Surface modification of polyolefin separators for lithium ion batteries to reduce thermal shrinkage without thickness increase

Surface chemical modification of polyolefin separators for lithium ion batteries is attempted to reduce the thermal shrinkage, which is im- portant for the battery energy density. In this study, we grafted organic/inorganic hybrid crosslinked networks on the separators, simply by grafting polymerization and condensation reaction. The considerable silicon-oxygen crosslinked heat-resistance networks are responsible for the reduced thermal shrinkage. The strong chemical bonds between networks and separators promise enough mechanical support even at high temperature. The shrinkage at 150 ℃ for 30 min in the mechanical direction was 38.6% and 4.6% for the pristine and present graft-modified separators, respectively. Meanwhile, the grafting organic-inorganic hybrid crosslink networks mainly occupied part of void in the internal pores of the separators, so the thicknesses of the graft-modified separators were similar with the pristine one. The half cells prepared with the modified separators exhibited almost identical electrochemical properties to those with the commercial separators, thus proving that, in order to enhance the thermal stability of lithium ion battery, this kind of grafting-modified separators may be a better alternative to conventional silica nanoparticle layers-coated polyolefin separators.

Factors Affecting Thermal Shrinkage of Mouthguard Sheet during Thermoforming: Model Shape and Sheet Material Thickness

The effectiveness and safety of the mouthguard depend on the sheet material thickness. The thickness of the thermoformed mouthguard is affected by the model undercut and the thermal shrinkage that occurs when the extruded-molded sheet is reheated. The aim of this study was to clarify the influence of the undercut amount of the model and the thickness of the sheet material on the thermal shrinkage of the extruded sheet. The mouthguard sheet used ethylene-vinyl acetate resin with a thickness of 4.0 mm (4M) and 3.0 mm (3M) and was manufactured by extrusion molding. The working models were three hard gypsum models with the undercut amount on the labial side trimmed to 0? (U0), 10? (U10), and 20? (U20). Mouthguard thickness after vacuum formation was compared between the conditions formed so that the extrusion direction was vertical (condition V) or parallel (condition P) to the model midline. Differences in the reduction rate of the mouthguard thicknesses of the labial and buccal side depending on the sheet extrusion direction, model angle, and sheet material thickness were analyzed by three-way ANOVA and Bonferroni method. The reduction rate of the thickness in condition P was significantly greater than in condition V under all conditions except U0-4M on the labial side and U0-4M and U10-4M on the buccal side. In all models, the reduction rate of the thicknesses was significantly greater in 3M than in 4M in the same extrusion direction. In both 4M and 3M, the reduction rate of the thicknesses tended to increase as the amount of undercut increased in each extrusion direction. This study suggested that a model with a large amount of undercut on the labial side or a thin sheet had a significant effect on the thermal shrinkage of the mouthguard sheet during thermoforming, which leads to the thinning of the mouthguard.

Thermal Behavior and Determination of the Heated Structure of 11ÅAnomalous Tobermorite by in situ X-ray Diffraction

This article presents the thermal transitions of a tobermorite-bearing sample when heated from 30℃ up to 1200℃,both in vacuum and in static air,including tobermorite transforming to wollastonite,aragonite to calcite and calcite to lime.Characteristics obtained by in situ high temperature X-ray diffraction,field emission scanning electron microscopy and scanning transmission electron microscopy analyses jointly indicate that the investigated tobermorite is anomalous.The variations along the a,b,c axes and the volume changes of tobermorite with increasing temperature are described,and its thermal shrinkage coefficients therefore determined.The comparison between the refined structures at 30℃ and 800℃ demonstrates that the shrinkage degree(Δa/a0)along the a axis is higher than those(Δb/b0,Δc/c0)along the b and c axes.The wollastonite is formed in two ways:Tobermorite converting to wollastonite and lime reacting with quartz to form wollastonite.

Effect of silica nanoparticles/poly(vinylidene fluoride-hexafluoropropylene) coated layers on the performance of polypropylene separator for lithium-ion batteries

In an effort to reduce thermal shrinkage and improve electrochemical performance of porous polypropylene （PP） separators for lithium-ion batteries, a new composite separator is developed by introducing ceramic coated layers on both sides of PP separator through a dip-coating process. The coated layers are comprised of heat-resistant and hydrophilic silica nanoparticles and polyvinylidene fluoride-hexafluoropropylene （PVDF-HFP） binders. Highly porous honeycomb structure is formed and the thickness of the layer is only about 700 nm. In comparison to the pristine PP separator, the composite separator shows significant reduction in thermal shrinkage and improvement in liquid electrolyte uptake and ionic conduction, which play an important role in improving cell performance such as discharge capacity, C-rate capability, cycle performance and coulombic efficiency.