Redox shuttles for safer lithium-ion batteries

Overcharge protection is not only critical for preventing the thermal runaway of lithium-ion batteries during operation, but also important for automatic capacity balancing during battery manufacturing and repair. A redox shuttle is an electrolyte additive that can be used as intrinsic overcharge protection mechanism to enhance the safety characteristics of lithium-ion batteries. The advances on stable redox shuttles are briefly reviewed. Fundamental studies for designing stable redox shuttles are also discussed.     

Polymerization kinetics of indene, methyl methacrylate and acrylonitrile and characterization of their terpolymer

The free radical terpolymerization of indene (In), methyl methacrylate (MMA) and acrylonitrile (AN) has been investigated. The rate of polymerization of all the binary systems involved has been measured dilatometrically for the homogeneous polymerization. The reactivity ratios of the three binary systems were calculated and were found to be equal to 0.031 and 0.397 for In/AN copolymers and 0.02 and 3.82 for In/MMA copolymers and finally 0.152 and 1.20 for AN/MMA copolymers. The rate of terpolymerization in bulk has been measured as well as the relationship between the monomer mixture composition and the obtained terpolymer in order to construct the compositional triangle. Also the effect of initiator concentration on the rate of terpolymerization was investigated. The activation energy of terpolymerization was determined. The terpolymers were characterized by spectral and thermo-gravimetric analyses. The data indicates that polyindene improves the thermal stability of the prepared terpolymers.     

New optically active poly(amide-imide)s based on N,N′-(pyromellitoyl)-bis-L-amino acid and 1,3-bis(4-aminophenoxy) propane: Synthesis and characterization

Five new poly(amide-imide)s 8a–e were synthesized through the direct polycondensation reaction of five chiral N,N′-(pyromellitoyl)-bis-L -amino acids 3a–e with 1,3-bis(4-aminophenoxy) propane 7 in a medium consisting of N-methyl-2-pyrrolidone, triphenyl phosfite, calcium chloride, and pyridine. The polycondensation reaction produced a series of novel poly(amide-imide)s containing trimethylene moiety in the main chain in high yield with inherent viscosities between 0.34 and 0.65 dL/g. The resulted polymers were fully characterized by means of FTIR spectroscopy, elemental analyses, inherent viscosity, and solubility tests. Thermal properties of these polymers were investigated by using thermal gravimetric analysis (TGA) and differential thermal gravimetric (DTG). All of the polymers were soluble at room temperature in polar solvents such as N,N-dimethyl acetamide, N,N-dimethyl formamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. N,N′-(pyromellitoyl)-bis-L -amino acids 3a–e were prepared in quantitative yields by the condensation reaction of pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic acid 1,2,4,5-dianhydide) 1 with L -alanine 2a , L -valine 2b , L -leucine 2c , L -isoleucine 2d , and L -phenyl alanine 2e in acetic acid. Also 1,3-bis(4-aminophenoxy) propane 7 was synthesized by using a two-step reaction. At first 1,3-bis(4-nitrophenoxy) propane 6 was prepared from the reaction of 4-nitrophenol 4 with 1,3-dibromoprapane 5 in NaOH solution. Then, dinitro compound 6 was reduced by using Na₂S. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface Modification of Ready-to-Use Hollow Fiber Ultrafiltration Modules for Oil/Water Separation

Reusing wastewater from oil-related industries is becoming increasingly important, especially in water-stressed oil-producing countries. Before oily wastewater can be discharged or reused, it must be properly treated, e.g., by membrane-based processes like ultrafiltration. A major issue of the applied membranes is their high fouling propensity. This paper reports on mitigating fouling inside ready-to-use ultrafiltration hollow-fiber modules used in a polishing step in oil/water separation. For this purpose, in-situ polyzwitterionic hydrogel coating was applied. The membrane performance was tested with oil nano-emulsions using a mini-plant system. The main factors influencing fouling were systematically investigated using statistical design of experiments.     

Photo- and bio-degradation of poly(ester-urethane)s films based on poly[(R)-3-Hydroxybutyrate] and poly(ε-Caprolactone) blocks

Biodegradable segmented poly(ester-urethane)s derived from telechelic dihydroxy-poly[(R)-3-hydroxybutyrate], acting as hard segments, and poly(ε-caprolactone)-diols, acting as soft segments, using 1,6-hexamethylene diisocyanate, as non toxic connecting agent, were synthesized. The copolymers were characterized with regard to their molecular weight by GPC and their main thermal transitions by DSC. These copolymers as well as PHB were exposed to UV-irradiation for different time intervals and the changes in the chemical structure were analyzed by FTIR spectroscopy. Under our experimental conditions, it was found that the increase of irradiation time was accompanied by increase of the proportion of the gel fraction and the decrease of the intrinsic viscosity of the soluble fraction of the investigated copolymers. The biodegradability of PHB and poly(ester-urethane) sample containing ~40 wt% PHB before and after UV-irradiation was investigated under soil burial. The results showed that the photolysis in air prior to biodegradation increased the rate of degradation.     

Fused ring and linking groups effect on overcharge protection for lithium-ion batteries

The derivatives of 1,3-benzodioxan (DBBD1) and 1,4-benzodioxan (DBBD2) bearing two tert-butyl groups have been synthesized as new redox shuttle additives for overcharge protection of lithium-ion batteries. Both compounds exhibit a reversible redox wave over 4 V vs Li/Li⁺ with better solubility in a commercial electrolyte (1.2 M LiPF₆ dissolved in ethylene carbonate/ethyl methyl carbonate (EC/EMC 3/7) than the di-tert-butyl-substituted 1,4-dimethoxybenzene (DDB). The electrochemical stability of DBBD1 and DBBD2 was tested under charge/discharge cycles with 100% overcharge at each cycle in MCMB/LiFePO₄ and Li₄Ti₅O₁₂/LiFePO₄ cells. DBBD2 shows significantly better performance than DBBD1 for both cell chemistries. The structural difference and reaction energies for decomposition have been studied by density functional calculations.     

Numerical analysis of natural convection heat transfer in a horizontal annulus partially filled with a fluid-saturated porous substrate

The current study centers around a numerical investigation of natural convection heat transfer within a two-dimensional, horizontal annulus that is partially filled with a fluid-saturated porous medium. In addition, the porous sleeve is considered to be press fitted to the inner surface of the outer cylinder. Both cylinders are maintained at constant and uniform temperatures with the inner cylinder being subjected to a relatively higher temperature than the outer one. Moreover, the Forchheimer and Brinkman effects are taken into consideration when simulating the fluid motion inside the porous sleeve. Furthermore, the local thermal equilibrium condition is assumed to be applicable for the current investigation. The working fluid is air while copper is used to represent the solid phase. The porosity is considered to be uniform and constant with ε = 0.9. The main objective of this study is to examine the effect of the porous sleeve on the buoyancy induced flow motion under steady-state condition. Such an effect is studied using the following dimensionless parameters: Pr = 0.05–50, Ra = 10²–10⁶ and Da = 10^?4–10^?6. Also, the study highlights the effect of the dimensionless porous sleeve thickness (b) and thermal conductivity ratio (k_s/k_f) in the range between 1.1–1.9 and 1–150, respectively.     

Management of quality of service enabled VPNs

New emerging IP services based on differentiated services and the IP security architecture offer the level of communication support that corporate Internet applications need nowadays. However, these services add an additional degree of complexity to IP networks which will require sophisticated management support. The management of enhanced IP services for their customers is thus an emerging important task for Internet service providers. This article describes a potential management architecture service providers will need for that task, considering problems such as multiprovider services and service automation. We focus on a quality-enhanced virtual private network service which is particularly useful for corporate internetworking     

SRAM dynamic stability estimation using MPFP and its applications

In this paper, an accurate approach for estimating the dynamic stability of static random access memory (SRAM) is proposed. The conventional methods of SRAM stability estimation suffer from two major drawbacks: (1) using static failure criteria, such as SNM, which does not capture the transient and dynamic behavior of SRAM operation, and (2) using quasi-Monte-Carlo simulation, which approximates the failure distribution, resulting in large errors at the tails where the desired failure probabilities exist. These drawbacks are eliminated by employing accurate simulation-based dynamic failure criteria along with a new distribution-independent, Most-probable-failure-point search technique for accurate probability calculation. Compared to previously published techniques, the proposed dynamic stability technique offers orders of magnitude improvement in accuracy. Furthermore, the proposed dynamic stability technique enables the correct evaluation of stability in real operation conditions and for different dynamic circuit techniques, such as dynamic write back, where the conventional methods are not applicable.     

Electrochemical study on the effect of Schiff base and its cobalt complex on the acid corrosion of steel

The effect of the Schiff base N,N′-bis (salicylaldehyde)-1,3-diaminopropane (Salpr) and its corresponding cobalt complex on the corrosion behaviour of steel in 1 M sulphuric acid solution were studied by electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization techniques. Spectrophotometry measurements were employed to investigate the stability of the complex in acid media. The inhibitive effect of Salpr and its stable octahedral cobalt complex is argued to their adsorption over the steel surface. Theoretical fitting of different isotherms, Langmuir, Flory–Huggins and the kinetic–thermodynamic model were tested to clarify the nature of adsorption. The data revealed that there might be non-ideal behaviour in the adsorption processes of Co(Salpr) complex on the steel surface. The Co(Salpr) could displace more water molecules from the steel surface than the corresponding Salpr. The bulky Co(Salpr) molecule could cover more than one active site.