title: Li7La3Zr2O12 Interface Modification for Li Dendrite Prevention.
abstract: Al-contaminated Ta-substituted Li7La3Zr2O12 (LLZ:Ta), synthesized via solid-state reaction, and Al-free Ta-substituted Li7La3Zr2O12, fabricated by hot-press sintering (HP-LLZ:Ta), have relative densities of 92.7% and 99.0%, respectively. Impedance spectra show the total conductivity of LLZ:Ta to be 0.71 mS cm(-1) at 30 °C and that of HP-LLZ:Ta to be 1.18 mS cm(-1). The lower total conductivity for LLZ:Ta than HP-LLZ:Ta was attributed to the higher grain boundary resistance and lower relative density of LLZ:Ta, as confirmed by their microstructures. Constant direct current measurements of HP-LLZ:Ta with a current density of 0.5 mA cm(-2) suggest that the short circuit formation was neither due to the low relative density of the samples nor the reduction of Li-Al glassy phase at grain boundaries. TEM, EELS, and MAS NMR were used to prove that the short circuit was from Li dendrite formation inside HP-LLZ:Ta, which took place along the grain boundaries. The Li dendrite formation was found to be mostly due to the inhomogeneous contact between LLZ solid electrolyte and Li electrodes. By flatting the surface of the LLZ:Ta pellets and using thin layers of Au buffer to improve the contact between LLZ:Ta and Li electrodes, the interface resistance could be dramatically reduced, which results in short-circuit-free cells when running a current density of 0.5 mA cm(-2) through the pellets. Temperature-dependent stepped current density galvanostatic cyclings were also carried out to determine the critical current densities for the short circuit formation. The short circuit that still occurred at higher current density is due to the inhomogeneous dissolution and deposition of metallic Li at the interfaces of Li electrodes and LLZ solid electrolyte when cycling the cell at large current densities.
authors.affiliation: Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), Forschungszentrum Jülich GmbH , 52425 Jülich, Germany.|Jülich Aachen Research Alliance: JARA-Energy.
authors.forename: Chih-Long
authors.initials: CL
authors.lastname: Tsai
authors.affiliation: Institute of Materials Physics, University of Göttingen , Friedrich-Hund-Platz 1, 37077 Göttingen, Germany.
authors.forename: Vladimir
authors.initials: V
authors.lastname: Roddatis
authors.affiliation: Institute of Physical Chemistry and Electrochemistry, Leibniz University Hannover , Callinstrasse 3-3a, 30167 Hannover, Germany.
authors.forename: C Vinod
authors.initials: CV
authors.lastname: Chandran
authors.affiliation: Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), Forschungszentrum Jülich GmbH , 52425 Jülich, Germany.|Jülich Aachen Research Alliance: JARA-Energy.
authors.forename: Qianli
authors.initials: Q
authors.lastname: Ma
authors.affiliation: Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), Forschungszentrum Jülich GmbH , 52425 Jülich, Germany.|Jülich Aachen Research Alliance: JARA-Energy.
authors.forename: Sven
authors.initials: S
authors.lastname: Uhlenbruck
authors.affiliation: Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), Forschungszentrum Jülich GmbH , 52425 Jülich, Germany.|Jülich Aachen Research Alliance: JARA-Energy.
authors.forename: Martin
authors.initials: M
authors.lastname: Bram
authors.affiliation: Institute of Physical Chemistry and Electrochemistry, Leibniz University Hannover , Callinstrasse 3-3a, 30167 Hannover, Germany.
authors.forename: Paul
authors.initials: P
authors.lastname: Heitjans
authors.affiliation: Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), Forschungszentrum Jülich GmbH , 52425 Jülich, Germany.|Jülich Aachen Research Alliance: JARA-Energy.|Institute of Mineral Engineering, Rheinisch-Westfälische Technische Hochschule (RWTH) Aachen University, Mauerstrasse 5, 52064 Aachen, Germany.
authors.forename: Olivier
authors.initials: O
authors.lastname: Guillon
keywords: LLZ; Li ion conductivity; Li7La3Zr2O12; dendrite; solid electrolyte