is a promising solid electrolyte for next-generation solid-state Li batteries. However, sufficiently fast Li-ion mobility required for battery applications only emerges at high temperatures, upon a phase transition to cubic structure. A well-known strategy to stabilize the cubic phase at room temperature relies on aliovalent substitution; in particular, the substitution of Li + by Al 3+ and Ga 3+ ions. Yet, despite having the same formal charge, Ga 3+ substitution yields higher conductivities (10 −3 S/cm) than Al 3+ (10 −4 S/cm). The reason of such difference in ionic conductivity remains a mystery. Here we use molecular dynamic simulations and advanced sampling techniques to precisely unveil the atomistic origin of this phenomenon. Our results show that Li + vacancies generated by Al 3+ and Ga 3+ substitution remain adjacent to Ga 3+ and Al 3+ ions, without contributing to the promotion of Li + mobility. However, while Ga 3+ ions tend to allow limited Li + diffusion within their immediate surroundings, the less repulsive interactions associated with Al 3+ ions lead to a complete blockage of neighboring Li + diffusion paths. This effect is magnified at lower temperatures, and explains the higher conductivities observed for Ga-substituted systems. Overall this study provides a valuable insight into the fundamental ion transport mechanism in the bulk of Ga/Al-substituted Li 7 La 3 Zr 2 O 12 and paves the way for rationalizing aliovalent substitution design strategies for enhancing ionic transport in these materials.

Unlocking the full potential of solid-state electrolytes (SSEs) is key to enabling safer and more-energy dense technologies than today's Li-ion batteries. In particular, composite materials comprising a conductive, flexible polymer matrix embedding ceramic filler particles are emerging as a good strategy to provide the combination of conductivity, mechanical and chemical stability demanded from SSEs. Yet, the electrochemical

is a promising solid electrolyte candidate for solidstate Li-ion batteries, but at room temperature it crystallizes in a poorly Li-ion conductive tetragonal phase. To this end, partial substitution of Li + by Al 3+ ions is an effective way to stabilize the highly conductive cubic phase at room temperature. Yet, fundamental aspects regarding this aliovalent substitution remain poorly understood. In this work, we use molecular dynamics and advanced hybrid Monte Carlo methods for systematic study of the room temperature Li-ion diffusion in tetragonal and cubic LLZO to shed light on important open questions. We find that Al substitution in tetrahedral sites of the tetragonal LLZO allows previously inaccessible sites to become available, which enhances Li-ion conductivity. In contrast, in the cubic phase Li-ion diffusion paths become blocked in the vicinity of Al ions, resulting in a decrease of Li-ion conductivity. Moreover, combining the conductivities of individual phases through an effective medium approximation allowed us to estimate the conductivities of cubic/tetragonal phase mixtures that are in good agreement with those reported in several experimental works. This suggests that phase coexistence (due to phase equilibrium or gradients in Al content within a sample) could have a significant impact on the conductivity of Al-substituted LLZO, particularly at low contents of Al 3+. Overall, by making a thorough comparison with reported experimental data, the theoretical study and simulations of this work advance our current understanding of Li-ion mobility in Al-substituted LLZO garnets and might guide future in-depth characterization experiments of this relevant energy storage material.

The microscopic modeling of surfactant systems is of the utmost importance in understanding the mechanisms related to the micellization process because it allows for prediction and comparison with experimental data of diverse equilibrium system properties. In this work, we present a coarse-grained model for Pluronics, a trademarked type of triblock copolymer, from simulations based on a single-chain mean-field theory (SCMF). This microscopic model is used to quantify the micellization process of these nonionic surfactants at 37 °C and has been shown to be able to quantitatively reproduce experimental data of the critical micelle concentration (CMC) along with other equilibrium properties. In particular, these results correctly capture the experimental behavior with respect to the lengths of the hydrophobic and hydrophilic moieties of the surfactants for low and medium hydrophobicities. However, for the more highly hydrophobic systems with low CMCs, a deviation is found which has been previously attributed to nonequilibrium effects in the experimental data (Garcı́a Daza, F. A.; Mackie, A. D. Low Critical Micelle Concentration Discrepancy between Theory and Experiment. J. Phys. Chem. Lett. 2014, 5, 2027-2032).