| 1. |
- Forestier, C., et al.
(author)
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Comparative investigation of solid electrolyte interphases created by the electrolyte additives vinyl ethylene carbonate and dicyano ketene vinyl ethylene acetal
- 2017
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In: Journal of Power Sources. - : Elsevier BV. - 0378-7753. ; 345, s. 212-220
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Journal article (peer-reviewed)abstract
- The effect of the replacement of the carbonyl oxygen in VEC additive by =C(CN)(2) in the analogous dicyano ketene vinyl ethylene acetal (DCKVEA) on the electrochemical reduction profile is significant. Yet, the additives were proven, through IR spectroscopy supported by DFT computations, by applying EELS techniques and performing synthesis of a reduction product, to reduce in a similar way. Interestingly, the reduction-induced capacities were found to be quite different and can be explained either by the different properties of the SEI, from lithium carbonate and its malononitrile homologue, or by the different abilities of the two additives to solvate Li+.
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| 2. |
- Forestier, C., et al.
(author)
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Facile reduction of pseudo-carbonates: Promoting solid electrolyte interphases with dicyanoketene alkylene acetals in lithium-ion batteries
- 2016
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In: Journal of Power Sources. - : Elsevier BV. - 0378-7753. ; 303, s. 1-9
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Journal article (peer-reviewed)abstract
- Dicyanoketene ethylene and propylene acetals, DCKEA and DCKPA respectively, have been investigated as electrolyte additives for Li-ion batteries. The purpose was to assess the changes in reduction behaviour and solid electrolyte interphase (SEI) passivation properties upon replacing the carbonyl group of ethylene carbonate (EC) and propylene carbonate (PC) solvents, respectively, by the slightly more electronegative and highly conjugated =C(CN)(2) group. The experimental reduction potentials and the IR spectroscopy characterisation efforts were further supported by density functional theory (DFT) computations. The two additives were found to, in relatively small amount (0.5 wt%), provide beneficial effects on the capacity retention of 8 mAh cells cycled at 20 and 45 degrees C. Moreover, the additives proved to enhance the thermal stability of the lithiated graphite/electrolyte interface, as deduced from DSC measurements.
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| 3. |
- Grugeon, S., et al.
(author)
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Towards a better understanding of vinylene carbonate derived SEI-layers by synthesis of reduction compounds
- 2019
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In: Journal of Power Sources. - : Elsevier BV. - 0378-7753. ; 427, s. 77-84
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Journal article (peer-reviewed)abstract
- Here two chemical reduction pathways to synthesize the vinylene carbonate (VC)and poly(VC)reduction products are investigated, with the precise aim of further deciphering the lithium-ion battery solid electrolyte interphase (SEI)layer composition and the associated reduction mechanisms. The liquid synthesis pathway offers the opportunity of varying the concentration of Li-4,4′-Di-tert-butylbiphenyl reducing agent, whereas the dry synthesis pathway by ball milling allows to solve issues related to solvent-induced side reactions and washing procedure. As a result, the two syntheses do not unveil the same reduction mechanisms, favouring either carboxylate or carbonate salts as the major end product. The latter pathway is very efficient in terms of providing SEI-layers products resulting in well-defined IR spectra and comparisons with simulated spectra enable us to obtain IR fingerprints of the Li di-vinylene di-carbonate (LDVD)compound. Taken together the synthesis procedures provide information on conditions favouring radical polymerization and further poly(VC)reduction into Li 2 CO 3 and polyacetylene. Overall, this chemical simulation of SEI-layers formation assists in a proper characterization of the SEI-layers created on graphite surfaces by their IR spectra showing that Li 2 CO 3 , LDVD and poly(VC)are all present in different proportions dependent on the VC content in the electrolyte.
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| 4. |
- Laruelle, G. G., et al.
(author)
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Anthropogenic perturbations of the silicon cycle at the global scale: Key role of the land-ocean transition
- 2009
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In: Global Biogeochemical Cycles. - 0886-6236 .- 1944-9224. ; 23
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Research review (peer-reviewed)abstract
- Silicon (Si), in the form of dissolved silicate (DSi), is a key nutrient in marine and continental ecosystems. DSi is taken up by organisms to produce structural elements (e.g., shells and phytoliths) composed of amorphous biogenic silica (bSiO(2)). A global mass balance model of the biologically active part of the modern Si cycle is derived on the basis of a systematic review of existing data regarding terrestrial and oceanic production fluxes, reservoir sizes, and residence times for DSi and bSiO(2). The model demonstrates the high sensitivity of biogeochemical Si cycling in the coastal zone to anthropogenic pressures, such as river damming and global temperature rise. As a result, further significant changes in the production and recycling of bSiO(2) in the coastal zone are to be expected over the course of this century.
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| 5. |
- Abi-Dargham, A, et al.
(author)
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Measurement of striatal and extrastriatal dopamine D1 receptor binding potential with [11C]NNC 112 in humans: validation and reproducibility
- 2000
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In: Journal of cerebral blood flow and metabolism : official journal of the International Society of Cerebral Blood Flow and Metabolism. - : SAGE Publications. - 0271-678X. ; 20:2, s. 225-243
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Journal article (peer-reviewed)abstract
- To evaluate the postulated role of extrastriatal D1 receptors in human cognition and psychopathology requires an accurate and reliable method for quantification of these receptors in the living human brain. [11C]NNC 112 is a promising novel radiotracer for positron emission tomography imaging of the D1 receptor. The goal of this study was to develop and evaluate methods to derive D1 receptor parameters in striatal and extrastriatal regions of the human brain with [11C]NNC 112. Six healthy volunteers were studied twice. Two methods of analysis (kinetic and graphical) were applied to 12 regions (neocortical, limbic, and subcortical regions) to derive four outcome measures: total distribution volume, distribution volume ratio, binding potential (BP), and specific-to-nonspecific equilibrium partition coefficient ( k3/ k4). Both kinetic and graphic analyses provided BP and k3/ k4 values in good agreement with the known distribution of D1 receptors (striatum > limbic regions = neocortical regions > thalamus). The identifiability of outcome measures derived by kinetic analysis was excellent. Time-stability analysis indicated that 90 minutes of data collection generated stable outcome measures. Derivation of BP and k3/ k4 by kinetic analysis was highly reliable, with intraclass correlation coefficients (ICCs) of 0.90 ± 0.06 (mean ± SD of 12 regions) and 0.84 ± 0.11, respectively. The reliability of these parameters derived by graphical analysis was lower, with ICCs of 0.72 ± 0.17 and 0.58 ± 0.21, respectively. Noise analysis revealed a noise-dependent bias in the graphical but not the kinetic analysis. In conclusion, kinetic analysis of [11C]NNC 112 uptake provides an appropriate method with which to derive D1 receptor parameters in regions with both high (striatal) and low (extrastriatal) D1 receptor density.
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| 9. |
- Saunois, Marielle, et al.
(author)
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The Global Methane Budget 2000–2017
- 2020
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In: Earth System Science Data. - : Copernicus GmbH. - 1866-3516 .- 1866-3508. ; 12:3, s. 1561-1623
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Journal article (peer-reviewed)abstract
- Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. Atmospheric emissions and concentrations of CH4 continue to increase, making CH4 the second most important human-influenced greenhouse gas in terms of climate forcing, after carbon dioxide (CO2). The relative importance of CH4 compared to CO2 depends on its shorter atmospheric lifetime, stronger warming potential, and variations in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in reducing uncertainties in the atmospheric growth rate arise from the variety of geographically overlapping CH4 sources and from the destruction of CH4 by short-lived hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate new research aimed at improving and regularly updating the global methane budget. Following Saunois et al. (2016), we present here the second version of the living review paper dedicated to the decadal methane budget, integrating results of top-down studies (atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up estimates (including process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations).For the 2008–2017 decade, global methane emissions are estimated by atmospheric inversions (a top-down approach) to be 576 Tg CH4 yr−1 (range 550–594, corresponding to the minimum and maximum estimates of the model ensemble). Of this total, 359 Tg CH4 yr−1 or ∼ 60 % is attributed to anthropogenic sources, that is emissions caused by direct human activity (i.e. anthropogenic emissions; range 336–376 Tg CH4 yr−1 or 50 %–65 %). The mean annual total emission for the new decade (2008–2017) is 29 Tg CH4 yr−1 larger than our estimate for the previous decade (2000–2009), and 24 Tg CH4 yr−1 larger than the one reported in the previous budget for 2003–2012 (Saunois et al., 2016). Since 2012, global CH4 emissions have been tracking the warmest scenarios assessed by the Intergovernmental Panel on Climate Change. Bottom-up methods suggest almost 30 % larger global emissions (737 Tg CH4 yr−1, range 594–881) than top-down inversion methods. Indeed, bottom-up estimates for natural sources such as natural wetlands, other inland water systems, and geological sources are higher than top-down estimates. The atmospheric constraints on the top-down budget suggest that at least some of these bottom-up emissions are overestimated. The latitudinal distribution of atmospheric observation-based emissions indicates a predominance of tropical emissions (∼ 65 % of the global budget, < 30∘ N) compared to mid-latitudes (∼ 30 %, 30–60∘ N) and high northern latitudes (∼ 4 %, 60–90∘ N). The most important source of uncertainty in the methane budget is attributable to natural emissions, especially those from wetlands and other inland waters.Some of our global source estimates are smaller than those in previously published budgets (Saunois et al., 2016; Kirschke et al., 2013). In particular wetland emissions are about 35 Tg CH4 yr−1 lower due to improved partition wetlands and other inland waters. Emissions from geological sources and wild animals are also found to be smaller by 7 Tg CH4 yr−1 by 8 Tg CH4 yr−1, respectively. However, the overall discrepancy between bottom-up and top-down estimates has been reduced by only 5 % compared to Saunois et al. (2016), due to a higher estimate of emissions from inland waters, highlighting the need for more detailed research on emissions factors. Priorities for improving the methane budget include (i) a global, high-resolution map of water-saturated soils and inundated areas emitting methane based on a robust classification of different types of emitting habitats; (ii) further development of process-based models for inland-water emissions; (iii) intensification of methane observations at local scales (e.g., FLUXNET-CH4 measurements) and urban-scale monitoring to constrain bottom-up land surface models, and at regional scales (surface networks and satellites) to constrain atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) development of a 3D variational inversion system using isotopic and/or co-emitted species such as ethane to improve source partitioning.The data presented here can be downloaded from https://doi.org/10.18160/GCP-CH4-2019 (Saunois et al., 2020) and from the Global Carbon Project.
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