ELECTROCHEMICAL REDUCTION OF BI2SR2CA1CU2O8 SUPERCONDUCTOR SINGLE-CRYSTALS

Single crystals and polycrystalline pellets of the high-temperature cuprate superconductor Bi2Sr2Ca1Cu2O8 were doped at room temperature by electrochemical reduction at > 95% Coulombic efficiency using lithium dopant ions in propylene carbonate electrolyte. Cyclic voltammetry and potential step measurements on single crystals suggest an unusual reduction mechanism, with a diffusion coefficient for Li+ in the c-axis direction of bulk superconductor of ca. 3 x 10(-11) cm2s-1. Sintered pellets of polycrystalline powder could be doped more rapidly, with an apparent diffusion coefficient of 7 x 10(-8) cm2s-1. X-ray susceptibility analysis show extensive disordering occurs on heavy Li doping, with a first-order transition from a crystalline/superconducting to an amorphous/non-superconducting phase. Single, crystals of Bi2Sr2Ca1Cu2O8 exhibited a color change on reduction from metallic gray to golden bronze. The reduced material was highly air-sensitive, forming a hydroxide surface film on exposure to ambient atmosphere.