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Structural and computational assessment of the influence of wet-chemical post-processing of the Al-substituted cubic Li7La3Zr2O12

: Kun, Róbert; Langer, Frederieke; Delle Piane, Massimo; Ohno, Saneyuki; Zeier, Wolfgang G.; Gockeln, Michael; Colombi Ciacchi, Lucio; Busse, Matthias; Fekete, István


ACS applied materials & interfaces 10 (2018), Nr.43, S.37188-37197
ISSN: 1944-8244
ISSN: 0013-936X
ISSN: 1944-8252
Fraunhofer IFAM ()
all-solid-state Li-ion battery; wet-processing; solvent compatibility; lithium ion conductor; garnet type Li7La3Zr2O12; composite electrolyte

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.