Lithium alloys with metallic or semi-metallic elements are attractive candidate materials for the next-generation rechargeable Li-ion battery anodes, thanks to their large specific and volumetric capacities. The key challenge, however, has been the large volume changes, and the associated stress buildup and failure during cycling. The chemo-mechanics of alloy-based electrode materials entail interactions among diffusion, chemical reactions, plastic flow, and material property evolutions.
In this study, a continuum theory of two-way coupling between diffusion and deformation is formulated and numerically implemented. Analyses based on this framework reveal three major conclusions. First, the stress-to-diffusion coupling in Li/Si is much stronger than what has been known in other electrode materials. Practically, since the beneficial effect of stress-enhanced diffusion is more pronounced at intermediate or higher concentrations, lower charging rates should be used during the initial stages of charging. Second, when plastic deformation and lithiation-induced softening take place, the effect of stress-enhanced diffusion is neutralized. Because the mechanical driving forces tend to retard diffusion when constraints are strong, even in terms of operational charging rate alone, Li/Si nano-particles are superior to Li/Si thin films or bulk materials. Third, the diffusion of the host atoms can lead to significant stress relaxation even when the stress levels are below the yield threshold of the material, a beneficial effect that can be leveraged to reduce stresses because the host diffusivity in Li/Si can be non-negligible at higher Li concentrations.
A theory of coupled chemo-mechanical fracture driving forces is formulated in order to capture the effect of deformation-diffusion coupling and lithiation-induced softening on fracture. It is shown that under tensile loading, Li accumulates in front of crack tips, leading to an anti-shielding effect on the energy release rate. For a pre-cracked Li/Si thin-film electrode, it is found that the driving force for fracture is significantly lower when the electrode is operated at higher Li concentrations -- a result of more effective stress relaxation via global yielding. The results indicate that operation at higher concentrations is an effective means to minimize failure of thin-film Li/Si alloy electrodes.
| Identifer | oai:union.ndltd.org:GATECH/oai:smartech.gatech.edu:1853/49027 |
| Date | 20 September 2013 |
| Creators | Gao, Yifan |
| Contributors | Zhou, Min |
| Publisher | Georgia Institute of Technology |
| Source Sets | Georgia Tech Electronic Thesis and Dissertation Archive |
| Language | en_US |
| Detected Language | English |
| Type | Dissertation |
| Format | application/pdf |
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