Micellar cathodes from Self-assembled Nitroxide-containing block copolymers in battery electrolytes

Abstract

This contribution describes the synthesis of block copolymers containing electrochemically active blocks, their micellization, and finally their use as micellar cathodes in a lithium battery. The self-assembly of the synthesized poly(styrene)-block-poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PS-b-PTMA) diblock copolymers is realized in a typical battery electrolyte made of 1 m lithium trifluoromethanesulfonate dissolved in a mixture of ethylene carbonate/diethyl carbonate/dimethyl carbonate(1:1:1, in volume). Dynamic light scattering and atomic force microscopy indicate the formation of well-defined spherical micelles with a PS core and a PTMA corona. The electrochemical properties of those micelles are further investigated. Cyclic voltammograms show a reversible redox reaction at 3.6 V (vs Li+/Li). The charge/discharge profiles indicate a flat and reversible plateau around 3.6 V (vs Li+/Li). Finally, the cycling performances of the micellar cathodes are demonstrated. Such self-assembled block copolymers open new opportunities for nanostructured organic radical batteries. The self-assembly of poly(styrene)-block-poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) diblock copolymers into micellar cathodes is described. The obtained micelles are characterized by dynamic light scattering and atomic force microscopy. The micelles are embedded into a carbon nanotubes buckypaper to form a solid state cathode. The cathodes are tested in a Li-ion battery in a half-cell configuration. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.