Electro-chemo-mechanical effects of lithium incorporation in zirconium oxide
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PhysRevMaterials.2.075405.pdf
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Author(s)
Yang, Jing
Youssef, Mostafa Youssef Mahmoud
Yildiz, Bilge
Date Issued
July 2018
Journal
Physical Review Materials
Publisher
American Physical Society
Citation
Yang, Jing et al. "Electro-chemo-mechanical effects of lithium incorporation in zirconium oxide." Physical Review Materials 2, 7 (July 2018): 075405 © 2018 American Physical Society
Version
Final published version
Abstract
Understanding the response of functional oxides to extrinsic ion insertion is important for technological applications including electrochemical energy storage and conversion, corrosion, and electronic materials in neuromorphic computing devices. Decoupling the complicated chemical and mechanical effects of ion insertion is difficult experimentally. In this work, we assessed the effect of lithium incorporation in zirconium oxide as a model system, by performing first-principles based calculations. The chemical effect of lithium is to change the equilibria of charged defects. Lithium exists in ZrO_{2} as a positively charged interstitial defect, and raises the concentration of free electrons, negatively charged oxygen interstitials, and zirconium vacancies. As a result, oxygen diffusion becomes faster by five orders of magnitude, and the total electronic conduction increases by up to five orders of magnitude in the low oxygen partial pressure regime. In the context of Zr metal oxidation, this effect accelerates oxide growth kinetics. In the context of electronic materials, it has implications for resistance modulations via ion incorporation. The mechanical effect of lithium is in changing the volume and equilibrium phase of the oxide. Lithium interstitials together with zirconium vacancies shrink the volume of the oxide matrix, release the compressive stress that is needed for stabilizing the tetragonal phase ZrO_{2} at low temperature, and promote tetragonal-to-monoclinic phase transformation. By identifying these factors, we are able to mechanistically interpret experimental results in the literature for zirconium alloy corrosion in different alkali-metal hydroxide solutions. These results provide a mechanistic and quantitative understanding of lithium-accelerated corrosion of zirconium alloy, as well as, and more broadly, show the importance of considering coupled electro-chemo-mechanical effects of cation insertion in functional oxides.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Massachusetts Institute of Technology. Department of Nuclear Science and Engineering
Massachusetts Institute of Technology. Laboratory for Electrochemical Interfaces
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DOI of Published Version
https://doi.org/10.1103/PhysRevMaterials.2.075405
