What Limits the Rate Capability of Li-S Batteries during Discharge: Charge Transfer or Mass Transfer?

Li-S batteries exhibit poor rate capability under lean electrolyte conditions required for achieving high practical energy densities. In this contribution, we argue that the rate capability of commercially-viable Li-S batteries is mainly limited by mass transfer rather than charge transfer during discharge. We first present experimental evidence showing that the charge-transfer resistance of Li-S batteries and hence the cathode surface covered by Li2S are proportional to the state-of-charge (SoC) and not to the current, directly contradicting previous theories. We further demonstrate that the observed Li-S behaviors for different discharge rates are qualitatively captured by a zero-dimensional Li-S model with transport-limited reaction currents. This is the first Li-S model to also reproduce the characteristic overshoot in voltage at the beginning of charge, suggesting its cause is the increase in charge transfer resistance brought by Li2S precipitation

Irreversible vs reversible capacity fade of lithium-sulfur batteries during cycling: the effects of precipitation and shuttle

Lithium-sulfur batteries could deliver significantly higher gravimetric energy density and lower cost than Li-ion batteries. Their mass adoption, however, depends on many factors, not least on attaining a predictive understanding of the mechanisms that determine their performance under realistic operational conditions, such as partial charge/discharge cycles. This work addresses a lack of such understanding by studying experimentally and theoretically the response to partial cycling. A lithium-sulfur model is used to analyze the mechanisms dictating the experimentally observed response to partial cycling. The zero-dimensional electrochemical model tracks the time evolution of sulfur species, accounting for two electrochemical reactions, one precipitation/dissolution reaction with nucleation, and shuttle, allowing direct access to the true cell state of charge. The experimentally observed voltage drift is predicted by the model as a result of the interplay between shuttle and the dissolution bottleneck. Other features are shown to be caused by capacity fade. We propose a model of irreversible sulfur loss associated with shuttle, such as caused by reactions on the anode. We find a reversible and an irreversible contribution to the observed capacity fade, and verify experimentally that the reversible component, caused by the dissolution bottleneck, can be recovered through slow charging. This model can be the basis for cycling parameters optimization, or for identifying degradation mechanisms relevant in applications. The model code is released as Supplementary material B

Simulating Charged Defects in Silicon Dangling Bond Logic Systems to Evaluate Logic Robustness

Recent research interest in emerging logic systems based on quantum dots has been sparked by the experimental demonstration of nanometer-scale logic devices composed of atomically sized quantum dots made of silicon dangling bonds (SiDBs), along with the availability of SiQAD, a computer-aided design tool designed for this technology. Latest design automation frameworks have enabled the synthesis of SiDB circuits that reach the size of $32\times10^3\,\text{nm}^{2}$ -- orders of magnitude more complex than their hand-designed counterparts. However, current SiDB simulation engines do not take defects into account, which is important to consider for these sizable systems. This work proposes a formulation for incorporating fixed-charge simulation into established ground state models to cover an important class of defects that has a non-negligible effect on nearby SiDBs at the $10\,\text{nm}$ scale and beyond. The formulation is validated by implementing it into SiQAD's simulation engine and computationally reproducing experiments on multiple defect types, revealing a high level of accuracy. The new capability is applied towards studying the tolerance of several established logic gates against the introduction of a single nearby defect to establish the corresponding minimum required clearance. These findings are compared against existing metrics to form a foundation for logic robustness studies.Comment: 7 pages, 5 figures, 2 table

Reference performance test Methodology for degradation assessment of lithium-sulfur batteries

Lithium-Sulfur (Li-S) is an emerging battery technology receiving a growing amount of attention due to its potentially high gravimetric energy density, safety, and low production cost. However, there are still some obstacles preventing its swift commercialization. Li-S batteries are driven by different electrochemical processes than commonly used Lithium-ion batteries, which often results in very different behavior. Therefore, the testing and modeling of these systems have to be adjusted to reflect their unique behavior and to prevent possible bias. A methodology for a Reference Performance Test (RPT) for the Li-S batteries is proposed in this study to point out Li-S battery features and provide guidance to users how to deal with them and possible results into standardization. The proposed test methodology is demonstrated for 3.4 Ah Li-S cells aged under different conditions

Subthreshold K+ production in deuteron and alpha induced nuclear reactions

Double differential cross sections have been measured for pi+ and K+ emitted around midraidity in d+A and He+A collisions at a beam kinetic energy of 1.15 GeV/nucleon. The total pi+ yield increases by a factor of about 2 when using an alpha projectile instead of a deuteron whereas the K+ yield increases by a factor of about 4. According to transport calculations, the K+ enhancement depends both on the number of hadron-hadron collisions and on the energy available in those collisions: their center-of-mass energy increases with increasing number of projectile nucleons

The effect of current inhomogeneity on the performance and degradation of Li-S batteries

The effect of thermal gradients on the performance and cycle life of Li-S batteries is studied using bespoke single-layer Li-S cells, with isothermal boundary conditions maintained by Peltier elements. A temperature difference is shown to cause significant current imbalance between parallel connected single-layer cells, causing the hotter cell to provide more charge and discharge capacities during cycling. During charge, significant shuttle is induced in the hotter Li-S cell, causing accelerated degradation of it. A bespoke multi-tab cell in which the inner layers are electrically connected to different tabs versus the outer layers, is used to demonstrate that noticeable current inhomogeneity occurs during the operation of practical multilayer Li-S pouch cells, which is expected to affect their performance and degradation. The observed thermal and current inhomogeneity should have a direct consequence on battery pack and thermal management system design for real world Li-S battery packs

Antidepressants for depression during pregnancy

The objectives are as follows: To assess the safety of antidepressant use, compared with placebo or psychological therapy, for the treatment of pre-existing and ante-natal depression during pregnancy. To assess the effectiveness of antidepressant use, compared with placebo or psychological therapy, for the treatment of pre-existing and ante-natal depression during pregnancy

Fragmentation of exotic oxygen isotopes

Abrasion-ablation models and the empirical EPAX parametrization of projectile fragmentation are described. Their cross section predictions are compared to recent data of the fragmentation of secondary beams of neutron-rich, unstable 19,20,21O isotopes at beam energies near 600 MeV/nucleon as well as data for stable 17,18O beams