The possibility of in situ activation of oxygen evolving anodes and hydrogen evolving cathodes in alkaline water electrolysers has been investigated. It is possible to activate anodes by depositing on them cobalt oxide or iron oxide or an even more active mixture of both. In all three cases the oxyg
Electrocatalytic and thermal activation of anodic oxygen- and cathodic hydrogen-evolution in alkaline water electrolysis
✍ Scribed by H. Wendt; V. Plzak
- Publisher
- Elsevier Science
- Year
- 1983
- Tongue
- English
- Weight
- 763 KB
- Volume
- 28
- Category
- Article
- ISSN
- 0013-4686
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✦ Synopsis
In micro-electrolysis cells (4 cm' electrode area) which possess a sandwichconfiguration as used irradvanced water electrolysis[ l] different anodic and cathodic electrocatalysts, which did not contain noble metals were investigated over the current density range from 10ea to 1.0 Acm-' and a temperature range from 30 to 130°C (electrolyte: SO wt % caustic potash). Mechanically activated nickel electrodes, RuOz doped anodes and Pt-black covered cathodes served as comparison standards for Hz and O2 evolution. IR-drop connections were not applied. Nonetheless the measuring-method used allowed to keep IRinduced mistakes in voltage-reading in single-electrode voltages below 40 mV even at the highest current densities of 1.0 Acm-'. Plots of voltage DS log current densities for anodic oxygen evolution possess slopes between 40 and 70 mV (lOO°C) de-c-' of current density which in some cases--especiaIly at low temperatures-increased up to a value of 2 R T/F at higher current densities. By increasing the temperature these steeper parts of the anodic current-voltage curves very often disappear. The current-voltage curves ofanodic oxygen evolution for different temperatures unexpectedly run nearly parallel to each other ia with a slope which is nearly independent of temperatureand thus cannot be dncribed according to the Butler-Volmer equation with a constant value of the formal charge-transfer coefficient 8'. The effective activation energies obtained from dln i,/d(l/T) range from 70 to 100 kJ mole-'. 0, overpotentials at current densities around 1 A cm-' are most efficiently decreased by (i) application of mixed oxides containing cobalt in at least two different valency states (Co n/Co 111 or Co In/Co Iv) and (ii) by use of higher working temperatures; roughened surfaccs, however, are only of limited value in this respect. Voltage US log current curves for cathodic hydrogen evolution show a pattern which is in agreement with the Butler-Volmer equation. The effective charge-transfer coefficient is close to 0.5 and increases slightly above this value for Raney-metal activated cathodes. The effective activation energies lie between the limits of 40 and 55 kJ mol-'. Hydrogen evolution overpotenrials are most efficiently decreased by (i) preparation of cathode surfaces with high roughness factors, (ii) using Ni, Co or Fe as cathode material and (iii) by increasing the working temperatures.
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