Freestanding Bipolar Membranes with an Electrospun Junction for High Current Density Water Splitting.

Freestanding bipolar membranes (BPMs) with an extended-area water splitting junction were fabricated utilizing electrospinning. The junction layer was composed of a mixed fiber mat that was made by concurrently electrospinning sulfonated poly(ether ether ketone) (SPEEK) and quaternized poly(phenylene oxide) (QPPO), with water splitting catalyst nanoparticles intermittently deposited between the fibers. The mat was sandwiched between solution cast SPEEK and QPPO films and hot-pressed to form a dense trilayer BPM with an extended-area junction of finite thickness, composed of QPPO nanofibers embedded in a SPEEK matrix with the catalyst nanoparticles interspaced between the two polymers. The composition, ion-exchange capacity, and catalyst type/loading in the junction were varied, and the water splitting characteristics of the membranes were assessed. The best BPMs fabricated in this work employed a graphene oxide catalyst and exhibited a low trans-membrane voltage drop of about 0.82 V at 1000 mA/cm2 in water splitting experiments with 0.5 M Na2SO4 and stable water splitting operation for 60 h at 800 mA/cm2.

High-Voltage Aqueous Redox Flow Batteries Enabled by Catalyzed Water Dissociation and Acid-Base Neutralization in Bipolar Membranes.

Aqueous redox flow batteries that employ organic molecules as redox couples hold great promise for mitigating the intermittency of renewable electricity through efficient, low-cost diurnal storage. However, low cell potentials and sluggish ion transport often limit the achievable power density. Here, we explore bipolar membrane (BPM)-enabled acid-base redox flow batteries in which the positive and negative electrodes operate in the alkaline and acidic electrolytes, respectively. This new configuration adds the potential arising from the pH difference across the membrane and enables an open circuit voltage of ∼1.6 V. In contrast, the same redox molecules operating at a single pH generate ∼0.9 V. Ion transport in the BPM is coupled to the water dissociation and acid-base neutralization reactions. Interestingly, experiments and numerical modeling show that both of these processes must be catalyzed in order for the battery to function efficiently. The acid-base concept provides a potentially powerful approach to increase the energy storage capacity of aqueous redox flow batteries, and insights into the catalysis of the water dissociation and neutralization reactions in BPMs may be applicable to related electrochemical energy conversion devices.

Electrospun Hybrid Perfluorosulfonic Acid/Sulfonated Silica Composite Membranes.

Electrospinning was employed to fabricate composite membranes containing perfluorosulfonic acid (PFSA) ionomer, poly(vinylidene fluoride) (PVDF) reinforcement and a sulfonated silica network, where the latter was incorporated either in the PFSA matrix or in the PVDF fibers. The best membrane, in terms of proton conductivity, was made by incorporating the sulfonated silica network in PFSA fibers (Type-A) while the lowest conductivity membrane was obtained when sulfonated silica was incorporated into the reinforcing PVDF fibers (Type-B). A Type-A membrane containing 65 wt.% PFSA with an embedded sulfonated silica network (at 15 wt.%) and with 20 wt.% PVDF reinforcing fibers proved superior to the pristine PFSA membrane in terms of both the proton conductivity in the 30-90% RH at 80 °C (a 25-35% increase) and lateral swelling (a 68% reduction). In addition, it was demonstrated that a Type-A membrane was superior to that of a neat 660 EW perfluoroimide acid (PFIA, from 3M Co.) films with respect to swelling and mechanical strength, while having a similar proton conductivity vs. relative humidity profile. This study demonstrates that an electrospun nanofiber composite membrane with a sulfonated silica network added to moderately low EW PFSA fibers is a viable alternative to an ultra-low EW fluorinated ionomer PEM, in terms of properties relevant to fuel cell applications.

Pt-Co truncated octahedral nanocrystals: a class of highly active and durable catalysts toward oxygen reduction.

We report a facile and scalable synthesis of Pt-Co truncated octahedral nanocrystals (TONs) by employing Pt(acac)2 and Co(acac)2 as precursors, together with CO molecules and Mn atoms derived from the decomposition of Mn2(CO)10 as a reductant and a {111} facet-directing agent, respectively. Both the composition and yield of the Pt-Co TONs could be varied through the introduction of CHCl3. When tested at 80 °C using membrane electrode assembly (MEA), the 4 nm Pt2.6Co TONs gave a mass activity of 294 A gPt-1 at beginning-of-life (BOL) and it increased to 384 A gPt-1 during recovery cycles. The mass activity at BOL only dropped by 24% after 30 000 voltage cycles at end-of-life (EOL) in a metal dissolution accelerated stress test. The Pt2.6Co/C catalyst outperformed the commercial TKK Pt3Co/C (230 A gPt-1 at BOL and 40% loss after 30 000 cycles at EOL) in terms of both activity and durability. Our systematic analysis suggested that the enhancement in activity can be attributed to the combination of small, uniform size and well-defined {111} facets. This new class of catalysts holds promise for applications in proton-exchange membrane fuel cells.

Electric Response and Conductivity Mechanism of Blended Polyvinylidene Fluoride/Nafion Electrospun Nanofibers.

The electrical relaxation and polarization phenomena of electrospun PVDF (P)/Nafion (N) blended fiber mats ([P/N0.9]M and ß-[P]M) and membranes ([P/N0.9]MM) are compared with those of the solvent-cast membrane of identical composition ([N]C and [P/N0.9]C). The nature of the interactions between the two blended polymer components, that plays a pivotal role in the electrical nature of the resulting materials, is found to be governed by the fabrication method, with those materials obtained via electrospinning undergoing a "reciprocal templating" phenomenon that renders their electrical behavior (especially when in the dry state) significantly different from that of the blended membrane obtained via solvent casting. Broadband Electrical Spectroscopy (BES) demonstrates that the electric response of the blended materials is modulated by polarization phenomena and by α, ß, and γ dielectric relaxation events of Nafion domains supported on ß-PVDF. The coupling between the relaxations of ß-PVDF with those of Nafion matrix is directly correlated to the "reciprocal templating" effect, which modulates the interactions between Nafion and PVDF in electrospun membranes. Two types of conductivity mechanisms characterize the H+ migration within the polymer blends: (1) interdomain H+ migration events by "charge-exchange" phenomena along percolation pathways and (2) H+ exchange between delocalization bodies (DBs) at binding sites at the interface between domains with different ε, size, and morphology. The electrical response of the electrospun membranes also suggests that they do not comprise water clusters with a large size such as those typically observed in pristine Nafion. Rather, the adsorbed H2O molecules, under wet conditions, form thin solvation shells wrapping the polar side chains of the Nafion component. At T = 80 °C, the conductivity of the studied materials decreases in the order [N]C (0.043 S·cm-1) ≈ [P/N0.9]C (0.042 S·cm-1) > [P/N0.9]M (0.031 S·cm-1) > [P/N0.9]MM (0.011 S·cm-1).

Sulfated chitosan/PVA absorbent membrane for removal of copper and nickel ions from aqueous solutions-Fabrication and sorption studies.

Novel absorbents for the removal of Cu2+ and Ni2+ ions from aqueous solutions were prepared from solution cast sulfated chitosan/polyvinyl alcohol membranes (SCS/PVA) and their properties were investigated. FTIR, SEM, XRD and TGA analyses were used to determine membrane structure. The effect of environmental parameters on absorption was studied, including pH, contact time, temperature and the initial concentration of Ni2+ and Cu2+ ions. Freundlich and Langmuir absorption isotherms were fitted to experimental data and a pseudo-second order rate equation was employed to model the kinetics of uptake for several copper and nickel ion concentrations. The results indicate that the affinity of an SCS/PVA membrane for Cu2+ ions was higher than that for Ni2+ ions. The study demonstrated that the SCS/PVA system can be utilized as highly efficient sorbents, to extract Ni2+ and Cu2+ from aqueous feed solutions.

High Areal Capacity Si/LiCoO2 Batteries from Electrospun Composite Fiber Mats.

Freestanding nanofiber mat Li-ion battery anodes containing Si nanoparticles, carbon black, and poly(acrylic acid) (Si/C/PAA) are prepared using electrospinning. The mats are compacted to a high fiber volume fraction (≈0.85), and interfiber contacts are welded by exposing the mat to methanol vapor. A compacted+welded fiber mat anode containing 40 wt % Si exhibits high capacities of 1484 mA h g-1 (3500 mA h g-1Si ) at 0.1 C and 489 mA h g-1 at 1 C and good cycling stability (e.g., 73 % capacity retention over 50 cycles). Post-mortem analysis of the fiber mats shows that the overall electrode structure is preserved during cycling. Whereas many nanostructured Si anodes are hindered by their low active material loadings and densities, thick, densely packed Si/C/PAA fiber mat anodes reported here have high areal and volumetric capacities (e.g., 4.5 mA h cm-2 and 750 mA h cm-3 , respectively). A full cell containing an electrospun Si/C/PAA anode and electrospun LiCoO2 -based cathode has a high specific energy density of 270 Wh kg-1 . The excellent performance of the electrospun Si/C/PAA fiber mat anodes is attributed to the: i) PAA binder, which interacts with the SiOx surface of Si nanoparticles and ii) high material loading, high fiber volume fraction, and welded interfiber contacts of the electrospun mats.

High Performance Particle/Polymer Nanofiber Anodes for Li-ion Batteries using Electrospinning.

Electrospun nanofiber mats containing carbon nanoparticles in a poly(vinylidene fluoride) binder were prepared and characterized as Li-ion battery anodes. The mats exhibited an initial capacity of 161 mAh g(-1) with 91.7% capacity retention after 510 cycles at 0.1 C (1 C=372 mA gcarbon (-1)). Whereas many nanoscale electrodes are limited to low areal and/or volumetric capacities, the particle/polymer nanofiber anodes can be made thick with a high fiber volume fraction while maintaining good rate capabilities. Thus, a nanofiber anode with a fiber volume fraction of 0.79 exhibits a volumetric capacity of 55 mAh cm(-3) at 2 C, which is twice that of a typical graphite anode. Similarly, thick nanofiber mats with a high areal capacity of 4.3 mAh cm(-2) were prepared and characterized. The excellent performance of electrospun anodes is attributed to electrolyte intrusion throughout the interfiber void space and efficient Li(+) transport between the electrolyte and carbon nanoparticles in the radial fiber direction.

Electrospun Nafion®/Polyphenylsulfone Composite Membranes for Regenerative Hydrogen Bromine Fuel Cells.

The regenerative H2/Br2-HBr fuel cell, utilizing an oxidant solution of Br2 in aqueous HBr, shows a number of benefits for grid-scale electricity storage. The membrane-electrode assembly, a key component of a fuel cell, contains a proton-conducting membrane, typically based on the perfluorosulfonic acid (PFSA) ionomer. Unfortunately, the high cost of PFSA membranes and their relatively high bromine crossover are serious drawbacks. Nanofiber composite membranes can overcome these limitations. In this work, composite membranes were prepared from electrospun dual-fiber mats containing Nafion® PFSA ionomer for facile proton transport and an uncharged polymer, polyphenylsulfone (PPSU), for mechanical reinforcement, and swelling control. After electrospinning, Nafion/PPSU mats were converted into composite membranes by softening the PPSU fibers, through exposure to chloroform vapor, thus filling the voids between ionomer nanofibers. It was demonstrated that the relative membrane selectivity, referenced to Nafion® 115, increased with increasing PPSU content, e.g., a selectivity of 11 at 25 vol% of Nafion fibers. H2-Br2 fuel cell power output with a 65 µm thick membrane containing 55 vol% Nafion fibers was somewhat better than that of a 150 µm Nafion® 115 reference, but its cost advantage due to a four-fold decrease in PFSA content and a lower bromine species crossover make it an attractive candidate for use in H2/Br2-HBr systems.

Poly(ε-caprolactone)-carbon nanotube composite scaffolds for enhanced cardiac differentiation of human mesenchymal stem cells.

AIM: To evaluate the efficacy of electrically conductive, biocompatible composite scaffolds in modulating the cardiomyogenic differentiation of human mesenchymal stem cells (hMSCs). MATERIALS & METHODS: Electrospun scaffolds of poly(ε-caprolactone) with or without carbon nanotubes were developed to promote the in vitro cardiac differentiation of hMSCs. RESULTS: Results indicate that hMSC differentiation can be enhanced by either culturing in electrically conductive, carbon nanotube-containing composite scaffolds without electrical stimulation in the presence of 5-azacytidine, or extrinsic electrical stimulation in nonconductive poly(ε-caprolactone) scaffolds without carbon nanotube and azacytidine. CONCLUSION: This study suggests a first step towards improving hMSC cardiomyogenic differentiation for local delivery into the infarcted myocardium.

Development of multilayered cell-hydrogel composites using an acoustic focusing technique.

Multilayered composites, composed of mammalian cells arranged in a hydrogel, have been prepared using an acoustic focusing technique. Acoustic focusing is a simple, nonchemical technique that allows for the fast arrangement of cells in matrices where the control of cell geometry is beneficial. Breast cancer cells (MDA-MB231) were dispersed in a 30 wt % solution of poly(ethylene glycol) diacrylate (PEGDA) of molecular weight 400 at a density of 5 x 10(6) cells/mL of PEGDA solution. An ultrasonic field was used to organize the cells before polymerization of PEGDA. Disk-shaped hydrogel composites, typically 1 cm in diameter and 2-mm thick were prepared based on a PEGDA solution volume of 130 microL. At an acoustic frequency of 2.32 MHz, composites having cells positioned within concentric cylindrical shells interspersed with zones of cell-free hydrogel were produced. The cells were located in annuli approximately 80-microm thick and about 300 microm apart. The structure and viability of the cells within these constructs were studied using a fluorescent LIVE/DEAD assay. The viability of the cells was on the order of 50%. For the conditions used in this study, cell death was primarily attributed to exposure of cells to the PEGDA solution prior to polymerization, rather than adverse effects of polymerization or the sound field itself.

Mechanical and cell viability properties of crosslinked low- and high-molecular weight poly(ethylene glycol) diacrylate blends.

There is a strong need for tissue engineering scaffolds that are mechanically robust, exhibit good biocompatibility, and can be made from readily available materials. To this end, blends of commercially available poly(ethylene glycol) diacrylate (PEGDA) with molecular weights of 400 and 3400 were UV-crosslinked at total polymer concentrations that varied systematically from 20 to 40 wt %. The compressive strength and cell viability were determined for each PEGDA mixture. The compressive modulus of the blends was maximized when the weight percent ratio PEGDA3400/400 was about 40/60, with the compressive strength reaching 1.7 MPa. Cell viability results with a LIVE/DEAD fluorescence assay show an average viability of approximately 80% at a total PEGDA concentration of 20 wt % for all blends. Increasing the total polymer concentration increased the compressive modulus of a polymer, but adversely affected cell viability for all the PEGDA blend compositions. The blend composition affected the mechanical behavior of the discs, where a higher degree of crosslinking was achieved by increasing the concentration of shorter chained PEGDA400, whereas elasticity was gained by incorporating longer chained PEGDA3400 into the blends. These results can be exploited for use in tissue engineering applications, where a mechanically robust scaffold is advantageous.