Multiple Electron Charge Transfer Chemistries for Electrochemical Energy Storage Systems: The Metal Boride and Metal Air Battery
Open AccessThe primary focus of this work has been to develop high-energy capacity batteries capable of undergoing multiple electron charge transfer redox reactions to address the growing demand for improved electrical energy storage systems that can be applied to a range of applications. As the levels of carbon dioxide (CO2) increase in the Earth’s atmosphere, the effects on climate change become increasingly apparent. According to the Energy Information Administration (EIA), the U.S. electric power sector is responsible for the release of 2,039 million metric tons of CO2 annually, equating to 39% of total U.S. energy-related CO2 emissions. Both nationally and abroad, there are numerous issues associated with the generation and use of electricity aside from the overwhelming dependence on fossil fuels and the subsequent carbon emissions, including reliability of the grid and the utilization of renewable energies. Renewable energy makes up a relatively small portion of total energy contributions worldwide, accounting for only 13% of the 3,955 billion kilowatt-hours of electricity produced each year, as reported by the EIA. As the demand to reduce our dependence on fossils fuels and transition to renewable energy sources increases, cost effective large-scale electrical energy storage must be established for renewable energy to become a sustainable option for the future. A high capacity energy storage system capable of leveling the intermittent nature of energy sources such as solar, wind, and water into the electric grid and provide electricity at times of high demand will facilitate this transition. In 2008, the Licht Group presented the highest volumetric energy capacity battery, the vanadium diboride (VB2) air battery, exceedingly proficient in transferring eleven electrons per molecule. This body of work focuses on new developments to this early battery such as fundamentally understanding the net discharge mechanism of the system, evaluation of the properties and performance of nanoscopic anodic materials in addition to the previously developed macroscopic system, as well as the exploration of a high-energy capacity TiB2/VB2 composite anode. However, the greatest challenge to this room temperature VB2 primary battery is to develop a means to electrochemically recharge the anodic material (how to reinsert the eleven electrons per molecule that are removed during the battery’s discharge). Rechargeable batteries, such as the new molten air battery presented in this thesis, offer a high intrinsic capacity mode for energy storage and overcome problems such as the need for higher energy capacity, cost-effective batteries for a range of electronic, transportation, and large-scale power storage devices. Molten air batteries presented and discussed in this work are viable systems that provide a means to electrochemically recharge the VB2-air battery and deliver large-scale energy storage due to their scalability, location flexibility, construction from readily available resources, and offer increased energy storage capacity for the electric grid. One example is the VB2 molten air battery, which discharges according to:VB2 + 11/4 O2 → 1/2 V2O5 + B2O3 (1) Previously, our group has shown that carbon dioxide can be captured from atmospheric air concentrations at solar efficiencies as high as 50%, and that carbon dioxide emissions associated with the production of several commodities can be electrochemically avoided in by the Solar Thermal Electrochemical Process (STEP). Utilizing this process, the carbon molten air battery relies on carbon dioxide directly from the air:Charging: CO2 (g) → C (solid) + O2 (g) (2)Discharging: C (solid) + O2 (g) → CO2 (g) (3) More specifically, in a molten carbonate electrolyte containing added oxide, such as lithium carbonate with lithium oxide, the four-electron charging reaction, Equation 2, approaches 100% faradic efficiency and can be described as the following two equations:O2- (dissolved) + CO2 (g) → CO32- (molten) (2a)CO32- (molten) → C (solid) + O2 (g) + O2- (dissolved) (2b) Thus, powered by the oxidation of carbon formed directly from the CO2 in our earth’s atmosphere, the carbon molten air battery is a viable system to provide large-scale energy storage. These batteries are rechargeable and have amongst the highest intrinsic battery storage capacities available. The electron charge transfer chemistry is demonstrated through three examples. These examples utilize iron, carbon, and vanadium diboride as reactive materials, each containing intrinsic volumetric energy capacities of 10,000 Wh/L for Fe to Fe (III), 19,000 Wh/L for C to CO2, and 27,000 Wh/L for VB2 to B2O3 and V2O5, compared to 6,200 Wh/L for the lithium air battery.
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