JPH10265888A - Hydrogen storage alloy, its production and nickel-hydrogen secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydrogen storage alloy excellent in hydrogen occluding characteristics and corrosion resistance by preparing an alloy composed of specified ratios of Ti, Ni, Al, B or the like, and in which fine crystal phases having specified grain size are precipitated. SOLUTION: This hydrogen storage allot having a compsn. expressed by the general formula of Aa Tb Mc M'd (A denotes one or more kinds selected from among Ti, Zr, Hf and V, T denotes one or more kinds of elements selected from among Ni, Co, Fe, Cu, Mu and Cr, M denotes one or more kinds of elements selected from among Al, Si, Ga, Ge, Zn, Sn, In and Sb, M' denotes one or more kinds of elements selected from among B, C, N and P, and as for (a), (b), (c) and (d), by atomic %, respectively 20<=a<=70, 30<=b<=60, 5<=c<=40, 0.1<=d<=10 and (a)+(b)+(c)+(d)=100 are satisfied), and in which fine crystal phases having <=10 μm grain size are precipitated into a part of the alloy structure is prepd. By using this hydrogen storage alloy for the negative electrode material of a battery, the battery capable of satisfying long life characteristics and high rate dischargiability can be obtd.

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, a method for producing the same, and a nickel-metal hydride battery using the alloy, and particularly to a high electrode capacity (battery) when the alloy is used for a negative electrode of a secondary battery. TECHNICAL FIELD The present invention relates to a hydrogen storage alloy capable of satisfying both long life characteristics (long cycle characteristics) that can withstand repeated use and high rate discharge performance, a method for producing the same, and a nickel-metal hydride secondary battery.

[0002]

2. Description of the Related Art Unlike conventional fossil fuels such as petroleum-based fuels, hydrogen, which is converted into H ₂ O without generating harmful gases even when burned, has attracted attention as a clean energy source.
In order to realize this specific use of hydrogen, a method of storing and transporting hydrogen on a practical scale is important. However, when hydrogen is stored as a gas in a normal cylinder, the volume of the cylinder becomes excessive.On the other hand, when hydrogen is stored at a very low temperature as a liquid, auxiliary equipment such as a refrigeration facility is required. Anyway, there is a problem that the storage equipment becomes large. Therefore, a hydrogen storage alloy that absorbs hydrogen as a metal oxide by reacting with hydrogen and releases hydrogen by heating or the like has attracted attention as a means for storing and transporting hydrogen.
The application range of hydrogen storage alloys is wide, and in addition to the above-mentioned hydrogen storage means and transport means, fuel sources for hydrogen-powered vehicles, negative electrode materials for secondary batteries, hydrogen separation / recovery / purification equipment, heat pumps, cooling / heating systems, refrigeration Applications in various fields such as systems, heat storage devices, actuators, compressors, temperature sensors, and catalysts are being studied. In particular, applications of the hydrogen storage alloy as a negative electrode material of a secondary battery are steadily expanding.

In other words, recent advances in electronic technology have led to power savings, and advances in packaging technology have led to smaller and more portable electronic devices that could not be expected in the past. Accordingly, there is a particular demand for a secondary battery as a power source of the electronic device to have a high capacity, a long life, and a stable discharge current. For example, in OA devices, telephones, and AV devices that are becoming more personalized and portable, there is a demand for the development of a high-performance battery, particularly for the purpose of reducing the size and weight and extending the use time of the device cordlessly. As a battery corresponding to such a demand, a non-sintered Ni-Cd secondary battery having a three-dimensional structure using an electrode substrate of a conventional sintered nickel cadmium (Ni-Cd) battery has been developed. No significant capacity increase has been achieved.

Therefore, in recent years, an alkaline secondary battery (nickel-metal hydride secondary battery) using a structure in which a hydrogen storage alloy powder is fixed to a current collector as a negative electrode has been proposed and attracted attention. The negative electrode used in this nickel-metal hydride battery is
Generally, it is manufactured by the following procedure. That is, after the hydrogen storage alloy is melted by a high-frequency melting method or an arc melting method, the mixture is cooled and pulverized, and a conductive agent and a binder are added to the obtained pulverized powder to form a kneaded material, and the kneaded material is collected. It is manufactured by coating or crimping on an electric body. A negative electrode using this hydrogen storage alloy can increase the effective energy density per unit weight or unit volume as compared with cadmium (Cd), which is a conventional representative negative electrode material for alkaline secondary batteries. In addition to being able to increase the capacity of the battery, it has the characteristics of being less toxic and less likely to cause environmental pollution.

[0005] However, the negative electrode containing the hydrogen storage alloy is immersed in a concentrated alkaline aqueous solution as an electrolytic solution in a state where the negative electrode is incorporated in a secondary battery, and is exposed to oxygen generated from the positive electrode particularly during overcharge. In addition, the hydrogen storage alloy is corroded and the electrode characteristics are likely to deteriorate. Further, at the time of charging and discharging, the volume expands and contracts in accordance with the occlusion and release of hydrogen in the hydrogen storage alloy, so that the hydrogen storage alloy cracks and the hydrogen storage alloy powder becomes finer. As the pulverization of the hydrogen storage alloy progresses, the specific surface area of the hydrogen storage alloy increases at an accelerated rate, so that the ratio of the area of the surface of the hydrogen storage alloy deteriorated by the alkaline electrolyte increases. Moreover, since the conductivity between the hydrogen storage alloy powder and the current collector also deteriorates,
The cycle life is reduced and the electrode characteristics are also deteriorated.

Therefore, in order to solve the above-mentioned problem, the hydrogen storage alloy is diversified, or a nickel thin film or a copper thin film is adhered to the surface of the hydrogen storage alloy powder or the negative electrode including the hydrogen storage alloy by plating, vapor deposition, or the like. Improve corrosion resistance by preventing direct contact with the electrolyte, prevent mechanical cracks by increasing mechanical strength, or suppress deterioration of the hydrogen storage alloy surface by immersing it in an alkaline solution and drying it. However, it has not always been possible to achieve a sufficient improvement, and in some cases, the electrode capacity is reduced.

[0007] As the hydrogen storage alloy used for the alkaline secondary battery, there is AB ₅ type alloy represented by LaNi _5. The negative electrode using the alloy system having the hexagonal structure has a more effective battery per unit weight or unit volume than the case of using cadmium which is a conventional representative negative electrode material for an alkaline secondary battery. Energy density can be increased, the battery capacity can be increased, and there is little risk of environmental pollution such as cadmium pollution, and the battery characteristics are good. .
In the battery using the AB ₅ type alloy, there is a characteristic that can be discharged at a high current value, there is an advantage that it is possible to so-called high rate discharge.

[0008]

[SUMMARY OF THE INVENTION However, for example, the electrode capacitance of the Lm-Ni-Co-Al alloy (Lm is La enriched misch metal) conventional AB ₅ type hydrogen-absorbing alloy comprising the current 300 mAh / g It was slightly exceeded, and the cycle life due to charge and discharge was not sufficient in a situation where higher capacity and longer life of the battery were desired.

On the other hand, in a battery using a so-called AB ₂ -based hydrogen storage alloy as a negative electrode material, which is made of a composition material such as ZrNi ₂ or ZrMn _2, a capacity of 400 mAh / g or more can be obtained, but a high-rate discharge Then, there is a problem that the battery function is remarkably reduced, such as a sudden decrease in capacity and an insufficient life, and in any case, a problem that operation reliability of the device using the battery is greatly reduced. There was a point.

The present invention has been made in order to solve the above problems, and when used as a negative electrode material for a battery, both high electrode capacity, long life characteristics that can withstand repeated use, and high rate discharge characteristics are satisfied. It is an object of the present invention to provide a hydrogen storage alloy which can be used, a method for producing the same, and a nickel-metal hydride secondary battery using the alloy.

[0011]

In order to achieve the above object, the present inventors have prepared alloys having various metal structures, crystal structures, and compositions, and the structures, crystal grain sizes, and compositions of the alloys have different capacities and lifetimes. The characteristics and effects on high rate discharge were comparatively studied. As a result, an alloy material having a non-equilibrium phase such as an amorphous phase is temporarily prepared by rapidly solidifying a molten alloy having a predetermined composition or by performing mechanical processing such as mechanical alloying or mechanical grinding on the alloy raw material. After that, when an alloy obtained by heat-treating this alloy material to precipitate a fine crystal phase is prepared, a hydrogen storage alloy having excellent hydrogen storage properties and corrosion resistance is obtained. It has been found that a nickel-hydrogen secondary battery having excellent battery characteristics such as electrode capacity, life characteristics, and high-rate discharge performance can be obtained when used as a negative electrode material of (1). The present invention has been completed based on the above findings.

Namely the hydrogen-absorbing alloy according to the present invention have the general formula _{A a T b M c M '} d ( where, A is Ti, Zr, Hf
And at least one element selected from V
T is at least one element selected from Ni, Co, Fe, Cu, Mn and Cr, and M is Al, Si,
At least one element selected from Ga, Ge, Zn, Sn, In and Sb; M ′ is at least one element selected from B, C, N and P;
b, c, and d are atomic% and 20 ≦ a ≦ 70, 30 ≦
b ≦ 60, 5 ≦ c ≦ 40, 0.1 ≦ d ≦ 10, a + b +
c + d = 100. ), Wherein at least a part of the alloy structure has a grain size of 1
It is characterized in that a fine crystal phase of 0 μm or less is precipitated. The average crystal grain size of the alloy is preferably in the range of 1 nm to 5 μm.

[0013] The method for producing a hydrogen storage alloy according to the present invention is characterized in that an alloy having the above-mentioned predetermined composition and at least a part of which has a non-equilibrium phase is prepared, and then the obtained alloy is heat-treated. It is characterized in that a fine crystal phase having an average crystal grain size of 1 nm to 5 μm is precipitated.

Further, in the nickel-hydrogen secondary battery according to the present invention, an electrically insulating separator is interposed between a negative electrode containing a hydrogen storage alloy having the above-mentioned predetermined composition and crystal structure and a positive electrode containing nickel oxide. The sealed container is housed in a closed container, and the closed container is filled with an alkaline electrolyte.

In the hydrogen storage alloy according to the present invention, in the general formula, the A component is at least one element selected from Ti, Zr, Hf and V, all of which are basic elements that provide the hydrogen storage capacity of the alloy. It is an element that is effective for making alloy crystal grains fine and uniform. When the addition amount a of the component A is less than 20 atom (at)%, the capacity becomes too low. On the other hand, when the addition amount a exceeds 70 atom%, it becomes difficult to release hydrogen after occlusion, resulting in a decrease in battery capacity. Let it. Therefore, the addition amount of the component A is set in the range of 20 to 70 atomic%. When a hydrogen storage alloy is used as a negative electrode material for a battery, from the viewpoint of improving charge / discharge performance and life, 60% by atom or more of the component A is Ti and Z.
It is preferable that r is occupied.

The T component is Ni, Co, Fe, Cu,
It is at least one element selected from Mn and Cr, and each of these elements enhances the diffusion of hydrogen penetrating into the alloy and the catalytic action on the alloy surface, improves the corrosion resistance of the alloy, and further improves the hydrogen resistance of the alloy. It is an element that has an effect of improving the life by suppressing cracking of the alloy due to expansion of the lattice during occlusion. When the added amount b of these T components is less than 30 atomic%, the above-mentioned improvement effect is insufficient, while when the added amount b exceeds 60 atomic%, the decrease in capacity becomes remarkable. Therefore, the addition amount b of the T component is in the range of 30 to 60 at%, but more preferably in the range of 35 to 55 at%. In order to enhance the catalytic action on the alloy surface, Ni is particularly preferable among the above T components. Further, Co is particularly preferable as an element that suppresses cracks caused by lattice expansion during hydrogen storage and improves the life characteristics.

The M component is Al, Si, Ga, Ge,
It is at least one element selected from Zn, Sn, In and Sb, all of which have an effect of improving the corrosion resistance of the alloy, and have an effect of improving the life characteristics as a battery material. When the addition amount c of the M component is less than 5 atomic%,
While the above life improvement effect becomes insufficient, the addition amount c is 40
If it exceeds atomic%, the capacity becomes too low and is not practical. Therefore, the addition amount c of the M component is in the range of 5 to 40 atomic%.

M 'is at least one element selected from B, C, N and P. The M ′ component is an element effective when added simultaneously with the A component to refine the crystal grains when the alloy material obtained by the quenching treatment is heat-treated. That is, the M ′ component and the A component that have been once dissolved in the supersaturated state by the quenching treatment become compounds such as ZrB and HfC by heat treatment and precipitate in the structure as ultra-fine crystal nucleus components, thereby producing a large amount of fine crystal phases. Has the function of generating. It also has the effect of promoting the alloy to be amorphous by quenching. When the addition amount d of the M ′ component is less than 0.1 atomic%, the effect of refining the crystal grains becomes insufficient, while the addition amount d is 1%.
When the content exceeds 0 atomic%, the hydrogen storage amount is significantly reduced. Therefore, the addition amount d of the M ′ component is set in the range of 0.1 to 10 atomic%.

Further, among the above alloy components, particularly Ni is M
A- which is alloyed with component A and component A and has excellent corrosion resistance
M-Ni is an element effective for forming and absorbing and releasing hydrogen by forming a hydrogen storage alloy. Elements such as Co, Fe, and Cu all improve the corrosion resistance of the alloy,
It is an element that effectively suppresses the occurrence of cracks due to the expansion of the lattice during hydrogen storage and exhibits a life-improving effect. Elements such as Mn, Al, and Si are all elements that contribute to improving the life of the alloy. Further, Si, Cr, Ga, S
All elements such as n are effective for improving the life of the alloy.

Of the above-mentioned T components, Mn is effective in increasing the capacity of the negative electrode containing a hydrogen storage alloy, improving corrosion resistance by accelerating the formation of a passive film, and adjusting the hydrogen storage / release pressure (equilibrium pressure). is there. On the other hand, Al in the M component is Mn.
In the same manner as described above, the hydrogen storage and release pressure (dissociation pressure) can be reduced to an operation pressure suitable for a sealed battery, and the durability can be increased.

Further, Co as a T component is effective in improving the corrosion resistance of the alloy against an electrolytic solution or the like, and the pulverization of the alloy is remarkably suppressed, and the life characteristics of the battery are improved. When the amount of Co added is increased, the cycle life is improved, but the electrode capacity tends to decrease. Therefore, it is necessary to optimize the amount of Co added according to the use of the battery.

In addition, the hydrogen storage alloy according to the present invention includes:
Elements such as O, F and Cl may be contained as impurities as long as the properties of the alloy of the present invention are not impaired. The content of these impurities was 6000 ppm each.
It is preferable to be within the following range. More preferably 50
The content is preferably not more than 00 ppm, more preferably not more than 4000 ppm.

In the method for producing a hydrogen storage alloy according to the present invention, for example, a raw material mixture prepared so as to have a predetermined composition is heated in a high-frequency induction furnace to prepare a molten alloy, and thereafter, the obtained molten alloy is used. A quenched alloy having a non-equilibrium phase formed at least in part by injecting it onto a cooling body moving at a high speed and solidifying it by rapid cooling at a cooling rate of 100 ° C./sec or more; It can be manufactured by heat treatment to precipitate a fine crystal phase having an average particle size of 1 nm to 10 μm. By the rapid solidification treatment, it is possible to obtain a molten metal quenched alloy having a non-equilibrium phase in which the additional components are uniformly dispersed in the alloy structure. As a method of performing such rapid solidification treatment, there are a molten metal quenching method such as a gas atomizing method, a rotating disk method, a centrifugal spraying method, a single roll method and a twin roll method.

When cooling the molten alloy, the cooling rate is 100 ° C./sec or more, preferably 300 ° C./sec or more.
More preferably, by setting the temperature to 1800 ° C./second or more, even when a rare earth element such as La or an element that easily segregates is contained in a relatively large amount, the structure is uniform.
An alloy with less segregation can be obtained.

As a specific method of cooling and solidifying the molten alloy, for example, the molten alloy is injected onto a high-speed moving cooling body,
There is a method of obtaining a flake-like sample having a thickness of about 10 to 500 μm.

As a method of cooling and solidifying the molten alloy, a quenching method for rapidly cooling the molten molten alloy such as a gas atomizing method, a rotating disk method, a centrifugal spraying method, a single roll method, a twin roll method, etc. is used. The material and surface properties of the cooling roll, the number of revolutions of the cooling roll (peripheral speed of the running surface), the temperature of the molten metal, the temperature of the cooling water for the cooling roll, the gas type in the cooling chamber, the pressure, the diameter of the molten metal injection nozzle, the injection amount By optimizing the manufacturing conditions, the alloy can be manufactured stably in large quantities.

Single Roll Method FIG. 1 shows an apparatus for producing a hydrogen storage alloy by a single roll method. This manufacturing apparatus stores a cooling roll 5 having a diameter of about 400 mm, which is excellent in heat conductivity such as copper and nickel, and a hydrogen storage alloy melt 3 supplied from a ladle 2 and then sprays the same onto the running surface of the cooling roll 5. And a pouring nozzle 4 to be used. The cooling roll 5 and the like are housed in a cooling chamber 1 adjusted to an inert gas atmosphere. The rotation speed of the cooling roll 5 depends on the wettability and the cooling speed of the cooling roll 5 and the injection amount of the hydrogen storage alloy melt 3, but is generally set to 100 to 5000 rpm.

In the manufacturing apparatus shown in FIG. 1, the molten hydrogen storage alloy 3 supplied from the ladle 2
When the molten alloy is further sprayed onto the running surface of the cooling roll 5, the alloy melt solidifies from the surface in contact with the cooling roll 5, and crystal growth starts,
The solidification is completely completed before the solidification is removed from the cooling roll 5. Thereafter, the cooling proceeds further while flying in the cooling chamber 1, and the hydrogen storage alloy 6 with less segregation and a uniform crystal growth direction is manufactured.

The twin roll method Figure 2 is a hydrogen storage alloy manufacturing apparatus according twin roll method. This manufacturing apparatus includes one or more pairs of cooling rolls 5 a, which are arranged in the cooling chamber 1 such that respective running surfaces face each other.
5b, a melting furnace 7 for melting the raw material metal to prepare a hydrogen storage alloy melt 3, and a hydrogen storage alloy melt 3 from the melting furnace 7.
Is provided between the cooling rolls 5a and 5b via a tundish 8.

The cooling rolls 5a and 5b are formed of a material having excellent heat conductivity such as copper and iron and have a diameter of about 300 mm. The cooling rolls 5a and 5b are 0 to 0.5
100 to 200 while maintaining a small gap d of about mm.
It rotates at a high speed of about 0 rpm. In addition, as a cooling roll, as shown in FIG. 2, the running surface is parallel, and the running surface has a U-shaped or V-shaped cross-sectional shape.
A so-called mold roll can also be employed. Further, if the gap d between the cooling rolls 5a and 5b is excessively large, a cooling direction is not uniform, and as a result, a hydrogen storage alloy in which the crystal growth direction is not uniform is manufactured.

In the manufacturing apparatus shown in FIG. 2 described above, the molten hydrogen storage alloy 3 is poured from the pouring nozzle 4 into the cooling rolls 5a,
When the molten hydrogen storage alloy is injected in the gap direction of 5b, solidification and crystal growth of the hydrogen storage alloy melt start from the sides in contact with the cooling rolls 5a, 5b on both sides, and complete solidification by the time the metal is separated from the cooling rolls 5a, 5b. Thereafter, the cooling proceeds further while flying in the cooling chamber 1, and the hydrogen storage alloy 6 with less segregation and a uniform crystal growth direction is manufactured.

When a ribbon-shaped, flake-shaped or granular hydrogen-absorbing alloy is produced by using the cooling and solidifying method as described above, the temperature gradient in the sample during solidification and cooling of the molten alloy, the material of the cooling roll and the rotating disk Depending on conditions such as the supply amount of the molten alloy, a non-equilibrium structure such as an amorphous phase, or a crystal structure including a non-equilibrium phase as a main phase and partially including fine crystal grains is formed in the alloy.

That is, in the production process of the alloy particles, 100 ° C./sec or more, preferably 300 ° C./sec or more,
More preferably, when the molten metal is quenched at a cooling rate of 1800 ° C./sec or more to produce a hydrogen storage alloy, the alloy structure is formed of only an amorphous phase or a non-equilibrium phase as a main phase and 1 nm to An alloy structure having fine crystal grains of about 5 μm is obtained.

Further, by using a mechanical processing method such as a mechanical alloying method or a mechanical grinding method instead of the molten metal quenching method, it is possible to produce alloy particles composed of fine crystal grains. is there. In other words, a planetary ball mill, which mechanically promotes the reaction between particles while applying a certain degree of impact force to the sample particles, and controls the metal structure of a sample prepared or alloyed in advance to have a predetermined composition, etc. May be used to produce alloy particles. In this mechanical processing method,
The processing time is about 1 to 100 hours, and the processing is preferably performed in an inert gas atmosphere such as argon or nitrogen gas or a reducing atmosphere such as hydrogen gas. The material of the ball mill pot or ball used is not particularly limited, but stainless steel and ceramics are preferred. The particle size of the alloy powder obtained by this mechanical treatment is preferably in the range of 0.1 to 100 μm.

As described above, alloys prepared by the molten metal quenching method or the mechanical treatment method are liable to cause internal strain and segregation. In any case, when the alloy is used as a negative electrode material, the electrode capacity and the life are reduced. Often do. In addition, a non-equilibrium phase such as an amorphous phase formed in a quenched alloy does not have a plateau region in a hydrogen storage capacity-pressure diagram.Therefore, when an alloy containing many non-equilibrium phases is used as a battery material, The operating pressure during the hydrogen storage / release reaction becomes unstable.

Therefore, the alloy prepared by rapid solidification is
Basically, if the temperature is 200-1000 ° C, which is higher than the crystallization temperature,
It is necessary to perform a heat treatment of heating for 0 minute to 10 hours. By this heat treatment, a fine crystal phase is precipitated in the non-equilibrium phase formed by the quenching treatment, and the internal strain is removed to obtain a homogeneous alloy structure. Further, since a plateau region is clearly formed in the crystallized metal phase, the operating pressure of a battery using this alloy can be stabilized.

If the temperature of the heat treatment is lower than 200 ° C., the crystallization of the non-equilibrium phase becomes insufficient, and it becomes difficult to remove the internal strain. When the temperature exceeds 1000 ° C., a composition change occurs due to oxidation of elements such as Ti and Zr. Therefore, heat treatment temperature is 200 ~ 1000 ℃
Is set in the range. In particular, in order to improve the electrode characteristics, a range of 400 to 800 ° C. is preferable.

If the heat treatment time is less than 10 minutes, the crystallization becomes non-uniform and the characteristics vary greatly. on the other hand,
If the treatment time is prolonged to more than 10 hours, the oxidation of the alloy surface is apt to progress, and the alloy composition is significantly shifted, which is not preferable. Therefore, in consideration of the production efficiency, 10 minutes to 10 hours is preferable.

The heat treatment atmosphere is preferably an inert gas atmosphere such as Ar or a vacuum in order to prevent high-temperature oxidation of the hydrogen storage alloy.

It is preferable from the viewpoint of improving the battery characteristics that the average particle size of the crystals precipitated in the alloy structure by the above heat treatment be adjusted to a range of 1 nm to 5 μm. That is, if the average crystal grain size is too small, less than 1 nm, the hydrogen absorption characteristics of the alloy are insufficient, and the plateau region becomes unclear, which makes it particularly difficult to apply as a battery material. On the other hand, when the average crystal grain size is too large to exceed 5 μm, the high-rate discharge ratio is reduced. Therefore, the average grain size of the crystal is 1 nm to 5 μm.
m, preferably in the range of 1 nm to 3 μm,
Furthermore, the range of 1 nm to 1 μm is more preferable.

When a non-equilibrium phase such as an amorphous phase is finely crystallized by heat treatment in this way, a large amount of grain boundary phases, which serve as a diffusion path of hydrogen during hydrogen storage and desorption, are formed in a large amount. It is considered that a long-life alloy can be realized.

By performing the following surface treatment on the hydrogen storage alloy prepared by the molten metal quenching method or the mechanical treatment method as described above, the electrode characteristics can be improved when used as an electrode material. Can be. That is,
By performing a surface treatment such as an acid treatment, an alkali treatment, a fluoride treatment, and a plating treatment, the activity and corrosion resistance of the alloy surface can be enhanced. Among the above surface treatments, in particular, KO
An alkali treatment using an H solution or a NaOH solution is particularly effective. The alkali treatment temperature is preferably in the range of 45 ° C. to the boiling point of the alkaline solution, and the treatment time is preferably in the range of 5 minutes to 24 hours. These surface treatments may be performed in a state where the solidified solid remains rapidly quenched. Further, it may be carried out in a state after pulverization or during pulverization in an alkaline solution.

Next, a nickel-metal hydride secondary battery (cylindrical nickel-metal hydride secondary battery) according to the present invention using the above-mentioned hydrogen storage alloy as a negative electrode active material will be described with reference to FIG.

The nickel-hydrogen secondary battery according to the present invention, electricity between the positive electrode 12 including the negative electrode 11 and the nickel oxide containing the above general formula _{A a} T _b M _c M 'hydrogen-absorbing alloy represented by _d It is housed in a closed container 14 with an insulating separator 13 interposed, and the closed container 14 is filled with an alkaline electrolyte.

That is, the hydrogen storage alloy electrode (negative electrode) 11 including the hydrogen storage alloy is a non-sintered nickel electrode (positive electrode).
12 are wound spirally with a separator 13 interposed therebetween, and housed in a bottomed cylindrical container 14. The alkaline electrolyte is contained in the container 14. A circular sealing plate 16 having a hole 15 in the center is arranged at the upper opening of the container 14. The ring-shaped insulating gasket 17 is disposed between the peripheral edge of the sealing plate 16 and the inner surface of the upper opening of the container 14, and is sealed to the container 14 by caulking to reduce the diameter of the upper opening inward. Board 1
6 is hermetically fixed via the gasket 17.
One end of the positive electrode lead 18 is connected to the positive electrode 12, and the other end is connected to the lower surface of the sealing plate 16. The cap-shaped positive electrode terminal 19 is provided on the sealing plate 16 with the hole 15.
It is attached to cover. Rubber safety valve 20
Is disposed so as to close the hole 15 in a space surrounded by the sealing plate 16 and the positive electrode terminal 19. The insulating tube 21 is used to fix the positive electrode terminal 19 and the flange paper 22 placed on the upper end of the container 14.
It is attached near the upper end of.

As the hydrogen storage alloy electrode 11, a paste type and a non-paste type described below are used. (1) The paste-type hydrogen storage alloy electrode is prepared by mixing a hydrogen storage alloy powder obtained by pulverizing the above-mentioned hydrogen storage alloy, a polymer binder, and a conductive powder to be added as necessary. The paste is applied to a conductive substrate serving as a current collector, filled, dried, and then subjected to a roller press or the like. (2) The non-paste type hydrogen storage alloy electrode is obtained by stirring the above-mentioned hydrogen storage alloy powder, the polymer binder, and the conductive powder to be added as required, and spraying the mixed powder on the conductive substrate serving as a current collector. It is produced by applying a roller press or the like.

As a method of pulverizing the hydrogen storage alloy, for example, a mechanical pulverization method such as a ball mill, a pulperizer, or a jet mill, or a method in which high-pressure hydrogen is occluded / released and pulverized by volume expansion at that time, is employed. .

Examples of the polymer binder include sodium polyacrylate and polytetrafluoroethylene (PTF).
E), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA) and the like. Such a polymer binder is preferably blended in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the hydrogen storage alloy. However, when preparing the non-paste type hydrogen storage alloy electrode of the above (2), the hydrogen storage alloy powder and the conductive powder to be added as required are formed into a three-dimensional shape (mesh shape) by fiberization by stirring. It is preferable to use immobilizable polytetrafluoroethylene (PTFE) as the polymer binder.

Examples of the conductive powder include carbon powder such as graphite powder and Ketjen black, and metal powder such as nickel, copper and cobalt. Such conductive powder can be used as the hydrogen storage alloy 10
It is preferable to add 0.1 to 5 parts by weight to 0 part by weight.

As the conductive substrate, for example, a two-dimensional substrate such as a punched metal, an expanded metal, or a wire mesh, or a three-dimensional substrate such as a foamed metal substrate, a net-like sintered fiber substrate, or a felt-plated substrate obtained by plating a metal on a nonwoven fabric is used. Can be mentioned. However, when producing the non-paste type hydrogen storage alloy electrode of the above (2), it is preferable to use a two-dimensional substrate as the conductive substrate since a mixture containing the hydrogen storage alloy powder is sprayed.

The non-sintered nickel electrode 12 combined with the hydrogen storage alloy electrode is made of, for example, nickel hydroxide and cobalt hydroxide (Co (O
H) ₂ ), carboxymethyl cellulose (CMC), a mixture with cobalt monoxide (CoO), metallic cobalt, etc.
A polyacrylic acid salt such as sodium polyacrylate is appropriately blended to form a paste, and this paste is used as a foam metal substrate,
It is prepared by filling a substrate having a three-dimensional structure such as a reticulated sintered fiber substrate or a felt-plated substrate obtained by plating a metal on a non-woven fabric, drying it, and then performing roller pressing or the like.

The polymer fiber non-woven fabric used for the separator 13 is, for example, nylon, polypropylene,
Examples thereof include simple polymer fibers such as polyethylene, and composite polymer fibers obtained by blending these polymer fibers.

As the alkaline electrolyte, for example, a potassium hydroxide solution having a concentration of 6N to 9N or a mixture of the potassium hydroxide solution with lithium hydroxide, sodium hydroxide or the like is used.

According to the hydrogen storage alloy having the above-described structure, the types and composition ratios of the various elements constituting the alloy are properly set, and a fine crystal phase having excellent hydrogen storage characteristics is formed in the alloy structure. Therefore, a hydrogen storage alloy having excellent hydrogen storage characteristics and corrosion resistance can be obtained. Therefore, when this alloy is used as a negative electrode material, the battery capacity is increased, and the pulverization of the alloy due to the alkali solution can be prevented from being deteriorated. A battery can be provided.

[0055]

Next, embodiments of the present invention will be described more specifically with reference to the following examples.

Examples 1 to 10 Various metal raw material powders were blended so as to have the alloy compositions shown in the left column of Table 1, and the obtained raw material mixture was heated and melted in a vacuum furnace to obtain an alloy melt for each example. (Master alloy) were prepared.

Next, the obtained molten alloy was cooled and solidified in an Ar atmosphere according to the following processing conditions to prepare ingot-shaped or flake-shaped alloy samples, respectively.

That is, the alloy melts for Examples 1 to 5 were rapidly solidified by a single roll method as shown in FIG. 1 to prepare flake-shaped alloy samples. As the cooling roll, a Cu roll having a diameter of 400 mm was used, the gap between the pouring nozzle (injection nozzle) and the cooling roll was set to 10 mm, the injection temperature was set to the melting point of each alloy + 150 ° C, and the injection pressure was set to 0.5 kg / cm ² . The quenching operation was performed in an Ar atmosphere, and the roll peripheral speed was set at 25 m / sec.

On the other hand, the alloy melts for Examples 6 to 10 were rapidly solidified by a twin roll method as shown in FIG. 2 to prepare flake-like alloy samples. The processing atmosphere in the twin roll method was an Ar gas atmosphere as in the case of the single roll method. The material of the cooling roll is Fe (SUJ-
2), and an iron roll having a diameter of 300 mm was used.
Further, the roll circumferential speed was set to 10 m / S with the roll gap of the cooling roll set to zero, and the injection pressure was set to 0.5 kg / cm ^2.
Set to.

Of the alloy samples thus obtained, the quenched alloy samples produced by the single roll method and the twin roll method are both flake-like and have a thickness of 150 to 20 mm.
It was 0 μm. These flake-like alloy samples were subjected to a heat treatment according to the temperature and time conditions shown in Table 1 to achieve crystallization and homogenization of the alloy structure.

Comparative Examples 1 and 2 Raw material powders were blended so as to satisfy the alloy composition shown in the left column of Table 1, and the obtained raw material mixture was heated and melted in a vacuum furnace to obtain a molten alloy for each comparative example. Each was prepared. Incidentally, the alloy composition according to Comparative Example 1 shows a typical composition of a conventional AB ₅ type hydrogen storage alloy, the alloy composition of Comparative Example 2, another exemplary conventional AB ₅ type hydrogen storage alloy An example of a suitable composition is shown below.

Then, each alloy melt is cast by a normal casting method.
The cooling rate is set at 5 to 60 ° C./minute to cool and solidify,
Block-shaped alloy samples (hydrogen storage alloy) according to Comparative Examples 1 and 2 each having a thickness of 50 mm were prepared. Further, the obtained alloy samples of Comparative Examples 1 and 2 were heated at 1000 ° C. for 5 hours to perform a heat treatment.

Next, each of the obtained alloy samples was coarsely pulverized and then finely pulverized by a hammer mill. The obtained pulverized powder was passed through a sieve and classified to a particle size of 75 μm or less. Powder. The average particle size is 35 to 40.
μm. Further, the hydrogen-absorbing alloy powder for each battery after the heat treatment was subjected to X-ray diffraction, and the average crystal grain size was calculated from the obtained half-width based on Scheerer's formula, and the results shown in Table 1 were obtained.

Next, in order to evaluate the characteristics of the hydrogen storage alloy for a battery according to each of the above Examples and Comparative Examples as a battery material, an electrode was prepared by using each of the above hydrogen storage alloys for a battery according to the following procedure. Was formed, and its electrode capacity, number of charge / discharge cycles (life), and high rate discharge were measured.

First, the hydrogen-absorbing alloy powder for a battery, the PTFE powder, and the carbon powder according to the above Examples and Comparative Examples were adjusted to 95.5%, 4.0%, and 0.5% by weight, respectively. After weighing, each electrode sheet was prepared by kneading and rolling. The electrode sheet was cut out to a predetermined size, and pressed to a nickel current collector to prepare a hydrogen storage alloy electrode.

On the other hand, a small amount of CMC (carboxymethylcellulose) and water were added to 90% by weight of nickel hydroxide and 10% by weight of cobalt monoxide and mixed by stirring to prepare a paste. This paste was filled in a porous nickel body having a three-dimensional structure, dried, and then rolled by a roller press to produce a nickel electrode.

The capacity of each of the above-mentioned hydrogen storage alloy electrodes and the nickel electrode was combined and measured by the unipolar evaluation. On the other hand, the life was evaluated by the nickel-metal hydride battery (4 / 3-A size, 4000
(mAh specification battery) was assembled and evaluated. Here, an 8N aqueous potassium hydroxide solution was used as the electrolytic solution.

In the evaluation of the capacity of each hydrogen storage alloy electrode, the battery was charged to 400 mAh / g at a current value of 200 mA per gram of alloy (200 mA / g) in a constant temperature bath at 40 ° C. With respect to the reference electrode,
The battery was discharged until the potential reached 0.5 V, and the charge and discharge were repeated, and the value when the amount of discharge reached the maximum was measured as the capacity.

The high-rate dischargeability is determined by measuring the capacities at discharge currents per unit weight of 20 mA / g and 200 mA / g as C ₂₀ and C ₂₀₀ , respectively, and their ratio (C ₂₀₀ / C ₂₀ ). Was defined as a high rate discharge ratio, and the ratio was evaluated according to the magnitude of the ratio.

In the life evaluation, 4 A
After charging for 1.1 hours, until the battery voltage reaches 0.9 V
The charge / discharge cycle of discharging with the current of A is repeated, and the number of cycles until the battery capacity becomes 80% of the initial capacity is set to 40 ° C.
And measured as battery life. Table 1 below shows the measurement results.

[0071]

[Table 1]

As is clear from the results shown in Table 1 above,
After properly setting the types of the elements constituting the A, T, M and M 'components in the general formula, and the composition ratio of each component, and solidifying by cooling, heat treatment is performed to obtain a fine crystal phase. In the electrode and the battery formed using the hydrogen storage alloy according to each of the examples prepared by precipitating the alloy, the electrode capacity, life, and It was confirmed that all the characteristics of the high-rate discharge property were good and that excellent battery performance could be exhibited.

[0073] On the other hand, in the conventional AB ₅ type hydrogen storage alloy a is Comparative Example 1 Alloy although the high rate discharge properties are equivalent to Example, found that capacity and service life may be reduced as compared with Example did. Further, in another conventional AB ₅ type hydrogen storage alloy a is Comparative Example 2 alloy, but approximates example for capacity, high-rate discharge properties and lifetime was confirmed to be reduced. That is, it was found that by setting the composition range specified in the present example and forming a fine crystal phase, a nickel-hydrogen secondary battery having a high capacity, a long life, and an excellent high-rate discharge property can be obtained. did.

[0074]

As described above, according to the hydrogen storage alloy of the present invention, the type of various elements constituting the alloy and the composition ratio thereof are properly set, and the fine crystalline phase excellent in hydrogen storage characteristics is obtained. Is formed in the alloy structure, so that a hydrogen storage alloy having excellent hydrogen storage characteristics and corrosion resistance can be obtained. Therefore, when this alloy is used as a negative electrode material, a nickel-hydrogen secondary battery having a large battery capacity, a long life, and excellent high-rate discharge performance can be provided.

[Brief description of the drawings]

FIG. 1 is a perspective view showing the configuration of a hydrogen storage alloy manufacturing apparatus using a single roll method.

FIG. 2 is a cross-sectional view showing a configuration of a hydrogen storage alloy manufacturing apparatus using a twin-roll method.

FIG. 3 is a perspective view showing a configuration example of a nickel-metal hydride secondary battery according to the present invention, partially cut away;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cooling chamber 2 Ladle 3 Hydrogen storage alloy melt 4 Pouring nozzle 5, 5a, 5b Cooling roll 6 Hydrogen storage alloy 7 Melting furnace 8 Tundish 11 Hydrogen storage alloy electrode (negative electrode) 12 Non-sintered nickel electrode (positive electrode) DESCRIPTION OF SYMBOLS 13 Separator 14 Container 15 Hole 16 Sealing plate 17 Insulating gasket 18 Positive electrode lead 19 Positive electrode terminal 20 Safety valve 21 Insulating tube 22 Flange paper d Gap

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01M 4/38 H01M 4/38 A 10/30 10/30 Z // B22D 11/06 360 B22D 11/06 360B 360C C22F 1/00 661 C22F 1/00 661C

Claims (4)

[Claims] 1. A general formula _{A a T b M c M '} d ( provided that at least 1 A is selected Ti, Zr, and Hf and V
T is at least one element selected from Ni, Co, Fe, Cu, Mn and Cr;
M is at least one element selected from Al, Si, Ga, Ge, Zn, Sn, In and Sb;
Is at least one element selected from B, C, N, and P, and a, b, c, and d are each 20% ≦ at%.
a ≦ 70, 30 ≦ b ≦ 60, 5 ≦ c ≦ 40, 0.1 ≦ d
≦ 10, a + b + c + d = 100. A hydrogen storage alloy comprising an alloy having a composition represented by the formula (1), wherein a fine crystal phase having a crystal grain size of 10 μm or less is precipitated in at least a part of the alloy structure. 2. The hydrogen storage alloy according to claim 1, wherein the average crystal grain size of the alloy is in the range of 1 nm to 5 μm. 3. A general formula A _a T _b M _c M ′ _d (where A is at least one selected from Ti, Zr, Hf and V)
T is at least one element selected from Ni, Co, Fe, Cu, Mn and Cr;
M is at least one element selected from Al, Si, Ga, Ge, Zn, Sn, In and Sb;
Is at least one element selected from B, C, N, and P, and a, b, c, and d are each 20% ≦ at%.
a ≦ 70, 30 ≦ b ≦ 60, 5 ≦ c ≦ 40, 0.1 ≦ d
≦ 10, a + b + c + d = 100. An alloy having a composition represented by the formula (1) and having at least a part formed in a non-equilibrium phase is prepared, and then the obtained alloy is heat-treated to precipitate a fine crystal phase having an average crystal grain size of 1 nm to 5 μm. A method for producing a hydrogen storage alloy, comprising: 4. A general formula A _a T _b M _c M ′ _d (where A is at least one selected from Ti, Zr, Hf and V)
T is at least one element selected from Ni, Co, Fe, Cu, Mn and Cr;
M is at least one element selected from Al, Si, Ga, Ge, Zn, Sn, In and Sb;
Is at least one element selected from B, C, N, and P, and a, b, c, and d are each 20% ≦ at%.
a ≦ 70, 30 ≦ b ≦ 60, 5 ≦ c ≦ 40, 0.1 ≦ d
≦ 10, a + b + c + d = 100. A) a negative electrode containing a hydrogen storage alloy in which a fine crystal phase having a crystal grain size of 10 μm or less is precipitated in at least a part of the alloy structure, and a positive electrode containing nickel oxide. A nickel-metal hydride secondary battery, comprising a sealed container with an electrically insulating separator interposed between the sealed containers and filling the sealed container with an alkaline electrolyte.