The Material Design of Stable Cathodes in Li-Oxygen Batteries and Beyond

Thesis advisor: Dunwei WangNon-aqueous Li-O2 batteries promise the highest theoretical specific energy among all rechargeable batteries. It is the only candidate that can be comparable with the internal combustion engine in terms of gravimetric energy density. This makes Li-O2 batteries preferable in the application of electric vehicles or drones. However, the materialization of this technology has been hindered by the poor cycling performance. The major reason for the degradation of the battery at the current research stage has been identified as the decomposition of the electrolyte and the cathode. These parasitic reactions will lower the yield of the desired product and induce huge overpotential during the recharge process. By carefully examining the degradation mechanism, we have identified the reactive oxygen species as the culprit that will corrode the cathode and attack the organic solvents. While parallel efforts have been devoted to reduce the reactivity of these species toward electrolyte, the main focus of this thesis is to identify suitable material platforms that can provide optimum performance and stability as cathodes. A bio-inspired wood-derived N-doped carbon is first introduced to demonstrate the benefit of hierarchical pore structures for Li-O2 cathodes. But the instability of the carbon cathode itself limits the lifetime of the battery. To improve the stability of carbon, we further introduce a catalytic active surface coating of FeOx on a three dimensionally ordered mesoporous carbon. The isolation of carbon from the reactive intermediates greatly improves the stability of the cathode. Yet the imperfections of the protection layer on carbon calls for a stable substrate that can replace carbon. TiSi2 is explored as the candidate. With the decoration of Pd catalysts, the Pd/TiSi2 cathode can provide extraordinary stability toward reactive oxygen species. But this composite cathode suffers from the detachment of the Pd catalyst. A Co3O4 surface layer is further introduced to enhance the adhesion of the catalyst, which doubles the lifetime of the cathode. To achieve a fully stable cathode, Ru catalyst with stronger adhesion on TiSi2 directly is explored and identified to be robust in the operating conditions of Li-O2 batteries. The expedition for stable cathodes in Li-O2 batteries is expected to provide a clean material platform. This platform can simplify the study in evaluating the effectiveness of catalysts, the reaction mechanism at the cathode and the stability of the electrolyte. Toward the end of this thesis, an exploration is made to enable rechargeable Mg metal battery with a conversion Br2 cathode. This new system can avoid the dendritic growth of Li metal by the adoption of Mg as the anode and can promise better cathode kinetics by forming a soluble discharge product.Thesis (PhD) — Boston College, 2017.Submitted to: Boston College. Graduate School of Arts and Sciences.Discipline: Chemistry