Some Directions for Performance Improvement of Li-Ion Batteries out of Usual Paths

Recent developments at IMN will be shared on several research directions out of usual paths for performance improvement of Li-ion batteries. We will focus on innovative surface modifications of electrode components, new electrode compositions and architectures, and failure mechanism upon cycling by in-depth characterization through coupled advanced spectroscopic techniques. A molecular grafting approach has been proposed as a way to modify the interfacial chemical reactivity of oxide materials, which is detrimental to their long-term energy storage properties as electrodes of Li-ion batteries. Surface derivatization of powder oxide materials such as Li1.2V3O8 and Li(Mn,Ni)2O4 was accomplished by in situ electrografting of a diazonium salt during Li-ion intercalation, leading to a covalently bonded organic multilayer. Charge transfer is not impeded, while electrolyte decomposition is inhibited thus increasing the cycle life and decreasing the self-discharge. Carbon additives of classical porous electrodes occupy a large volume fraction which is lost for charge storage. Redox functionalization of the surface of some carbon additives has been successfully achieved through non-covalent grafting chemistry using multi-redox pyrene molecules synthesized on purpose. Such functionalized carbon additives have been used to increase the stored energy and power of C-coated LFP porous electrodes. Thicker electrodes are needed for higher energy density Li-ion batteries. We evaluate different directions in order to design new innovative electrode architectures for such a purpose. Our grafting chemistry has been further developed to achieve molecular junctions between non-carbon-coated LFP and multiwall carbon nanotubes (MWCNT) using a designed thiophene-based conjugated molecule. The strategy enables original architecturing of the cathode of Li-ion batteries, with the individual MWCNT being electronically nanocontacted at the surface of LFP grains. This advancement leads to much higher specific capacity and better capacity retention for non calendared thick electrodes, for which the electronic wiring of the electroactive material grains is a critical issue. Another direction followed is the use of conducting polymer additives in porous electrodes, which are able to act as both conducting fillers and mechanical reinforcement materials. We have synthesized a new form of lithium doped PANI, the excellent properties of which in terms of specific capacity, stability on cycling and rate capability will be presented. The coating of bare LFP particles with thin layers of this new Li-doped PANI allows surpassing the performance of commercial carbon coated LFP thick electrodes. The role of this PANI additive into millimetric thick electrodes of NMC material will also be discussed. Future developments of higher energy density Si-based Li-ion batteries depend on the mastering of side reactions at the Si anode. We will compare the SEI composition and morphology at the Si surface upon cycling in half cell and full Li-ion cell configurations using a combination of 7Li, 19F MAS NMR, XPS, TOF-SIMS and STEM-EELS. The origin of the much faster aging of Si-based full cells versus half cells and future directions for improvement will be discusse

Dietary phospholipids are more efficient than neutral lipids for long‐chain polyunsaturated fatty acid supply in European sea bass Dicentrarchus labrax larval development

International audienceAbstract We evaluated the effects of dietary lipid class (phospholipid vs. neutral lipid) and level of n−3 long‐chain PUFA (LC‐PUFA) on the growth, digestive enzymatic activity, and histological organization of the intestine and liver in European sea bass larvae. Fish were fed from the onset of exogenous feeding at 7 to 37 d post‐hatch with five isoproteic and isolipidic compound diets with different levels of EPA and DHA. Diet names indicated the percentage of EPA and DHA contained in the phospholipids (PL) and neutral lipids (NL), as follows: PL5, PL3, PL1, NL1, and NL3. Histological observations showed different patterns of lipid absorption and accumulation in the intestinal mucosa depending on the level and nature of the dietary lipid fraction. Fish fed high levels of neutral lipids (11%, NL3 diet: 2.6% of EPA+DHA in the NL fraction) showed large intracellular and intercellular lipid deposits in the anterior intestine, but no such lipid accumulation was detected when larvae were fed with low and moderate levels of EPA and DHA in the phospholipid and neutral lipid fractions of the diet (PL and NL1 diets). PL were preferentially absorbed in the postvalvular intestine, and the accumulation of marine PL was inversely correlated to their dietary level. The postvalvular intestinal mucosa and liver showed signs of steatosis; large lipid vacuoles were observed in this region of the intestine and in the liver and were inversely correlated with the level of dietary neutral lipids. The best results in terms of growth, survival, and development (maturation of the digestive system and histological organization of the liver and intestinal mucosa) were obtained in the group fed with 2.3% of EPA and DHA in the PL fraction of the diet (PL3 diet), revealing that European sea bass larvae use the LC‐PUFa contained in the PL fraction more efficiently than those from the NL fraction of the diet

Genomic organization and spatio-temporal expression of the hemoglobin genes in European sea bass (Dicentrarchus labrax)

Hemoglobins (Hb) play a critical role in satisfying the oxygen demand of vertebrate aerobic metabolism. The present study reports the characterization of the European sea bass (Dicentrarchus labrax) Hb genes, including genomic organization, phylogeny, and spatio-temporal gene expression. These Hb genes are divided into two unlinked clusters, the “MN” cluster containing eleven genes (five Hbα genes named MN-Hbα1-5 and six Hbβ genes named MN-Hbβ1–6) and the “LA” cluster consisting of three genes (two Hbα genes named LA-Hbα1-2 and one Hbβ gene named LA-Hbβ1). Comparative analysis of Hb amino acid sequences indicates that most of the important amino acid residues involved in hemoglobin-oxygen binding, particularly in the Bohr and Root effects, are generally well conserved, except in MN-Hbβ3. Six genes were mainly expressed during early life (MN-Hbα3-5, MN-Hbβ4–6), while the others were predominantly expressed at juvenile–adult stages. Adult fish expressed Hb genes at high levels in the head kidney and spleen; the main organs involved in blood formation. The Hb genes expressed in non-hematopoietic organs (intestine, gills, heart, brain, and liver) may facilitate oxygen homeostasis or be involved in antimicrobial defense. Stage- and tissue-specific gene expression patterns, together with the sequence features of the different Hb proteins, suggest a broad range of roles in European sea bass

Multiprobe Study of the Solid Electrolyte Interphase on Silicon-Based Electrodes in Full-Cell Configuration

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The effects of dietary marine protein hydrolysates on the development of sea bass larvae, Dicentrarchus labrax, and associated microbiota

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