U.S. patent application number 10/588061 was filed with the patent office on 2009-01-22 for alkaline battery.
Invention is credited to Nobuharu Koshiba, Harunari Shimamura, Koshi Takamura.
Application Number | 20090023068 10/588061 |
Document ID | / |
Family ID | 35394440 |
Filed Date | 2009-01-22 |
United States Patent
Application |
20090023068 |
Kind Code |
A1 |
Shimamura; Harunari ; et
al. |
January 22, 2009 |
Alkaline battery
Abstract
An alkaline battery of this invention includes: a negative
electrode including a negative electrode mixture that contains a
zinc alloy as an active material, the zinc alloy containing at
least aluminum; an alkaline electrolyte; and a positive electrode.
The alkaline electrolyte includes an aqueous KOH solution and LiOH
and an aluminum compound that are dissolved in the aqueous KOH
solution. The alkaline battery has excellent high-rate discharge
characteristics.
Inventors: |
Shimamura; Harunari; (Osaka,
JP) ; Takamura; Koshi; (Osaka, JP) ; Koshiba;
Nobuharu; (Nara, JP) |
Correspondence
Address: |
MCDERMOTT WILL & EMERY LLP
600 13TH STREET, N.W.
WASHINGTON
DC
20005-3096
US
|
Family ID: |
35394440 |
Appl. No.: |
10/588061 |
Filed: |
March 17, 2005 |
PCT Filed: |
March 17, 2005 |
PCT NO: |
PCT/JP05/04782 |
371 Date: |
August 1, 2006 |
Current U.S.
Class: |
429/229 |
Current CPC
Class: |
H01M 4/244 20130101;
H01M 6/04 20130101; Y02E 60/10 20130101; H01M 6/045 20130101; H01M
6/06 20130101; H01M 2300/0085 20130101 |
Class at
Publication: |
429/229 |
International
Class: |
H01M 4/42 20060101
H01M004/42 |
Foreign Application Data
Date |
Code |
Application Number |
May 13, 2004 |
JP |
2004-143430 |
Claims
1. An alkaline battery comprising: a negative electrode including a
negative electrode mixture that contains a zinc alloy as an active
material, said zinc alloy containing at least aluminum; an alkaline
electrolyte; and a positive electrode, wherein said alkaline
electrolyte comprises an aqueous KOH solution and LiOH and an
aluminum compound that are dissolved in said aqueous KOH
solution.
2. The alkaline battery in accordance with claim 1, wherein the
amounts of the LiOH and the aluminum compound contained in the
electrolyte in said negative electrode mixture are 0.1 to 2 wt %
and 0.001 to 0.2 wt % of the negative electrode mixture,
respectively.
3. The alkaline battery in accordance with claim 1, wherein the
amounts of the LiOH and the aluminum compound contained in the
electrolyte in said negative electrode mixture are 0.15 to 3 parts
by weight and 0.0015 to 0.3 parts by weight per 100 parts by weight
of said zinc alloy.
4. The alkaline battery in accordance with claim 1 or 2, wherein
the weight ratio of the whole alkaline electrolyte to the zinc
alloy of the negative electrode is 0.1 to 2.
Description
TECHNICAL FIELD
[0001] The present invention relates to alkaline batteries such as
alkaline dry batteries and air batteries, and, more particularly,
to an improvement in the alkaline electrolyte to prevent gas
production and improve high-rate discharge characteristics.
BACKGROUND ART
[0002] A conventional problem with alkaline batteries using zinc or
a zinc alloy as a negative electrode active material is that the
active material corrodes in an alkaline electrolyte to produce
hydrogen gas. Accumulation of this gas in the battery increases the
battery inner pressure, thereby causing the electrolyte to leak
out, which is disadvantageous.
[0003] To solve this problem, various techniques have been
examined. Patent Document 1 discloses that adding lithium hydroxide
to an electrolyte decreases the reactivity of the electrolyte with
the surface of an active material powder, thereby reducing the
amount of gas produced.
[0004] Patent Document 1: Japanese Laid-Open Patent
Publication No. Hei 2000-82503
DISCLOSURE OF INVENTION
[0005] Problem that the Invention is to Solve
[0006] However, in the case of a zinc alloy containing at least
aluminum, even if LiOH is added to an alkaline electrolyte, a large
amount of aluminum is dissolved in the electrolyte. Thus, there is
a problem in that the addition of LiOH does not produce the effect
of suppressing gas production from zinc, thereby resulting in
degradation of high-rate discharge characteristics of the battery.
The reason why the addition of LiOH suppresses gas production is
probably that Zn(OH).sub.4.sup.2- produced during discharge is
prevented from changing into a passivation film on the active
material surface and that a conductive film comprising Zn, O, and K
is formed. However, in the case of using an aluminum-containing
zinc alloy as a negative electrode active material, part of this
conductive film is destroyed when the aluminum in the alloy is
dissolved in an electrolyte. Hence, the zinc alloy is exposed at
the surface, so that gas production cannot be sufficiently
suppressed. As a result, a passivation film is formed to increase
the resistance, thereby leading to a significant degradation of
discharge characteristics, particularly high-rate discharge
characteristics.
Means for Solving the Problem
[0007] In order to solve the above-mentioned problems, the present
invention is directed to an alkaline battery including: a negative
electrode including a negative electrode mixture that contains a
zinc alloy as an active material, the zinc alloy containing at
least aluminum; an alkaline electrolyte; and a positive electrode.
The alkaline electrolyte includes an aqueous KOH solution and LiOH
and an aluminum compound that are dissolved in the aqueous KOH
solution.
[0008] According to this configuration, the aluminum in the
negative electrode active material can be prevented from dissolving
into the electrolyte, and the LiOH in the electrolyte can produce
the effect of preventing Zn(OH).sub.4.sup.2-produced during
discharge from depositing onto the active material surface as ZnO.
That is, the LiOH added to the electrolyte suppresses formation of
a passivation film (ZnO) on the zinc alloy surface during
discharge, so that a conductive film comprising Zn, O, and K is
formed. Also, the aluminum compound suppresses dissolution of the
aluminum in the zinc alloy into the electrolyte. Accordingly, it is
possible to improve the discharge characteristics, particularly
high-rate discharge characteristics, of the battery.
[0009] If the amounts of LiOH and aluminum compound in the negative
electrode mixture are less than 0.1 wt % and less than 0.001 wt %,
respectively, relative to the whole amount of the negative
electrode mixture, the dissolution of aluminum from the zinc alloy
is not suppressed, and the addition of LiOH is not effective. Also,
if the amounts of LiOH and aluminum compound are more than 2 wt %
and 0.2 wt %, respectively, relative to the whole amount of the
negative electrode mixture, it is difficult to maintain the pH of
the electrolyte at a constant level among lots due to the influence
of carbon dioxide, etc., depending on the management condition.
[0010] Therefore, in order to ensure the effects obtained by the
addition of LiOH and the aluminum compound and improve the
discharge characteristics, particularly high-rate discharge
characteristics, of the battery, it is preferred that the amounts
of LiOH and aluminum compound contained in the electrolyte in the
negative electrode mixture be in the range of 0.1 to 2 wt % and in
the range of 0.001 to 0.2 wt %, respectively, relative to the whole
negative electrode mixture. As used therein, the negative electrode
mixture refers to a mixture of the active material zinc alloy and
the electrolyte, and if the electrolyte is gelled, the negative
electrode mixture contains a gelling agent.
[0011] Further, if the weight ratio of the whole electrolyte (i.e.,
the electrolyte contained in the entire battery, not the
electrolyte contained in the negative electrode mixture) to the
weight of the active material zinc alloy is less than 0.1, the
concentration of Zn(OH).sub.4.sup.2- around the zinc alloy sharply
increases, so that the addition is not effective and the high-rate
discharge characteristics of the battery deteriorates. Also, if
this weight ratio is greater than 2, the ratio of the electrolyte
to the negative electrode mixture increases excessively, so that
the amount of active material powder in the negative electrode
mixture decreases, thereby resulting in a decrease in battery
capacity. It is therefore preferred that the weight ratio of the
whole alkaline electrolyte to the zinc alloy of the negative
electrode mixture be in the range of 0.1 to 2.
[0012] With respect to the composition of the zinc alloy, if an
element selected from the group consisting of bismuth, indium,
calcium, tin, and lead, which have high hydrogen overvoltages, is
contained in addition to aluminum, the effect of suppressing gas
production increases.
[0013] Also, exemplary aluminum compounds added include those
soluble in the alkaline aqueous solution, such as Al(OH).sub.3 and
aluminate. They are believed to exist in the electrolyte as
aluminate ions (Al(OH).sub.4(H.sub.2O).sub.2.sup.-,
Al(OH).sub.6(H.sub.2O).sup.3-, etc).
EFFECTS OF THE INVENTION
[0014] The present invention can optimize the relation between the
zinc alloy and the electrolyte and improve both electrolyte-leakage
resistance and high-rate discharge characteristics of the
battery.
BRIEF DESCRIPTION OF DRAWINGS
[0015] FIG. 1 is a partially sectional front view of an alkaline
dry battery according to Embodiment 1 of the present invention;
and
[0016] FIG. 2 is a partially sectional front view of an air battery
according to Embodiment 2 of the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
[0017] Embodiments of the present invention are hereinafter
described with reference to drawings.
Embodiment 1
[0018] The structure of an alkaline dry battery is described with
reference to FIG. 1, which is a partially sectional front view.
[0019] A battery case 1 contains a positive electrode mixture 2 in
the form of short cylindrical pellets, a separator 4, and a gelled
negative electrode mixture 3. The battery case 1 may be a steel
case whose inner face is plated with nickel. A plurality of the
positive electrode mixture pellets 2 are contained in the battery
case 1 so as to closely adhere to the inner face thereof. The
separator 4 is placed on the inner side of the positive electrode
mixture 2, and the gelled negative electrode mixture 3 is filled in
the space on the inner side of the separator 4.
[0020] The positive electrode mixture 2 is prepared as follows.
First, manganese dioxide, graphite, and an electrolyte are mixed
together in a weight ratio of 90:6:1. The resultant mixture is
sufficiently stirred and then compression molded into flakes.
Subsequently, the positive electrode mixture flakes are crushed to
obtain positive electrode mixture granules, and the positive
electrode mixture granules are then classified with a sieve to
obtain granules of 10 to 100 mesh. The resultant granules are
compression molded into hollow cylinders to obtain the positive
electrode mixture pellets 2. Four positive electrode mixture
pellets 2 are inserted into the battery case 1, and the positive
electrode mixture 2 is again molded by means of a compressing
device so as to closely adhere to the inner wall of the battery
case 1.
[0021] The separator 4, which is a cylinder with a bottom, is
placed in the middle of the positive electrode mixture 2 that is
placed in the battery case 1 in the above manner, and a
predetermined amount of an alkaline electrolyte is injected into
the space on the inner side of the separator 4. After the lapse of
a predetermined time, the gelled negative electrode mixture 3,
which comprises the alkaline electrolyte, a gelling agent, and a
zinc alloy powder, is filled into the space on the inner side of
the separator 4. The gelled negative electrode mixture 3 used is
composed of 1 part by weight of sodium polyacrylate serving as the
gelling agent, 33 parts by weight of the alkaline electrolyte, and
66 parts by weight of the zinc alloy powder. Also, the separator 4
used is a 220-.mu.m-thick non-woven fabric composed of polyvinyl
alcohol fibers and rayon fibers in a weight ratio of 7:10. The
density of the separator is 0.30 g/cm.sup.3, and the size of the
separator fibers is 0.3 denier. The ratio of the fibers is not
limited to this, and other fibers may be added as a binder.
[0022] Subsequently, a negative electrode current collector 6 is
inserted into the middle of the gelled negative electrode mixture
3. The negative electrode current collector 6 is integrally
combined with a gasket 5 and a bottom plate 7 serving as the
negative electrode terminal. The open edge of the battery case 1 is
crimped onto the circumference of the bottom plate 7 with the edge
of the gasket 5 interposed therebetween, to seal the opening of the
battery case 1. Lastly, the outer face of the battery case 1 is
covered with an outer label 8.
[0023] The electrolyte used is an alkaline electrolyte prepared by
dissolving KOH in water. The KOH concentration of the alkaline
electrolyte is 30 wt % to 45 wt %. In order to suppress the
self-discharge of zinc, ZnO may be dissolved in the electrolyte,
and with respect to the dissolution amount, ZnO may be dissolved
until it becomes saturated at each alkali concentration. To reduce
the production of hydrogen gas, an organic anti-corrosive agent may
be dispersed in the electrolyte. The LiOH and aluminum compound
contained in the negative electrode mixture are preferably added to
the electrolyte at concentrations of 0.34 to 7.0 wt % and 0.0034 to
0.070 wt %, respectively.
[0024] Any organic anti-corrosive agent may be used as long as it
suppresses the production of hydrogen, and an example is
fluoroalkyl polyoxyethylene (trade name: Surflon #S-161). Also, the
electrolyte may be in the state of gel. Any gelling agent may be
used if it combines with the alkaline electrolyte to form gel, and
examples other than sodium polyacrylate include carboxymethyl
cellulose, polyvinyl alcohol, polyethylene oxide, polyacrylic acid,
sodium polyacrylate, chitosan gel, and modified materials thereof
obtained by changing the polymerization reaction, cross-linking
degree, or molecular weight.
[0025] With respect to the form of the zinc alloy, for example,
powder, a porous material obtained by sintering the powder, or a
plate is effective. A zinc alloy powder can be obtained by
synthesis from predetermined amounts of constituent elements by
atomization and classification of the synthesized alloy. In
addition to Zn, the zinc alloy contains Al, or contains Al and at
least one element selected from the group consisting of Bi, In, Ca,
Sn, and Pb. The suitable contents of other elements than Zn in the
zinc alloy are 20 to 5000 ppm.
[0026] A porous zinc alloy obtained by sintering a zinc alloy
powder is prepared by molding or hot-pressing a zinc alloy powder
into pellets and sintering them in a reducing atmosphere in the
range of 350 to 500.degree. C.
[0027] A zinc alloy plate is prepared by forming lumps of a zinc
alloy into a plate by using a roll press or the like. The thickness
of this plate is arbitrarily adjusted so as to conform to the
battery case. The plate surface may be flat, irregular due to
punching, or perforated with through-holes.
Embodiment 2
[0028] The structure of an air battery is described with reference
to FIG. 2. FIG. 2 is a partially sectional front view of an air
battery. FIG. 2 illustrates the structure immediately after the
fabrication; due to discharge, zinc in the negative electrode
changes to a zinc oxide and undergoes a volume expansion, so that
the space in an air diffusion chamber 16 changes to a size that is
so large as to accommodate only an air diffusion paper 15.
[0029] A case serving as the positive electrode terminal is
represented by numeral 11 and contains a separator 12, an air
electrode 13 and a water-repellent film 14 on the bottom. Under
them is the air diffusion chamber 16 for accommodating the air
diffusion paper 15. The water-repellent film 14 allows oxygen to be
supplied to the air electrode 13 and prevents an electrolyte from
leaking out of the battery. The air diffusion paper 15 permits
uniform diffusion of air that is introduced from an air vent 17 in
the bottom of the case 11 into the case.
[0030] A sealing plate 18 serving as the negative electrode
terminal contains a negative electrode mixture 19 comprising a zinc
alloy powder and an electrolyte, and a ring-shaped insulating
gasket 20 is fitted to the periphery thereof. The sealing plate is
combined with the case 11, and the edge of the case 11 is crimped
onto the sealing plate with the insulating gasket 20 therebetween,
to seal the power generating element. Seal paper 21 affixed to the
outer bottom face of the case closes the air vent 17 when the
battery is not used, thereby blocking the entrance of air and
preventing battery deterioration due to self-discharge. The air
electrode 13 is produced by bonding a catalyst composition mainly
composed of a metal oxide such as manganese dioxide, graphite,
activated carbon, and a fluorocarbon binder to a current collector
net under pressure.
EXAMPLES
[0031] Examples of the present invention are hereinafter
described.
Example 1
[0032] AA-type alkaline dry batteries and coin-type PR2330 air
batteries as described in Embodiments 1 and 2 were fabricated and
evaluated for their characteristics.
[0033] As shown in Table 1, the zinc alloys of these negative
electrodes are alloys containing Al or containing Al and one or
more elements selected from the group consisting of Bi, In, Ca, Sn,
and Pb, and there are three forms: powder, porous sintered
material, and plate. Also, as shown in Table 2, the electrolytes
used were 34 wt % aqueous KOH solutions to which LiOH and
Al(OH).sub.3 were added in various ratios. These electrolytes
contain 1.5 wt % of ZnO dissolved therein. The contents of Al and
other elements in the negative electrode zinc alloy are as
follows.
[0034] Al; 5 to 70 ppm, Bi; 50 to 400 ppm, In; 100 to 800 ppm, Ca;
2 to 50 ppm, Sn; 10 to 400 ppm, Pb; 2 to 50 ppm.
TABLE-US-00001 TABLE 1 Material Element added to zinc Zinc form A1
Al Powder A2 Al and Bi Powder A3 Al and In Powder A4 Al and Ca
Powder A5 Al and Sn Powder A6 Al and Pb Powder A7 Al, Bi and In
Powder A8 Al, In and Ca Powder A9 Al, Sn and Pb Powder A10 Al, Bi,
In and Ca Powder A11 Al, Bi, In and Sn Powder A12 Al, Bi, In and Pb
Powder A13 Al, Bi, In, Ca and Sn Powder A14 Al, Bi, In, Ca, Sn and
Pb Powder B1 Al Porous sintered material B2 Al and Bi Porous
sintered material B3 Al and In Porous sintered material B4 Al and
Ca Porous sintered material B5 Al and Sn Porous sintered material
B6 Al and Pb Porous sintered material B7 Al, Bi and In Porous
sintered material B8 Al, In and Ca Porous sintered material B9 Al,
Sn and Pb Porous sintered material B10 Al, Bi, In and Ca Porous
sintered material B11 Al, Bi, In and Sn Porous sintered material
B12 Al, Bi, In and Pb Porous sintered material B13 Al, Bi, In, Ca
and Sn Porous sintered material B14 Al, Bi, In, Ca, Sn and Pb
Porous sintered material C1 Al Plate C2 Al and Bi Plate C3 Al and
In Plate C4 Al and Ca Plate C5 Al and Sn Plate C6 Al and Pb Plate
C7 Al, Bi and In Plate C8 Al, In and Ca Plate C9 Al, Sn and Pb
Plate C10 Al, Bi, In and Ca Plate C11 Al, Bi, In and Sn Plate C12
Al, Bi, In and Pb Plate C13 Al, Bi, In, Ca and Sn Plate C14 Al, Bi,
In, Ca, Sn and Pb Plate
[0035] The respective batteries were placed in a constant
temperature oven at 20.degree. C. and a relative humidity of 60%.
The air batteries were discharged at a current of 160 mA, and the
alkaline dry batteries were discharged at a current of 1 A, whereby
the discharge capacity C1 (mAh) was obtained. Also, the theoretical
capacity C2 (mAh) was calculated from the weight of Zn contained in
the negative electrode of each battery. The proportion P (%) of the
discharge capacity Cl to the theoretical capacity C2 was calculated
from the following formula (1), to evaluate the high-rate discharge
characteristics of each battery. The higher P value a battery has,
the better high-rate discharge characteristics the battery has.
Also, to obtain battery capacity, the air batteries were discharged
at a current of 3 mA and the alkaline dry batteries were discharged
at a current of 50 mA. Table 2 shows the results. In the following
Table 2 and Table 3, the wt % of LiOH and Al(OH).sub.3 represents
the ratio relative to the negative electrode mixture.
P(%)=(C1/C2).times.100 (1)
TABLE-US-00002 TABLE 2 Air battery Alkaline dry battery Electrolyte
additive Discharge Discharge LiOH Al (OH).sub.3 capacity capacity
Material (wt %) (wt %) P (%) (mAh) P (%) (mAh) A1 0 0 45 855 46
2223 A2 0.01 0.0001 62 865 63 2249 A3 0.05 0.0005 64 875 65 2275 A4
0.08 0.0008 65 899 66 2337 A5 0.1 0.001 91 920 93 2392 A6 0.2 0.005
93 925 95 2405 A7 0.8 0.01 91 922 93 2397 A8 1 0.05 92 919 94 2389
A9 1.3 0.1 89 930 91 2418 A10 1.5 0.15 88 925 90 2405 A11 1.8 0.18
87 915 89 2379 A12 2 0.2 86 905 88 2353 A13 2.5 0.25 66 878 67 2283
A14 3 0.3 62 869 63 2259 B1 0 0 46 860 47 2236 B2 0.01 0.0001 63
870 64 2262 B3 0.05 0.0005 65 880 66 2288 B4 0.08 0.0008 66 904 67
2350 B5 0.1 0.001 92 925 94 2405 B6 0.5 0.005 94 930 96 2418 B7 0.8
0.01 92 927 94 2410 B8 1 0.05 93 924 95 2402 B9 1.3 0.1 90 935 92
2431 B10 1.5 0.15 89 930 91 2418 B11 1.8 0.18 88 920 90 2392 B12 2
0.2 87 910 89 2366 B13 2.5 0.25 67 883 68 2296 B14 3 0.3 63 874 64
2272 C1 0 0 48 868 49 2257 C2 0.01 0.0001 65 878 66 2283 C3 0.05
0.0005 67 888 68 2309 C4 0.08 0.0008 68 912 69 2371 C5 0.1 0.001 94
933 95 2426 C6 0.5 0.005 96 938 97 2439 C7 0.8 0.01 94 935 95 2431
C8 1 0.05 95 932 96 2423 C9 1.3 0.1 92 943 94 2452 C10 1.5 0.15 91
938 93 2439 C11 1.8 0.18 90 928 92 2413 C12 2 0.2 89 918 91 2387
C13 2.5 0.25 69 891 70 2317 C14 3 0.3 65 882 66 2293
[0036] As is clear from Table 2, when LiOH and the aluminum
compound are not added to the electrolyte, the P values of the air
batteries are as low as 50% or less and the P values (%) of the
alkaline dry batteries are also as low as 50% or less, in
comparison with those when they are added. Although not shown in
Table 2, when the electrolyte contains no aluminum compound and
contains only LiOH, the aluminum in the zinc alloy dissolves in the
electrolyte, thereby breaking the conductive film comprising Zn, O,
and K. Also, when the electrolyte contains no LiOH and contains
only the aluminum compound, a passivation film is formed on the
zinc alloy surface. For these reasons, the P values (%) of both air
batteries and alkaline dry batteries are as low as 50% or less.
[0037] As is clear from the above, in air batteries and alkaline
dry batteries including as an active material a zinc alloy that
contains at least aluminum, an alkaline electrolyte, and a positive
electrode, the addition of LiOH and an aluminum compound to the
alkaline electrolyte provides high discharge capacity on a
high-rate discharge.
[0038] With respect to the amounts of LiOH and aluminum compound
added, when the contents of LiOH and aluminum compound in the
negative electrode mixture are lower than 0.1 wt % and 0.001 wt %,
respectively, or higher than 2 wt % and 0.2 wt %, respectively, the
P values (%) are in the 60% range. However, when the contents of
LIOH and aluminum compound are 0.1 to 2 wt % and 0.001 to 0.2 wt %,
respectively, the P values (%) are high, specifically 85% or more,
which means that the high-rate discharge characteristics are
excellent. Further, when the contents of LiOH and aluminum compound
are 0.1 to 1 wt % and 0.001 to 0.05 wt %, respectively, the P
values are high, specifically 92% or more, which means that the
high-rate discharge characteristics are more preferable.
[0039] Note that the LiOH contents of 0.1 to 2 wt % in the negative
electrode mixture correspond to 0.15 to 3 parts by weight per 100
parts by weight of the zinc alloy. Also, the aluminum compound
contents of 0.001 to 0.2 wt % in the negative electrode mixture
correspond to 0.0015 to 0.3 parts by weight per 100 parts by weight
of the zinc alloy.
[0040] Also, if the amount of each element of Al, Bi, In, Ca, Sn,
and Pb added to the zinc alloy used in the negative electrode is in
the range of 20 ppm to 5000 ppm, gas production can be effectively
prevented. If it is in the range of 50 ppm to 1000 ppm, gas
production can be more effectively prevented.
Example 2
[0041] Next, using the alloy containing Al, Bi, and In in the
negative electrode, air batteries and alkaline dry batteries were
fabricated in the same manner as the above. Table 3 shows the
electrolyte additives and the weight ratios of the electrolyte to
the zinc alloy. It should be noted that in Example 1 the weight
ratio of the electrolyte to the zinc alloy is 0.5.
[0042] These batteries were placed in a constant temperature oven
at 20.degree. C. and a relative humidity of 60%. The air batteries
were discharged at a current of 165 mA, and the alkaline dry
batteries were discharged at a current of 1050 mA, whereby the
discharge capacity C1 was obtained. In the same manner as the
above, the theoretical capacity C2 was calculated from the weight
of Zn contained in the negative electrode of each battery, and the
proportion P (%) of the discharge capacity C1 to the theoretical
capacity C2 was calculated. Also, to obtain battery capacity, the
air batteries were discharged at a current of 2 mA and the alkaline
dry batteries were discharged at a current of 45 mA. Table 3 shows
the results.
TABLE-US-00003 TABLE 3 Air battery Alkaline dry battery Electrolyte
additive Electrolyte/ Discharge Discharge LiOH Al (OH).sub.3 zinc
alloy capacity capacity Material (wt %) (wt %) (weight ratio) P (%)
(mAh) P (%) (mAh) A7 0.21 0.001 0.05 82 921 84 2579 A7 0.21 0.001
0.08 85 923 87 2584 A7 0.21 0.001 0.1 90 925 92 2590 A7 0.21 0.001
0.8 91 925 93 2590 A7 0.21 0.001 1.5 92 920 94 2576 A7 0.21 0.001 2
93 910 95 2548 A7 0.21 0.001 2.5 94 720 96 2016 A7 0.21 0.001 3 94
500 96 1400 B7 0.21 0.001 0.05 83 926 85 2592 B7 0.21 0.001 0.08 86
928 88 2597 B7 0.21 0.001 0.1 91 930 93 2603 B7 0.21 0.001 0.8 92
930 94 2603 B7 0.21 0.001 1.5 93 925 95 2589 B7 0.21 0.001 2 94 915
96 2561 B7 0.21 0.001 2.5 95 724 97 2026 B7 0.21 0.001 3 95 503 97
1407 C7 0.21 0.001 0.05 85 933 86 2612 C7 0.21 0.001 0.08 88 935 89
2618 C7 0.21 0.001 0.1 93 937 94 2624 C7 0.21 0.001 0.8 94 937 95
2624 C7 0.21 0.001 1.5 95 932 96 2610 C7 0.21 0.001 2 96 922 97
2581 C7 0.21 0.001 2.5 97 729 98 2042 C7 0.21 0.001 3 97 507 98
1418
[0043] As is clear from Table 3, when the weight ratio of the whole
electrolyte to the zinc alloy is less than 0.1, the P values (%) of
the air batteries and the alkaline dry batteries were in the 80%
range, and when the weight ratio of the whole electrolyte to the
zinc alloy is greater than 2, the discharge capacities of the air
batteries and the alkaline dry batteries at the discharge currents
of 2 mA and 45 mA, respectively, were not more than 750 mAh and not
more than 2100 mAh, respectively.
[0044] This shows that when the weight ratio of the whole
electrolyte to the zinc alloy is in the range of 0.1 to 2, the P
values (%) of the air batteries and the alkaline dry batteries are
good, specifically 90% or higher, and that the discharge capacities
of the air batteries and the alkaline dry batteries at the
discharge currents of 2 mA and 45 mA, respectively, are good,
specifically not less than 900 mAh and not less than 2500 mAh,
respectively. Further, when the weight ratio of the whole
electrolyte to the zinc alloy is in the range of 0.1 to 0.8,
batteries having higher capacity can be obtained.
[0045] Also, if the amount of each element of Al, Bi, In, Ca, Sn,
and Pb added to the zinc alloy used in the negative electrode is in
the range of 20 ppm to 5000 ppm, gas production can be effectively
prevented. If it is in the range of 50 ppm to 1000 ppm, gas
production can be more effectively prevented.
INDUSTRIAL APPLICABILITY
[0046] The present invention is applied to alkaline batteries, such
as air batteries and alkaline dry batteries, that use an
aluminum-containing zinc alloy as a negative electrode active
material.
* * * * *