An extended conductive matrix facilitates a 100-fold enhancement in charge storage for reversible Fe(III/VI) super-iron thin films. These films were deposited, by electrochemical reduction of Na2FeO4, with an intrinsic high capacity 3 e- cathodic storage of 485 mAh g(-1). Whereas 3 nm Fe(III/VI) films exhibited a high degree of reversibility (throughout 100 charge/discharge cycles), thicker films had been increasingly passive toward the Fe(VI) charge transfer. Films were alternatively deposited on either smooth or on extended conductive matrixes composed of high-surface-area Pt, Ti, and Au and probed galvanostatically and via cyclic voltammetry. A 100 nm Fe(VI) cathode, on the extended conductive matrixes, sustained 100-200 reversible three-electrode charge/discharge cycles, and a 19 nm thin film cathode sustained 500 such cycles. With a metal hydride anode, full cell storage was probed, and a 250 nm super-iron film cathode film sustained 40 charge/discharge cycles, and a 25 nm film was reversible throughout 300 cycles. Fe(VI) salts exhibit higher cathodic capacity and environmental advantages, and the films are of relevance toward the next generation charge storage chemistry for reversible cathodes.

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