Several “Beyond Li-Ion Battery” concepts such as all solid-state batteries and hybrid liquid/solid systems envision the use of a solid electrolyte to protect Li-metal anodes. These configurations are very attractive due to the possibility of exceptionally high energy densities and high (dis)charge rates, but they are far from being realized practically due to a number of issues including high interfacial resistance and difficulties associated with fabrication. One of the most promising solid electrolyte systems for these applications is Al or Ga stabilized Li₇La₃Zr₂O₁₂ (LLZO) based on high ionic conductivities and apparent stability against reduction by Li metal. Nevertheless, the fabrication of dense LLZO membranes with high ionic conductivity and low interfacial resistances remains challenging; it definitely requires a better understanding of the structural and electrochemical properties. In this study, the phase transition from garnet (Ia3̅d, No. 230) to “non-garnet” (I4̅3d, No. 220) space group as a function of composition and the different sintering behavior of Ga and Al stabilized LLZO are identified as important factors in determining the electrochemical properties. The phase transition was located at an Al:Ga substitution ratio of 0.05:0.15 and is accompanied by a significant lowering of the activation energy for Li-ion transport to 0.26 eV. The phase transition combined with microstructural changes concomitant with an increase of the Ga/Al ratio continuously improves the Li-ion conductivity from 2.6 × 10^–4 S cm^–1 to 1.2 × 10^–3 S cm^–1, which is close to the calculated maximum for garnet-type materials. The increase in Ga content is also associated with better densification and smaller grains and is accompanied by a change in the area specific resistance (ASR) from 78 to 24 Ω cm², the lowest reported value for LLZO so far. These results illustrate that understanding the structure–properties relationships in this class of materials allows practical obstacles to its utilization to be readily overcome.

Li NMR spectroscopy reveals rapid Li ion dynamics in the poor Li ion conductor Li ₆ PS ₅ I; long-range motion is, however, only possible for Li ₆ PS ₅ Br and Li ₆ PS ₅ Cl with anion site disorder.

Solid electrolytes potentially enable rechargeable batteries with lithium metal anodes possessing higher energy densities than today's lithium ion batteries. To do so the solid electrolyte must suppress instabilities that lead to poor coulombic efficiency and short circuits. In this work, lithium electrodeposition was performed on single-crystal Li₆La₃ZrTaO₁₂ garnets to investigate factors governing lithium penetration through brittle electrolytes. In single crystals, grain boundaries are excluded as paths for lithium metal propagation. Vickers microindentation was used to introduce surface flaws of known size. However, operando optical microscopy revealed that lithium metal penetration propagates preferentially from a different, second class of flaws. At the perimeter of surface current collectors smaller in size than the lithium source electrode, an enhanced electrodeposition current density causes lithium filled cracks to initiate and grow to penetration, even when large Vickers defects are in proximity. Modeling the electric field distribution in the experimental cell revealed that a 5-fold enhancement in field occurs within 10 micrometers of the electrode edge and generates high local electrochemomechanical stress. This may determine the initiation sites for lithium propagation, overriding the presence of larger defects elsewhere.

Li-oxide garnets such as Li₇La₃Zr₂O₁₂ (LLZO) are among the most promising candidates for solid-state electrolytes to be used in next-generation Li-ion batteries. The garnet-structured cubic modification of LLZO, showing space group Ia-3d, has to be stabilized with supervalent cations. LLZO stabilized with Ga³⁺ shows superior properties compared to LLZO stabilized with similar cations; however, the reason for this behavior is still unknown. In this study, a comprehensive structural characterization of Ga-stabilized LLZO is performed by means of single-crystal X-ray diffraction. Coarse-grained samples with crystal sizes of several hundred micrometers are obtained by solid-state reaction. Single-crystal X-ray diffraction results show that Li_7–3xGa_xLa₃Zr₂O₁₂ with x > 0.07 crystallizes in the acentric cubic space group I-43d. This is the first definite record of this cubic modification for LLZO materials and might explain the superior electrochemical performance of Ga-stabilized LLZO compared to its Al-stabilized counterpart. The phase transition seems to be caused by the site preference of Ga³⁺. ⁷Li NMR spectroscopy indicates an additional Li-ion diffusion process for LLZO with space group I-43d compared to space group Ia-3d. Despite all efforts undertaken to reveal structure–property relationships for this class of materials, this study highlights the potential for new discoveries.

We investigate theoretically the site occupancy of Al³⁺ in the fast-ion-conducting cubic-garnet Li_7–3xAl³⁺_xLa₃Zr₂O₁₂ (Ia-3d) using density functional theory. By comparing calculated and measured ²⁷Al NMR chemical shifts an analysis shows that Al³⁺ prefers the tetrahedrally coordinated 24d site and a distorted 4-fold coordinated 96h site. The site energies for Al³⁺ ions, which are slightly displaced from the exact crystallographic sites (i.e., 24d and 96h), are similar leading to a distribution of slightly different local oxygen coordination environments. Thus, broad ²⁷Al NMR resonances result reflecting the distribution of different isotropic chemical shifts and quadrupole coupling constants. From an energetic point of view, there is evidence that Al³⁺ could also occupy the 48g site with its almost regular octahedral coordination sphere. Although this has been reported by neutron powder diffraction, the NMR chemical shift calculated for such an Al³⁺ site has not been observed experimentally.