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International audience; This paper is a contribution to fasten integration of battery pack innovation in commercial Electric Vehicles (EV) through massive digitalization: a seamless process detailed for battery design, battery safety, and battery management. Selected results of studies carried out on the EV value chain from design to recycling steps are presented, highlighting the importance of seamless integration and holistic state of mind when designing EV. Association between experimental and numerical approaches for efficient innovative EV production is crucial to achieve easy commercialisation. Successful forecasting of aging and thermal runaway evolution from single cell failure at module level using such methods illustrates their great potential. Hardware key counterparts under development are also introduced and give an idea of future architecture of EV battery packs and overall improvement of EV energy efficiency. Finally, a flexible and easily modifiable solution for battery electric vehicle (BEV) that allows rapid and cost-effective integration of future innovation is presented. This paper globally illustrates key breakthroughs gained in the context of the collaborative research project named ‘DEMOBASE’, for DEsign and MOdelling for improved BAttery Safety and Efficiency successfully submitted for funding by the European Commission in response to a 2017 call dedicated to ‘Green Vehicles’ under the EU Horizon 2020 work programme “Smart, green and integrated transport”.

This study presents a novel process of wood modification employing humins, i.e. polydisperse furanic macromolecules formed during sugar dehydration. Humin valorization is more and more in the spotlight, thanks to the increased research efforts being placed by industries on biomass valorization. Here, a water soluble liquid fraction of humins was employed to impregnate wood and was polymerized within the wood using heat. This so-called ‘humination’ process was compared with the more classical furfurylation, which consists of impregnating with furfuryl alcohol (FA), and the polymerization of FA inside the wood. Confocal laser scanning fluorescence microscopy proved that furanic entities contained in the liquid fraction of humins polymerized within the wood cell walls and resulted in fluorescence similar to that seen for furfurylated wood. The humin modified wood showed lower mass increase and identical dimensional stability compared to furfurylated wood after immersion in water. Both treatments resulted in higher hydrophobicity compared to untreated wood. The elastic modulus of humin treated wood, measured by dynamic mechanical analysis (DMA), was similar to that of furfurylated wood for T < 75 °C and slightly higher than untreated wood. Finally, reaction-to-fire properties were investigated. Humin treated wood showed some advantages over furfurylated wood such as longer ignition time, slower heat release rate (−13%) and lower CO formation. This study demonstrates for the first time that humins can be used as an alternative to FA for wood modification to obtain enhanced wood products.

A “waste-valorization” approach was developed to transform recalcitrant hydrolysis lignin (HL) from second-generationbioethanol productioninto multifunctional bio-based products. The hydrolysis lignin (HL) was extracted with aqueousacetone, yielding two fractions enriched in lignin and cellulose, respectively. The soluble hydrolysis lignin (SHL) was converted into anionic and cationic colloidal lignin particles (CLPs and c-CLPs). The insoluble cellulose-rich fraction was transformed intolignocellulosicnanofibrils that were further combined with CLPs or c-CLPs to obtainnanocomposite filmswithtailored mechanical properties,oxygen permeabilityand antioxidant properties. To enable prospective applications of lignin in nanocomposite films and beyond, CLPs and c-CLPs were also produced from a soda lignin (SL) and the influence of the lignin type on the particle size and ecotoxicity was evaluated. Finally, the carbon footprint of the entire process from hydrolysis lignin to films was assessed and an integration to industrial scale was considered to reduce the energy consumption. While most previous work utilizes purified lignin and pristine and often purified cellulose fibers to produce nanomaterials, this work provides aproof of conceptfor utilizing the recalcitrant lignin-rich side stream of thebioethanolprocess as raw material for functional nanomaterials and renewable composites.

International audience; En septembre 2019, un incendie a démarré dans le stockage de l’usine Lubrizol, spécialisée dans la fabrication d’additifs pour lubrifiant et située près de la ville de Rouen. Cet incendie a déclenché une crise importante en raison d’un panache visible de 22 km de long, qui a survolé la ville et induit des restrictions temporaires à plus de 100 km du sinistre. L’objectif de ce travail est de proposer une approche pragmatique de la gestion des incendies mettant en jeu de nombreux produits stockés à différents endroits, à différentes phases de leur cycle de vie, depuis le site du producteur jusqu’à l’utilisateur final en passant par les grands entrepôts de stockage. L’analyse proposée porte sur la gestion de crise, sur les demandes associées au développement d’un tel sinistre et aux données techniques disponibles pour y répondre. Elle expose les leçons tirées de l’incendie de l’usine Lubrizol pour l’amélioration de la gestion opérationnelle d’un tel sinistre, certes rare mais susceptible d’avoir des conséquences graves sur la santé et l’environnement à court, moyen et long termes.

A reliable heating device coupled with a FTIR gas analyzer has been tailored with the aim of evaluating the role of state-of-the-art lithium-ion battery components and environmental conditions on thermal and toxic hazards. Here, we demonstrate its effectiveness in accurately assessing the role of fully charged 0.6 Ah pouch cells confinement, electrolyte composition and separator coating on heat release and toxic gas generation-related risks. The fire safety international standards developed by the ISO TC92 SC3 subcommittee were used to determine the asphyxiant and irritant gases toxicity. Cells tighting confinement proves to be a very efficient way to diminish and delay (from 180 to 245 °C) the thermal runaway phenomenon occurrence and relating toxic gas release. Vinylene carbonate as electrolyte additive is able to shift (+20 °C) the onset temperature, while substitution of 1/3 M LiPF6 by LiFSI does not modify the thermal behavior, nor the toxic risks. The coating of a tri-layer separator influences the irritant gas toxicity related risk, by decreasing fluorinated components release. This study highlights that some improvements regarding LIB safety can be achieved through appropriate component selection and cells integration design at a module/pack level.

International audience; Li-ion secondary rechargeable batteries are becoming the preferred solution to store energy on board of new generation electric and hybrid vehicles or manage renewable energy in stationary applications. However, Li-ion batteries (LIBs) are still suffering limited lifetime, high cost and significant safety issues increasing their time to mass market. Thermal runaway is still nowadays considered as a major hazard of LIBs. This multiscale and multistep phenomenon originating at the microscale level potentially leads to uncontrolled fire and explosion of the battery. This work is focused on the development and validation of a 3D physical model of the LIB electro-thermal behavior nearby thermal runaway conditions. A combined modeling and experimental investigation provides a better understanding of the mechanisms leading to thermal runaway of LIBs, and of the ageing influence on this process. One major outcome of this work is also the proven fact that calendar ageing leads to a delayed onset of the cell self-heating temperature with a thermal runaway starting at a lower temperature. This is supported by computer simulations showing that the thickening of the solid electrolyte interface (SEI) hinders the diffusion of Li ions, which delays the degradation of the negative electrode and the occurrence of thermal runaway. HIGHLIGHTS  Development of an original 3D thermal runaway model including calendar ageing.  Model includes 3D thermal, 3D chemical reaction, and 0D calendar ageing sub-models.  Calibration of the model for cylindrical 26650 LFP/C cells using a BTC.  Validation of the model for fresh as well as 10% and 30% aged cells in oven tests.  Fresh and aged cells are compared in terms of critical temperatures under overheating

The main safety issue pertaining to operating lithium-ion batteries (LIBs) relates to their sensitivity to thermal runaway. This complex multiphysics phenomenon was observed in two commercial 18650 Ni-rich LIBs, namely a Panasonic NCR GA and a LG HG2, which were based on L i ( N i 0.8 C o 0.15 A l 0.05 ) O 2 (NCA) and L i ( N i 0.8 M n 0.1 C o 0.1 ) O 2 (NMC811), respectively, for positive electrodes, in combination with graphite-SiOx composite negative electrodes. At pristine state, the batteries were charged to different levels of state of charge (SOC) (100% and 50%) and were investigated through thermal abuse tests in quasi-adiabatic conditions of accelerating rate calorimetry (ARC). The results confirmed the proposed complete thermal runaway of exothermic chain reactions. The different factors impacting the thermal runaway kinetics were also studied by considering the intertwined impacts of SOC and the related properties of these highly reactive Ni-rich technologies. All tested cells started their accelerated thermal runaway stage at the same self-heating temperature rate of ~48 &deg, C/min. Regardless of technology, cells at reduced SOC are less reactive. Regardless of SOC levels, the Panasonic NCR GA battery technology had a wider safe region than that of the LG HG2 battery. This technology also delayed the hard internal short circuit and shifted the final venting to a higher temperature. However, above this critical temperature, it exhibited the most severe irreversible self-heating stage, with the highest self-heating temperature rate over the longest duration.

International audience; Within the Zelcor European project, INRA applied a newly-developed process in ionic liquids to depolymerise and functionalise lignin (increase the phenol content) to two reference lignin samples (Protobind 1000 from GreenValue and Futurol residue) and their fractions. Advantages of the process are to combine short reaction time (max 40 min) and low temperatures (max 110°C) compared to alternative catalytic processes. The process conditions were selected according to the prior optimisation performed on phenolic model compounds (monomer, dimer and milled wood isolated lignins ). Thioacidolysis, 31P NMR, and SEC were applied to the ethyl acetate soluble and insoluble reaction products so as to assess the degree of depolymerisation and demethylation. The results indicate that: i) a prior extraction of the ethyl acetate soluble compounds is beneficial to the process; ii) up to 30% solubility can be reached after the treatment of insoluble fractions; iii) demethylation occurs for all samples. The samples were then tested for antioxidant properties study to assess whether the process generates fractions with improved performances compared to the lignin samples and fractions already available. In parallel to the technical development of the process, security assessment has been undertaken through close interaction with INERIS to identify possible safety advantages of the process and to check that there is no major obstacle to future industrial development of the process.

International audience; With the growing interest of a circular economy, the use of lignocellulosic residues such as lignins and humins as potential renewable feedstock for biorefining processes looks more and more promising. With humins, many challenges are still remaining for their sustainable use, starting from the need of providing reference data reflecting actual usable feedstocks of such materials. With this perspective, this paper offers a first outlook on the potential environmental fate of those materials and components, all related to furanics, a family of compounds for which toxicity is still a matter of debate. During the assessment, the conventional OECD ecotoxicity and biodegradability tests demanded by the European REACH regulation for a primary evaluation of environmental hazards were performed in combination with fish immunomarker tests to study the possible long-term effects on aquatic ecosystems. These first results are promising as humins did not exhibit any immediate ecotoxicological concerns and hence would allow considering their use in environmental-friendly applications.

International audience; Industrial humins from biorefining process of sugars were used as reactive thermoset matrix for the preparation of humins-jute fibre composites. This material was investigated and benchmarked with jute composites prepared with polyfurfurylalcohol (PFA), a well-known biobased thermosetting resin The Dynamic Mechanical Analyses (DMA) showed glass transition temperature (Tg) associated to the relaxation of the cross-linked humins’ chains at 75 °C similar to the Tg of PFA. The two types of composites revealed tensile properties in the same range and both materials demonstrated very low water uptake and good dimensional stability after immersion in liquid water. Such higher hydrophobicity compared to raw jute mat is the consequence of the good interfacial interaction of both furanic matrix with the jute fibres in agreement with SEM observations. Fire performance of materials was also investigated, demonstrating that the fire hazard of composites was not increased by the presence of furanic matrix. Interestingly, humins composites were slightly better than PFA composites for both the thermal and fire-induced toxicity threats. This study demonstrated the possibility of using industrial humins instead of PFA as a thermoset-like resin for the next generation of biobased composites.

Selecting the most appropriate flow measurement techniques with related devices to characterize potentially hazardous chemicals which emit flammable or toxic gases due to their hydro-reactivity poses a difficult but required task for official classification of such materials. This paper offers a careful examination of three such potential methods that differ from each other by the flow rate measurement device which includes one manual and two automatic systems. Experiments for comparative testing and validation limits have been defined and carried out for two known hydro-reactive chemicals: aluminum chloride and sodium borohydride. The main conclusions are reported here. From the results obtained, the possible selection of the best investigated methods is suggested according to performance based criteria.

Our knowledge of fire has advanced rapidly over the last few decades to a point where we now have a good understanding of the complex interactions between combustion chemistry, fluid dynamics and heat transfer. It took many centuries before the basic principles were resolved and we should not forget the remarkable achievements of early generations of scientists in the 17th and 18th centuries. This article traces the ideas that led to the development of our understanding oxidation, combustion and fire, from the age of the alchemist to the discovery of oxygen at the end of the 18th century. Fire was first understood in terms of its chemical aspect before its thermal one, but the discovery took time, as earlier theories adopted by alchemists were only replaced at the end of the 17th century by the ‘phlogiston’ theory from Becher and Stahl. This theory has been replaced less than a century after by the actual theory of oxidation, established on the basis of a rigorous theoretical and experimental work from Lavoisier and the discovery of oxygen by Priestley. In a few years, this theory passed from being marginal and resisted strongly by partisans of phlogiston, to being the only one commonly adopted. This history is an excellent example of how science advances, with conflicting theories being tested until one gains general acceptance after careful experimental work and subjection to the peer-review process.

Since the commercialization of Lithium-Ion Battery (LIB) by Sony Inc. in 1991 until today, recurrent incidents involving LIBs have been reported worldwide. During these incidents, the most energetic catastrophic failure of a LIB system is a cascading thermal runaway event. It is characterized by a deficit of energy dissipation versus energy accumulation in the cells leading to uncontrollable overheating of the battery system [1,2]. This complex event involves multi-scale phenomena ranging from internal parallel or cascading physico-chemical to battery components reactions (electrodes, electrolytes & separator) and further to the thermal propagation of cell core & safety features. Complexity of the comprehensive understanding of the thermal runaway hazard also lies in the fact that both normal operation (through aging and relating medium/long term degradation effects) and abuse conditions can contribute to a thermal runaway event, as recently discussed by [2] or [3]. Battery safety is becoming even more critical with the emergence of highly reactive Ni-rich LIBs in the market. These batteries are commercialized to meet novel energy- or power-demanding applications and are expected to dominate the market in the coming years, likely until the occurrence of a new technological breakthrough. Therefore, these newly introduced LIBs presenting such high energy density characteristics and integrating more intrinsically reactive materials could possibly lead to more catastrophic events subsequent to the thermal runaway. Therefore, there is a clear need to better understand the underlying specific electrochemical and thermal behaviors of these technologies in both normal and abuse conditions across their lifetime. Inspired by the former collaborative IFPEN/INERIS research works on the thermal runaway of LIBs (essentially focused on LFP/Graphite and relating batteries) [2], this work aims to go deeper into the understanding & modeling of this complex phenomenon at cell scale, taking into account the influence of novel highly reactive technologies and the influence of aging with 2 target degradation mechanisms: SEI growth and Li Plating, in order to understand what the keys are towards inherently safer design and operation of highly reactive LIBs. It is a matter of establishing the link between the materials used (electrodes, electrolytes) in high energy density & intrinsically reactive LIB technologies, the degradation products during cell calendar and cycling aging (mainly analyzed through SEI evolution during cell lifetime and Li deposition during cold recharges) as well as the thermal runaway kinetics. The selected technologies studied in this research are two commercial 18650 Ni-rich LIBs, namely a Panasonic NCR GA and a LG HG2, which were based on Li(Ni0.8Co0.15Al0.05)O2 (NCA) and Li(Ni0.8Mn0.1Co0.1)O2 (NMC811), respectively, for positive electrodes, in combination with graphite-SiOx composite negative electrodes. With the goal of finding the keys factors that can improve the safety of these highly reactive LIBs during usage, the research strategy relies on the achievements of the previous projects and on the synergism offered by combined experimental and modeling studies as illustrated in Figure 1. The experimental study includes the 3 interconnected experimental processes here after specified: a complete multi-scale cell analysis in order to analyze the pristine, aged and thermally abused cells; a safety-focused aging campaign in order to artificially age battery samples, focusing on each target mechanism (SEI growth, Lithium plating) in a controlled and measurable way; accelerating rate calorimetry (ARC)thermal abuse tests in quasi-adiabatic conditions at cell level in order to qualifying the thermal runaway phenomenon as well as calibrating the thermal runaway model. The modeling study leads to the development of an extended thermal runaway model in order to predict the behaviors of different LIBs nearby and during thermal runaway under field conditions. This coupled multi-physics model will improve and extend the initial thermal runaway model built by [2] by integrating the impact of Li plating & SEI-driven cycling aging. The final result will be a multi-dimensional multiphysical model of LIB capable of accounting for the triggering of runaway under different thermal and electrical conditions and as a function of the state of aging. The predictions of the models will be validated based on other thermal abuse tests. This model will further be implemented to understand the electrical or thermal initiation of the phenomenon of thermal runaway and its propagation within a battery pack regarding its design. They will eventually be transposed into tools enabling the best design of the packs and avoidance of this undesirable phenomenon. References 1. S. Abada et al, Journal of Power Sources, 306, 178–192 (2016). 2. S. Abada et al, Journal of Power Sources, 399, 264–273 (2018). 3. F. H. Gandoman et al, Applied Energy, 251, 113343 (2019). Figure 1

International audience; The concept of circular economy is aiming at promoting innovative use of wastes, residues, or byproducts into marketable chemicals and intermediates, while enhancing process economics and environmental sustainability. Within biorefineries, the focus has now shifted toward “humins”, polymeric condensation byproducts far less investigated than lignins. Humins are produced in many biobased value chains that start from polysaccharides pretreatment, targeting access to C6 and C5 sugars and further conversion to furanics- or levulinics-based platform chemicals. They are complex and versatile substrates, and combustible because of their organic nature. A first insight on safety issues of humins is therefore proposed in this paper, considering the growing interest in humins as new biobased feedstocks for various applications. The current study provides characterization details necessary to establish safety information on a global context. This first attempt has brought in preliminary safety data mainly focusing on thermal and fire hazards of humins, to ensure safe storage, handling, transportation, and processing. The obtained results show that overall fire risk of humins so far is similar to that of the conventional cellulosic fuels such as woody materials. Further consolidation of safety information shall be done with a scenario-based risk assessment approach for conditioning safe use of humins in further innovative applications.

International audience

A comprehensive insight into the thermal hazard and combustion behaviour in fire conditions of a series of pyrrolidinium based ionic liquids (ILs) associated with a fluorine-containing anion targeted for energy storage applications is provided. The work has been carried out in collaboration with the German institute HUI. Results constitute a solid database for sustainable use of these alternative solvents to conventional organic carbonate to build up safer electrolytes for lithium and sodium batteries, integrating tradeoff between safety and functionality in terms of conductivity and viscosity of pyrrolidinium based ILs. Safety advantages are clearly rated with their bias according to changes in alkyl chain length, anion used and use or an ether function., Depuis 2010, l’Ineris consolide l’évaluation des profils de danger présenté par les liquides ioniques (LIs) [1 ; 2 ] dont l’utilisation est étudiée pour diverses applications, en particulier le stockage d’énergie [3]. Pour les batteries lithium et sodium-ion, un intérêt de plus en plus marqué pour les LIs de type pyrrolidinium [PYR1,y]+[anion fluoré] est confirmé par la littérature. Dans le cadre d’une recherche collaborative avec l’institut de recherche allemand Helmoltz-Institut Ulm (HIU), l’Ineris a mené une étude paramétrique sur une dizaine de liquides ioniques appartenant à cette sous-famille de LIs construite sur le cation pyrrolidinium. Les structures chimiques détaillées des liquides ioniques étudiés ainsi que les paramètres de l’étude sont illustrés à la Figure 1.

To characterize environmental risks linked to former uranium mines in the Limousin region of France, a study was conducted on fish health effects from uranium releases. Two private ponds were compared in this study, one with uranium contamination and one background site, upstream of the mining zone. Roach, Rutilus rutilus, were caged for 28 days in both ponds. Physico-chemical parameters of water and sediments and bioaccumulation of metals in several organs were determined. After 14 and 28 days of caging, immune, oxidative stress, biotransformation, neurotoxicity and physiological parameters were measured. Iron and aluminium were quantified in the water of both sites however, barium and manganese were only present in the water of the uranium contaminated site. Uranium was present in both sites but at very different concentrations. The sediments from the uranium contaminated site contained high levels of radioactive elements coming from the disintegration chain of uranium. Results of biological parameters indicated stimulation of immune parameters and of oxidative stress and a decrease of AChE in fish caged in the uranium contaminated pond compared to the uranium-free pond. Overall, the results determined roach health status in the context of pollution from poly-metallic mining. The data strengthen our knowledge of the environmental risk assessment associated with radioactive substances in the environment.

International audience; A detailed investigation of the combustion behavior of LiPF6 or LiFSI-based carbonate electrolytes was conducted with the objective of getting better knowledge of lithium-ion battery system fire induced thermal and chemical threats. The well-controlled experimental conditions provided by the Tewarson calorimeter have enabled the accurate evaluation of fire hazard rating parameters such as heat release rate and effective heat of combustion and the quantification of toxic effluents (HF, SO2, NOx...). Results have shown that all the electrolytes tested burn in phases depending on the flammability nature of their mixture constituents. The first stage of combustion is solely governed by the more volatile solvent (linear carbonate) and the influence of adding salt comes into effect predominantly in the second stage. It has been also shown that combustion enthalpy of electrolytes lies in the solvent mixture, irrespective of the salt added. The fire induced toxicity in well-ventilated conditions is found to be mainly dictated by the salt and its chemical structure, showing very limited concerns that emanate from the organic solvents.

The use of ionic liquids (ILs) as advanced electrolyte components in electrochemical energy-storage devices is one of the most appealing and emerging options. However, although ILs are hailed as safer and eco-friendly electrolytes, to overcome the limitations imposed by the highly volatile/combustible carbonate-based electrolytes, full-scale and precise appraisal of their overall safety levels under abuse conditions still needs to be fully addressed. With the aim of providing this level of information on the thermal and chemical stabilities, as well as actual fire hazards, herein, a detailed investigation of the short- and long-term thermal stabilities, biodegradability, and combustion behavior of various pyrrolidinium-based ILs, with different alkyl chain lengths, counteranions, and cations, as well as the effect of doping with lithium salts, is described.

La recherche permanente de nouvelles technologies de production hydrogène toujours plus efficaces d'un point de vue énergétique est en passe de conduire à l'émergence industrielle de nouveaux procédés décarbonés avec système de capture de CO2 intégré. Une technologie particulièrement prometteuse par exemple est la technologie RES (qui permet de réaliser au sein même d'un réacteur des réactions de reformage, de gaz à l'eau et de capture du CO2. Comparativement aux technologies classiques, la technologie RES n'utilise que deux réacteurs au lieu de 5 pour un système de reformage à la vapeur avec un système de capture CO2 séparé. L'intensification de la production de H2 est ici rendue possible grâce à l'utilisation de sorbants solides qui permettent non seulement de travailler à basse température mais également d'avoir un taux de production d'hydrogène supérieur à 95%mol en une seule étape contrairement aux procédés conventionnels. Afin d'accompagner le développement industriel de technologies plus efficaces et plus propres, les aspects relatifs à la sécurité doivent être traités le plus tôt possible afin de promouvoir des technologies intrinsèquement plus sûres (ISD) et durables. Dans ce contexte, l'INERIS présentera les résultats propres à l'analyse des risques liés aux technologies RES. Ces résultats seront mis en perspective par rapport aux procédés de reformage conventionnels. L'intégration de ces technologies pour la production d'électricité sera également discutée.

International audience; The risk of thermal runaway is, for Li-ion batteries, a critical issue for large-scale applications. This results in manufacturers and researchers placing great emphasis on minimizing the heat generation and thereby mitigating safety-related risks through the search for suitable materials or additives. To this end an in-depth stepwise investigation has been undertaken to provide a better understanding of the exothermic processes that take place at the negative electrode/electrolyte interface as well as an increased visibility of the role of the state-of-the-art electrode binders, additives and lithium salt by means of the classical DSC technique.A reliable experimental set up helped quantify the beneficial or harmful contribution of binder polymers to the exothermic behavior of the CMC/SBR containing graphite electrode film in contact with 1 M LiPF6 in EC:DMC:EMC (1:1:1 v/v/v) electrolyte. Further, the role of the VC, FEC and VEC electrolyte additives (2 wt.%) in reinforcing the protective SEI layer towards thermally induced electrolyte reduction is discussed in the light of infrared spectroscopy and transmission electron microscopy analyzes results.Moreover, after a preliminary corrosion study of LiPF6/LiFSI mixtures, we showed that the 0.66/0.33 molar composition can be used in commercial NMC-based LiBs with a positive effect on the thermal runaway.

To reduce health and environmental risks of chemicals and to minimize the environmental footprint of human activities, green chemistry searches for alternative, environment-friendly reaction media and at the same time strives to increase reaction rates and milder reaction conditions. A growing area of research is devoted to ionic liquids (ILs) often termed as “designer” solvents due to the extreme tunability of sought functional properties. As the aftermath of earlier misleading messages reporting ILs generically as intrinsically “safe and risk free” whatever ILs considered, their increase in potential or emerging applications in key domains (like bio-refining, energy storage, nano-material processing, pollution remediation…) dictates a more scientifically-sound approach of actual risk profiles of ILs, including both physico-chemical, health and environmental risks that might be triggered by inadequate selection of use of ionic liquids. In this context, we proposed a advanced approach serving comprehensive evaluation of environmental hazard by combined use of OECD standardized tests (Daphnia magna acute immobilization test ; algal growth inhibition test) and fish ex vivo leucocyte mortality analysis. This innovative approach integrating multicriteria assessment has been tested to on a first set of seven imidazolium-based ([BMIM][Cl], [EMIM][Cl], [EMIM][DCA], [EMIM][MeSO3], [EMIM][EtOSO3], [EMIM][BF4], [HMIM][Cl]) and four phosphonium-based ionic liquids ([P6,6,6,14][Cl], [P6,6,6,14][DCA], [P6,6,6,14][(iC8)2PO2], [Pi4,i4,i4,1][TOS]) and is expected to be further used to examine other ILs (biobased, ILs, pyrrolidinium, …) in soon future. Results of ecotoxicity tests obtained so far have revealed a clear potential to rank clearly the families of ILs according to the studied risk and even to identify influencing structural factors within a same family of ILs and compounds within the same family. Complementarity of these tests and ecotoxic properties of IL will be discussed specifically in terms of ecological footprint reduction strategies in chemical engineering processes for successful IL utilization in the future.

The development of high energy Li-ion batteries with improved durability and increased safety mostly relies on the use of newly developed electrolytes. A detailed appraisal of fire-induced thermal and chemical threats on LiPF 6 - and LiFSI-based electrolytes by means of the so-called “fire propagation apparatus” had highlighted that the salt anion was responsible for the emission of a non negligible content of irritant gas as HF (PF 6 − ) or HF and SO 2 (FSI − ). A more thorough comparative investigation of the toxicity threat in the case of larger-size 0.4 kWh Li-ion modules was thus undertaken. A modeling approach that consists in extrapolating the experimental data obtained from 1.3Ah LiFePO 4 /graphite pouch cells under fire conditions and in using the state-of-the-art fire safety international standards for the evaluation of fire toxicity was applied under two different real-scale simulating scenarios. The obtained results reveal that critical thresholds are highly dependent on the nature of the salt, LiPF 6 or LiFSI, and on the cells state of charge. Hence, this approach can help define appropriate fire safety engineering measures for a given technology (different chemistry) or application (fully charged backup batteries or batteries subjected to deep discharge).

International audience; Safety issues pertaining to Li-ion batteries justify intensive testing all along their value chain. However, progress in scientific knowledge regarding lithium based battery failure modes, as well as remarkable technologic breakthroughs in computing science, now allow for development and use of prediction tools to assist designers in developing safer batteries. Subsequently, this paper offers a review of significant modeling works performed in the area with a focus on the characterization of the thermal runaway hazard and their relating triggering events. Progress made in models aiming at integrating battery ageing effect and related physics is also discussed, as well as the strong interaction with modeling-focused use of testing, and the main achievements obtained towards marketing safer systems. Current limitations and new challenges or opportunities that are expected to shape future modeling activity are also put in perspective. According to market trends, it is anticipated that safety may still act as a restraint in the search for acceptable compromise with overall performance and cost of lithium-ion based and post lithium-ion rechargeable batteries of the future. In that context, high-throughput prediction tools capable of screening adequate new components properties allowing access to both functional and safety related aspects are highly desirable.

This paper deals with a sensitivity analysis of main parameters affecting the measurement of the gas flowrate emitted during testing substances for their potential to emit flammables gases in dangerous quantities where in contact with water, according to the UN N.5 test procedure. UN N.5 is described in the Manual of Tests and Criteria of United Nations (part of the Orange Book) (ONU Manual of Test and Criteria, 2008), serving both applications of international transport regulations as well as classifications of dangerous substances according to Globally the Harmonized System (GHS) and the derived regulation applying in the EU known as 'CLP' Regulation (Regulation (EC) No 1271/2008). The main reason that justifies the present research is that the measurement of emitted gases is highly critical in the final classification resulting from the interpretation of the test results. Moreover, that idea has been raised to adapt the UN N.5 test protocol for classifying, in the future, substances that by contact with water would emit dangerous quantities of toxic gases. Experiments have been carried out to cover the analysis of the influence of ambient temperature, overall volume of glassware, nature of aqueous media, mass sample and sample-to-liquid mass ratio, since such parameters are not fixed within any defined range in the UN N.5 test procedure. The influence of the flow rate measuring device was also considered. Results confirm that the above mentioned parameters may play a significant role to such an extent as to finally alter the final classification resulting from the testing. Guiding principles have also been derived from our measurements and observations towards an improved and more robust UN test protocol in the future.

This study focuses on the development of reliable methods for predicting heats of combustion of ionic liquids. A review of 18 existing empirical correlations giving heats of combustion developed in the early times of combustion science has been performed and re-examined in a scientifically sound manner for their ability to predict heats of combustion of ionic liquids. On the basis of a database of appropriate thermodynamic data established for 53 ionic liquids, the work showed that at least five models making use of constitutional descriptors give pretty good predictions. Moreover, a new purpose-built model for heats of combustion of ionic liquids has been developed using a multilinear regression. The model obtained from a training set of 40 molecules, meeting Organization for Economic Co-operation and Development guiding principles, revealed a good fit with literature values (R2 = 0.989). This work is considered a starting point for better consideration of the safe use of ionic liquids in the context of green chemistry and biorefining.

International audience; The use of the high energy Li-ion battery technology for emerging markets like electromobility requires precise appraisal of their safety levels in abuse conditions. Combustion tests were performed on commercial pouch cells by means of the Fire Propagation Apparatus also called Tewarson calorimeter in the EU, so far used to study flammability parameters of polymers and chemicals. Well-controlled conditions for cell combustion are created in such an apparatus with the opportunity to analyse standard decomposition/combustion gases and therefore to quantify thermal and toxic threat parameters governing the fire risk namely the rate of heat release and the effective heat of combustion as well as the toxic product releases. Using the method of O2 consumption, total combustion heats and its kinetic of production were determined as a function of the cell state of charge unveiling an explosion risk in the case of a charged cell. The resulting combustion heat is revealed to be consistent with cumulated contribution values pertaining to each organic part of the cell (polymers and electrolytes) as calculated from thermodynamic data. The first order evaluation of the dangerousness of toxic gases resulting from fire induced combustion such as HF, CO, NO, SO2 and HCl was undertaken and stressed the fact that HF is the most critical gas originating from F-containing cell components in our test conditions.

Biofuel production has been expanding for more than five years, leading to an increasing number of production sites worldwide and also to a tremendous diversification of processes and approaches to producing biofuel. Such a fast move in industry has sometimes proven in the past to potentially lead to underestimating safety management needs. The significant number of existing facilities producing so called first generation biofuel allows for a reasonable survey of safety issues from incidents. In 2006, INERIS initiated research work devoted to the analysis of safety-related issues including the implementation of an incidents database. Its purpose is to collect known and reasonably well documented incidents (explosions, fires, spills, derailments, and road accidents) that relate to the life cycle of biofuel supply chains. This paper focuses on the analysis of this database, which contains 100 incidents that occurred from January 2000 to early 2009. From the database, an attempt has been made to identify the root factors of incidents potentially impacting biofuel supply chains, using statistical methods like multiple correspondence analysis and ascendant hierarchical clustering. This multivariate analysis exercise has led us to identify five main incident typologies, which in turn allows us to draw appropriate information on safety issues pertaining to first-generation biofuel supply chains. Each typology is illustrated by actual cases of accidents. Copyright © 2009 Society of Chemical Industry and John Wiley & Sons, Ltd

Three decades after the pioneering development of sugarcane ethanol in Brazil, the arrival of the new century has seen a worldwide boom in the automotive biofuel industry. Although fire safety of biofuels has not been perceived so far as a potential barrier to sustainability of their development, very limited scientific work can be found on the matter. This paper is a first contribution to the discussion of these issues within the fire safety community. It aims at identifying research needs from an initial overview based on existing safety data pertaining to currently available biofuels for transport. The paper comprises a first analysis of fire risk typology presented by such biofuel technologies, including first lessons from recent accidents. At first sight, when considering aspects of fire safety from a technical point of view, it seems a simple problem, but analysis shows that from the point of view of safety of biofuels, it is not correct to summarize the regulatory position by simply saying that fuel ethanol is a flammable product, whereas biodiesel is not. Clearly, a more in-depth analysis of fire safety issues is needed that will also have to consider significant changes in biofuel technologies in the future. Copyright © 2008 John Wiley & Sons, Ltd.

International audience; The Heat Release Rate (HRR) is a critical parameter to characterise a fire. Different methods have been developed to estimate it. The most widespread techniques are based on mass balance. If the heat of combustion of the fuel is known, the measure of the mass loss allows its evaluation. If the burning material can not be identified, calorimetric principles can be used. They rely on oxygen consumption (OC) or carbon dioxide and carbon monoxide generation (CDG) measurements. Their asset comes from the observation that the amount of energy release per unit mass of O2 consumed or per unit mass of CO2 produced is relatively constant for a large number of materials. Thus, an accurate HRR can be obtained without knowing the composition of the burning fuel. The aim of this work is to assess this last statement and define how essential the knowledge of the chemistry to calculate HRR for complex materials such as polymers including fire retardants and/or nanocomposites, energetic materials or pine needles is. This assessment ends in an OC and CDG calorimetry comparison of several materials in order to investigate the propensity to determine whether converging or diverging HRR results when average energy constants are used

Ionic liquids (ILs), often termed as "designer" solvents due to the extreme tunability of sought functional properties, are promoted by many stakeholders as green alternatives to the conventional volatile organic solvents. Nevertheless, this qualification was stated without sufficient caution versus versatility of ILs chemical structures which could induce significant variations in hazardous properties. Moreover, this class of compounds which contained organic cations and most inorganic anions may often present a high water solubility and poor biodegradability. These specific properties could influence the environmental behavior of these ILs and implied IL potential environmental and health effects. With regards to the exponential increase of applications, publications and patent for ten years, concerning ILs without halogen atoms, we may anticipate that some ILs could attain multi ton industrial production in the near future. In this context, according to the EC regulation 1907/2006 regarding REACH, each manufacturer or importer of a substance in quantity of minimum one ton by year should submit a registration application to the European Chemicals Agency (ECHA). In this context, a global view of some physico-chemical, toxicological and ecotoxicological data available in the literature, in accordance with the information requested by REACH regulation, is proposed here. In fact, it seems to be important to identify the relationship between LI structures and their (eco-)toxicological properties to help manufacturer for design of the more safe IL structures.