We report a thorough, multitechnique investigation of the structure and transport properties of a UV-cross-linked polymer electrolyte based on poly(ethylene oxide), tetra(ethylene glycol)dimethyl ether (G4), and lithium bis(trifluoromethane)sulfonimide. The properties of the cross-linked polymer electrolyte are compared to those of a non-cross-linked sample of same composition. The effect of UV-induced cross-linking on the physico/chemical characteristics is evaluated by X-ray diffraction, differential scanning calorimetry, shear rheology, 1H and 7Li magic angle spinning nuclear magnetic resonance (NMR) spectroscopy, 19F and 7Li pulsed field gradient stimulated echo NMR analyses, electrochemical impedance spectroscopy, and Fourier transform Raman spectroscopy. Comprehensive analysis confirms that UV-induced cross-linking is an effective technique to suppress the crystallinity of the polymer matrix and reduce ion aggregation, yielding improved Li+ transport number (>0.5) and ionic conductivity (>0.1 mS cm–1) at ambient temperature, by tailoring the structural/morphological characteristics of the polymer matrix. Finally, the polymer electrolyte allows reversible operation with stable profile for hundreds of cycles upon galvanostatic test at ambient temperature of LiFePO4-based lithium-metal cells, which deliver full capacity at 0.05 or 0.1C current rate and keep high rate capabilities up to 1C. This enforces the role of UV-induced cross-linking in achieving excellent electrochemical characteristics, exploiting a practical, easy up-scalable process.
Recent studies suggest that operating anion exchange membrane (AEM) fuel cells at high temperatures has enormous technological potential. However, obtaining a fundamental understanding of the effect of temperature on hydroxide conductivity and membrane stability remains a key hurdle to realizing the full potential of high-temperature AEM fuel cells. In this work, we present a combined theoretical and experimental study to explore the effect of temperature on hydroxide ion and water diffusivities in AEMs. Both fully atomistic ab initio molecular dynamics simulations and 1H pulsed field gradient NMR measurements confirm that the OH– diffusion changes non-monotonically with increasing temperature. Specifically, the D OH– versus T curve exhibits a region in which dD OH– /dT < 0, indicating the presence of a kink in the curve, which we refer to as a “diffusion kink”. The simulations show that the underlying causes of this behavior vary with the hydration level. Furthermore, we were able to rationalize the conditions underlying this counterintuitive behavior and to suggest ways to identify the optimal operating temperature for each model AEM system. We expect that the discovery of this unusual temperature dependence of the diffusivity will play an important role in the design of new, stable, and highly conductive AEM-based devices such as electrolyzers, redox flow batteries, and fuel cells.
Graphene oxide (GO) is well known as an excellent amphiphilic material due to its oxygen-containing functional groups and its chemical tunability. By intercalation chemistry, organo-modified GO containing sulfonilic terminal groups were prepared and used as nanoadditive in Nafion polymer for the creation of hybrid exfoliated composites. The incorporation of hydrophilic 2D platelike layers in the Nafion membranes is expected to induce advantages in terms of thermal stability and mechanical and barrier properties (limitation of the methanol crossover by increased tortuosity and obstruction effect), although it may negatively affect the proton conductivity. In this work, we show how different preparation methods of the nanocomposites influence morphology, transport properties, and barrier effect to methanol. The hybrid membranes are characterized by powder X-ray diffraction and microscopies (SEM, TEM, and AFM). Water and methanol transport properties inside the nanocomposites are investigated by NMR spectroscopy (diffusivity and relaxation times), unveiling a reduction of the methanol diffusion and, nevertheless, an increase in the proton mobility and water retention at high temperatures. Finally, the electrochemical properties are investigated by direct methanol fuel cell (DMFC) tests, showing a significant reduction of the ohmic losses at high temperatures, extending in this way the operating range of a DMFC.
Autonomic self-healing (SH), namely, the ability to repair damages from mechanical stress spontaneously, is polarizing attention in the field of new-generation electrochemical devices. This property is highly attractive to enhance the durability of rechargeable Li-ion batteries (LIBs) or Na-ion batteries (SIBs), where high-performing anode active materials (silicon, phosphorus, etc. ) are strongly affected by volume expansion and phase changes upon ion insertion. Here, we applied a SH strategy, based on the dynamic quadruple hydrogen bonding, to nanosized black phosphorus (BP) anodes for Na-ion cells. The goal is to overcome drastic capacity decay and short lifetime, resulting from mechanical damages induced by the volumetric expansion/contraction upon sodiation/desodiation. Specifically, we developed novel ureidopyrimidinone (UPy)-telechelic systems and related blends with poly(ethylene oxide) as novel and green binders alternative to the more conventional ones, such as polyacrylic acid and carboxymethylcellulose, which are typically used in SIBs. BP anodes show impressively improved (more than 6 times) capacity retention when employing the new SH polymeric blend. In particular, the SH electrode still works at a current density higher than 3.5 A g –1 , whereas the standard BP electrode exhibits very poor performances already at current densities lower than 0.5 A g –1 . This is the result of better adhesion, buffering properties, and spontaneous damage reparation.
Electrochromic devices (ECDs) represent one of the most promising energy saving and solar control technology for the market of energy‐efficient building and optoelectronic devices. A continuous and intense effort is currently devoted to the development of effective solid‐state ECDs and their integration in multifunctional systems, such as photoelectrochromics. Here, the fabrication of simplified all‐solid‐state WO3 based ECDs on single‐substrate is reported, demonstrating how the rational design of highly interconnected WO3 columnar nanostructures with Nafion polymer matrix remarkably decreases the charge transport barrier at the hybrid electrolyte/electrochromic interface (EEI), thus determining an impressive improvement of overall device performances. The soft polymer substrate of the electrolyte plays a key role on the formation of WO3 pillar‐like structures and on the increase of interfacial contact area by affecting the vacuum‐deposition WO3 growth. Apart from providing higher transmittance in bleached state, the resulting device, entirely manufactured at room temperature by bottom‐up process, exhibits lower activation voltages (0.5–3 V) and faster switching kinetics (5–10 s) compared with monolithic ECDs based on both bulk and mesoporous WO3 films. Furthermore, the enhanced EEI enables the scale‐up on large area and flexible substrate ensuring simultaneously a wide optical contrast (ΔT = 70%), and high coloration efficiency.
Polyethersulphone (PES) is an aromatic thermoplastic, at low environmental impact, evaluated in this work as a promising candidate for new polymer electrolytes in the PEMFCs technology. A sulfonation procedure has been tuned in order to graft sulfonic acid groups on the polymer chains (sPES) and to make it hydrophilic. Homogeneous membranes with different polymer's sulfonation degrees (SD%) have demonstrated excellent mechanical properties and very low permeability toward methanol (important in the DMFCs), even if low proton conductivity. Nanocomposite sPES membranes were prepared by dispersion of highly hydrophilic lamellar particles such as layered double hydroxide (LDH) in the polymer. Deep investigations performed by a combination of PFG-NMR, EIS, XRD, DMA, and scanning electron microscopy have evidenced the exfoliation of the lamellae in polymer matrix. However, a certain anisotropy was evidenced both in the morphology and molecular diffusion, favored in the longitudinal direction (parallel to surface), while completely inhibited in the cross-section. This finding is most likely induced by the polymer structure, therefore particular attention must be paid to the choice of the filler and preparation of the composites.
Single lithium-ion conducting polymer electrolytes are an innovative concept of solid-state polymer electrolytes (SPEs) for lithium-battery technology. In this work, a lithiated Nafion nanocomposite incorporating sulfonated graphene oxide (sGO-Li+), as well as a filler-free membrane, have been synthesized and characterized. Ionic conductivities and lithium transference number, evaluated by electrochemical techniques after membrane-swelling in organic aprotic solvents (ethylene carbonate-propylene carbonate mixture), display significant values, with σ ≈ 5 × 10–4 S cm–1 at 25 °C and t Li+ close to unity. The absence of solvent leaching on thermal cycles is also noteworthy. The description at molecular level of the lithium transport mechanism has been carefully tackled through a systematic study by 7Li NMR spectroscopy (pulsed field gradient-PFG and relaxation times), while the mechanical properties of the film electrolytes have been evaluated by dynamic mechanical analysis (DMA) in a wide temperature range. The electrochemical performances of the graphene-based electrolyte in Li/Li symmetric cells and in secondary cells using LiFePO4 as positive electrode show good compatibility and functionality with the Li-metal anode by forming a stable interphase, as well as displaying promising performance in galvanostatic cells.
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