Centrifugally spun carbon fibers prepared from aqueous poly(vinylpyrrolidone) solutions as binder-free anodes in lithium-ion batteries

Aqueous solutions of poly(vinylpyrrolidone) (PVP) of various concentrations (20, 25, and 28 wt%) were successfully spun into fibers by centrifugal spinning. The pristine PVP fibers were annealed and carbonized to produce flexible carbon fibers for use as binder-free anodes in lithium-ion batteries. These flexible carbon fibers were prepared by developing a novel three-step heat treatment to reduce the residual stresses in the pristine PVP precursor fibers, and to prevent fiber degradation during carbonization. The thermogravimetric analysis data showed that the annealed fibers yielded a residual mass percentage of 36.0% while the pristine PVP fibers suffered a higher mass loss and only retained 26.5% of original mass above 450 °C (under nitrogen). The electrochemical performance of the carbon-fiber anodes was evaluated by conducting galvanostatic charge/discharge, rate performance, and cycle voltammetry experiments. The 20, 25, and 28 wt% derived binder-free anodes delivered specific charge capacities of 205, 189, and 275 mAh g⁻¹, respectively, after the first cycle at a current density of 100 mA g⁻¹. The results obtained in this work indicate that a feasible pathway towards a large-scale production of carbon-fiber anodes from a 100% aqueous solution can be achieved via centrifugal spinning and subsequent heat treatment.     

The propagation of pressure in a gelled waxy oil pipeline as studied by particle imaging velocimetry

Paraffinic crude oils in pipelines may form waxy gels during flow shutdowns. These gels can be dislodged by applying pressure if the wall shear stress, proportional to the local pressure gradient, exceeds the gel yield stress. The simplest models assume that the axial pressure profile becomes linear immediately after a jump in upstream pressure, but this fails to account for gel time‐dependent rheology or the effect of gel voids on pressure wave propagation. To investigate the former factor, pressure profile and particle imaging velocimetry (PIV) measurements were performed on a model oil gelled under pressure to reduce void formation. After a jump in upstream pressure to a value insufficient to restart flow, the axial pressure profile becomes linear in a two‐step process, with an immediate small rise in downstream pressure followed by a time‐delayed jump. The local downstream gel deformation measured by PIV exhibits similar two‐step time dependence. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

The production of carbon nanotube reinforced poly(vinyl) butyral nanofibers by the Forcespinning® method

Poly(vinyl) butyral (PVB) nanofibers (NFs) and carbon nanotube (CNT) reinforced PVB NF composites were developed by using the Forcespinning® technology. PVB was dissolved in a mixture of ethanol and methanol (7:3 wt/wt) at various concentrations, and the solutions were spun at rotational speeds varying between 3,000 and 9,000 rpm. The CNT/PVB solutions were prepared using the same solvent ratio with varying the concentration of CNTs. The results show that the diameter of the PVB fibers increased with increasing rotational speed; however the standard deviation of the fiber diameter distribution decreased. The morphology and thermal properties of the developed fiber systems were studied by DSC, TGA, Raman, and FTIR. The effect of CNT on the mechanical properties of the developed fibers was investigated by carrying out tensile tests at different strain rates. Raman and FTIR analyses indicate a noncovalent π–π stacking interactions and hydrogen bonding between CNT and the PVB NFs. Adding CNT to the PVB NF matrix resulted in improved tensile strength by 150%. POLYM. ENG. SCI., 55:81–87, 2015. © 2014 Society of Plastics Engineers     

Preparation and electrochemical characterization of ionic-conducting lithium lanthanum titanate oxide/polyacrylonitrile submicron composite fiber-based lithium-ion battery separators

Lithium lanthanum titanate oxide (LLTO)/polyacrylonitrile (PAN) submicron composite fiber-based membranes were prepared by electrospinning dispersions of LLTO ceramic particles in PAN solutions. These ionic-conducting LLTO/PAN composite fiber-based membranes can be directly used as lithium-ion battery separators due to their unique porous structure. Ionic conductivities were evaluated after soaking the electrospun LLTO/PAN composite fiber-based membranes in a liquid electrolyte, 1 M lithium hexafluorophosphate (LiPF₆) in ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (1:1 vol). It was found that, among membranes with various LLTO contents, 15 wt.% LLTO/PAN composite fiber-based membranes provided the highest ionic conductivity, 1.95 × 10⁻³ S cm⁻¹. Compared with pure PAN fiber membranes, LLTO/PAN composite fiber-based membranes had greater liquid electrolyte uptake, higher electrochemical stability window, and lower interfacial resistance with lithium. In addition, lithium//1 M LiPF₆/EC/EMC//lithium iron phosphate cells containing LLTO/PAN composite fiber-based membranes as the separator exhibited high discharge specific capacity of 162 mAh g⁻¹ and good cycling performance at 0.2 C rate at room temperature.     

ForceSpinning of polyacrylonitrile for mass production of lithium‐ion battery separators

We present results on the Forcespinning^® (FS) of Polyacrylonitrile (PAN) for mass production of polymer nanofiber membranes as separators for Lithium‐ion batteries (LIBs). Our results presented here show that uniform, highly fibrous mats from PAN produced using Forcespinning^®, exhibit improved electrochemical properties such as electrolyte uptake, low interfacial resistance, high oxidation limit, high ionic conductivity, and good cycling performance when used in lithium ion batteries compared to commercial PP separator materials. This article introduces ForceSpinning^®, a cost effective technique capable of mass producing high quality fibrous mats, which is completely different technology than the commonly used in‐house centrifugal method. This Forcespinning^® technology is thus the beginning of the nano/micro fiber revolution in large scale production for battery separator application. This is the first time to report results on the cycle performance of LIB‐based polymer nanofiber separators made by Forcespinning^® technology. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42847.     

The effect of physical ageing on the relaxation time spectrum of amorphous polymers: the fractional calculus approach

Empirical models corresponding to a constitutive equation with fractional derivatives are proposed for linear viscoelastic polymers. For these models, the relaxation modulus, the dynamic moduli, the relaxation time spectra, and other material functions can be calculated as a function of a few parameters that characterise the behaviour of a viscoelastic polymer. The fractional calculus approach allows us to calculate the relaxation time spectrum H() via the Stieltjes inversion in the linear viscoelastic zone. Polymethylmethacrylate (PMMA) is chosen as a model amorphous polymer in a temperature range from T_g + 90°C to T_g + 25°C. This polymer is characterised by a non-equilibrium state between at least the and relaxations. The structural recovery of PMMA has been investigated using dynamic mechanical thermal analysis (DMTA) by varying the preparational history. The effect of time and temperature on the model parameters and on the relaxation time spectra are also investigated in the neighbourhood of the glass transition.     

A comparison of concentration-glasses and temperature-hyperquenched glasses: CO2-formed glass versus temperature-formed glass

Prior work from this laboratory has reported anomalous differences in the viscoelastic responses between temperature-jump formed glasses and carbon dioxide pressure-jump or relative humidity formed glasses. In the present work, we investigate the anomalous behaviour further by examining the structural response of an epoxy resin after pre-annealing treatments. In particular, we have measured the volume change of amine-cured diglycidyl ether of bisphenol A after thermal and carbon dioxide pressure (PCO₂) treatments. Our results show that contrary to prior interpretations in the literature, a plasticizer quench is different from a temperature hyperquench. Consistent with our prior work, the CO₂-formed glass is more stable than the temperature-formed glass in spite of the former having a higher excess volume. Our new results show that the stability persists to above the nominal glass temperature, contrary to what happens in a temperature hyperquench.     

Electrospun nanofiber‐coated separator membranes for lithium‐ion rechargeable batteries

Nanofiber‐coated composite membranes were prepared by electrospinning polyvinylidene fluoride‐co‐chlorotrifluoroethylene (PVDF‐co‐CTFE) and PVDF‐co‐CTFE/polyvinylidene fluoride‐co‐hexafluoropropylene (PVDF‐co‐HFP) onto six different Celgard® microporous battery separator membranes. Application of a PVDF‐based copolymer nanofiber coating onto the surface of the battery separator membrane provides a method for improving the electrolyte absorption of the separator and the separator‐electrode adhesion. Peel tests showed that both PVDF‐co‐CTFE and PVDF‐co‐CTFE/PVDF‐co‐HFP nanofiber coatings have comparable adhesion to the membrane substrates. Electrolyte uptake capacity was investigated by soaking the nanofiber‐coated membranes in a liquid electrolyte solution. PVDF‐co‐CTFE and PVDF‐co‐CTFE/PVDF‐co‐HFP nanofiber‐coated membranes exhibited higher electrolyte uptake capacities than uncoated membranes. It was also found that PVDF‐co‐CTFE nanofiber‐coated membranes have higher electrolyte uptakes than PVDF‐co‐CTFE/PVDF‐co‐HFP nanofiber‐coated membranes due to the smaller diameters of PVDF‐co‐CTFE nanofibers and higher polarity of PVDF‐co‐CTFE. The separator–electrode adhesion properties were also investigated. Results showed PVDF‐co‐CTFE and PVDF‐co‐CTFE/PVDF‐co‐HFP nanofiber coatings improved the adhesion of all six membrane substrates to the electrode. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Sulfonated polystyrene fiber network-induced hybrid proton exchange membranes

A novel type of hybrid membrane was fabricated by incorporating sulfonated polystyrene (S-PS) electrospun fibers into Nafion for the application in proton exchange membrane fuel cells. With the introduction of S-PS fiber mats, a large amount of sulfonic acid groups in Nafion aggregated onto the interfaces between S-PS fibers and the ionomer matrix, forming continuous pathways for facile proton transport. The resultant hybrid membranes had higher proton conductivities than that of recast Nafion, and the conductivities were controlled by selectively adjusting the fiber diameters. Consequently, hybrid membranes fabricated by ionomers, such as Nafion, incorporated with ionic-conducting nanofibers established a promising strategy for the rational design of high-performance proton exchange membranes.