International Journal of Hydrogen Energy 27 (2002) 627 633

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Zincnickel alloy electrodeposits for water electrolysis

G. Sheela, Malathy Pushpavanam , S. Pushpavanam
Central Electrochemical Research Institute, Karaikudi 630 006, India

Abstract Electrodeposited zincnickel alloys of various compositions were prepared. A suitable electrolyte and conditions to produce alloys of various compositions were identied. Alloys produced on electroformed nickel foils were etched in caustic to leach out zinc and to produce the Raney type, porous electro catalytic surface for hydrogen evolution. The electrodes were examined by polarization measurements, to evaluate their Tafel parameters, cyclic voltammetry, to test the change in surface properties on repeated cycling, scanning electron microscopy to identify their microstructure and X-ray di raction. The catalytic activity as well as the life of the electrode produced from 50% zinc alloy was found to be better than others. ? 2002 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.

Keywords: Zinc alloy; Electrodeposition; Hydrogen evolution; Polarization studies; Surface structure; Surface area; Raney nickel precursor

1. Introduction Electrodeposited zinc-nickel alloy is used for the production of low hydrogen and oxygen overvoltage porous nickel electrodes in alkaline water electrolysis [17]. The alloy, as a precursor to produce the Raney nickel catalyst [8,9] by preferential leaching of zinc from the alloy, has the advantage of being easily applicable on any substrate irrespective of size, shape or pattern. Caustic leaching of the alloy is accompanied by volume losses leading to pore and crack formation, yielding a highly porous catalytic nickel surface suitable for use in alkaline water electrolysis [10,11]. Although studies world wide [1215] suggest that a 50 : 50 alloy is most suitable for this purpose, recent reports [16 20] claim that alloys containing more zinc (up to 88 mole.%) can be used e ectively. In this study, electrodeposited zinc nickel alloys of di erent compositions are evaluated as cathodes for alkaline water electrolysis.

2. Experimental 2.1. Bath standardization Nickel foil of about 0:2 mm thickness was electroformed using a sulfamate bath and a stainless-steel mandrel. The bright and smooth side of the foil, that was in contact with the mandrel, was used as the surface for alloy deposition. Foils of 10 1 cm2 area were cut and masked suitably to expose an e ective area of 5 1 cm2 . For zincnickel alloy deposition, a dual anode system with anodes of equal area was used. The current was maintained at 4:0 A dm2 and the deposits were produced for 30 min maintaining the solution pH as 3.5. The electrolyte for the alloy deposition was prepared in the following manner: 2:2 M solution of nickel chloride (analytical-grade chemicals were used) was puried by the conventional treatments to remove the impurities and stored as a stock solution. 2:0 M solution of zinc chloride was prepared and puried by carbon and zinc dust treatment and stored as a stock solution. The solutions were then mixed in various proportions and diluted with a stock solution of 1:0 M boric acid, as required. The composition of the alloy produced at di erent Zn= Ni ratio was determined by plating the alloy on a polished, degreased,

Corresponding author. Fax: +91-04565-427779. E-mail address: malathypush@yahoo.com (M. Pushpavanam).

0360-3199/02/$ 22.00 ? 2002 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved. PII: S 0 3 6 0 - 3 1 9 9 ( 0 1 ) 0 0 1 7 0 - 7

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Table 1 Details of the solutions prepared for the study Molarity in solution Ni Zn 1.1 1.1 1.1 1.1 1.1 1.1 0.3 0.6 0.9 1.2 1.8 2.7 Total molarity 1.4 1.7 2.0 2.3 2.9 3.8 Ni= Zn ratio 3.66 1.83 1.22 0.92 0.61 0.41

2.4. Testing the electrodes Estimation of the leaching solution: The alkali solution in which the alloy was stripped was made up to a known volume and then analyzed for dissolved zinc and nickel using atomic absorption spectroscopy (AAS). Surface analysis: The leached surfaces of the alloys of di erent compositions were examined using XRD with Cu K radiation. From the d and 2 values and I=I0 values the peaks were identied. Surface topography: The electrodes before and after leaching were examined for their topography using scanning electron microscope (SEM). 2.5. Polarization studies Galvanostatic polarization studies of the electrodes were conducted in 6:25 N sodium hydroxide using platinum counter electrode and Hg= HgO= 0:1 N NaOH reference electrode. Current was varied from 1 to 400 mA cm2 at regular intervals and the corresponding change in potential was recorded. Ohmic correction was made using current interrupter technique using an oscilloscope (Tektronix Model 7613). 2.6. Surface area measurement Using cyclic voltammetry, the surface areas of the activated cathodes were estimated before and after leaching. The electrodes were cycled between 400 and 1400 mV at a rate of 50 mV s1 in a two-compartment cell. A platinum counter electrode and Hg= HgO= 0:1 N NaOH reference electrode were used. A Wenking potentiostat connected to a scan generator and X-Yt recorder was used for the experiment. The total charge was calculated by integrating current and time in the voltammogram [21]. Prior to each experiment, the treated electrodes were cycled in the above potential range for about 5 min in order to produce the real catalytic surface since, even after thorough leaching, a few percent of zinc may remain on the surface [2,13]. The e ect of repeated cycling of potential on the voltammogram was also examined since this is indicative of the performance of the electrode after long-time use. The electrodes were cycled at the above potential range for 20 times and the variation in the charges was evaluated. The experiments were conducted in triplicate, and near reproducible results were presented. 2.7. Cell performance The best electrodes were assembled in a laboratory model cell of 1 l capacity, containing 6:25 N NaOH as cathode and change in cell voltage in 40 h was compared with the performance of pure nickel cathode.

electrocleaned mild steel substrates of 7:5 2:5 cm2 size. The unwanted portions were masked so as to expose an e ective area of 6:25 cm2 . The mass of the deposits was used to calculate the current e ciency of alloy deposition. The deposits were stripped in concentrated nitric acid and the solution was analyzed spectrophotometrically and later conrmed with X-ray uorescence spectroscopy for nickel. The percentage of nickel in the alloy was estimated from the total mass of the deposit. Zinc content was found by the di erence. The electrolytes used for producing alloys of di erent composition are given in Table 1. From the thickness of the deposits calculated, the rate of deposition for each alloy was determined and alloys of 25 m thickness were produced in each composition for further studies.

2.2. Alloy deposition The electroformed nickel foils were suitably masked to expose an e ective area of 1 5 cm2 on one side. This surface was cathodically cleaned to have a water wettable surface, washed and then anodically treated in a Woods nickel solution at 10 A dm2 for 1 min, followed by cathodic treatment at 4:0 A dm2 for 10 min. This treatment was given to get an adherent alloy lm subsequently. The substrate was then washed well, rinsed and then used for depositing the required alloy. A plastic frame was attached to the cathode to enable uniformity in deposit thickness.

2.3. Electrode preparation One set of deposits produced under each composition was treated in 25 ml of 10 M potassium hydroxide for 8 h. Then they were washed, rinsed, and treated in boiling triple distilled water for 4 h to remove the reaction products and kept immersed in distilled water [2]. Treatment in alkali dissolves zinc in the deposit producing a porous nickel of high surface area [1,2].

G. Sheela et al. / International Journal of Hydrogen Energy 27 (2002) 627 633 Table 2 E ect of Ni= Zn ratio on the composition of the alloy and the deposition e ciency pH 3.5, C.D. 4:0 A dm2 , 30 C Nickel in solution 0.29 0.38 0.55 0.65 0.79 Cathode e ciency, % 85.29 84.52 80.19 73.10 68.40 Rate of deposition, m= Hr 55.16 50.60 47.68 39.04 37.48

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Ni in deposit, % 15.32 25.00 40.06 53.25 75.20

Table 3 E ect of leaching on the alloy deposit Electrode Zn15% Zn25% Zn50% Zn75% Ni Ni Ni Ni Zinc content (mg) Initial 78.58 67.21 50.00 26.84 Final 7.34 8.28 6.86 25.28 Dissoln. % 90.65 87.79 86.28 5.81 Nickel content (mg) Initial 13.86 26.14 50.00 80.53 Final 10.03 19.19 37.54 79.53 Dissoln. % 27.60 26.58 24.92 1.24

Fig. 1. Photomicrograph of 85%Zn-15%Ni alloy electrodeposits after leaching in 10 M KOH.

Fig. 2. Photomicrograph of 75%Zn-25%Ni alloy electrodeposits after leaching in 10 M KOH.

3. Results and discussion Composition of the alloy depends mainly on the Ni= Zn ratio in solution. Table 2 shows the e ect of Ni= Zn ratio on the alloy composition, current e ciency and rate of deposition of the alloy. It was observed that nickel-rich deposits are more compact and semi-bright, whereas zinc-rich deposits have a grayish appearance. Deposits containing 75%, 50%, 25% and 15% nickel were selected for the study. Table 3 shows the mass of zinc present in the deposit before leaching and the nal mass remaining in the alloy after subtracting the amount of zinc detected in AAS

in the stripped solution. From the percentage dissolution, it could be understood that zinc alone undergoes dissolution, which is around 85% up to 50% zinc in the alloy. Alloys having still lower zinc content show little dissolution. Only negligible amount of nickel was detected in the stripped solution. It can also be inferred that some amount of zinc still remains on the surface, which has to be removed before estimating the real surface area using cyclic voltammetry. SEM micrographs of the surface topography of the alloy deposit after leaching treatment are shown in Figs. 13. The alloy containing 75% nickel resembled pure nickel and is not shown in the paper. It is evident that

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Fig. 3. Photomicrograph of 50%Zn-50%Ni alloy electrodeposits after leaching in 10 M KOH.

di erent kinds of cracks are formed in all the three electrodes. Many smaller cracks are found on the electrodes prepared from the 50% nickel alloy. These cracks extend even up to the nickel substrate. Due to the shrinkage of the coating during caustic leaching of zinc, approximately 40% of the initial volume of the alloy is lost [22]. The formation of

these cracks is vital for higher utilization of Raney nickel because cracks, being lled with the electrolyte, render a greater part of the internal surface of the Raney nickel, accessible to electrochemical gas evolution, than would be possible in closed Raney nickel layers. Numerous cracks, as generated by leaching, lead to su ciently short di usion paths of dissolved hydrogen, for the fastest release of the gas and for avoiding excessive gas accumulation and concentration polarization in the micropores [11]. With increasing nickel content up to 50%, this high surface area nickel portion increases, whereas the 75% alloy did not undergo any leaching. The progressive increase in the surface area up to 50% nickel results in lower overvoltage for hydrogen evolution reaction which is re ected in the Tafel parameters derived from the polarization studies, given in Fig. 4 and Table 4. Figs. 5 and 6 show the di raction patterns of 15 and 50% nickel alloy in the as-plated condition and after leaching. It can be seen from Figs. 5a and 6a that 15% nickel alloy exists only in Ni3 Zn22 phase, whereas 50% nickel alloy shows slight contribution from other phases also, though, the predominant peak is NiZn ( phase as indicated by Wendt [12]). Provided the estimation of the alloy composition is accurate, minor contributions by other phases need not be treated seriously, since they are

Fig. 4. Polarization curves for nickel and di erent alloys (a) nickel (b) 15% nickel (c) 25% nickel (d) 50% nickel and (e) 75% nickel alloy.

Table 4 E ect of nickel content on the Tafel parameters Electrode Ni Zn75% Zn50% Zn25% Zn15% a 0.57 0.54 0.60 0.60 0.63 b 0.54 0.56 0.28 0.36 0.33 H2 (mV) 105 110 100 100 95 I0 (A cm2 ) 8:9615 106 8:1113 106 1:5848 103 2:52120 104 2:9764 104

Ni Ni Ni Ni

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Fig. 5. X-ray di ractogram of (a) 15% Ni alloy before leaching (b) after leaching.

Fig. 6. X-ray di ractogram of (a) 50% Ni alloy before leaching (b) after leaching.

quite common in commercial plating. Figs. 5b and 6b conrm that after thorough leaching, peaks due to high surface area nickel alone is remaining and the peak counts are nearly double for the 50% alloy compared with the other. Figs. 7(a) (e) show the cyclic voltammograms of the alloys after leaching. Of all the alloys 50% alloy showed highest area, as understood from the charge calculated by integrating time and current. The cycling was repeated for 20 times till there was no appreciable change in the charge. It was understood that the charge of the 50% nickel alloy alone remained same, whereas that of the other alloys showed reduction, as given in Table 5. The amount of nickel remaining after leaching zinc in 15% and 25% nickel alloys is not su cient to form a continuous porous structure with smaller cracks as observed from the microTable 5 E ect of repeated cycling on the voltammetric charge Electrode Total charge calculated (coulombs) Initial 0.064 1.630 1.100 2.798 0.117

graphs, because of the dissolution of higher amounts of zinc. The voltammogram of 75% nickel alloy was similar to nickel only. The ndings proved that the 50% nickel alloy is the best suited one to produce high surface area cathodes for alkaline water electrolysis. To conrm the above results, the electrodes were assembled in a laboratory cell and tested for the cell voltage. In 40 h of continuous operation of each electrode at 1.0 and 4:0 A dm2 , the cells containing activated cathodes showed a reduction in cell voltage of 250 and 320 mV with 15% and 50% nickel electrodes at 1:0 A dm2 , and 320 and 390 mV at 4:0 A dm2 , respectively. However, these results need conrmation by testing the electrodes in a long run in higher capacity cells.

% Reduction Final 0.056 1.170 0.806 2.800 0.099 13.35 28.00 26.00 0.60 26.00

Ni Zn15% Zn25% Zn50% Zn75%

Ni Ni Ni Ni

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Fig. 7. E ect of repeated cycling on the voltammograms of (a) Ni, (b) 15% Ni alloy (c) 25% Ni alloy (d) 50% Ni alloy and (e) 75% Ni alloy. I: Initial, F: Final.

4. Conclusions Zincnickel alloy electrodes containing 50% zinc are e ective in producing high surface area cathodes for use in alkaline water electrolysis and alloys having still higher nickel contents are not so useful.

Acknowledgements The authors thank the Director, Central Electrochemical Research Institute, Karaikudi-630 006 for his kind permission to publish this paper. Thanks are also due to Dr. S. Madhu and Mr.J. Kennedy for their help in AAS analysis and Dr. A. Mani for his help in XRD analysis.

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