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

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

A23

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 b

Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore-560 012, India 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 considered a mature technology, signicant research and development efforts are currently under way to enhance their performance. Since its ` , many improvements have been invention in 1859 by Gaston Plante 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 leadacid 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. Scientic fundamentals and evolution of gas-recombination lead-acid cells and batteries 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 rst 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 proposing the use of auxiliary electrodes and sensing circuitry to maintain 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 Between 1950 and 1970, efforts were intensied to realize commercially 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 water 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 selfdischarge 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 efcient catalyst that could combine gaseous hydrogen and oxygen generated during various 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 batteries have been claimed to function at about 98% recombination

efciency, with less than 5% loss in their water content over their life span. However, some sealed lead-acid batteries have been reported to fail within 5 years. The use of a hydrogen-oxygen recombinant catalyst, such as the one reported here, will not only improve the performance of sealed lead-acid batteries but would also simplify 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 corrosion, which would enhance battery life. A superior hydrogenoxygen recombination will provide increased uniformity in the oatlife 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 during its recharge, into water. As a consequence, there is no net change in the quantity or concentration of the sulfuric-acid electrolyte 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 nitrate NH42CeNO36 , chloroplatinic acid (H2PtCl6), and oxalyldihydrazide (C2H2N4O2) in the molar ratios 0.98:0.02:2.35. Oxalyldihydrazide 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 Laboratories 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 introduced into a mufe 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 ame temperature at ca. 1000C yielding a voluminous and nely dispersed ceria-supported platinum catalyst as a solid product within about 5 min.

E-mail: shukla@sscu.iisc.ernet.in

Downloaded 27 Nov 2008 to 220.227.207.12. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp

A24

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

Figure 2. Pt4f XPS of the 2 atom % Pt/CeO2 catalyst.

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 catalyst 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 VGScientic spectrometer using AlKradiation. 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 batteries 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 nely divided quartz on their lids. Provision was also made to measure the pressure of the gases evolved from each of the cells while charging the battery at various schedules between C/10 and C/2. Embedding a chromel-alumel thermocouple 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 temperatures 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 catalyst is shown in Fig. 1A. The XRD pattern agrees well with CeO2 in uorite structure. The XRD pattern was devoid of any diffraction lines due to Pt-metal particles or any oxides of platinum. To estab-

lish the stability of the catalyst in concentrated sulfuric acid and strong aq. KOH, we soaked the catalyst in these mediums for prolonged periods and subsequently recorded their XRD patterns as shown in Fig. 1B. There is little difference in XRD patterns suggesting 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 nding the ceria-supported platinum catalyst to exhibit 100% conversion for H2 2 O2H2O reaction 100 mol g1 s1 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 ceriasupported catalyst plugs, with the provision to measure the buildup of gaseous pressure in the battery. Typical galvanostatic chargedischarge data for such a lead-acid battery at 25C and at C/5 rate are shown in Fig. 3. The data suggest a faradaic efciency of about 90%. In Fig. 4A and B, we show the variation in the internal pressure 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 nally remains invariant 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 nally 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
1

Downloaded 27 Nov 2008 to 220.227.207.12. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp

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

A25

Figure 3. Typical charge-discharge data for a sealed lead-acid battery assembled 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 commercial 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 tted with the catalyst plug. These data suggest a complete recombination of hydrogen and oxygen gases evolved during the charging of the

Figure 5. A Internal gas-pressure and B catalyst-bed temperature observed while charging a sealed lead-acid battery having the recombinant catalyst-plug at C/5 rate at 5 and 10C.

VRLA cells tted 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 subjected 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 specic gravity of the sulfuric-acid electrolyte. This would enhance the life span of the battery substantially. We consider it a major-step forward in leadacid battery technology. The catalyst is equally effective for recombining hydrogen and oxygen in sealed alkaline-storage-batteries. The catalyst will be particularly advantageous in realizing commercially viable sealed nickel-iron batteries. In the past, nickel-iron batteries 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 4. A Internal gas-pressure and B catalyst-bed temperature observed while charging a sealed lead-acid battery having the recombinant catalyst-plug at C/2, C/5, and C/10 rates at 25C.

Figure 6. Mechanism of hydrogen and oxygen recombination to water on Pt/CeO2 catalyst.

Downloaded 27 Nov 2008 to 220.227.207.12. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp

A26

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

9. S. Sarkar and I. N. Basumallick, J. Power Sources, 31, 89 1990. 10. J. A. Magyar, M. A. Kepros, and R. F. Nelson, J. Power Sources, 31, 93 1990. ring, J. Garche, and K. Wiesener, J. Power Sources, 31, 11. H. Dietz, S. Voss, H. Do 107 1990. 12. M. Maja and N. Penazzi, J. Power Sources, 31, 115 1990. 13. M. K. Dimitrov, J. Power Sources, 31, 121 1990. 14. D. A. Crouch, Jr. and J. W. Reitz, J. Power Sources, 31, 125 1990. niak, J. Power Sources, 31, 15. J. Kwasnik, T. Pukacka, M. Paszkiewicz, and B. Szczes 135 1990. , J. Power Sources, 31, 139 1990. 16. J. Mrha, J. Jindra, and M. Musilova hle and R. Kiessling, J. Power Sources, 31, 145 1990. 17. C. Bo 18. K.-H. Christian and R. Ackerman, J. Power Sources, 31, 151 1990. 19. T. A. Edison, U.S. Pat. 1,016,874 1912. 20. R. L. Tichenor, U.S. Pat. 2,578, 027 1951. 21. A. Dassler, U.S. Pat. 2, 104, 973 1938. 22. A. E. Lange, E. Langguth, E. Breuning, and A. Dassler, U.S. Pat. 2, 131, 591 1938. 23. R. B. Levy and M. Boudart, Science, 181, 547 1973. 24. I. Nikolov, G. Papazov, and V. Naidenov, J. Power Sources, 40, 333 1992. 25. I. Nikolov, G. Papazov, and V. Naidenov, J. Power Sources, 40, 341 1992. 26. H. Dietz, L. Dittmar, D. Ohms, M. Radwan, and K. Wiesener, J. Power Sources, 40, 175 1992. 27. S. C. Levy and M. E. Fiorino, Electrochem. Soc. Interface, 4, 25 1995. 28. P. D. Bennet, K. R. Bullock, and M. E. Fiorino, Electrochem. Soc. Interface, 4, 26 1995. 29. B. Brecht, Batteries International, 39, 35 1999. 30. B. Dick, Batteries International, 40, 39 1999. 31. W. E. M. Jones and D. O. Feder, in Proceedings of the Eighteenth International Telecom Energy Conference, Boston, MA 1996. 32. S. S. Misra, T. M. Noveske, S. L. Mraz, A. J. Williamson, and L. S. Holden, in Proceedings of the Twenty-First International Telecom Energy Conference, Copenhagen, Denmark, 1999. 33. S. S. Misra, S. L. Mraz, T. M. Noveske, and L. S. Holden, in Proceedings of the Fourteenth Annual Battery Conference, Long Beach, CA 1999. 34. S. S. Misra, T. Noveske, and A. Williamson, in Proceedings of the Twenty-Second International Telecom Energy Conference, Phoenix, AZ 2000. 35. T. M. Noveske, S. S. Misra, S. L. Mraz, and J. D. Dillon III, in Proceedings of the Fifteenth Annual Battery Conference, Long Beach, CA 2000. 36. K. C. Patil, S. T. Arnua, and S. Ekambaram, Curr. Opin. Solid State Mater. Sci., 2, 158 1997. 37. P. Bera, K. C. Patil, V. Jayaram, G. N. Subbanna, and M. S. Hegde, J. Catal., 196, 293 2000. 38. J. Knecht and G. Stark, Frensius Z. Anal. Chem., 289, 206 1978. 39. A. K. Shukla, M. K. Ravikumar, and T. S. Balasubramanian, J. Power Sources, 51, 29 1994.

primarily because it has not been possible to seal these batteries owing to the insurmountable difculty 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 1 ceria crystallites which has 100% efciency for H2 2 O2 H2O reaction and hence can be effectively used as a hydrogenoxygen recombinant catalyst in sealed lead-acid batteries. This will help in maintaining the batteries with little change in their internal resistance and oat currents during their service life. In addition, with the use of recombinant catalyst, it would be possible to eliminate premature battery failures arising due to the negative-plate sulfating and positive-grid corrosion. Furthermore, the use of the recombinant catalyst will make the batteries more design-exible to grid-alloy compositions, and free from positive-plate capacity limitations 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. Financial support from the Department of Science and Technology and Department of Atomic Energy, Government of India is gratefully acknowledged. P. Bera thanks the Council of Scientic and Industrial Research, New Delhi for a Research Fellowship.
Dr. Shukla assisted in meeting the publication costs of this article.

References
D. A. J. Rand, J. Power Sources, 64, 157 1997. R. F. Nelson, J. Power Sources, 31, 3 1990. N. E. Bagshaw, J. Power Sources, 31, 23 1990. S. Warrell, J. Power Sources, 31, 35 1990. J. Strebe, B. Reichman, B. Mahato, and K. R. Bullock, J. Power Sources, 31, 43 1990. 6. H. Tuphorn, J. Power Sources, 31, 57 1990. 7. I. Nikolov, G. Papazov, D. Palov, T. Vitanov, and V. Naidenov, J. Power Sources, 31, 69 1990. 8. G. Papazov, I. Nikolov, D. Pavlov, T. Vitanov, P. Andrew, and M. Bojinov, J. Power Sources, 31, 79 1990. 1. 2. 3. 4. 5.

Downloaded 27 Nov 2008 to 220.227.207.12. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp