Freeze Tape Cast Thick Mo Doped Li 4 Ti 5 O 12 Electrodes for Lithium-Ion Batteries

Abstract

Lithium titanate (Li 4 Ti 5 O 12 ) powders with and without molybdenum doping (LTO and MoLTO respectively) were synthesized by a solid-state method and used to fabricate electrodes on Cu foil using a normal tape-cast method and a novel freeze-tape-cast method. Modest molybdenum doping produces a significant electronic conductivity increase (e.g. 1 mS cm −1 for MoLTO vs 10− 7 mS cm −1 for LTO) that is thought to reflect a partial Ti 4+ reduction to Ti 3+ with charge compensation by the Mo 6+ dopant, producing a stable mixed-valent Ti 4+/3+ state. Freeze-tape-cast electrodes were fabricated by a variant of the normal tape-cast method that includes a rapid freezing step in which the solvent in the Cu-foil-supported slurry is rapidly frozen on a cold finger then subsequently sublimed to create unidirectional columnar macropores in the electrode. The resulting electrodes exhibit high porosity and low tortuosity which enhances electrolyte accessibility throughout the full electrode thickness. Freeze-tape-cast electrodes subjected to galvanostatic charge-discharge testing as cathodes in cells vs. a lithium metal anode exhibit higher specific capacity and lower capacity loss at high discharge rates compared with normal-tape-cast electrodes of the same mass loading, despite the fact that the freeze-tape-cast electrodes are nearly twice as thick as the normal tape cast electrodes.