Kun, R., Langer, F., Delle Piane, M., Ohno, S., Zeier, W.G., Gockeln, M., Colombi Ciacchi, L., Busse, M., Fekete, I.

ACS Applied Materials and Interfaces (2018) , . Article in Press. 

https://pubs.acs.org/doi/10.1021/acsami.8b09789

Li₇La₃Zr₂O₁₂ (LLZO) and related compounds are considered as promising candidates for future all-solid-state Li-ion battery applications. Still, the processing of those materials into thin membranes with the right stoichiometry and crystal structure is difficult and laborious. The sensitivity of the Li-ion conductive garnets against moisture and the associated Li⁺/H⁺ cation exchange makes their processing even more difficult. Formulation of suitable polymer/ceramic hybrid solid state electrolytes could be a prosperous way to reach the future large scale production of solid state Li-ion batteries. In fact, solvent mediated and/or slurry based wet-processing of the LLZO, e.g., tape-casting, could result in irreversible Li-ion loss of the pristine material due to Li⁺/H⁺ cation exchange. The concomitant structural changes and loss in functionality in terms of Li-ion conductivity are the results of the above process. Therefore, in the present work a systematic study on the chemical stability and structural retention of Al-substituted LLZO in different solvents is reported. It was found that Li⁺/H⁺ exchange in LLZO occurs upon solvent immersion, and its magnitude is dependent on the availability of −OH functional groups of the solvent molecules. As a result, a larger degree of Li⁺/H⁺ exchange causes higher increase of the lattice parameter of the LLZO, determined by synchrotron diffraction analyses. The expansion of the cubic unit cell was ascertained, when Li⁺ was replaced by H⁺ in the host lattice, by ab initio computational studies. The application of the most common solvent as dispersion medium, i.e., high purity water, causes the most significant Li⁺/H⁺ exchange and, therefore, structural change, while acetonitrile was proven to be the best suitable solvent for wet postprocessing of LLZO. Finally, computational calculations suggested that the Li⁺/H⁺ exchange could result in diminished ionic, i.e., mixed Li⁺–H⁺, conductivity due to the insertion of protons with lower mobility than that of Li-ions.