A simple, experiment-based model of the initial self-discharge of lithium-sulphur batteries

Al-Mahmoud, Saddam Mohammed; Dibden, James W.; Owen, John R.; Denuault, Guy; Garcı́a-Aráez, Nuria

doi:10.1016/j.jpowsour.2015.12.031

Cited by 35 publications

(25 citation statements)

References 32 publications

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“…The mechanism and kinetics of Li 2 S precipitation has been studied using chronoamperometry . In terms of the shuttle behavior of polysulfides, methods to experimentally quantify the rate of the shuttle process have been proposed, as well as models of the process and its effect on capacity, charge efficiency and self‐discharge . Indeed, there have been efforts to model the behavior of Li−S cells more generally, including the effect of reaction kinetics and transport properties .…”

Section: Introductionmentioning

confidence: 97%

Quantitative Galvanostatic Intermittent Titration Technique for the Analysis of a Model System with Applications in Lithium−Sulfur Batteries

et al. 2017

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The galvanostatic intermittent titration technique (GITT) is a powerful characterization tool for batteries, which provides key thermodynamic and kinetic information about battery performance. However, the quantitative analysis of GITT measurements for lithium−sulfur batteries has so far been limited to the evaluation of the internal resistance of the cell and the equilibrium voltage profiles. In this work, we provide the mathematical framework to characterize the mass‐transport kinetics in lithium−sulfur batteries from GITT data, and we demonstrate the validity of the approach through the application to a model and well‐behaved system, ethyl viologen, whose diffusion coefficient is corroborated by cyclic voltammetry data. The present approach is also advantageous for the analysis of ion‐insertion electrodes, where non‐linearity of concentration and voltage changes would produce unrealistic evaluations of the diffusion coefficient by the classical analysis of GITT data.

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Section: Introductionmentioning

confidence: 97%

Quantitative Galvanostatic Intermittent Titration Technique for the Analysis of a Model System with Applications in Lithium−Sulfur Batteries

et al. 2017

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“…Ren et al incorporated the Li 2 S precipitation kinetics into their model. Al‐Mahmoud et al described the self‐discharge of an Li‐S cell via a simple, experiment‐based model. Marinescu et al developed a zero‐dimensional model based on the electrochemical reactions proposed by Mikhaylik and Akridge to describe the voltage response of an Li‐S cell during discharge/charge.…”

Section: Introductionmentioning

confidence: 99%

Modeling the effect of key cathode design parameters on the electrochemical performance of a lithium-sulfur battery

et al. 2018

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Summary A 1D model is developed for the Li‐S cell to predict the effect of critical cathode design parameters—carbon‐to‐sulfur (C/S) and electrolyte‐to‐sulfur (E/S) ratios in the cathode—on the electrochemical performance. Cell voltage at 60% depth of discharge corresponding to the lower voltage plateau is used as a metric for calculating the cell performance. The cathode kinetics in the lower voltage plateau is defined with a single electrochemical reaction; thus, the model has a single apparent kinetic model parameter, the cathode exchange current density (i0,pe). The model predicts that cell voltage increases considerably with increasing carbon content until a C/S ratio of 1 is attained, whereas the enhancement in the cell voltage at higher ratios is less obvious. The model can capture the effect of the C/S ratio on the cathode kinetics by expressing the electrochemically active area in the cathode in carbon volume fraction; the C/S ratio in the cathode does not affect i0,pe in the model. On the other hand, the electrolyte amount has a significant impact on the kinetic model parameter such that increasing electrolyte amount improves the cell voltage as a result of increasing i0,pe. Therefore, in the model, i0,pe needs to be defined as a function of the electrolyte volume fraction, which is known to have a crucial effect on reaction kinetics.

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“…While several physics-based models have been developed for Li-S cells [16,17,18,19,20,21,22,23,24,25,26], they fail to capture the utilization of sulfur at different discharge currents, e.g. the rate capability.…”

Section: Introductionmentioning

confidence: 99%

Modelling transport-limited discharge capacity of lithium-sulfur cells

Zhang

Marinescu

Waluś

et al. 2016

Electrochimica Acta

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Lithium-sulfur (Li-S) battery could bring a step-change in battery technology with a potential specific energy density of 500 -600 Wh/kg. A key challenge for further improving the specific energy-density of Li-S cells is to understand the mechanisms behind reduced sulfur utilisation at low electrolyte loadings and high discharge currents. While several Li-S models have been developed to explore the discharge mechanisms of Li-S cells, they so far fail to capture the discharge profiles at high currents. In this study, we propose that the slow ionic transport in concentrated electrolyte is limiting the rate capability of Li-S cells. This transport-limitation mechanism is demonstrated through a one-dimensional Li-S model which qualitatively captures the discharge capacities of a sulfolane-based Li-S cell at different currents. Furthermore, our model predicts that a discharged Li-S cell is able regain some capacity with a short period of relaxation. This capacity recovery phenomenon is validated experimentally for different discharge currents and relaxation durations. The transport-limited discharge behavior of Li-S cells highlights the importance of optimizing the electrolyte loading and electrolyte transport property in Li-S cells.

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A simple, experiment-based model of the initial self-discharge of lithium-sulphur batteries

Cited by 35 publications

References 32 publications

Quantitative Galvanostatic Intermittent Titration Technique for the Analysis of a Model System with Applications in Lithium−Sulfur Batteries

Quantitative Galvanostatic Intermittent Titration Technique for the Analysis of a Model System with Applications in Lithium−Sulfur Batteries

Modeling the effect of key cathode design parameters on the electrochemical performance of a lithium-sulfur battery

Modelling transport-limited discharge capacity of lithium-sulfur cells

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