JP2003272616A - Manufacturing method of nonaqueous primary battery and active material for battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To augment discharge capacity and lower operation voltage while realizing miniaturization for a primary battery. <P>SOLUTION: With the primary battery with a positive electrode active material with nickel oxyhydroxide as a main ingredient and a negative electrode active material made of light metal arranged between a positive electrode terminal and a negative electrode terminal separated by a separator and provided with a nonaqueous electrolyte, is discharge capacity can be greatly increased, as the positive electrode active material is formed of a β-type nickel oxyhydroxide dissolving a required amount of either cobalt, copper or neodymium, whereby, not only a miniaturization of the primary battery is realized, but also an operation voltage can be lowered. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous primary battery which is used as a power source for, for example, a small portable electronic device and is compatible with an alkaline manganese battery or an alkaline secondary battery, and a positive electrode of the battery. The present invention relates to a method for producing an active material used as an active material.

[0002]

2. Description of the Related Art In recent years, portable type portable electronic devices such as portable game machines and digital cameras have been remarkably popular. It is believed that the demand for primary batteries and secondary batteries, which are power sources, will grow rapidly at the same time as it is expected that they will become more and more popular, and at the same time, the development of high-performance batteries is demanded. Has been done.

Portable electronic devices such as portable game machines and digital cameras generally have a high operating voltage and require a large current. Therefore, the battery serving as a power source thereof has excellent discharge characteristics under heavy load. There must be.

Further, portable electronic devices and the like tend to be smaller, lighter, and more sophisticated, and a battery serving as a power source thereof is expected to be smaller, lighter, and more durable. That is, it can be said that the larger the capacity per unit weight (mAh / g) and the capacity per volume (mAh / cm ³ ) of the positive electrode active material and the negative electrode active material which are the constituent materials of the battery, the better.

In order to meet such requirements, a nickel-zinc battery has been conventionally proposed, which is a battery using nickel oxyhydroxide as a positive electrode active material and zinc as a negative electrode active material. It is a battery with higher operating voltage and excellent heavy load characteristics.

[0006] In addition, the operating voltage of portable electronic devices tends to decrease year by year in order to reduce power consumption and heat generation. For example, the operating voltage of the MPU of a personal computer was generally about 1.5V,
Recently, some of the batteries operate at about 1.0 V, and it is expected that they will operate at a lower voltage in the future. Therefore, it is also desired that the operating voltage of the power supply battery be low.

[0007]

[Problems to be Solved by the Invention]
Assuming that the operating voltage is low among the primary batteries,
MnO used_Two/ Zn system, Ag_TwoO / Zn system, organic solvent
Using FeS as electrolyte _Two/ Li system etc. are mentioned,
Each of these primary batteries is related to its positive electrode active material.
Low capacity per weight (mAh / g) or after discharge
There is a problem that the volume expansion of
It is an obstacle. In addition, these primary batteries are
Battery voltage is 1.8-1.5V,
There is a problem that the pressure needs cannot be sufficiently satisfied.

Therefore, the primary battery of the conventional example has a problem to be solved while increasing the discharge capacity and lowering the operating voltage while attempting to reduce the size and weight.

[0009]

As a concrete means for solving the above-mentioned problems of the prior art, the first invention according to the present invention is mainly composed of nickel oxyhydroxide between the positive electrode terminal and the negative electrode terminal. A positive electrode active material and a negative electrode active material made of a light metal, which are separately arranged with a separator, and a primary battery provided with a non-aqueous electrolyte, wherein the positive electrode active material is cobalt,
The present invention provides a non-aqueous primary battery characterized by being formed from β-type nickel oxyhydroxide in which a required amount of copper or neodymium is solid-dissolved.

In the first invention, the solid solution amount of cobalt which is solid-dissolved in the positive electrode active material is 0.5 to 16.0 wt% of β-type nickel oxyhydroxide, and the solid solution amount of copper is Is 0.5 wt% or more of β-type nickel oxyhydroxide, and the solid solution amount of neodymium is 0.2 wt% or more of β-type nickel oxyhydroxide; Nickel hydroxide is formed into substantially spherical particles; and the light metal of the negative electrode active material is lithium, lithium alloy, magnesium, sodium, potassium, calcium, or aluminum; as additional requirements.

A second invention according to the present invention is a method for producing an active material used as a positive electrode active material of a battery, which comprises mixing sulfuric acid or nickel nitrate with a metal compound in an aqueous solution, and ammonium. A step of stirring and mixing an ion supplier and an alkaline aqueous solution to prepare metal-solid-solution nickel hydroxide; mixing the metal-soluble nickel hydroxide into a mixed solution of the alkaline aqueous solution and an oxidizing agent. The present invention provides a method for producing an active material for a battery, which is characterized in that nickel oxyhydroxide is obtained by chemical oxidation.

In the second aspect of the invention, the metal compound is one of cobalt, copper and neodymium as an additional requirement.

In the non-aqueous primary battery according to the present invention, β-type nickel oxyhydroxide is formed into a substantially spherical particle shape as a positive electrode active material, and either cobalt, copper or neodymium is solid-dissolved, The charging amount can be increased to increase the discharge capacity and the operating voltage can be lowered.

Further, in the method for producing an active material for a battery according to the present invention, nickel oxyhydroxide in which a predetermined amount of a predetermined metal is solid-dissolved can be obtained by a simple process.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in detail based on specific embodiments. FIG. 1 shows a cross-sectional view of a coin battery 1 which is an example of a non-aqueous primary battery according to the present invention. The coin-type battery 1 is configured by combining a positive electrode can 2 that is a positive electrode terminal and a negative electrode cup 3 that is a negative electrode terminal in pairs.

Inside a coin-type battery 1 constructed by combining a positive electrode can 2 and a negative electrode cup 3, a positive electrode pellet 4 as a positive electrode active material and a negative electrode active material 5 made of a light metal are arranged. The positive electrode pellet 4 is formed by pressing a positive electrode mixture composed of β (beta) type nickel oxyhydroxide (β-NiOOH), a conductive agent, and a binder into a disc shape together with a metal mesh body (not shown). It is a thing. The positive electrode pellets 4 are arranged so as to be in electrical contact with the positive electrode can 2 that is the positive electrode terminal, whereby the positive electrode can 2
Serves as an external positive electrode terminal.

The positive electrode pellet 4 used in the present invention is a β-type nickel oxyhydroxide (NiO) having a substantially spherical particle shape, as is apparent from the electron micrograph shown in FIG.
OH) 8, and the required amount of cobalt, copper, or neodymium is solid-dissolved in this β-type nickel oxyhydroxide 8.

The light metal serving as the negative electrode active material 5 is not particularly limited, but for example, lithium metal (Li),
Alternatively, a lithium alloy obtained by adding an alloying element such as aluminum to lithium, magnesium, sodium, potassium, calcium, aluminum or the like can be used. Similar to the positive electrode pellet 4, the negative electrode active material 5 is molded into a disk shape and is disposed so as to be in electrical contact with the negative electrode cup 3, which is the negative electrode terminal. As a result, the negative electrode cup 3 serves as an external negative electrode terminal. Is the function of.

A separator 6 is provided between the positive electrode pellet 4 and the negative electrode active material 5 so that the positive electrode pellet 4 and the negative electrode active material 5, which are positive electrode active materials, do not come into electrical contact with each other. Has been done.

A sealing gasket 7 is arranged on the inner peripheral edge of the coin type battery 1, and the positive electrode can 2 and the negative electrode cup 3 are provided.
Are fitted and united through the sealing gasket 7 to be integrated.

The positive electrode pellet 4 used in the present invention is a β-type nickel oxyhydroxide (NiO) having a substantially spherical particle shape, as is apparent from the electron micrograph shown in FIG.
OH) 8, and the required amount of cobalt, copper, or neodymium is solid-dissolved in this β-type nickel oxyhydroxide 8.

In order to manufacture such a coin-type battery 1 using β-type nickel oxyhydroxide as a positive electrode active material, a positive electrode pellet 4 is placed inside a positive electrode can 2 and a separator 6 is placed thereon. Then, a required amount of non-aqueous electrolyte (electrolyte solution) is injected. Subsequently, the negative electrode active material 5 is disposed on the separator 6, the sealing gasket 7 is disposed on the peripheral portion of the negative electrode cup 3, and the negative electrode cup 3 is fitted into the positive electrode can 2 via the sealing gasket 7. The coin-type battery 1, which is a kind of non-aqueous primary battery, is formed by pressing and sealing the both.

As the non-aqueous electrolyte, for example, an electrolyte solution in which a lithium salt is used as an electrolyte and this is dissolved in an organic solvent can be used. Here, as the organic solvent, for example, a solvent such as cyclic carbonic acid ester, cyclic ester, chain carbonic acid ester, chain ester, sulfolane, cyclic ether, chain ether, nitriles, specifically, propylene carbonate, ethylene. Carbonate, 1,2-dimethoxyethane, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, sulfolane, acetonitrile, dimethylcarbonate, methylethylcarbonate, dipropylcarbonate and the like can be used, and two or more kinds of them can be used. It is also possible to use a mixed solvent in which

As the non-aqueous electrolyte, a solid electrolyte,
It is also possible to use a polymer electrolyte, a non-aqueous electrolyte prepared by mixing / dissolving an electrolyte in a polymer compound, a gel electrolyte prepared by mixing a polymer compound with a non-aqueous electrolytic solution, and the like.

As the electrolyte of the lithium salt, for example,
Lithium perchlorate (LiClO_Four), Hexafluorophosphate
Tium (LiPF₆), Lithium tetrafluoroborate (Li
BF _Four), Lithium trifluoromethanesulfonate (C
F_ThreeSO_ThreeLi) or the like can be used.

As the separator 6, for example, a polyolefin microporous film such as polypropylene or polyethylene can be used.

As a method for producing β-type nickel oxyhydroxide, for example, there is a chemical oxidation method. As an example of the chemical oxidation method, nickel hydroxide is oxidized in an alkaline liquid phase containing sodium hypochlorite. Can be obtained at.

In order to understand the nickel oxyhydroxide of the present invention, FIG. 3 shows nickel oxyhydroxide 9 having a rock-like (non-spherical) particle shape by an electron micrograph. The nickel oxyhydroxide 9 having the rock-like particle shape is for performance comparison with the nickel oxyhydroxide 8 having the substantially spherical particle shape.

First, in a coin type battery of the same size, the filling amount and the discharge capacity of the β-type nickel oxyhydroxide 8 having a substantially spherical particle shape and the β-type nickel oxyhydroxide 9 having a rock-like particle shape are compared. In order to compare and understand the difference, Comparative Examples 1 and 2 will be described. However, β-type nickel oxyhydroxides 8 and 9 having substantially spherical and rock-like particle shapes used in these Comparative Examples 1 and 2 include those in which neither cobalt, copper nor neodymium is solid-dissolved. It is used.

Comparative Example 1 In Comparative Example 1, 78% by weight of β-type nickel oxyhydroxide 9 having a rock-like (non-spherical) particle shape, 20% by weight of graphite as a conductive agent,
2% by weight of polyvinylidene fluoride (PVdF) as a binder is mixed and dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode mixture slurry.

This positive electrode mixture slurry was heated at 120 ° C. for 2 hours.
It was dried for a period of time to evaporate NMP and crushed into powder in a mortar to obtain a positive electrode mixture. This positive electrode mixture was pressure-molded into a disc shape with a predetermined pressure using a metal mesh made of aluminum, which is a metal mesh, as a support to give a diameter of 15.5 mm and a thickness of 250 μm.
m positive electrode pellet which is the positive electrode active material.

Then, a coin-type battery having an outer diameter of 20 mm and a height of 1.6 mm was manufactured through the same steps as those in the above-mentioned embodiment.

(Comparative Example 2) Also in Comparative Example 2, the rock-like (non-spherical) particle shape 9 of β-type nickel oxyhydroxide in Comparative Example 1 was replaced with a substantially spherical particle-shaped β-type oxywater. A coin type battery having the same size was manufactured in the same manner as in Comparative Example 1 except that nickel oxide 8 was used.

First, Table 1 shows the filling amount of the positive electrode mixture in Comparative Examples 1 and 2.

[Table 1]

When the positive electrode mixture is filled, the β-type nickel oxyhydroxide having a substantially spherical particle shape 8 is larger than the β-type nickel oxyhydroxide having a rock-like (non-spherical) particle shape 9 in the shape of Tap.
Since the density and the bulk density are high and a larger amount can be filled in a fixed volume, the capacity of the active material can be increased.

In the coin type batteries of Comparative Example 1 and Comparative Example 2 thus produced, the open circuit voltage immediately after the production was about 3.
Although it is about 5V, it has a characteristic that the voltage is drastically reduced by discharging and shows a substantially flat potential in the vicinity of about 1.0 to 1.2V.

Therefore, the discharge characteristics of this coin type battery are
The discharge test will be performed in a state where the preliminary discharge is performed and the initial part of the discharge is excluded. In this preliminary discharge, a constant current of 1 mA is discharged until the battery voltage reaches 1.3 V, and then a full day is passed.

After the preliminary discharge, a constant current of 1 mA and 5 mA,
A discharge test in which discharge is performed until the battery voltage reaches 0.5 V is performed, and the discharge capacities of the coin type batteries of Comparative Example 1 and Comparative Example 2 at that time are shown in Table 2.

[0039]

[Table 2]

As is clear from Table 2, in both cases of 1 mA discharge and 5 mA discharge, Comparative Example 2 using β-type nickel oxyhydroxide 8 having a substantially spherical particle shape as the positive electrode active material is more preferable. It can be understood that the discharge capacity is larger than that of Comparative Example 1 using β-type nickel oxyhydroxide 9 having a rock-like (non-spherical) particle shape.

This is because the amount of the positive electrode mixture that can be filled at a constant pressure with respect to a constant volume is β-type nickel oxyhydroxide 8 having a substantially spherical particle shape, which is more rock-like (non-spherical) particles. It is considered that this is because there are more than β-type nickel oxyhydroxide 9 in shape. From this, it is understood that when β-type nickel oxyhydroxide is used as the non-aqueous primary battery, it is better to use β-type nickel oxyhydroxide 8 having a substantially spherical particle shape.

Therefore, a specific example according to the present invention, that is, one in which β-type nickel oxyhydroxide 8 having a substantially spherical particle shape is used and the solid capacity of cobalt, copper or neodymium is changed, , Some comparative examples will be described.

(Examples 1 to 14) In each of Examples 1 to 14, β-type nickel oxyhydroxide 8 having a substantially spherical particle shape was used, and 0.5 to 16.
In the range of 0% by weight, the amount of cobalt (Co) was changed to form a solid solution. Except for using β-type nickel oxyhydroxide 8 having a substantially spherical particle shape in which the amount of cobalt is changed to form a solid solution, preparation of a positive electrode mixture, molding of a positive electrode pellet 4, preparation of a negative electrode active material 5, separator 6 With respect to the interposition, etc., coin type battery 1 was produced in the same manner as described in the above embodiment.

As a method for producing β-type nickel oxyhydroxide in which cobalt is solid-dissolved, for example, an aqueous solution in which nickel sulfate and cobalt sulfate which is a metal compound are mixed at a predetermined ratio, an ammonium feed such as ammonium sulfate,
Stir and mix with an alkaline aqueous solution such as sodium hydroxide to prepare nickel hydroxide containing cobalt as a solid solution.

An alkaline aqueous solution such as sodium hydroxide,
The nickel hydroxide prepared above is put into a mixed solution of an oxidizing agent such as sodium hypozincate, and chemically oxidized to prepare β-type nickel oxyhydroxide having a substantially spherical cobalt solid solution.

Since it suffices if cobalt can be solid-dissolved in such β-type nickel oxyhydroxide, the method for producing β-type nickel oxyhydroxide in which cobalt is solid-solved is not limited to the above-mentioned method. If it is a method that can produce β-type nickel oxyhydroxide in which cobalt is dissolved,
Other methods can also be used.

Regarding the solid solution amount of cobalt, the whole metal element was quantified by chelate titration, and then the trace elements other than nickel were quantified by ICP (high frequency plasma emission spectrometry).

(Comparative Examples 3 to 4) In Comparative Examples 3 to 4, the solid solution amount of cobalt in Examples 1 to 14 was changed to 0.5% by weight or less, that is, 0.3 to 0.4% by weight. And the others are described in Examples 1 to 1.
It produced like 4th.

(Comparative Examples 5 to 7) In Comparative Examples 5 to 7, the solid solution amount of cobalt in Examples 1 to 14 was changed to 16% by weight or more, that is, 16.1 to 17.0% by weight. In other respects, it was manufactured in the same manner as in Examples 1 to 14.

Comparative Example 2 using β-type nickel oxyhydroxide 8 having a substantially spherical particle shape without solid solution of cobalt
And β of a substantially spherical particle shape in which a predetermined amount of cobalt is dissolved.
Examples 1 to 14 in which type 8 nickel oxyhydroxide is used
Table 3 shows the discharge capacities when 1 mA and 5 mA discharges were carried out for Comparative Examples 3 to 7, and FIG. 4 shows the changes in the discharge capacities with respect to the solid solution amount of cobalt (Co).
Shown in.

FIG. 5 shows the change in discharge capacity at a constant current of 1 mA for representative Comparative Examples 1, 2, 7 and Examples 3 and 7, and shows the change in discharge capacity at a constant current of 5 mA. Figure 6
Shown in. In these figures, the change characteristics of the discharge capacity of Comparative Example 1 are shown by curves 11 and 21, the change characteristics of the discharge capacity of Comparative Example 2 are shown by curves 12a and 22a, and the change characteristics of the discharge capacity of Comparative Example 7 are shown. Shown by curves 15 and 25, Example 3
The change characteristics of the discharge capacity of No. 3 are shown by curves 13 and 23, and the change characteristics of the discharge capacity of Example 7 are shown by curves 14 and 24, respectively.

[0052]

[Table 3]

As can be understood from Table 3 and FIGS. 5 and 6, when the required amount of cobalt is dissolved in β-type nickel oxyhydroxide, which is the positive electrode active material, the discharge capacity can be improved. The solid solution amount of cobalt is 0.5 to 16.0.
Examples 1 to 14 in the range of 0.3% by weight and 0.3 to 0.
Comparative Examples 3 to 4 in the range of 4% by weight and 16.1 to 1
In Comparative Examples 5 to 7 in which the range is 7.0% by weight, it is clear that Examples 1 to 14 are more effective.

As described above, when the solid solution amount of cobalt is less than 0.5% by weight, the effect of improving the discharge capacity is not sufficient, and when it is 0.5% by weight or more, the effect of improving the discharge capacity is obtained. However, it is understood that the effect of improving the discharge capacity is gradually attenuated when the content exceeds 16.0% by weight.

Although the detailed mechanism of this is not clarified, when cobalt is solid-dissolved in nickel oxyhydroxide, the nickel site is replaced with cobalt, and at this time, some nickel oxyhydroxide is partially dissolved. Cobalt oxyhydroxide (CoOOH) is produced in, but since cobalt oxyhydroxide has higher conductivity than nickel oxyhydroxide, the conductivity as a positive electrode active material is improved,
Since cobalt oxyhydroxide is a substance that does not contribute to the discharge capacity, it is presumed that if the solid capacity is too large, the discharge capacity will be reduced.

In the case of Example 7 as an example, 1 mA
The discharge capacity during constant current discharge is 82.6 mAh from Table 3, and when this is calculated using the filling amount of the positive electrode active material,
The capacity per weight is approximately 1060 mAh / g (= 8
The result is 2.6 / 0.1 / 0.78), which is a very large value as compared with the conventional battery positive electrode material.

Therefore, the solid solution amount of cobalt dissolved in the positive electrode active material is 0.5 to 1 of β-type nickel oxyhydroxide.
When it is 6.0% by weight, cobalt does not form a solid solution, for example, Comparative Example 2 and the solid capacity of cobalt is 16.
When it exceeds 0% by weight, for example, as compared with Comparative Example 7,
Since the discharge capacity can be remarkably improved, and in particular, the value can be made extremely large as compared with the conventional positive electrode material for batteries, the solid solution amount of cobalt is 0.5 to 16.0% by weight. Preferably.

(Examples 15 to 25) Examples 15 to 2
In Example 5, β-type nickel oxyhydroxide 8 having a substantially spherical particle shape was used, and the amount of copper (Cu), which is a metal compound, was changed in the range of 0.5 to 10.0 wt% to obtain a solid content. It is melted. Except for using β-type nickel oxyhydroxide 8 having a substantially spherical particle shape in which the amount of copper is changed to form a solid solution, preparation of the positive electrode mixture, formation of the positive electrode pellet 4, preparation of the negative electrode active material 5, and formation of the separator 6 Regarding the interposition and the like, the coin-type battery 1 was produced in the same manner as described in the above embodiment.

As a method for producing β-type nickel oxyhydroxide in which copper is solid-dissolved, for example, an aqueous solution in which nickel sulfate and copper sulfate are mixed at a predetermined ratio, an ammonium supply such as ammonium sulfate, and sodium hydroxide are used. Stir and mix with an alkaline aqueous solution to prepare nickel hydroxide in which copper is solid-dissolved.

An alkaline aqueous solution such as sodium hydroxide,
Into a mixed solution of an oxidizer such as sodium hypozincate, the above-mentioned nickel hydroxide in which copper is solid-dissolved is added and chemically oxidized to prepare substantially spherical β-type nickel oxyhydroxide in which copper is solid-dissolved. . In this case as well, in short, β that is a solid solution of copper
Other methods may be used as long as they can produce the nickel oxyhydroxide type.

Regarding the solid solution amount of copper, the whole metal element was quantified by chelate titration, and then the trace elements other than nickel were quantified by ICP (high frequency plasma emission analysis).

Comparative Examples 8 to 9 In Comparative Examples 8 to 9, the solid solution amount of copper in Examples 15 to 25 was 0.5% by weight.
The content was set in the range of 0.3 to 0.4% by weight below, and the other parts were manufactured in the same manner as in Examples 15 to 25.

Β having a substantially spherical particle shape in which copper is not solid-dissolved
Comparative Examples 2 using the nickel oxyhydroxide type 8 and Examples 15 to 25 using β-type nickel oxyhydroxide 8 having a substantially spherical particle shape in which a required amount of copper is solid-dissolved. For Examples 8-9, 1 mA or 5 mA
The discharge capacity when discharging is shown in Table 4, and the change of the discharge capacity with respect to the solid solution amount of copper (Cu) at this time is shown in FIG.

[0064]

[Table 4]

As is clear from Table 4 and FIG. 7, when the required amount of copper is dissolved in β-type nickel oxyhydroxide, which is the positive electrode active material, the discharge capacity can be improved.
In Examples 15 to 25 in which the solid solution amount of copper was in the range of 0.5 to 10.0% by weight and Comparative Examples 8 to 9 in which the amount of copper solid solution was in the range of 0.3 to 0.4% by weight, Example 15 was used. It can be seen that the effects of Nos. 25 to 25 are greater.

As described above, when the solid solution amount of copper is less than 0.5% by weight, the effect of improving the discharge capacity is not sufficient, and when it is 0.5% by weight or more, the effect of improving the discharge capacity is obtained. It can be understood that can be obtained sufficiently.

Although the detailed mechanism has not been elucidated, the nickel site is replaced with copper. At that time, copper has a larger ionic radius than nickel. It is presumed that the crystal of nickel oxide is distorted, which improves the reactivity with lithium as the negative electrode active material.

Further, with respect to β-type nickel oxyhydroxide having a substantially spherical particle shape 8 exemplifying the representative Examples 15, 20, 23 and Comparative Example 2, relative to the solid solution amount of copper at a constant current of 1 mA. The change in discharge capacity is shown in FIG. 8, and the change in discharge capacity with respect to the solid solution amount of copper at a constant current of 5 mA is shown in FIG.

As is clear from FIGS. 8 and 9, 1 mA
In both cases of discharge and 5 mA discharge, the discharge characteristics 33 and 43 of Example 15 containing copper as a solid solution and the discharge characteristics of Example 20 were larger than the discharge characteristics 12b and 22b of Comparative Example 2 containing no solid solution of copper. Characteristics 34 and 44, discharge characteristics 35 and 45 of Example 23
It can be seen that the discharge capacity is larger in the case of. Further, it is understood that the discharge capacity can be improved only by increasing the solid solution amount of copper.

However, although the discharge capacity can be improved by increasing the solid solution amount of copper, as described above, since copper has a larger ionic radius than nickel, the current technology is 10. 0% by weight is the limit of solid solution, and 1
In the present invention, the range including the solid solution is included in the meaning of increasing the discharge capacity if the solid solution of 0.0 wt% or more becomes possible.

In the case of taking Example 25 as an example, 1 m
A discharge capacity at constant current discharge is 76.2 mAh from Table 4.
When calculated using the filling amount of the positive electrode active material, the capacity per weight is about 977 mAh / g (= 7
The result is 6.2 / 0.1 / 0.78), which is a very large value compared with the conventional positive electrode material for batteries.

Therefore, the copper solid-dissolved in the positive electrode active material is β
When it is in the range of 0.5 to 10.0% by weight of the nickel oxyhydroxide type, the discharge capacity can be remarkably improved as compared with Comparative Example 2 in which copper is not solid-dissolved, and the conventional battery can be used. Since it can be set to a very large value compared with the positive electrode material for use in the present invention, the solid solution amount of copper is 0.5 to 10.0 at this stage.
It is preferably set to wt%.

(Examples 26 to 31) Examples 26 to 3
In No. 1, β-type nickel oxyhydroxide 8 having a substantially spherical particle shape was used, and neodymium (Nd), which is a metal compound in the range of 0.2 to 2.5% by weight, was used.
The amount is changed to form a solid solution. Except for using β-type nickel oxyhydroxide 8 having a substantially spherical particle shape in which the amount of this neodymium is changed to form a solid solution, preparation of the positive electrode mixture, molding of the positive electrode pellet 4, preparation of the negative electrode active material 5, and separation of the separator 6 Regarding the interposition and the like, the coin-type battery 1 was produced in the same manner as described in the above embodiment.

As a method for producing β-type nickel oxyhydroxide in which neodymium is solid-dissolved, for example, an aqueous solution in which nickel sulfate and neodymium oxide are mixed at a predetermined ratio, an ammonium feed such as ammonium sulfate, and sodium hydroxide are used. Stir and mix with an alkaline aqueous solution to prepare nickel hydroxide having a solid solution of neodymium.

An alkaline aqueous solution such as sodium hydroxide,
The above-mentioned nickel hydroxide in which neodymium is solid-dissolved is put into a mixed solution of an oxidizing agent such as sodium hypozincate, and chemically oxidized to prepare an approximately spherical β-type nickel oxyhydroxide in which neodymium is solid-dissolved. . Also in this case, in short, any other method may be used as long as it is a method capable of producing β-type nickel oxyhydroxide in which copper is solid-dissolved.

Regarding the solid solution amount of neodymium, the whole metal element was quantified by chelate titration and then IC
Trace elements other than nickel were quantified by P (high frequency plasma emission spectrometry).

Comparative Example 10 In Comparative Example 10, the solid solution amount of neodymium in Examples 26 to 31 was 0.2% by weight.
The following content was 0.1% by weight, and the other components were manufactured in the same manner as in Examples 26 to 31.

Using β-type nickel oxyhydroxide 8 having a substantially spherical particle shape in which neodymium is not solid-dissolved, for example, Comparative Example 2 described above and a substantially spherical particle shape in which a required amount of neodymium is solid-dissolved are used. Regarding Examples 26 to 31 and Comparative Example 10 using β-type nickel oxyhydroxide 8, 1
Table 5 shows the discharge capacities when mA or 5 mA discharge was performed, and FIG. 10 shows changes in the discharge capacities with respect to the solid solution amount of neodymium (Nd) at this time.

[0079]

[Table 5]

As is clear from Table 5 and FIG. 10, when a required amount of neodymium is dissolved in β-type nickel oxyhydroxide, which is the positive electrode active material, the discharge capacity can be improved. 0.2 to 2.5% by weight
It can be seen that in Examples 26 to 31 in which the range is set to 0.1 and Comparative Example 10 in which the amount is 0.1% by weight, Examples 26 to 31 are more effective.

Thus, the solid solution amount of neodymium is 0.2.
It can be understood that when the amount is less than wt%, the effect of improving the discharge capacity is not sufficient, and when the amount is 0.2 wt% or more, the effect of improving the discharge capacity is sufficiently obtained.

Regarding this as well, although the detailed mechanism has not been elucidated, the site of nickel is replaced with neodymium. At that time, neodymium has a larger ionic radius than nickel. It is speculated that the nickel oxide crystals are distorted, which improves the reactivity with lithium, which is the negative electrode active material.

Further, with respect to β-type nickel oxyhydroxide 8 having a substantially spherical particle shape, which is representative of Examples 27 and 30 and Comparative Example 2, the discharge capacity with respect to the solid solution amount of neodymium at a constant current of 1 mA. Of the discharge capacity with respect to the amount of solid solution of copper at a constant current of 5 mA is shown in FIG.
Shown in.

As is clear from FIGS. 11 and 12, 1
In both cases of mA discharge and 5 mA discharge, the discharge characteristic 5 of Example 27 in which neodymium was dissolved was more than the discharge characteristics 12c and 22c of Comparative Example 2 in which neodymium was not dissolved.
3, 63 and the discharge characteristics 54 and 64 of Example 30 have larger discharge capacities. Further, it can be seen that the discharge capacity is improved by increasing the solid solution amount of neodymium.

However, although the discharge capacity can be improved by increasing the solid solution amount of neodymium, as described above, neodymium has a larger ionic radius than nickel. The solid solution limit is 5% by weight, and if 2.5% by weight or more is possible,
In the sense of increasing the discharge capacity, the present invention includes the range in which solid solution is possible.

When the example 30 is taken as an example, 1 m
A discharge capacity at constant current discharge is 71.0 mAh from Table 5.
When calculated using the filling amount of the positive electrode active material, the capacity per weight is approximately 910 mAh / g (= 7
The result is 1.0 / 0.1 / 0.78), which is a very large value as compared with the conventional battery positive electrode material.

Therefore, when the neodymium solid-dissolved in the positive electrode active material is in the range of 0.2 to 2.5% by weight of β-type nickel oxyhydroxide, it is compared with Comparative Example 2 in which neodymium is not solid-dissolved. In comparison, since the discharge capacity can be remarkably improved and the value can be made extremely large as compared with the conventional battery positive electrode material, the solid solution amount of neodymium is 0.2 to 2 at the present stage. It is preferably set to 0.5% by weight.

Although the coin type battery 1 has been described,
Since it suffices to use β-type nickel oxyhydroxide 8 having a substantially spherical particle shape, such a non-aqueous primary battery is not limited to the shape of the coin type battery 1.

Although not described as an example, for example, β-type nickel oxyhydroxide having a rock-like particle shape 9
Even when used, the filling capacity is not changed by solid solution of the required amount of nickel, copper, or neodymium, but the discharge capacity is considerably improved compared to the conventional example in which these metals are not solid solution. In essence, the present invention resides in the fundamental technical improvement in the solid solution of the required amount of nickel, copper, or neodymium in β-type nickel oxyhydroxide.

[0090]

As described above, the non-aqueous primary battery according to the present invention includes the positive electrode active material containing nickel oxyhydroxide as the main component and the negative electrode active material containing the light metal between the positive electrode terminal and the negative electrode terminal. And a primary battery provided with a non-aqueous electrolyte, wherein the positive electrode active material is a β-type oxyhydroxide containing a required amount of cobalt, copper, or neodymium as a solid solution. Since it is made of nickel, its discharge capacity can be significantly increased,
As a result, not only the size and weight of the primary battery can be reduced, but also the operating voltage can be lowered, which is an excellent effect.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a coin battery according to an embodiment of the present invention.

FIG. 2 is an electron micrograph of nickel oxyhydroxide having a substantially spherical particle shape used in the same embodiment.

FIG. 3 is a rock shape (non-spherical) used in the battery of Comparative Example 1.
2 is an electron micrograph of nickel oxyhydroxide.

FIG. 4 is a table showing a change in discharge capacity with respect to a solid solution amount of cobalt at a constant current of 1 mA and 5 mA in a coin-type battery using a cobalt solid solution positive electrode active material according to an embodiment of the present invention.

FIG. 5 is a table showing a change in discharge capacity at a constant current of 1 mA of the coin type batteries of Specific Examples 3 and 7 of the present invention and Comparative Examples 1 to 2 and Comparative Example 7.

FIG. 6 is a table showing changes in discharge capacity of the coin type batteries of Specific Examples 3 and 7 of the present invention and Comparative Examples 2 to 2 and Comparative Example 7 at a constant current of 5 mA.

FIG. 7 is a table showing a change in discharge capacity with respect to a solid solution amount of copper at a constant current of 1 mA and 5 mA in a coin-type battery using a positive electrode active material of copper solid solution according to an embodiment of the present invention.

FIG. 8 is a table showing changes in discharge capacity of the coin type batteries according to specific examples 15, 20, and 23 of the present invention and comparative example 2 at a constant current of 1 mA.

FIG. 9 is a table showing changes in discharge capacity of a coin type battery according to specific examples 15, 20, and 23 of the present invention and comparative example 2 at a constant current of 5 mA.

FIG. 10 is a table showing a change in discharge capacity with respect to a solid solution amount of neodymium at a constant current of 1 mA and 5 mA in a coin-type battery using a positive electrode active material of neodymium solid solution according to an embodiment of the present invention.

FIG. 11: Concrete examples 27 and 30 of the present invention and Comparative example 2
4 is a table showing a change in discharge capacity of the coin-type battery according to Example 1 at a constant current of 1 mA.

FIG. 12: Concrete examples 27 and 30 of the present invention and Comparative example 2
5 is a table showing a change in discharge capacity of the coin-type battery according to Example 1 at a constant current of 5 mA.

[Explanation of symbols]

1 coin type battery (non-aqueous primary battery); 2 positive electrode can (positive electrode terminal) 3 negative electrode cup (negative electrode terminal); 4 positive electrode pellet (positive electrode active material) 5 negative electrode active material; 6 separator; 7 sealing gasket 8 substantially spherical particles Shaped β-type nickel oxyhydroxide; 9
Rock-shaped (non-spherical) particle-shaped β-type nickel oxyhydroxide 11, 21 Discharge characteristics 12a, 12b, 12c, 22a, 22b, 22c of Comparative Example 1
Discharge characteristics 13 and 23 of Comparative Example 2 Discharge characteristics of Example 3; 14,24 Discharge characteristics 15 and 25 of Example 7 Discharge characteristics of Comparative Example 7; 33 and 43 Discharge characteristics 34 and 44 of Example 15 Example 20 Discharge characteristics of 35; 45 Discharge characteristics of Example 23 53,63 Discharge characteristics of Example 27; 54,64 Discharge characteristics of Example 30

Claims (6)

[Claims] 1. A positive electrode active material containing nickel oxyhydroxide as a main component and a negative electrode active material made of a light metal are separately provided between a positive electrode terminal and a negative electrode terminal with a separator, and a non-aqueous electrolyte is provided. A non-aqueous primary battery, wherein the positive electrode active material is formed of β-type nickel oxyhydroxide in which a required amount of cobalt, copper, or neodymium is solid-solved. 2. The amount of cobalt solid-dissolved in the positive electrode active material is 0.5 to 16.
0% by weight, the solid solution amount of copper is 0.5% by weight or more of β-type nickel oxyhydroxide, and the solid solution amount of neodymium is 0.2% by weight or more of β-type nickel oxyhydroxide. The non-aqueous primary battery according to claim 1, wherein the non-aqueous primary battery is present. 3. The non-aqueous primary battery according to claim 1, wherein the β-type nickel oxyhydroxide of the positive electrode active material is formed into substantially spherical particles. 4. The light metal of the negative electrode active material is lithium, lithium alloy, magnesium, sodium,
The non-aqueous primary battery according to claim 1, which is potassium, calcium or aluminum. 5. A method for producing an active material used as a positive electrode active material for a battery, comprising the steps of mixing sulfuric acid or nickel nitrate and a metal compound in an aqueous solution, an ammonium ion supplier, and an alkaline aqueous solution. A step of stirring and mixing to prepare a metal solid solution nickel hydroxide, and mixing the metal solid solution nickel hydroxide in a mixed solution of an alkaline aqueous solution and an oxidizing agent to chemically oxidize the solution to form an oxyhydroxide. A method for producing a battery active material, characterized in that nickel is obtained. 6. The method for producing an active material for a battery according to claim 5, wherein the metal compound is any one of cobalt, copper and neodymium.