U.S. patent application number 15/545219 was filed with the patent office on 2018-01-11 for alkaline battery.
The applicant listed for this patent is FDK ENERGY CO., LTD.. Invention is credited to Takahiro Endo, Yuki Natsume, Takeo Nogami, Hidenori Tsuzuki.
Application Number | 20180013174 15/545219 |
Document ID | / |
Family ID | 56416692 |
Filed Date | 2018-01-11 |
United States Patent
Application |
20180013174 |
Kind Code |
A1 |
Endo; Takahiro ; et
al. |
January 11, 2018 |
ALKALINE BATTERY
Abstract
An alkaline battery has a positive electrode mixture containing
manganese dioxide and a conductive material filling a tubular
positive electrode can that is closed at one end. A negative
electrode mixture containing a zinc powder filling on an inner
peripheral side of a separator is disposed on an inside of the
positive electrode mixture. The negative electrode mixture contains
zinc particles with a granularity of 75 .mu.m or less at 25 to 40
mass %. The positive electrode mixture has a plurality of tubular
pellets stacked inside the positive electrode can coaxially with
the positive electrode can. A sum s of lengths of gaps between the
pellets is set at 1 to 14% with respect to a sum d of lengths of
the pellets. Thus, a sufficient amount of the electrolyte is held
in the gaps and between the pellets in the positive electrode.
Inventors: |
Endo; Takahiro; (Kosai-shi,
JP) ; Natsume; Yuki; (Kosai-shi, JP) ; Nogami;
Takeo; (Kosai-shi, JP) ; Tsuzuki; Hidenori;
(Kosai-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FDK ENERGY CO., LTD. |
Kosai-shi |
|
JP |
|
|
Family ID: |
56416692 |
Appl. No.: |
15/545219 |
Filed: |
January 23, 2015 |
PCT Filed: |
January 23, 2015 |
PCT NO: |
PCT/JP2015/051918 |
371 Date: |
July 20, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
Y02E 60/10 20130101;
H01M 4/50 20130101; H01M 6/185 20130101; H01M 10/283 20130101; H01M
4/24 20130101; H01M 4/42 20130101; H01M 4/06 20130101; H01M 2220/30
20130101; H01M 4/502 20130101; H01M 6/02 20130101; H01M 6/08
20130101; H01M 4/244 20130101 |
International
Class: |
H01M 10/28 20060101
H01M010/28; H01M 6/18 20060101 H01M006/18; H01M 4/24 20060101
H01M004/24; H01M 4/06 20060101 H01M004/06; H01M 4/42 20060101
H01M004/42; H01M 4/50 20100101 H01M004/50; H01M 6/02 20060101
H01M006/02 |
Claims
1. An alkaline battery comprising: a positive electrode mixture
filling a tubular positive electrode can closed at one end; a
separator disposed on an inner peripheral side of the positive
electrode mixture; a negative electrode mixture filling an inner
peripheral side of the separator, the negative electrode mixture
containing a powder mainly containing zinc; a negative electrode
current collector inserted into the negative electrode mixture; a
negative electrode terminal plate to seal an opening of the
positive electrode can; and an alkaline electrolyte, the positive
electrode mixture containing manganese dioxide and a conductive
material, the powder containing particles with a granularity of 75
.mu.m or less in a range of 25 to 40 mass %, the positive electrode
mixture constituted of a plurality of tubular pellets, the
plurality of tubular pellets stacked and loaded inside the positive
electrode can in such a manner as to be stacked coaxially with the
positive electrode can, a gap disposed between the pellets, the
gaps and the pellets having a ratio of a sum s of length of the
gaps axially along the positive electrode can to a sum d of lengths
of the pellets axially along the positive electrode can, the ratio
being 1 to 14%.
2. The alkaline battery according to claim 1, wherein the pellets
have a density in a range of 3.0 to 3.7 g/cm.sup.3,
3. The alkaline battery according to claim 1, wherein the pellets
contain graphite as the conductive material in a range of 5 to 20
mass % with respect to the manganese dioxide.
Description
TECHNICAL FIELD
[0001] The present disclosure relates to discharge performance of
an alkaline battery and especially relates to improvement in heavy
load discharge performance.
BACKGROUND ART
[0002] Recently, electronic devices such as digital cameras, video
cameras, mobile phones, and smart phones have been improved their
performance and downsizing, and requests for improvement in
performance of alkaline batteries, which are used as power supplies
for such electronic devices, have been increased. Especially,
requests for improvement in heavy load discharge performance (high
load discharge characteristics) have been increased.
[0003] For example, Patent Literature 1 describes a technique to
improve the high load discharge characteristics of an alkaline
battery as follows. The alkaline battery includes a negative
electrode that contains a zinc alloy powder containing fine powders
having a grain diameter of 75 .mu.m or less at 20 to 50 weight %, a
positive electrode, a separator arranged between the negative
electrode and the positive electrode, and an electrolyte. The
alkaline battery is configured such that a time period for an
electric potential of the negative electrode to rise becomes
shorter than a time period for an electric potential of the
positive electrode to fall, in constant resistance discharge.
CITATION LIST
Patent Literature
[0004] Patent Literature 1: Japanese Patent No. 5172181
SUMMARY OF INVENTION
Technical Problem
[0005] In the above-described Patent Literature 1, the zinc alloy
powder containing fine powders having a grain diameter of 75 .mu.m
or less at 20 to 50 weight % is used as a negative electrode
material to improve heavy load discharge characteristics. However,
even when the fine powders are used for the negative electrode
material, the heavy load discharge characteristics may not be
improved. A reason why this occurs is considered as follow. Such a
fine powder of a small grain diameter has a large specific surface,
and thus the electrolyte is likely to be held on the negative
electrode side. This reduces the electrolyte on the positive
electrode side and increases electrical resistance on the positive
electrode side.
[0006] An aspect of the present disclosure is to improve discharge
performance of an alkaline battery, and especially to provide the
alkaline battery excellent in heavy load discharge performance.
Solution to Problem
[0007] One of the present disclosure to achieve such an aspect is
an alkaline battery comprising: a positive electrode mixture
filling a tubular positive electrode can closed at one end; a
separator disposed on an inner peripheral side of the positive
electrode mixture; a negative electrode mixture filling an inner
peripheral side of the separator, the negative electrode mixture
containing a powder mainly containing zinc; a negative electrode
current collector inserted into the negative electrode mixture; a
negative electrode terminal plate to seal an opening of the
positive electrode can; and an alkaline electrolyte, the positive
electrode mixture containing manganese dioxide and a conductive
material, the powder containing particles with a granularity of 75
.mu.m or less in a range of 25 to 40 mass %, the positive electrode
mixture constituted of a plurality of tubular pellets, the
plurality of tubular pellets loaded inside the positive electrode
can in such a manner as to be stacked coaxially with the positive
electrode can, one or more gaps disposed between the pellets, the
gaps and the pellets having a ratio of a sum s of length of the
gaps axially along the positive electrode can to a sum d of lengths
of the pellets axially along the positive electrode can, the ratio
being 1 to 14%.
[0008] Another one of the present disclosure according to the
above-described alkaline battery is configured as follows. The
pellets have a density in a range of 3.0 to 3.7 g/cm.sup.3.
[0009] Another one of the present disclosure according to the
above-described alkaline battery is configured as follows. The
pellets contain graphite as the conductive material in a range of 5
to 20 mass % with respect to the manganese dioxide.
[0010] Aspects disclosed in the present application and solution
thereof will be apparent from Description of Embodiments and the
drawings.
Advantageous Effects
[0011] The present disclosure can provide an alkaline battery
excellent in discharge performance, especially, heavy load
discharge performance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a diagram illustrating a configuration of a common
cylindrical alkaline battery.
DESCRIPTION OF EMBODIMENTS
[0013] FIG. 1 illustrates a configuration of a common cylindrical
alkaline battery (LR6 (AA size) alkaline battery), to which the
present disclosure is applied (hereinafter referred to as an
alkaline battery 1). FIG. 1 is a vertical cross-sectional view
illustrating the alkaline battery 1 (cross-sectional view of the
alkaline battery 1 when an extension direction of a cylinder axis
is set as an up-down (vertical) direction).
[0014] As illustrated in FIG. 1, the alkaline battery 1 includes: a
tubular metallic battery can closed at one end (hereinafter
referred to as a positive electrode can 11); a positive electrode
mixture 21 inserted into the positive electrode can 11; a
cylindrical separator 22 closed at one end disposed on an inner
peripheral side of the positive electrode mixture 21; a negative
electrode mixture 23 filling on an inner peripheral side with
respect to the separator 22; a negative electrode terminal plate 32
fitted into an opening of the positive electrode can 11 via a
sealing gasket 35 made of resin; and a rod-shaped negative
electrode current collector 31 made of a material such as a brass.
The negative electrode current collector 31 is fixedly installed
inside the negative electrode terminal plate 32 by a spot welding
or a similar method. The positive electrode mixture 21, the
separator 22, and the negative electrode mixture 23 constitute a
power generating element 20 of the alkaline battery 1.
[0015] The positive electrode can 11 has a conductive property, and
is formed, for example, by performing presswork onto a metal
material such as a nickel plated steel plate. The positive
electrode can 11 doubles as a positive electrode current collector
and a positive electrode terminal. A protruding positive electrode
terminal portion 12 is formed integrally with a bottom portion of
the positive electrode can 11.
[0016] The positive electrode mixture 21 is formed as follows.
Electrolytic manganese dioxide (EMD) as a positive electrode active
material, graphite as a conductive material, and an electrolyte
mainly containing a potassium hydroxide (KOH) are mixed together
with a binder such as polyacrylic acid. Such a mixture is processed
through steps of rolling, disintegration, granulation,
classification, and the like, and thereafter is compressed and
shaped into rings. As illustrated in FIG. 1, the positive electrode
can 11 have the positive electrode mixture 21 that is configured
with a plurality of (three) pellets 21a, 21b, and 21c of a tubular
shape press-fitted into the positive electrode can 11 in such a
manner as to be stacked in a vertical direction, with their
cylinder axes being coaxial with the cylinder axis of the positive
electrode can 11. The pellets 21a, 21b, and 21c axially along the
positive electrode can 11 have respective lengths of d1, d2, and d3
in this order. Although the respective lengths of the pellets 21a,
21b, and 21c coincide with one another (d1=d2=d2) in this
embodiment, these lengths may not coincide.
[0017] As illustrated in FIG. 1, a gap 51 is disposed between the
pellet 21a and the pellet 21b and a gap 52 is disposed between the
pellet 21b and the pellet 21c. The gap 51, which is disposed
between the pellet 21a and the pellet 21b, has a length of s1
axially along the positive electrode can 11. The gap 52, which is
disposed between the pellet 21b and the pellet 21c, has a length of
s2 axially along the positive electrode can 11. A surface, of the
pellet 21c, on the positive electrode terminal portion 12 side
closely contacts the positive electrode can 11.
[0018] The negative electrode mixture 23 is produced by
gelatinizing a zinc alloy powder as a negative electrode active
material. The zinc alloy powder is produced by a gas atomization
method or a centrifugal spray method. The zinc alloy powder
contains: zinc; an alloy component (e.g., bismuth, aluminum, and
indium) added to reduce gas (to prevent liquid leakage); and
potassium hydroxide as the electrolyte. The negative electrode
current collector 31 is penetrated into the center of the negative
electrode mixture 23.
[0019] In order to verify the effects of improvement in discharge
performance, especially heavy load discharge performance, of the
alkaline battery 1 configured as described above, the following
Tests 1 to 3 were conducted.
<Test 1>
[0020] In Test 1, in order to verify appropriate ranges of
granularity of the zinc alloy powder in the negative electrode
mixture 23 as well as the gaps 51 and 52 between the pellets
constituting the positive electrode mixture 21, the granularity of
the zinc alloy powder of the negative electrode mixture 23 was
varied (the content percentage of the particles with a granularity
of 75 .mu.m or less (hereinafter also referred to as a "proportion
of particles with 75 .mu.m or less") was varied in a range of 20.0
to 45.0 mass %), and also the sizes of the gaps 51 and 52 were
varied (the ratio of the sum of lengths of the gaps 51 and 52
axially along the positive electrode can 11, i.e., s=s1+s2, to the
sum of lengths of the pellets axially along the positive electrode
can 11, i.e., d=d1+d2+d3, (hereinafter also referred to as
"gap/mixture height") was varied). Thus, the plurality of alkaline
batteries 1 was manufactured to compare their discharge
performance. All alkaline batteries 1 employed the positive
electrode mixture 21 having a density (hereinafter also referred to
as a "positive electrode mixture density") of 3.2 g/cm.sup.3 and
having a ratio of graphite to manganese dioxide in the positive
electrode mixture 21 (hereinafter also referred to as a
"graphite/manganese dioxide") of 10.0 mass %.
[0021] The discharge performance was compared as follows. A cycle
discharge test assuming heavy load discharge, for example, during
the use of a digital camera (a cycle of discharge for two seconds
at 1500 mW and discharge for 28 seconds at 650 mW was performed ten
times for one hour (an idle period for one hour was about 55
minutes)) was conducted. Then, the number of cycles until reaching
a cutoff voltage (1.05 V) was counted for comparison.
[0022] Table 1 shows results of the discharge performance
comparisons among the alkaline batteries 1. The values indicating
the discharge performance in Table 1 are relative values, assuming
the discharge performance of the alkaline battery 1 in Comparative
Example 3 as 100.
TABLE-US-00001 TABLE 1 Positive electrode Proportion of particles
with Clearance/mixture mixture Graphite/manganese Discharge 75
.mu.m or less (Mass %) height (%) density (g/cm3) dioxide (Mass %)
performance Working Example 1 25.0 5.0 3.2 10.0 118 Working Example
2 30.0 5.0 3.2 10.0 125 Working Example 3 40.0 5.0 3.2 10.0 120
Comparative Example 1 20.0 5.0 3.2 10.0 95 Comparative Example 2
45.0 5.0 3.2 10.0 100 Working Example 4 30.0 1.0 3.2 10.0 120
Working Example 5 30.0 8.0 3.2 10.0 127 Working Example 6 30.0 12.0
3.2 10.0 120 Working Example 7 30.0 14.0 3.2 10.0 110 Comparative
Example 3 30.0 0.0 3.2 10.0 100 Comparative Example 4 30.0 0.5 3.2
10.0 105 Comparative Example 5 30.0 15.0 3.2 10.0 95
[0023] As shown in Table 1, it has been confirmed that the alkaline
batteries 1 which contain the particles with a granularity of 75
.mu.m or less, as the zinc alloy powder of the negative electrode
mixture 23, in a range of 25 to 40 mass % and which have a ratio of
the sum s of the gaps 51 and 52 to the sum d of the axial lengths
of the pellets (gap/mixture height) of 1 to 14%, exhibit the high
discharge performance (Working Examples 1 to 7). It has been also
confirmed that the alkaline batteries 1 containing the particles
with a granularity of 75 .mu.m or less, as the zinc alloy powder of
the negative electrode mixture 23, in a range of 30 mass % and
having a ratio of the sum s of the gaps 51 and 52 to the sum d of
the axial lengths of the pellets (gap/mixture height) of 8.0%
exhibit outstandingly high discharge performance (Working Example
5).
[0024] It has been found from Comparative Example 2 that the
excessively large amount of fine powders of the negative electrode
mixture 23 does not improve discharge performance. It is considered
that this is because the electrolyte was likely to be held on the
negative electrode side due to the fine powders having a small
grain diameter and a large specific surface, and this reduced the
electrolyte on the positive electrode side, resulting in an
increase in electrical resistance on the positive electrode
side.
[0025] Further, it has been found from Comparative Examples 3 and 4
that the excessively small gaps 51 and 52 do not improve discharge
performance. It is considered that this is because the sufficient
amount of electrolyte results in not being held on the positive
electrode side due to the excessively small gaps 51 and 52.
[0026] Furthermore, it has been found from Comparative Example 5
that the excessively large gaps 51 and 52 do not improve discharge
performance. It is considered that this is because the excessively
large gaps 51 and 52 reduce the amount of negative electrode active
material oppose to the positive electrode active material,
resulting in an increase in current density.
<Test 2>
[0027] Subsequently, in order to verify an appropriate range of the
density of the positive electrode mixture 21 (positive electrode
mixture density), the plurality of alkaline batteries 1 including
the positive electrode mixtures 21 with their densities varied (the
densities of the positive electrode mixtures 21 were varied in a
range of 2.8 to 3.7 g/cm.sup.3) were manufactured to compare their
discharge performance. It should be noted that all the alkaline
batteries 1 had a ratio of the sum s of the gaps 51 and 52 to the
sum d of the axial lengths of the pellets (gap/mixture height) of
5.0%. Further, all the alkaline batteries 1 employed the positive
electrode mixture 21 having a ratio of graphite to manganese
dioxide in the positive electrode mixture 21 (graphite/manganese
dioxide) of 10.0 mass %. The discharge performance was obtained by
a method similar to Test 1.
[0028] Table 2 shows the results of the discharge performance
comparisons among the alkaline batteries 1. It should be noted that
the values indicating the discharge performance in Table 2 are
relative values, assuming the discharge performance of the alkaline
battery 1 in Comparative Example 3 shown in Table 1 as 100.
TABLE-US-00002 TABLE 2 Clearance/ Positive electrode Proportion of
particles with mixture mixture Graphite/manganese Discharge 75
.mu.m or less (Mass %) height (%) density (g/cm3) dioxide (Mass %)
performance Working Example 8 30.0 5.0 3.0 10.0 128 Working Example
9 30.0 5.0 3.7 10.0 123 Comparative 30.0 5.0 3.9 10.0 Mixture
cannot be manufactured. Example 6 Comparative 30.0 5.0 2.8 10.0 86
Example 7
[0029] As shown in Table 2, it has been confirmed that the
discharge performance of the alkaline batteries 1 is enhanced with
the density of the positive electrode mixture 21 (positive
electrode mixture density) in a range of 3.0 to 3.7 g/cm.sup.3
(Working Examples 8 and 9). It has been also confirmed that the
discharge performance is outstandingly enhanced with the density of
the positive electrode mixture 21 of 3.0 g/cm.sup.3 (Working
Example 8).
[0030] The excessively high density of the positive electrode
mixture 21 was likely to cause cracking, resulting in difficulty in
compression molding, thereby failing to manufacture the pellets
(Comparative Example 6).
[0031] The excessively low density of the positive electrode
mixture 21 failed to obtain the sufficient discharge performance
(Comparative Example 7). It is considered that this is because the
excessively low density of the positive electrode mixture 21 causes
insufficient conductivity inside the positive electrode mixture
21.
<Test 3>
[0032] Subsequently, in order to verify an appropriate range of the
ratio of graphite to manganese dioxide in the positive electrode
mixture 21 (graphite/manganese dioxide), the plurality of alkaline
batteries 1 with their ratios varied (the ratios were varied in a
range of 2.0 to 25.0 mass %) were manufactured to compare their
discharge performance. The discharge performance was obtained by
the method similar to the above-described method. All the alkaline
batteries 1 had a ratio of the sum s of the gaps 51 and 52 to the
sum d of the axial lengths of the pellets (gap/mixture height) of
5.0%. Further, all the alkaline batteries 1 employed the density of
the positive electrode mixture 21 (positive electrode mixture
density) of 3.2 g/cm.sup.3.
[0033] Table 3 shows the results of the discharge performance
comparisons among the respective alkaline batteries 1. It should be
noted that the values indicating the discharge performance in Table
3 are relative values, assuming the discharge performance of the
alkaline battery 1 in Comparative Example 3 shown in Table 1 as
100.
TABLE-US-00003 TABLE 3 Clearance/ Positive electrode Proportion of
particles with mixture mixture Graphite/manganese Discharge 75
.mu.m or less (Mass %) height (%) density (g/cm3) dioxide (Mass %)
performance Working Example 10 30.0 5.0 3.2 5.0 126 Working Example
11 30.0 5.0 3.2 15.0 132 Working Example 12 30.0 5.0 3.2 20.0 119
Comparative Example 8 30.0 5.0 3.2 2.0 77 Comparative Example 9
30.0 5.0 3.2 25.0 85
[0034] As shown in Table 3, it has been confirmed that the
discharge performance is enhanced with the ratio of graphite to
manganese dioxide in the positive electrode mixture 21
(graphite/manganese dioxide) in a range of 5 to 20 mass % (Working
Examples 10 to 12). It has been also confirmed that the discharge
performance is outstandingly enhanced with the ratio of graphite to
manganese dioxide in the positive electrode mixture 21
(graphite/manganese dioxide) of 15.0 mass % (Working Example
11).
[0035] The excessively small ratio of the graphite failed to obtain
sufficient discharge performance (Comparative Example 8). It is
considered that this is caused by insufficient conductivity inside
the positive electrode mixture 21.
[0036] The excessively large ratio of the graphite failed to obtain
sufficient discharge performance (Comparative Example 9). It is
considered that this is because the amount of electrolyte was
reduced in the positive electrode mixture 21 due to an influence
from the water-repellent graphite.
<Effects>
[0037] As described above, the following has been found. The
discharge performance of the alkaline battery 1 is enhanced in the
case where the negative electrode mixture 23 contains, as the zinc
alloy powder, particles with a granularity of 75 .mu.m or less in a
range of 25 to 40 mass % and the ratio of the sum s of the gaps 51
and 52 to the sum d of the axial lengths of the pellets are set to
1 to 14%. The satisfactory results are obtained especially in the
case where the negative electrode mixture 23 containing, as the
zinc alloy powder, particles with a granularity of 75 .mu.m or less
in the range of 30 mass % is employed and the ratio of the sum s to
the gaps 51 and 52 to the sum d of the axial lengths of the pellets
is set to 8.0%.
[0038] It has been confirmed that the discharge performance is
enhanced in the case where the positive electrode mixture 21 has a
density in a range of 3.0 to 3.7 g/cm.sup.3. It has been found that
the satisfactory results are obtained especially in the case where
the positive electrode mixture 21 has a density of 3.0
g/cm.sup.3.
[0039] It has been confirmed that the discharge performance is
enhanced in the case where the ratio of graphite to manganese
dioxide in the positive electrode mixture 21 (graphite/manganese
dioxide) is in a range of 5 to 20 mass %. It has been found that
the satisfactory results are obtained especially in the case where
the ratio of graphite to manganese dioxide in the positive
electrode mixture 21 (graphite/manganese dioxide) is 15.0 mass
%.
[0040] The description of the above-described embodiment is for
ease of understanding of the present disclosure and does not limit
the present disclosure. The present disclosure may be modified or
improved without departing from the gist and includes the
equivalents.
[0041] For example, the above-described embodiment configures the
number of pellets constituting the positive electrode mixture 21 to
be three. However, the number of pellets may be two or four or
more. In short, it is only necessary that the ratio of the sum s of
the lengths of the gap(s) between the pellets axially along the
positive electrode can 11 to the sum d of the lengths of the
pellets axially along the positive electrode can 11 meets the
above-described conditions, together with other necessary
conditions. This ensures the above-described effects.
REFERENCE SIGNS LIST
[0042] 1 alkaline battery [0043] 11 positive electrode can [0044]
12 positive electrode terminal portion [0045] 20 power generating
element [0046] 21 positive electrode mixture [0047] 21a, 21b, 21c
pellet [0048] 22 separator [0049] 23 negative electrode mixture
[0050] 31 negative electrode current collector [0051] 32 negative
electrode terminal plate [0052] 35 sealing gasket [0053] 51, 52
gap
* * * * *