Understanding the role of aliovalent cation substitution on the li-ion diffusion mechanism in Li6+xP1-xSixS5Br argyrodites.

Due to their high ionic conductivity, lithium-ion conducting argyrodites show promise as solid electrolytes for solid-state batteries. Aliovalent substitution is an effective technique to enhance the transport properties of Li6PS5Br, where aliovalent Si substitution triples ionic conductivity. However, the origin of this experimentally observed increase is not fully understood. Our density functional theory (DFT) study reveals that Si4+ substitution increases Li diffusion by activating Li occupancy in the T4 sites. Redistribution of Li-ions within the lattice results in a more uniform distribution of Li around the T4 and neighboring T5 sites, flattening the energy landscape for diffusion. Since the T4 site is positioned in the intercage jump pathway, an increase in the intercage jump rate is found, which is directly related to the macroscopic diffusion and bulk conductivity. Analysis of neutron diffraction experiments confirms partial T4 site occupancy, in agreement with the computational findings. Understanding the aliovalent substitution effect on interstitials is crucial for improving solid electrolyte ionic conductivity and advancing solid-state battery performance.

Exploring the Relationship Between Halide Substitution, Structural Disorder, and Lithium Distribution in Lithium Argyrodites (Li6-xPS5-xBr1+x).

Lithium argyrodite superionic conductors have recently gained significant attention as potential solid electrolytes for all-solid-state batteries because of their high ionic conductivity and ease of processing. Promising aspects of these materials are the ability to introduce halides (Li6-xPS5-xHal1+x, Hal = Cl and Br) into the crystal structure, which can greatly impact the lithium distribution over the wide range of accessible sites and the structural disorder between the S2- and Hal- anion on the Wyckoff 4d site, both of which strongly influence the ionic conductivity. However, the complex relationship among halide substitution, structural disorder, and lithium distribution is not fully understood, impeding optimal material design. In this study, we investigate the effect of bromide substitution on lithium argyrodite (Li6-xPS5-xBr1+x, in the range 0.0 ≤ x ≤ 0.5) and engineer structural disorder by changing the synthesis protocol. We reveal the correlation between the lithium substructure and ionic transport using neutron diffraction, solid-state nuclear magnetic resonance (NMR) spectroscopy, and electrochemical impedance spectroscopy. We find that a higher ionic conductivity is correlated with a lower average negative charge on the 4d site, located in the center of the Li+ "cage", as a result of the partial replacement of S2- by Br-. This leads to weaker interactions within the Li+ "cage", promoting Li-ion diffusivity across the unit cell. We also identify an additional T4 Li+ site, which enables an alternative jump route (T5-T4-T5) with a lower migration energy barrier. The resulting expansion of the Li+ cages and increased connections between cages lead to a maximum ionic conductivity of 8.55 mS/cm for quenched Li5.5PS4.5Br1.5 having the highest degree of structural disorder, an 11-fold improvement compared to slow-cooled Li6PS5Br having the lowest degree of structural disorder. Thereby, this work advances the understanding of the structure-transport correlations in lithium argyrodites, specifically how structural disorder and halide substitution impact the lithium substructure and transport properties and how this can be realized effectively through the synthesis method and tuning of the composition.

Re-investigating the structure-property relationship of the solid electrolytes Li 3-x In1-x Zr x Cl6 and the impact of In-Zr(iv) substitution.

Chloride-based solid electrolytes are considered interesting candidates for catholytes in all-solid-state batteries due to their high electrochemical stability, which allows the use of high-voltage cathodes without protective coatings. Aliovalent Zr(iv) substitution is a widely applicable strategy to increase the ionic conductivity of Li3M(iii)Cl6 solid electrolytes. In this study, we investigate how Zr(iv) substitution affects the structure and ion conduction in Li3-x In1-x Zr x Cl6 (0 ≤ x ≤ 0.5). Rietveld refinement using both X-ray and neutron diffraction is used to make a structural model based on two sets of scattering contrasts. AC-impedance measurements and solid-state NMR relaxometry measurements at multiple Larmor frequencies are used to study the Li-ion dynamics. In this manner the diffusion mechanism and its correlation with the structure are explored and compared to previous studies, advancing the understanding of these complex and difficult to characterize materials. It is found that the diffusion in Li3InCl6 is most likely anisotropic considering the crystal structure and two distinct jump processes found by solid-state NMR. Zr-substitution improves ionic conductivity by tuning the charge carrier concentration, accompanied by small changes in the crystal structure which affect ion transport on short timescales, likely reducing the anisotropy.

Li5NCl2: A Fully-Reduced, Highly-Disordered Nitride-Halide Electrolyte for Solid-State Batteries with Lithium-Metal Anodes.

Most highly Li-conducting solid electrolytes (σRT > 10-3 S cm-1) are unstable against lithium-metal and suffer from detrimental solid-electrolyte decomposition at the lithium-metal/solid-electrolyte interface. Solid electrolytes that are stable against lithium metal thus offer a direct route to stabilize lithium-metal/solid-electrolyte interfaces, which is crucial for realizing all-solid-state batteries that outperform conventional lithium-ion batteries. In this study, we investigate Li5NCl2 (LNCl), a fully-reduced solid electrolyte that is thermodynamically stable against lithium metal. Combining experiments and simulations, we investigate the lithium diffusion mechanism, different synthetic routes, and the electrochemical stability window of LNCl. Li nuclear magnetic resonance (NMR) experiments suggest fast Li motion in LNCl, which is however locally confined and not accessible in macroscopic LNCl pellets via electrochemical impedance spectroscopy (EIS). With ab-initio calculations, we develop an in-depth understanding of Li diffusion in LNCl, which features a disorder-induced variety of different lithium jumps. We identify diffusion-limiting jumps providing an explanation for the high local diffusivity from NMR and the lower macroscopic conductivity from EIS. The fundamental understanding of the diffusion mechanism we develop herein will guide future conductivity optimizations for LNCl and may be applied to other highly-disordered fully-reduced electrolytes. We further show experimentally that the previously reported anodic limit (>2 V vs Li+/Li) is an overestimate and find the true anodic limit at 0.6 V, which is in close agreement with our first-principles calculations. Because of LNCl's stability against lithium-metal, we identify LNCl as a prospective artificial protection layer between highly-conducting solid electrolytes and strongly-reducing lithium-metal anodes and thus provide a computational investigation of the chemical compatibility of LNCl with common highly-conducting solid electrolytes (Li6PS5Cl, Li3YCl6, ...). Our results set a framework to better understand and improve highly-disordered fully-reduced electrolytes and highlight their potential in enabling lithium-metal solid-state batteries.

Investigation of Structure, Ionic Conductivity, and Electrochemical Stability of Halogen Substitution in Solid-State Ion Conductor Li3YBr x Cl6-x.

Li3YX6 (X = Cl, Br) materials are Li-ion conductors that can be used as solid electrolytes in all solid-state batteries. Solid electrolytes ideally have high ionic conductivity and (electro)chemical compatibility with the electrodes. It was proven that introducing Br to Li3YCl6 increases ionic conductivity but, according to thermodynamic calculations, should also reduce oxidative stability. In this paper, the trade-off between ionic conductivity and electrochemical stability in Li3YBr x Cl6-x halogen-substituted compounds is investigated. The compositions of Li3YBr1.5Cl4.5 and Li3YBr4.5Cl1.5 are reported for the first time, along with a consistent analysis of the whole Li3YBr x Cl6-x (x = 0-6) tie-line. The results show that, while Br-rich materials are more conductive (5.36 × 10-3 S/cm at 30 °C for x = 4.5), the oxidative stability is lower (∼3 V compared to ∼3.5 V). Small Br content (x = 1.5) does not affect oxidative stability but substantially increases ionic conductivity compared to pristine Li3YCl6 (2.1 compared to 0.049 × 10-3 S/cm at 30 °C). This work highlights that optimization of substitutions in the anion framework provide prolific and rational avenues for tailoring the properties of solid electrolytes.

Disentangling Cation and Anion Dynamics in Li3PS4 Solid Electrolytes.

A prerequisite for the realization of solid-state batteries is the development of highly conductive solid electrolytes. Li3PS4 is the archetypal member of the highly promising thiophosphate family of Li-ion conductors. Despite a multitude of investigations into this material, the underlying atomic-scale features governing the roles of and the relationships between cation and anion dynamics, in its various temperature-dependent polymorphs, are yet to be fully resolved. On this basis, we provide a comprehensive molecular dynamics study to probe the fundamental mechanisms underpinning fast Li-ion diffusion in this important solid electrolyte material. We first determine the Li-ion diffusion coefficients and corresponding activation energies in the temperature-dependent γ, ß, and α polymorphs of Li3PS4 and relate them to the structural and chemical characteristics of each polymorph. The roles that both cation correlation and anion libration play in enhancing the Li-ion dynamics in Li3PS4 are then isolated and revealed. For γ- and ß-Li3PS4, our simulations confirm that the interatomic Li-Li interaction is pivotal in determining (and restricting) their Li-ion diffusion. For α-Li3PS4, we quantify the significant role of Li-Li correlation and anion dynamics in dominating Li-ion transport in this polymorph for the first time. The fundamental understanding and analysis presented herein is expected to be highly applicable to other solid electrolytes where the interplay between cation and anion dynamics is crucial to enhancing ion transport.

In Situ Reflectometry and Diffraction Investigation of the Multiscale Structure of p-Type Polysilicon Passivating Contacts for c-Si Solar Cells.

The integration of passivating contacts based on a highly doped polycrystalline silicon (poly-Si) layer on top of a thin silicon oxide (SiOx) layer has been identified as the next step to further increase the conversion efficiency of current mainstream crystalline silicon (c-Si) solar cells. However, the interrelation between the final properties of poly-Si/SiOx contacts and their fabrication process has not yet been fully unraveled, which is mostly due to the challenge of characterizing thin-film stacks with features in the nanometric range. Here, we apply in situ X-ray reflectometry and diffraction to investigate the multiscale (1 Å-100 nm) structural evolution of poly-Si contacts during annealing up to 900 °C. This allows us to quantify the densification and thinning of the poly-Si layer during annealing as well as to monitor the disruption of the thin SiOx layer at high temperature >800 °C. Moreover, results obtained on a broader range of thermal profiles, including firing with dwell times of a few seconds, emphasize the impact of high thermal budgets on poly-Si contacts' final properties and thus the importance of ensuring a good control of such high-temperature processes when fabricating c-Si solar cells integrating such passivating contacts. Overall, this study demonstrates the robustness of combining different X-ray elastic scattering techniques (here XRR and GIXRD), which present the unique advantage of being rapid, nondestructive, and applicable on a large sample area, to unravel the multiscale structural evolution of poly-Si contacts in situ during high-temperature processes.

Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy.

Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na+ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperature range 30 < T < 600 °C through combined experimental-computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅21 c) to the cubic polymorph (ß, I4̅3m) above ∼250 °C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 °C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na3PS4 and are relevant for a range host of high-performance materials deriving from the Na3PS4 structural archetype.

On the underestimated influence of synthetic conditions in solid ionic conductors.

The development of high-performance inorganic solid electrolytes is central to achieving high-energy- density solid-state batteries. Whereas these solid-state materials are often prepared via classic solid-state syntheses, recent efforts in the community have shown that mechanochemical reactions, solution syntheses, microwave syntheses, and various post-synthetic heat treatment routines can drastically affect the structure and microstructure, and with it, the transport properties of the materials. On the one hand, these are important considerations for the upscaling of a materials processing route for industrial applications and industrial production. On the other hand, it shows that the influence of the different syntheses on the materials' properties is neither well understood fundamentally nor broadly internalized well. Here we aim to review the recent efforts on understanding the influence of the synthetic procedure on the synthesis - (micro)structure - transport correlations in superionic conductors. Our aim is to provide the field of solid-state research a direction for future efforts to better understand current materials properties based on synthetic routes, rather than having an overly simplistic idea of any given composition having an intrinsic conductivity. We hope this review will shed light on the underestimated influence of synthesis on the transport properties of solid electrolytes toward the design of syntheses of future solid electrolytes and help guide industrial efforts of known materials.

Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte Na3PS4.

Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na3PS4 are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg and pair distribution function), spectroscopy (impedance, Raman, NMR and INS), and ab initio simulations aimed at elucidating the synthesis-property relationships in Na3PS4. We consolidate previously reported interpretations regarding the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na+ migration in Na3PS4, which is ∼30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na3PS4 to ∼10-4 S/cm can be reproduced by applying external pressure on a sample from conventional high-temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain, and activation volume.

Fundamentals of inorganic solid-state electrolytes for batteries.

In the critical area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-density and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorganic solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochemical and mechanical properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of physical contact, the solutions to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials.

Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries.

Solid electrolytes are generating considerable interest for all-solid-state Li-ion batteries to address safety and performance issues. Grain boundaries have a significant influence on solid electrolytes and are key hurdles that must be overcome for their successful application. However, grain boundary effects on ionic transport are not fully understood, especially at the atomic scale. The Li-rich anti-perovskite Li3OCl is a promising solid electrolyte, although there is debate concerning the precise Li-ion migration barriers and conductivity. Using Li3OCl as a model polycrystalline electrolyte, we apply large-scale molecular dynamics simulations to analyze the ionic transport at stable grain boundaries. Our results predict high concentrations of grain boundaries and clearly show that Li-ion conductivity is severely hindered through the grain boundaries. The activation energies for Li-ion conduction traversing the grain boundaries are consistently higher than that of the bulk crystal, confirming the high grain boundary resistance in this material. Using our results, we propose a polycrystalline model to quantify the impact of grain boundaries on conductivity as a function of grain size. Such insights provide valuable fundamental understanding of the role of grain boundaries and how tailoring the microstructure can lead to the optimization of new high-performance solid electrolytes.