Lithium-ion battery separator membranes based on poly(L-lactic acid) biopolymer

Sustainable materials are increasingly needed in lithium ion batteries in order to reduce their environmental impact and improve their recyclability. This work reports on the production of separators using poly (L-lactic acid) (PLLA) for lithium ion battery applications. PLLA separators were obtained by solvent casting technique, by varying polymer concentration in solution between 8 wt.% and 12 wt.% in order to evaluate their morphology, thermal, electrical and electrochemical properties. It is verified that morphology and porosity can be tuned by varying polymer concentration and that the separators are thermally stable up to 250 ºC. The best ionic conductivity of 1.6 mS/cm was obtained for the PLLA separator prepared from 10 wt.% polymer concentration in solution, due to the synergistic effect of the morphology and electrolyte uptake. For this membrane, a high discharge capacity value of 93 mAh.g-1 was obtained at the rate of 1C. In this work, it is demonstrated that PLLA is a good candidate for the development of separator membranes, in order to produce greener and environmentally friendly batteries in a circular economy context.Work supported by the Portuguese Foundation for Science and Technology (FCT) undes strategic funding UID/FIS/04650/2020 and UID/QUI/0686/2020, project PTDC/FISMAC/28157/2017, and Grants SFRH/BD/140842/2018 (J.C.B.), SFRH/BPD/121526/2016 (D.M.C), CEECIND/00833/2017 (R.G.) and SFRH/BPD/112547/2015 (C.M.C.). Financial support from the Basque Government Industry Department under the ELKARTEK and HAZITEK programs is also acknowledged. Technical and human support provided by SGIker (UPV/EHU, MICINN, GV/EJ, EGEF and ESF) is gratefully acknowledge

Potential implication of mitochondrial fusion proteins in the ontogeny of muscle bioenergetics in birds

Les jeunes oiseaux exposés au froid assurent leur homéothermie en stimulant les oxydations mitochondriales dans les muscles squelettiques. L’exposition prolongée au froid accroit les capacités de thermogenèse musculaire grâce à une plasticité bioénergétique mitochondriale dont le contrôle reste hypothétique. Chez les mammifères, des protéines de fusion (les mitofusines (Mfns) et OPA1(OPtic Atrophy 1)) participent au remaniement des réseaux dynamiques mitochondriaux dans de multiples types cellulaires. Le but de ce travail de thèse était de caractériser l’expression d’homologues aviaires des protéines de fusion mammaliennes et d’étudier leurs variations d’expression lors de la mise en place des processus bioénergétiques chez l’oiseau en croissance, lors d’une exposition aiguë ou prolongée au froid ou lors de challenges nutritionnels ou endocrines.Sur le plan méthodologique, une approche intégrative a été utilisée de l’animal entier (calorimétrie indirecte) à l’expression protéique (western blot) ou transcriptionnelle (RT-PCR) en passant par des mesures de la fonctionnalité bioénergétique sur des fibres musculaires perméabilisées et mitochondries isolées. Deux modèles animaux ont été utilisés, une espèce naturellement adaptée aux conditions extrêmes de l’Antarctique, le manchot Adélie (Pygoscelisadeliae), et un modèle de laboratoire, le canard de Barbarie (Cairina moschata). Nos résultats ont permis de caractériser chez l’oiseau l’expression de protéines de fusion (Mfn2, OPA1) immunoréactives homologues à celles des mammifères. Le séquençage d’une partie de la séquence codante des gènes codant les Mfns a montré une bonne similitude entre les espècesd’oiseaux et les mammifères. Chez le manchot, l’abondance relative de ces protéines dans lesmitochondries musculaires variait avec la croissance et l’exposition thermique en corrélation positiveavec les capacités bioénergétiques musculaires. Chez le canard, l’activité respiratoire et l’abondance relative de ces protéines étaient également corrélées suite à un jeûne de 60h ou, bien que dans une moindre mesure, après altération pharmacologique du statut thyroïdien.Ces résultats montrent pour la première fois chez l’oiseau l’expression de protéines homologues aux protéines de fusion des mammifères. L’association entre les variations d’expression de ces protéines et les modifications bioénergétiques du muscle squelettique indiquent qu’elles pourraient contribuer à la plasticité bioénergétique observée chez l’oiseau en croissance. Ces résultats suggèrent que des modifications potentielles de l’organisation des réseaux mitochondriaux musculaires pourraient contribuer aux réponses adaptatives des organismes face aux contraintes environnementales.Cold-exposed young birds maintain their homeothermy by stimulating mitochondrial oxidations in skeletal muscle. Prolonged cold exposure enhances muscle thermogenic capacities through mitochondrial bioenergetics plasticity which control still remains hypothetical. In mammals, fusion proteins (mitofusins (Mfns) and OPA1 (Optic Atrophy 1)) contribute to the permanent and dynamic changes in mitochondrial networks in multiple cell types. The aim of our work was to characterize the expression of avian homologues of mammalian fusion proteins and to study the variations of their expression during the establishment of bioenergetics processes in growing birds, during an acute or a prolonged cold exposure and finally during nutritional or endocrine challenges. Methodologically, an integrative approach has been used from whole animal (indirect calorimetry) to protein (western-blot) or gene (RT-PCR) expression through measurements of the bioenergetics functionality of permeabilized muscle fibers and isolated mitochondria. Two animal models were used, a species naturally adapted to Antarctica harsh conditions, the Adélie penguin (Pygoscelis adeliae), and a laboratory model, the Muscovy duck (Cairina moschata).Our results allowed us to characterize, in birds, the expression of immunoreactive fusion proteins (Mfn2, OPA1) which were homologous to those of mammals. The sequencing of a part of the coding sequence of Mfns genes showed a great similitude between avian and mammalian species. In penguins, the relative abundance of these proteins in muscle mitochondria was modified by growth in the cold and was positively correlated with muscle bioenergetics capacities. In ducks, the respiratory activity and the relative abundance of these proteins were also correlated after a 60h fasting period or,though a lesser extent, after a pharmacological alteration of thyroid status. Our results show, for the first time in birds, the expression of proteins homologous to mammalian fusion proteins. The association between the changes in expression of these proteins and the bioenergetics modifications in skeletal muscle indicates that these proteins could contribute to thebioenergetics plasticity observed in growing chicks. These results suggest that potential modifications of the muscle mitochondrial network organization could play a role in the adaptive responses of organisms to the environmental constraints

Implication potentielle des protéines de fusion mitochondriale dans l'ontogenèse des processus bioénergétiques musculaires chez l'oiseau

Cold-exposed young birds maintain their homeothermy by stimulating mitochondrial oxidations in skeletal muscle. Prolonged cold exposure enhances muscle thermogenic capacities through mitochondrial bioenergetics plasticity which control still remains hypothetical. In mammals, fusion proteins (mitofusins (Mfns) and OPA1 (Optic Atrophy 1)) contribute to the permanent and dynamic changes in mitochondrial networks in multiple cell types. The aim of our work was to characterize the expression of avian homologues of mammalian fusion proteins and to study the variations of their expression during the establishment of bioenergetics processes in growing birds, during an acute or a prolonged cold exposure and finally during nutritional or endocrine challenges. Methodologically, an integrative approach has been used from whole animal (indirect calorimetry) to protein (western-blot) or gene (RT-PCR) expression through measurements of the bioenergetics functionality of permeabilized muscle fibers and isolated mitochondria. Two animal models were used, a species naturally adapted to Antarctica harsh conditions, the Adélie penguin (Pygoscelis adeliae), and a laboratory model, the Muscovy duck (Cairina moschata).Our results allowed us to characterize, in birds, the expression of immunoreactive fusion proteins (Mfn2, OPA1) which were homologous to those of mammals. The sequencing of a part of the coding sequence of Mfns genes showed a great similitude between avian and mammalian species. In penguins, the relative abundance of these proteins in muscle mitochondria was modified by growth in the cold and was positively correlated with muscle bioenergetics capacities. In ducks, the respiratory activity and the relative abundance of these proteins were also correlated after a 60h fasting period or,though a lesser extent, after a pharmacological alteration of thyroid status. Our results show, for the first time in birds, the expression of proteins homologous to mammalian fusion proteins. The association between the changes in expression of these proteins and the bioenergetics modifications in skeletal muscle indicates that these proteins could contribute to thebioenergetics plasticity observed in growing chicks. These results suggest that potential modifications of the muscle mitochondrial network organization could play a role in the adaptive responses of organisms to the environmental constraints.Les jeunes oiseaux exposés au froid assurent leur homéothermie en stimulant les oxydations mitochondriales dans les muscles squelettiques. L’exposition prolongée au froid accroit les capacités de thermogenèse musculaire grâce à une plasticité bioénergétique mitochondriale dont le contrôle reste hypothétique. Chez les mammifères, des protéines de fusion (les mitofusines (Mfns) et OPA1(OPtic Atrophy 1)) participent au remaniement des réseaux dynamiques mitochondriaux dans de multiples types cellulaires. Le but de ce travail de thèse était de caractériser l’expression d’homologues aviaires des protéines de fusion mammaliennes et d’étudier leurs variations d’expression lors de la mise en place des processus bioénergétiques chez l’oiseau en croissance, lors d’une exposition aiguë ou prolongée au froid ou lors de challenges nutritionnels ou endocrines.Sur le plan méthodologique, une approche intégrative a été utilisée de l’animal entier (calorimétrie indirecte) à l’expression protéique (western blot) ou transcriptionnelle (RT-PCR) en passant par des mesures de la fonctionnalité bioénergétique sur des fibres musculaires perméabilisées et mitochondries isolées. Deux modèles animaux ont été utilisés, une espèce naturellement adaptée aux conditions extrêmes de l’Antarctique, le manchot Adélie (Pygoscelisadeliae), et un modèle de laboratoire, le canard de Barbarie (Cairina moschata). Nos résultats ont permis de caractériser chez l’oiseau l’expression de protéines de fusion (Mfn2, OPA1) immunoréactives homologues à celles des mammifères. Le séquençage d’une partie de la séquence codante des gènes codant les Mfns a montré une bonne similitude entre les espècesd’oiseaux et les mammifères. Chez le manchot, l’abondance relative de ces protéines dans lesmitochondries musculaires variait avec la croissance et l’exposition thermique en corrélation positiveavec les capacités bioénergétiques musculaires. Chez le canard, l’activité respiratoire et l’abondance relative de ces protéines étaient également corrélées suite à un jeûne de 60h ou, bien que dans une moindre mesure, après altération pharmacologique du statut thyroïdien.Ces résultats montrent pour la première fois chez l’oiseau l’expression de protéines homologues aux protéines de fusion des mammifères. L’association entre les variations d’expression de ces protéines et les modifications bioénergétiques du muscle squelettique indiquent qu’elles pourraient contribuer à la plasticité bioénergétique observée chez l’oiseau en croissance. Ces résultats suggèrent que des modifications potentielles de l’organisation des réseaux mitochondriaux musculaires pourraient contribuer aux réponses adaptatives des organismes face aux contraintes environnementales

Optimisation d'électrodes composites pour accumulateurs Li-ion de puissance élaborées en milieux aqueux

Ces travaux portent sur l'optimisation d'électrodes composites positives et négatives, respectivement à base de LiFePO4 et de Li4Ti5O12, pour accumulateurs Li-ion de puissance. Dans le cadre de l'élaboration d'électrodes par voie aqueuse, des formulations optimisées ont été définies pour les deux matériaux d'électrodes LiFePO4 (thèse W. Porcher 2007) et Li4Ti5O12 par étude couplée des dispersions d'encre, des morphologies d'électrodes et des performances finales. A partir de ces électrodes, dont les performances électrochimiques sont évaluées en configuration demi-pile par rapport à du lithium métal, une étude systématique est menée sur les courbes de décharge qui caractérisent l'insertion du lithium dans la structure cristalline des matériaux d'électrodes. La réponse électrochimique du système est étudiée précisément suivant les paramètres de formulation (modification de l'agent conducteur et/ou des additifs polymères), de mise en oeuvre (épaisseur, grammage) et de structure des électrodes (porosité, tortuosité). Il en résulte une discrimination des différentes contributions résistives et des différentes limitations cinétiques de l'électrode (matériau d'électrode et son environnement) selon le grammage, la porosité et le régime de fonctionnement. Par l'identification de ces limitations, un début de diagnostic peut alors être avancé quant aux paramètres sur lesquels agir (conduction électronique, conduction ionique, architecture d'électrode, morphologie du matériau d'électrode) pour optimiser les performances des électrodes considéréesThis work focuses on the optimization of composite positive and negative electrodes, respectively based on LiFePO4 and Li4Ti5O12 materials, for Li-ion power accumulators. In the framework of electrodes elaboration via aqueous route, optimized formulations were defined for both LiFePO4 (W. Porcher's PhD - 2007) and Li4Ti5O12 electrode materials by coupling studies of ink dispersions, electrode morphologies and final performance. From these electrodes, electrochemically tested in coin cells vs. a lithium foil electrode, a systematic study is carried out on the discharge curves that characterize the lithium insertion in the electrode materials crystalline structure. The electrochemical response of the system is studied precisely as a function of the electrode formulation (modification of the conductive agent and/or polymer additives), the electrode processing (thickness, loading) and the electrode structure (porosity, tortuosity). This thorough analysis leads to a discrimination of the electrode different resistive contributions and kinetics limitations (electrode material and its environment) as a function of the electrode loading and porosity, and of the discharge rate. By identifying these limitations, a diagnosis can be propounded regarding the electrodes parameters on which one could play (electronic conduction, ionic conduction, electrode architecture, electrode material morphology) so as to optimize the electrode performanceNANTES-BU Sciences (441092104) / SudocSudocFranceF

Electronic and Ionic Wirings Versus the Insertion Reaction Contributions to the Polarization in LiFePO4 Composite Electrodes

International audienceThe different contributions to the polarization of a LiFePO4 electrode are experimentally discriminated in this work. The electrode total resistance is dominated at high rate by the contribution of the electronic and the ionic wires, the former being more important in the case of electrodes with low compaction, while the latter being more important in the case of electrodes with high compaction. A porosity in the 35%-40% range allows to minimize the electrode polarization. At low rate, the electrode resistance is dominated by the resistance to lithium insertion into the active mass and follows the predictions of M. Gaberscek and J. Jamnik [ Solid State Ionics , 177 , 2647 (2006)] . We show here that the resistance to lithium insertion decreases with the increase of the specific current, a feature that suggests an increase of the active particle conductivity with rate. The easy-handling methodology described in this work should enable a more rational optimization of the electrode formulation and processing conditions for better electrochemical performance

Nuclear defects in skeletal muscle from a Dynamin 2-linked centronuclear myopathy mouse model

Abstract Dynamin 2 (DNM2) is a key protein of the endocytosis and intracellular membrane trafficking machinery. Mutations in the DNM2 gene cause autosomal dominant centronuclear myopathy (CNM) and a knock-in mouse model expressing the most frequent human DNM2 mutation in CNM (Knock In-Dnm2 R465W/+) develops a myopathy sharing similarities with human disease. Using isolated muscle fibres from Knock In-Dnm2 R465W/+ mice, we investigated number, spatial distribution and morphology of myonuclei. We showed a reduction of nuclear number from 20 weeks of age in Tibialis anterior muscle from heterozygous mice. This reduction is associated with a decrease in the satellite cell content in heterozygous muscles. The concomitant reduction of myonuclei number and cross-section area in the heterozygous fibres contributes to largely maintain myonuclear density and volume of myonuclear domain. Moreover, we identified signs of impaired spatial nuclear distribution including alteration of distance from myonuclei to their nearest neighbours and change in orientation of the nuclei. This study highlights reduction of number of myonuclei, a key regulator of the myofiber size, as a new pathomechanism underlying muscle atrophy in the dominant centronuclear myopathy. In addition, this study opens a new line of investigation which could prove particularly important on satellite cells in dominant centronuclear myopathy

Thyroid status affects membranes susceptibility to free radicals and oxidative balance in skeletal muscle of Muscovy ducklings (Cairina moschata)

International audienceThyroid hormones (TH) are major contributor to oxidative stress in mammals because they (1) stimulate reactive oxygen species generation (ROS), (2) impair antioxidant defenses, and (3) increase the susceptibility to free radicals of most tissues. Unlike mammals, THs seem to diminish mitochondrial ROS while they have limited effect on the antioxidant machinery in birds. However, how THs modify the susceptibility to ROS has never been explored in an avian model, and very little is known about their effect on oxidative balance in birds. Therefore, the objective of our study was to examine the effect of chronic pharmacological hypo␣ and hyperthyroidism on (i) the susceptibility of mitochondrial membranes to ROS; and (ii) the level of oxidative stress assessed by measuring oxidative damage to lipids, nucleic acids and proteins in the gastrocnemius muscle of ducklings. We show that hypothyroidism had no effect on the susceptibility of mitochondrial membranes to free radicals. Hypothyroid ducklings had lower oxidized lipids (-31%) and DNA (+25%) but a similar level of protein carbonylation relative to controls. Conversely, mitochondrial membranes of hyperthyroid ducklings exhibited higher unsaturation (þ12%) and peroxidation (þ31%) indexes than in controls indicating a greater susceptibility to free radicals. However, hyperthyroid ducklings exhibited more oxidative damages on proteins (+67%) only, whereas lipid damages remained unchanged, and there was a slight reduction (-15%) in damages to DNA compared to euthyroid controls. Our results indicate that birds and mammals present fundamental differences in their oxidative stress response to thyroid status

Toward the Aqueous Processing of Li4Ti5O12: A Comparative Study with LiFePO4

International audienc