Journal article

Publication year: 2018

Pages: 37188-37197

Journal: ACS Applied Materials & Interfaces

Volume number: 10

Issue number: 43

ISSN: 1944-8244

eISSN: 1944-8252

Open access status: Green

DOI Link: https://doi.org/10.1021/acsami.8b09789

Publisher: American Chemical Society

Abstract: 
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.

Harvard Citation style: Kun, R., Langer, F., Delle Piane, M., Ohno, S., Zeier, W., Gockeln, M., et al. (2018) Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li₇La₃Zr₂O₁₂, ACS Applied Materials & Interfaces, 10(43), pp. 37188-37197. https://doi.org/10.1021/acsami.8b09789

APA Citation style: Kun, R., Langer, F., Delle Piane, M., Ohno, S., Zeier, W., Gockeln, M., Ciacchi, L., Busse, M., & Fekete, I. (2018). Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li₇La₃Zr₂O₁₂. ACS Applied Materials & Interfaces. 10(43), 37188-37197. https://doi.org/10.1021/acsami.8b09789