Single potential electrodeposition of nanostructured battery materials for lithium-ion batteries

The increasing reliance on portable electronics is continuing to fuel research in the area of low power lithium-ion batteries, while a new surge in research for high power lithium-ion batteries has been sparked by the demand for plug-in hybrid electric vehicles (PHEV) and plug-in electric vehicles (PEV). To compete with current lead-acid battery chemistry, a few of the shortcomings of lithium-ion battery chemistry need to be addressed. The three main drawbacks of lithium-ion batteries for this application are: (1) low power density, (2) safety, and (3) the high cost of manufacturing. This dissertation covers the development of a low cost fabrication technique for an alternative anode material with high surface area geometries. The anode material is safer than the conventional anode material in lithium-ion batteries and the high surface area geometries permit higher power densities to be achieved.;Electrodeposition is an inexpensive alternative method for synthesizing materials for electronics, energy conversion and energy storage applications relative to traditional solid state techniques. These techniques led to expensive device fabrication. Unlike most solid state synthesis routes, electrodeposition can usually be performed from common solutions and at moderate conditions. Three other benefits of using electrodeposition are: (1) it allows precise control of composition and crystallinity, (2) it provides the ability to deposit on complex shapes, and (3) it can deposit materials with nanoscale dimensions. The use of electrodeposition for alternative anode materials results in the deposition of the material directly onto the current collector that is used for the battery testing and applications without the need of additional binders and with excellent electrical contact. While this improves the characterization of the material and lowers the weight of the non-active materials within a battery, it also allows the anode to be deposited onto current collectors with different sizes, shapes, and surface areas. This is advantageous because high surface area materials benefit from improved kinetics for solid state transformations and from decreases in mechanical degradation that occurs during the lithiation and delithiation of battery materials.;Intermetallic materials are an alternative to conventional anode materials because they have high capacities and react reversibly with lithium at potentials that hinder the dendrite formation of metallic lithium. Unfortunately, the volume expansion associated with the lithiation and delithiation of intermetallic materials is usually large (over 300%). With this in mind a procedure for the electrodeposition of Cu2Sb from aqueous solutions was developed and is presented in this thesis. Cu2Sb is an intermetallic that lithiates at potentials more positive than the potential needed to plate lithium metal, and has a volume expansion less than 100%. Electrodeposition of an intermetallic with a relatively small volume expansion and with high surface area morphology should dramatically reduce material degradation during battery cycling, thus promoting the life of the material.;To electrodeposit Cu2Sb from aqueous solutions, soluble salts of Cu2+ and Sb3+ were needed. There are many Cu2+ salts that are highly soluble in water, but most Sb 3+ salts cause formation of Sb2O3 in aqueous solutions. To obtain Sb3+ in aqueous solutions, citric acid was used as a complexing agent. The results presented in this dissertation show that solution speciation plays an important role in the electrochemistry of aqueous citrate solutions of both copper and antimony. The cyclic voltammograms (CVs) presented here show that the reduction potential of Cu2+ shifted in the negative direction and the reduction potential of Sb 3+ shifted in the positive direction with an increase in pH. Also, Cu2Sb films were deposited at a single potential (-1050 mV vs. SSCE) from aqueous solutions at pH 6. We determined that the deposition potential not only affected the crystallinity of the deposited Cu2Sb, but also the ratio of antimony to copper. The temperature of the solution bath, as well as the smoothness of the growth substrate, were found to provide control over the crystallinity of the deposited Cu2Sb. The ability to electrodeposit crystalline Cu2Sb onto a variety of conducting surfaces is uncommon for intermetallics.;The ability to deposit Cu2Sb onto transmission electron microscopy (TEM) grids has allowed the investigation of the morphology, composition, and crystallinity of Cu2Sb during the nucleation and growth of the material. This investigation demonstrated that multiple transformations occur during the early stage of the nucleation of Cu2Sb. A deeper understanding of this electrodeposition procedure for this compound will be useful for extending this technique to other crystalline intermetallics. Using the procedure developed for the single potential deposition of Cu2Sb films, the information from the TEM investigation and the results of a qualitative mathematical treatment, a pulse potential deposition procedure for depositing Cu2Sb nanowire arrays was developed. This procedure leads not only to the deposition of crystalline Cu2Sb nanowires, but also to uniform filling of the templates to afford wires of uniform composition and length.;After the development of the procedures for the electrodeposition of Cu2Sb films and nanowire arrays from aqueous solutions at a single potential, the battery performance of the deposited Cu2Sb was examined. The ability to directly electrodeposit Cu2Sb onto the current collector has: (1) improved the characterization of the material during the lithiation and delithiation processes, (2) decreased the weight of inactive components, and (3) allowed for the deposition of high surface area Cu2Sb. The preliminary battery testing of electrodeposited Cu2Sb supported the absence of impurities in the deposited material and demonstrated that the electrodeposited Cu2Sb lithiated and delithiated similarly to Cu2Sb synthesized with different techniques. The deposition of Cu2Sb onto TEM grids was used for the first time without binder to characterize the morphology, composition and crystallinity changes that occur during the lithiation and delithiation of Cu2Sb. Superior capacity retention and rate performance was achieved with Cu2Sb electrodeposited onto high surface area copper foil. This superior performance demonstrates the improvement in battery performance that is expected from Cu2Sb nanowires, which have an order of magnitude higher surface area relative to the copper foam.