sealed to obtain a sealed battery. This battery has a nominal capacity of 1.6 Ah according to the positive electrode capacity regulation. No. Ten batteries were prepared for each of the alloys 1 to 18 and evaluated by a charge / discharge cycle test.

These batteries were charged at 25 ° C. at 0.1 C for 15 hours, discharged at 0.2 C for the first charge / discharge, then left at 50 ° C. for 2 days, and then subjected to the same conditions as the initial charge / discharge for 10 hours. Cycle charge / discharge was performed. During this time, all the batteries showed a discharge capacity of 95% or more of the theoretical capacity. next,
These batteries were charged at 0.2 C and 150% at 20 ° C. and discharged at 0 ° C. and 1 C to a final voltage of 1.0 V, and the low temperature high rate discharge characteristics of the batteries were examined. 1 at 0 ° C
The discharge voltage ratio to the intermediate voltage and the positive electrode theoretical capacity during C discharge is shown in FIG. The battery using the electrode according to the present invention has an intermediate voltage of 1.145 at 1C discharge at 0 ° C.
Two conditions of V or more and discharge capacity ratio of 80% or more were satisfied, and excellent low temperature and high rate discharge characteristics were exhibited.

Example 2 Commercially available Zr, Ti, Mn,
Using V, Mo, Cr, Co, and Ni metals as raw materials,
By heating and melting in a high-frequency induction heating furnace, alloys having compositions shown in Tables 3 and 4 were produced. Then
It heat-processed at 1100 degreeC in vacuum for 12 hours, and it was set as the alloy sample.

[0021]

[Table 3]

[0022]

[Table 4]

Some of these alloy samples were used for alloy analysis such as X-ray diffraction and hydrogen absorption-desorption amount measurement (normal P-C-T measurement) in a hydrogen gas atmosphere, and the rest were used for electrode characteristic evaluation. I was there. Sample No. Sample Nos. 19 to 29 are comparative examples having different constituent elements or compositions from the present invention. 30
-39 are some examples of the hydrogen storage alloy of the present invention. First, X-ray diffraction measurement was performed on each alloy sample. As a result, No. In No. 29, the C14 phase was the main component. In all other alloy samples, the main component of the alloy phase is C15 type Larvus phase (MgCu ₂ type fcc structure)
It was confirmed that the sample No. In 26 and 27, C14 type Larvus phase (MgZn ₂ type hexagonal structure)
It was found that the alloy was mixed in a large amount and the homogeneity of the alloy was low. Also, after the vacuum heat treatment, the peak of fcc was larger and sharper than that before the heat treatment, so the heat treatment increased the proportion of the C15 type Larvus phase and improved the homogeneity and crystallinity of the alloy. I understood. In addition, from the results of PCT measurement, No. with a large amount of Co, Ni, and Ti was obtained. In Nos. 22, 25 and 29, it was confirmed that the hydrogen equilibrium pressure was high and the occlusion amount was small, and that the lattice constant increased and the equilibrium pressure decreased with the addition of Mo or V.

Sample No. For the alloys Nos. 19 to 39, a single cell test was conducted to evaluate the electrode characteristics as an anode for an alkaline storage battery by an electrochemical charge / discharge reaction, particularly the initial discharge characteristics and the maximum discharge capacity. The manufacturing method of the alloy negative electrode, the configuration of the unit cell, and the charging / discharging conditions are the same as in Example 1. The discharge capacity and maximum discharge capacity in the first cycle of each electrode are shown in FIG. The discharge capacity in the first cycle was No. 1 with a large amount of Cr. 24, N not containing Co and Mo
o. Nos. 20, 28, and No. It became a low value at 23. In addition, No. Nos. 19 and 21 showed high initial activity, but the elution of Mn and the like was severe, so that the capacity deterioration was large and the maximum capacity was small. It was found that all the electrodes according to the present invention showed a discharge capacity of 250 mAh / g or more from the first cycle, high initial activity was obtained, and the maximum discharge capacity was about 350 to 400 mAh / g. .

Next, using an alloy electrode, in the same manner as in Example 1, a nominal capacity of 1.6 A regulated by the positive electrode was used.
A sealed battery of h was constructed. No. Ten batteries were prepared for each of the alloys 19 to 39 and evaluated by a charge / discharge cycle test. First, put these batteries at 25 ℃
At 15 ° C. for 15 hours and then discharged at 0.2 C for the first charge / discharge, then left at 50 ° C. for 2 days, then
Charging / discharging was performed for 10 cycles under the same conditions as the initial charging / discharging. During this time, all the batteries showed a discharge capacity of 95% or more of the theoretical capacity. These batteries are charged to 150% at 0.2C at 20 ° C, and the final voltage of 1.0V at 1C at 0 ° C.
The low temperature high rate discharge characteristics of the battery were investigated by discharging up to. The discharge capacity ratio to the intermediate voltage and the positive electrode theoretical capacity during 1 C discharge at 0 ° C. is shown in FIG. All the batteries using the electrodes according to the present invention have an intermediate voltage of 1.C at 1C discharge at 0 ° C.
It satisfied two conditions of 145 V or more and a discharge capacity ratio of 85% or more, and showed excellent low temperature high rate discharge characteristics.

[Embodiment 3] As is clear from the above embodiment, it has been found that by adding Mo, a hydrogen storage alloy having a high capacity, excellent initial activation and high rate discharge characteristics can be obtained. It is considered that this is due to the chemical properties of Mo. Therefore, in order to further investigate whether or not there is a factor that improves the characteristics in terms of alloy structure, the cross section of the alloy was analyzed by SEM and an electron probe X-ray microanalyzer (EPMA). Then, M in the alloy
It was confirmed that there were at least two phases, one with more o and the other with less o. As a result of EPMA analysis of the composition of this phase, for example, No. ZrMn _0.59 V for alloy No. 12
_0.11 Mo _0.08 Cr _0.22 Co _0.13 Ni _1.33 and ZrMn _0.51
Two phases of V _0.09 Mo _0.41 Cr _0.25 Co _0.12 Ni _1.03 were observed, and No. 32, ZrTi _0.21 Mn _0.56 V _0.10 M
o _0.04 Cr _0.25 Co _0.11 Ni _1.24 and ZrTi _0.20 Mn
_0.52 V _0.09 Mo _0.24 Cr _0.28 Co _0.09 Ni _1.01 and ZrT
Three phases of i _0.2 Ni _1.6 were observed.

Further, although it is not the alloy according to the above-mentioned embodiment, it is an alloy containing Mo. Also in the alloy of 2,
ZrMn _0.38 V _0.10 Mo _0.11 Cr _0.28 Ni _1.31 and ZrM
Two phases of n _0.41 V _0.09 Mo _0.37 Cr _0.21 Ni _1.05 were observed. In either case, the phase with less Mo becomes the parent phase, and M
The o-rich phase and the other segregated phases were distributed in island or dendritic form. In order to investigate the influence of these multi-phases, alloys were prepared by rapidly quenching the above three types of alloys by the twin roll method. 1 in vacuum as before with those alloys
What was heat-treated at 100 ° C. for 12 hours was used as a sample. It was confirmed by SEM and EPMA that these alloys were uniform and no segregated phase was observed, and that X-ray diffraction confirmed that they were not amorphous but mainly C15 type Larvous phase.

These alloys were molded into electrodes in the same manner as in Examples 1 and 2, and the electrode characteristics were evaluated. No. Two, one
Table 5 shows a comparison of the electrode characteristics between the alloys having a multi-phase of 2, 32 and the alloys having a single phase by quenching. It was found that the alloy that became a uniform phase by ultra-quenching did not change much in the maximum discharge capacity, but was inferior in initial activity and low-temperature high-rate discharge characteristics. This is similar to the alloy according to the present invention, otherwise No. The effect was confirmed with the alloy of 2, M
It is considered to be unique to alloys containing o. Although three types of alloys are shown here, similar results were obtained for alloys having other compositions. Therefore, when preparing an alloy containing Mo, an alloy having excellent electrode characteristics can be obtained by preparing it so that it has multiple phases.

[0029]

[Table 5]

[0030]

As described above, according to the present invention, by adding Mo to a conventional hydrogen storage alloy, an electrode having a high hydrogen storage capacity and excellent initial activity and low-temperature high-rate discharge characteristics can be obtained. A given hydrogen storage alloy is obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing a discharge capacity and a maximum discharge capacity in a first cycle in an open system of electrodes of an example of the present invention and a conventional example.

FIG. 2 is a diagram showing a discharge capacity ratio to a theoretical capacity and an intermediate voltage at a low temperature high rate discharge of a positive electrode capacity regulated battery using a negative electrode of an example of the present invention and a conventional example.

FIG. 3 is a diagram showing the discharge capacity and the maximum discharge capacity in the first cycle in the open system of the electrode of the example of the present invention and the conventional example.

FIG. 4 is a diagram showing a discharge capacity ratio with respect to a theoretical capacity and an intermediate voltage of a positive electrode capacity regulated battery using a negative electrode of an example of the present invention and a conventional example at low temperature and high rate discharge.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hajime Seri Hajime 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. Within the corporation

Claims (5)

[Claims] 1. A general formula _{ZrMn a V b Mo c Cr d} Co e N
_if (0.4 ≦ a ≦ 0.8, 0 ≦ b <0.3, 0 <c ≦
0.3, 0 <d ≦ 0.3, 0 <e ≦ 0.1, 1.0 ≦ f
≦ 1.5, 0.1 ≦ b + c ≦ 0.3, and 2.0 ≦ a +
b + c + d + e + f ≦ 2.4), and the main component of the alloy phase is a C15 (MgCu ₂ ) -type Lavas phase, a hydrogen storage alloy. 2. A general formula _{Zr 1-x Ti x Mn a} V b Mo c Cr d
_{Co e Ni f (0 <x} ≦ 0.5,0.4 ≦ a ≦ 0.8,0
≦ b <0.3, 0 <c ≦ 0.3, 0 <d ≦ 0.3, 0 <
e ≦ 0.1, 1.0 ≦ f ≦ 1.5, 0.1 ≦ b + c ≦
0.3, x ≦ b + c + d + e, and 1.7 ≦ a + b + c
+ D + e + f ≦ 2.2) and the main component of the alloy phase is C
Hydrogen storage alloy that is a 15 (MgCu ₂ ) type Rabus phase. 3. A hydrogen storage alloy, characterized in that at least two phases, a phase having a larger amount of Mo and a phase having a smaller amount of Mo, are present in the alloy. 4. The hydrogen storage alloy according to claim 1, which is subjected to homogenizing heat treatment in a vacuum at 1000 to 1300 ° C. or in an inert gas atmosphere. 5. A hydrogen storage alloy electrode comprising the hydrogen storage alloy according to claim 1 or a hydride thereof.