Electrode and Electrolyte Design for High Energy Density Batteries

Abstract

With the fast development of society, the demand for batteries has been increasing dramatically over the years. To satisfy the ever-increasing demand for high energy density, different chemistries were explored. From the first-generation lead–acid batteries to the state-of-the-art LIBs (lithium ion batteries), the energy density has been improved from 40 to over 200 Wh kg⁻¹. However, the development of LIBs has approached the upper limit. Electrode materials based on insertion chemistry generally deliver a low capacity of no more than 400 mAh/g. To break the bottleneck of current battery technologies, new chemistries are needed. Moving from the intercalation chemistry to conversion chemistry is a trend. The conversion electrode materials feature much higher capacity than the conventional intercalation-type materials, especially for the O₂ cathode and Li metal anode. The combination of these two can bring about a ten-folds of energy density increase to the current LIBs. Moreover, to satisfy the safety requirements, either using non-flammable electrolytes to reduce the safety risk of Li metal anode or switch to dendrite-free Mg anode is a good strategy toward high energy density batteries. First, to enable the conversion-type O₂ cathode, a wood-derived, free-standing porous carbon electrode was demonstrated and successfully be applied as a cathode in Li-O₂ batteries. The spontaneously formed hierarchical porous structure exhibits good performance in facilitating the mass transport and hosting the discharge products of Li₂O₂. Heteroatom (N) doping further improves the catalytic activity of the carbon cathode with lower overpotential and higher capacity. Next, to solve the irreversible Li plating/stripping and safety issues related with Li metal anode, we introduced O₂ as additives to enable Li metal anode operation in non-flammable triethyl phosphate (TEP) electrolyte. The electrochemically induced chemical reaction between O₂- derived species and TEP solvent molecules facilitated the beneficial SEI components formation and effectively suppressed the TEP decomposition. The promise of safe TEP electrolyte was also demonstrated in Li-O₂ battery and Li-LFP battery. If we think beyond Li chemistries, Mg anode with dendrite-free property can be a promising candidate to further reduce the safety concerns while remaining the high energy density advantage. Toward the end of this thesis, we developed a thin film metal–organic framework (MOF) for selective Mg²⁺ transport to solve the incompatibility issues between the anode and the cathode chemistry for Mg batteries.