U.S. patent application number 10/295755 was filed with the patent office on 2003-05-08 for electrode having multi-modal distribution of zinc-based particles.
This patent application is currently assigned to Duracell Inc., a Delaware corporation. Invention is credited to Durkot, Richard Edward, Harris, Peter Bayard, Lin, Lifun.
Application Number | 20030087153 10/295755 |
Document ID | / |
Family ID | 27381734 |
Filed Date | 2003-05-08 |
United States Patent
Application |
20030087153 |
Kind Code |
A1 |
Durkot, Richard Edward ; et
al. |
May 8, 2003 |
Electrode having multi-modal distribution of zinc-based
particles
Abstract
An electrode containing zinc-based particles suspended in a
fluid medium is disclosed. The zinc-based particles have a
multi-modal distribution, such as a bi-modal distribution, of
particle sizes, particle morphologies and/or particle compositions.
The electrode can be used as the anode in an alkaline battery, such
as a primary alkaline battery.
Inventors: |
Durkot, Richard Edward;
(Walpole, MA) ; Lin, Lifun; (Lincoln, MA) ;
Harris, Peter Bayard; (Stow, MA) |
Correspondence
Address: |
ROBERT C. NABINGER
Fish & Richardson P.C.
225 Franklin Street
Boston
MA
02110-2804
US
|
Assignee: |
Duracell Inc., a Delaware
corporation
|
Family ID: |
27381734 |
Appl. No.: |
10/295755 |
Filed: |
November 15, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10295755 |
Nov 15, 2002 |
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09156915 |
Sep 18, 1998 |
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6521378 |
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09156915 |
Sep 18, 1998 |
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09115867 |
Jul 15, 1998 |
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09115867 |
Jul 15, 1998 |
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08905254 |
Aug 1, 1997 |
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6284410 |
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Current U.S.
Class: |
429/229 ;
252/182.1; 428/546 |
Current CPC
Class: |
H01M 2004/021 20130101;
H01M 4/06 20130101; H01M 4/62 20130101; H01M 6/06 20130101; H01M
12/06 20130101; B22F 1/05 20220101; H01M 4/622 20130101; H01M 4/42
20130101; Y10T 428/12014 20150115; Y02E 60/10 20130101; H01M 4/12
20130101; H01M 4/621 20130101; H01M 4/244 20130101 |
Class at
Publication: |
429/229 ;
252/182.1; 428/546 |
International
Class: |
H01M 004/42; C22C
018/00 |
Claims
What is claimed is:
1. An electrode, comprising: zinc-based particles in a fluid
medium, the zinc-based particles having a multi-modal distribution
of particle sizes.
2. The electrode of claim 1, wherein the multi-modal distribution
is a bi-modal distribution.
3. The electrode of claim 2, wherein the zinc-based particles in
one mode of the multi-modal distribution have an average particle
size of from about 15 microns to about 120 microns.
4. The electrode of claim 2, wherein the zinc-based particles in
one mode of the multi-modal distribution have an average particle
size of from about 30 microns to about 40 microns.
5. The electrode of claim 2, wherein the zinc-based particles in
one mode of the multi-modal distribution have an average particle
size of from about 95 microns to about 105 microns.
6. The electrode of claim 2, wherein the zinc-based particles in a
first mode of the multi-modal distribution have an average particle
size of from about 200 microns to about 330 microns.
7. The electrode of claim 6, wherein the zinc-based particles in a
second mode of the multi-modal distribution have an average
particle size of from about 15 microns to about 120 microns, and
wherein the second mode is different than the first mode.
8. The electrode of claim 2, wherein the zinc-based particles in a
first mode of the multi-modal distribution have an average particle
size of from about 290 microns to about 300 microns.
9. The electrode of claim 1, wherein the zinc-based particles have
a multi-modal distribution of particle morphologies.
10. The electrode of claim 1, wherein the zinc-based particles have
a multi-modal distribution of particle compositions.
11. An electrode, comprising: zinc-based particles in a fluid
medium, the zinc-based particles having a multi-modal distribution
of particle morphologies.
12. The electrode of claim 11, wherein the multi-modal distribution
is a bi-modal distribution.
13. The electrode of claim 11, wherein a first mode of the
multi-modal distribution comprises spherical zinc-based
particles.
14. The electrode of claim 13, wherein a second mode of the
multi-modal distribution comprises nonspherical zinc-based
particles, and wherein the second mode is different than the first
mode.
15. The electrode of claim 14, wherein the nonspherical zinc-based
particles are flakes.
16. The electrode of claim 14, wherein the nonspherical zinc-based
particles are acicular particles.
17. The electrode of claim 11, wherein one mode of the multi-modal
distribution comprises nonspherical zinc-based particles.
18. The electrode of claim 17, wherein the nonspherical zinc-based
particles are flakes.
19. The electrode of claim 17, wherein the nonspherical zinc-based
particles are acicular particles.
20. The electrode of claim 11, wherein the zinc-based particles
have a multi-modal distribution of particle compositions.
21. An electrode, comprising: zinc-based particles in a fluid
medium, the zinc-based particles having a multi-modal distribution
of particle compositions.
22. The electrode of claim 21, wherein the zinc-based particles in
at least one mode include zinc and at least one gassing
inhibitor.
23. The electrode of claim 21, wherein a first mode of the
multi-modal distribution comprises zinc-based particles comprising
zinc, indium and bismuth.
24. The electrode of claim 21, wherein a second mode of the
multi-modal distribution comprises zinc-based particles comprising
zinc, indium and bismuth, and wherein the second mode is different
than the first mode.
25. The electrode of claim 21, wherein the multi-modal distribution
is a bi-modal distribution.
26. The electrode of claim 21, wherein one mode of the bi-modal
distribution comprises zinc-based particles comprising about 500
ppm indium relative to zinc and about 500 ppm bismuth relative to
zinc.
27. The electrode of claim 21, wherein one mode of the bi-modal
distribution comprises zinc-based particles comprising about 350
ppm indium relative to zinc and about 150 ppm bismuth relative to
zinc.
28. The electrode of claim 21, wherein one mode of the bi-modal
distribution comprises zinc-based particles comprising about 150
ppm indium relative to zinc and about 230 ppm bismuth relative to
zinc.
29. A battery, comprising: an anode; a cathode; and a separator
disposed between the anode and the cathode, wherein the anode
comprises zinc-based particles in a fluid medium, the zinc-based
particles having a multi-modal distribution of particle sizes.
30. The electrode of claim 29, wherein the battery is a AA
battery.
31. The electrode of claim 29, wherein the battery is a AAA
battery.
32. The electrode of claim 29, wherein the battery is a AAAA
battery.
33. A battery, comprising: an anode; a cathode; and a separator
disposed between the anode and the cathode, wherein the anode
comprises zinc-based particles in a fluid medium, the zinc-based
particles having a multi-modal distribution of particle
morphologies.
34. The electrode of claim 33, wherein the battery is a AA
battery.
35. The electrode of claim 33, wherein the battery is a AAA
battery.
36. The electrode of claim 33, wherein the battery is a AAAA
battery.
37. A battery, comprising: an anode; a cathode; and a separator
disposed between the anode and the cathode, wherein the anode
comprises zinc-based particles in a fluid medium, the zinc-based
particles having a multi-modal distribution of particle
compositions.
38. The electrode of claim 37, wherein the battery is a AA
battery.
39. The electrode of claim 37, wherein the battery is a AAA
battery.
40. The electrode of claim 37, wherein the battery is a AAAA
battery.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S. Ser. No.
08/905,254, filed Aug. 1, 1997, and entitled "Zinc Electrode
Particle Form", and a continuation-in-part of U.S. Ser. No.
09/115,867, filed Jul. 15, 1998, and entitled "Zinc-Based Electrode
Particle Form".
BACKGROUND OF THE INVENTION
[0002] The present invention relates to improvements in
electrochemical cells, particularly cells having negative
electrodes comprising zinc-based particles, such as in alkaline
batteries.
[0003] An electrochemical cell (i.e., a galvanic cell or battery)
has the following basic components: a negative electrode (sometimes
called an anode), a positive electrode (sometimes called a
cathode), and an ion-conductive solution (sometimes called an
electrolyte) providing a path for the transfer of charged ions
between the two electrodes when they are connected through an
external load.
[0004] Some alkaline cells have anodes with zinc as an active
element, and cathodes with manganese dioxide (MnO.sub.2) as an
active element. Anodes do not have to be solid; in fact,
conventional alkaline cells have a gelled zinc anode mixture. The
mixture contains individual zinc-based particles suspended in a
thickened liquid or gel containing a gelling agent, an alkaline
electrolyte such as potassium hydroxide (KOH), and minor amounts of
other additives, such as indium or bismuth (gassing inhibitors for
reducing the undesirable tendency for hydrogen gas to build up
inside the cell). The zinc-based particles are characterized by a
specific size range, commonly indicated by the standard mesh size
through which the particles pass. Typically, average anode particle
sizes fall in the range of about -50/+200 mesh, indicating
particles that pass through a 50 mesh screen and do not pass
through a 200 mesh screen (the larger the screen number, the
smaller the aperture size of the screen).
[0005] Common gelling agents used in anodes include
carboxymethycellulose, polyacrylic acid (e.g., Carbopol 940.TM.
from B. F. Goodrich in Brecksville, Ohio, or POLYGEL-4P.TM. from 3V
in Bergamo, Italy), sodium polyacrylate (e.g., CL-15.TM. from
Allied Colloids in Yorkshire, England), and salts. Non-limiting
examples of gassing inhibitors include inorganic additives such as
indium, bismuth, tin and lead and organic inhibitors such as
phosphate esters and anionic and non-ionic surfactants. See U.S.
Pat. Nos. 5,283,139, 5,168,018, 4,939,048, 4,500,614, 3,963,520,
4,963,447, 4,455,358, and 4,195,120 for examples of various anode
mixtures.
[0006] The gel anode is typically separated from the cathode by a
separator, such as a thin layer of non-woven material or paper,
that prohibits electronic conduction between the anode and the
cathode but allows ions to pass between them.
[0007] Alkaline Zn/MnO.sub.2 cells have been commercially available
for over 30 years, during which time their performance
characteristics have been incrementally optimized by the industry
in an attempt to provide the "longest lasting" battery (i.e., one
with the greatest overall capacity, measured in ampere-hours)
within the volume constraints imposed by the international size
standards (e.g., AAAA, AAA, AA, C, D cylindrical and 9 volt
prismatic sizes). The volume within such standard cells, into which
the active materials are packed, is more or less fixed. The amount
of energy available from any given cell size (which is a function
of the total amount of the active elements in the cell) has a
theoretical upper limit which is defined by the internal cell
volume and the practical densities of the active components that
are employed.
[0008] In addition to trying to produce the "longest-lasting"
battery, battery manufacturers are also trying to increase the
maximum instantaneous rate of electrical current that can be
generated from a battery under a given load without the battery
voltage dropping below a minimum value. The motivation for
increasing this "maximum discharge rate" capability includes the
ongoing development of electronic products, such as cellular
phones, which require high currents from small packages. Some of
these new devices automatically test the voltage levels of their
batteries, and therefore may cause the premature disposal of
batteries which have remaining overall capacity, if the sensed
voltage dips excessively during a period of high current draw.
[0009] When a high current is being drawn from a battery, the
voltage of the battery may drop due to zinc-based particle surface
"passivation" or anode polarization which can indicate a localized
lack of sufficient hydroxide ions to sustain the chemical reaction
of the cell. It is believed that a certain amount of porosity is
necessary for the free supply of OH.sup.- ions coming from the
electrolyte and the free disposal of Zn(OH).sub.4.sup.-,
Zn(OH).sub.2 or ZnO reaction products back into the electrolyte. If
the zinc-based particles are too densely crowded, or if their
surfaces are inaccessible due to accumulation of reaction products,
the reaction cannot keep up with the rate of current draw.
Batteries with densely packed zinc-based particles in their anodes
may perform acceptably with very stable voltage levels while
supplying low continuous currents, but drop to very low,
unacceptable voltages when a high current is drawn due to zinc
crowding (sometimes referred to as "choking" or being "electrolyte
starved").
[0010] In addition, too little electrolyte can starve the overall
chemical reaction of the cell or cause the battery to "dry out", as
water from the electrolyte is continuously consumed during
discharge. The net reaction inside the cell is:
Zn+2MnO.sub.2+H.sub.2O.fwdarw.ZnO+2MnOOH.
[0011] Thus, competing with the desire to pack as much zinc-based
material as possible into the available anode volume to increase
overall capacity for "long life" is the need to provide a
sufficient amount of electrolyte to avoid "choking" during periods
of high discharge rate.
SUMMARY OF THE INVENTION
[0012] The invention is based upon the discovery that including
very small zinc-based particles (i.e., fines or dust) among the
zinc-based particles of the anode of an alkaline electrochemical
cell can provide good cell performance characteristics, especially
those characteristics related to high discharge rate performance.
The combination of smaller zinc-based particles and larger
zinc-based particles can result in a multi-modal, such as a
bi-modal distribution, of zinc-based particles in terms of particle
size, particle morphology and/or particle composition.
[0013] As used herein, "fines" are particles small enough to pass
through a standard 200 mesh screen in a normal sieving operation
(i.e., with the sieve shaken by hand). "Dust" consists of particles
small enough to pass through a standard 325 mesh screen in a normal
sieving operation.
[0014] A zinc-based particle can be formed of, for example, zinc or
a zinc alloy. Materials that can be alloyed with zinc to provide
zinc-based particles include gassing inhibitors, such as indium
and/or bismuth. Generally, a zinc-based particle formed of a zinc
alloy will be mostly zinc. A zinc-based particle can be spun or air
blown.
[0015] The zinc-based particles can include a plating material,
such as indium and/or bismuth.
[0016] As used herein, a "zinc-based particle" refers to a singular
or primary particle of zinc-based material rather than an
agglomeration of more than one particle of zinc-based material. An
anode can contain primary particles of zinc-based material and/or
agglomerates of primary particles of zinc-based material.
[0017] According to one aspect of the invention, a negative
electrode for an electrochemical cell contains zinc-based particles
suspended in a fluid medium, with at least about 1 percent, by
weight, of the zinc-based particles being of -200 mesh size or
smaller. Even higher weight percentages (e.g., 6 percent, 10
percent, 25 percent, 50 percent, 80 percent, 90 percent or 100
percent) of zinc-based fines can be preferable.
[0018] In some embodiments, the zinc-based particles also include
at least about 25 percent, by weight, (e.g., at least about 50
percent, 75 percent, 90 percent or 99 percent) of particles between
about 20 and 200 mesh size or larger.
[0019] In certain embodiments, it is preferable that a substantial
percentage (e.g., 10, 45, 80, 90 or 100 weight percent) of the
zinc-based particles are dust (of -325 mesh size or smaller, as
defined above). However, in other embodiments, less than 10 weight
percent of the zinc-based particles may be of -325 mesh size or
smaller (e.g., about 1 weight percent to about 10 weight percent,
such as about 6 weight percent).
[0020] The negative electrode may include a surfactant. The fluid
medium preferably includes both an electrolyte and a thickening
agent.
[0021] The zinc-based particles can be spherical or nonspherical in
shape. Nonspherical particles can be a circular in shape (having a
length along a major axis at least two times a length along a minor
axis) or of flake form (having a thickness of no more than about 20
percent of their maximum linear dimension).
[0022] According to another aspect, a negative electrode mixture
for an electrochemical cell contains zinc-based particles suspended
in a fluid medium with the zinc-based particles comprising less
than about 68 percent (e.g., less than about 64 percent, 60
percent, 55 percent or even 45 percent) of the electrode mixture,
by weight. The zinc-based particles include a sufficient proportion
of particles of about -200 mesh size or smaller to provide an
electrode resistivity of less than about 0.2 ohm-centimeters.
Preferably, at least about 1 percent, by weight, of the zinc-based
particles are of -200 mesh size (more preferably, of -325 mesh
size) or smaller.
[0023] According to another aspect, the invention features a
primary electrochemical cell having a cathode, an anode with
zinc-based particles suspended in a fluid medium, at least 1
percent, by weight, of the zinc-based particles being of -200 mesh
size or smaller, and a separator between the cathode and the
anode.
[0024] The anode of the electrochemical cell may include other
features, such as zinc-based particle sizes, mentioned above.
[0025] According to a further aspect, a negative electrode slurry
for an electrochemical cell contains zinc-based particles suspended
in a fluid medium including an electrolyte. The slurry has a
resistivity of less than about 0.2 ohm-centimeters and the
zinc-based particles comprise less than about 68 percent, by
weight, of the slurry. The slurry can contain less than about 64
percent, 60 percent, 55 percent or even 45 percent, by weight,
zinc-based particles.
[0026] According to another aspect of the invention, a method of
generating an electric current includes accumulating ions on the
surface of zinc-based particles suspended in a fluid medium
containing an electrolyte, at least about 1 percent, by weight, of
the zinc-based particles being of -200 mesh size or smaller.
[0027] In one aspect, the invention features a composition that
includes a fluid medium and zinc-based particles contained in the
fluid medium. The zinc-based particles have an average particle
size of less than about 175 microns.
[0028] In another aspect, the invention features a battery that
includes an anode, a cathode, and a separator disposed between the
anode and the cathode. The anode includes a fluid medium and
zinc-based particles contained in the fluid medium. The zinc-based
particles have an average particle size of less than about 175
microns.
[0029] In a further aspect, the invention features a battery that
includes an anode, a cathode, and a separator disposed between the
anode and the cathode. The anode includes an active material in the
form of zinc-based particles. All the zinc-based particles are of
-200 mesh size or smaller.
[0030] In another aspect, the invention features an electrode
including zinc-based particles in a fluid medium. The zinc-based
particles have a multi-modal, such as a bi-modal, distribution of
particle sizes.
[0031] In another aspect, the invention features an electrode
including zinc-based particles in a fluid medium. The zinc-based
particles have a multi-modal, such as a bi-modal, distribution of
particle morphologies.
[0032] In another aspect, the invention features an electrode
including zinc-based particles in a fluid medium. The zinc-based
particles have a multi-modal, such as a bi-modal, distribution of
particle compositions.
[0033] In another aspect, the invention features a battery
including a cathode, an anode and a separator disposed between the
cathode and the anode. The anode contains zinc-based particles in a
fluid medium. The zinc-based particles can have a multi-modal, such
as a bi-modal, distribution of particles sizes, particle
morphologies and/or particle compositions. The battery can be a
standard size battery, such as a AA battery, a AAA battery, a AAAA
battery, a C battery, a D cylindrical battery or a 9 volt prismatic
size battery.
[0034] Cells constructed according to the invention have displayed
high tolerance for mechanical shock. They have also demonstrated
high running voltages at high rate drains, low internal impedances
under load, and good overall performance under various pulsed rate
discharge loads.
[0035] In addition, the high proportion of zinc-based fines or dust
can enable the total amount of zinc to be reduced (i.e., the cell
can have a lower zinc "loading") while maintaining overall capacity
on practical drains and without the typical loss in mechanical
stability normally associated with a reduction in zinc loading.
This is believed to be due, in part, to a high efficiency of zinc
usage and good particle-to-particle connectivity.
[0036] By reducing the total zinc loading needed to achieve a given
performance level, water and alkaline electrolyte can be added
which may reduce the risk of anode choking.
[0037] In some embodiments, it is desirable for the anode to have a
relatively low resistivity. In these embodiments, the anode can
have a resistivity of about 0.2 ohm-centimeters or less.
[0038] Other advantages and features will become apparent from the
following description and claims.
BRIEF DESCRIPTION OF THE DRAWING
[0039] FIG. 1 is a cross sectional view through an alkaline
cell.
[0040] FIG. 2 illustrates zinc-based-particle size
distributions.
[0041] FIG. 3 shows a circular particles.
[0042] FIG. 4 shows flake particles.
[0043] FIG. 5 shows the effect of anode solids loading on anode
resistivity using different zinc-based particle size
distributions.
[0044] FIGS. 6A and 6B show battery voltage traces taken during
pulse impedance tests of the cells of Example 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0045] Referring to FIG. 1, cylindrical cell 10 has a casing 12
closed at its open end by seal member 14 being crimped in place.
The cathode 16 is an annular structure with an outer surface in
electrical contact with the inner surface of the casing, which
serves as the positive external terminal of the cell. Cathode 16 is
formed by stacking multiple cathode pellets 16a, as shown. Each
cathode pellet is made from a mixture of MnO.sub.2, a conductive
agent, and electrolyte. Alternatively, the cathode may be formed
directly in the casing by pressure compaction, without stacking
individual pellets.
[0046] A separator 18 lines the inner surfaces of annular cathode
16 and electronically separates the cathode from the anode 20.
Separator 18 can be any of a number of well known separator
materials, such as cellulose or rayon.
[0047] Anode 20 is of gel form, having a desired amount of
zinc-based material, in particulate form, suspended in a mixture of
alkaline electrolyte and a gelling agent. Gassing inhibitors, such
as those described above, are preferably added to the anode gel or
as a coating on the zinc-based particles. Generally, the zinc-based
particles and alkaline electrolyte together make up about 96%, and
more preferably about 98%, by weight, of the anode.
[0048] Anode collector 22 passes through seal member 14 and extends
into anode 20. The upper end of anode collector 22 electrically
contacts a negative end cap 24, which serves as the negative
external terminal of the cell. Upon assembly, additional liquid
alkaline electrolyte is added to the cell and becomes distributed
throughout the anode, cathode, and separator.
[0049] Anode 20 contains zinc-based particles having a multi-modal
distribution, such as a bi-modal distribution, of zinc-based
particles in terms of particle size, particle morphology and/or
particle composition. A multi-modal distribution refers to a
distribution having at least two distinct peaks. Thus, a plot of
relative percent of particles as a function of particle size for
zinc-based particles having a multi-modal distribution of particle
sizes would have at least two distinct peaks. For example, FIG. 2,
which is described below, shows several bi-modal particle size
distributions. Similarly, a plot of relative percent of particles
as a function of particle morphology for zinc-based particles
having a multi-modal distribution of particle morphologies would
have at least two distinct peaks, and a plot of relative percent of
particles as a function of particle composition for zinc-based
particles having a multi-modal distribution of particle
compositions would have at least two distinct peaks.
[0050] For zinc-based particles having a multi-modal distribution
of particle sizes, each mode has a different average particle size.
For example, in a bi-modal distribution of particle sizes, one mode
can have a relatively small average particle size (fines or dust),
while the other mode can have a larger average particle size.
[0051] For zinc-based particles having a multi-modal distribution
of particle sizes, one mode can have an average particle size of
from about 15 microns to about 120 microns. For example, this mode
can have an average particle size of from about 30 microns to about
40 microns, or this mode can have an average particle size of from
about 95 microns to about 105 microns.
[0052] For zinc-based particles in a mode having an average
particle size of from about 30 microns to about 40 microns, at
least about 90 volume percent of the zinc-based particles can have
a particle size of from about 5 microns to about 100 microns, and
at least about 75 volume percent of the zinc-based particles can
have a particle size of from about 15 microns to about 75 microns.
The zinc-based particles in this mode can have a Scott density of
about 53 grams per inch as measured by ASTM B-417.
[0053] For zinc-based particles in a mode having an average
particle size of from about 95 microns to about 105 microns, at
least about 90 volume percent of the zinc-based particles can have
a particle size of from about 15 microns to about 200 microns, and
at least about 75 volume percent of the zinc-based particles can
have a particle size of from about 25 microns to about 140 microns.
The zinc-based particles in this mode can have a Scott density of
about 53 grams per cubic inch as measured by ASTM B-417.
[0054] Another mode of the zinc-based particles can have an average
particle size of from about 200 microns to about 330 microns. For
example, the average particle size of this mode can be from about
290 microns to about 300 microns. For this mode, at least about 90
volume percent of the particles can have a particle size of from
about 50 microns to about 850 microns, and at least about 75 volume
percent of the particles can have a particle size of from about 100
microns to about 550 microns. For this mode, the zinc-based
particles can have a Scott density of from about 50 grams per cubic
inch to about 56 grams per cubic inch as measured by ASTM
B-417.
[0055] For zinc-based particles having a multi-modal distribution
of particle morphologies, more than one mode can be formed of
nonspherical particles, with each mode being more or less
nonspherical than other modes. Alternatively, one mode can be
formed of spherical zinc-based particles, while another mode can be
formed of nonspherical particles (e.g., flakes or a circular
particles).
[0056] For zinc-based particles having a multi-modal distribution
of particle compositions, one mode can be formed of zinc-based
particles of one composition, while another mode can be formed of
zinc-based particles of another composition. For example, one mode
can include zinc-based particles formed of zinc and a certain
amount of one or more gassing inhibitors (e.g., bismuth and/or
indium), whereas another mode can include zinc-based particles
formed of zinc and a different amount of one or more gassing
inhibitors (e.g., bismuth and/or indium).
[0057] For zinc-based particles having a multi-modal distribution
of particle compositions, one mode can include zinc-based particles
formed of zinc, about 500 parts per million (ppm) indium relative
to zinc and about 500 ppm bismuth relative zinc. Alternatively,
this mode can include zinc-based particles formed of zinc, about
350 ppm indium relative to zinc and about 150 ppm bismuth relative
zinc.
[0058] For zinc-based particles having a multi-modal distribution
of particle compositions, another mode can include zinc-based
particles formed of zinc, about 150 ppm indium relative to zinc and
about 230 ppm bismuth relative to zinc.
[0059] The zinc-based particles in anode 20 can include as little
as 1% by weight to 10% by weight of fines. Alternatively, the
zinc-based particles in anode 20 can include at least 10% by
weight, preferably at least 50% by weight, and more preferably at
least 80% by weight. In some embodiments, 100% by weight of the
zinc-based particles in anode 20 can be fines. High performance has
also been noticed, as described more fully below, when there is a
significant proportion of zinc-based particles in the form of dust
in the anode.
[0060] The average size of the zinc-based particles can be
relatively small. Preferably, the zinc-based particles have an
average size of less than about 175 microns, more preferably less
than about 150 microns, and most preferably less than about 120
microns. The manner in which the average particle size of the
zinc-based particles is determined is discussed below.
[0061] The desired distribution of particle sizes can be produced
by several processes. For instance, standard mesh sieves can be
employed to sort zinc-based particles produced by centrifugal
atomization, gas atomization, or any other known method. Once
sorted, by sieving or air classification, for instance, various
size ranges of particles can be mixed in proper proportions to
produce the desired size distribution. Alternatively, the average
size of the particles, as produced, can be controlled, along with
the distribution of particle sizes about an average, to produce a
statistical distribution having a significant proportion of fines
and dust. Once formed, the particles can be mixed with surfactants,
gassing inhibitors, gelling agents, electrolyte and other additives
by standard processes.
[0062] FIG. 2 illustrates some of the distributions of zinc-based
particles that have been tested in anode 20. The distributions are
shown as a function of effective particle diameter as measured with
the particle diameter measurement technique described below. As a
rough correspondence between mesh sizes and effective particle
diameters, it should be noted that spherical particles with a
diameter of 74 microns, for instance, will just sift through a 200
mesh screen, and spherical particles with a diameter of 44 microns
will just sift through a 325 mesh screen. This correspondence is
less accurate for particles of other shapes. Distribution 32 is of
centrifugally atomized zinc-based particles that were sifted
through a 325 mesh screen (i.e., dust), and has a peak at an
effective particle diameter of about 57 microns. Distribution 34 is
of gas atomized particles. Distributions 36 and 38 are of
centrifugally atomized particles of -20/+200 and -200 mesh size,
respectively. Distribution 40 is a combination of 50%, by weight,
of the zinc-based dust of distribution 34 and 50%, by weight, of
the particles of distribution 36.
[0063] One of the effects of including significant proportions of
very small zinc-based particles is an increase in the bulk surface
area (i.e., the aggregate surface area) of the zinc-based particles
in the anode. This is due to the inherent relationship between
particle surface area and volume: namely that, for particles of
similar shape, decreasing the particle size increases the surface
area to volume ratio of the particle. High bulk surface area for a
given particle mass is offered as a possible explanation of some of
the high performance demonstrated by batteries with zinc-based
particles in the form of fines.
[0064] Particle surface area can be further enhanced by controlling
the production or subsequent processing of the zinc-based particles
to produce particles with extended, nonspherical shapes, such as
flakes or a circular particles. A cicular shapes (see particle 42
in FIG. 3, for instance) having a length L.sub.1 along a major axis
at least two times a length L.sub.2 along a minor axis are
considered to be appropriate. Flakes, such as particle 44 in FIG.
4, have a thin cross-section and two broad, opposite sides (such as
a wafer or potato chip). Preferably, such a flake-form particle has
an average thickness between its broad sides of no more than about
20% of the maximum dimension of the particle, to have a very low
volume to surface area ratio.
[0065] One plausible theory for the mechanism that results in the
good performance characteristics of batteries with anodes having
high proportions of zinc-based dust or fines concerns
particle-to-particle connectivity. This theory is only offered as a
possible explanation of the observed results, and is not intended
to limit the scope of the invention. In effect, it is believed that
the additional fines form a mechanical network, particularly under
electrical load and at low zinc loadings. This theory is supported
by slurry resistivity measurements taken at various zinc loadings,
as plotted in FIG. 5. In this figure, the solid line is of an anode
mixture with zinc-based particles of -20/+200 mesh size and the
dashed line is of an anode mixture with zinc-based particles of
-200 mesh size. It is believed that improved connectivity between
large particles, fines and dust results in higher conductivity at
loadings down to 50% or less. As a result, more electrolyte may be
added to the mixture to increase zinc utilization (i.e., increase
zinc volumetric usage efficiency) while maintaining low anode
resistance. This improvement in connectivity, if the above theory
is correct, would also tend to account for the high slurry
viscosity, as well as good tolerance for mechanical shock (e.g.,
tap load voltage stability and drop voltage stability, as described
below) of anodes with high proportions of fines and dust.
[0066] Continuous Load Test
[0067] This test simulates constant discharge in medium current
draw applications, such as in some toys. A constant load (e.g., 30
ohms for a AAAA battery and 3.9 ohms for a AA battery) is applied
across the battery terminals and the battery is continuously
discharged through the load. The amount of time from the
application of the load to when the battery voltage drops to a
cut-off voltage is recorded.
[0068] Continuous Load Test
[0069] In this test power is discharged from the battery at a
constant rate of (e.g., 0.25 watts for a AAAA battery or one watt
for a AA battery), with the load automatically adjusted to account
for changing battery voltage. This test is generally considered to
be a more strenuous test than a continuous load (i.e., resistance)
test, especially toward the end of the test as the battery voltage
nears the cutoff value. The amount of time from the application of
the load to when the battery voltage drops to a cut-off voltage is
recorded.
[0070] Pulse Impedance Test
[0071] This test is a measure of the maximum dip in voltage that
occurs when a fixed load is rapidly applied to the cell, and is an
indication of the lag between voltage and current that can be
exacerbated by the use of organic corrosion inhibitors to reduce
gassing. Though of short duration, instantaneous drops in voltage
can have significant consequences, as in devices which monitor
instantaneous battery voltage and signal that the battery should be
replaced if a low voltage is measured. A 3.9 ohm load is applied to
the cell through a fast-acting relay, and the cell voltage is
monitored on an oscilloscope. The load is maintained for 400
milliseconds. The minimum voltage during the test, which occurs
upon application of the load, is measured.
[0072] High Current Pulse Test
[0073] AA Battery
[0074] This test was designed to simulate the performance of a
battery in a camera application. A controlled 1.1 amp current is
intermittently drawn from the AA battery in a series of pulses,
each of 10 seconds duration with a 50 second pause in between each
pulse. The pulse series is continued for one hour each day until
the AA battery voltage drops to a predetermined cut-off level, at
which point the total number of pulses is recorded. This test is
also performed on AA cells that have been stored for two weeks at
55.degree. C. to determine how storage at elevated temperatures
affects high discharge rate performance.
[0075] AAAA Battery
[0076] This test was designed to simulate the performance of a
flashlight. A 5.1 ohm resistance was intermittently applied to a
AAAA battery in a series of pulses. The resistance was applied for
four minutes per hour for eight hours in each day of service life
until the AAAA battery voltage drops to a predetermined cut-off
level, at which point the number of total service hours is
recorded.
[0077] Anode AC Bulk Resistivity
[0078] This test measures how well the anode performs as an
electrical conductor. A small alternating current, oscillating at
about 1000 Hz, is applied to a volume of prepared anode mixture
(with proper proportions of zinc-based particles, gelling agent,
electrolyte and additives for use in an electrochemical cell), and
the bulk resistivity of the mixture is measured.
[0079] Tap Load Voltage Instability
[0080] This test is a measure of the mechanical stability of the
anode during a physical bump or shock. It is common for the voltage
of batteries to dip under load during a bump (such as when they are
tapped against a hard surface). This test measures the magnitude of
such undesirable voltage dips. A constant 3.9 ohm load is applied
to the battery, and the battery is struck once with an automated
hammer (with a force of about 50-60 pounds, inducing an effective
peak acceleration of about 20-50 kilometers/second/second with high
attenuation) once every 60 seconds, while monitoring the battery
voltage. Generally, when the battery reaches about a 25 percent
discharge, the magnitude of the voltage dips reaches a maximum
value, decreasing as the battery continues to discharge. The
severity of the maximum voltage drop is used as a measure of cell
performance.
[0081] Particle Diameter Measurement
[0082] The data in FIG. 2 were generated by analyzing dry
zinc-based particles, in bulk. A representative amount of sample
powder to be analyzed was transferred into the funnel of a
RODOS-VIBRI.TM. Sample Dispersion unit, available from Sympatec,
which dispersed the powder into a stream of air to form an aerosol.
The aerosol of the zinc-based particles in the form of powder is
then passed through a HELOS.TM. Particle Size Analyzer, also
available from Sympatec, which measures the intensity and
distribution of light diffused through the aerosol of spinning
particles. Various optical lenses with different focal lengths are
used, in accordance with manufacturer's recommendations, with
particles of different size ranges.
[0083] For a given sample of zinc-based particles, the average
particle size is calculated using the following equation: 1
Averageparticlesize = d 4 d 3
[0084] where d represents the diameter of a given zinc-based
particle.
EXAMPLE 1
[0085] Cylindrical alkaline batteries of Type AA were built with
gel anodes having the following two compositions to test the effect
of zinc-based particles in the form of fines (the composition
values listed are in percent by weight):
1 Composition 1A 1B Zinc alloy particles 67.97 67.97 Indium acetate
(42% Indium) 0.03 0.03 Phosphate ester (6% concentration) 0.06 0.06
Polyacrylic acid 0.53 0.53 Sodium polyacrylate 0.38 0.38 Acetic
acid (2.5% concentration) 0.09 0.09 Electrolyte solution (2% ZnO,
35% KOH) 30.94 30.94 Total: 100.00 100.00 Particle sieve size
-20/+200 -200 Average particle size 335 microns 86 microns
[0086] The above compositions were prepared by first mixing the
indium acetate powder with the dry zinc alloy particles. Next, the
acetic acid and phosphate ester were applied, followed by the
polyacrylic acid and sodium polyacrylate. After blending and
crushing any lumps, the electrolyte solution was added and the
mixture was blended until uniform. The zinc alloy particles in both
1A and 1B included 150 ppm In and 200 ppm Bi.
[0087] In each of the following tests, four individual batteries
were tested.
2 Example 1 test results: 1A 1B Continuous 3.9 ohm load test Hours
to 1.0 volts 1.51 1.57 Hours to 0.9 volts 1.70 1.86 Hours to 0.8
volts 1.73 2.01 One watt continuous load test Hours to 1.0 volts
0.58 0.51 Hours to 0.9 volts 0.74 0.66 Hours to 0.8 volts 0.84 0.77
High current pulse test Pulses to 1.0 volts 174 221 Pulses to 0.9
volts 233 337 Pulses to 0.8 volts 306 421 Pulse impedance test
Actual voltage trace FIG. 6B
[0088] Note that in the pulse impedance tests the peak voltage dip
50 of 1A (FIG. 6A) is much more pronounced than the voltage dip 52
of 1B (FIG. 6B).
EXAMPLE 2
[0089] Cylindrical alkaline batteries of Type AA were built with
gel anodes having the following two compositions (the composition
values listed are in percent by weight):
3 Composition 2A 2B 2C Zinc alloy particles 69.80.sup.1 69.80.sup.2
69.80.sup.3 Indium acetate (42% Indium) 0.04 0.04 0.04 Phosphate
ester (6% concentration) 0.06 0.06 0.06 Polyacrylic acid (Carbopol
940) 0.51 0.45 0.45 Acetic acid (2.5% concentration) 1.12 1.12 1.12
Electrolyte solution (2% ZnO, 35% KOH) 28.47 28.53 28.53 Total:
100.00 100.00 100.00 .sup.1Alloy includes 150 ppm In, 200 ppm Bi;
particles sieved to -20/+200 mesh size (average particle size of
354 micron; distribution 36, FIG. 2) .sup.2Alloy includes 150 ppm
In, 200 ppm Bi; particles seived to -325 mesh size (average
particle size of 57 micron; distribution 32, FIG. 2). .sup.3An
equal mixture, by weight, of particles as in 2A and gas atomized
zinc particles alloyed with 500 ppm In and 500 ppm Bi. The gas
atomized particles had a average particle size of about 41 micron
(distribution 34, FIG. 2). The particle mixture corresponds to
distribution 40. The average particles size of the mixture was 184
microns.
[0090] For each of the following tests, at least four individual
batteries of each composition were tested. The results of the
individual batteries are averaged.
4 Example 2 test results: 2A 2B 2C High current pulse test to 1.0 V
Pulses as built 226 293 299 Pulses after storage 217 278 244 Tap
load voltage instability (max voltage drop, mV) 374 112 71
EXAMPLE 3
[0091] Cylindrical alkaline batteries of Type AA were built with
gel anodes having the following two compositions to test the effect
of zinc-based particles in the form of fines (the composition
values listed are in percent by weight):
5 Composition 3A 3B Zinc alloy particles 70.00 70.00 Indium acetate
(42% Indium) 0.03 0.03 Phosphate ester (6% concentration) 0.06 0.06
Polyacrylic acid (Carbopol 940) 0.51 0.48 Acetic acid (2%
concentration) 0.11 0.11 Electrolyte solution (2% ZnO, 35% KOH)
29.29 29.32 Total: 100.00 100.00 Average particle size 298 microns
112 microns
[0092] The above compositions were prepared by first mixing the
indium acetate powder with the dry zinc alloy particles. The
electrolyte solution was mixed with the polyacrylic acid to form a
gel. After blending and crushing any lumps, the gel was added to
the indium acetate/zinc alloy combination and the resulting mixture
was blended until uniform.
[0093] The zinc alloy in 3A included 150 ppm In and 200 ppm Bi.
[0094] 3B was a mixture of 6 weight percent gas atomized zinc alloy
particles (500 ppm In and 500 ppm Bi) of size -200 mesh or smaller,
and 94 weight percent gas atomized zinc alloy particles (300 ppm In
and 300 ppm Bi) between 150 and 200 mesh size.
[0095] In each of the following tests, four individual batteries
were tested.
6 Example 3 test results: 3A 3B Continuous 3.9 ohm load test Hours
to 1.0 volts 4.86 4.98 Hours to 0.8 volts 5.36 5.68 One watt
continuous load test Hours to 1.0 volts 0.75 0.79 Hours to 0.8
volts 1.03 1.063 High current pulse test Pulses to 1.0 volts 188.8
235 Pulses to 0.8 volts 455 458
EXAMPLE 4
[0096] Cylindrical alkaline batteries of Type AAAA were built with
gel anodes having the following two compositions to test the effect
of zinc-based particles in the form of fines (the composition
values listed are in percent by weight):
7 Composition 4A 4B Zinc alloy particles 70.00 70.00 Indium acetate
(42% Indium) 0.04 0.04 Phosphate ester (6% concentration) 0.06 0.06
Polyacrylic acid 0.51 0.51 Electrolyte solution (2% ZnO, 35% KOH)
29.39 29.39 Total: 100.00 100.00 Particle sieve size -20/+200 -200
Average particle size 335 microns 86 microns
[0097] The above compositions were prepared by first mixing the
indium acetate powder with the dry zinc alloy particles. Next,
phosphate ester was applied, followed by the polyacrylic acid.
After blending and crushing any lumps, the electrolyte solution was
added and the mixture was blended until uniform. The zinc alloy
particles in both 4A and 4B included 150 ppm In and 200 ppm Bi.
[0098] In each of the following tests, four individual batteries
were tested.
8 Example 4 test results: 4A 4B Continuous 30 ohm load test Hours
to 1.0 volts 11.9 11.9 Hours to 0.9 volts 12.7 12.7 Hours to 0.8
volts 13.7 13.8 0.25 watt continuous load test Hours to 1.0 volts
0.72 0.85 Hours to 0.9 volts 0.78 0.89 Hours to 0.8 volts 0.79 0.90
High current pulse test (hours) Pulses to 1.0 volts 0.97 1.43
Pulses to 0.9 volts 1.66 1.90
[0099] Very small zinc-based particles, such as fines and dust,
tend to be more unstable in oxygen-rich environments than larger
particles and must therefore be processed with due care. Such
issues, together with physical bulk handling issues of powders and
fines, may need to be considered when determining the absolute
minimum practical particle size for production anodes.
[0100] Other embodiments are also within the scope of the following
claims.
* * * * *