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The Incorporation of Lithium Alloying Metals into Carbon Matrices for Lithium Ion Battery Anodes Open Access

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An increased interest in renewable energies and alternative fuels has led to recognition of the necessity of wide scale adoption of the electric vehicle. Automotive manufacturers have striven to produce an electric vehicle that can match the range of their petroleum-fueled counterparts. However, the state-of-the-art lithium ion batteries used to power the current offerings still do not come close to the necessary energy density. The energy and power densities of the lithium ion batteries must be increased significantly if they are going to make electric vehicles a viable option.The chemistry of the lithium ion battery, based on lithium cobalt oxide cathodes and graphite anodes, is limited by the amount of lithium the cathode can provide and the anode will accept. While these materials have proven themselves in portable electronics over the past two decades, plausible higher energy alternatives do exist. The focus is of this study is on anode materials that could achieve a capacity of more than 3 times greater than that of graphite anodes.The lithium alloying anode materials investigated and reported herein include tin, arsenic, and gallium arsenide. These metals were synthesized with nanoscale dimensions, improving their electrochemical and mechanical properties. Each exhibits their own benefits and challenges, but all display opportunities for incorporation in lithium ion batteries. Tin is incorporated in multilayer graphene nanoshells by introducing small amounts of metal in the core and, separatedly, on the outside of these spheres. Electrolyte decomposition on the anode limits cycle life of the tin cores, however, tinviioxides introduced outside of the multilayer graphene nanoshells have greatly improved long term battery performance.Arsenic is a lithium alloying metal that has largely been ignored by the research community to date. One of the first long term battery performance tests of arsenic is reported in this thesis. Anodes were made from nanoscale arsenic particles that were synthesized on multiwall carbon nanotubes by akalide reduction. The performance of these anodes proved sensitive to electrolyte composition, which was significantly improved by using fluorinated ethylene carbonate. Additionally, further gains in capacity retention can be made by limiting the loading voltage to 0.75 V vs lithium metal. The arsenic and multiwall carbon nanotube composite was found to have excellent cycle life and capacity at high mass loading (80% arsenic) when the nanoparticles were directly synthesized on the multiwall carbon nanotubes.Gallium arsenide is well known for its semiconducting properties, but its performance as in Li-ion battery anodes is first reported here. Gallium is a metal with a low melting point that has been touted as a possible self-healing material for lithium ion anodes. Alone, gallium proves to be unstable as a lithium ion battery anode, but when synthesized as gallium arsenide nanoparticles and mixed with multiwall carbon nanotubes it can charge and discharge in a battery 100 times with approximately twice the capacity of graphite anodes. This first study of gallium arsenide shows dramatic cycle life improvements by using nanoscale rather that micron size gallium arsenide.

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