Tianyu Zhu

Date of Award

Fall 2019

Document Type

Open Access Dissertation


Chemistry and Biochemistry

First Advisor

Chuanbing Tang

Second Advisor

Brian C. Benicewicz


Metal-containing polyelectrolytes (or metallo-polyelectrolytes) represent a new class of polymeric materials with distinct properties compared to traditional organo- polyelectrolytes or neutral metallopolymers. This emerging class of synthetic materials is ubiquitous for a myriad of utilities ranging from traditional electrolyte chemistry to biomedicals to sustainable applications, to name just a few. This dissertation work is focused on the design, synthesis, characterization and application of advanced metallo- cations and metallo-polyelectrolytes for energy storage applications. First, a template method to prepare metallo-polyelectrolytes based on cationic cobaltocene and polyethylene backbone was described. The resulting membranes are mechanically tough, ionically conductive and chemically inert. Second, a family of substituted cobaltocenium cations and their derivatives was designed by theoretical calculation and experimentally synthesized for the first time. The redox behaviors and chemical stability of these metallo- cations were systematically examined and complemented those of state-of-the-art organic cations. Furthermore, substituted cobaltocene cation was integrated to construct solid polyelectrolyte membranes for energy storage devices (e.g. solid-state alkaline fuel cells). The device performance of these polyelectrolytes under highly basic and oxidative environments is also discussed.

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