Accumulateur lithium/soufre : développement et compréhension des mécanismes électrochimiques

In this work two main aspects has been conducted in parallel. The first one was focused on betterunderstanding the very complex working mechanism of Li/S cell. Structural changes evolution ofactive material upon real time battery operation was explored, giving a clear answer on thesolid/liquid reaction evolution, which govern the electrochemistry of Li/S technology. Formationof another allotropic form of sulfur (monoclinic beta-S8) during recharging the battery have beenreported for the first time ever in Li/S community. Impedance technique applied to such systemprovided additional information concerning the kinetics of these reactions. Apart from that,another aspect targeted rather on improvements of already existing solutions (making better sulfurelectrodes, with significantly improved specific capacities) as well as development the alternativesolutions, i.e. fabrication and test of new Li2S-based positive electrodes, which could be apromising transition from classical Li/S cells into safer Li-ion/S batteries.Dans ce travail de thèse, deux objectifs ont été fixés. Le premier a été de mieux comprendre le mécanisme très complexe qui est en jeu dans les accumulateurs Li/S. Pour cela, les modifications structurales du matériau actif ont été observées in operando et ont permis de valider un modèle clair concernant les réactions de transformations de phases qui contrôlent le lithium/soufre. La cristallisation d’une forme métastable du soufre (bêta-S8 monoclinique) en fin de recharge a ainsi été observée pour la première fois lors d’expériences au synchrotron de l’ESRF. La technique d’impédance électrochimique a également donné d’importantes informations sur les cinétiques deces réactions. Le deuxième objectif visait l’amélioration du système Li/S par l’optimisation des électrodes de soufre afin d’augmenter leurs performances mais également par la fabrication d’électrodes de Li2S efficaces permettant la transition vers le Li-ion/S, plus sécuritaire

Methodology for assessing the lithium-sulfur battery degradation for practical applications

Lithium-Sulfur (Li-S) battery is an emerging battery technology receiving growing amount of attention due to its potential high contributions of gravimetric energy density, safety and low production cost. However, there are still some obstacles preventing their swift commercialization. Li-S batteries are driven by different electrochemical processes than commonly used Lithium-ion batteries, which often results in their very different behavior. Therefore, the modelling and testing have to be adjusted to reflect this unique behavior to prevent possible biases. A methodology for a reference performance test for the Li-S batteries is proposed in this study to point out the Li-S battery features and provide guidance to users how to deal with them and possible results into standardization

Lithium-sulfur cell equivalent circuit network model parameterization and sensitivity analysis

Compared to lithium-ion batteries, lithium-sulfur (Li-S) batteries potentially offer greater specific energy density, a wider temperature range of operation, and safety benefits, making them a promising technology for energy storage systems especially in automotive and aerospace applications. Unlike lithium-ion batteries, there is not a mature discipline of equivalent circuit network (ECN) modelling for Li-S. In this study, ECN modelling is addressed using formal ‘system identification’ techniques. A Li-S cell’s performance is studied in the presence of different charge/discharge rates and temperature levels using precise experimental test equipment. Various ECN model structures are explored, considering the trade-offs between accuracy and speed. It was concluded that a ‘2RC’ model is generally a good compromise, giving good accuracy and speed. Model parameterization is repeated at various state-of-charge (SOC) and temperature levels, and the effects of these variables on Li-S cell’s ohmic resistance and total capacity are demonstrated. The results demonstrate that Li-S cell’s ohmic resistance has a highly nonlinear relationship with SOC with a break-point around 75% SOC that distinguishes it from other types of battery. Finally, an ECN model is proposed which uses SOC and temperature as inputs. A sensitivity analysis is performed to investigate the effect of SOC estimation error on the model’s accuracy. In this analysis, the battery model’s accuracy is evaluated at various SOC and temperature levels. The results demonstrate that the Li-S cell model has the most sensitivity to SOC estimation error around the break-point (around 75% SOC) whereas in the middle SOC range, from 20% to 70%, it has the least sensitivity

Recent progress and emerging application areas for lithium-sulfur battery technology

Electrification is progressing significantly within the present and future vehicle sectors such as large commercial vehicles (e. g. trucks and busses), high altitude long endurance (HALE), high altitude pseudo satellites (HAPS), and electric vertical take‐off and landing (eVTOL). The battery systems performance requirements differ across these applications in terms of power, cycle life, system cost, etc. However, the need for high gravimetric energy density, 400 Wh kg−1 and beyond, is common across them all, since it will enable vehicles to achieve extended range, longer mission duration, lighter weight or increased payload. The system level requirements of these emerging applications can be broken down into the component level developments required to integrate Li‐S technology as the power system of choice. In order to adapt the batteries’ properties, such as energy and power density, to the respective application, the academic research community has a key role to play in component level development. However, materials and component research must be conducted within the context of a viable Li‐S cell system. Herein, the key performance benefits, limitations, modelling and recent progress of the Li‐S battery technology and its adaption towards real world application are discusse

Lithium/Sulfur batteries : development and understanding of the working mechanisms

Dans ce travail de thèse, deux objectifs ont été fixés. Le premier a été de mieux comprendre le mécanisme très complexe qui est en jeu dans les accumulateurs Li/S. Pour cela, les modifications structurales du matériau actif ont été observées in operando et ont permis de valider un modèle clair concernant les réactions de transformations de phases qui contrôlent le lithium/soufre. La cristallisation d’une forme métastable du soufre (bêta-S8 monoclinique) en fin de recharge a ainsi été observée pour la première fois lors d’expériences au synchrotron de l’ESRF. La technique d’impédance électrochimique a également donné d’importantes informations sur les cinétiques deces réactions. Le deuxième objectif visait l’amélioration du système Li/S par l’optimisation des électrodes de soufre afin d’augmenter leurs performances mais également par la fabrication d’électrodes de Li2S efficaces permettant la transition vers le Li-ion/S, plus sécuritaire.In this work two main aspects has been conducted in parallel. The first one was focused on betterunderstanding the very complex working mechanism of Li/S cell. Structural changes evolution ofactive material upon real time battery operation was explored, giving a clear answer on thesolid/liquid reaction evolution, which govern the electrochemistry of Li/S technology. Formationof another allotropic form of sulfur (monoclinic beta-S8) during recharging the battery have beenreported for the first time ever in Li/S community. Impedance technique applied to such systemprovided additional information concerning the kinetics of these reactions. Apart from that,another aspect targeted rather on improvements of already existing solutions (making better sulfurelectrodes, with significantly improved specific capacities) as well as development the alternativesolutions, i.e. fabrication and test of new Li2S-based positive electrodes, which could be apromising transition from classical Li/S cells into safer Li-ion/S batteries

Lithium-Sulfur battery technology readiness and applications – a review

Lithium Sulfur (Li-S) battery is generally considered as a promising technology where high energy density is required at different applications. Over the past decade, there has been an ever increasing volume of Li-S academic research spanning materials development, fundamental understanding and modelling, and application-based control algorithm development. In this study, the Li-S battery technology, its advantages and limitations from the fundamental perspective are firstly discussed. In the second part of this study, state-of-the-art Li-S cell modelling and state estimation techniques are reviewed with a focus on practical applications. The existing studies on Li-S cell equivalent-circuit-network modelling and state estimation techniques are then discussed. A number of challenges in control of Li-S battery are also explained such as the flat open-circuit-voltage curve and high sensitivity of Li-S cell’s behavior to temperature variation. In the last part of this study, current and future applications of Li-S battery are mentioned