Development of the High Rate Metal-Air Depolarized Batteries

Charkey, A.

doi:10.21236/ad0635490

1966

DOI: 10.21236/ad0635490

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Development of the High Rate Metal-Air Depolarized Batteries

A. Charkey¹

Abstract: This report covers the work done during the second quarter of the investigation for the U. S. Army Electronics Command. The study is being conducted to determine the performance characteristics and operational parameters for various metal-air couples. The anode materials being examined are Al,

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“…The addition of calcium hydroxide to the zinc electrode decreases zincate concentration and increases the life of secondary zinc batteries. 6,7 The reason is that calcium hydroxide reacts with the discharge product ZnO to give a compound calcium zincate with the molecular structure of Ca͑OH͒ 2 •2Zn͑OH͒ 2 •2H 2 O. 7,8 According to the chemical changes during cycling, the reduction of calcium zincate can be represented by From Eq.…”

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Effect of Surface Modification with In(OH)[sub 3] on Electrochemical Performance of Calcium Zincate

Wang

Yang

Zeng

2009

J. Electrochem. Soc.

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Quadrangular calcium zincate materials coated with indium hydroxide were prepared by chemical deposition. The properties of the samples were characterized by X-ray diffraction ͑XRD͒, scanning electron microscopy ͑SEM͒, electrical impedance spectroscopy ͑EIS͒, cyclic voltammetry, Tafel plot, and charge-discharge cycle measurement of simulated Ni/Zn cells. XRD patterns indicated that the coating was In͑OH͒ 3 . The SEM showed that In͑OH͒ 3 could be deposited and distributed on the surface of calcium zincate and in the interstice of calcium zincate particles. The coating of In͑OH͒ 3 decreases the direct contact of core calcium zincate with electrolyte and therefore suppresses the dissolution of calcium zincate in the electrolyte and retains calcium zincate at the electrode. The results of EIS and the Tafel plot indicated that the In͑OH͒ 3 -coated calcium zincate had a better alkali-tolerant performance than that of pure calcium zincate. The In͑OH͒ 3 -coated sample showed a much better capacity retention.The secondary zinc batteries have advantages of high specific energy, high specific power, and low cost. Nevertheless, the secondary zinc batteries are usually limited in widespread commercialization by poor cycling characteristics, which mainly resulted from the high solubility of discharge products of zinc electrode in alkaline electrolyte. Approaches reducing the problems include the use of additives in either the anode 1-3 or the electrolyte, 4,5 so that there are very few discharge products available in the electrolyte. These additives include alkaline earth metal hydroxides, halides, sulfates, and titanates. The addition of calcium hydroxide to the zinc electrode decreases zincate concentration and increases the life of secondary zinc batteries. 6,7 The reason is that calcium hydroxide reacts with the discharge product ZnO to give a compound calcium zincate with the molecular structure of Ca͑OH͒ 2 ·2Zn͑OH͒ 2 ·2H 2 O. 7,8 According to the chemical changes during cycling, the reduction of calcium zincate can be represented byFrom Eq. 1, we can see that neither of Ca͑OH͒ 2 and H 2 O is active material, only the Zn͑OH͒ 2 participates the electrochemical reduction to form zinc. 9 Researchers 10 found that a little amount of ZnO exists in the calcium zincate electrodes at the end of the discharge state; the possible explanation is that some ZnO cannot promptly react with Ca͑OH͒ 2 forming calcium zincate at the given discharge state.However, further study 10 indicates that an increase in the concentration of KOH solution leads to a higher capacity loss of calcium zincate. Because calcium zincate is stable only in weak or moderate alkaline solutions, 8,11 the increase in KOH solution concentration deteriorates the cyclic stability. In fact, a high concentration of electrolyte is a very important method to guarantee the highrate discharge ability for sealed cylindrical batteries. Thus, whether the difficulties in high-concentration electrolyte can be solved is very important for the commercialization of secondary zinc ba...

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Effect of Surface Modification with In(OH)[sub 3] on Electrochemical Performance of Calcium Zincate

Wang

Yang

Zeng

2009

J. Electrochem. Soc.

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“…The chemistry of the zinc electrodes containing Ca͑OH) 2 has been the subject of numerous investigations. [1][2][3][4][5][6]9,[12][13][14][15][16][17][18][19] Because the zinc electrode discharge products were too soluble in strong alkaline solutions, the addition of Ca͑OH) 2 was used to trap soluble zincate within its structure to form insoluble calcium zincate. This resulted in a reduced shape change of the zinc electrodes and longer cycle life.…”

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Calcium Zincate Synthesized by Ballmilling as a Negative Material for Secondary Alkaline Batteries

Yang

Zhang

Wang

et al. 2004

J. Electrochem. Soc.

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Calcium zincate has been successfully synthesized by a high-energy ballmilled method. The crystal structure, chemical composition, surface morphology, granularity distribution, and electrochemical performance have been investigated to compare with that prepared by a conventional chemical precipitation method. X-ray powder diffraction results revealed that the calcium zincate prepared by the two methods had a well-defined monoclinic structure using a Rietveld refinement method. Scanning electron microscope images and granularity analysis indicated that the ballmilled material was a finer powder with a higher specific surface area. The thermogravimetric and differential thermal analysis showed that there was a slight difference in the crystalline water content in the chemical composition of the powders prepared by the two methods. The galvanostatic charge and discharge results showed that the ballmilled powder had a promising cyclic behavior due to the better electrochemical stability as revealed from the cyclic voltammetry. It is suggested that the ballmilled calcium zincate is more suitable for applications in secondary alkaline batteries.

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Development of the High Rate Metal-Air Depolarized Batteries

Cited by 2 publications

References 0 publications

Effect of Surface Modification with In(OH)[sub 3] on Electrochemical Performance of Calcium Zincate

Effect of Surface Modification with In(OH)[sub 3] on Electrochemical Performance of Calcium Zincate

Calcium Zincate Synthesized by Ballmilling as a Negative Material for Secondary Alkaline Batteries

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