JP2003197206A - Sealed alkaline zinc primary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To make it excel in large electric discharge characteristics, to suppress the fall of the electric discharge capacity by the self-discharging at the time of storage, and to raise the maintained rate of electric discharging capacity, while taking the inside-out structure which is excellent in productivity. <P>SOLUTION: With respect to a sealed alkaline zinc primary battery, which has a battery outer can, a positive electrode mixture, which contains at least nickel hydroxide system compound particles and carbon system particles accommodated in the above battery outer can, and has been formed in the shape of a hollow pipe, and a negative-electrode material containing the alloy particles, which make zinc as the main ingredient, accommodated and arranged in the above hollow pipe of the mixture of the positive electrode through separator, this sealed alkaline zinc primary battery is characterized in that the above negative-electrode material contains the compound, which consists of at least one kind, which is chosen from a group of Mg, Ca, Y, Yb, Er, Mo, and W. <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 sealed alkaline zinc primary battery, and more particularly to a sealed alkaline zinc primary battery with improved discharge capacity due to storage.

[0002]

2. Description of the Related Art A sealed manganese-alkali zinc primary battery is used as a power source for portable electronic devices such as portable radios and cassette recorders.
Further, in the structure of this type of sealed alkaline primary battery, for example, alkaline zinc primary battery, it is also known that the cost is reduced by making the battery element (electromotive part) an inside-out type structure.

That is, an inside-out type structure is adopted in which the positive electrode has a hollow cylindrical shape, a cylindrical separator with a bottom is inserted and arranged in the hollow, and a negative electrode substance is filled in the cylindrical separator with a bottom. As a result, productivity is improved compared to the case where a spiral structure in which a sheet-shaped positive electrode, a separator and a negative electrode laminate are wound is adopted, resulting in low cost and high capacity alkaline zinc primary battery. Can be provided.

As described above, when the battery element is a primary battery having an inside-out structure, it is advantageous in terms of productivity and cost reduction, but the positive electrode and the negative electrode are opposed to each other as compared with the spiral structure. Since the area is small, there is generally a problem that the high rate discharge characteristics are inferior.

Therefore, as the positive electrode active material of the alkaline zinc primary battery for improving the high rate discharge capacity, nickel hydroxide particles are used to add a cobalt compound or the like or to coat the surface of the positive electrode active material to obtain a high rate discharge capacity. Have been tried to improve. The alkaline zinc primary battery using this nickel-based compound is characterized by high capacity, excellent high rate discharge characteristics, and high energy density per unit weight. However, this nickel-based compound has a problem that it is more reductive than manganese oxide, which is a positive electrode active material for alkaline manganese primary batteries, causes self-discharge during storage, and reduces the discharge capacity.

[0006]

As described above, compared with the manganese-alkali zinc primary battery, the sealed alkaline zinc primary battery using the nickel-based positive electrode active material is superior in high rate discharge characteristics, but it is stable in storage. In terms of sex, it is still insufficient for practical use. The present invention has been made in response to the above circumstances, while adopting an inside-out type structure excellent in productivity, excellent in high rate discharge characteristics, and suppressing a decrease in discharge capacity due to self-discharge during storage, The purpose is to improve the maintenance rate of the discharge capacity.

[0007]

Means for Solving the Problems That is, according to the present invention, a battery outer can and a hollow cylindrical shape containing a nickel hydroxide-based compound particle and a carbon-based particle housed and mounted in the battery outer can are formed. A sealed alkaline zinc primary battery comprising a positive electrode mixture and a negative electrode material containing alloy particles containing zinc as a main component housed in a hollow cylinder of the positive electrode mixture via a separator, wherein the negative electrode is Material is Mg, Ca,
A sealed alkaline zinc primary battery comprising a negative electrode material additive component composed of a compound of at least one element selected from the group of Y, Yb, Er, Mo and W.

In the present invention, Mg, C are used as the negative electrode material.
By adding a compound of at least one element selected from a, Y, Yb, Er, Mo, and W, the amount of the electrolyte solution consumed by the self-discharge of the positive electrode and the amount of the electrolyte solution moving from the negative electrode to the positive electrode By reducing the amount and maintaining the amount of the electrolytic solution contained in the negative electrode, it is possible to prevent the discharge capacity from decreasing due to storage and to improve the discharge capacity retention rate.

Further, in the present invention, as the negative electrode material additive component, MgF ₂ , CaF ₂ , Y ₂ O ₃ and Y are used.
When at least one selected from b ₂ O ₃ , Er ₂ O ₃ , K ₂ MoO ₄ , and K ₂ WO ₄ is used as an additive component, the oxygen overvoltage of the positive electrode increases and the reducibility of nickel oxyhydroxide is weakened, that is, in the electrolytic solution. By lowering the oxygen gas generation reaction, which is the decomposition of water, it is effective in suppressing self-discharge and maintaining the discharge capacity. Further, in the present invention, the amount of the negative electrode material additive component is 0.1 to the negative electrode material.
It is preferably 2.0% by mass. If the amount of the negative electrode material additive component is less than this range, the desired effect of maintaining the discharge capacity retention ratio is not exhibited. Also, the amount of the compound is
If it exceeds this range, the electric resistance of the negative electrode material increases and the battery characteristics deteriorate.

Further, in the present invention, the nickel hydroxide-based compound is a simple substance of zinc and cobalt or nickel oxyhydroxide obtained by eutecticizing them, which is accompanied by a change in crystal structure even at a low electrolytic solution ratio. It is preferable because stable discharge can be performed. further,
In the present invention, the nickel hydroxide-based compound particles are zinc oxyhydroxide coated on the surface with a cobalt high-order oxide or a simple substance of cobalt, or nickel oxyhydroxide obtained by eutecticizing them. Property is improved, and discharge capacity and high rate discharge characteristics are improved, which is preferable. By selecting such a material as the positive electrode active material, it is possible to realize an alkaline zinc primary battery having excellent high rate discharge characteristics as compared with the alkaline manganese zinc primary battery.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION (Battery Structure) Detailed embodiments of a battery of the present invention will be described below in detail with reference to the drawings. FIG. 1 shows a JIS standard LR6 type (AA), which is a so-called inside-out structure (structure in which a battery can body is a positive electrode side and a battery lid side is a negative electrode side) of the present invention.
This is an example of application to a battery of type).

In FIG. 1, reference numeral 1 denotes a battery outer case made of a metal having a bottomed cylindrical shape which also serves as a positive electrode terminal. Inside the battery outer case 1, a positive electrode mixture 2 containing a hollow cylindrical positive electrode active material is provided. It is housed. The hollow inside of the positive electrode mixture 2 is filled with a gelled zinc negative electrode material 4 through a bottomed cylindrical separator 3 made of a non-woven fabric or the like. And
A negative electrode current collector rod 5 made of a metal rod is inserted into the negative electrode material 4, and one end of the negative electrode current collector rod 5 projects from the surface of the negative electrode material 4 to form a ring-shaped metal plate 7 and a metal sealing plate 8 also serving as a cathode terminal. It is electrically connected. An insulating gasket 6 made of a double annular plastic resin is disposed on the inner surface of the battery case 1 that serves as a positive electrode and the outer peripheral surface of the protruding portion of the negative electrode current collector rod 5, and these are insulated. The opening of the battery outer can 1 is crimped and liquid-tightly sealed.

Hereinafter, a positive electrode mixture, a negative electrode material, an electrolytic solution used in the nickel hydroxide alkaline zinc primary battery of the present invention,
The separator and the separator will be described in detail.

(1) Positive Electrode Mixture The positive electrode mixture of the present invention comprises a positive electrode active material composed of nickel hydroxide compound particles, a conductive material composed of a carbon material such as graphite,
It comprises an alkaline electrolyte which is the above-mentioned aqueous solution, and optionally a binder and a lubricant.

(Positive Electrode Active Material) The nickel hydroxide-based compound, which is the positive electrode active material used in the present invention, contains nickel hydroxide partially or partially in order to enable immediate discharge without charging after battery production. It is desirable to oxidize all to nickel oxyhydroxide. In the present invention, the discharge reaction at the positive electrode of the battery using the nickel oxyhydroxide compound as the positive electrode active material is represented by the following chemical formula. NiOOH + H ₂ O + e ⁻ → Ni (OH)
₂ + OH ^- The nickel oxyhydroxide may be β-nickel oxyhydroxide or γ-nickel oxyhydroxide whose nickel atom has a valence of 3, or may be the valence of nickel atom of nickel hydroxide. It may be a compound having an intermediate valence of 3 between the valent nickel atom and the nickel atom which is completely oxyhydroxide.

The surface of the nickel hydroxide compound particles used in the present invention is cobalt oxyhydroxide,
Dicobalt trioxide, cobalt monoxide, cobalt hydroxide,
It is coated with at least one substance selected from metallic nickel and metallic cobalt. By covering the surfaces of the nickel oxyhydroxide compound particles with a substance having high electric conductivity, the electric conductivity of the entire positive electrode is increased, and the discharge capacity and high rate discharge characteristics are improved. Among these substances, it is preferable to use cobalt oxyhydroxide, nickel metal, or metal cobalt because it has higher conductivity. The amount of the coating layer is 2.
The range of 0 to 6.0 mass% is desirable. When the amount of the coating layer exceeds this range, there is a problem of high cost, and when the amount of the coating layer is below this range, there is a problem of reduction of current collecting property, which is not preferable.

Further, the nickel hydroxide-based compound itself which is the positive electrode active material may itself be eutectic with zinc or cobalt alone or both. This positive electrode active material has a characteristic that stable discharge can be performed even with a low electrolytic solution ratio. The amount of zinc or cobalt to be eutecticized with this nickel hydroxide-based compound is 4.0 to 1
The range of 2.0% is preferable. This is because if the amount of zinc is less than this range, the utilization factor will decrease, and if it exceeds this range, the specific gravity will decrease and the capacity density will decrease.

Among the nickel hydroxide compounds as the positive electrode active material of the present invention, nickel oxyhydroxide which is particularly preferable for the present invention can be produced, for example, by the following method. That is, cobalt hydroxide is added to nickel hydroxide particles doped with zinc and cobalt, and an aqueous sodium hydroxide solution is sprayed while stirring in an air atmosphere. Subsequent microwave heating produces composite nickel hydroxide particles in which a layer of cobalt higher oxide is formed on the surface of nickel hydroxide. Then, an oxidizing agent such as sodium hypochlorite is added to this reaction system to proceed with the oxidation to produce a composite nickel oxyhydroxide coated with a cobalt higher oxide. As a result, a positive electrode active material having extremely excellent conductivity can be obtained.

(Carbon-based particles) In the present invention,
It is preferable to add carbon-based particles to the positive electrode mixture to improve conductivity. Examples of the carbon-based particles used in the present invention include acetylene black, carbon black, artificial graphite, and natural graphite.
40 μm graphite is preferred. The reason is that the average particle size is
If it is less than this range, the ability of graphite to bind the positive electrode mixture component originally possessed decreases, and the strength of the formed positive electrode mixture decreases, which not only causes a problem in workability of battery production. This is because the conductivity of the positive electrode mixture is lowered. On the other hand, if the average particle size of graphite exceeds the above range, the size becomes larger than that of the particles of the active material, and the conductivity decreases. In the present invention, it is desirable that the content of the graphite particles in the positive electrode mixture be 10% by mass or less. If the content of the graphite particles in the positive electrode mixture is made too large, the amount of the positive electrode active material that can be filled in the limited volume of the metal can itself decreases, and the carbonate ions generated by the oxidation of the graphite particles. Accelerates self-discharge,
This is because the discharge capacity decreases. For that purpose, the content of carbon particles in the positive electrode mixture is preferably 10% by mass or less, and more preferably 7% by mass or less.

(Other Additive Components) The binder is added in order to bind the constituent components of the positive electrode mixture and to improve the shape retention of the positive electrode mixture molded article. For example, polytetrafluoroethylene (PTFE), Polyvinylidene fluoride (PVdF),
Modified PVdF obtained by substituting at least one of hydrogen or fluorine of PVdF with another substituent, a copolymer of vinylidene fluoride-6-fluorinated propylene and terpolymer of polyvinylidene fluoride-tetrafluoroethylene-6-fluorinated propylene. A copolymer or the like can be used. It is appropriate to use these binder components in the range of 0.05 to 0.5 mass% with respect to the positive electrode mixture. In addition, a lubricant for improving workability at the time of molding the positive electrode mixture can be added to the positive electrode mixture. As the lubricant, stearic acid compounds such as zinc stearate, calcium stearate, and ethylene bisstearamide are preferable. The amount of this addition is appropriately in the range of 0.05 to 0.5 mass% with respect to the positive electrode mixture.

(Molding of Positive Electrode Molded Body) The positive electrode mixture is mixed and molded into a hollow cylindrical shape whose outer diameter is approximately equal to the inner diameter of the battery outer can made of metal by a press to produce a positive electrode molded body. . In the molded positive electrode mixture, the positive electrode active material particles and the conductive material particles are bound to each other, and the grain boundary between the particles is filled with the electrolytic solution. The nickel hydroxide compound particles of the present invention are molded into a positive electrode by the following steps. 1) Mixing of Positive Electrode Mixture Component The positive electrode mixture is obtained by mixing the positive electrode active material with the above-mentioned positive electrode mixture additive such as a conductive material, a binder, a lubricant and an electrolytic solution. The electrolytic solution is used for increasing the ionic conductivity in the positive electrode mixture and for improving the moldability. This electrolyte is preferably the same as the electrolyte used to maintain the ionic conductivity between the positive electrode and the negative electrode of the battery. The preferred electrolyte is a 40% KOH aqueous solution. The compounding ratio of these positive electrode mixture components is 90 to 90 in terms of mass ratio of positive electrode active material: conductive agent: binder: lubricant: electrolytic solution.
92: 4-6: 0.05-0.5: 0.05-0.3
A compounding ratio of 0: 4 to 6 is preferable. These components are mixed with a stirring device such as a rotary mixer or a Henschel mixer.

2) Compression granulation and classification step The positive electrode mixture compounded in the above step is then compressed and pressed by a roller compactor to increase the packing density for granulation.

The roller compaction-treated positive electrode mixture is in the form of a compressed mass. In order to produce a molded product using this, it is necessary to once granulate. For that purpose, a granulation process is performed by a granulator using twin rolls having protrusions fitted to each other on the roll surface.

The positive electrode material mixture particles obtained in the above step are classified according to their size. In the present invention, 200-
By using particles in the range of 800 μm, a positive electrode mixture molded body having a high packing density can be obtained. 200 μm
Granulated powders of less than 1 are not suitable because it takes time to measure the granulated powders at the time of mold molding. Further, the granulated powder having a particle size of more than 800 μm is not suitable because the weight of the molded body varies during the molding with a die.

3) Molding The positive electrode mixture particles granulated in the above step are then molded into a positive electrode molded body using a mold. The inside-out type positive electrode mixture has a hollow cylindrical shape, has a central mandrel, and fills the positive electrode mixture particles in a cylindrical mold having a required volume and press-fits the male mold. By doing so, molding is performed. The molding pressure at this time is 0.5 × 10 ⁸ to
A pressure of 9.8 × 10 ⁸ Pa is preferred. If the molding pressure is lower than the above range, the required packing density of the positive electrode mixture cannot be obtained, and it is difficult to secure contact between particles,
When used as a battery, a predetermined discharge capacity cannot be obtained. on the other hand,
If the molding pressure exceeds the above range, the electrolytic solution is less likely to penetrate into the positive electrode mixture, and the utilization rate thereof is reduced.

(2) Negative Electrode Material The negative electrode material used in the present invention is a negative electrode material containing a zinc alloy, which is a negative electrode active material, as a main component, and is a zinc gel used in a known manganese dioxide-zinc primary battery. Can be used. As described above, the negative electrode material of the present invention contains M
It is characterized in that it contains a compound of at least one element selected from the group consisting of g, Ca, Y, Yb, Er, Mo and W. Examples of this compound include MgF ₂ , CaF ₂ , and Y ₂ O.
₃ , Yb ₂ O ₃ , Er ₂ O ₃ , K ₂ MoO ₄ , and K
It is desirable that at least one selected from the group of ₂ WO ₄ is used. These compounds are blended into the negative electrode material in the form of particles. The average particle size is preferably in the range of 0.1 to 10 μm. These compounds dissolve in the electrolytic solution in the negative electrode material, deposit on the surface of the zinc alloy particles as the negative electrode active material, and achieve the function of holding the electrolytic solution. Therefore, a small particle size having a high dissolution rate in the electrolytic solution is preferable, but an average particle size smaller than the above range is difficult to handle and is not practical. From the viewpoint of handling, it is desirable that this negative electrode material be in the form of gel. In order to make the negative electrode gel-like, it is possible to easily make the gel-like substance by dispersing the zinc alloy of the negative electrode active material in the gel-like electrolytic solution prepared from the electrolytic solution and the thickener.

The zinc alloy used in the present invention may be a zinc alloy containing neither mercury nor lead, which is known as a smoothed zinc alloy. Specifically, a zinc alloy containing 0.06% by mass of indium, 0.014% by mass of bismuth, and 0.0035% by mass of aluminum is preferable because it has an effect of suppressing hydrogen gas generation. Indium and bismuth are particularly preferable because they improve discharge performance. The reason for using zinc alloy instead of pure zinc as the negative electrode acting substance is to slow down the self-dissolution rate in alkaline electrolyte and suppress hydrogen gas generation inside the battery when it is used as a sealed battery product to prevent leakage. This is to prevent accidents caused by liquids.

Further, it is desirable that the shape of the zinc alloy is powdery so that the zinc alloy can have a large surface area and can handle a large current discharge. In the present invention, the preferable average particle size of the zinc alloy is in the range of 100 to 350 μm. If the average particle size of the zinc alloy exceeds the above range, the surface area becomes relatively small and it becomes difficult to cope with large current discharge. Further, if the average particle size is less than the above range, it is difficult to handle at the time of battery assembly, it becomes difficult to uniformly mix with the electrolytic solution and the gelling agent, and the surface is active, so that it is oxidized. Easy and unstable.

As the thickener used in the present invention, polyvinyl alcohol, polyacrylate, C
MC, alginic acid, etc. can be used. In particular, sodium polyacrylate is preferable because it has an excellent water absorption capacity for a strong alkaline aqueous solution.

(3) Electrolyte Solution The electrolyte solution used in the present invention is preferably an aqueous solution using an alkali salt such as potassium hydroxide, sodium hydroxide or lithium hydroxide as a solute, and particularly potassium hydroxide is used. ,preferable. Further, in the present invention, the alkaline salt such as potassium hydroxide is dissolved in water to prepare an electrolytic solution, and it is desirable to further add a zinc compound to the electrolytic solution. As such a zinc compound, zinc oxide,
Examples thereof include compounds such as zinc hydroxide, but zinc oxide is particularly preferable.

The use of an alkaline aqueous solution containing at least a zinc compound as the electrolytic solution means that the self-dissolution of the zinc alloy in the alkaline aqueous solution is much less than that of the acidic electrolytic solution, and furthermore, the alkaline electrolysis of the zinc alloy is performed. This is because self-dissolution in the liquid is further suppressed by dissolving a zinc compound, for example, zinc oxide and allowing zinc ions to be present in advance.

(4) Separator The separator used in the present invention comprises cellulose fibers and
It is made of non-woven fabric of fibers such as polyvinyl alcohol fiber, woven fabric, and papermaking. In these fibers, cellulose fibers are used to enhance liquid retention because of their good affinity with alkaline electrolytes, while,
Polyvinyl alcohol fiber has excellent alkali resistance, and by using these together, a separator having a good balance of these properties can be obtained. In the present invention, the cellulose fiber and the polyvinyl alcohol fiber may be mixed with each other for paper making, or may be separately made and then laminated. To make a separator using this separator paper,
The separator paper is wound and the bottom is adhered to form a bottomed cylinder. At this time, the side of the wound separator paper may be adhered. For this adhesion, heat may be applied after molding the separator paper, or an adhesive may be used.
If an adhesive is used, it must be chemically resistant.

[0033]

EXAMPLES [Example 1] (Production of positive electrode) Composite nickel hydroxide particles 9 having a high-order cobalt layer formed on the surface obtained by the production method of the positive electrode active material described above.
0 parts by mass of graphite powder having a specific surface area of 3.4 m ² / g.
4 parts by mass, and polyethylene resin as a binder.
Add 1 part by weight and stir mix for 10 minutes. Then 40
4.6 parts by mass of a mass% potassium hydroxide aqueous solution is added and mixed for 30 minutes in a general-purpose mixing container to obtain a mixture. Then
This mixture is pressure-molded into a hollow cylindrical shape having an outer diameter of 13.3 mm, an inner diameter of 9.0 mm, and a height (length) of 13.7 mm to prepare a positive electrode material mixture pellet.

(Production of Negative Electrode) 0.01 parts by weight of indium, 0.01 parts by weight of bismuth and 0.00 of aluminum
To 64.58 parts by mass of zinc alloy powder having an average particle size of 100 to 300 μm including 3 parts by mass, MgF ₂ particles having an average particle size of 3 μm were added at a ratio of 0.5% by mass with respect to the negative electrode material,
Further, 0.381 parts by mass of polyacrylic acid (gelling agent) was added, and the mixture was stirred and mixed for 5 minutes in a general-purpose mixing container to obtain a uniform mixed system. On the other hand, 35% by mass of zinc oxide was dissolved in 35
Add 0.0006 parts by mass of tetrabutylammonium hydroxide to 35 parts by mass of an aqueous solution of potassium hydroxide having a mass% of 1
Stir and mix for 0 minutes to thoroughly disperse. Then, the zinc alloy powder-based mixture was gradually added to this dispersion system over 4 minutes, and at the same time, 200 × 10 ⁵ Pa (150 m
Stir and mix under reduced pressure below mHg), then
The gelled negative electrode having a substantially uniform composition system was produced by stirring and mixing for 5 minutes under a reduced pressure of 3.3 × 10 ⁵ Pa (10 mmHg) or less.

(Assembly of Battery) Next, using the prepared positive electrode material mixture pellets and gelled negative electrode, according to a conventional method, a single 3-type alkali whose sectional structure is schematically shown in FIG. 1 is used. Assemble the zinc primary battery. In FIG. 1, 1
Is a bottomed cylindrical metal can (exterior can) that also serves as a positive electrode terminal, and 3 positive electrode mixture pellets are placed in the hollow of the metal can 1.
The positive electrode mixture (9.
0g) 2 is filled and installed. Further, in the hollow portion of the positive electrode mixture 2, a bottomed cylindrical separator 3 made of a nonwoven fabric of acetalized polyvinyl alcohol fiber is attached,
The inside of the separator 3 is filled with the gelled negative electrode 4.

In the gelled negative electrode 4, one end side of a brass negative electrode current collector rod 5 is inserted and arranged, and the outer peripheral surface of the other end side of the negative electrode current collector rod 5 protruding from the gelled negative electrode 4 is inserted. , And a double annular insulating gasket 6 made of polyamide resin is arranged between the inner peripheral surface of the opening of the metal can 1. Further, a ring-shaped metal plate 7 is fitted and arranged between the double rings of the insulating gasket 6, and a hat-shaped metal sealing plate 8 also serving as a negative electrode terminal abuts on the tip of the negative electrode current collector rod 5. It is arranged. The opening edge of the metal can 1 is bent inward to seal the opening edge of the metal can 1 with the insulating gasket 6 and the metal sealing plate 8.

(Evaluation) The obtained battery was stored at room temperature and the discharge capacity after a predetermined period was measured. The results are shown in Table 1 and FIG.

[Examples 2 to 7] CaF ₂ , Y ₂ O ₃ , Yb ₂ O ₃ and Er ₂ O were used as compounds added to the negative electrode material.
_A battery was manufactured in the same manner as in Example 1 except that ₃ , K ₂ MoO ₄ , and K ₂ WO ₄ were used, and the capacity retention rate after storage at room temperature was measured in the same manner as in Example 1. The results are also shown in Table 1 and FIG.

[Comparative Example 1] In Example 1, MgF ₂
Example 1 except that no particles were added to the negative electrode material.
A battery was manufactured in the same manner as in Example 1, and the capacity retention rate was determined in Example 1.
It measured similarly to. The results are also shown in Table 1 and FIG.

[0040]

[Table 1]

As is clear from the above results, the battery of Comparative Example 1 in which the compound to be added to the negative electrode material of the present invention was not added, the capacity dropped to 77.7% after 720 days of storage. On the other hand, in the examples in which the compound of the present invention was added, all the batteries maintained the capacity exceeding 80%.

[Examples 8 to 14] As the components to be added to the negative electrode material, the compounds shown in Table 2 were used, and the compounding amounts thereof are also shown in Table 2.
A battery was manufactured and the discharge capacity was measured in the same manner as in Example 1 except that the adjustment was performed as shown in FIG. The results are shown in Table 2 and FIG. As is clear from this result, an improvement in discharge capacity was observed when the compound addition amount was in the range of 0.1 to 2 mass%.

[0043]

[Table 2]

[0044]

According to the present invention described above, in an alkaline zinc primary battery using a nickel-based compound as a positive electrode active material, by adding a compound such as MgF _{2 to} the negative electrode material, the self-contained It was possible to suppress discharge and effectively prevent the discharge capacity from decreasing after storage.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a battery to which the present invention can be applied.

FIG. 2 is a graph showing the effect of the present invention.

FIG. 3 is a graph showing the effect of the present invention.

[Explanation of symbols]

1-Battery exterior can 2 ... Positive electrode mixture 3 ... Separator 4 ... Negative electrode material 5: Negative electrode collector rod 6 ... Insulation gasket 7 ... Ring-shaped metal plate 8: Metal sealing plate

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Miyamoto             3-4-10 Minami-Shinagawa, Shinagawa-ku, Tokyo Toshiba             Battery Co., Ltd. (72) Inventor Kazuhiko Kudo             3-4-10 Minami-Shinagawa, Shinagawa-ku, Tokyo Toshiba             Battery Co., Ltd. F term (reference) 5H024 AA01 AA14 BB07 BB08 BB11                       CC02 CC14 CC19 DD17 EE06                       EE07 FF07 HH01                 5H050 AA02 AA09 BA04 CA03 CB13                       DA03 DA09 DA10 EA12 EA15                       FA07 FA17 FA18 GA10 GA11                       GA17 GA22 HA01 HA02 HA12

Claims (5)

[Claims] 1. A battery outer can, and a positive electrode mixture molded into a hollow cylinder containing at least nickel hydroxide compound particles and carbon particles housed and mounted in the battery outer can.
In a sealed alkaline zinc primary battery having a negative electrode material containing alloy particles containing zinc as a main component, which is housed and arranged via a separator in a hollow cylinder of the positive electrode mixture, wherein the negative electrode material is Mg, Ca, Y. , Yb, Er, Mo, W
A sealed alkaline zinc primary battery comprising a negative electrode material additive component composed of a compound of at least one element selected from the group: 2. The negative electrode material additive component is MgF._Two, Ca
F_Two, Y_TwoO_Three, Yb_TwoO_Three, Er _TwoO_Three, K_TwoMoO
_Four, And K_TwoWO_FourAt least one selected from the group
The sealed alkali according to claim 1, wherein
Zinc primary battery. 3. The sealed alkaline zinc primary battery according to claim 1, wherein the amount of the component added to the negative electrode material is 0.1 to 2 mass% with respect to the negative electrode material. 4. The sealed alkaline zinc primary battery according to claim 1, wherein the nickel hydroxide-based compound is a simple substance of zinc and cobalt or nickel oxyhydroxide obtained by eutecticizing them. 5. The nickel oxyhydroxide-based compound is particles of zinc oxyhydroxide whose surface is coated with a cobalt high-order oxide, simple substance of zinc and cobalt, or eutectic thereof. The sealed alkaline zinc primary battery according to claim 1 or claim 4.