September 15, 2012
Journal Article

H+ diffusion and electrochemical stability of Li1+x+yAlxTi2-xSiyP3-yO12 glass in aqueous Li/air battery electrolytes

Abstract

It is well known that LATP (Li1+x+y AlxTi2-x SiyP3-yO12) glass is a good lithium ion conductor. However, the interaction between LATP glass and H+ ions (including its diffusion and surface adsorption) needs to be well understood before the long-term application of LATP glass in an aqueous electrolyte based Li-air batteries where H+ always present. In this work, we investigate the H+ ion diffusion properties in LATP glass and their surface interactions using both experimental and modeling approaches. Our analysis indicates that the apparent H+ related current observed in the initial cyclic voltammetry scan should be attributed to the adsorption of H+ ions on the LATP glass rather than the bulk diffusion of H+ ions in the glass. Furthermore, the density functional theory calculations indicate that the H+ ion diffusion energy barrier (3.21 eV) is much higher than that of Li+ ion (0.79 eV) and Na+ ion (0.79 eV) in NASICON type LiTi2(PO4)3 material. As a result, the H+ ion conductivity in LATP glass is negligible at room temperature. However, significant surface corrosion was found after the LATP glass was soaked in strong alkaline electrolyte for extended time. Therefore, appropriate electrolytes have to be developed to prevent the corrosion of LATP glass before its practical application for Li-air batteries using aqueous electrolyte.

Revised: February 21, 2013 | Published: September 15, 2012

Citation

Ding F., W. Xu, Y. Shao, X. Chen, Z. Wang, F. Gao, and X. Liu, et al. 2012. H+ diffusion and electrochemical stability of Li1+x+yAlxTi2-xSiyP3-yO12 glass in aqueous Li/air battery electrolytes. Journal of Power Sources 214. PNNL-SA-85600. doi:10.1016/j.jpowsour.2012.04.058