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Effects of the Silicon Content on the Dimensional Changes of Electrodes for Lithium-ion Cells: An Electrochemical Dilatometry Study
Title
Effects of the Silicon Content on the Dimensional Changes of Electrodes for Lithium-ion Cells: An Electrochemical Dilatometry Study
Creator
Rodrigues Prado, Andressa Yasmim
Date
2021
Description
The continuous growth of the electric vehicle market has significantly increased the demand for Li-ion batteries (LIBs). However, state-of-the...
Show moreThe continuous growth of the electric vehicle market has significantly increased the demand for Li-ion batteries (LIBs). However, state-of-the-art LIBs are not yet able to meet the EV industry demand for high energy density and long cycle life rechargeable batteries, prompting efforts to improve the performance of Li-ion cells. In this context, silicon became the most promising next-generation active material for LIBs negative electrodes, especially because Si can significantly increase the lithium storage capacity of the commonly available anodes. Nonetheless, commercialization of Si-based electrodes has been hindered by the poor electrochemical performance of these electrodes, which is mainly attributed to the severe volumetric changes in the silicon particles related to the electrochemical reactions with Li. Since the electrodes are composites with a complex combination of various materials interspaced by pores, the electrode-level swelling may differ significantly from the particle-scale expansion. Furthermore, an increase in electrode thickness due to silicon expansion can have a direct effect on how Li-ion cells are designed, as the accommodation of electrode dilation requires additional cell space to prevent significant dynamic stresses. Thus, the actual volumetric energy density of a LIB cell depends on the electrode swelling, since the higher the magnitude of the electrode expansion, the lower the gains in energy density. Monitoring the electrode dilation is just as important as the electrochemical evaluation when designing cells with Si-based anodes.In this work, we use high-resolution operando electrochemical dilatometry to quantify the (de)lithiation-induced expansion/contraction of silicon, blended silicon-graphite and graphite electrodes, upon electrochemical cycling. We evaluate the relationship between electrode capacity and dilation and observe that while the lithiation capacity improved with increasing the silicon content, the electrode swelling is highly aggravated. For silicon-rich anodes, the electrode dilation can be higher than 300%, and the expansion profile consists of a combination of slow swelling at low levels of lithiation followed by an accelerated increase at higher lithium contents. This non-linear dilation allows for narrowing the swelling by limiting the electrode capacity. In addition, we investigate how electrode properties, such as porosity, affect the dilation profile, and quantify the irreversible expansion of the electrodes. Finally, we discuss some of the challenges associated with the dilatometry technique and suggest experimental approaches for obtaining consistent and reliable data.
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Melt Growth of Indium-Iodide on Earth and in Microgravity
Title
Melt Growth of Indium-Iodide on Earth and in Microgravity
Creator
Riabov, Vladimir
Date
2023
Description
Indium Iodide is a heavy metal halide and a wide band-gap semiconductor which has a potential for application in room temperature γ- and X-ray...
Show moreIndium Iodide is a heavy metal halide and a wide band-gap semiconductor which has a potential for application in room temperature γ- and X-ray detectors. Its physical properties are similar to those of other materials used as room temperature radiation detectors. Over the years the technology of purification and crystal growth of InI was developed. Significant advances were made to improve purity, crystal structure and resulting electronic properties of the material. Nevertheless, the desired detector performance has not been achieved yet. Stress-induced crystal lattice defects resulting from solidification in contact with crucible are suspected to be responsible for the limited performance. Microgravity environment was previously used to study its effects on the process of crystal growth from the melt applied to semiconductors. It was observed that unlike on Earth materials can solidify without contact with the wall, when the sample is confined by the crucible. It was also shown that such detached solidification can drastically reduce stress-induced defects of the crystal lattice and improve electronic properties of the material. In this study crystal growth of InI was studied in microgravity, attempting to achieve detached solidification, and observe it in a transparent zone of a furnace. Partially detached solidification (a large free surface) has occurred in one of the samples. The resulting crystals were characterized by measuring their electronic properties and estimating the radiation detector performance of the devices manufactured using the crystals.
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