JPH0969362A - Secondary battery and power source using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a secondary battery having the large capacity, and excellent in rapid charging characteristics and rapid discharging characteristics. SOLUTION: In a secondary battery, a positive pole 5 and a negative pole 6 are formed through electrolyte. Either the positive pole 5 or the negative pole 6 contains material grains related to the rapid discharging reaction, the grain is composed of at least two or more phases capable of relating to the charging or discharging reaction, and at least one phase of the phases is provided with thin holes to be formed by melting, and cracks. By this structure, a secondary battery having the high capacity, and in which the rapid charging and discharging characteristics are improved is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a secondary battery and a system using the secondary battery, and more particularly to a secondary battery excellent in quick charge and quick discharge characteristics and a power supply system using the secondary battery.

[0002]

2. Description of the Related Art The demand for batteries as a power source is increasing with the rapid spread of various small cordless devices. Particularly, from the viewpoint of ease of use, a high capacity that can extend the usage time of the device by one charge is provided. The demand for is increasing. Consumer demand for higher capacity is persistent. In recent years, nickel-metal hydride batteries and lithium secondary batteries have been rapidly developed. In a nickel-metal hydride battery, a negative electrode containing a hydrogen storage alloy as a main component is used. The nickel-metal hydride battery has almost the same compatibility as the nickel-cadmium battery in terms of battery voltage, discharge characteristics, etc., and has a battery capacity of 50-100.
It is attracting attention as a battery that can be expected to increase in%. Further, the lithium secondary battery has a high battery voltage and is light in weight, and thus has a high capacity like a nickel-metal hydride battery.

Considering the usability of a battery, it is required to improve the rapid charging characteristic, which shows how the battery can be charged in a short time. In addition, the rapid discharge characteristic is important from the side of a device such as an electric vehicle that requires a large current discharge.
Lead-acid batteries and nickel-cadmium batteries have some satisfactory characteristics for rapid charging and rapid discharging, but nickel-metal hydride batteries and lithium secondary batteries have satisfactory rapid charging and rapid discharging. is not.

Conventionally, several methods have been considered for improving the rapid charge / discharge characteristics of nickel-metal hydride batteries. For example, a hydrogen storage alloy electrode composed of ultrafine particles having an average particle size of 5 microns or less may be used (Japanese Patent Application Laid-Open No. S60-18753).
No. 60-119079), a sheet-shaped hydrogen storage alloy electrode containing a binder is provided with pores having a diameter of 30 μm or more (JP-A-61-61).
No. 153947), the surface of hydrogen storage alloy particles (base particles) is coated with particles of a metal simple substance having an average particle size of 1/10 to 1/200, a nickel-based alloy, and stainless steel (Japanese Patent Laid-Open No. 64-6439).
-6366), a hydrogen storage alloy composed of disordered multi-component materials combining amorphous, microcrystalline, and polycrystals lacking long-range structural order (Japanese Patent Publication No. 4-80512). In a lithium battery, the surface of the current collector is coated with nickel or titanium (Japanese Patent Laid-Open No. 5-159781) or the carbon material is expanded to cause cracks (Japanese Patent Laid-Open No. 3-13497).
No. 0) to improve the rapid charge and discharge characteristics.

[0005]

Generally, in an electrode, after particles of a substance involved in a battery reaction are made into fine particles, a binder is added to adhere them in a sheet form, or the particles are bonded to each other by a sintering method. This produces a porous electrode plate. Therefore, if the average particle size of the particles is reduced, the area of the reaction field of the substance layer involved in the battery reaction also increases. However, in practice, the finer the particles involved in the battery reaction are, the more the particles fall out of the electrode, and the capacity is reduced. Is generated, which becomes a factor that hinders the battery reaction and causes a problem that the rapid charge / discharge characteristics are warped and deteriorated.

Here, it is considered that the formation of pores on the surface of the substance involved in the battery reaction is effective in improving the reaction area, but pores are formed in the contact portion with the binder and in the gap layer between particles. However, it has no effect. Providing a plurality of holes in the electrode causes a decrease in the packing density of the substance involved in the battery reaction of the electrode rather than an increase in the reaction area, and the capacity actually decreases. In addition, the generation of such pores lowers the electrical contact between particles, so that the rapid charging / discharging characteristics are rather deteriorated. The same applies to the generation of cracks that do not stay.

The method of arranging the conductive particles around the material particles involved in the battery reaction, the shape of the particles to be arranged may be fibrous or film-like, and the kind of particles does not hinder the conductivity. If present, a reaction catalyst other than carbon or metal may be used. However, if such a substance that does not act as a substance involved in the battery reaction or has a low action is added, there is a problem that the capacity density is lowered when added.

[0008] The method of making the crystal structure of a substance involved in a battery reaction into a disordered multi-component substance by combining amorphous, microcrystalline, and low-crystallinity polycrystals is a disordered structure, and the storage site and active Sites appear, resulting in a substantial increase in surface area that does not depend solely on the presence of cracks, holes, and grain boundaries.
In the above disordered materials, grain boundaries are also disordered and unclear, and therefore stress due to expansion and contraction at the time of charging and discharging is relaxed, and cracks and pores are less likely to be generated. The storage capacity is large and the cycle life is long. However, in the battery reaction during rapid charge and discharge, the charge transfer reaction on the surface is rate-determining, and even if many storage sites and active sites are created three-dimensionally inside the substance, if the reaction area on the surface is small, it becomes charge transfer rate-determining. , Can not keep up with the speed of rapid charge and discharge. That is, it is necessary to consider a method of smoothly proceeding the charge transfer on the surface and an increase in the reaction area of the surface.

There are various methods for coating the current collector, but it is carried out in order to reduce the contact resistance between the current collector and the substance involved in the battery reaction. However, in reality, the resistance inside the electrode is more important than the contact resistance between the current collector and the substance involved in the battery reaction, such as the contact resistance between particles and the reaction resistance at the interface between particles and the electrolyte. Is much larger.

Since the expansion treatment of the material facilitates the formation of cracks, it is effective for increasing the reaction area of the surface. However, the expansion of the lattice volume causes drawbacks such as impairing the reversibility of charge and discharge and reducing the discharge capacity.

As described above, no effective method has been found for improving the rapid charge / discharge characteristics of the battery.

An object of the present invention is to improve the rapid charge / discharge characteristics of a secondary battery and to provide a secondary battery which is used for a wide range of purposes and a power supply system using the secondary battery.

[0013]

The present invention provides an output of 580.
Provided is a secondary battery capable of discharging for 15 minutes or more at W / l or more.

In the secondary battery of the present invention, the positive electrode or the negative electrode is
It is characterized in that it contains particles of a substance involved in a charge / discharge reaction, the particles are composed of at least two phases, and at least one of the phases is composed of an electrode having pores.

The particles are characterized in that they are composed of at least two phases, and that at least one of the phases has pores and has cracks.

Further, at least one of the phases has pores formed by dissolution or evaporation.

The particles are characterized by having pores formed by dissolving or evaporating at least one of the phases and having cracks formed by the formation of charge products or discharge products. .

It is characterized in that at least two of the phases are substances which can independently participate in a charging or discharging reaction and which have different charging capacities or discharging capacities. The size of the charge capacity or the discharge capacity does not matter. Comparing the charge capacities or the discharge capacities of the two phases and having different values causes stress fracture, that is, it is necessary for the formation of cracks.

At least two of the phases are substances showing different expansion rates or contraction rates in charge or discharge reaction. The respective magnitude of expansion or contraction does not matter. Comparing the expansion rates or contraction rates of the two phases and different values cause stress fracture, that is, it is necessary for the formation of cracks.
The expansion coefficient or the contraction coefficient can be calculated by increasing or decreasing the lattice constant calculated from the X-ray diffraction measurement result.

The particles are selected from the group consisting of at least one of the phases capable of participating in a charge or discharge reaction, of the pores, at their boundaries, and any combination thereof. It is characterized in that cracks are generated in at least one region. The cracks pin the phases that are not involved in the charge or discharge reaction or the phases that remain inside without being completely dissolved or evaporated, and the cracks do not spread further. Therefore, the crack does not progress, the cavity is generated from the deep crack, and the electrical contact is not interrupted. However, there are two phases involved in the charge or discharge reaction.
There are more than one phase, the charge capacity or discharge capacity of each phase is different, the expansion coefficient is different, the presence of pores, etc., there are many sources of cracks, many short cracks occur, and the surface The reaction area of can be increased. Furthermore, the particles of the present invention have a clear boundary between the phases involved in the charge or discharge reaction. Therefore,
Cracks can also be formed along this boundary.

The particles have cracks due to the charging reaction of the battery,
Formed by at least one means selected from the group consisting of a discharge reaction, a reaction similar thereto, a reaction with at least one of an electrolytic solution, an acid, an alkali, an oxidizing agent, a reducing agent, and any combination thereof. It is characterized by In the case of a hydrogen storage alloy of a nickel-metal hydride secondary battery, the similar reaction means, for example, reacting hydrogen in the gas phase with hydrogen at a temperature and a pressure at which hydrogen can be stored and released. Alternatively, it is a reaction in which hydrogen is occluded in the alloy by using a reaction involving generation of hydrogen gas in the liquid phase. Speaking of a lithium secondary battery, for example, it is a thermodynamic reaction with lithium. The reaction with the electrolytic solution is a corrosion or oxidation reaction of the electrolytic solution and the alloy generally used in the nickel-metal hydride secondary battery, in the case of the hydrogen storage alloy of the nickel-metal hydride secondary battery. Speaking of lithium secondary batteries, the decomposition reaction of the electrolytic solution on the surface of the negative electrode or the positive electrode,
Alternatively, it is a reaction between impurities in the negative electrode or the positive electrode, active sites such as radicals, and the electrolytic solution.

The pores are present on the surface of the particles that come into contact with the electrolytic solution. Since the pores contribute to the battery reaction, it is sufficient that they exist at least on the surface of the particles that come into contact with the electrolytic solution.

The substance particles involved in the charging / discharging reaction constituting the electrode of the battery of the present invention have pores on the surface of the pores, and the composition of the surface of the pores is the composition of the surface of the particles around the pores. It is characterized by being different from. The particles are so-called primary particles. Unlike pores that are formed between particles by aggregating particles, due to elements that exist in the dissolved or evaporated phase or elements that exist in the grain boundary between the phase due to dissolution and other phases The surface of the resulting pores can have an active coating.

The particles are composed of a plurality of phases, the pores are formed by dissolving or evaporating at least one phase among the phases, and the pore surfaces have at least one transition metal or noble metal. And For example, it is a state of a film of a transition metal or noble metal oxide, hydroxide, carbonate, chelate complex, or solid solution with a different metal. When the particles consist of an alloy, it is an alloy containing at least two or more elements, and the alloy has a first phase and at least one second phase precipitated in the first phase, Second
Of these phases, at least one phase has pores formed by dissolution or evaporation. At least one of the second phases
It is characterized in that the phase alone is a substance capable of participating in a charge or discharge reaction that exhibits a charge capacity or a discharge capacity different from that of the first phase. Further, cracks are formed in the particles.

When the main component of the particles is carbon, it is carbon having at least one kind of phase,
The carbon surface has pores formed by dissolving or evaporating at least one of the phases.
The pores may be present only on the surface that can come into contact with the electrolytic solution, and the pores may not exist inside the particles that cannot come into contact with the electrolytic solution. When the particles include carbon and an additive component, the one or more phases may include an additive component or a compound of the additive component and carbon. It is characterized in that at least one of the phases is a substance capable of participating in a charging or discharging reaction having a charging capacity or a discharging capacity different from that of carbon alone. Moreover, a crack is formed in the particles.

When the particles are composed of oxides or sulfides, they are oxides or sulfides containing at least two kinds of elements, and these compounds are at least precipitated in the first phase and the first phase. It is characterized by having one kind of second phase and having pores formed by dissolving or evaporating at least one phase of the second phase. It is characterized in that at least one of the second phases is a substance capable of participating in a charge or discharge reaction which shows a charge capacity or a discharge capacity different from that of the first phase by itself. A crack is formed in the particles.

The particles are particles having an average particle size of 2 millimeters or less, and the particles have an average particle size of ½ or less 15
It is characterized in that it has pores having an average diameter of 1/0 or more. This particle size is a so-called primary particle. The substance involved in the charge / discharge reaction of the present invention is a particle having a particle size of 2 millimeters or less, preferably 20 nanometers or more and 500 micrometers or less, and the particles are bonded with a binder or mechanically pressed. The porous electrode is formed by powdering, thermally sintering, or chemically aggregating. If the particles are larger than 2 millimeters, even if the pores of the present invention are provided, the remarkable effect of improving the characteristics is not recognized. The effect of the present invention can be recognized with active material particles having a particle size of preferably 20 nanometers or more and 500 micrometers or less.

The average diameter of the pores is not more than ½ and not more than 150 times, preferably not more than ⅕ of the average particle diameter of the particles 50.
It is more than one-third. When the average diameter of the pores is larger than one-half of the average particle diameter of the particles, the holding power of the electrolytic solution is lowered, the liquid holding amount is reduced, and the area of the reaction field is reduced. On the other hand, if it is smaller than 1/150, bubbles are less likely to escape, so that the electrolytic solution is not retained and the area of the reaction field decreases.

The above-mentioned particles are characterized in that the surface area occupied by the pores is in the range of 0.15% to 80% of the surface area of the particles.

The pores present in the particles occupy a pore area of 0.15% to 80%, preferably 10% to 50% of the surface area of the particles. If it is less than 0.15%, the effect of improving the characteristics is small, and if it is more than 80%, the packing density of the particles is lowered and the capacity density is lowered.

The proportion of the pores in the particles is characterized by being in the range of 0.2% by volume to 60% by volume of the particle volume.

The ratio of the pores is 0.2 of the particle volume.
It is in the range of 60% by volume to 60% by volume, preferably 1% to 40% by volume. When it is less than 0.2% by volume, the effect of improving the characteristics is small, and when it is more than 60% by volume, the packing density of the active material is lowered and the capacity density is lowered.

Of the above-mentioned phases, at least two of the phases that can participate in the charge or discharge reaction have a smaller charge capacity or discharge capacity, or a larger charge capacity than the smaller charge capacity or discharge capacity. Alternatively, the discharge capacity ratio is 1.05 or more.

Of the above-mentioned phases, at least two of the phases that can participate in the charge or discharge reaction have a smaller charge capacity or discharge capacity, and a larger charge capacity or discharge capacity than the smaller charge capacity. Alternatively, the discharge capacity ratio is 1.05 or more, preferably in the range of 1.5 to 3.5. When it is less than 1.05, cracks are less likely to be generated and the effect of improving the characteristics is small.

The volume expansion rate or contraction rate that occurs in the charge or discharge reaction of at least two of the phases that can participate in the charge or discharge reaction is larger than the smaller expansion rate or contraction rate. The ratio of the expansion rate or the contraction rate of the other is 1.1 or more.

The ratio of the expansion rate or contraction rate of the phase having a large volume expansion rate or contraction rate generated in the charge or discharge reaction of any two of the phases to the expansion rate or contraction rate of the small phase is It is 1.1 or more, preferably in the range of 1.7 to 4.5. If it is less than 1.1, cracks are less likely to be generated and the effect of improving the characteristics is small.

When the negative electrode has hydrogen absorbing alloy particles,
The particles are magnesium, lanthanum, cerium, praseodymium, neodymium, titanium, zirconium, hafnium, niobium, palladium, yttrium, scandium, calcium, aluminum, cobalt, chromium, vanadium, manganese, tin, boron, molybdenum, tungsten, carbon, lead. , An alloy containing at least one of iron, nickel, potassium, sodium, lithium, and at least two phases, and at least one of the phases is melted or evaporated to form pores. It is characterized by having.

For example, the phase to be dissolved is in a state of being dispersed in the mother phase. The dissolved phase is an alkali-soluble phase. In the present invention, the phase formed by dissolution includes a phase dissolved by an acid, an alkali, an oxidizing agent and a reducing agent, and a phase formed by evaporating upon contact with a reaction gas. Furthermore, as in the gas atomizing method, a small amount of oxygen is contained inside and on the surface of the particle, and the metal element in the molten state reacts with oxygen to change into a gaseous oxide,
The present invention also includes those that evaporate to form pores in the particles. The above-mentioned gaseous oxide can be changed into a solid oxide during the cooling process and can form pores inside the particles due to volume contraction, which is also included in the present invention.

The hydrogen-absorbing alloy particles have pores of at least one of the phases that can participate in the charge or discharge reaction due to the formation of charge products or by-products during charge / discharge. Of the cracks and at least one region selected from the group consisting of any combination thereof. The charge product is, for example, a metal hydride or a solid solution phase of hydrogen. Also,
By-products at the time of charging / discharging are hydroxides, oxides, or precipitates of the elements that make up the hydrogen storage alloy particles. It is characterized in that at least two of the phases are substances that are capable of participating in a charge or discharge reaction that show different charge capacities or discharge capacities by themselves.

The above alloy (intermetallic compound) was prepared by arc melting or high frequency melting, powder atomization, molten metal quenching,
It can be prepared by gradually cooling or holding the molten metal at a temperature at which an alkali-soluble phase or a second phase capable of participating in a charge or discharge reaction is obtained.

In the negative electrode having the above hydrogen storage alloy particles, the phase to be dissolved is at least aluminum, vanadium, manganese, tin, boron, magnesium, molybdenum, tungsten, zirconium, potassium, sodium, lithium, nickel, titanium. It is preferable to contain one of them in an amount of 40% by weight or more. The phase in which the content of the above components is in the above range is suitable for dissolving and forming fine pores, and can form good fine pores.

This dissolved phase forms a very soluble phase in the alkaline electrolyte.

It can also be manufactured by sintering or melting, or by mixing by a mechanical alloying method or a mechanical grinding method. In the mechanical alloying method and mechanical grinding method, the degree of alloying is adjusted by optimizing the number of rotations and the time, and it is possible to participate in the phase that dissolves in alkali without homogenization and the charge or discharge reaction. The phase is segregated to produce the desired negative electrode (or particles that form the negative electrode).

The pores may be formed by being dissolved in the electrolytic solution. The electrolytic solution may be one generally used in nickel-hydrogen batteries. The pores may be present only on the surface that can come into contact with the electrolytic solution, and the pores may not exist inside the particles that cannot come into contact with the electrolytic solution.

In the secondary battery of the present invention, the negative electrode is
At least one of carbon, iron, nickel, sulfur, boron, molybdenum, tungsten, vanadium, niobium, silicon, tin, lithium, sodium, potassium, lead and silver, or an oxide. One phase may be contained, and at least one of the phases may have pores formed by dissolution or evaporation with at least one of acid, alkali, oxidizing agent and reducing agent. The negative electrode is preferably applied to, for example, a negative electrode of a lithium secondary battery.

The negative electrode particles have a boundary between pores of at least one of the phases that can participate in the charge or discharge reaction among the phases due to the formation of charge products or by-products during charge and discharge. And a crack is generated in at least one region selected from the group consisting of any of these and combinations thereof.

It is characterized in that at least one of the above-mentioned phases is a substance capable of participating in a charging or discharging reaction which shows a charging capacity or a discharging capacity different from that of carbon alone.

In the secondary battery of the present invention, the positive or negative electrode is made of a conductive polymer, or the conductive polymer is iron, nickel, sulfur, boron, molybdenum, tungsten, vanadium, niobium, silicon, tin, It contains at least one phase consisting of at least one element of lead, lithium, sodium, potassium and silver or an oxide, and at least one phase of the phase is dissolved by at least one of acid, alkali, oxidizing agent and reducing agent. It may have pores formed by evaporation. It is preferable that the positive electrode or the negative electrode is, for example, a positive electrode or a negative electrode of a lithium secondary battery.

The positive electrode or negative electrode particles are charged products,
By the generation of discharge products or by-products during charging and discharging,
A crack is formed in at least one region selected from the group consisting of pores, their boundaries, and any combination thereof in at least one of the phases capable of participating in a charge or discharge reaction. It is characterized by generating.

At least one of the phases is a substance which is capable of participating in a charging or discharging reaction having a charging capacity or discharging capacity different from that of the conductive polymer by itself.

In the secondary battery of the present invention, the negative electrode is made of nickel, silicon, germanium, magnesium, copper,
It is composed of an alloy containing at least one of manganese, niobium, boron and silver, and is composed of at least two phases, at least one of which is dissolved or evaporated by at least one of acid, alkali, oxidizing agent and reducing agent. It is characterized by having pores formed by. The negative electrode is preferably applied to, for example, a negative electrode of a lithium secondary battery.

The negative electrode particles have pores in at least one of the phases that can participate in the charge or discharge reaction among the phases due to the formation of charge products or by-products during charge and discharge. It is characterized in that cracks are generated in at least one region selected from the group consisting of the boundary and any combination thereof.

It is characterized in that at least two of the phases are substances which can independently participate in a charging or discharging reaction and which have different charging capacities or discharging capacities.

In the secondary battery of the present invention, the positive electrode is made of lead, manganese, vanadium, iron, nickel, cobalt,
Copper, chromium, molybdenum, titanium, niobium, tantalum,
An oxide containing at least one of strontium, bismuth, tungsten and boron, or titanium, molybdenum, iron, tantalum, strontium, lead, niobium, copper,
A first phase comprising a sulfide containing at least one of nickel, vanadium, bismuth and manganese, or a complex oxide containing the above oxide or a sulfide and lithium, and aluminum, tin, boron, magnesium, potassium, sodium , At least one of vanadium or at least one second phase containing an oxide, and at least one of the second phases is dissolved by an acid, an alkali, an oxidizing agent or a reducing agent. It is characterized by having pores formed by The positive electrode is preferably applied to, for example, a lithium secondary battery positive electrode.

In the secondary battery of the present invention, the positive electrode is lead, manganese, vanadium, iron, nickel, cobalt,
Copper, chromium, molybdenum, titanium, niobium, tantalum,
An oxide containing at least one of strontium, bismuth, boron, tungsten, aluminum, tin, magnesium, potassium and sodium, or titanium, molybdenum, iron, tantalum, strontium, lead, niobium, copper, nickel, vanadium, bismuth, manganese,
Aluminum, tin, boron, magnesium, potassium,
A charge capacity or a sulfide containing at least one of sodium, or at least two phases of the oxide or a composite oxide containing sulfide and lithium, and at least two of the phases having different charge capacities or It is characterized in that it is a substance capable of participating in charging or discharging reaction showing a discharge capacity.

The positive electrode particles have pores of at least one of the phases that can participate in the charge or discharge reaction among the phases due to the formation of charge products or by-products during charge and discharge. It is characterized in that cracks are generated in at least one region selected from the group consisting of the boundary and any combination thereof.

At least two of the above-mentioned phases are characterized in that they are substances capable of participating in a charge or discharge reaction which show different charge capacities or discharge capacities by themselves.

The present invention is a method for producing a positive electrode or a negative electrode used in a secondary battery in which a positive electrode and a negative electrode are provided with an electrolytic solution, and the negative electrode is produced by collecting and forming particles of substances involved in a battery reaction. A first phase containing a phase capable of participating in at least two or more charge or discharge reactions,
A second phase which is dissolved or evaporated to form pores is present in the first phase, and at least one of the second phases is an acid, an alkali, an oxidizing agent or a reducing agent. And a step of dissolving or evaporating to form pores.

Further, a step of manufacturing the positive electrode or the negative electrode by gathering and molding particles of substances involved in a battery reaction, charging or discharging reaction or a similar reaction to the electrode, and partially charging product. Or a step of generating a discharge product to form a crack.

According to the present invention, in the method for producing an electrode used in a secondary battery having a positive electrode and a negative electrode with an electrolyte interposed, a first phase and at least one or more types of charge or discharge other than the first phase. Substance particles involved in a battery reaction in which a second phase capable of participating in a reaction and a third phase forming a pore by dissolution or evaporation are present are used as a component of the first phase and a component of the second phase. A step of combining the components of the third phase with the first phase to allow these phases to be dispersed and present, the second phase being added to the first phase
Of crushing the dispersed phase and the third phase, and subjecting the crushed particles to a charge reaction, a discharge reaction or a similar reaction, and a part of the charge product or the discharge product And forming cracks, and forming particles having the cracks into a plate shape.

In the case of combining the compounds, a synthetic method such as a mechanical alloying method, a solid phase reaction, a liquid phase reaction, a gas phase reaction, and a gas atomization (such as spraying near the temperature at which the second phase is precipitated) can be used. At that time, the particle size and the size of the second phase are as defined above.

Alternatively, a third phase component that dissolves or evaporates the first phase component and at least one or more second phase components other than the first phase that can participate in the charge or discharge reaction to form pores The components of the first phase are melted, the components of the first phase are melted, then cooled and crushed, and the third phase of the crushed particles is treated with an acid, an alkali, an oxidizing agent or a reducing agent. Can be dissolved to form pores on the surface of the particles, and the particles having the pores can be molded into a plate shape. Of course, as described above, it is possible to form the pores by contacting the reaction gas and selectively evaporating the third phase.

The second phase and the third phase are added to the melt of the first phase component.
The second phase and the third phase can be formed by adding the components of the phase.

As the phase to be dissolved, a third phase (precipitation phase) of an alloy, an intermetallic compound or a simple substance which is selectively dissolved by any of an acid, an alkali, an oxidizing agent and a reducing agent is prepared, and the phase is dissolved. It can be formed into an electrode shape (for example, a plate shape) after being dissolved using a reagent capable of forming the pores. Alternatively, it is also possible to first form the electrode shape and then melt it to form the pores.

The present invention can be applied to a secondary battery composed of a positive electrode, a negative electrode, and an electrolytic solution distributed in each part thereof. A separator is provided between the positive electrode and the negative electrode as needed. The present invention is particularly preferably applied to sealed secondary batteries such as nickel-metal hydride batteries and lithium batteries.

The alloys used in the present invention are understood to include so-called intermetallic compounds. For example, it can be a secondary battery in which a positive electrode and a hydrogen storage alloy negative electrode are housed in a container and have an electrolytic solution. The hydrogen storage alloy negative electrode is preferably formed by assembling hydrogen storage alloy particles. A separator may be interposed between the positive electrode and the negative electrode.

By using the present invention for a hydrogen storage alloy negative electrode, a catalytic action of hydrogen storage reaction can be obtained.
Due to the active species remaining in the pores (which are considered to be vacancies, active elements having unpaired electrons, etc.), the rapid charge / discharge characteristics are improved and the life can be extended.

For a secondary battery in which a positive electrode and a negative electrode are housed in a container and filled with a non-aqueous electrolyte, an alkaline metal (for example, lithium) ion is inserted into and discharged from the positive electrode and the negative electrode for charging and discharging. Can be adapted.

In the case of carbon or a conductive polymer negative electrode, for example, in carbon, lithium is inserted from the edge portion of the six-membered ring and the intercalation reaction is carried out. Since there are many edge portions, so-called terminals, of the six-membered ring due to the present pores, the reaction can be facilitated. Thereby, the rapid charge / discharge property can be improved and the capacity can be increased.

In the case of the conductive polymer positive electrode, since the active material of the positive electrode is an anion in the electrolytic solution, the amount of the electrolytic solution absorbed in the pores can be increased, and the charge / discharge reaction proceeds smoothly. be able to.

In the case of a metal oxide or sulfide positive electrode, addition of a transition metal causes substitution with the metal in the positive electrode to generate a defect, and lithium can be added to this defect. It is possible to increase the number of lithium reaction sites and increase the capacity.

The shape of the substance particles and the shape of the pores involved in the battery reaction can be spherical, elliptical, conical, fibrous, donut-shaped, cubic, rectangular parallelepiped, or irregular.

For example, the present invention can be used in the following battery electrodes. Needless to say, other battery electrodes can be applied as long as the performance can be improved by forming pores as in the present invention.

As the substance involved in the charge / discharge reaction of the negative electrode of the nickel-hydrogen battery, a hydrogen storage alloy containing the following components can be used. In addition to the first phase, the following second phase having at least one second phase capable of participating in a charge or discharge reaction and a third phase that dissolves or evaporates to form pores Alloys, etc. can be used.

An alloy composed of a combination of nickel and at least one of magnesium, lanthanum, cerium, neodymium, praseodymium, titanium, zirconium, hafnium, niobium, palladium, yttrium, scandium and calcium.

An alloy composed of a combination of the above combination with at least one of aluminum, cobalt, chromium, vanadium, manganese, tin, barium, molybdenum, tungsten, carbon, lead, iron, potassium, sodium, lithium and boron. .

For example, the following alloys can be applied.

(La-Ce-Nd-Pr)-(Ni-M
n-Al-Co), (La-Ce-Nd-Pr)-(N
i-Mn-Al-Co-B), (La-Ce-Nd-P)
r)-(Ni-Mn-Al-Co-W), (La-Ce
-Nd-Pr)-(Ni-Mn-Al-Co-Mo) and in terms of atomic ratio, the above () / () = 1 / 4.5-
The range is 5.5. Of these, the second phase involved in the charge or discharge reaction is La _{0.5 to 2.5} Co, La _{0.5 to 2.5} N
i, La _{0.5 to 2.5} Mn, Ce _{0.5 to 2.5} Co, La
_{0.5 to 2.5} Al and Ce _{0.5 to 2.5} Ni. In addition to the above elements, V, Fe, Ti, Nb, Ca, etc. are added to _obtain Ti _{0.5 to 2.5} Ni, Nb _{0.5 to 2.5} Ni, Ca.
_A second phase containing a combination of _{0.5 to 2.5} Ni, Ti _{0.5 to 2.5} Fe, Ti _{0.5 to 2.5} V and the like may be precipitated.

Further, (Zr)-(Ni-V-Mn) may be used. On the (Ni-V-Mn) side, Co and F are further added.
At least one of e, Cr, Sn, B, Mo, W, and C, or a combination thereof, and in terms of atomic ratio, () / () = 1 / 1.5 to 2 The range is 0.5. Alternatively, Ti, Hf, and
It may have at least one of Y and Nb, or a combination thereof. The combination is Co and M
It may be o, Co and B, Cr and Mo, Co and W, or the like.

Of these, the second phase involved in the charge or discharge reaction is Zr _{0.5 to 2.5} Co, Ti _{0.5 to 2.5} V, Zr.
_{0.5 ~ 2.5} Ni, Zr _{0.5 ~ 2.5} Mn, Zr _{0.5 ~ 2.5} V, T
i _{0.5 to 2.5} Ni, Nb _{0.5 to 2.5} Ni, and the like. Also,
In addition to the above elements, Ca, La, Ce, etc. are added.
_{0.2 to 2.5} Ni, Ce _{0.2 to 2.5} Ni, Ca _{0.2 to 2.5} NiL
It is also possible to precipitate a second phase containing a combination of _{0.2 to 2.5} Fe, Ce _{0.2 to 2.5} Co, Ca _{0.2 to 2.5} V and the like.

Alternatively, (Mg)-(Ni-Al-M
n), (Mg)-(Ni-V-Mn) This (Ni-V-
Mn) and (Ni-Al-Mn) side further have Co and F
At least one of e, Cr, Sn, B, Mo, W, and C, or a combination thereof, and in terms of atomic ratio, () / () = 2 / 0.5 to 1 The range is 0.5. Alternatively, on the (Mg) side, Zr, Ti,
At least one of Hf, Y, and Nb, or a combination thereof may be included.

Of these, the second phase involved in the charge or discharge reaction is Mg _{0.5 to 2.5} Co, Mg _{0.5 to 2.5} Ni, Mg
_{0.5 to 2.5} Mn, Ti _{0.5 to 2.5} Co, Ti _{0.5 to 2.5} Fe,
Ti _{0.5 to 2.5} V, Ti _{0.5 to 2.5} Ni, Ti _{0.5 to 2.5} M
n, Zr _{0.5 to 2.5} Ni and Hf _{0.5 to 2.5} Ni. In addition to the above elements, Ca, La, Ce, etc. are added,
La _{0.2 to 2.5} Ni, Ce _{0.2 to 2.5} Ni, Ca _{0.2 to 2.5} N
iLa _{0.2 to 2.5} Fe, Ce _{0.2 to 2.5} Co, Ca _{0.2 to 2.5}
A second phase containing a combination of V and the like may be precipitated.

Alternatively, (Ti)-(Ni-Al-M
n), (Ti)-(Ni-V-Mn) This (Ni-V-
Mn) and (Ni-Al-Mn) side further have Co and F
At least one of e, Cr, Sn, B, Mo, W, and C, or a combination thereof, and in terms of atomic ratio, () / () = 1 / 0.5-2 The range is 0.5. Alternatively, Zr, Mg, H is further added to the (Ti) side.
You may have at least 1 of f, Y, Nb, or these combinations.

Of these, the second phase involved in the charge or discharge reaction is Mg _{0.5 to 2.5} Co, Mg _{0.5 to 2.5} Ni, Mg
_{0.5 to 2.5} Mn, Ti _{0.5 to 2.5} Co, Ti _{0.5 to 2.5} Fe,
Ti _{0.5 to 2.5} V, Ti _{0.5 to 2.5} Ni, Ti _{0.5 to 2.5} M
n, Zr _{0.5 to 2.5} Ni, Hf _{0.5 to 2.5} Ni and the like.
In addition to the above elements, Ca, La, Ce, etc. are added,
La _{0.2 to 2.5} Ni, Ce _{0.2 to 2.5} Ni, Ca _{0.2 to 2.5} Ni
A second phase containing a combination of La _{0.2 to 2.5} Fe, Ce _{0.2 to 2.5} Co, Ca _{0.2 to 2.5} V and the like may be precipitated.

As the phase in which the hydrogen storage alloy is dissolved, for example, the phases of the following components can be used. In addition to V and Ti, B, C, Cr, W, Mo, Sn, Mg, K, Li,
Alternatively, in addition to the phase having any of Na, Al and Mn, the phase having any of B, W or Mo, Ni-
Ti, Zr-Ni, Zr-Mn, B-Al-Co, B-
Ni-Mn etc. are mentioned.

As a substance that contributes to the charge / discharge reaction of the positive electrode of the lithium battery, a compound (alloy or the like) composed of the following components can be used. The following compounds having the dissolving phase and the second phase involved in charge / discharge can be used.

Compound containing at least one of lead, manganese, vanadium, iron, nickel, cobalt, copper, chromium, boron, aluminum, magnesium, tungsten, molybdenum, titanium, niobium, tantalum, strontium and bismuth and oxygen. (Alloy) (can be in the so-called complex oxide state).

Compound containing at least one of titanium, molybdenum, iron, tantalum, strontium, lead, niobium, copper, boron, aluminum, magnesium, tungsten, nickel, vanadium, bismuth and manganese and sulfur (so-called sulfide) Can be in the state of things).

A compound (alloy) containing lithium in the above compound having two oxygen or a compound having sulfur may be in a so-called sulfide state.

Conductive polymer (eg polyaniline,
Polyparaphenylene, polyacene, polypyrrole). Or conductive polymer and iron, silicon, sulfur, copper, lead,
A compound with at least one of nickel, vanadium, silver, boron, molybdenum, tungsten, carbon, aluminum and magnesium can be used.

-Carbon. Alternatively, with the carbon,
Iron, silicon, sulfur, copper, lead, nickel, vanadium,
A compound with at least one of silver, boron, molybdenum, tungsten, aluminum and magnesium can be used.

As the substance contributing to the charge / discharge reaction of the positive electrode of the lithium battery, for example, one containing at least one of the following compositions can be used. The following compounds having the dissolving phase and the second phase involved in charge / discharge can be used.

LiCoO _x , LiMnO _x , LiNi
O _x , LiFeO _x , LiNi _0.5 Co _0.5 O _x , LiCo _0.5
Mn _0.5 O _x , LiNi _0.5 Mn _0.5 O _x , LiNi _0.5 Fe
_0.5 O _x , LiFe _0.5 Co _0.5 O _x , LiFe _0.5 Mn _{0.5
O x, LiMn 2 O 2x,} TiS x, MoS x, LiV
₃ O _2x or CuV ₂ O _3x .

Further, for example, LiAl _0.5 Co _0.5 O _x ,
LiAl _0.5 Mn _0.5 O _x , LiMg _0.5 Mn _0.5 O _x , Li
Al _0.5 Fe _0.5 O _x , LiFe _0.5 Mg _0.5 O _x , LiNi
_0.5 Al _0.5 O _x . For this compound, the total of transition metal components should be 0.8 to 1.3, and it is not necessary to evenly distribute the transition metal components to 0.5. The x is in the range of 1.5 to 2.5.

As the substance that contributes to the charge / discharge reaction of the negative electrode of the lithium battery, a substance containing at least one of the following compounds (alloy etc.) can be used. The following compounds having the dissolving phase and the second phase involved in charge / discharge can be used.

Carbon (carbon black, furnace black, pitch carbon, mesophase carbon, PAN carbon, glassy carbon, graphite, amorphous carbon, or a combination thereof). Alternatively, the carbon and iron, silicon, sulfur,
It is also possible to use a compound with at least one of copper, lead, nickel, vanadium, silver, boron, molybdenum, tungsten, aluminum and magnesium.

Conductive polymer (eg polyaniline,
Polyacene, polypyrrole). Alternatively, a compound of the conductive polymer and at least one of iron, silicon, sulfur, copper, lead, nickel, vanadium, silver, boron, molybdenum, tungsten, aluminum, magnesium, and carbon can be used.

Manganese, nickel, copper, calcium,
At least one of magnesium and germanium,
An alloy that combines at least one of silicon, tin, lead, and silver.

Specifically, for example, Si-Ni, Ge-S
i, Mg-Si, Si-Ni-Ge, Si-Ni-M
g, Si-Ni-Mn, Si-Ni-Cu, etc. can be used.

When producing a substance which is composed of an alloy and contributes to the charge / discharge reaction, the above-mentioned components are dissolved, and a precipitation phase (that dissolves in acid, alkali, etc. by aging treatment or cooling (for example, cooling) speed adjustment ( It forms a segregation phase), a second phase involved in charging and discharging, and cracks. As an alloy component, an additive element may be contained and adjusted in order to disperse a precipitation phase having a predetermined size. The additional element preferably has a function of inducing precipitation. For example, the melted phase is formed so as to be dispersed in the produced alloy (so-called primary particles when present in the form of particles).

Alternatively, it can be prepared by mixing by a mechanical alloying method or a mechanical grinding method. In the mechanical alloying method and mechanical grinding method, the degree of alloying is adjusted by optimizing the rotation speed and time to segregate the phase that dissolves in alkali and the second phase that is involved in charging / discharging, without homogenization. A target negative electrode (or particles forming the negative electrode) is produced in this manner. The soluble phase is preferably dispersed in the mother phase so as to have the above size.

When producing a substance consisting of carbon or a conductive polymer that contributes to the charge / discharge reaction, the components of the phase that dissolves in the raw material are mixed and melted to form the carbon (if it exists in the form of particles). Is preferably formed so that the soluble phase and the second phase involved in charge / discharge are dispersed in so-called primary particles. This can also be applied to the case where the substance that contributes to the charge / discharge reaction is an oxide (composite oxide) or a sulfide (composite sulfide).

For example, the soluble phase can be dispersed by mixing carbon or a conductive polymer and the components of the soluble phase and heat-treating them. Heat treatment temperature is 300 ℃ ~ 3500
It is preferable to set the temperature to ℃. When used as a positive electrode of a lithium battery, it is preferably carbonized at about 300 ° C to several hundreds of ° C and when used as a negative electrode at about 1000 ° C to 3500 ° C.

For example, after dissolving with acid to form pores,
Further, heat treatment can be performed to obtain a substance (so-called active material) that is suitable for a battery and that participates in a charge / discharge reaction. Instead of the dissolution, the reaction gas may be contacted and evaporated. By a predetermined heat treatment (for example, homogenization treatment), a substance that contributes to the charge / discharge reaction (so-called primary particles when present in the form of particles) is formed to have a uniform composition as a whole. On the other hand, the present invention is difficult to apply. It is preferable that a precipitation phase that is more easily dissolved than a mother phase (first phase) in an acid or an alkali and a second phase involved in charge / discharge are dispersed.

As described above, the melting phase and the second phase involved in charging / discharging may form a phase by precipitation as long as it is an alloy. In the molecule, particles may be mixed as a phase that dissolves in a mother phase (first phase) made of carbon or a conductive polymer or as a second phase that participates in charge / discharge.

The electrode of the present invention is prepared by bonding the particles with a binder, mechanically compacting, thermally sintering, or chemically aggregating the particles. It can be a porous electrode.

The electrode particularly suitable for the present invention is preferably adapted to a so-called intercalation type substance which contributes to the charge / discharge reaction in the electrode. The components of the substance involved in the charge-discharge reaction in the electrode are sequentially dissolved from the surface by the charge-discharge reaction, so-called dissolution-deposition type electrodes, the pores of the present invention when charging and discharging are repeated. It is difficult to fully exert the effect of.

A crack forming method particularly suitable for the present invention is
This is a method of precharging or precharging after assembling into a battery. Thereby, a charge product or a discharge product is generated, and the crack of the present invention is formed.

Acids, alkalis, oxidants, which are used to dissolve and form pores or cracks as in the present application,
Examples of the reducing agent include the following. Needless to say, it is not limited to this as long as it is used for this purpose.

Acid: nitric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid Alkali: potassium hydroxide, sodium hydroxide Oxidizing agent: sodium hypochlorite, potassium hypochlorite, hydrogen peroxide solution Reducing agent: formalin, hydroboric acid Sodium, potassium hypophosphite, sodium hypophosphite Further, as a gas used for evaporating to form pores, a reaction gas such as halogen or oxygen can be used. For example, a halogen gas such as F ₂ , Cl ₂ , Br ₂ or the like or a phase in which O ₂ is vaporized is brought into contact with the vapor to selectively vaporize the phase, or pores are formed by a volume change.

The present invention can be directly applied to the electrode.

The present invention is a power supply system using a secondary battery in which a positive electrode and a negative electrode interpose an electrolytic solution, wherein the positive electrode or the negative electrode contains substance particles involved in a charge / discharge reaction, and the particles are at least It is composed of two or more phases, at least one of the phases is an electrode having pores and cracks, and the secondary battery is capable of discharging at 580 W / l or more for 15 minutes or more. And a fuel cell, a solar cell, an air cell, or a sodium-sulfur battery, and the secondary battery is used for discharging at high output. The power supply system is provided with an operation control unit for that purpose.

The secondary battery, the power supply and the power supply system are an electric vehicle, an elevator, a power storage power supply, an emergency power supply,
It can be used for uninterruptible power supply.

When the output of this secondary battery is 580 W / l or more, 1
Needless to say, the present invention is not limited to this as long as it is used for the purpose of discharging for 5 minutes or more.

According to the present invention, the rapid charge characteristic and the rapid discharge characteristic of the secondary battery are significantly improved. In addition, high capacity and long life can be achieved.

There are a plurality of phases involved in the charge / discharge reaction, which have different discharge capacities or charge capacities or different expansion or contraction rates during charge / discharge. In addition to this, there are pores generated by dissolution or evaporation. In these phases, stress expansion progresses and cracks occur due to the expansion and contraction of crystals during charge and discharge.
The formation of cracks leads to an increase in the reaction area, and the rapid charge characteristics and rapid discharge characteristics are greatly improved.

This crack has an extremely large number of sources. One is the phase involved in charge / discharge. The other is a crack that occurs along the grain boundary. Then, there are cracks generated from the pores. The phases involved in charging / discharging are composed of a plurality of phases having different discharge capacities or charging capacities or different expansion or contraction rates during charging / discharging, and each phase is formed of a highly ordered and highly crystalline substance. There is. There is a clear grain boundary between the phases. As described above, a large stress is accumulated between the phases having high crystallinity due to expansion and contraction during charge and discharge. Therefore, the generation of cracks is easy. However, this crack does not lead to deep cracks or cavities. That is, the undissolved dissolved phase existing inside the particles and the precipitated phase not involved in charging / discharging are pinned to prevent the progress of cracks.

The generation of such fine cracks increases the reaction area by a factor of 2 to 10 so that the charge transfer reaction on the surface can proceed smoothly. Since the charge transfer reaction is rate-determining in rapid charge and rapid discharge, the rapid charge and rapid discharge characteristics can be dramatically improved, and discharge of 580 W / l for 15 minutes or more is possible.

The substance that contributes to the charge / discharge reaction (so-called primary particles in the case of particles) has pores formed by dissolution with acid or alkali. Compared with the one that has pores that are formed between particles or that is present in the electrode produced by compression or molding of particles, or that the specific surface area is increased by providing an adhered substance (such as a carrier) on the surface of the primary particles. It is possible to improve the packing density of the substance that contributes to the charge / discharge reaction in the electrode. Thereby, the capacity can be further improved.

First of all, the particles provided with pores of the present invention are
Unlike the case where metal powder or catalyst powder is added, the specific surface area of the substance involved in the charge / discharge reaction increases and the area of the reaction field expands. Therefore, rapid charge and rapid discharge reactions proceed smoothly. The particles provided with the pores of the present invention can sufficiently participate in the reaction. Therefore, compared to a case where the electrode surface is simply treated by high temperature treatment after the electrode is manufactured, current concentration is less likely to occur and the life can be extended.

Since the electrolytic solution is retained in the pores, the amount of the retained solution is larger than in the conventional case, and the charge / discharge reaction can be smoothly performed.

Further, the pores of the present invention dissolve the phase to be dissolved by using a highly reactive reagent such as an acid, an alkali, an oxidizing agent or a reducing agent. Unlike pores formed by voids between particles, it is difficult to form an inactive film (for example, an insulating film) such as a strong oxide film that normally occurs, so that the reactivity can be further increased. A film that is not as strong as a normal oxide film formed on the surface of the peripheral portion of the pores and is highly active (for example, a conductive oxide film) can be formed. The surface of the pores formed by melting the phase becomes discontinuous, non-equilibrium atomic arrangement, causing defects and vacancies, and can form an electronically positively or negatively charged state, contributing to the enhancement of activity. it seems to do.

A large difference in the dissolution rate occurs in a short time depending on the kind of the element existing in the phase to be dissolved or the element existing in the grain boundary between the phase to be dissolved and another phase, and the composition of the pore surface is The composition changes to an active layer different from the composition before treatment. Therefore, the catalyst layer has a high activity on the surface of the pores and has not only mere pores but also holes and holes for electrons, or a finely etched catalyst layer (layer that contributes to promoting the reaction). , Unstable layers (eg, the charged layer)
Is formed. Therefore, not only the capillary phenomenon, but also the electrolytic solution is held in the pores by electronic adsorption,
There, the reaction material is catalytically activated and the reaction rate increases. As described above, the pores of the present invention are distinctly different from each other in terms of the pores formed between particles in the porous electrode and their reactivity.

Since the pores of the present invention dissolve the phase to be dissolved (second phase, precipitation phase) using a reagent such as acid, alkali, oxidizing agent, reducing agent, etc. It is formed. For example, pores are present only on the surface that can come into contact with the electrolytic solution to form an active reaction field. Therefore, the components of the phase to be dissolved (second phase, precipitation phase) that could not be dissolved in the closed part inside the particle remain in the inside as they are, so the presence can be easily confirmed by analysis. it can. Since this portion is originally added for dissolution, it does not participate in the charge / discharge reaction or has a small action or capacity. Therefore, it is important to optimize the dissolution conditions with the reagent in order to reduce the residual amount as much as possible. In order to surely dissolve, it is preferable to apply heat from the outside such as hot acid or hot alkali to surely dissolve. When the dissolved phase (second phase, precipitation phase) that could not be completely dissolved in the dissolution operation when the electrolytic solution is an acid or an alkali is dissolved in the electrolytic solution, when contacting with the electrolytic solution in the battery Dissolve again. Therefore, the components of the phase to be dissolved (second phase, precipitation phase) are eluted in the electrolytic solution, and its presence can be confirmed by analysis of the electrolytic solution.

When the phase to be dissolved is one that can be dissolved in the electrolytic solution, the pores on the surface of the particles involved in the charging / discharging reaction will not be damaged even if the particles are broken by the operation of the battery. By contacting with the electrolyte, new pores are formed, and the charge / discharge reaction can be favorably maintained.

The eluted components do not have to utilize the action of actively depositing them in other places. The effect of the present invention can be obtained by dissolving and forming pores. In addition, the components of the electrolytic solution and the reaction product may remain in the pores. At the time of charging / discharging, even if a substance involved in the charging / discharging reaction in the electrode disintegrates (including cracking, division, etc.) and a new surface is formed in contact with the electrolytic solution, the dissolved phase facing the new surface is not subjected to the electrolysis It reacts with the liquid and new pores are formed.

[0127]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to Examples in which it is applied to a secondary battery.

(Example 1) T was used as a hydrogen storage alloy for the negative electrode.
with _{i 0.2 Zr 0.8 Ni 1.1 Mn 0.6} V 0.2 B 0.03 alloy. The alloy melts between 1100 ° C and 1500 ° C and is cooled at a rate of 0.01 ° C / min to 0.5 ° C / min,
It was obtained by annealing in the range of 300 ° C to 900 ° C for about 2 hours.
The alloy was ground to particles with an average particle size of 50 microns. The surface of this alloy was analyzed using a scanning electron microscope-wavelength dispersive X-ray analyzer (SEM-WDX), and the average diameter was 5
A micronized V, B and Ti segregation phase was formed. FIG. 1 shows the distribution state. This alloy was dissolved in a 30 wt% KOH aqueous solution at 70 ° C. for 2 hours, washed thoroughly with water, and then the alloy powder was analyzed again using SEM-WDX and shown in FIG. Average diameter 5
V and B in the micron segregated phase were completely dissolved, and Ti remained in the pores, indicating a compositional discontinuity with the surrounding phase caused by the difference in dissolution rate due to the elements. The ratio of the pores at this time was 15% of the particle surface area and 5% of the particle volume. In addition to the dissolution treatment with a hot KOH aqueous solution, the same kind of result was obtained by causing chlorine gas or fluorine gas to flow to react and evaporate the segregated phase. Hydroxypropylmethylcellulose was added to this as a binder to fill the foamed nickel substrate, and a metal hydride electrode having a predetermined thickness was obtained by roller pressing. As the nickel electrode, a paste-type electrode using foamed nickel having a porosity of 95% as an electrode substrate was used. An AA sealed nickel-metal hydride battery was produced with these electrodes. FIG. 3 shows the structure. The positive electrode and the negative electrode were wound with a 0.17 mm-thick polypropylene resin nonwoven fabric separator interposed therebetween and inserted into a battery can. The electrolyte used was an aqueous solution containing 31 wt% potassium hydroxide to which a small amount of lithium hydroxide was added. The battery capacity was designed to be 1400 mAh. Charge at 150% of capacity at 0.3CmA and 3CmA at room temperature, 1
After a certain rest time, the battery was discharged to a final voltage of 1.0 V at 0.2 CmA and 3 CmA. Capacity is 0.3 CmA
The discharge capacity of 0.2 CmA discharge after charging and this capacity is 10
A capacity ratio of 0.2 CmA discharge after 3 CmA charge and a capacity ratio of 3 CmA discharge after 0.3 CmA charge when the value was 0 were measured. After charging 0.3CmA, the capacity of discharging 0.2CmA is 14
It is as high as 50 mAh and has a long cycle life of 520 times. 3
A capacity of 95% was obtained by CmA discharge and a capacity of 92% was obtained by 3 CmA charge, and discharge was possible for 15 minutes or more at an output of 580 W / l.

(Comparative Example 1) T was used as a hydrogen storage alloy for the negative electrode.
An i _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 alloy was used. The alloy was melted between 1100 ° C and 1500 ° C and homogenized at 1050 ° C for 3 to 10 hours in an argon gas atmosphere. The alloy was ground to particles with an average particle size of 50 microns.
When the surface of this alloy was analyzed by SEM-WDX, a second phase of Ti and Ni was formed, but a segregation phase was not obtained. The distribution state is shown in FIG. Dissolution was attempted under the same conditions as in Example 1, but no pores appeared due to dissolution as shown in FIG. An electrode was prepared in the same manner as in Example 1,
AA sealed nickel-metal hydride batteries were prepared and their capacities were measured. The capacity of 0.2 CmA discharge after charging of 0.3 CmA is as high as 1410 mAh, but the cycle life is short at 380 times. 45% for 3 CmA discharge, 5 for 3 CmA charge
The capacity was as low as 6%.

(Comparative Example 2) T was used as a hydrogen storage alloy for the negative electrode.
Using the i _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 alloy, alloy particles having an average particle size of 50 microns were prepared in the same manner as in Comparative Example 1. Hydroxypropylmethyl cellulose was added to this as a binder, and the foamed nickel substrate was filled and pressure-molded to a predetermined thickness by a roller press. This molded body 1
Holes of 00 micron were made at a rate of 100 holes / cm ² on both sides to make electrodes. In the same manner as in Example 1, a sealed AA nickel-metal hydride battery was prepared and the capacity was measured. 0.
After 3CmA charge, 0.2CmA discharge capacity is 1250mAh
The cycle life is as short as 325 times. The capacity was slightly low at 72% for 3 CmA discharge and 70% for 3 CmA charge.

(Comparative Example 3) T was used as a hydrogen storage alloy for the negative electrode.
Using the i _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 alloy, alloy particles having an average particle size of 50 micron were produced in the same manner as in Comparative Example 1. Hydroxypropylmethylcellulose as a binder and Raney nickel catalyst powder were added to this, and the foamed nickel substrate was filled and pressure-molded to a predetermined thickness by a roller press. In the same manner as in Example 1, a sealed AA nickel-metal hydride battery was prepared and the capacity was measured. 0.3C
The capacity of 0.2 CmA discharge after mA charging is a little low at 1350 mAh, and the cycle life is short at 383 times. The capacity was slightly low, that is, 72% at 3 CmA discharge and 68% at 3 CmA charge.

Example 2 T was used as a hydrogen storage alloy for the negative electrode.
with _{i 0.2 Zr 0.8 Ni 1.1 Mn 0.6} V 0.2 B 0.03 alloy. The alloy was melted between 1100 ° C and 1500 ° C and homogenized at 800 ° C for 3 to 10 hours in an argon gas atmosphere. The alloy was ground to particles with an average particle size of 50 microns. When the surface of this alloy was analyzed by SEM-WDX, four kinds of segregation phases were obtained. The distribution state is shown in FIG. Zr precipitate, TiNi, Ti ₂ Ni, B and V
And Ti segregation phases. TiNi, Ti ₂ N
i alone has a discharge capacity of 150 mAh / g,
200 mAh / g, Ti _0.2 Zr _0.8 Ni of the mother phase
The discharge capacity of _1.1 Mn _0.6 V _0.2 was 330 mAh / g. Therefore, the discharge capacity ratio is (mother phase) / (TiNi) 2.
2, and (matrix) / (Ti ₂ Ni) is 1.65.
The expansion coefficient of the lattice volume after charging obtained from the measurement of X-ray diffraction was 10% for TiNi, 18% for Ti ₂ Ni, and 22% for Ti _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _{0.2 of} the matrix phase. there were. Therefore, the ratio of expansion coefficients is (mother phase) / (iNi) 2.
2, and (mother phase) / (Ti ₂ Ni) is 1.22. This alloy is mixed with 30 wt% KOH aqueous solution and 1 wt% NaBH ₄
It was dissolved in a mixed solution of an aqueous solution and a 5 wt% CH ₃ COOH aqueous solution at 70 ° C. for 2 hours, and washed thoroughly with water. In the segregation phase of B, V and Ti having an average diameter of 1 micron, V and B are completely dissolved, and Ti remains in the pores, resulting in a discontinuity in composition with the surrounding phase caused by the difference in dissolution rate due to elements. It has been shown. Further, when the alloy particles were observed by SEM, a plurality of fine cracks were observed in the particles as shown in FIG. At this time, the ratio of the pores was 5% of the particle surface area and 0.2% of the particle volume. An electrode was prepared in the same manner as in Example 1, and an AA sealed nickel-metal hydride battery was prepared and the capacity was measured. After charging 0.3CmA and discharging 0.2CmA, the capacity is as high as 1470mAh.
The cycle life is as long as 550 times. 95 at 3 CmA discharge
%, 3CmA charge gives 90% capacity, 580W
It was possible to discharge for 15 minutes or more at an output of / l.

(Comparative Example 4) T was used as a hydrogen storage alloy for the negative electrode.
i _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 alloy is used, the alloy melts between 1100 ° C and 1500 ° C, and 100 ° C / se
Cooled at a cooling rate of c. The surface of this alloy is SEM-W
When analyzed using DX, four types of segregated phases were obtained. There were four kinds of Zr precipitates, a segregated phase of Ti and Ni, a segregated phase of V and Ti, and a V precipitated phase. Microscopic X-ray diffraction and TEM-EPMA for segregated phase of Ti and Ni, and V and T
It was observed that the segregated phase of i was a phase having a very low crystallinity from amorphous to microcrystalline. The alloy was ground to particles having an average particle size of 50 microns. In the same manner as in Example 1, an AA sealed nickel-metal hydride battery was prepared and the capacity was measured. The capacity of 0.2CmA discharge after charging 0.3CmA is as low as 1150mAh, and the cycle life is 38.
3 times as short. The capacity was slightly low, that is, 72% at 3 CmA discharge and 68% at 3 CmA charge.

Example 3 Graphite powder was used as a carbon material for the negative electrode. The graphite powder was crushed to have an average particle size of 0.1 micron or less, 0.2 wt% of 0.01 micron copper powder was added, and heat treatment was performed at 3000 ° C. for 5 hours while mixing. Then, it was pulverized to obtain particles of the size of the present invention. This was dissolved in an aqueous nitric acid solution at 70 ° C. for 2 hours, washed thoroughly with water, and then analyzed using SEM-WDX, with an average diameter of 0.0.
Porosity of 1 to 0.05 micron and traces of copper were confirmed.
Similar results were obtained by flowing chlorine gas or fluorine gas and reacting and evaporating the precipitation phase, in addition to the dissolution treatment with a hot KOH aqueous solution. A fluorine-based binder was added to this and applied on a copper foil, and a carbon electrode having a predetermined thickness was obtained by roller pressing. An electrode containing LiCoO ₂ as a main component was used for the positive electrode. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured. The battery capacity was designed to be 600 mAh. 0.3CmA 0.2C after charging
The capacity of mA discharge is as high as 650 mAh, and the cycle life is as long as 520 times. 92% at 3 CmA discharge, 3 CmA
A capacity of 89% was obtained by charging, and a discharge of 580 W / l was possible for 15 minutes or more.

(Comparative Example 5) Graphite powder was used as a carbon material for the negative electrode. The graphite powder was crushed to have an average particle size of 0.1 micron or less, and heat-treated at 3000 ° C. for 5 hours while mixing. The surface of this carbon was analyzed using SEM-WDX and subjected to dissolution treatment under the same conditions as in Example 2, but no pores appeared. A fluorine-based binder was added to this and applied on a copper foil, and a carbon electrode having a predetermined thickness was obtained by roller pressing. An electrode containing LiCoO ₂ as a main component was used for the positive electrode. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured. The battery capacity was designed to be 600 mAh. 0.2 CmA after charging 0.2
The capacity of CmA discharge is a little low at 550 mAh, and the cycle life is a little short at 420 times. 72 at 3 CmA discharge
%, Low at 69% with 3 CmA charging.

Example 4 Graphite powder was used as a carbon material for the negative electrode. The graphite powder was crushed to have an average particle size of 0.1 micron or less, 0.2 wt% of 0.01 micron copper powder was added, and heat treatment was performed at 3000 ° C. for 5 hours while mixing. Then, it was pulverized to obtain particles of the size of the present invention. Further 0.2% by weight of 0.01 micron silver powder was added and ball milled at 250 rpm. This was dissolved in a mixed solution of a 2 wt% formalin aqueous solution and a 5 wt% ammonia aqueous solution at 60 ° C. for 2 hours and washed sufficiently with water, and then SEM-W
Analysis using DX confirmed pores with an average diameter of 0.01 to 0.05 microns, traces of copper, and silver deposits.
A fluorine-based binder was added to this and applied on a copper foil, and a carbon electrode having a predetermined thickness was obtained by roller pressing. An electrode containing LiCoO ₂ as a main component was used for the positive electrode. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured. The battery capacity was designed to be 600 mAh.
After charging 0.3CmA, discharge capacity of 0.2CmA is 680mAh
The cycle life is as long as 570 times. With 3CmA discharge, 94% capacity and with 3CmA charge, 91% capacity,
It was possible to discharge for 15 minutes or more at an output of 580 W / l. When the battery was disassembled and SEM observation of carbon particles was carried out, several fine cracks were observed in the silver particles, and X
The peak of LiAg was observed from the measurement result of the line diffraction. At this time, the expansion coefficient of Ag was 18% and the expansion coefficient of carbon was 25%. The discharge capacity of Ag alone is 15
It is 0 mAh / g, and the discharge capacity of carbon in the matrix is 37
It was 0 mAh / g. Therefore, the discharge capacity ratio is (mother phase) /
(Ag) is 2.47. Further, the ratio of the expansion coefficient of the lattice volume after charging obtained from the measurement of X-ray diffraction is (mother phase) / (A
g) is 1.39.

Example 5 Lithium-cobalt oxide was used for the positive electrode. This was crushed to an average particle size of 1 micron or less, and 0.2 wt% of 0.1 micron Al powder was added to make it 3
It heat-processed, mixing at 00 degreeC for 5 hours. Then, it was pulverized to obtain particles of the size of the present invention. 70% of this with KOH aqueous solution
After dissolution treatment at 2 ° C. for 2 hours and sufficient washing with water, analysis using SEM-WDX confirmed that pores having an average diameter of 0.2 micron were formed. The same result was obtained by causing chlorine gas or fluorine gas to react and evaporate the precipitated phase. A fluorine-based binder was added to this and applied on an Al foil, and an electrode having a predetermined thickness was obtained by roller pressing.
A carbon negative electrode was used as the negative electrode. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured.
The battery capacity was designed to be 600 mAh. The capacity of 0.2 CmA discharge after charging of 0.3 CmA is as high as 710 mAh, and the cycle life is as long as 580 times. 85% for 3 CmA discharge,
80% capacity is obtained with 3 CmA charging, 580 W / l
It was possible to discharge for 15 minutes or more.

(Comparative Example 6) Lithium-cobalt oxide was used for the positive electrode. This was crushed to an average particle size of 1 micron or less and heat-treated at 300 ° C. for 5 hours while mixing. This surface was analyzed using SEM-WDX and subjected to dissolution treatment under the same conditions as in Example 3, but no pores appeared. A fluorine-based binder was added to this and applied on an Al foil, and a carbon electrode having a predetermined thickness was obtained by roller pressing. A carbon negative electrode was used as the negative electrode. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured. 0.3
The capacity of 0.2CmA discharge after CmA charging is a little low at 570mAh, and the cycle life is short at 380 times. It is as low as 65% for 3 CmA discharge and 57% for 3 CmA charge.

Example 6 Lithium-cobalt oxide was used for the positive electrode. This was crushed to an average particle size of 1 micron or less, and 0.1 wt.% Al powder and V powder were added in an amount of 2% by weight and heat-treated at 370.degree. Then, it was pulverized to obtain particles of the size of the present invention. This is 15w
The solution was dissolved in a t% KOH aqueous solution at 70 ° C. for 1 h, washed thoroughly with water, and then treated at 40 ° C. for 1 h with a mixed solvent of ethylene carbonate and dimethoxyethane. SEM-WDX analyzed using, traces of pore portion and the Al average size of 0.1 microns, further precipitate V, and _{LiCo 1-X V X O 2} (x = 0~0.
The parent phase of 5) was confirmed. A fluorine-based binder was added to this and applied on an Al foil, and an electrode having a predetermined thickness was obtained by roller pressing. A carbon negative electrode was used as the negative electrode. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured. The battery capacity was designed to be 600 mAh. 0.
After 3CmA charge, 0.2CmA discharge capacity is 750mAh
The cycle life is as long as 640 times. 88% capacity is obtained with 3 CmA discharge, and 85% capacity is obtained with 3 CmA charge,
It was possible to discharge for 15 minutes or more at an output of 580 W / l. When the battery was disassembled and the particles were observed by SEM, V
A plurality of fine cracks were observed in the precipitated particles, and a Li _X V _Y O ₂ peak was observed from the X-ray diffraction measurement results. At this time, the expansion rate of the V precipitate was 14%, and the expansion rate of the mother phase was 20%. The discharge capacity of Li _X V _Y O ₂ alone was 50 mAh / g, and the discharge capacity of the mother phase was 150 mA.
h / g. Therefore, the discharge capacity ratio is (mother phase) / (Li _X
V _Y O ₂ ) is 3.0. Further, the ratio of the expansion coefficient of the lattice volume after charging obtained from the measurement of X-ray diffraction is (mother phase) / (L
i _X V _Y O ₂ ) is 1.43.

(Embodiment 7) As a hydrogen storage alloy, T was used for the negative electrode.
i _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 alloy was used, and B having an average particle size of 10 to 0.1 micron was used in an atomic ratio of 0.1 to 0.0.
1 was added and an alloy was prepared in the same manner as in Example 1. The alloy was ground to particles with an average particle size of 50 microns. The fine pores were prepared in the same manner as in Example 1. The average diameter of the fine pores obtained at this time was 25 to 0.4 micron (1/2 to 150 times the average grain size of the alloy). This is Example 1
An electrode was prepared in the same manner as above, and the AA sealed nickel-
A metal hydride battery was prepared and the capacity was measured. FIG. 8 shows the relationship between the average diameter of the pores and the capacity ratio at 3 CmA charging and 3 CmA discharging. The capacity of 0.2 CmA discharge after charging 0.3 CmA is as high as 1100 to 920 mAh, and the cycle life is long as 680 to 500 times. 95 to 7 at 3 CmA discharge
It is as high as 98-75% with 5% and 3 CmA charging, 580 W
It was possible to discharge for 15 minutes or more at an output of / l. The average diameter of the pores was 1/5 to 1/5 of the average particle diameter of the alloy, and the capacity was particularly high.

(Comparative Example 7) T was used as a hydrogen storage alloy for the negative electrode.
Using an i _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 alloy, B having an average particle size of 0.05 micron was added in an atomic ratio of 0.1, and an alloy was prepared in the same manner as in Example 1. The alloy has an average particle size of 50
Grinded to micron particles. The fine pores were prepared in the same manner as in Example 1. The average diameter of the fine pores obtained at this time is 0.1.
It was 3 microns or less (less than 1/150 of the average grain size of the alloy). An electrode was prepared in the same manner as in Example 1, and an AA sealed nickel-metal hydride battery was prepared and the capacity was measured. FIG. 8 shows the relationship between the average diameter of the pores and the capacity ratio at 3 CmA charging and 3 CmA discharging. 0.
After 3CmA charge, 0.2CmA discharge capacity is 950-91
It is as high as 0 mAh and has a long cycle life of 520 to 480 times, but is low at 45 to 65% in 3 CmA discharge and 55 to 68% in 3 CmA charge.

(Comparative Example 8) T was used as a hydrogen storage alloy for the negative electrode.
i _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 alloy was used, and B having an average particle size of 15 μm was added in an atomic ratio of 0.1.
An alloy was prepared in the same manner as in. The alloy was ground to particles with an average particle size of 50 microns. The fine pores were prepared in the same manner as in Example 1. The average diameter of the fine pores obtained at this time was 30 microns or more (larger than one half of the average particle diameter of the alloy). An electrode was prepared in the same manner as in Example 1, and an AA sealed nickel-metal hydride battery was prepared and the capacity was measured. Fig. 8 shows the average diameter of the pores and 3 CmA charge and 3
The relationship with the capacity ratio in CmA discharge is shown. The capacity of 0.2CmA discharge after 0.3CmA charge is as high as 970-920mAh, and the cycle life is as long as 500-450 times, but 3C
45 to 63% for mA discharge, 66 to 4 for 3 CmA charge
It is as low as 8%.

Example 8 T was used as a hydrogen storage alloy for the negative electrode.
i _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 B _x (X = 0.01 to 0.0)
8) Pores were made in the same manner as in Example 1 using the alloy. The ratio of the pores obtained at this time is 0.15 to 80% of the particle surface area, and 0.1 to the particle volume.
2 to 60%. An electrode was prepared in the same manner as in Example 1, and an AA sealed nickel-metal hydride battery was prepared and the capacity was measured. FIG. 9 shows the ratio of the cross-sectional area of the pores to the surface area of the particles, the charge of 3 CmA and
FIG. 10 shows the relationship between the capacity ratio in A discharge and the ratio of the volume of pores to the volume of particles, 3 CmA charge and 3 Cm.
The relationship with the capacity ratio in A discharge is shown. The capacity of 0.2 CmA discharge after charging of 0.3 CmA is as high as 1550 to 1420 mAh, and the cycle life is as long as 580 to 430 times. 3 Cm
95-75% for A discharge, 98-75 for 3 CmA charge
%, And the ratio of pores to the particle surface area is 10
To 50%, or 1 to 40% based on the particle volume, the capacity was particularly high.

(Comparative Example 9) T was used as a hydrogen storage alloy for the negative electrode.
i _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 B _x (X = 0.001
.About.0.005, X = 1.0 to 1.8) An alloy was used to form the fine pores in the same manner as in Example 1. The ratio of the pores obtained at this time was 0.03% to the particle surface area and 0.1% to the particle volume. An electrode was prepared in the same manner as in Example 1, and an AA sealed nickel-metal hydride battery was prepared and the capacity was measured. Fig. 9 shows the ratio of the cross-sectional area of the pores to the particle surface area and 3 CmA.
FIG. 10 shows the relationship between the charge ratio and the capacity ratio at 3 CmA discharge.
Ratio of pore volume to particle volume and 3 CmA
The relationship with the capacity ratio at charge and 3 CmA discharge is shown.
After charging 0.3CmA, discharge capacity of 0.2CmA is 1400m
Although it is as high as Ah, the cycle life is as short as 320 times. 3 Cm
It is as low as 50% for A discharge and 55% for 3 CmA charge.

(Comparative Example 10) Ti _0.2 Zr _0.8 Ni _1.1 Mn _0.6 V _0.2 B _x (X = 1.0 to 1.) as a hydrogen storage alloy for the negative electrode.
8) Pores were made in the same manner as in Example 1 using the alloy. The ratio of the pores obtained at this time was 90% with respect to the particle surface area and 70% with respect to the particle volume. An electrode was prepared in the same manner as in Example 1, and an AA sealed nickel-metal hydride battery was prepared and the capacity was measured. FIG. 9 shows the relationship between the ratio of the pore area cross-sectional area to the particle surface area and the capacity ratio at 3 CmA charge and 3 CmA discharge. FIG. 10 shows the relationship between the ratio of the pore volume to the particle volume and 3 CmA charge and 3 CmA discharge. Shows the relationship with the capacity ratio of. The capacity of 0.2 CmA discharge after 0.3 CmA charge is a little low at 1120 mAh, and the cycle life is short at 300 times. 55% for 3 CmA discharge, 6 for 3 CmA charge
It is as low as 0%.

Example 9 A segregation phase was formed in the negative electrode by using the hydrogen storage alloys shown in Table 1. A in the segregation phase
l, V, Mn, Sn, B, Mg, Mo, W, Zr, K,
Na, Li, Ni, and Ti include 30% by weight or more. 50 ℃ at an aqueous solution containing acid, alkali, oxidizer, and reducing agent
After dissolving for 1 h and washing with water, an electrode was prepared in the same manner as in Example 1, and an AA sealed nickel-metal hydride battery was prepared and the capacity was measured. The results are shown in Table 1. 0.3
After CmA charging, the capacity of 0.2 CmA discharging is 1510-14
It is as high as 00 mAh and has a long cycle life of 550 to 480 times. It is as high as 95 to 78% for 3 CmA discharge and 98 to 88% for 3 CmA charge.

[0147]

[Table 1] Example 10 Graphite powder was used as a carbon material for the negative electrode. Grind this to an average particle size of 0.1 micron or less,
0.2% by weight of 0.01 micron powder shown in Table 2 was added and heat-treated at 3000 ° C. for 5 hours while mixing. Then, it was pulverized to obtain the powder of the present invention. This was dissolved in a nitric acid aqueous solution at 70 ° C. for 2 hours, washed thoroughly with water, and then analyzed using SEM-WDX to confirm that pores having an average diameter of 0.01 micron were formed. In the same manner as in Example 3, an AA sealed lithium battery was prepared and the capacity was measured. The results are shown in Table 2.
After the charge of 0.3CmA, the capacity of discharge of 0.2CmA is 750 ~
It is as high as 670 mAh and has a long cycle life of 520 to 480 times. The capacity is as high as 85 to 82% for 3 CmA discharge and 85 to 79% for 3 CmA charge.

[0148]

[Table 2] (Comparative Example 11) Graphite powder was used as a carbon material for the negative electrode. Grind this to an average particle size of 0.1 micron or less,
Addition of 55% by weight of 0.01 micron iron powder to 3000
It heat-processed, mixing at 5 degreeC for 5 hours. This was dissolved in an aqueous nitric acid solution at 70 ° C. for 2 hours, washed thoroughly with water, and then SEM-WDX.
It was confirmed that a fine pore having an average diameter of 0.08 micron was formed. In the same manner as in Example 3, an AA sealed lithium battery was prepared and the capacity was measured. 0.3C
The capacity of 0.2 CmA discharge after mA charging is as low as 470 mAh, and the cycle life is as short as 380 times. The capacity is as low as 50 to 71% with 3 CmA discharge and 55 to 64% with 3 CmA charge.

(Comparative Example 12) Graphite powder was used as a carbon material for the negative electrode. This was crushed to an average particle size of 0.1 micron or less, 0.01 weight% of 0.01 micron iron powder was added, and the mixture was heat-treated at 3000 ° C. for 5 hours while mixing. This was dissolved in an aqueous nitric acid solution at 70 ° C. for 2 hours, washed thoroughly with water, and then analyzed using SEM-WDX, and it was confirmed that pores having an average diameter of 0.004 micron were formed. Example 3
In the same manner as above, an AA sealed lithium battery was prepared and the capacity was measured. Although the capacity of 0.2 CmA discharge after charging 0.3 CmA is as high as 670 mAh, the cycle life is short at 280 times, and the capacity is 57-72% for 3 CmA discharging and 55-69% for 3 CmA charging.

Example 11 Polyacetylene powder was used as a conductive polymer material for the positive electrode. This was crushed to an average particle size of 0.1 micron or less, and 0.2 wt% of the powder having the size of 0.05 micron shown in Table 3 was added to the powder at 300 to 500 ° C.
Heat treatment was performed while mixing. Then, it was crushed to obtain a powder of the size of the present invention. This was dissolved in an aqueous nitric acid solution at 70 ° C. for 2 hours, washed thoroughly with water, and then analyzed using SEM-WDX, and it was confirmed that pores having an average diameter of 0.08 micron were formed. Flowing chlorine gas or fluorine gas to react the precipitation phase,
Similar results were obtained by evaporation. A fluorine-based binder was added to this and applied on an Al foil, and an electrode having a predetermined thickness was obtained by roller pressing. A carbon negative electrode was used as the negative electrode. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured. Battery capacity is 5
Designed with 00 mAh. The results are shown in Table 3. 0.3 Cm
A charge after 0.2CmA discharge capacity is 640-570mA
The cycle life is as long as 670 to 490 times. 3
91-81% for CmA discharge, 87- for 3 CmA charge
A volume of 78% was obtained.

[0151]

[Table 3] Example 12 Polyacene powder was used as a conductive polymer material for the negative electrode. This was crushed to an average particle size of 0.1 micron or less and 0.2 micron of the powder shown in Table 4 was used.
It was added by weight% and heat-treated at 1000 to 3000 ° C. for 5 hours while mixing. This was dissolved in an aqueous nitric acid solution at 70 ° C. for 2 hours, washed thoroughly with water, and then analyzed using SEM-WDX to confirm that pores having an average diameter of 0.02 micron were formed. Flowing chlorine gas or fluorine gas to react the precipitation phase,
Similar results were obtained by evaporation. A fluorine-based binder was added to this and applied on a copper foil, and an electrode having a predetermined thickness was obtained by roller pressing. For the positive electrode, Li
An electrode containing CoO ₂ as a main component was used. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured. The battery capacity was designed to be 600 mAh. Table 4 shows the results. After 0.3CmA charge, 0.2CmA discharge capacity is 86
It has a high value of 0 to 700 mAh and a long cycle life of 700 to 580 times. A capacity of 93 to 88% was obtained with 3 CmA discharge, and a capacity of 90 to 82% was obtained with 3 CmA charge.

[0152]

[Table 4] (Example 13) The alloy shown in Table 5 was used for the negative electrode. The alloy melts between 1100 ° C and 1500 ° C.
Cool at a rate of 1 ℃ / min to 0.5 ℃ / min, 300 ℃
It was obtained by annealing for about 2 hours in the range from 1 to 500 ° C. This is crushed to an average particle size of 50 microns or less and then treated with an aqueous nitric acid solution at 70 ° C.
After dissolution treatment for 2 h and sufficient washing with water, it was analyzed using SEM-WDX, and it was confirmed that pores having an average diameter of 2 μm were formed. The same result was obtained by causing chlorine gas or fluorine gas to react and evaporate the precipitated phase. A fluorine-based binder was added to this and applied on a copper foil, and an electrode having a predetermined thickness was obtained by roller pressing. An electrode containing LiCoO ₂ as a main component was used for the positive electrode. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured. The battery capacity was designed to be 600 mAh. Table 5
The results are shown in. The capacity of 0.2CmA discharge after charging 0.3CmA is as high as 760-700mAh, and the cycle life is 530.
~ 480 times long. 91-85%, 3C in 3CmA discharge
A capacity of 98 to 88% was obtained by mA charging.

[0153]

[Table 5] (Example 14) The oxides and sulfides shown in Table 6 were used for the positive electrode. This is ground to an average particle size of 1 micron or less,
1 micron of powder shown in Table 6 was added in an amount of 0.2% by weight, and
It heat-processed, mixing at 00-300 degreeC for 5 hours. Then, it was crushed to obtain a powder of the size of the present invention. This was dissolved in an aqueous nitric acid solution at 70 ° C. for 2 hours, washed thoroughly with water, and then SEM-WDX.
It was confirmed that a fine pore having an average diameter of 0.2 micron was formed. The same result was obtained by causing chlorine gas or fluorine gas to react and evaporate the precipitated phase. A fluorine-based binder was added to this and applied on an Al foil, and an electrode having a predetermined thickness was obtained by roller pressing. A carbon negative electrode was used as the negative electrode. AA-type sealed lithium batteries were produced from these electrodes and their capacities were measured. The battery capacity was designed to be 600 mAh. Table 6 shows the results. The capacity of 0.2CmA discharge after charging 0.3CmA is 770
~ 680mAh and cycle life is 640-490
Times and long. A capacity of 90 to 81% was obtained with 3 CmA discharge, and a capacity of 85 to 78% was obtained with 3 CmA charge.

[0154]

[Table 6] (Example 15) An alloy containing two types of phases shown in Table 7 was used as a hydrogen storage alloy for the negative electrode, and 1 wt% of B was added. The alloy was prepared by using a melting method, a mechanical alloying method, a mechanical gliding method, a molten metal quenching method, and a powder mist method, and heat treatment was performed at 650 to 1100 ° C.
This was dissolved in a KOH aqueous solution at 60 to 100 ° C. for 1 to 50 hours and washed with water, and then the formation of the pores of the present invention was confirmed.
An electrode was prepared in the same manner as in Example 1, and a sealed AA nickel-metal hydride battery was prepared and the capacity was measured. The results are shown in Table 7. After charging 0.3CmA and 0.2CmA, the discharge capacity is as high as 1560 to 1400mAh, and the cycle life is 10
It is as long as 20 to 880 times. 97-77 with 3 CmA discharge
%, It is as high as 98 to 79% at 3 CmA charge. When the battery was disassembled and the electrode was observed by SEM, it was confirmed that fine cracks were generated.

[0155]

[Table 7] (Example 16) Using a material containing two kinds of phases shown in Table 8 as a carbon material for the negative electrode, adding 1 wt% of B,
Heat treatment was performed at 500 to 2600 ° C. This is mixed with an aqueous solution of KOH and an aqueous solution of sodium borohydride to 50-
After dissolution treatment at 100 ° C for 1 to 50 hours and washing with water, 30 to 30 with a mixed solution of propylene carbonate and dimethoxyethane.
After treatment at 60 ° C. for 1 to 50 hours, formation of pores of the present invention was confirmed. An electrode was prepared in the same manner as in Example 3, and a sealed AA lithium battery was prepared and the capacity was measured. The results are shown in Table 8. After the charge of 0.3CmA, the discharge capacity of 0.2CmA is 83
High as 0-610mAh and cycle life of 980-78
0 times long. 93-83% in 3 CmA discharge, 3 CmA
The charge is as high as 95-86%. Dismantle the battery and replace the electrode with S
It was confirmed by EM observation that fine cracks were generated.

[0156]

[Table 8] (Example 17) A material containing two kinds of phases shown in Table 9 as oxides and sulfides was used for the positive electrode, 1 wt% of B was added, and heat treatment was performed at 250 to 600 ° C. This was dissolved in an aqueous acetic acid solution at 50 to 100 ° C. for 1 to 50 hours and washed with water, and then the formation of pores of the present invention was confirmed. An electrode was prepared in the same manner as in Example 3, and a sealed AA lithium battery was prepared and the capacity was measured. The results are shown in Table 9. The capacity of 0.2 CmA discharge after charging 0.3 CmA is as high as 810 to 680 mAh, and the cycle life is long as 820 to 580 times. 3 Cm
95 to 80% for A discharge, 98 to 82 for 3 CmA charge
% And high. When the battery was disassembled and the electrode was observed by SEM, it was confirmed that fine cracks were generated.

[0157]

[Table 9] (Example 18) anode _{Nb 0.1 Zr 0.9 Ni 1.1 Mn 0.6} V
A hydrogen storage alloy having a composition of _0.2 Co _0.1 B _0.03 was used. The alloy was produced by atomization in an Ar gas atmosphere containing 10 to 1000 ppm of oxygen by the atomization method (gas atomizing method) and heat treatment at 650 to 1100 ° C. When a cross section of this was observed by SEM, a plurality of pores were confirmed, and further, when the composition of the pores was examined, oxygen and Z
The formation of a film composed of r was confirmed. An electrode was prepared in the same manner as in Example 1, and a sealed AA nickel-metal hydride battery was prepared and the capacity was measured. After charging 0.3CmA.
The capacity of 2 CmA discharge is as high as 1540 mAh, and the cycle life is as long as 1080 times. 97% for 3 CmA discharge, 3
It is as high as 89% for CmA charging. Dismantle the battery and replace the electrode with S
It was confirmed by EM observation that fine cracks were generated.

[0158]

As described above, according to the present invention, the capacity of the secondary battery is increased, and the rapid charge characteristic and the rapid discharge characteristic are greatly improved.

[Brief description of drawings]

FIG. 1 is a diagram showing a result of analysis of a segregated phase according to Example 1.

FIG. 2 is a diagram showing an analysis result after dissolution of a segregated phase according to Example 1.

FIG. 3 is a diagram showing a structure of a sealed battery.

FIG. 4 is a diagram showing an analysis result of an alloy according to Comparative Example 1.

5 is a diagram showing an analysis result after melting of an alloy according to Comparative Example 1. FIG.

FIG. 6 is a diagram showing analysis results of a segregated phase according to Example 2.

FIG. 7 is a diagram showing the formation of cracks according to the second embodiment.

FIG. 8 is a table showing the relationship between the ratio of the average diameter of the fine pores to the average particle diameter of the alloys of Example 7 and Comparative Examples 7 and 8 and the capacity ratio.

FIG. 9 is a table showing the relationship between the ratio of the area of pores to the surface area of particles and the capacity ratio of Examples 8 and Comparative Examples 9 and 10.

FIG. 10 is a table showing the relationship between the ratio of the volume of pores to the volume of particles and the volume ratio of Example 8 and Comparative Examples 9 and 10.

[Explanation of symbols]

1 ... SEM photograph of alloy of Example 1; 2 ... Surface analysis of each element of alloy of Example 1; 3 SE after melting of alloy of Example 1
M photograph, 4 ... Surface analysis of each element after melting the alloy of Example 1, 5 ... Positive electrode, 6 ... Negative electrode, 7 ... Separator, 8 ... Battery can, 9 ... SEM photograph of alloy of Comparative Example 1, 10. Comparative Example 1
Surface analysis of each element of the alloy of No. 11, 11 ... SEM photograph of the alloy of Comparative Example 1 after melting, 12 ... Surface analysis of each element of the alloy of Comparative Example 1 after melting, 13 ... SEM photograph of the alloy of Example 2 , 14
Surface analysis of each element of the alloy of Example 2, 15 ... SEM photograph of the alloy of Example 2 after melting.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Komatsu 7-1-1, Omika-cho, Hitachi-shi, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Tatsuo Horiba 7-chome, Omika-cho, Hitachi-shi, Ibaraki No. 1 Hitachi Ltd. Hitachi Research Laboratory

Claims (55)

[Claims] 1. A secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, wherein the positive electrode or the negative electrode contains substance particles involved in a charge / discharge reaction, and the particles are composed of at least two phases. In addition, at least one of the phases is composed of an electrode having pores, and the output of the secondary battery is 580 W / l or more.
A secondary battery capable of discharging for 5 minutes or more. 2. A secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, wherein the positive electrode or the negative electrode contains substance particles involved in a charge / discharge reaction, and the particles are composed of at least two phases. And at least one of the phases has pores,
A secondary battery comprising an electrode having cracks and capable of discharging for 15 minutes or more at an output of the secondary battery of 580 W / l or more. 3. A secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, wherein the positive electrode or the negative electrode contains substance particles involved in a charge / discharge reaction, and the particles are composed of at least two phases. Further, at least one of the phases is composed of an electrode having pores formed by melting or evaporating, and the secondary battery can discharge for 15 minutes or more at an output of 580 W / l or more. Next battery. 4. A secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, wherein the positive electrode or the negative electrode contains substance particles involved in a charge / discharge reaction, and the particles are composed of at least two phases. And an electrode having pores formed by dissolving or evaporating at least one of the phases and having cracks formed by the generation of charge products or discharge products, and the output of the secondary battery is 580 W A secondary battery characterized by being capable of discharging for 15 minutes or more at 1 / l or more. 5. The secondary battery according to any one of claims 1 to 4, wherein at least two of the phases are substances that can independently participate in a charge or discharge reaction and have different charge capacities or discharge capacities. Rechargeable battery. 6. The secondary battery according to any one of claims 1 to 4, wherein at least two of the phases are substances showing different expansion rates or contraction rates in charge or discharge reaction. 7. The secondary battery according to claim 2 or 4, wherein at least one of the phases that can participate in a charge or discharge reaction, the pores, their boundaries, and any one of them. A secondary battery characterized in that cracks are generated in at least one region selected from the group consisting of: 8. The secondary battery according to claim 2, wherein the crack is formed by at least one of a charge reaction, a discharge reaction of the battery, a reaction similar to these, an electrolytic solution, an acid, an alkali, an oxidizing agent, and a reducing agent. And a secondary battery formed by at least one means selected from the group consisting of the above reaction and any combination thereof. 9. The secondary battery according to any one of claims 1 to 4, wherein the pores are present on the surface of the particles in contact with the electrolytic solution. 10. A secondary battery comprising a positive electrode and a negative electrode with an electrolytic solution interposed therebetween, wherein the positive electrode or the negative electrode contains substance particles involved in a charge / discharge reaction, and the surface of the particles has fine pores, A secondary battery, wherein the composition of the surface of the pores is composed of an electrode different from the composition of the surface of the particles around the pores, and the secondary battery is capable of discharging for 15 minutes or more at an output of 580 W / l or more. 11. The secondary battery according to claim 10, wherein the particles are composed of a plurality of phases, the pores are formed by dissolving or evaporating at least one phase out of the phases, and at least the surfaces of the pores have at least one phase. A secondary battery having one kind of transition metal or noble metal. 12. The secondary battery according to any one of claims 1 to 11, wherein the particles are an alloy containing at least two kinds of elements, and the alloy is at least precipitated in a first phase and the first phase. A secondary battery having one kind of second phase and having pores formed by dissolving or evaporating at least one phase of the second phase. 13. The secondary battery according to claim 12, wherein the second
2. A secondary battery, wherein at least one of the phases is a substance capable of participating in a charge or discharge reaction that exhibits a charge capacity or a discharge capacity different from that of the first phase by itself. 14. The secondary battery according to claim 12,
A secondary battery, wherein cracks are formed in the particles. 15. The secondary battery according to claim 1, wherein the particles are carbon having at least one phase, and at least one of the phases is dissolved or evaporated on the carbon surface. A secondary battery having the following pores. 16. The secondary battery according to claim 15, wherein at least one phase among the phases is a substance capable of participating in a charging or discharging reaction showing a charging capacity or a discharging capacity different from that of carbon alone. Characteristic secondary battery. 17. The secondary battery according to claim 15, wherein
A secondary battery, wherein cracks are formed in the particles. 18. The secondary battery according to claim 1, wherein the particles are oxides or sulfides containing at least two kinds of elements, and the oxides or sulfides are the first phase and the first phase. A secondary battery having at least one kind of second phase precipitated in one phase and having pores formed by dissolving or evaporating at least one phase of the second phase. 19. The secondary battery according to claim 18, wherein the second
2. A secondary battery, wherein at least one of the phases is a substance capable of participating in a charge or discharge reaction that exhibits a charge capacity or a discharge capacity different from that of the first phase by itself. 20. The secondary battery according to claim 18,
A secondary battery, wherein cracks are formed in the particles. 21. The secondary battery according to any one of claims 1 to 4, wherein the particles are particles having an average particle diameter of 2 mm or less, and the average particle diameter of the particles is ½ or less and 1/150 or more of the average particle diameter. A secondary battery having pores having a diameter. 22. The secondary battery according to claim 1, wherein the surface area occupied by the pores of the particles is 0.15 of the particle surface area.
% To 80% of the secondary battery. 23. The secondary battery according to any one of claims 1 to 4, wherein the proportion of the pores in the particles is in the range of 0.2% by volume to 60% by volume of the volume of the particles. battery. 24. The secondary battery according to claim 1, wherein at least two of the phases that can participate in a charge or discharge reaction have a small charge capacity or discharge capacity. The ratio of the larger charge capacity or discharge capacity to the larger charge capacity or discharge capacity is 1.0
A secondary battery which is 5 or more. 25. The secondary battery according to any one of claims 1 to 4, wherein a volume expansion rate or a contraction rate generated in a charge or discharge reaction of at least two phases of the phases capable of participating in a charge or discharge reaction is A secondary battery characterized in that the ratio of the expansion rate or contraction rate of the larger one to the expansion rate or contraction rate of the smaller one is 1.1 or more. 26. A secondary battery comprising a positive electrode and a negative electrode with an electrolytic solution interposed therebetween, wherein the negative electrode has hydrogen storage alloy particles, and the particles are magnesium, lanthanum, cerium, praseodymium, neodymium, titanium, zirconium, hafnium,
From alloys containing one or more of niobium, palladium, yttrium, scandium, calcium, aluminum, cobalt, chromium, vanadium, manganese, tin, boron, molybdenum, tungsten, carbon, lead, iron, nickel, potassium, sodium, lithium Composed,
A secondary battery comprising at least two phases and having pores formed by melting or evaporating at least one of the phases. 27. The secondary battery according to claim 26, wherein the hydrogen-absorbing alloy particles are one of the phases capable of participating in a charge or discharge reaction due to generation of a charge product or a by-product during charge / discharge. The secondary battery, wherein cracks are generated in at least one region selected from the group consisting of at least one phase, pores, boundaries thereof, and any combination thereof. 28. The secondary battery according to claim 26, wherein
A secondary battery, wherein at least two of the phases are substances capable of participating in a charge or discharge reaction which show different charge capacities or discharge capacities by themselves. 29. The secondary battery according to claim 26, wherein the dissolved phase is aluminum, vanadium, manganese,
Tin, boron, magnesium, molybdenum, tungsten, zirconium, potassium, sodium, lithium,
A secondary battery containing at least 40% by weight or more of nickel and titanium. 30. The secondary battery according to claim 26, wherein the pores are formed by being dissolved by at least one of the electrolytic solution, acid, other alkali, oxidizing agent, reducing agent, or a combination thereof. Characteristic secondary battery. 31. In a secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, the negative electrode contains carbon as a main component, and the carbon is iron, nickel, sulfur, boron, molybdenum, tungsten, vanadium, niobium, silicon,
It contains at least one phase consisting of at least one element of tin, lithium, sodium, potassium, lead and silver or an oxide, and at least one phase of the phase contains an acid, an alkali,
A secondary battery having pores formed by dissolution or evaporation with at least one of an oxidizing agent and a reducing agent. 32. The secondary battery according to claim 31, wherein the negative electrode particles are formed of at least one of the phases capable of participating in a charge or discharge reaction due to generation of a charge product or a by-product at the time of charge / discharge. One-phase, of pores, of their boundaries,
And a secondary battery in which cracks are generated in at least one region selected from the group consisting of any combination thereof. 33. The secondary battery according to any one of claims 31 to 32,
A secondary battery characterized in that at least one of the phases is a substance capable of participating in a charging or discharging reaction showing a charging capacity or a discharging capacity different from that of carbon alone. 34. A secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, wherein the positive electrode or the negative electrode has a conductive polymer, and the conductive polymer is iron, nickel, sulfur, boron,
It contains at least one phase consisting of at least one element of molybdenum, tungsten, vanadium, niobium, silicon, tin, lead, lithium, sodium, potassium, silver or an oxide, and at least one phase of the phase contains an acid, an alkali, A secondary battery having pores formed by dissolution or evaporation with at least one of an oxidizing agent and a reducing agent. 35. The secondary battery according to claim 34, wherein the positive electrode or the negative electrode particles are charged or discharged in the phase by generating a charge product, a discharge product, or a by-product at the time of charge / discharge. At least one of the phases that can be involved,
A secondary battery characterized in that cracks are generated in at least one region selected from the group consisting of pores, their boundaries, and any combination thereof. 36. The secondary battery according to claim 34,
A secondary battery characterized in that at least one of the phases is a substance capable of participating in a charging or discharging reaction having a charging capacity or a discharging capacity different from that of the conductive polymer by itself. 37. A secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, wherein the negative electrode is made of an alloy containing at least one of nickel, silicon, germanium, magnesium, copper, manganese, niobium, boron and silver. A secondary battery comprising at least two or more phases, at least one of which has pores formed by dissolution or evaporation with at least one of an acid, an alkali, an oxidizing agent and a reducing agent. . 38. The secondary battery according to claim 38, wherein the negative electrode particles are one of phases that can participate in a charge or discharge reaction among the phases due to generation of a charge product or a by-product during charge / discharge. A secondary battery characterized in that cracks are generated in at least one region selected from the group consisting of at least one phase, pores, their boundaries, and any combination thereof. 39. The secondary battery according to claim 38,
A secondary battery, wherein at least two of the phases are substances capable of participating in a charge or discharge reaction which show different charge capacities or discharge capacities by themselves. 40. A secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, wherein the positive electrode is lead, manganese, vanadium,
Iron, nickel, cobalt, copper, chromium, molybdenum, titanium, niobium, tantalum, strontium, bismuth,
An oxide containing at least one of tungsten and boron, or a sulfide containing at least one of titanium, molybdenum, iron, tantalum, strontium, lead, niobium, copper, nickel, vanadium, bismuth and manganese,
Alternatively, a first phase formed of a complex oxide containing the above oxide or sulfide and lithium, and aluminum, tin, boron,
At least one second phase containing at least one element or an oxide of magnesium, potassium, sodium and vanadium, and at least one phase of the second phase contains an acid, an alkali, an oxidizing agent, A secondary battery having pores formed by being dissolved by a reducing agent. 41. A secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, wherein the positive electrode is lead, manganese, vanadium,
Iron, nickel, cobalt, copper, chromium, molybdenum, titanium, niobium, tantalum, strontium, bismuth,
Oxide containing at least one of boron, tungsten, aluminum, tin, magnesium, potassium and sodium, or titanium, molybdenum, iron, tantalum, strontium, lead, niobium, copper, nickel, vanadium, bismuth, manganese, aluminum, Tin, boron,
A sulfide containing at least one of magnesium, potassium and sodium, or at least two phases of the above oxide or a composite oxide containing sulfide and lithium, and at least two of the phases are independent. A secondary battery characterized by being a substance capable of participating in a charge or discharge reaction, which exhibits different charge or discharge capacities. 42. The secondary battery according to claim 40, wherein
The positive electrode particles have pores of at least one of the phases that can participate in the charge or discharge reaction among the phases due to the formation of charge products, discharge products, or by-products at the time of charge / discharge. A secondary battery, characterized in that cracks are generated in at least one region selected from the group consisting of the boundary of, and a combination of any of these. 43. A method for producing a positive electrode or a negative electrode for use in a secondary battery, wherein the positive electrode and the negative electrode have an electrolytic solution therebetween,
A step of manufacturing the negative electrode by assembling and molding substance particles involved in a battery reaction, a first phase containing at least two or more kinds of phases capable of participating in a charge or discharge reaction, and the first phase A second phase which dissolves or evaporates to form pores, and at least one of the second phases is acid,
And a step of dissolving or evaporating with any of an alkali, an oxidizing agent, and a reducing agent to form pores. 44. A method for producing a positive electrode or a negative electrode for use in a secondary battery comprising a positive electrode and a negative electrode with an electrolytic solution interposed therebetween,
A step of manufacturing the positive electrode or the negative electrode by assembling and forming particles of a substance involved in a battery reaction, performing a charge reaction or a discharge reaction or a similar reaction on the electrode, and a part of the charge product or the discharge product And a step of forming a crack, and a method for manufacturing a secondary battery electrode. 45. A method of manufacturing an electrode used in a secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, the method comprising: a first phase; and a charge or discharge reaction of at least one kind other than the first phase. The second phase that can participate and the third phase that dissolves or evaporates to form the third phase and that participates in the battery reaction are mixed with the first phase component, the second phase component, and the third phase. Combining the components of the phase of (1) to disperse these phases in the first phase, and disperse the second and third phases in the first phase. The process of crushing the
The second phase acid, alkali, oxidizer of the crushed particles,
An electrode for a secondary battery, comprising: a step of dissolving or evaporating with any of a reducing agent to form pores on the surface of the particles; a step of shaping particles having the pores into a plate shape. Production method. 46. A method of manufacturing an electrode used in a secondary battery comprising a positive electrode and a negative electrode via an electrolytic solution, wherein in the first phase and at least one or more kinds of charge or discharge reaction other than the first phase. The second phase that can participate and the third phase that dissolves or evaporates to form the third phase and that participates in the battery reaction are mixed with the first phase component, the second phase component, and the third phase. Combining the components of the phase of (1) to disperse these phases in the first phase, and disperse the second and third phases in the first phase. The process of crushing the
A step of performing a charge reaction, a discharge reaction or a reaction similar to the crushed particles to partially generate a charge product or a discharge product to form a crack, and molding the particle having the crack into a plate shape. A method of manufacturing an electrode for a secondary battery, comprising: 47. In an electrode used in a battery, the positive electrode or the negative electrode contains particles of a substance involved in a charge / discharge reaction, the particles are composed of at least two phases, and at least one of the phases is formed. An electrode for a secondary battery, comprising an electrode having pores, and capable of discharging for 15 minutes or more at an output of the secondary battery of 580 W / l or more. 48. In an electrode used in a battery, the positive electrode or the negative electrode contains particles of a substance involved in a charge / discharge reaction, and the particles are composed of at least two phases, and at least one phase of the phases is included. An electrode for a secondary battery, comprising an electrode having pores and having cracks, and capable of discharging for 15 minutes or more at an output of the secondary battery of 580 W / l or more. 49. In an electrode used for a battery, the positive electrode or the negative electrode contains particles of a substance involved in a charge / discharge reaction, the particles are composed of at least two phases, and at least one of the phases is contained. It consists of electrodes with pores formed by melting or evaporation, and the output of the secondary battery is 580W.
An electrode for a secondary battery, which is capable of discharging for 15 minutes or more at 1 / l or more. 50. In an electrode used for a battery, the positive electrode or the negative electrode contains particles of a substance involved in a charge / discharge reaction, and the particles are composed of at least two phases, and at least one phase of the phases is included. It is composed of an electrode having pores formed by dissolution or evaporation and having cracks formed by the generation of charge products or discharge products, and the output of the secondary battery is 580 W / l or more for 15 minutes or more. An electrode for a secondary battery, which is capable of discharging. 51. The electrode used in the battery according to any one of claims 47 to 50, which contains a substance involved in the charge / discharge reaction, wherein the particle surface has pores, and the composition of the pore surface is the pores. An electrode for a secondary battery, wherein the composition of the surface of the particles is different from that of the surrounding particles. 52. An electrode for use in a battery according to any one of claims 47 to 50, wherein the pore surface has at least one kind of transition metal or noble metal. 53. In the electrode for use in the battery according to claim 48, at least two of the phases are substances that are capable of participating in a charging or discharging reaction that show different charging capacities or discharging capacities by themselves. Characteristic secondary battery electrode. 54. The secondary battery according to any one of claims 48 to 51, wherein at least two of said phases are substances showing different expansion rates or contraction rates in charge or discharge reaction. Electrodes. 55. In a power supply system using a secondary battery having a positive electrode and a negative electrode with an electrolyte interposed, the positive electrode or the negative electrode contains particles of a substance involved in a charge / discharge reaction, and the particles are at least 2 or more. And an electrode having cracks in at least one of the phases, and capable of discharging for 15 minutes or more when the output of the secondary battery is 580 W / l or more. And a fuel cell, a solar cell, an air cell, and a sodium-sulfur cell, and the secondary cell is used at the time of discharging at a high output, and a power supply therefor. Power supply system with operation control unit.