Poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) lithium-ion battery separator membranes prepared by phase inversion

Separator membranes based on poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) were prepared by solvent casting technique based on its phase diagram in N,Ndimethylformamide (DMF) solvent. The microstructure of the PVDF-CTFE separator membranes depends on the initial position (temperature and concentration) of the solution in the phase diagram of the PVDF-CTFE/DMF system. A porous microstructure is achieved for PVDF-CTFE membranes with solvent evaporation temperature up to 50 ºC for a polymer/solvent relative concentration of 20 wt%. The ionic conductivity of the separator depends on the degree of porosity and electrolyte uptake, the highest room temperature value being 1.5 mS.cm-1 for the sample with 20 wt% of polymer concentration and solvent evaporation temperature at 25 ºC saturated with 1 mol L-1 lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) in propylene carbonate (PC). This PVDF-CTFE separator membrane in Li/C-LiFePO4 half-cell shows good cyclability and rate capability, showing a discharge value after 50 cycles of 92 mAh.g-1 at 2 C, which is still 55% of the theoretical value. PVDF-CTFE separators are thus excellent candidates for high-power and safety lithium-ion batteries applications.

Effect of the degree of porosity on the performance of poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) blend membranes for lithium-ion battery separators

Porous polymer membranes based on poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) copolymers, P(VDF-TrFE)/PEO, are prepared through the, from partial to total, elimination of PEO, leading to interconnected micropores in the polymer blends. Electrolyte uptake, thermal and mechanical properties depend on the amount of PEO present in the polymer blend. Further, the degree of crystallinity of PEO and the elastic modulus (E´) of the polymer blend decrease with increasing PEO removal. Electrical properties of the polymer blend membranes are influenced by the porosity and are dominated by diffusion. The temperature dependence of ionic conductivity follows the Arrhenius behavior. It is the highest for the membranes with a volume fraction of pores of 44% (i.e, 90% PEO removal), reaching a value of 0.54 mS.cm-1 at room temperature. Battery performance was determined by assembling Li/C-LiFePO4 swagelok cells. The polymer blends with 90% PEO removal exhibit rate (124 mAhg-1 at C/5 and 47 mAhg-1 at 2C) and cycling capabilities suitable for lithium ion battery applications.

Modeling separator membranes physical characteristics for optimized lithium ion battery performance

The effect of varying separator membrane physical parameters such as degree of porosity, tortuosity and thickness, on battery delivered capacity was studied in order to optimize performance of lithium-ion batteries. This was achieved by a theoretical mathematical model relating the Bruggeman coefficient with the degree of porosity and tortuosity. The inclusion of the separator membrane in the simulation model of the battery system does not affect the delivered capacity of the battery. The ionic conductivity of the separator and consequently the delivered capacity values obtained at different discharge rates depends on the value of the Bruggeman coefficient, which is related with the degree of porosity and tortuosity of the membrane. Independently of scan rate, the optimal value of the degree of porosity is above 50% and the separator thickness should range between 1 μm at 32 μm for improved battery performance.

Lithium ion rechargeable batteries: State of the art and future needs of microscopic theoretical models and simulations

This review deals with the recent developments and present status of the theoretical models for the simulation of the performance of lithium ion batteries. Preceded by a description of the main materials used for each of the components of a battery -anode, cathode and separator- and how material characteristics affect battery performance, a description of the main theoretical models describing the operation and performance of a battery are presented. The influence of the most relevant parameters of the models, such as boundary conditions, geometry and material characteristics are discussed. Finally, suggestions for future work are proposed.

Ion exchange dependent electroactive phase content and electrical properties of poly(vinylidene fluoride)/Na(M)Y composites

Different metal-ion exchanged NaY zeolite, Na(M)Y, were used to prepare poly(vinylidene fluoride) based composites by solvent casting and melting crystallization. The effect of different metal ion-exchanged zeolites on polymer crystallization and electrical properties was reported. Cation-framework interactions and hydration energy of the cations determined that K+ is the most efficient exchanged ion in NaY zeolite, followed by Cs+ and Li+. The electroactive phase crystallization strongly depends on the ions present in the zeolite, leading to variations of the surface energy characteristics of the Na(M)Y zeolites and the polymer chain ability of penetration in the zeolite. Thus, Na(Li)Y and NaY induces the complete electroactive -phase crystallization of the crystalline phase of PVDF, while Na(K)Y only induces it partly and Na(Cs)Y is not able to promote the crystallization of the electroactive phase. Furthermore, different ion size/weigh and different interaction with the zeolite framework results in significant variations in the electrical response of the composite. In this way, iinterfacial polarization effects in the zeolite cavities and zeolite-polymer interface, leads to strong increases of the dielectric constant on the composites with lightest ions weakly bound to the zeolite framework. Polymer composite with Na(Li)Y show the highest dielectric response, followed by NaY and Na(K)Y. Zeolite Na(Cs)Y contribute to a decrease of the dielectric constant of the composite. The results show the relevance of the materials for sensor development.

Search for heavy lepton resonances decaying to a Z boson and a lepton in pp collisions at s√=8 TeV with the ATLAS detector

A search for heavy leptons decaying to a Z boson and an electron or a muon is presented. The search is based on pp collision data taken at s√=8 TeV by the ATLAS experiment at the CERN Large Hadron Collider, corresponding to an integrated luminosity of 20.3 fb−1. Three high-transverse-momentum electrons or muons are selected, with two of them required to be consistent with originating from a Z boson decay. No significant excess above Standard Model background predictions is observed, and 95% confidence level limits on the production cross section of high-mass trilepton resonances are derived. The results are interpreted in the context of vector-like lepton and type-III seesaw models. For the vector-like lepton model, most heavy lepton mass values in the range 114-176 GeV are excluded. For the type-III seesaw model, most mass values in the range 100-468 GeV are excluded.

Search for a Heavy Neutral Particle Decaying to eμ, eτ, or μτ in pp Collisions at s√=8 TeV with the ATLAS Detector

This Letter presents a search for a heavy neutral particle decaying into an opposite-sign different-flavor dilepton pair, e±μ∓, e±τ∓, or μ±τ∓ using 20.3 fb−1 of pp collision data at s√=8 TeV collected by the ATLAS detector at the LHC. The numbers of observed candidate events are compatible with the Standard Model expectations. Limits are set on the cross section of new phenomena in two scenarios: the production of ν~τ in R-parity-violating supersymmetric models and the production of a lepton-flavor-violating Z′ vector boson.

Search for heavy long-lived multi-charged particles in pp collisions at √s = 8 TeV using the ATLAS detector

A search for heavy long-lived multi-charged particles is performed using the ATLAS detector at the LHC. Data collected in 2012 at s√=8 TeV from pp collisions corresponding to an integrated luminosity of 20.3 fb−1 are examined. Particles producing anomalously high ionisation, consistent with long-lived massive particles with electric charges from |q|=2e to |q|=6e are searched for. No signal candidate events are observed, and 95% confidence level cross-section upper limits are interpreted as lower mass limits for a Drell--Yan production model. The mass limits range between 660 and 785 GeV.

Search for type-III Seesaw heavy leptons in pp collisions at s√=8 TeV with the ATLAS Detector

A search for the pair-production of heavy leptons (N0,L±) predicted by the type-III seesaw theory formulated to explain the origin of small neutrino masses is presented. The decay channels N0→W±l∓ (ℓ=e,μ,τ) and L±→W±ν (ν=νe,νμ,ντ) are considered. The analysis is performed using the final state that contains two leptons (electrons or muons), two jets from a hadronically decaying W boson, and large missing transverse momentum. The data used in the measurement correspond to an integrated luminosity of 20.3fb−1 of pp collisions at s√=8 TeV collected by the ATLAS detector at the LHC. No evidence of heavy lepton pair-production is observed. Heavy leptons with masses below 325--540 GeV are excluded at the 95% confidence level, depending on the theoretical scenario considered.

On line pre-concentration for simultaneous determination of low molecular weight organic acids and inorganic anions in Amazonian river water samples employing ion chromatography with conductivity detection

An ion chromatography procedure, employing an IonPac AC15 concentrator column was used to investigate on line preconcentration for the simultaneous determination of inorganic anions and organic acids in river water. Twelve organic acids and nine inorganic anions were separated without any interference from other compounds and carry-over problems between samples. The injection loop was replaced by a Dionex AC15 concentrator column. The proposed procedure employed an auto-sampler that injected 1.5 ml of sample into a KOH mobile phase, generated by an Eluent Generator, at 1.5 mL min-1, which carried the sample to the chromatographic columns (one guard column, model AG-15, and one analytical column, model AS15, with 250 x 4mm i.d.). The gradient elution concentrations consisted of a 10.0 mmol l-1 KOH solution from 0 to 6.5 min, gradually increased to 45.0 mmol l-1 KOH at 21 min., and immediatelly returned and maintained at the initial concentrations until 24 min. of total run. The compounds were eluted and transported to an electro-conductivity detection cell that was attached to an electrochemical detector. The advantage of using concentrator column was the capability of performing routine simultaneous determinations for ions from 0.01 to 1.0 mg l-1 organic acids (acetate, propionic acid, formic acid, butyric acid, glycolic acid, pyruvate, tartaric acid, phthalic acid, methanesulfonic acid, valeric acid, maleic acid, oxalic acid, chlorate and citric acid) and 0.01 to 5.0 mg l-1 inorganic anions (fluoride, chloride, nitrite, nitrate, bromide, sulfate and phosphate), without extensive sample pretreatment and with an analysis time of only 24 minutes.

Search for dark matter in events with heavy quarks and missing transverse momentum in pp collisions with the ATLAS detector

This article reports on a search for dark matter pair production in association with bottom or top quarks in 20.3fb−1 of pp collisions collected at s√=8 TeV by the ATLAS detector at the LHC. Events with large missing transverse momentum are selected when produced in association with high-momentum jets of which one or more are identified as jets containing b-quarks. Final states with top quarks are selected by requiring a high jet multiplicity and in some cases a single lepton. The data are found to be consistent with the Standard Model expectations and limits are set on the mass scale of effective field theories that describe scalar and tensor interactions between dark matter and Standard Model particles. Limits on the dark-matter--nucleon cross-section for spin-independent and spin-dependent interactions are also provided. These limits are particularly strong for low-mass dark matter. Using a simplified model, constraints are set on the mass of dark matter and of a coloured mediator suitable to explain a possible signal of annihilating dark matter.

Search for heavy Majorana neutrinos with the ATLAS detector in pp collisions at s√=8 TeV

A search for heavy Majorana neutrinos in events containing a pair of high-pT leptons of the same charge and high-pT jets is presented. The search uses 20.3fb−1 of pp collision data collected with the ATLAS detector at the CERN Large Hadron Collider with a centre-of-mass energy of s√=8 TeV. The data are found to be consistent with the background-only hypothesis based on the Standard Model expectation. In the context of a Type-I seesaw mechanism, limits are set on the production cross-section times branching ratio for production of heavy Majorana neutrinos in the mass range between 100 and 500 GeV. The limits are subsequently interpreted as limits on the mixing between the heavy Majorana neutrinos and the Standard Model neutrinos. In the context of a left-right symmetric model, limits on the production cross-section times branching ratio are set with respect to the masses of heavy Majorana neutrinos and heavy gauge bosons WR and Z′.

Searches for heavy long-lived charged particles with the ATLAS detector in proton--proton collisions at s√ = 8 TeV

Searches for heavy long-lived charged particles are performed using a data sample of 19.8 fb−1 from proton--proton collisions at a centre-of-mass energy of s√ = 8 TeV collected by the ATLAS detector at the Large Hadron Collider. No excess is observed above the estimated background and limits are placed on the mass of long-lived particles in various supersymmetric models. Long-lived tau sleptons in models with gauge-mediated symmetry breaking are excluded up to masses between 440 and 385 GeV for tan(beta) between 10 and 50, with a 290 GeV limit in the case where only direct tau slepton production is considered. In the context of simplified LeptoSUSY models, where sleptons are stable and have a mass of 300 GeV, squark and gluino masses are excluded up to a mass of 1500 and 1360 GeV, respectively. Directly produced charginos, in simplified models where they are nearly degenerate to the lightest neutralino, are excluded up to a mass of 620 GeV. R-hadrons, composites containing a gluino, bottom squark or top squark, are excluded up to a mass of 1270, 845 and 900 GeV, respectively, using the full detector; and up to a mass of 1260, 835 and 870 GeV using an approach disregarding information from the muon spectrometer.

Titanium oxide adhesion layer for high temperature annealed Si/Si3N4/TiOx/Pt/LiCoO2 battery structures

This work describes the influence of a high annealing temperature of about 700C on the Si(substrate)/Si3N4/TiOx/Pt/LiCoO2 multilayer system for the fabrication of all-solid-state lithium ion thin film microbatteries. Such microbatteries typically utilize lithium cobalt oxide (LiCoO2) as cathode material with a platinum (Pt) current collector. Silicon nitride (Si3N4) is used to act as a barrier against Li diffusion into the substrate. For a good adherence between Si3N4 and Pt, commonly titanium (Ti) is used as intermediate layer. However, to achieve crystalline LiCoO2 the multilayer system has to be annealed at high temperature. This post-treatment initiates Ti diffusion into the Pt-collector and an oxidation to TiOx, leading to volume expansion and adhesion failures. To solve this adhesion problem, we introduce titanium oxide (TiOx) as an adhesion layer, avoiding the diffusion during the annealing process. LiCoO2, Pt and Si3N4 layers were deposited by magnetron sputtering and the TiOx layer by thermal oxidation of Ti layers deposited by e-beam technique. Asdeposited and annealed multilayer systems using various TiOx layer thicknesses were studied by scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) and x-ray photoelectron spectroscopy (XPS). The results revealed that an annealing process at temperature of 700C leads to different interactions of Ti atoms between the layers, for various TiOx layer thicknesses (25–45 nm).

Effect of argon ion energy on the performance of silicon nitridemultilayer permeation barriers grown by hot-wire CVD on polymers

One of the authors (S.M.) acknowledges Direction des Relations Extérieures of Ecole Polytechnique for financial support.