The charge injection limits of a Pt electrode using 0.2 ms charge balanced, biphasic current pulses ranged from 50 to 150 microC/cm2 geometric if the potential excursions of the electrode are kept below those at which H2 or O2 is produced. These charge densities are three to ten times smaller than the currently accepted value based on earlier experiments in which the reversible surface reactions were fully utilized and the pulse widths were longer.
Smaller, more charge-intensive electrodes are needed for "safe" stimulation of the nervous system. In this paper we review critical concepts and the state of the art in electrodes. Control of charge density and charge balance are essential to avoid tissue electrolysis. Chemical criteria for "safe" stimulation are reviewed ("safe" is equated with "chemically reversible"). An example of a safe, but generally impractical, charge-injection process is double-layer charging. The limit here is the onset of irreversible faradaic processes. More charge can be safely injected with so-called "capacitor" electrodes, such as porous intermixtures of Ta/Ta2O5. BaTiO3 has excellent dielectric properties and may provide a new generation of capacitor electrodes. Faradaic charge injection is usually partially irreversible since some of the products escape into the solution. With Pt, up to 400 muc/cm2 real area can be absorbed by faradaic reactions of surface-adsorbed species, but a small part is lost due to metal dissolution. The surface of "activated" Ir is covered with a multilayer hydrated oxide. Charge injection occurs via rapid valence change within this oxide. Little or no metal dissolution is observed, and gassing limits are not exceeded even under stringent conditions.
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