A UV-crosslinked polymer electrolyte membrane for quasi-solid dye-sensitized solar cells with excellent efficiency and durability.

Here we report on a novel polymer electrolyte membrane for quasi-solid dye-sensitized solar cells (DSSCs) with excellent efficiency and extended durability. The electrolyte is prepared by an elegant, rapid and cheap UV-induced polymerization method and the chemometric approach is used for the first time, to the best of our knowledge, for the optimization and the fine tuning of the experimental conditions.

Large conductance modulation of gold thin films by huge charge injection via electrochemical gating.

By using an electrochemical gating technique with a new combination of polymer and electrolyte, we were able to inject surface charge densities n(2D) as high as 3.5×10(15) e/cm(2) in gold films and to observe large relative variations in the film resistance, ΔR/R', up to 10% at low temperature. ΔR/R' is a linear function of n(2D)-as expected within a free-electron model-if the film is thick enough (≥25 nm); otherwise, a tendency to saturation due to size effects is observed. The application of this technique to 2D materials might allow extending the field-effect experiments to a range of charge doping where large conductance modulations and, in some cases, even the occurrence of superconductivity are expected.

Single-Ion Block Copoly(ionic liquid)s as Electrolytes for All-Solid State Lithium Batteries.

Polymer electrolytes have been proposed as replacement for conventional liquid electrolytes in lithium-ion batteries (LIBs) due to their intrinsic enhanced safety. Nevertheless, the power delivery of these materials is limited by the concentration gradient of the lithium salt. Single-ion conducting polyelectrolytes represent the ideal solution since their nature prevents polarization phenomena. Herein, the preparation of a new family of single-ion conducting block copolymer polyelectrolytes via reversible addition-fragmentation chain transfer polymerization technique is reported. These copolymers comprise poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) and poly(ethylene glycol) methyl ether methacrylate blocks. The obtained polyelectrolytes show low Tg values in the range of -61 to 0.6 °C, comparatively high ionic conductivity (up to 2.3 × 10(-6) and 1.2 × 10(-5) S cm(-1) at 25 and 55 °C, respectively), wide electrochemical stability (up to 4.5 V versus Li(+)/Li), and a lithium-ion transference number close to unity (0.83). Owing to the combination of all mentioned properties, the prepared polymer materials were used as solid polyelectrolytes and as binders in the elaboration of lithium-metal battery prototypes with high charge/discharge efficiency and excellent specific capacity (up to 130 mAh g(-1)) at C/15 rate.

Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion.

Lithium-ion solvation and diffusion properties in ethylene carbonate (EC) and propylene carbonate (PC) were studied by molecular simulation, experiments, and electronic structure calculations. Studies carried out in water provide a reference for interpretation. Classical molecular dynamics simulation results are compared to ab initio molecular dynamics to assess nonpolarizable force field parameters for solvation structure of the carbonate solvents. Quasi-chemical theory (QCT) was adapted to take advantage of fourfold occupancy of the near-neighbor solvation structure observed in simulations and used to calculate solvation free energies. The computed free energy for transfer of Li+ to PC from water, based on electronic structure calculations with cluster-QCT, agrees with the experimental value. The simulation-based direct-QCT results with scaled partial charges agree with the electronic structure-based QCT values. The computed Li+/PF6- transference numbers of 0.35/0.65 (EC) and 0.31/0.69 (PC) agree well with NMR experimental values of 0.31/0.69 (EC) and 0.34/0.66 (PC) and similar values obtained here with impedance spectroscopy. These combined results demonstrate that solvent partial charges can be scaled in systems dominated by strong electrostatic interactions to achieve trends in ion solvation and transport properties that are comparable to ab initio and experimental results. Thus, the results support the use of scaled partial charges in simple, nonpolarizable force fields in future studies of these electrolyte solutions.

Photopolymer Electrolytes for Sustainable, Upscalable, Safe, and Ambient-Temperature Sodium-Ion Secondary Batteries.

The first example of a photopolymerized electrolyte for a sodium-ion battery is proposed herein. By means of a preparation process free of solvents, catalysts, purification steps, and separation steps, it is possible to obtain a three-dimensional polymeric network capable of efficient sodium-ion transport. The thermal properties of the resulting solid electrolyte separator, characterized by means of thermogravimetric and calorimetric techniques, are excellent for use in sustainable energy systems conceived for safe large-scale grid storage. The photopolymerized electrolyte shows a wide electrochemical stability window up to 4.8 V versus Na/Na(+) along with the highest ionic conductivity (5.1 mS cm(-1) at 20 °C) obtained in the field of Na-ion polymer batteries so far and stable long-term constant-current charge/discharge cycling. Moreover, the polymeric networks are also demonstrated for the in situ fabrication of electrode/electrolyte composites with excellent interfacial properties, which are ideal for all-solid-state, safe, and easily upscalable device assembly.

Newly Elaborated Multipurpose Polymer Electrolyte Encompassing RTILs for Smart Energy-Efficient Devices.

Profoundly ion-conducting, self-standing, and tack-free ethylene oxide-based polymer electrolytes encompassing a room-temperature ionic liquid (RTIL) with specific amounts of lithium salt are successfully prepared via a rapid and easily upscalable process including a UV irradiation step. All prepared materials are thoroughly characterized in terms of their physical, chemical, and morphological properties and eventually galvanostatically cycled in lab-scale lithium batteries (LIBs) exploiting a novel direct polymerization procedure to get intimate electrode/electrolyte interfacial characteristics. The promising multipurpose characteristics of the newly elaborated materials are demonstrated by testing them in dye-sensitized solar cells (DSSCs), where the introduction of the iodine/iodide-based redox mediator in the polymer matrix assured the functioning of a lab-scale test cell with conversion efficiency exceeding 6% at 1 sun. The reported results enlighten the promising prospects of the material to be successfully implemented as stable, durable, and efficient electrolyte in next-generation energy conversion and storage devices.

Temperature dependence of electric transport in few-layer graphene under large charge doping induced by electrochemical gating.

The temperature dependence of electric transport properties of single-layer and few-layer graphene at large charge doping is of great interest both for the study of the scattering processes dominating the conductivity at different temperatures and in view of the theoretically predicted possibility to reach the superconducting state in such extreme conditions. Here we present the results obtained in 3-, 4- and 5-layer graphene devices down to 3.5 K, where a large surface charge density up to about 6.8·10(14) cm(-2) has been reached by employing a novel polymer electrolyte solution for the electrochemical gating. In contrast with recent results obtained in single-layer graphene, the temperature dependence of the sheet resistance between 20 K and 280 K shows a low-temperature dominance of a T(2) component - that can be associated with electron-electron scattering - and, at about 100 K, a crossover to the classic electron-phonon regime. Unexpectedly, this crossover does not show any dependence on the induced charge density, i.e. on the large tuning of the Fermi energy.

UV-Induced Radical Photo-Polymerization: A Smart Tool for Preparing Polymer Electrolyte Membranes for Energy Storage Devices.

In the present work, the preparation and characterization of quasi-solid polymer electrolyte membranes based on methacrylic monomers and oligomers, with the addition of organic plasticizers and lithium salt, are described. Noticeable improvements in the mechanical properties by reinforcement with natural cellulose hand-sheets or nanoscale microfibrillated cellulose fibers are also demonstrated. The ionic conductivity of the various prepared membranes is very high, with average values approaching 10-3 S cm-1 at ambient temperature. The electrochemical stability window is wide (anodic breakdown voltages > 4.5 V vs. Li in all the cases) along with good cyclability in lithium cells at ambient temperature. The galvanostatic cycling tests are conducted by constructing laboratory-scale lithium cells using LiFePO4 as cathode and lithium metal as anode with the selected polymer electrolyte membrane as the electrolyte separator. The results obtained demonstrate that UV induced radical photo-polymerization is a well suited method for an easy and rapid preparation of easy tunable quasi-solid polymer electrolyte membranes for energy storage devices.

UV-Induced Radical Photo-Polymerization: A Smart Tool for Preparing Polymer Electrolyte Membranes for Energy Storage Devices.

In the present work, the preparation and characterization of quasi-solid polymer electrolyte membranes based on methacrylic monomers and oligomers, with the addition of organic plasticizers and lithium salt, are described. Noticeable improvements in the mechanical properties by reinforcement with natural cellulose hand-sheets or nanoscale microfibrillated cellulose fibers are also demonstrated. The ionic conductivity of the various prepared membranes is very high, with average values approaching 10-3 S cm-1 at ambient temperature. The electrochemical stability window is wide (anodic breakdown voltages > 4.5 V vs. Li in all the cases) along with good cyclability in lithium cells at ambient temperature. The galvanostatic cycling tests are conducted by constructing laboratory-scale lithium cells using LiFePO4 as cathode and lithium metal as anode with the selected polymer electrolyte membrane as the electrolyte separator. The results obtained demonstrate that UV induced radical photo-polymerization is a well suited method for an easy and rapid preparation of easy tunable quasi-solid polymer electrolyte membranes for energy storage devices.

Metallopolymer capacitor in "one pot" by self-directed UV-assisted process.

Silver metalized methacrylate films are prepared by single-step UV curing process with good conductivity on both sides. The major component of the composite is Bisphenol A ethoxylate dimethacrylate, which can be photopolymerized by a photoreactive initiator under UV light. Under the same conditions of UV irradiation, silver ions are deposited as metal nanoparticles while the pyrrole is oxidized to polypyrrole. The migration of silver ions and pyrrole toward both surfaces during polymerization leads to the formation of a metallo-polymer capacitor. The composite films are characterized by SEM-EDX and electrical measurements for possible applications as capacitors in flexible and/or nonplanar electronics.