Electrochemical and Solid-State Letters, 4 3 A23-A26 2001 A23

1099-0062/2001/43/A23/4/$7.00 The Electrochemical Society, Inc.

Ceria-Supported Platinum as Hydrogen-Oxygen Recombinant

Catalyst for Sealed Lead-Acid Batteries
B. Hariprakash,a Parthasarathi Bera,a S. K. Martha,a S. A. Gaffoor,b
M. S. Hegde,a and A. K. Shuklaa,z
a
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore-560 012, India
b
NED Energy Limited, Nav Bharat Chambers, Hyderabad-500 082, India

Ceria-supported platinum synthesized by a novel solution-combustion method results in ionically substituted platinum sites on
nanosized ceria crystallites, and is found to be an excellent hydrogen and oxygen recombinant catalyst at room temperature for
recovery of water in sealed lead-acid batteries. The use of this catalyst prevents any change in the quantity or concentration of the
sulfuric acid electrolyte in the battery during its operation, which is pivotal to enhancing both its performance and life span. The
catalyst could be equally advantageous to alkaline storage batteries, and, in particular, in realizing sealed nickel-iron batteries
giving them a revived commercial interest.
2001 The Electrochemical Society. DOI: 10.1149/1.1346537 All rights reserved.

Manuscript submitted November 1, 2000; revised manuscript received November 27, 2000. Available electronically January 25,
2001.

The lead-acid battery is the most widely used secondary battery
in the world. Although conventional lead-acid batteries are consid-
ered a mature technology, significant research and development ef-
forts are currently under way to enhance their performance. Since its
invention in 1859 by Gaston Plante, many improvements have been
made in lead-acid battery technology, and although the essential
electrochemistry remains unchanged, modern lead-acid batteries
bear little semblance to those produced 50 years ago. Over the years,
seminal advances have been made, particularly in the lead alloys
used, in the materials and design of separators, in battery packaging,
and in their construction methods.1 These changes have led to lead-
acid batteries with improved performance, lighter weight, and lower
cost.
In recent years, gas-recombination valve-regulated or sealed
lead-acid batteries have been developed which require almost no
maintenance and may be used in any orientation. Scientific funda-
mentals and evolution of gas-recombination lead-acid cells and bat-
teries have been discussed at length in various papers presented at
the Proceedings of the International Conference on Lead-Acid
Batteries.2-18 Edison19 was the first to patent the use of platinum
wire and sponge in the head space of the lead-acid cells to achieve
gas recombination. Tichenor20 extended Edisons approach by pro-
posing the use of auxiliary electrodes and sensing circuitry to main-
tain the proper stoichiometry by enhancing overcharge at one of the
electrodes via independent charging. Subsequently, Dassler patented
the recombination of H2 and O2 gases in both alkaline and lead-acid
secondary cells using auxiliary21 as well as exposed lead
electrodes.22 But Dasslers methods for recombining H2 and O2
gases were found impracticable for large-scale production.2 Be-
tween 1950 and 1970, efforts were intensified to realize commer-
cially viable sealed lead-acid batteries using auxiliary electrodes,
exposed negative electrode surface, and catalyst plugs. Following
Levy and Boudart,23 several other authors24-26 also reported that,
like platinum, tungsten carbide could catalyze the formation of wa-
ter from hydrogen and oxygen at room temperature. In the past few
years, virtually every reputed lead-acid battery company has been
developing and/or manufacturing sealed lead-acid batteries. But
even now, certain problems, in particular negative-plate self-
discharge and battery dry-out, need to be mitigated to make sealed
lead-acid batteries infallible. It has been argued that these problems
could be easily alleviated with the use of an efficient catalyst that
could combine gaseous hydrogen and oxygen generated during vari-
ous charging schedules of the lead-acid batteries.27-29 Recent studies
on the use of palladium catalyst is one such effort.30-35
It is noteworthy that appropriately designed sealed lead-acid bat-
teries have been claimed to function at about 98% recombination
z
E-mail: shukla@sscu.iisc.ernet.in
efficiency, with less than 5% loss in their water content over their
life span. However, some sealed lead-acid batteries have been re-
ported to fail within 5 years. The use of a hydrogen-oxygen recom-
binant catalyst, such as the one reported here, will not only improve
the performance of sealed lead-acid batteries but would also sim-
plify their process of manufacture and battery cost. This is because
the elimination of water loss will lessen the complexities associated
with design of acid-limited sealed lead-acid batteries and would
thereby provide the possibility of increasing the energy density of
the batteries. This would also help to reduce the positive-grid cor-
rosion, which would enhance battery life. A superior hydrogen-
oxygen recombination will provide increased uniformity in the float-
life characteristics of the battery, and the possibility of using any
type of grid which will make the batteries cost-effective. In addition,
it would be possible to charge the batteries at faster rates particularly
with constant current recharge.
In this paper, we report on a novel ceria-supported platinum
catalyst prepared by a rapid solution-combustion reaction and its
effectiveness in realizing a sealed lead-acid battery with nearly
100% recombination of hydrogen and oxygen gases, generated dur-
ing its recharge, into water. As a consequence, there is no net
change in the quantity or concentration of the sulfuric-acid electro-
lyte over the charge-discharge cycles of the lead-acid battery. In
addition, because there is almost no rise in the internal pressure of
the battery during its operation, it could, in principle, be sealed
without any regulatory valve. Thus, the emission of acid fumes
which causes corrosion of metallic parts in the vicinity of the battery
is completely averted.
Experimental
CeO2-supported platinum catalyst (2 atom % Pt/CeO2) employed
in the present study was prepared by a rapid solution-combustion
reaction.36 The combustion mixture comprised ceric ammonium ni-
trate NH42CeNO36 , chloroplatinic acid (H2PtCl6), and ox-
alyldihydrazide (C2H2N4O2) in the molar ratios 0.98:0.02:2.35. Ox-
alyldihydrazide derived from diethyl oxalate, and hydrazine hydrate
acts as the fuel. Initially, 10 g of ceric ammonium nitrate E-Merck
India, 99.9% purity, 0.193 g of chloroplatinic acid Ranbaxy Labo-
ratories India, 99% purity, and 5.175 g of oxalyldihydrazide were
dissolved in a minimum volume of water in a borosilicate-glass
dish. Subsequently, the borosilicate-glass dish containing the redox
mixture and an appropriate quantity of hydrazine hydrate was intro-
duced into a muffle furnace maintained at 350C. The solution was
found to froth and foam with concomitant loss of water. When the
removal of water was complete, the redox mixture ignited with the
flame temperature at ca. 1000C yielding a voluminous and finely
dispersed ceria-supported platinum catalyst as a solid product within
about 5 min.

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A24 Electrochemical and Solid-State Letters, 4 3 A23-A26 2001
Figure 1. XRD patterns of the 2 atom % Pt/CeO2 catalyst A as prepared
and B after soaking in strong sulfuric acid for a prolonged duration.
A powder X-ray diffraction XRD pattern of the 2 atom %
Pt/CeO2 catalyst thus prepared was obtained on a Siemens D-5005
X-ray diffractometer using CuK-radiation at a scan rate of 2
min1. The Brunauer-Emmett-Teller BET surface area of the cata-
lyst was measured on a Carlo-Erba Sorptomatic-1900 surface-area
analyzer. Electron micrographs of the catalyst were obtained on a
JEOL JEM-200CX transmission electron microscope TEM. The
X-ray photoelectron spectrum XPS of the catalyst was recorded on
an ESCA-3 Mark-II VGScientific spectrometer using AlK-
radiation.
Lead-acid batteries 6 V, 3.5 Ah were constructed from fully
formed negative-lead and positive-lead oxide plates using aq. H2SO4
sp.gr. 1.25) in a Plexiglas container with three compartments to
house the constituent lead-acid cells connected in series. The batter-
ies were sealed with each of the cells having a plug containing 1 g of
2 atom % Pt/CeO2 hydrogen-oxygen recombinant catalyst mixed
with an equal amount of finely divided quartz on their lids. Provi-
sion was also made to measure the pressure of the gases evolved
from each of the cells while charging the battery at various sched-
ules between C/10 and C/2. Embedding a chromel-alumel thermo-
couple in the catalyst bed monitored the temperature of the catalyst
bed during the recombination of hydrogen and oxygen gases in each
of the cells. The experiments were carried out over a range of tem-
peratures between 5 and 25C. Similarly, sealed batteries without
the catalyst plug were assembled.
Results and Discussion
Powder XRD pattern for the as-prepared 2 atom % Pt/CeO2 cata-
lyst is shown in Fig. 1A. The XRD pattern agrees well with CeO2 in
fluorite structure. The XRD pattern was devoid of any diffraction
lines due to Pt-metal particles or any oxides of platinum. To estab-
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Figure 2. Pt4f XPS of the 2 atom % Pt/CeO2 catalyst.
lish the stability of the catalyst in concentrated sulfuric acid and
strong aq. KOH, we soaked the catalyst in these mediums for pro-
longed periods and subsequently recorded their XRD patterns as
shown in Fig. 1B. There is little difference in XRD patterns suggest-
ing the stability of the catalyst both in sulfuric acid and aq. KOH.
The catalyst has a surface area of 18 m2 g1. TEMs of the catalyst
depict the absence of any platinum particles on ceria support.37
In Fig. 2, we show the Pt 4f X-ray photoelectron spectrum of
the 2 atom % Pt/CeO2 catalyst. The spectrum could be deconvoluted
into only two components labeled as 1 and 2 at respective binding
energies of 71.9 and 74.4 eV. We can assign the 4f7/2 signal at 71.9
eV to Pt2 and the signal at 74.4 eV to Pt4 species.38 Interestingly,
the spectrum showed complete absence of metallic or zero-valent
platinum species in the catalyst since the signal associated Pt-4f7/2 at
71.1 eV for Pt metal is altogether absent. These data suggest that
platinum in the catalyst is present only in Pt2 and Pt4 states. As
would be discussed later, Pt2 and Pt4 species facilitate the
1
H2 2 O2 H2O reaction.
After finding the ceria-supported platinum catalyst to exhibit
100% conversion for H2 2 O2H2O reaction 100 mol g1 s1
1
at room temperature, attempts were made to test it as hydrogen and
oxygen recombinant catalyst in lead-acid batteries. For this purpose,
lead-acid batteries were assembled, both with and without the ceria-
supported catalyst plugs, with the provision to measure the buildup
of gaseous pressure in the battery. Typical galvanostatic charge-
discharge data for such a lead-acid battery at 25C and at C/5 rate
are shown in Fig. 3. The data suggest a faradaic efficiency of about
90%. In Fig. 4A and B, we show the variation in the internal pres-
sure of the battery and catalyst-bed temperature as the function of
battery charging rates at 25C, respectively. From the data in Fig.
4A, it appears that the pressure of the gases evolved while charging
the battery rises initially but then decreases and stays between 1-4
kNm2 depending on the rate of battery charging. Similarly, the
data in Fig. 4B suggest that the catalyst-bed temperature increases
when evolution of gases starts, owing to the exothermicity of the
hydrogen-oxygen recombination reaction, but finally remains invari-
ant between 50-60C depending on the charging rate of the battery.
To examine the performance of the catalyst at lower temperatures,
we also conducted these experiments at C/5 rate of battery charging
at 5 and 10C, and the data are shown in Fig. 5. Here too, the
gaseous pressure initially rises but finally stabilizes between 0.5-0.7
kNm2 depending on the battery charging rate. In a similar fashion,
the catalyst-bed temperature initially rises as the recombination of
gaseous hydrogen and oxygen begins but thereafter stays between
 Electrochemical and Solid-State Letters, 4 3 A23-A26 2001
Figure 3. Typical charge-discharge data for a sealed lead-acid battery as-
sembled for the present study.
23-25C. We did not observe any freezing in the catalyst as reported
in the literature for other recombinant catalysts.2 By contrast, the
batteries without the catalyst plug showed a continuous rise in the
gaseous pressure. Similar experiments were carried out with com-
mercial grade 2 V 200 Ah VRLA cells at 30C at various charging
rates between C and C/10. While there was a continuous increase in
the gaseous pressure beyond 2.6 V with cells without the catalyst
plug, no increase in gaseous pressure was observed with cells fitted
with the catalyst plug. These data suggest a complete recombination
of hydrogen and oxygen gases evolved during the charging of the
Figure 4. A Internal gas-pressure and B catalyst-bed temperature ob-
served while charging a sealed lead-acid battery having the recombinant
catalyst-plug at C/2, C/5, and C/10 rates at 25C.
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A25
Figure 5. A Internal gas-pressure and B catalyst-bed temperature ob-
served while charging a sealed lead-acid battery having the recombinant
catalyst-plug at C/5 rate at 5 and 10C.
VRLA cells fitted with the catalyst plug. On the basis of XPS data
Fig. 2, we suggest that the recombination of hydrogen and oxygen
into water on the catalyst occurs through the mechanism shown in
Fig. 6.
The battery with the recombinant-catalyst plug has been sub-
jected to over 100 charge-discharge cycles with almost no change in
the electrolyte level or battery capacity. During prolonged operation
of the battery, we observed little variation in its internal resistance,
which usually arises due to a change in the specific gravity of the
sulfuric-acid electrolyte. This would enhance the life span of the
battery substantially. We consider it a major-step forward in lead-
acid battery technology. The catalyst is equally effective for recom-
bining hydrogen and oxygen in sealed alkaline-storage-batteries.
The catalyst will be particularly advantageous in realizing commer-
cially viable sealed nickel-iron batteries. In the past, nickel-iron bat-
teries have been shown to sustain both mechanical and electrical
abuse, and have been found to provide cycle life of over 3000
charge-discharge cycles with a calendar life of about 20 years. But
nickel-iron batteries have failed to make any commercial impact
Figure 6. Mechanism of hydrogen and oxygen recombination to water on
Pt/CeO2 catalyst.
A26 Electrochemical and Solid-State Letters, 4 3 A23-A26 2001
primarily because it has not been possible to seal these batteries
owing to the insurmountable difficulty of recombining hydrogen and
oxygen gases.39
In summary, the solution-combustion method employed here
yields ionically substituted platinum sites on nanosized 15-25 nm
ceria crystallites which has 100% efficiency for H2 21 O2
H2O reaction and hence can be effectively used as a hydrogen-
oxygen recombinant catalyst in sealed lead-acid batteries. This will
help in maintaining the batteries with little change in their internal
resistance and float currents during their service life. In addition,
with the use of recombinant catalyst, it would be possible to elimi-
nate premature battery failures arising due to the negative-plate sul-
fating and positive-grid corrosion. Furthermore, the use of the re-
combinant catalyst will make the batteries more design-flexible to
grid-alloy compositions, and free from positive-plate capacity limi-
tations as well as void-volume requirements of the battery separator.
We strongly believe that it would be possible to realize a safer and
totally sealed lead-acid battery with the use of this recombinant
catalyst.
Acknowledgments
Our thanks to Professor K. C. Patil for helpful suggestions. Fi-
nancial support from the Department of Science and Technology
and Department of Atomic Energy, Government of India is grate-
fully acknowledged. P. Bera thanks the Council of Scientific and
Industrial Research, New Delhi for a Research Fellowship.
Dr. Shukla assisted in meeting the publication costs of this article.
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