Using Copper Nanoparticle Additive to Improve the Performance of Silicon Anodes in Lithium-Ion Batteries

Abstract

In the foreseeable future, global energy demand is expected to rapidly increase as a result of the swelling population and higher standards of living. Current energy generation and transportation methods predominantly involve the combustion of non-renewable fossil fuels, and greenhouse gas emissions from these processes have been shown to contribute to global climate change and to be detrimental to human and environmental health. To satisfy future energy needs and to reduce greenhouse gas emissions, the advancement of renewable energy generation and electric vehicles is important. The proliferation of intermittent renewable energy sources (such as solar and wind) and electric vehicles depends upon reliable, high-capacity energy storage to serve the practical needs of society. The present-day lithium-ion battery offers excellent qualities for this purpose; however, improvements in the capacity and cost-effectiveness of these batteries are needed for further growth. As an anode material, silicon has exceptionally high theoretical capacity and is an earth-abundant, low-cost option. However, silicon also suffers from poor conductivity and long-term stability, prompting many studies to investigate the use of additive materials to mitigate these issues. This thesis focuses on the improvement of silicon anode performance by using a nanoparticulate copper additive to increase material conductivity and an inexpensive, industry-compatible anode fabrication process. Three main fabrication processes were explored using differing materials and heat treatment techniques for comparison. Anodes were tested using CR2032 type coin cells. The final anodes with the most-improved characteristics were fabricated using a high-temperature heating step for the anode material, and an additional batch was formed to test the viability of the copper additive functioning as a full substitute for carbon black, which is the traditional choice of conductive additive for electrode materials. Anodes materials were characterized using a variety of techniques including scanning electron microscopy (SEM), electron dispersive spectroscopy (EDS), inductively coupled plasma optical emission spectrometry (ICP-OES), Raman spectroscopy, and X-ray diffraction (XRD) to evaluate surface qualities and material content. Electrochemical techniques including electrochemical impedance spectroscopy (EIS) and charge/discharge cycling were also used to determine the conductivity and functional behavior of the anode materials. Anodes from the final experimental study achieved initial capacities of 309 mA/g and 957 mA/g for the silicon-only control and silicon with copper additive anodes, respectively, demonstrating an over 300% increase in specific capacity. Si-Cu (NC) anodes also showed superior performance over control anodes with an initial capacity of 775 mA/g. For all three anodes, high efficiencies of over 96% were achieved for the testing duration of 100 cycles and reached near or over 99% in final cycles. Results also show a significant decrease in the resistance of anodes with copper additive, contributing to the improved performance of these anodes.