Silver electrodes were studied by means of potentials and x‐ray diffraction patterns. The silver was charged anodically in 35%KOH by means of either constant current or constant potential, and discharged at a low or high rate. Attempts were made to form an oxide higher than normalAgO by means of anodization. The products of anodization of silver in 2N H2SO4 were determined. The basis for the theory that the oxides of silver are formed by the introduction of oxygen into the octants of the face‐centered cubic silver lattice was examined.

Silver electrodes were examined in 20–50% KOH using a cell permitting simultaneous x‐ray diffraction and electrochemical studies. Highly oriented smooth rolled sheet Ag developed randomly oriented Ag on its surface during early cycles. Charge‐discharge capacity increased to a maximum as surface area increased. normalAgO crystal size and amount formed varied inversely with charging c. d. High charge rates gave tight coatings of small normalAgO crystals that limited further oxidation. Reactions took place initially at the outer surface of the electrode. Oxidation to Ag2O and normalAgO and reduction to Ag2O and Ag occurred by formation of distinct crystals rather than expansion or contraction of preexisting crystal lattices. Discharge capacity at the normalAgO/Ag2O potential plateau depended more on surface area than on quantity of normalAgO . A slow discharge produced smoother Ag surfaces, lowering capacity of the next cycle. There was never evidence of a suboxide, oxidation state higher than normalAgO , solid solution, or alloy of oxygen and silver.

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Characteristics of the active material in lead positive plates were determined by light and electron microscopy, and by surface area analysis as the plates were cycled. Average size of PbSO4 in discharged plates gradually decreased with cycling. Some PbO2 usually remained within the PbSO4 crystals. Capacity loss was mainly caused by large areas developing where the PbO2 did not reduce on discharge. The rate of capacity loss decreased from 1.7 to 0.9% per cycle as discharge current density increased from 125 to 2000 A/m2 (3 hr to 4 min discharge rates). Capacity loss was only 0.3% per cycle at 18 A/m2 (24 hr rate) which suggests a different reaction mechanism. Surface area of the active material increased as discharge current density increased. The values for charged and discharged surface areas tended to approach each other with cycling.

Silver electrodes that had been manufactured for Ag-Zn storage batteries were cycled in 35% KOH at 25~ The electrodes were examined by optical microscopy. The initial Ag20 formation during a discharge at the 1-hr rate usually occurred on the surfaces of AgO clumps at many scattered areas throughout the electrode. After discharge potential fell to the Ag20/Ag plateau, Ag formation occurred on the electrode surface and then gradually spread to the interior as a discharge was continued. When a slow (20-hr) discharge rate was used, however, Ag formed at the surface and at the interior of an electrode simultaneously. * Electrochemical Society Active Member. Key words" ~iLver electrode, silver oxides, microstrueture. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 137.99.31.134 Downloaded on 2015-06-17 to IP Vol. 1t6, No. 6 ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 137.99.31.134 Downloaded on 2015-06-17 to IP