JP2008034294A - Alkaline primary battery - Google Patents

Abstract

The present invention provides an alkaline primary battery excellent in heavy load discharge characteristics by suppressing an increase in internal resistance of the battery accompanying discharge.
A positive electrode of an alkaline primary battery includes nickel oxyhydroxide and λ-type manganese dioxide, and a part of Mn in the λ-type manganese dioxide is made of Ni, Co, Ti, Fe, Mg, Zn, and Sn. Substitution with at least one different element selected from the group.
[Selection figure] None

Description

  The present invention relates to an alkaline primary battery using at least nickel oxyhydroxide as a positive electrode active material.

Conventionally, manganese dioxide has been used as a positive electrode active material for alkaline primary batteries. Various studies have been actively conducted on manganese dioxide. Depending on the crystal structure of manganese dioxide, α-type, β-type, γ-type, δ-type, ε-type, η-type, λ-type, ramsdellite-type, etc. are categorized. Moreover, electrolytic manganese dioxide is often used as the positive electrode active material because it can be easily mass-produced and is inexpensive.
Conventionally, an alkaline primary battery including manganese dioxide as a positive electrode active material, zinc as a negative electrode active material, and an alkaline aqueous solution as an electrolytic solution has been widely spread and used. Since the alkaline primary battery has excellent heavy load discharge performance, it is widely used as a power source for portable devices such as digital cameras, information communication terminals, MD players, and liquid crystal televisions. In recent years, with higher performance of portable devices, higher performance and higher capacity are required for alkaline primary batteries that are power sources.

  In response to such a demand, improvement in utilization of the positive electrode active material and the negative electrode active material, improvement in filling properties of the positive electrode active material and the negative electrode active material, and the like have been studied. Specifically, for example, optimization of manganese oxide electrolysis conditions (Patent Document 2) for the purpose of improving the content of manganese dioxide in the positive electrode mixture (Patent Document 1) and improving the high-rate pulse characteristics has been studied. ing. Furthermore, for example, regarding non-aqueous secondary batteries, heat treatment of chemical manganese dioxide at 350 to 430 ° C. (Patent Document 3), heat treatment of chemical manganese dioxide doped with lithium (Patent Document 4), α doped with lithium ions The use of type or δ type manganese dioxide (Patent Document 5), spinel type, λ type, or the use of manganese dioxide having an intermediate crystal structure (Patent Document 6) has been studied.

  Regarding λ-type manganese dioxide, in addition to the above, improvement of cycle characteristics focusing on the high voltage characteristics and crystal structure of λ-type manganese dioxide in non-aqueous secondary batteries has been studied (Patent Document 7). Furthermore, regarding the alkaline button type battery of the aqueous solution type primary battery, the increase in capacity by using λ-type manganese dioxide and γ-type manganese dioxide as the positive electrode active material has been studied (Patent Document 8).

In addition, since nickel oxyhydroxide has a higher potential than manganese dioxide, it has long been known to use nickel oxyhydroxide as a positive electrode active material for the purpose of increasing battery output and improving heavy load discharge characteristics. (Patent Document 9). Also in recent years, for example, formation of a conductive film on the inner surface of the positive electrode case (Patent Document 10), formation of a conductive material on the nickel oxyhydroxide surface by a mechanochemical method (Patent Document 11), and fullerene in the positive electrode mixture Addition (Patent Document 12) and the like have been studied. Furthermore, a case where nickel oxyhydroxide is used alone as the positive electrode active material (Patent Document 13), or a case where nickel oxyhydroxide and manganese dioxide are mixed and used (Patent Document 14) has been studied.
Japanese Patent No. 34066782 JP 2004-137129 A JP-A-62-108456 JP 62-108457 A JP 63-148550 A Japanese Unexamined Patent Publication No. 63-187469 Japanese Patent No. 2807482 US Patent No. 2004-0058242 JP-A-57-72266 Japanese Patent No. 3552194 JP 2003-272617 A JP 2004-139807 A JP 2003-272617 A Japanese Patent No. 3552194

  However, since nickel oxyhydroxide changes to nickel hydroxide having low electron conductivity at the time of discharge, the internal resistance of the battery increases with the progress of discharge, and the battery voltage tends to drop rapidly at the end of discharge. In particular, recently, digital cameras that are remarkably widespread tend to be miniaturized and highly functional, and in order to increase the number of shots, batteries are required to have further improved heavy load discharge characteristics and higher capacities. Therefore, it is difficult to satisfy the above-mentioned requirements only by using nickel oxyhydroxide for the positive electrode.

  Accordingly, an object of the present invention is to provide an alkaline primary battery that suppresses an increase in internal resistance of the battery during discharge and is excellent in heavy load discharge characteristics in order to solve the above-described conventional problems.

  In order to achieve the above object, the alkaline primary battery of the present invention comprises a positive electrode, a negative electrode, an alkaline electrolyte, and a separator disposed between the positive electrode and the negative electrode. Characterized in that it contains nickel oxide and λ-type manganese dioxide in which a part of Mn is substituted with at least one different element selected from the group consisting of Ni, Co, Ti, Fe, Mg, Zn, and Sn. To do.

  According to the present invention, λ-type manganese dioxide in which a part of Mn is substituted with at least one different element selected from the group consisting of Ni, Co, Ti, Fe, Mg, Zn, and Sn By adding to the positive electrode containing nickel, the increase in the internal resistance of the battery during discharge can be significantly suppressed, and the voltage drop at the end of discharge can be greatly suppressed. can get.

An alkaline primary battery according to the present invention includes a positive electrode, a negative electrode, an alkaline electrolyte, and a separator disposed between the positive electrode and the negative electrode. The positive electrode includes nickel oxyhydroxide and λ-type manganese dioxide. In addition, a feature is that a part of Mn in the λ-type manganese dioxide is substituted with at least one different element selected from the group consisting of Ni, Co, Ti, Fe, Mg, Zn, and Sn.
Even when nickel oxyhydroxide is used as the positive electrode active material, by adding the above-mentioned λ-type manganese dioxide to the positive electrode, the increase in the internal resistance of the battery with the progress of discharge is greatly suppressed, and the battery voltage at the end of discharge is reduced. Rapid drop can be greatly suppressed, and excellent heavy load discharge characteristics can be obtained.

The mechanism by which the increase in the internal resistance of the battery is suppressed when the λ-type manganese dioxide is added to the positive electrode using nickel oxyhydroxide is not clear, but is presumed as follows. By removing lithium by the sulfuric acid treatment, the lattice spacing of the λ-type manganese dioxide contracts. During discharge, protons enter the contracted λ-type manganese dioxide and the interstitial spaces expand. This expansion provides good contact between the nickel oxyhydroxide and the γ-type manganese dioxide and graphite. For this reason, it is thought that increase of the internal resistance of the battery accompanying discharge is suppressed.
The λ-type manganese dioxide also acts as a positive electrode active material that contributes to the charge / discharge reaction of the battery.

The content of λ-type manganese dioxide in the positive electrode is 100 weights in total of nickel oxyhydroxide and λ-type manganese dioxide in that the effect of suppressing an increase in the internal resistance of the battery is sufficient and good heavy load discharge characteristics are obtained. 0.5 to 25 parts by weight per part is preferred. When the content of λ-type manganese dioxide in the positive electrode is less than 0.5 parts by weight per 100 parts by weight of the total of nickel oxyhydroxide and λ-type manganese dioxide, the effect of suppressing the increase in the internal resistance of the battery during discharge is obtained. Get smaller. When the content of λ-type manganese dioxide in the positive electrode exceeds 25 parts by weight per 100 parts by weight of the total of nickel oxyhydroxide and λ-type manganese dioxide, the content of nickel oxyhydroxide having a high capacity is relatively reduced. The effect of increasing battery capacity is reduced.
Furthermore, since the heavy load discharge characteristics are greatly improved, the content of λ-type manganese dioxide in the positive electrode is more preferably 1 to 10 parts by weight.

The λ-type manganese dioxide has, for example, a general formula: Li _x [M _y Mn _2-y ] O ₄ (0 <x ≦ 0.5 and 0.02 ≦ y ≦ 0.5, where M is Ni, And at least one element selected from the group consisting of Co, Ti, Fe, Mg, Zn, and Sn. Among the elements M, Ni is more preferable.
When x = 0 and 0.5 <x, the above-described expansion between the lattices of the λ-type manganese dioxide at the time of discharge is not sufficient, and thus the effect of suppressing an increase in the internal resistance of the battery is small.
When y <0.02, the above-described expansion between the lattices of the λ-type manganese dioxide at the time of discharge is not sufficient, and thus the effect of suppressing an increase in the internal resistance of the battery is reduced. On the other hand, when 0.5 <y, the capacity of λ-type manganese dioxide decreases.

The λ type manganese dioxide to be used in alkaline primary battery of the present invention, for example, represented by as described above _{Li x [M y Mn 2-} y] O 4 (0 <x ≦ 0.5), the lithium primary The part has a spinel structure with a defect which is undope. The spinel structure is known as one of typical crystal structure types found in AB ₂ O ₄ type compounds (A and B are metal elements) such as LiMn ₂ O ₄ which is a double oxide.

In the above-mentioned λ-type manganese dioxide (spinel structure having defects), all the Mn cations are tetravalent, and in the case of spinel structure Li _x [M _y Mn _2-y ] O ₄ having no defects, trivalent and 4 It is thought that valent Mn cations are mixed. In spinel _{Li x [M y Mn 2-} y] O 4, Li is located in the tetrahedral center, since Mn is located in octahedral sites sharing edges to each other, a part of the lithium is dedoped However, the spinel structure is maintained. For this reason, Li _x [M _y Mn _{2− y} ] O ₄ exhibits an X-ray diffraction pattern that is almost the same as that in the case of having no defects even when some of the lithium has a dedoped defect. When there is a defect, lithium is removed by dedoping and the interstitial space shrinks, so that the position of the X-ray diffraction peak is shifted to a lower angle side than when there is no defect.

The above-mentioned λ-type manganese dioxide can be obtained by using lithium manganese spinel in which a part of Mn such as Ni, Co, Ti, Fe, Mg, Zn and Sn is substituted with a different element as an oxidizing agent such as acid or sodium perchlorate. It is obtained by processing with. Lithium manganese spinel in which a part of Mn is substituted with a different element includes, for example, a Li salt such as Li ₂ CO ₃ that is a Li source, MnO ₂ and MnCo ₃ that are Mn sources, and Ni (OH) ₂ . It can be obtained by mixing hydroxides and oxides containing different kinds of different elements and firing the mixture in air. In addition to this, a compound having a high purity can be obtained by using, as a Mn source, a substance in which a part of Mn in Mn (OH) ₂ obtained by the coprecipitation method is substituted with a different element.
The λ-type manganese dioxide is, for example, electrolytic manganese dioxide.

In order to further improve the discharge characteristics, the positive electrode preferably further contains γ-type manganese dioxide as a positive electrode active material.
The λ-type manganese dioxide content in the positive electrode is preferably 0.5 to 25 parts by weight per 100 parts by weight in total of nickel oxyhydroxide, λ-type manganese dioxide, and γ-type manganese dioxide. Furthermore, since the heavy load discharge characteristics are greatly improved, the content of λ-type manganese dioxide in the positive electrode is 1 to 10 parts by weight per 100 parts by weight in total of nickel oxyhydroxide, λ-type manganese dioxide, and γ-type manganese dioxide. It is more preferable that

  In addition, the content of nickel oxyhydroxide, λ-type manganese dioxide, and γ-type manganese dioxide in the positive electrode is based on a total of 100 parts by weight of nickel oxyhydroxide, λ-type manganese dioxide, and γ-type manganese dioxide. It is preferable that 30 to 60 parts by weight of nickel oxyhydroxide, 1 to 10 parts by weight of λ-type manganese dioxide, and 30 to 70 parts by weight of γ-type manganese dioxide.

  For the positive electrode, for example, a positive electrode mixture made of a mixture of the positive electrode active material powder, a graphite powder as a conductive agent, and an alkaline electrolyte is used. For the conductive agent, for example, a carbon material such as graphite is used. The average particle diameter of the nickel oxyhydroxide powder is, for example, 5 to 35 μm. The average particle diameter of the λ-type manganese dioxide powder is, for example, 10 to 40 μm. Moreover, the average particle diameter of graphite powder is 5-30 micrometers, for example.

  The content of graphite in the positive electrode mixture is preferably 3 to 8 parts by weight per 100 parts by weight of the positive electrode active material. When the content of graphite in the positive electrode mixture is less than 3 parts by weight per 100 parts by weight of the positive electrode active material, the electron conductivity of the positive electrode mixture is reduced, the discharge time is shortened, and the strength of the positive electrode mixture is reduced. . When the content of graphite in the positive electrode mixture exceeds 8 parts by weight per 100 parts by weight of the positive electrode active material, the amount of the active material is relatively reduced, so that the discharge time is shortened.

For the negative electrode, for example, a gelled negative electrode made of a mixture of zinc powder or zinc alloy powder as a negative electrode active material, sodium polyacrylate as a gelling agent, and an alkaline electrolyte is used. Examples of the zinc alloy include those containing In, Bi, and Al.
As the alkaline electrolyte, an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution is used. The average particle diameter of the zinc alloy or zinc alloy powder is, for example, 75 to 250 μm.
For the separator, for example, a nonwoven fabric mainly composed of polyvinyl alcohol fiber and rayon fiber is used.

Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.
Example 1
(1) Preparation of λ-type manganese dioxide Li _x [M _y Mn _2-y ] O ₄ Electrolytic manganese dioxide (made by DELTA, TA), Li ₂ Co ₃ (made by Kanto Chemical Co., Inc.), and different element M As a hydroxide, Ni (OH) ₂ was mixed at a molar ratio of Ni: Mn: Li = 7: 93: 55. The mixture was heated from room temperature to 850 ° C. in 10 hours and then heated at 850 ° C. for 20 hours. Thereafter, the temperature was lowered to room temperature in 10 hours and cooled.

100 g of this product was suspended in about 200 ml of pure water, and 500 ml of 2N aqueous sulfuric acid solution was added with slow stirring. The solution was filtered to separate the solid components and washed with pure water until the washing solution became neutral. This residual solid component was dried at 100 ° C. for 12 hours. As a result, Li _x [M _y Mn _2-y ] O ₄ (x = 0.1, y = 0.14, M = Ni) was obtained as λ-type manganese dioxide.

(2) Preparation of positive electrode mixture As positive electrode active materials, λ-type manganese dioxide powder (average particle size: 20 μm), γ-type manganese dioxide powder (average particle size 35 μm) obtained above, and nickel oxyhydroxide powder ( An average particle diameter of 10 μm) and artificial graphite powder (SP-20 manufactured by Nippon Graphite Industry Co., Ltd.) (average particle diameter of 15 μm) as a conductive material were mixed at a weight ratio shown in Table 1.
Furthermore, 1 part by weight of an electrolytic solution was added to 100 parts by weight of the positive electrode active material. As the electrolytic solution, a 40 wt% potassium hydroxide aqueous solution containing zinc oxide was used. Then, it stirred and mixed with the mixer and granulated by the fixed particle size. The obtained granular material was pressure-formed into a hollow cylindrical shape to produce a positive electrode mixture.

(3) Assembly of Alkaline Primary Battery Using the positive electrode mixture obtained above, an AA alkaline primary battery (LR6) having the structure shown in FIG. 1 was produced by the following procedure.
A graphite coating film was applied to the inner surface of a bottomed cylindrical positive electrode case 1 made of a nickel-plated steel plate that also serves as a positive electrode terminal. Thereafter, a plurality of the positive electrode mixtures 3 obtained as described above were inserted into the positive electrode case 1 and repressurized in the positive electrode case 1, thereby bringing the positive electrode mixture 3 into close contact with the inner surface of the positive electrode case 1. In the hollow part of the positive electrode mixture 3, a separator 4 and an insulating cap 5 are arranged. For the separator 4, a non-woven fabric mainly composed of polyvinyl alcohol fiber and rayon fiber was used. Next, an electrolytic solution was injected for the purpose of wetting the separator 4 and the positive electrode mixture 3. A 40 wt% aqueous potassium hydroxide solution was used as the electrolytic solution.

  Thereafter, the gelled negative electrode 6 was filled inside the separator 4. In the gelled negative electrode 6, sodium polyacrylate as a gelling agent, a 40 wt% aqueous potassium hydroxide alkaline electrolyte as an alkaline electrolyte, and a negative electrode active material in a weight ratio of 1.5: 55.0 : A mixture of 100.0 was used. As the negative electrode active material, a zinc alloy powder containing 0.05% by weight of In, 0.025% by weight of Bi, and 0.003% by weight of Al and containing no Hg, Pb, or Cd was used.

  Next, the negative electrode current collector 10 made of brass integrated with the resin sealing body 7, the bottom plate 8 serving also as the negative electrode terminal, and the insulating washer 9 was inserted into the gelled negative electrode. Then, the opening end portion of the positive electrode case 1 was caulked to the peripheral edge portion of the bottom plate 8 via the end portion of the resin sealing body 7 to seal the opening portion of the positive electrode case 1. Next, the outer surface of the positive electrode case 1 was covered with an exterior label 11.

[Evaluation]
About each battery produced above, the pulse discharge test shown below was done in a 20 degreeC environment. After discharging at a constant power of 1500 mW for 2 seconds, it was discharged at a constant power of 650 mW for 28 seconds. This was repeated as 10 cycles continuously, and then rested for 55 minutes. This was repeated until the discharge voltage reached 1.05 V, and the discharge duration at this time was measured. This discharge test is suitable as a battery evaluation method assuming that the battery is used in a digital camera, and standardization to the ANSI standard is being studied. The discharge test results are shown in Table 1. The discharge duration in Table 1 was expressed as the number of cycles until the discharge voltage reached 1.05V.
Further, the voltage drop width at each cycle number when pulse discharge was performed under the same conditions as described above was measured. The voltage drop width (V) is a difference between a discharge voltage at a constant power of 1500 mW at the time of discharge for 2 seconds and a discharge voltage at a time of discharge at 28 seconds with a constant power of 650 mW in each cycle. The results are shown in Table 2.

  From Table 1, when comparing batteries 1 to 3 each using λ-type manganese dioxide, γ-type manganese dioxide, and nickel oxyhydroxide alone, the discharge capacity of the battery 2 using γ-type manganese dioxide is The discharge capacity of the battery 1 using nickel is about 65%, and the discharge capacity of the battery using different element-substituted λ-type manganese dioxide is about 26% of the discharge capacity of the battery using nickel oxyhydroxide. It was found that the discharge capacities of the batteries 2 and 3 were lower than those of 1.

  Batteries 4 and 5 in which 5 parts by weight of λ-type manganese dioxide were added to 95 parts by weight of nickel oxyhydroxide or γ-type manganese dioxide showed a larger discharge capacity than batteries 1 and 2 to which λ-type manganese dioxide was not added. It was. Further, from Table 2, it was found that the voltage drop width during discharge was smaller in the batteries 4 and 5 than in the batteries 1 and 2. In particular, the battery 4 of the example of the present invention showed excellent heavy load discharge characteristics.

Example 2
λ-type manganese dioxide powder, γ-type manganese dioxide powder, nickel oxyhydroxide powder, and artificial graphite powder (SP-20 manufactured by Nippon Graphite Industry Co., Ltd.) were mixed at a weight ratio shown in Table 3. Except for this, a battery was produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3 together with the results of batteries 1 to 4.

Compared to the battery 13 in which the γ-type manganese dioxide content in the positive electrode mixture is 50 parts by weight per 100 parts by weight of the active material, the λ-type manganese dioxide content in the positive electrode mixture is 10 parts by weight per 100 parts by weight of the active material. The battery 18 as shown showed better discharge characteristics. From this, it was found that the addition effect of λ-type manganese dioxide was greater than that of γ-type manganese dioxide.
In addition, when the content of λ-type manganese dioxide or γ-type manganese dioxide in the positive electrode mixture is less than 25 parts by weight per 100 parts by weight of the active material, λ-type manganese dioxide has a larger additive effect than γ-type manganese dioxide. It was. When λ-type manganese dioxide is added to nickel oxyhydroxide, the content of λ-type manganese dioxide in the positive electrode mixture is 0.5 to 25 parts by weight per 100 parts by weight of the active material, particularly 1 to 10 weights. It was found that the effect was noticeable in the part.

Example 3
λ-type manganese dioxide, γ-type manganese dioxide, nickel oxyhydroxide, and artificial graphite powder (SP-20, manufactured by Nippon Graphite Industry Co., Ltd.) were mixed in the weight ratio shown in Table 4 in the same manner as in Example 1. A battery was prepared and evaluated. The evaluation results are shown in Table 4 together with the results of the battery 3.

  From Table 4, in the batteries 24-32 in which λ-type manganese dioxide was further added to a mixture of nickel oxyhydroxide and γ-type manganese dioxide, the same effect as in Examples 1 and 2 was obtained, and the discharge characteristics are shown in Table 3. It was found to be better than the case where λ-type manganese dioxide was added only to the nickel oxyhydroxide shown. When λ-type manganese dioxide is further added to the mixture of nickel oxyhydroxide and γ-type manganese dioxide, the content of λ-type manganese dioxide in the positive electrode mixture is 0.5 to 25 parts by weight per 100 parts by weight of the active material. The effect was particularly noticeable at 1 to 10 parts by weight. As in the case of Examples 1 and 2, it was confirmed that when λ-type manganese dioxide was added, the voltage drop width during discharge was small.

Example 4
Electrolytic manganese dioxide (manufactured by DELTA, TA), Li ₂ Co ₃ (manufactured by Kanto Chemical Co., Inc.) and Ni (OH) ₂ as a hydroxide of the different element M, molar ratio Ni: Mn: Li = Mixing was performed at a ratio of y: 2-y: 1.1. The mixture was heated from room temperature to 850 ° C. in 10 hours and then heated at 850 ° C. for 20 hours. Thereafter, the temperature was lowered to room temperature in 10 hours and cooled.
100 g of this product was suspended in about 200 ml of pure water, and 500 ml of 2N aqueous sulfuric acid solution was added with slow stirring. The solution was filtered to separate the solid components and washed with pure water until the washing solution became neutral. This residual solid component was dried at 100 ° C. for 12 hours. In this way, λ-type manganese dioxide Li _x [M _y Mn _2-y ] O ₄ (x = 0.1, M = Ni) shown in Table 5 was obtained.
As described above, except that λ type manganese dioxide _{Li x [M y Mn 2-} y] O substitution amount to Mn of the different element in the ₄ y / 2 × 100 (atomic%) was changed to the values shown in Table 5 implementation A battery was prepared and evaluated in the same manner as the battery 4 of Example 1. The evaluation results are shown in Table 5.

  Batteries 4 and 34 to 37 using λ-type manganese dioxide in which 1 to 25 atomic% of Mn was substituted with a different element Ni exhibited excellent discharge characteristics.

Example 5
Electrolytic manganese dioxide (manufactured by DELTA, TA), Li ₂ Co ₃ (manufactured by Kanto Chemical Co., Inc.), and a hydroxide of a different element M having a molar ratio M: Mn: Li = 7: 93: 55 Mixed in proportion. The mixture was heated from room temperature to 850 ° C. in 10 hours and then heated at 850 ° C. for 20 hours. Thereafter, the temperature was lowered to room temperature in 10 hours and cooled.
100 g of this product was suspended in about 200 ml of pure water, and 500 ml of 2N aqueous sulfuric acid solution was added with slow stirring. The solution was filtered to separate the solid components and washed with pure water until the washing solution became neutral. This residual solid component was dried at 100 ° C. for 12 hours. _{Thus, Li x [M y Mn 2} -y] O 4 (x = 0.1, y = 0.14) as a λ-type manganese dioxide was obtained.

When two kinds of different elements are used in combination, the molar ratio of the two kinds of different elements is 1: 1. For example, in the battery 45, assuming that two kinds of different elements are M1 and M2, Li _x [M1 _{y / 2} M2 _{y / 2} Mn _2-y ] O ₄ (x = 0.1, y = 0.14, M1) = Ni, M2 = Co) was obtained.
As described above, lambda-type manganese dioxide _{Li x [M y Mn 2-} y] O 4 (x = 0.1, y = 0.14) except for changing the different element M to the element shown in Table 6 in the A battery was produced and evaluated in the same manner as the battery 4 of Example 1. The evaluation results are shown in Table 6 together with the results of the battery 4.

The batteries 4, 38 to 43, in which the different element M of the λ-type manganese dioxide is Ni, Co, Ti, Fe, Mg, Zn, or Sn, all showed good heavy load discharge characteristics. Also, batteries 44 to 46 using a combination of two different kinds of elements showed good heavy load discharge characteristics.
In addition to the above, if the different element M is at least one element selected from the group consisting of Ni, Co, Ti, Fe, Mg, Zn, and Sn, good heavy load discharge characteristics similar to the above can be obtained. It is done.

  The alkaline primary battery of the present invention is suitably used as a power source for a digital camera or the like because it suppresses an increase in the internal resistance of the battery during discharge and has excellent heavy load discharge characteristics.

It is the front view which made some alkaline primary batteries of the example of the present invention into the section.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Positive electrode case 2 Graphite coating film 3 Positive electrode mixture 4 Separator 5 Insulation cap 6 Gel-like negative electrode 7 Resin sealing body 8 Bottom plate 9 Insulation washer 10 Negative electrode current collector 11 Exterior label

Claims (8)

An alkaline primary battery comprising a positive electrode, a negative electrode, an alkaline electrolyte, and a separator disposed between the positive electrode and the negative electrode,
The positive electrode includes nickel oxyhydroxide and λ-type manganese dioxide,
An alkaline primary battery, wherein a part of Mn in the λ-type manganese dioxide is substituted with at least one different element selected from the group consisting of Ni, Co, Ti, Fe, Mg, Zn, and Sn.   The alkaline primary battery according to claim 1, wherein the amount of substitution of the different element for Mn is 1 to 25 atomic%.   2. The alkaline primary battery according to claim 1, wherein the content of λ-type manganese dioxide in the positive electrode is 0.5 to 25 parts by weight per 100 parts by weight in total of the nickel oxyhydroxide and the λ-type manganese dioxide.   2. The alkaline primary battery according to claim 1, wherein the content of λ-type manganese dioxide in the positive electrode is 1 to 10 parts by weight per 100 parts by weight in total of the nickel oxyhydroxide and the λ-type manganese dioxide.   The alkaline primary battery according to claim 1, wherein the positive electrode further contains γ-type manganese dioxide.   The content of λ-type manganese dioxide in the positive electrode is 0.5 to 25 parts by weight per 100 parts by weight in total of the nickel oxyhydroxide, the λ-type manganese dioxide, and the γ-type manganese dioxide. Alkaline primary battery.   The alkali primary according to claim 5, wherein the content of λ-type manganese dioxide in the positive electrode is 1 to 10 parts by weight per 100 parts by weight in total of the nickel oxyhydroxide, the λ-type manganese dioxide, and the γ-type manganese dioxide. battery.   The alkaline primary battery according to claim 1, wherein the λ-type manganese dioxide is electrolytic manganese dioxide.

Images