New insights in the mechanism of cation migration induced by cation-anion dynamic coupling in superionic conductors

Understanding the ion diffusion mechanism is one of the key preconditions for designing superionic conductors in solid state lithium batteries and many other energy devices. Besides single-cation vacancy/interstitial-assisted and multi-cation...

Can substitutions affect the oxidative stability of lithium argyrodite solid electrolytes?

Lithium ion conducting argyrodites are among the most studied solid electrolytes due to their high ionic conductivities. A major concern in a solid-state battery is the solid electrolyte stability. Here we present a systematic study on the influence of cationic and anionic substitution on the electrochemical stability of Li6PS5X, using step-wise cyclic voltammetry, optical band gap measurements, hard X-ray photoelectron spectroscopy along with first-principles calculations. We observe that going from Li6PS5Cl to Li6+xP1-xMxS5I (M = Si4+, Ge4+), the oxidative degradation does not change. Considering the chemical bonding shows that the valence band edges are mostly populated by non-bonding orbitals of the PS43- units or unbound sulfide anions and that simple substitutions in these sulfide-based solid electrolytes cannot improve oxidative stabilities. This work provides insights on the role of chemical bonding on the stability of superionic conductors and shows that alternative strategies are needed for long-term stable solid-state batteries.

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T 1 3D 7Li NMR of superionic Li10GeP2S12

The use of independent component analysis (ICA) for the analysis of two-dimensional (2D) spin-alignment echo–T 1 7Li NMR correlation data with transient echo detection as a third dimension is demonstrated for the superionic conductor Li10GeP2S12 (LGPS). ICA was combined with Laplace inversion, or discrete inverse Laplace transform (ILT), to obtain spectrally resolved 2D correlation maps. Robust results were obtained with the spectra as well as the vectorized correlation maps as independent components. It was also shown that the order of ICA and ILT steps can be swapped. While performing the ILT step before ICA provided better contrast, a substantial data compression can be achieved if ICA is executed first. Thereby the overall computation time could be reduced by one to two orders of magnitude, since the number of computationally expensive ILT steps is limited to the number of retained independent components. For LGPS, it was demonstrated that physically meaningful independent components and mixing matrices are obtained, which could be correlated with previously investigated material properties yet provided a clearer, better separation of features in the data. LGPS from two different batches was investigated, which showed substantial differences in their spectral and relaxation behavior. While in both cases this could be attributed to ionic mobility, the presented analysis may also clear the way for a more in-depth theoretical analysis based on numerical simulations. The presented method appears to be particularly suitable for samples with at least partially resolved static quadrupolar spectra, such as alkali metal ions in superionic conductors. The good stability of the ICA analysis makes this a prospect algorithm for preprocessing of data for a subsequent automatized analysis using machine learning concepts.

Paradigms of frustration in superionic solid electrolytes

Superionic solid electrolytes have widespread use in energy devices, but the fundamental motivations for fast ion conduction are often elusive. In this Perspective, we draw upon atomistic simulations of a wide range of superionic conductors to illustrate some ways frustration can lower diffusion cation barriers in solids. Based on our studies of halides, oxides, sulfides and hydroborates and a survey of published reports, we classify three types of frustration that create competition between different local atomic preferences, thereby flattening the diffusive energy landscape. These include chemical frustration, which derives from competing factors in the anion–cation interaction; structural frustration, which arises from lattice arrangements that induce site distortion or prevent cation ordering; and dynamical frustration, which is associated with temporary fluctuations in the energy landscape due to anion reorientation or cation reconfiguration. For each class of frustration, we provide detailed simulation analyses of various materials to show how ion mobility is facilitated, resulting in stabilizing factors that are both entropic and enthalpic in origin. We propose the use of these categories as a general construct for classifying frustration in superionic conductors and discuss implications for future development of suitable descriptors and improvement strategies. This article is part of the Theo Murphy meeting issue ‘Understanding fast-ion conduction in solid electrolytes’.

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T1 3D 7Li NMR of superionic Li10GeP2S12

The use of independent component analysis (ICA) for the analysis of two-dimensional (2D) spin-alignment echo--T1 7Li NMR correlation data with transient echo detection as a third dimension is demonstrated for the superionic conductor Li10GeP2S12 (LGPS). ICA was combined with Laplace inversion, or discrete inverse Laplace transform (ILT), to obtain spectrally resolved 2D correlation maps. Robust results were obtained with the spectra as well as the vectorized correlation maps as independent components. It was also shown that the order of ICA and ILT steps can be swapped. While performing the ILT step before ICA provided better contrast, a substantial data compression can be achieved if ICA is executed first. Thereby the overall computation time could be reduced by one to two orders of magnitude, since the number of computationally expensive ILT steps is limited to the number of retained independent components. For LGPS, it was demonstrated that physically meaningful independent components and mixing matrices are obtained, which could be correlated with previously investigated material properties yet provided a clearer, better separation of features in the data. LGPS from two different batches was investigated, which showed substantial differences in their spectral and relaxation behavior. While in both cases this could be attributed to ionic mobility, the presented analysis may also clear the way for a more in-depth theoretical analysis based on numerical simulations. The presented method appears to be particularly suitable for samples with at least partially resolved static quadrupolar spectra, such as alkali metal ions in superionic conductors. The good stability of the ICA analysis makes this a prospect algorithm for preprocessing of data for a subsequent automatized analysis using machine learning concepts.

Diffuson-mediated thermal and ionic transport in superionic conductors

Ultra-low lattice thermal conductivity as often found in superionic compounds is greatly beneficial for thermoelectric performance, however, a high ionic conductivity can lead to device degradation. Conversely, high ionic conductivities are searched for materials in solid-state battery applications. It is commonly thought that ionic transport induces low thermal conductivity and that ion and thermal transport are not completely independent properties of a material. However, no direct comparison or underlying physical relationship has been shown between the two. Here we establish that ionic transport can be varied independent of thermal transport in Ag+ superionic conductors, even though both phenomena arise from atomic vibrations. Thermal conductivity measurements, in conjunction with two-channel lattice dynamics modeling, reveals that the vast majority of Ag+ vibrations have non-propagating diffuson-like character, which provides a rational for how these two transport properties can be independent. Our results provide conceptually novel lattice dynamical insights to ionic transport and confirm that ion transport is not a requirement for ultra-low thermal conductivity. Consequently, this work bridges the fields of solid state ionics and thermal transport, thus providing design strategies for functional ionic conducting materials from a vibrational perspective.