U.S. patent application number 10/944094 was filed with the patent office on 2005-03-03 for electrode.
This patent application is currently assigned to DELPHI TECHNOLOGIES, INC.. Invention is credited to Ayres, John Lewis, Chen, Rongrong.
Application Number | 20050048372 10/944094 |
Document ID | / |
Family ID | 27660332 |
Filed Date | 2005-03-03 |
United States Patent
Application |
20050048372 |
Kind Code |
A1 |
Chen, Rongrong ; et
al. |
March 3, 2005 |
Electrode
Abstract
An electrode comprising a noble-metal free grid comprising lead,
wherein the grid has an essentially PbO free PbO.sub.2 coating
covering all, or essentially all of the surface of the grid. Also
described is a method of forming an electrode, comprising applying
an essentially PbO free PbO.sub.2 coating to a noble-metal free
grid comprising lead, wherein the coating covers all, or
essentially all of the surface of the grid.
Inventors: |
Chen, Rongrong; (Fishers,
IN) ; Ayres, John Lewis; (Cicero, IN) |
Correspondence
Address: |
Jimmy L. Funke
DELPHI TECHNOLOGIES, INC.
Legal Staff, Mail Code: 480-410-202
P.O. Box 5052
Troy
MI
48007-5052
US
|
Assignee: |
DELPHI TECHNOLOGIES, INC.
|
Family ID: |
27660332 |
Appl. No.: |
10/944094 |
Filed: |
September 17, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10944094 |
Sep 17, 2004 |
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10080296 |
Feb 21, 2002 |
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6803151 |
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Current U.S.
Class: |
429/245 |
Current CPC
Class: |
Y02E 60/10 20130101;
Y10T 29/49115 20150115; H01M 4/685 20130101; H01M 4/73 20130101;
H01M 2004/021 20130101 |
Class at
Publication: |
429/245 |
International
Class: |
H01M 004/66 |
Claims
1. An electrode comprising: a noble-metal free grid comprising
lead, calcium, tin, or a combination comprising at least one of the
foregoing; wherein said grid has an essentially PbO free PbO.sub.2
coating essentially covering the surface of said grid; wherein the
surface area of said essentially PbO free PbO.sub.2 coating exceeds
the geometric surface area of said grid by more than about 60 area
percent; and wherein said essentially PbO free PbO.sub.2 coating
has an effective surface area greater than the geometric surface
area of said grid.
2. The electrode of claim 1, wherein said noble metal free grid
further comprises calcium, tin, or a combination comprising at
least one of the foregoing.
3. The electrode of claim 1, wherein said essentially PbO free
PbO.sub.2 coating has an effective surface area greater than the
geometric surface area of said grid.
4. A method of forming an electrode, comprising: applying an
essentially PbO free PbO.sub.2 coating to the surface of a
noble-metal free grid comprising lead, calcium, tin, or a
combination comprising at least one of the foregoing; wherein said
coating essentially covers the surface of said grid; wherein the
surface area of said essentially PbO free PbO.sub.2 coating exceeds
the geometric surface area of said grid by more than about 60 area
percent; and wherein said essentially PbO free PbO.sub.2 coating
has a density greater than about 8.5 grams per cubic
centimeter.
5. The method of claim 4, wherein said noble metal free grid
further comprises calcium, tin, or a combination comprising at
least one of the foregoing.
6. The method of claim 4, wherein said essentially PbO free
PbO.sub.2 coating has a density greater than about 8.5 grams per
cubic centimeter.
7. A method of forming an electrode, comprising: applying an
essentially PbO free PbO.sub.2 coating onto the surface of a
noble-metal free grid comprising lead, tin and calcium, wherein
said coating has a thickness not less than 5 microns and not more
than 500 microns, and wherein said coating covers all, or
essentially all of the surface of said grid to produce a coated
grid; applying a paste comprising lead and lead oxide to the
surface of said coated grid to produce a pasted grid; contacting
said pasted grid with steam for at least one hour to produce a
steamed grid; curing said steamed grid at about 50 percent humidity
and about 55.degree. C. for at least about 24 hours to produce a
cured grid; followed by contacting said grid with aqueous sulfuric
acid prior to passing an external electric current of sufficient
voltage and amperage through said cured grid for a sufficient
period of time to convert at least a portion of said applied paste
into lead dioxide.
Description
BACKGROUND OF THE INVENTION
[0001] Electrochemical storage batteries, and in particular, lead
sulfuric acid storage batteries are ubiquitous in automotive
applications. These batteries have electrochemical cells developing
about 2.15 Volts each. A generic lead acid battery cell has a
positive electrode, a negative electrode, and aqueous sulfuric acid
as part of the electrolyte. The electrodes are held in parallel and
electrically isolated by a porous separator to allow free movement
of charged ions. Generally, six of these cells are connected in
series to produce the 12 Volts common in automobile systems.
[0002] Lead acid battery cells are quite unique because the
electrolyte actively participates in the energy storage and release
process, as represented schematically in Equations 1, 2, 3, and 4
below:
1 1 Equation 1 Electrolyte H 2 SO 4 H + + HSO 4 - Equation 2
Negative Electrode Pb ( metal ) + HSO 4 - Discharge Charge PbSO 4 +
H + + 2 e - Equation 3 Positive Electrode PbO 2 + 3 H + + HSO 4 - +
2 e - Discharge Charge PbSO 4 + 2 H 2 O Equation 4 Total Reaction
Pb ( metal ) + PbO 2 + 2 H 2 SO 4 Discharge Charge 2 PbSO 4 + 2 H 2
O
[0003] Within the electrochemical cell, lead metal (Pb) supplied by
the negative electrode reacts with the ionized sulfuric acid
electrolyte to form various lead sulfates, generally represented
herein (Equation 2) as PbSO.sub.4. Charging of the battery cell via
an external electrical current converts these sulfates into the
positive active mass (hereinafter PAM), including electrically
conductive lead dioxide (PbO.sub.2 of Equation 3). In particular,
charging of the cell converts the PbSO.sub.4 into PAM, discharge
releases the stored electrical potential when the PAM is converted
back into PbSO.sub.4.
[0004] It is important to battery performance that the PAM be in
physical and electrical contact with the positive electrode.
Accordingly, the PAM must be supported by, adhered and/or attached
to, and in electrical communication with the positive electrode for
the battery to function properly. Separation of the PAM from the
positive electrode results in poor battery performance and
ultimately in battery failure, which is defined herein as a battery
no longer suitable for its intended purpose. Battery performance is
affected by the materials from which the positive electrode is
formed, the physical configuration of the positive electrode, and
the method by which a "green" metal grid (i.e., a bare metal grid
or core) is converted into the positive electrode.
[0005] Green battery grids are typically lead alloys formed into a
grid structure by a variety of methods. Historically, the processes
by which green grids are made (i.e., transformed) into positive
grid electrodes have a number of common steps including: pasting,
steaming, curing, pickling and/or forming.
[0006] In pasting, a paste including water, sulfuric acid, lead and
lead oxides is applied to the grid surface. The pasted grid may
then be steamed (i.e., 100.degree. C. and 100% humidity) to
facilitate crystal growth within the paste. The grid is then cured
at controlled temperature and humidity conditions to "set" the
paste, wherein the paste is chemically transformed into sulfates,
hydroxides, carbonates, and other lead compounds through a series
of complex hydration reactions requiring the presence of water.
These reactions take place within the paste itself, and between the
paste and the grid metal. Importantly, curing produces a "corrosion
layer" at the interface between the grid and the paste, which
provides physical and electrical communication between the PAM and
the positive grid electrode, as well as protection of the grid from
attack by the electrolyte.
[0007] Once cured, the grids are assembled into a battery package
and charging electrolyte added. By allowing the battery package to
stand for a period of time, the grids are "pickled". An external
electric current is then passed through the cells in the forming
step, wherein a majority of the paste is converted into PAM. The
charging electrolyte is then removed and the battery is filled with
shipping electrolyte to render the battery ready for use.
[0008] Phenomena that have a negative effect on battery performance
include fracture lines that form due to stress introduced into the
PAM layer as it accumulates on the positive electrode during
charging. Also, when the lead in the positive electrode grid reacts
with water as shown in Equation 5 below:
Pb.sub.(metal)+H.sub.2O.fwdarw.PbO+2H.sup.++2e.sup.- Equation 5
[0009] di-electric (i.e., non-conductive) lead oxide (PbO) is
formed on the surface of the grid, which renders the affected
portion non-conductive, and impacts support of the PAM layer. The
metal grid can also react with the sulfuric acid electrolyte to
form pits through pores, cracks, or holes in the corrosion layer,
and from non-uniformities in the chemical composition and
microstructure of the layer. Pits destroy the interface between the
grid and the PAM, break electrical communication, and destroy
physical contact (i.e., support) between the positive electrode
grid and the PAM layer. Accordingly, the afore mentioned phenomena,
either alone or in combination, result in decreased battery
performance (i.e., the cell losing its capacity to transfer and
store electrical energy), which eventually leads to battery
failure. While these phenomena are significant at room temperature,
they become even more significant at higher operational
temperatures.
[0010] The rates at which the afore mentioned chemical processes
proceed is proportional to temperature. The higher the temperature,
the faster the reaction rate (i.e., the higher the temperature, the
more PAM that forms, the more PbO that forms, and the more pitting
that takes place). Positive grid corrosion becomes particularly
significant under "high temperature" conditions (defined herein as
above 50.degree. C.), which have become common in automotive
applications as "under hood temperatures" rise due to automotive
design trends and space limitations.
[0011] Accordingly, it is desirable to reduce or substantially
eliminate high temperature effects on positive battery electrodes
of lead acid batteries. In particular, to provide a longer
useful-lifetime of the battery, preferably utilizing materials that
provide an economic incentive in doing so.
SUMMARY OF THE INVENTION
[0012] Provided herein is an electrode including or having a
noble-metal free grid containing lead, wherein the grid has an
essentially PbO free PbO.sub.2 coating covering all, or essentially
all of the surface of the grid. Also disclosed is a method of
forming an electrode that includes applying an essentially PbO free
PbO.sub.2 coating to the surface of a noble-metal free grid
containing lead, wherein the coating covers all, or essentially all
of the surface of the grid.
[0013] Furthermore a method of forming an electrode is disclosed
including electrolytically depositing an essentially PbO free
PbO.sub.2 coating onto the surface of a noble-metal free grid
containing lead, tin and calcium, wherein the essentially PbO free
PbO.sub.2 coating has a thickness not less than 5 microns and not
more than 500 microns, and wherein the essentially PbO free
PbO.sub.2 coating covers all, or essentially all of the surface of
the grid; applying a paste having lead and lead oxide to the
surface of the coated grid to produce a pasted grid; optionally
contacting the pasted grid with steam for at least about one hour
to produce a steamed grid; curing the steamed grid at about 50
percent humidity and about 55.degree. C. for at least 24 hours to
produce a cured grid; followed by contacting the grid with aqueous
sulfuric acid prior to passing an external electric current of
sufficient voltage and amperage through the cured grid for a
sufficient period of time to convert at least a portion of the
applied paste into lead dioxide.
[0014] Also disclosed herein is a battery having a noble-metal free
grid containing lead, wherein the grid has an essentially PbO free
PbO.sub.2 coating covering all, or essentially all of the surface
of the grid. A method of making a battery is also disclosed
including applying an essentially PbO free PbO.sub.2 coating to the
surface of a noble-metal free grid containing lead, wherein the
coating covers all, or essentially all of the surface of the
grid.
[0015] In addition, disclosed herein is a method of making a
battery including electrolytically depositing an essentially PbO
free PbO.sub.2 coating onto the surface of a noble-metal free grid
containing lead, tin and calcium, wherein the essentially PbO free
PbO.sub.2 coating has a thickness not less than 5 microns and not
more than 500 microns, and wherein the essentially PbO free
PbO.sub.2 coating covers all, or essentially all of the surface of
said grid; then applying a paste containing lead and lead oxide to
the surface of the coated grid to produce a pasted grid; optionally
contacting the pasted grid with steam for at least about one hour
to produce a steamed grid; and then curing the steamed grid at
about 50 percent humidity and about 55.degree. C. for at least
about 24 hours to produce a cured grid; followed by contacting the
cured grid with aqueous sulfuric acid prior to passing an external
electric current of sufficient voltage and amperage through the
cured grid for a sufficient period of time to convert at least a
portion of the applied paste into lead dioxide.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The improved electrode will now be described, by way of
example, with reference to the accompanying drawings, which are
meant to be exemplary, not limiting, and wherein like elements are
numbered alike in several figures.
[0017] FIG. 1 is an expanded view of a lead acid battery cell;
[0018] FIG. 2 is an expanded view of a lead acid battery using the
cell of FIG. 1;
[0019] FIG. 3 is a cross sectional view of a Comparative Example
battery electrode;
[0020] FIG. 4 is a cross sectional view of an exemplary embodiment
of a coated battery electrode;
[0021] FIG. 5 is a metallography image taken by scanning electron
microscopy at 100.times. magnification of the exemplary embodiment
of Example 2;
[0022] FIG. 6 is a metallography image of FIG. 5 at 500.times.
magnification;
[0023] FIG. 7 is a graph illustrating the open circuit potential of
Example 2;
[0024] FIG. 8 is a graph illustrating the cycling voltametry of
Example 2 at 75.degree. C.;
[0025] FIG. 9 is a graph illustrating the cycling voltametry of
Comparative Example 1 at 75.degree. C.;
[0026] FIG. 10 is a metallography image of a cross section of the
grid of Example 2 after 432 cycles;
[0027] FIG. 11 is a metallography image of a cross section of the
grid of Comparative Example 1 after 432 cycles;
[0028] FIG. 12 is a metallography image of a cross section of the
exemplary embodiment of Example 2 at 80.times. magnification taken
by scanning electron microscopy;
[0029] FIG. 13 is a metallography image taken by scanning electron
microscopy of section A of FIG. 12 at 100.times. magnification;
and
[0030] FIG. 14 represents the X-ray diffraction analysis of the
PbO.sub.2 coating of Example 2.
DETAILED DESCRIPTION OF THE INVENTION
[0031] It has been discovered that a positive grid electrode having
improved high temperature performance can be obtained by providing
a substantially continuous, non-porous coating or layer of
essentially PbO free PbO.sub.2 directly onto the surface of the
grid. Preferably, the essentially PbO free PbO.sub.2 coating has a
density and is non-porous so as to mitigate detrimental effects to
battery performance. Also, the grid is preferably coated prior to
pasting, steaming, curing, pickling, and/or forming by a controlled
process that results in an electrically conductive surface that
provides seed crystals that improve adhesion by actually
facilitating PAM formation directly onto the grid. Thus, formation
of an essentially PbO free layer of PbO.sub.2 obtains beneficial
mechanical and physiochemical properties consistent with high
temperature performance.
[0032] FIG. 1 depicts a generic lead acid battery cell 2, including
a positive grid electrode 4, a negative grid electrode 6, and an
electrolyte of aqueous sulfuric acid 8. The plates are held in
parallel and electrically isolated by a porous separator 10 to
allow free movement of charged ions. The positive active mass 12 is
adhered to the surface of the positive grid electrode 4
(hereinafter grid 4). FIG. 2 depicts a lead acid battery 3 having a
plurality of cells as shown in FIG. 1.
[0033] FIG. 3 depicts a cross section of a positive grid electrode
4 produced by the above-described historical process, wherein a
corrosion layer 14 covers grid 4 at interface 16, and adhered to
corrosion layer 14 is a layer of PAM 12. Also present in FIG. 3 are
a fracture line 24, PbO deposit 22, pores, cracks, and/or holes 18
in corrosion layer 14, pits 20, and interface 16.
[0034] An historical process of producing the electrode depicted in
FIG. 3 would include pasting, steaming, curing, pickling and
forming as described above, specifically: pure lead would be
converted into a 70-80% oxidized lead powder (lead oxide or leady
oxide coating a metallic lead center) and mixed with water and
H.sub.2SO.sub.4 under constant stirring at an elevated temperature
to form a lead lead-oxide paste. Analysis of the paste would show a
mixture of lead, lead oxide, lead sulfate, and basic lead sulfates
such as PbOPbSO.sub.4 (monobasic lead sulfate), 3PbOPbSO.sub.4
(tribasic lead sulfate), and 4PbOPbSO.sub.4 (tetrabasic lead
sulfate). The paste would then be applied to a noble metal free
expanded metal grids containing 98.4% lead, 0.08% calcium, and 1.5%
tin (Pb.sub.98.4--Ca.sub.0.08--Sn.sub.1.5). The pasted grids would
then be steamed for four hours at 100.degree. C. and 100% humidity.
After being steamed, the grids would be cured for 4 days at 50%
humidity and 55.degree. C. The cured (set) grids then assembled
into a battery and forming acid (aqueous sulfuric acid specific
gravity (s.g.) of 1.190) added. The battery would be aged about 1
hour to pickle the grids prior to a three step forming process.
Step one including application of a forming current between 20 and
25 amps at 14 volts to reach 100% of the theoretical capacity of
the battery. Step two involves allowing the same battery to cool
and rest for about 3 hours. Finally, a second forming current
between about 10 and 22 amps would be applied in an amount equal to
between 75% and 100% of the theoretical capacity of the battery.
Once fully formed, the forming acid would be removed and the
battery filled with shipping acid (aqueous sulfuric acid, specific
gravity 1.28).
[0035] Referring now to FIG. 4, an exemplary embodiment as
described herein of a coated electrode 30 is illustrated by way of
a cross section having a suitable noble metal free positive grid
electrode 4 with an essentially continuous PbO free coating of
PbO.sub.2 26, to which the PAM 12 is adhered.
[0036] A suitable electrode grid has high electrical conductivity,
mechanical strength sufficient to support the PAM, resistance to
corrosion in sulfuric acid, and acceptable processability in
formation of the grid. It has been discovered that grid composition
and grid formation, both individually and in combination, affect
the suitability of a grid. Specifically, while the properties of
lead render it unacceptable because in short, pure lead grids
simply fall apart during use, alloys of lead can be selected to
impart desired properties lacking in pure lead to produce suitable
grids.
[0037] Alloying metals include antimony (Sb), tin (Sn), silver
(Ag), gold (Au), and calcium (Ca). Antimony alloys have been found
to hydrolyze water during charging of the battery. Noble metal
alloys (i.e., silver, gold and the like) may improve grid
conductivity and corrosion resistance, however, noble metals are
expensive, result in poor PAM adhesion, and can cause severe self
discharge when present in the electrolyte in small amounts (i.e.,
>0.05 mg/l or more). Accordingly, the preferred grid material
for use herein does not contain antimony and is noble metal free;
defined herein as essentially free of noble metals in that while
noble metals may naturally occur in trace amounts within the metal
alloy, they are not intentionally added to the composition. Sn and
Ca are used to prevent passivation of the corrosion layer, and
impart conductivity, strength and processability into the lead
alloy without detrimental side effects to battery performance.
Thus, the preferred alloy for use herein includes lead, tin, and
calcium (Pb--Sn--Ca). Preferably, the alloy includes an upper
weight percent of lead (Pb Wt %) of about 99.5, with an upper Pb Wt
% of about 99 desired, and an upper Pb Wt % of about 98.5 more
desired. A lower Pb Wt % of about 50 can be employed, with a lower
Pb Wt % of about 90 desired, and a lower Pb Wt % of about 98.3 more
desired. Also, the alloy includes an upper weight percent of tin
(Sn Wt %) of about 5, with an upper Sn Wt % of about 3 desired, and
an upper Sn Wt % of about 2 more desired. A lower Sn Wt % of about
0.5 can be employed, with a lower Sn Wt % of about 1 desired, and a
lower Sn Wt % of about 1.4 more desired. In addition, the alloy
includes an upper weight percent of calcium (Ca Wt %) of about 1,
with an upper Ca Wt % of about 0.5 desired, and an upper Ca Wt % of
about 0.1 more desired. A lower Ca Wt % of about 0.01 can be
employed, with a lower Ca Wt % of about 0.05 desired, and a lower
Ca Wt % of about 0.07 more desired. The most preferred alloy
composition includes 98.5 wt % Pb, 1.5 Wt % Sn, and 0.08 Wt % Ca
(Pb.sub.98.5--Sn.sub.1.5--Ca.sub.0.08).
[0038] Various processes may be used to form the green grid
including, for example, casting, punching, and expanding metal. In
casting, molten lead alloy, often containing Sb to improve
castability, is fed into molds to produce a grid without
significant mechanical fabrication. Punching uses a die to cut a
desired shape out of a lead alloy strip. After being physically
removed, the punched material is recycled. Both casting and
punching result in a relatively dense grid having strength adequate
for use in lead acid batteries (i.e., they provide support for the
PAM). However, both processes are costly, time consuming, and may
require alloys inconsistent with optimal battery performance.
[0039] The use of expanded metal techniques includes making partial
cuts in a metal strip, and then stretching (i.e., expanding) the
strip normal to the cuts to produce the desired grid shape. The
tools and machinery required are expensive, the process is
intricate, and the grids formed have strength normal to the
direction in which the expansions were made, but not along the
so-called "flow lines" that result parallel with the expansion
event. However, the advantages of expanded metal grids include no
physical removal of material, the grids are lighter, and have a
higher surface area than grids made by the other two methods.
Accordingly, expansion is the preferred method of producing the
green grid for use herein.
[0040] Once formed, the grid must be coated with PbO.sub.2.
Preferably, the PbO.sub.2 coating (item 26 of FIG. 4) is uniform in
composition being essentially PbO free, which is important because
non-conductive PbO has a detrimental effect on the conductivity of
PbO.sub.2. As such, an essentially PbO free PbO.sub.2 coating
useful herein has less than about 10 weight percent PbO, preferably
less than about 5 weight percent PbO, most preferably less than
about 1 weight percent PbO based on the total amount of PbO and
PbO.sub.2 present in the coating by weight. The purity of the
coating can be determined by various methods including X-ray
diffraction and by measuring the open circuit potential of the
coated grid. For example, an essentially PbO free PbO.sub.2 coating
measured verses Hg/Hg.sub.2SO.sub.4 in a H.sub.2SO.sub.4 (1.280
s.g.) solution at 75.degree. C., will have an open circuit
potential at least about 1.0, preferably at least about 1.1, most
preferably at least about 1.2 Volts; and an open circuit potential
at most about 1.3, preferably at most about 1.25, most preferably
at most about 1.23 Volts.
[0041] PbO.sub.2 useful herein includes alpha-PbO.sub.2 (also known
as scrutinyite), which has a theoretical density of 9.825 grams per
cubic centimeter (g/cc), and beta-PbO.sub.2 (also known as
plattnerite), which has a theoretical density of 9.4 (g/cc). It is
believed that by using these "high density" PbO.sub.2 materials,
the coating provides improved protection of the electrode grid
resulting in improved high temperature battery performance.
[0042] In one embodiment, alpha-PbO.sub.2 is preferred because of
its low reactivity and higher density as compared to
beta-PbO.sub.2. In this preferred embodiment, the PbO.sub.2 coating
includes at least about 90, preferably at least about 95, most
preferably at least about 99 weight percent alpha-PbO.sub.2, based
on the total weight of PbO.sub.2 in the layer.
[0043] In an alternate exemplary embodiment, the coating will have
a greater content of beta-PbO.sub.2 than alpha-PbO.sub.2. It is
believed the lower density of beta-PbO.sub.2 (compared to
alpha-PbO.sub.2) renders the coating more corrosion-resistant and
more conductive than alpha-PbO.sub.2. In this alternate embodiment,
the coating includes at least about 90, preferably at least about
95, most preferably at least about 99 weight percent
beta-PbO.sub.2, based on the total amount of PbO.sub.2 present in
the coating layer.
[0044] Furthermore, the PbO.sub.2 coating preferably has an
effective surface area larger than the geometric surface area of
the grid. Most preferably, the essentially PbO free PbO.sub.2
coating includes epitaxial columns of PbO.sub.2 disposed normal to
the surface of electrode grid 4 such that the PbO.sub.2 coating has
an effective surface area of at least about 10%, preferably at
least about 30%, most preferably at least about 50% in excess of
the total geometric surface area of the electrode grid. The
PbO.sub.2 coating also preferably covers all, or essentially all of
electrode grid surface, such that the PbO.sub.2 coating covers at
least about 99%, preferably at least about 99.9%, most preferably
at least about 99.99% of the grid surface, based on the total
available surface area of the electrode grid. Also, the PbO.sub.2
coating preferably has an average thickness of at least about 5,
preferably at least about 10, most preferably at least about 15
microns as measured normal to the grid surface. The PbO.sub.2
coating also has an average thickness of at most about 500 microns,
preferably at most about 100 microns, most preferably at most about
50 microns.
[0045] Preferably, the PbO.sub.2 coating 26 is uniform in
composition, and is also continuous or essentially continuous over
the covered surface of the grid. By essentially continuous, it is
meant that a cross-section perpendicular to the grid surface yields
a continuous interface layer at the boundary between the PbO.sub.2
coating, and the grid over a particular distance when viewed at a
defined magnification level (e.g., 80.times., 80 times
magnification). Accordingly, an essentially continuous coating is
defined herein as being continuous at the interface over at least
about 1 micron, preferably at least about 5 microns, most
preferably at least about 15 microns when a cross section normal to
the grid surface is viewed at 80.times. magnification. This
definition accounts for the minor inconsistencies that occur within
the coating layer, and how an essentially continuous PbO free
PbO.sub.2 layer is not flat, but is in-fact a web of interconnected
epitaxial columns.
[0046] The essentially PbO free PbO.sub.2 coating is also
preferably non-porous, and has a density that approaches that of
pure PbO.sub.2. As used herein, porosity is determined at the
grid-coating interface by quantifying the void area (area not
occupied by the coating) as a percentage of the total area of the
voids and the coating (i.e. % voids of the total area, hereinafter
% void area). Preferably, the % void area is less than about 50,
preferably less than about 30, most preferably less than about 20%
of the total coating area. Related to porosity (% void area) is the
density of the coating, which is at least about 8.5, preferably at
least about 9.0, most preferably at least about 9.3 g/cc on
average.
[0047] The coating layer may also include various amounts of
additives including metal oxides that, for example, prevent
passivation of the corrosion layer such as SnO.sub.2 and the like;
and/or that improve electrical conductivity, and/or increase the
structural integrity of the coating, such as CaO and the like.
These optional oxides are preferably present in the coating at less
than about 10, preferably less than about 5, with a concentration
of less than about 1 wt % of the total weight of the coating being
most preferred.
[0048] Methods of applying the coating to the grid include both
constant current and constant voltage electrolytic deposition, as
well as non-electrolytic deposition processes. Once the grid has
been coated, the grid may then be converted into a suitable battery
electrode by subsequent processing including the afore mentioned
pasting, steaming, curing, pickling and/or forming steps.
[0049] The following examples, which are presented in order that
those skilled in the art may better understand how to practice the
present invention. These examples are merely presented by way of
illustration only, and are not intended to limit the invention
thereto.
EXAMPLES
Example 1-Comparative Example
[0050] Comparative Example 1 is represents a historical electrode
having the PAM layer removed. For purposes of testing, a test grid
was prepared from a noble metal free expanded metal grid containing
98.4% lead, 0.08% calcium, an 1.5% tin
(Pb.sub.98.4--Ca.sub.0.08--Sn.sub.1.5) to have an apparent surface
area of 12.69 cm.sup.2. Using a Hg/Hg.sub.2SO.sub.4 reference, the
test grid was evaluated with cycling voltametry at 75.degree. C. in
aqueous H.sub.2SO.sub.4 (1.280 s.g.). The electrode potential was
scanned from about 0.9 V (discharged)to about 1.3 V (overcharged)
at 1 mV/sec for a total of 432 cycles. The test grid was then
cleaned, sectioned, and evaluated via microscopy.
Example 2--Preferred Embodiment
[0051] Example 2 represents a preferred embodiment of a coated grid
electrode as disclosed herein. The essentially continuous coating
having a uniform composition of essentially PbO free PbO.sub.2 was
electrochemically deposited (coated) onto the surface of a grid
identical to the grid used in Comparative Example 1 (i.e., an
expanded metal Pb.sub.98.4--Ca.sub.0.08--Sn.sub.1.5 grid). The
coating was applied using a constant anodic current density of 14
mA/cm.sup.2 at 25.degree. C., over a 60 minute period from a 0.1M
Pb(NO.sub.3).sub.2 solution in 5M NaOH Using a pure lead strip with
a surface area 60 cm.sup.2 as a counter electrode, and a saturated
calomel electrode as the reference electrode. FIGS. 5, 6, 10, 12
and 13 show the PbO.sub.2 coating of Example 2.
[0052] The coated grid was then subjected to the same conditions as
was Comparative Example 1. After the cycling voltametry evaluation,
the electrode was cleaned, sectioned, and evaluated via microscopy
along with Comparative Example 1.
Evaluation of Data
[0053] FIG. 5 shows the coating of Example 2 at 100.times.
magnification by scanning electron microscopy (SEM). FIG. 6 is a
portion of FIG. 5 at 500.times. magnification by SEM. Both show the
columnar crystalline structure of the PbO.sub.2 coating of the
above the grid. FIG. 7 is a graphical representation of the open
cell voltage of the coated grid of Example 2, indicative of pure
alpha-PbO.sub.2, which has a theoretical value of 1.23 Volts. FIGS.
12 and 13 show a cross section of the coated grid of Example 2 at
80.times. and 1,000.times. magnification respectively, wherein the
non-uniform coating epitaxial columnar crystalline structure of the
coating can be seen surrounding the grid. FIG. 13 shows the
interface 16 between the grid 4 and the essentially PbO free
PbO.sub.2 coating 26. Even though cracks and/or pores 18 can be
seen in the coating, the grid is essentially continuous over more
than 10 microns at 1,000.times., which is far in excess to 1 micron
at 80.times.. FIG. 14 represents X-ray diffraction analysis of the
coating, which confirms the coating is essentially PbO free
alpha-PbO.sub.2.
[0054] FIGS. 8 and 9 depict graphically the cycling voltametry
evaluation of Example 2 and Comparative Example 1 respectively. The
broad anodic current peak in the 0.95 to 1.2 V region of FIG. 9
(see #32, FIG. 9), represents localized pitting corrosion of the
historical grid of Comparative Example 1. The absence of this broad
anodic peak in the same range of FIG. 8, suggests the absence of
such pitting corrosion in the preferred embodiment of Example
2.
[0055] FIG. 10 shows a cross section of Example 2, and FIG. 11
shows a cross section of the Comparative Example 1, both after the
cycling voltametry evaluation. FIG. 10 is representative of the
coating (similar to the prior art corrosion layer) that is well
adhered to the grid wire. The corrosion layer of Comparative
Example 2 shown in FIG. 11 however, clearly shows cracks, pits
(represented by dark circles) and consumption of the grid metal
wherein separation has occurred at the grid/corrosion layer
interface (see FIG. 11, No. 28). Comparison of the preferred
embodiment of Example 2 shown in FIG. 10 to Comparative Example 1
shown in FIG. 11 clearly and accurately depicts the improvement in
high temperature operation of the present invention over that of
historical Comparative Example 1.
[0056] While preferred embodiments have been shown and described,
various modifications and substitutions may be made thereto without
departing from the spirit and scope of the invention. Accordingly,
it is to be understood that the apparatus and method have been
described by way of illustration only, and such illustrations and
embodiments as have been disclosed herein are not to be construed
as limiting to the claims.
* * * * *