A zero dimensional model of lithium-sulfur batteries during charge and discharge

Lithium-sulfur cells present an attractive alternative to Li-ion batteries due to their large energy density, safety, and possible low cost. Their successful commercialisation is dependent on improving their performance, but also on acquiring sufficient understanding of the underlying mechanisms to allow for the development of predictive models for operational cells. To address the latter, we present a zero dimensional model that predicts many observed features in the behaviour of a lithium-sulfur cell during charge and discharge. The model accounts for two electrochemical reactions via the Nernst formulation, power limitations through Butler-Volmer kinetics, and precipitation/dissolution of one species, including nucleation. It is shown that the precipitation/dissolution causes the flat shape of the low voltage plateau, typical of the lithium-sulfur cell discharge. During charge, it is predicted that the dissolution can act as a bottleneck, as for large enough currents smaller amounts dissolve. This results in reduced charge capacity and an earlier onset of the high plateau reaction, such that the two plateaus merge. By including these effects, the model improves on the existing zero dimensional models, while requiring considerably fewer input parameters and computational resources. The model also predicts that, due to precipitation, the customary way of experimentally measuring the open circuit voltage from a low rate discharge might not be suitable for lithium-sulfur. This model can provide the basis for mechanistic studies, identification of dominant effects in a real cell, predictions of operational behaviour under realistic loads, and control algorithms for applications

Opportunities for disruptive advances through engineering for next generation energy storage

Throughout human history, major economic disruption has been due to technological breakthroughs. Since 1990 the energy density of lithium-ion cells has increased by a factor of four and the cost has dropped by a factor of 10. This has caused disruption to the energy industry, but advances are slowing. The manufacturing and supply chain complexity means that the next big technology will take 15 years to dominate. The academic literature charts this process of development and can be used to show what is in the pipeline. Three candidates that have had a large increase in publication count are: lithium sulphur, solid-state, and sodium-ion technology. From the level of investments in start-ups and academic publication counts, solid‑state cells are closest to maturity. To identify disruption potential, look at uncertainty in performance. Cell lifetime in lithium-ion cells indicates room for improvement. Define a new disruption metric: . Look for areas of industry that lower this metric. Thermal management is a lucrative area for improvement. Cooling the cell tabs of a 5Ah cell reduces the lifetime cost by 66%, compared to 8%/pa for 13 years relying on cost reduction. Second life applications lower the lifetime cost by using the remaining 75% of energy throughput available in a cell after use in an electric vehicle. Drop-in changes to standard manufacturing processes enable huge disruption. Electrolyte additives can increase cell life by 10 times, lowering lifetime cost by 90% in a simple manufacturing intervention

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

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

What is an endangered species?: judgments about acceptable risk

Judgments about acceptable risk in the context of policy may be influenced by law makers, policy makers, experts and the general public. While significant effort has been made to understand public attitudes on acceptable risk of environmental pollution, little is known about such attitudes in the context of species\u27 endangerment. We present survey results on these attitudes in the context of United States\u27 legal-political apparatus intended to mitigate species endangerment. The results suggest that the general public exhibit lower tolerance for risk than policy makers and experts. Results also suggest that attitudes about acceptable risk for species endangerment are importantly influenced by one\u27s knowledge about the environment and social identity. That result is consistent with notions that risk judgments are a synthesis of facts and values and that knowledge is associated with one\u27s social identity. We explain the implications of these findings for understanding species endangerment across the planet

Regularized MPC for power management of hybrid energy storage systems with applications in electric vehicles

This paper examines the application of Regularized Model Predictive Control (RMPC) for Power Management (PM) of Hybrid Energy Storage Systems (HESSs). To illustrate, we apply the idea to the PM problem of a battery-supercapacitors (SCs) powertrain to reduce battery degradation in Electric Vehicles (EVs). While the application of Quadratic MPC (QMPC) in PM of HESS is not new, the idea to examine RMPC here is motivated by its capabilities to prioritize actuator actions and efficiently allocate control effort, as advocated by recent works in the control and MPC literature. Thorough simulations have been run over standard urban test drive cycles. It is found out that QMPC and RMPC, compared to rule-based PM strategies, could reduce the battery degradation over 70%. It is also shown that RMPC can slightly outperform QMPC in reducing battery degradation. Moreover, RMPC, compared to QMPC, could potentially extend the range of that SCs can be used, thus exploiting the degree of freedom of the powertrain to a larger extent. We also make some discussions on the feasibility issues and tuning challenges that RMPC faces, among others

Strain induced electrochemical behaviors of ionic liquid electrolytes in an electrochemical double layer capacitor: Insights from molecular dynamics simulations.

Electrochemical Double Layer Capacitors (EDLCs) with ionic liquid electrolytes outperform conventional ones using aqueous and organic electrolytes in energy density and safety. However, understanding the electrochemical behaviors of ionic liquid electrolytes under compressive/tensile strain is essential for the design of flexible EDLCs as well as normal EDLCs, which are subject to external forces during assembly. Despite many experimental studies, the compression/stretching effects on the performance of ionic liquid EDLCs remain inconclusive and controversial. In addition, there is hardly any evidence of prior theoretical work done in this area, which makes the literature on this topic scarce. Herein, for the first time, we developed an atomistic model to study the processes underlying the electrochemical behaviors of ionic liquids in an EDLC under strain. Constant potential non-equilibrium molecular dynamics simulations are conducted for EMIM BF4 placed between two graphene walls as electrodes. Compared to zero strain, low compression of the EDLC resulted in compromised performance as the electrode charge density dropped by 29%, and the performance reduction deteriorated significantly with a further increase in compression. In contrast, stretching is found to enhance the performance by increasing the charge storage in the electrodes by 7%. The performance changes with compression and stretching are due to changes in the double-layer structure. In addition, an increase in the value of the applied potential during the application of strain leads to capacity retention with compression revealed by the newly performed simulations. [Abstract copyright: © 2023 Author(s). Published under an exclusive license by AIP Publishing.

OH emission from warm and dense gas in the Orion Bar PDR

As part of a far-infrared (FIR) spectral scan with Herschel/PACS, we present the first detection of the hydroxyl radical (OH) towards the Orion Bar photodissociation region (PDR). Five OH rotational Lambda-doublets involving energy levels out to E_u/k~511 K have been detected (at ~65, ~79, ~84, ~119 and ~163um). The total intensity of the OH lines is I(OH)~5x10^-4 erg s^-1 cm^-2 sr^-1. The observed emission of rotationally excited OH lines is extended and correlates well with the high-J CO and CH^+ J=3-2 line emission (but apparently not with water vapour), pointing towards a common origin. Nonlocal, non-LTE radiative transfer models including excitation by the ambient FIR radiation field suggest that OH arises in a small filling factor component of warm (Tk~160-220 K) and dense (n_H~10^{6-7} cm^-3) gas with source-averaged OH column densities of ~10^15 cm^-2. High density and temperature photochemical models predict such enhanced OH columns at low depths (A_V<1) and small spatial scales (~10^15 cm), where OH formation is driven by gas-phase endothermic reactions of atomic oxygen with molecular hydrogen. We interpret the extended OH emission as coming from unresolved structures exposed to far-ultraviolet (FUV) radiation near the Bar edge (photoevaporating clumps or filaments) and not from the lower density "interclump" medium. Photodissociation leads to OH/H2O abundance ratios (>1) much higher than those expected in equally warm regions without enhanced FUV radiation fields.Comment: Accepted for publication in A&A Letters. Figure B.2. is bitmapped to lower resolutio

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