Li7La3Zr2O12 Interface Modification for Li Dendrite Prevention.

ABSTRACT

Al-contaminated Ta-substituted Li7La3Zr2O12 (LLZTa), synthesized via solid-state reaction, and Al-free Ta-substituted Li7La3Zr2O12, fabricated by hot-press sintering (HP-LLZTa), have relative densities of 92.7% and 99.0%, respectively. Impedance spectra show the total conductivity of LLZTa to be 0.71 mS cm(-1) at 30 °C and that of HP-LLZTa to be 1.18 mS cm(-1). The lower total conductivity for LLZTa than HP-LLZTa was attributed to the higher grain boundary resistance and lower relative density of LLZTa, as confirmed by their microstructures. Constant direct current measurements of HP-LLZTa 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-LLZTa, 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 LLZTa pellets and using thin layers of Au buffer to improve the contact between LLZTa 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.