Physicochemical properties and functioning of negative electrodes with lead-based coatings as part of reserve chemical power sources

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Physicochemical properties of lead coating on steel substrates obtained by the galvanic method are studied by atomic force microscopy, scanning electron microscopy, X-ray diffraction phase analysis, voltammetry, and chronopotentiometry. The influence of the surface oxidized layer and through pores in the lead coating on the functioning of this coating as an anode of chemical power sources is studied. It is shown that at positive temperatures the process of anodic oxidation of the steel substrate can contribute to functioning of the anode at discharge. High discharge characteristics of lead-coated anodes without barrier layers on a steel substrate at temperatures from -50 to +50°C are confirmed by tests of pilot batches of reserve power sources of the Pb/HClO4/PbO2 system. Application of POS 63 tin-lead alloy on a copper substrate is shown to be promising for manufacturing anodes of chemical power sources.

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作者简介

P. Shcheglov

JSC Scientific and Production Association Pribor named after S. S. Golembiovsky

编辑信件的主要联系方式.
Email: godforsaken@inbox.ru
俄罗斯联邦, Moscow, 117587

D. Samsonov

JSC Scientific and Production Association Pribor named after S. S. Golembiovsky

Email: godforsaken@inbox.ru
俄罗斯联邦, Moscow, 117587

A. Pavlenkov

JSC Scientific and Production Association Pribor named after S. S. Golembiovsky

Email: godforsaken@inbox.ru
俄罗斯联邦, Moscow, 117587

T. Kulova

A. N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences

Email: tkulova@mail.ru
俄罗斯联邦, Moscow, 119071

A. Rychagov

A. N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences

Email: tkulova@mail.ru
俄罗斯联邦, Moscow, 119071

A. Skundin

A. N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences

Email: tkulova@mail.ru
俄罗斯联邦, Moscow, 119071

E. Postnova

Yu. A. Osipyan Institute of Solid State Physics, Russian Academy of Sciences

Email: tkulova@mail.ru
俄罗斯联邦, Chernogolovka, Moscow region, 142432

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2. Fig. 1. Typical surface profile of a lead coating on a steel substrate.

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3. Fig. 2. Images of the lead coating surface obtained by SEM at a magnification of 5×103 (a) and 5×104 (b).

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4. Fig. 3. Diffraction pattern of lead coating on steel substrate compared with literature data: a – diffraction pattern in a wide range of scanning angles; b – standard data for metallic lead (ICDD 96-153-1229); c – fragment of diffraction pattern on an enlarged scale; d, d, e – literature data for possible corrosion products: lead oxides and oxohydroxide (d); lead carbonate and oxocarbonates (d); lead hydroxycarbonate and oxohydroxycarbonates (e); 1 – metallic lead phase; 2 – impurity phases; 3 – litharge α-PbO2 (ICDD 5-0561); 4 – massikot β-PbO2 (ICDD 38-1477); 5 – Pb6O4(OH)4 [27–29]; 6 – cerussite PbCO3 (ICDD 47-1734); 7 – shannonite Pb2O(CO3) [30]; 8 – Pb3O2CO3 (ICDD 17-0731); 9 – hrutfonteinite Pb3O(CO3)2 [31]; 10 – hydrocerussite Pb3(OH)2(CO3)2 [32, 33]; 11 – plumbonacrite Pb5O(OH)2(CO3)3 [32]; 12 – somersetite Pb8O(OH)4(CO3)5 [32]; Irel – relative intensity; Θ – gliding angle.

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5. Fig. 4. External appearance of the surface of the lead coating on a steel substrate with through pores that appeared after treatment with a reagent solution in the form of dark blue spots.

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6. Fig. 5. Chronopotentiometric curves for anodes with lead coatings (1, 2, 3) in comparison with compact lead (4). Test temperature: +25°C (1), –50°C (2, 3, 4). Curve 3 was obtained with a repeated discharge cycle; E is potential; τ is time.

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7. Fig. 6. Potentiodynamic curves of samples made of 08kp steel tape in normal (a) and semi-logarithmic (b) coordinates at a temperature of +25°C (1) and –50°C (2). Designation: i – anode current density.

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8. Fig. 7. Chronopotentiometric discharge curves of Fe/HClO4/PbO2 (1, 2), Pb/HClO4/PbO2 (3, 4) and (Sn, Pb)/HClO4/PbO2 (5, 6) electrochemical cells. Test temperature: +50°C (1, 3, 5), +25°C (2), –50°C (4, 6); U – voltage.

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9. Fig. 8. Chronopotentiometric curves for anodes with tin-lead alloy coatings at temperatures of +25°C (1) and –50°C (2).

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10. Fig. 9. Discharge curves of pilot batches of current sources of the Pb/HClO4/PbO2 system at temperatures of +50 (1), +25 (2) and –50°C (3). The inset shows the initial sections of the discharge curves on an enlarged scale along the time axis.

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