Phase transformations and microstructural design of lithiated metal anodes for lithium-ion rechargeable batteries
Author(s)Limthongkul, Pimpa, 1975-
Massachusetts Institute of Technology. Dept. of Materials Science and Engineering.
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There has been great recent interest in lithium storage at the anode of Li-ion rechargeable battery by alloying with metals such as Al, Sn, and Sb, or metalloids such as Si, as an alternative to the intercalation of graphite. This is due to the intrinsically high gravimetric and volumetric energy densities of this type of anodes (can be over an order of magnitude of that of graphite). However, the Achilles' heel of these Li-Me alloys has been the poor cyclability, attributed to mechanical failure resulting from the large volume changes accompanying alloying. Me-oxides, explored as candidates for anode materials because of their higher cyclability relative to pure Me, suffer from the problem of first cycle irreversibility. In both these types of systems, much experimental and empirical data have been provided in the literature on a largely comparative basis (i.e. investigations comparing the anode behavior of some new material with older candidates). It is the belief of the author that, in order to successfully proceed with the development of better anode materials, and the subsequent design and production of batteries with better intrinsic energy densities, a fundamental understanding of the relationship between the science and engineering of anode materials must be achieved, via a systematic and quantitative investigation of a variety of materials under a number of experimental conditions. In this thesis, the effects of composition and processing on microstructure and subsequent electrochemical behavior of anodes for Li-ion rechargeable batteries were investigated, using a number of approaches.(cont.) First, partial reduction of mixed oxides including Sb-V-O, Sb-Mn-O, Ag-V-O, Ag-Mn-O and Sn-Ti-O, was explored as a method to produce anode materials with high cyclability relative to pure metal anodes, and decreased first cycle irreversibility relative to previously produced metal-oxides. The highest cyclability was achieved with anode materials where the more noble metal of the mixed oxide was reduced internally, producing nanoscale active particles which were passivated by an inactive matrix. Second, a systematic study of various metal anode materials, including Si, Sn, Al, Sb and Ag, of different starting particle sizes was undertaken, in order to better understand the micromechanical mechanisms leading to poor cyclability in these pure metals. SEM of these materials revealed fracture in particles of > 1 pm after a single discharge/charge cycle, consistent with literature models which predict such fracture due to volumetric strains upon lithiation. However, TEM of these materials revealed a nanocrystalline structure after one cycle that in some metals was mixed with an amorphous phase. STEM of anode materials after 50 cycles revealed a dissociation of this nanostructure into nanoparticles, suggesting a failure mechanism other than volumetric strains, such as chemical attack. Finally, the appearance of the amorphous phase was investigated in lithiated Si, Sn, Ag and Al metal anode systems. A new mechanism, electrochemically-induced solid-state amorphization was proposed and explored via experiments using calibrated XRD and TEM. Experimental observations of these various Me systems subjected to different degrees of lithiation supported such phenomenon...
Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2002.Includes bibliographical references.
DepartmentMassachusetts Institute of Technology. Dept. of Materials Science and Engineering.
Massachusetts Institute of Technology
Materials Science and Engineering.