Ionic Conductivity of Nanocrystalline and Amorphous Li10GeP2S12: The Detrimental Impact of Local Disorder on Ion Transport

Solid electrolytes with extraordinarily high Li-ionic conductivities are key for high performance all-solid-state batteries. So far, the thiophosphate Li10GeP2S12 (LGPS) belongs to the best Li ion conductors with an ionic conductivity exceeding 10 mS cm–1 at ambient. Recent molecular dynamics simulations performed by Dawson and Islam predict that the ionic conductivity of LGPS can be further enhanced by a factor of three if the crystallite size is reduced to the nanometer regime. A change in local ion coordination, hence local disorder, has been assumed to facilitate Li diffusion in the ab-plane of LGPS. As yet, no experimental evidence exists supporting this fascinating prediction. Here, we synthesized nanocrystalline LGPS by high-energy ball milling, characterized the material structurally and probed the Li+ ion transport parameters. Whereas X-ray powder diffraction and high-resolution 31P and 6Li magic angle spinning nuclear magnetic resonance (NMR) spectroscopy helped us to determine morphological changes and local structures upon milling, broadband conductivity spectroscopy in combination with electric modulus measurements allowed us to precisely follow the changes in Li+ ion dynamics. Surprisingly and against the behavior of other electrolytes, ionic conductivity turned out to decrease with increasing milling time, finally leading to a reduction of σ20°C by almost a factor of 10. This decrease affects both, bulk ion dynamics and total conductivity, which also comprises Li+ transport across grain boundary regions in LGPS. As could be shown by NMR, ball-milling leads to a structurally heterogeneous sample with the nm-sized LGPS crystallites being embedded in an amorphous matrix. This amorphous phase is responsible for the reduced performance of the milled electrolyte. Importantly, careful separation of the amorphous and (nano)crystalline contributions to the overall ionic conductivity revealed that even in the nanocrystalline regions Li+ ion dynamics is slowed down compared to untreated, coarse-grained LGPS. We conclude that defects introduced into the LGPS bulk structure via ball milling have a negative impact on ionic transport. We postulate that such kind of structural disorder is detrimental to fast ion transport in materials whose transport properties rely on crystallographically well-defined diffusion pathways.

Order-Stability in Complex Biological, Social, and AI-Systems from Quantum Information Theory

This paper is our attempt, on the basis of physical theory, to bring more clarification on the question “What is life?” formulated in the well-known book of Schrödinger in 1944. According to Schrödinger, the main distinguishing feature of a biosystem’s functioning is the ability to preserve its order structure or, in mathematical terms, to prevent increasing of entropy. However, Schrödinger’s analysis shows that the classical theory is not able to adequately describe the order-stability in a biosystem. Schrödinger also appealed to the ambiguous notion of negative entropy. We apply quantum theory. As is well-known, behaviour of the quantum von Neumann entropy crucially differs from behaviour of classical entropy. We consider a complex biosystem S composed of many subsystems, say proteins, cells, or neural networks in the brain, that is, S=(Si). We study the following problem: whether the compound system S can maintain “global order” in the situation of an increase of local disorder and if S can preserve the low entropy while other Si increase their entropies (may be essentially). We show that the entropy of a system as a whole can be constant, while the entropies of its parts rising. For classical systems, this is impossible, because the entropy of S cannot be less than the entropy of its subsystem Si. And if a subsystems’s entropy increases, then a system’s entropy should also increase, by at least the same amount. However, within the quantum information theory, the answer is positive. The significant role is played by the entanglement of a subsystems’ states. In the absence of entanglement, the increasing of local disorder implies an increasing disorder in the compound system S (as in the classical regime). In this note, we proceed within a quantum-like approach to mathematical modeling of information processing by biosystems—respecting the quantum laws need not be based on genuine quantum physical processes in biosystems. Recently, such modeling found numerous applications in molecular biology, genetics, evolution theory, cognition, psychology and decision making. The quantum-like model of order stability can be applied not only in biology, but also in social science and artificial intelligence.

Order-Stability in Complex Biosystems from the Viewpoint of the Theory of Open Quantum Systems

This paper is our attempt on the basis of physical theory to bring more clarification on the question ``What is life?'' formulated in the well-known book of Schr\"odinger in 1944. According to Schr\"odinger, the main distinguishing feature of biosystem's functioning is the ability to preserve its order structure or, in the mathematical terms, to prevent increasing of entropy. Since any biosystem is fundamentally open, it is natural to use open system's theory. However, Schr\"odinger's analysis shows that the classical theory is not able to adequately describe the order-stability in a biosystem. Schr\"odinger should also appeal to the ambiguous notion of negative entropy. We suggest to apply the quantum theory. As is well-known, behaviour of the quantum von Neumann entropy crucially differs from behaviour of the classical entropy. We consider a complex biosystem $S$ composed of many subsystems, say proteins, or cells, or neural networks in the brain, i.e., $S=(S_i).$ We study the following problem: if the composed system $S$ can preserve the ``global order'' in the situation of increase of local disorder and if $S$ can preserve its entropy while some of $S_i$ increase their entropies We show that within quantum information theory the answer is positive. The significant role plays entanglement of the subsystems states. In the absence of entanglement, increasing of local disorder generates disorder increasing in the compound system $S$ (as in the classical regime).

Vacancy cluster-induced local disordered structure for the enhancement of thermoelectric property in Cu2ZnSnSe4

Local disorder induced by vacancy clusters containing cation and intrinsic Se vacancies servers as thermoelectric performance booster in cation-deficient Cu2ZnSnSe4.