Date of Award

Spring 1-1-2013

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Mechanical Engineering

First Advisor

Se-Hee Lee

Second Advisor

Steven George

Third Advisor

Y. C. Lee

Fourth Advisor

Conrad Stoldt

Fifth Advisor

Chunmei Ban

Abstract

One of the greatest challenges of modern society is to stabilize a consistent energy supply that will meet our growing energy demand while decreasing the use of fossil fuels and the harmful green house gases which they produce. Developing reliable and safe solutions has driven research into exploring alternative energy sources for transportation including fuel cells, hydrogen storage, and lithium-ion batteries (LIBs). For the foreseeable future, though, rechargeable batteries appear to be the most practically viable power source. To deploy LIBs in next-generation vehicles, it is essential to develop electrodes with durability, high energy density, and high power. Unfortunately, the power capability of LIBs is generally hindered by Li+-ion diffusion in micrometer-sized materials and the formation of an insulating solid electrolyte interface (SEI) layer on the surface of the active material. In addition, degradation of the battery material due to chemical and electrochemical reactions with the electrolyte lead to both capacity fade and safety concerns both at room and higher temperatures. The current study focuses on mitigating these issues for high voltage cathode materials by both using nanoscale particles to improve Li+-ion diffusion and using ultrathin nanoscale coatings to protect the battery materials from undesirable side reactions. The electrode material is coated with Al2O3 using atomic layer deposition (ALD), which is a method to grow conformal thin films with atomic thickness (angstrom level control) using sequential, self-limiting surface reactions. First, nano-LiCoO2 is employed to demonstrate the effectiveness of ALD coatings and demonstrates a profound increase in rate performance (>250% improvement) over generally employed micrometer-sized particles. Second, the cathode materials LiNi0.8Co0.15Al0.05O2, LiNi0.33Mn0.33Co0.33O2, LiMn2O4, and LiNi0.5Mn1.5O4 were used to demonstrate the benefits ALD coatings have on thermal runaway. The results show a decrease in exothermic reactions at elevated temperatures (>180 °C) for the coated versus uncoated material. Third, impedance studies were carried out on LiNi0.5Mn1.5O4 to study the kinetic effects the ALD layer has on battery performance. These studies show that despite Al2O3 being electrically resistive in the bulk; the ultrathin coatings do not impede battery reaction kinetics. Finally, ALD coatings were studied for use in Li-O2 batteries. The results from these studies provide new opportunities for the battery industry to design other novel electrodes that are highly durable, safe, and provide good power performance. It also demonstrates that many of the issues that are detrimental to LIBs may simply be addressed by employing the scalable technique of atomic layer deposition.

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