Synthetic Tailoring of Ionic Conductivity in Multicationic Substituted, High-Entropy Lithium Argyrodite Solid Electrolytes.

Superionic conductors are key components of solid-state batteries (SSBs). Multicomponent or high-entropy materials, offering a vast compositional space for tailoring properties, have recently attracted attention as novel solid electrolytes (SEs). However, the influence of synthetic parameters on ionic conductivity in compositionally complex SEs has not yet been investigated.

Transition-metal interdiffusion and solid electrolyte poisoning in all-solid-state batteries revealed by cryo-TEM.

Using scanning transmission electron microscopy, along with electron energy loss spectroscopy, under cryogenic conditions, we demonstrate transition-metal dissolution from a layered Ni-rich oxide cathode material and subsequent diffusion into the bulk of a lithium thiophosphate solid electrolyte during electrochemical cycling. This problem has previously only been considered for liquid-electrolyte-based batteries.

Probing the Lithium Substructure and Ionic Conductivity of the Solid Electrolyte LiPSI.

In search of high-performance solid electrolytes, various materials have been discovered in the past, approaching or even exceeding the ionic conductivity of conventional liquid electrolytes. Among the reported classes of superionic electrolytes for solid-state battery applications, lithium thiophosphates appear to be the most promising owing to their high ionic conductivity and mechanical softness. A recent example is the LiPSI phase (4/).

Effect of surface carbonates on the cyclability of LiNbO-coated NCM622 in all-solid-state batteries with lithium thiophosphate electrolytes.

While still premature as an energy storage technology, bulk solid-state batteries are attracting much attention in the academic and industrial communities lately. In particular, layered lithium metal oxides and lithium thiophosphates hold promise as cathode materials and superionic solid electrolytes, respectively. However, interfacial side reactions between the individual components during battery operation usually result in accelerated performance degradation.

LiZrO-Coated NCM622 for Application in Inorganic Solid-State Batteries: Role of Surface Carbonates in the Cycling Performance.

All-inorganic solid-state batteries (SSBs) currently attract much attention as next-generation high-density energy-storage technology. However, to make SSBs competitive with conventional Li-ion batteries, several obstacles and challenges must be overcome, many of which are related to interface stability issues. Protective coatings can be applied to the electrode materials to mitigate side reactions with the solid electrolyte, with lithium transition metal oxides, such as LiNbO or LiZrO, being well established in research.

LiGeSBr-An Argyrodite Li-Ion Conductor Prepared by Mechanochemical Synthesis.

In recent years, the search for glassy and ceramic Li superionic conductors has received significant attention, mainly due to the renaissance of interest in all-solid-state batteries. Here, we report the mechanochemical synthesis of metastable LiGeSBr, which is, to the best of our knowledge, the first compound of the LiS-GeS-LiBr system. Applying combined synchrotron X-ray diffraction and neutron powder diffraction, we show LiGeSBr to crystallize in the 4̅3 space group and to be isostructural with argyrodite-type LiPSBr, but with a distinct difference in the S/Br site disorder (and improved anodic stability).

Gas Evolution in Lithium-Ion Batteries: Solid versus Liquid Electrolyte.

Gas evolution in conventional lithium-ion batteries using Ni-rich layered oxide cathode materials presents a serious issue that is responsible for performance decay and safety concerns, among others. Recent findings revealed that gas evolution also occurred in bulk-type solid-state batteries. To further clarify the effect that the electrolyte has on gassing, we report in this work-to the best of our knowledge-the first study comparing gas evolution in lithium-ion batteries with NCM622 cathode material and different electrolyte types, specifically solid (β-LiPS and LiPSCl) versus liquid (LP57).

Influence of electronically conductive additives on the cycling performance of argyrodite-based all-solid-state batteries.

All-solid-state batteries (SSBs) are attracting widespread attention as next-generation energy storage devices, potentially offering increased power and energy densities and better safety than liquid electrolyte-based Li-ion batteries. Significant research efforts are currently underway to develop stable and high-performance bulk-type SSB cells by optimizing the cathode microstructure and composition, among others. Electronically conductive additives in the positive electrode may have a positive or negative impact on cyclability.

Indirect state-of-charge determination of all-solid-state battery cells by X-ray diffraction.

Determining the state-of-charge of all-solid-state batteries via both ex situ and operando X-ray diffraction, rather than by electrochemical testing (may be strongly affected by electrically isolated/inactive material, irreversible side reactions, etc.), is reported. Specifically, we focus on bulk-type cells and use X-ray diffraction data obtained on a liquid electrolyte-based Li-ion cell as the reference standard for changes in lattice parameters with (de)lithiation.

Room temperature, liquid-phase AlO surface coating approach for Ni-rich layered oxide cathode material.

A room temperature, atomic-layer-deposition-like coating strategy for NCM811 (80% Ni) is reported. Trimethylaluminum is shown to readily react with adsorbed moisture, leading both to Al2O3 surface layer formation on NCM811 and to trace H2O removal in a single treatment step. Even more importantly, the cycling performance of pouch cells at 45 °C is greatly improved.

In-situ Measurement of Self-Atom Diffusion in Solids Using Amorphous Germanium as a Model System.

We present in-situ self-diffusion experiments in solids, which were carried out by Focussing Neutron Reflectometry on isotope multilayers. This new approach offers the following advantages in comparison to classical ex-situ measurements: (1) Identification and continuous measurement of a time dependence of diffusivities, (2) significant reduction of error limits of diffusivities, and (3) substantial reduction of the necessary experimental time. In the framework of a case study, yet unknown self-diffusivities in amorphous germanium are measured at various temperatures quasi-continuously, each during isothermal annealing.

Impact of Structural Polymorphism on Ionic Conductivity in Lithium Copper Pyroborate LiCuBO.

The search for high Li-ion conducting ceramics has regained tremendous interest triggered by the renaissance of the all-solid-state battery. Within this context we herein reveal the impact of structural polymorphism of lithium copper pyroborate LiCuBO on its ionic conductivity. Using combined in situ synchrotron X-ray and neutron powder diffraction, a structural and synthetic relationship between α- and β-LiCuBO could be established and its impact on ionic conductivity evolution was followed using electrochemical impedance spectroscopy.

Electrochemical behavior of BiBO towards lithium-reversible conversion reactions without nanosizing.

Conversion type materials, in particular metal fluorides, have emerged as attractive candidates for positive electrodes in next generation Li-ion batteries (LIBs). However, their practical use is being hindered by issues related to reversibility and large polarization. To minimize these issues, a few approaches enlisting the anionic network have been considered.

Synthesis, Structure, and Electrochemical Properties of NaMBO (M = Fe, Co) Containing M in Tetrahedral Coordination.

In the search for new cathode materials for sodium ion batteries, the exploration of polyanionic compounds has led to attractive candidates in terms of high redox potential and cycling stability. Herein we report the synthesis of the two new sodium transition-metal pentaborates NaMBO (M = Fe, Co), where NaFeBO represents the first sodium iron borate reported at present. By means of synchrotron X-ray diffraction, we reveal a layered structure consisting of pentaborate BO groups connected through M in tetrahedral coordination, providing possible three-dimensional Na-ion migration pathways.

Electrochemical activity and high ionic conductivity of lithium copper pyroborate Li6CuB4O10.

In the search for new cathode materials for Li-ion batteries, borate (BO3(3-)) based compounds have gained much interest during the last two decades due to the low molecular weight of the borate polyanions which leads to active materials with increased theoretical capacities. In this context we herein report the electrochemical activity versus lithium and the ionic conductivity of a diborate or pyroborate B2O5(4-) based compound, Li6CuB4O10. By combining various electrochemical techniques with in situ X-ray diffraction, we show that this material can reversibly insert/deinsert limited amounts of lithium (∼0.

Self-Diffusion in Amorphous Silicon.

The present Letter reports on self-diffusion in amorphous silicon. Experiments were done on ^{29}Si/^{nat}Si heterostructures using neutron reflectometry and secondary ion mass spectrometry. The diffusivities follow the Arrhenius law in the temperature range between 550 and 700 °C with an activation energy of (4.