Polyvinylidene Fluoride-Based Gel Polymer Electrolytes for Calcium Ion Conduction: A Study of the Influence of Salt Concentration and Drying Temperature on Coordination Environment and Ionic Conductivity.

Calcium-ion batteries emerged as a potential sustainable alternative energy storage system; however, there remains the need to further develop electrolytes to improve their performance. We report a gel polymer electrolyte (GPE)-based on polyvinylidene fluoride (PVDF) for calcium ion conduction. The gel electrolyte was synthesized by combining a PVDF polymer host, Ca(TFSI)2 salt, and N-methyl-2-pyrrolidone (NMP) solvent. Using Fourier transform infrared spectroscopy, we analyze the effect of salt concentration and drying temperature on the degree of salt dissociation in the electrolyte. Our results show that the concentration of free cations in the electrolyte is primarily coordinated with NMP as well as PVDF, generating a suitable network for ion transport, i.e., a liquid electrolyte encompassed within a polymer matrix. We find that processing conditions such as drying temperature, which varies solvent content, play a critical role in developing polymer electrolytes that demonstrate optimal electrochemical performance. The GPEs are semicrystalline and stable up to 120 °C, which is critical for their use in applications such as in electric vehicles and renewable energy storage systems. The ionic conductivity of the GPEs exhibit Arrhenius-type behavior, and the total ionic conductivity at room temperature is suitable for applications, with values of 0.85 × 10-4 S/cm for 0.5 M and 3.56 × 10-4 S/cm for 1.0 M concentrations. The results indicate that the GPE exhibits high conductivity and good stability, making it a promising candidate for use in high-performance calcium ion batteries.

Vinylimidazole-Based Polymer Electrolytes with Superior Conductivity and Promising Electrochemical Performance for Calcium Batteries.

Calcium batteries are next-generation energy storage technologies with promising techno-economic benefits. However, performance bottlenecks associated with conventional electrolytes with oxygen-based coordination chemistries must be overcome to enable faster cation transport. Here, we report an imidazole-based polymer electrolyte with the highest reported conductivity and promising electrochemical properties. The polymerization of vinylimidazole in the presence of calcium bis(trifluoromethanesulfonyl)imide (Ca(TFSI)2) salt creates a gel electrolyte comprising a polyvinyl imidazole (PVIm) host infused with vinylimidazole liquid. Calcium ions effectively coordinate with imidazole groups, and the electrolytes present room temperature conductivities of >1 mS/cm. Reversible redox activity in symmetric Ca cells is demonstrated at 2 V overpotentials, stable cycles at 0.1 mA/cm2, and areal capacities of 0.1 mAh/cm2. Softer coordination, polarizability, and closer coordinating site distances of the imidazole groups can explain the enhanced properties. Hence, imidazole is a suitable chemical benchmark for the future design and advancement of polymer electrolytes for calcium batteries.

Superhydrophobic Polymer Composite Surfaces Developed via Photopolymerization.

Fabrication of superhydrophobic materials using incumbent techniques involves several processing steps and is therefore either quite complex, not scalable, or often both. Here, the development of superhydrophobic surface-patterned polymer-TiO2 composite materials using a simple, single-step photopolymerization-based approach is reported. The synergistic combination of concurrent, periodic bump-like pattern formation created using irradiation through a photomask and photopolymerization-induced nanoparticle (NP) phase separation enables the development of surface textures with dual-scale roughness (micrometer-sized bumps and NPs) that demonstrate high water contact angles, low roll-off angles, and desirable postprocessability such as flexibility, peel-and-stick capability, and self-cleaning capability. The effect of nanoparticle concentration on surface porosity and consequently nonwetting properties is discussed. Large-area fabrication over an area of 20 cm2, which is important for practical applications, is also demonstrated. This work demonstrates the capability of polymerizable systems to aid in the organization of functional polymer-nanoparticle surface structures.

Gel Polymer Electrolytes Based on Cross-Linked Poly(ethylene glycol) Diacrylate for Calcium-Ion Conduction.

Calcium batteries are promising alternatives to lithium batteries owing to their high energy density, comparable reduction potential, and mineral abundance. However, to meet practical demands in high-performance applications, suitable electrolytes must be developed. Here, we report the synthesis and characterization of polymer gel electrolytes for calcium-ion conduction prepared by the photo-cross-linking of poly(ethylene glycol) diacrylate (PEGDA) in the presence of solutions of calcium salts in a mixture of ethylene carbonate (EC) and propylene carbonate (PC) solvents. The results show room-temperature conductivity between 10-5 and 10-4 S/cm, electrochemical stability windows of ∼3.8 V, full dissociation of the salt, and minimal coordination with the PEGDA backbone. Cycling in symmetric Ca metal cells proceeds but with increasing overpotentials, which can be attributed to interfacial impedance between the electrolyte and calcium surface, which inhibits charge transfer. Calcium may still be plated and stripped yielding high-purity deposits and no indication of significant electrolyte breakdown, indicating that high overpotentials are associated with an electrically insulating, yet ion-permeable solid electrolyte interface (SEI). This work provides a contribution to the study and understanding of polymer gel materials toward their improvement and application as electrolytes for calcium batteries.

Observation of intensity dependent phase-separation in photoreactive monomer-nanoparticle formulations under non-uniform visible light irradiation.

We report observations of photopolymerization driven phase-separation in a mixture of a photo-reactive monomer and inorganic nanoparticles. The mixture is irradiated with visible light possessing a periodic intensity profile that elicits photopolymerization along the depth of the mixture, establishing a competition between photo-crosslinking and thermodynamically favorable phase-separating behavior inherent to the system. In situ Raman spectroscopy was used to monitor the polymerization reaction and morphology evolution, and reveals a key correlation between irradiation intensity and composite morphology extending the entire depth of the mixture, i.e. unhindered phase-separation at low irradiation intensity and arrested phase-separation at high irradiation intensity. 3D Raman volume mapping and energy dispersive X-ray mapping confirm that the intensity-dependent irradiation process dictates the extent of phase separation, enabling single-parameter control over phase evolution and subsequent composite morphology. These observations can potentially enable a single-step route to develop polymer-inorganic composite materials with tunable morphologies.

Polymer Encapsulants Incorporating Light-Guiding Architectures to Increase Optical Energy Conversion in Solar Cells.

The fabrication of a new type of solar cell encapsulation architecture comprising a periodic array of step-index waveguides is reported. The materials are fabricated through patterning with light in a photoreactive binary blend of crosslinking acrylate and urethane, wherein phase separation induces the spontaneous, directed formation of broadband, cylindrical waveguides. This microstructured material efficiently collects and transmits optical energy over a wide range of entry angles. Silicon solar cells comprising this encapsulation architecture show greater total external quantum efficiencies and enhanced wide-angle light capture and conversion. This is a rapid, straightforward, and scalable approach to process light-collecting structures, whereby significant increases in cell performance may be achieved.

Increasing light capture in silicon solar cells with encapsulants incorporating air prisms to reduce metallic contact losses.

Silicon solar cells are the most widely deployed modules owing to their low-cost manufacture, large market, and suitable efficiencies for residential and commercial use. Methods to increase their solar energy collection must be easily integrated into module fabrication. We perform a theoretical and experimental study on the light collection properties of an encapsulant that incorporates a periodic array of air prisms, which overlay the metallic front contacts of silicon solar cells. We show that the light collection efficiency induced by the encapsulant depends on both the shape of the prisms and angle of incidence of incoming light. We elucidate the changes in collection efficiency in terms of the ray paths and reflection mechanisms in the encapsulant. We fabricated the encapsulant from a commercial silicone and studied the change in the external quantum efficiency (EQE) on an encapsulated, standard silicon solar cell. We observe efficiency enhancements, as compared to a uniform encapsulant, over the visible to near infrared region for a range of incident angles. This work demonstrates exactly how a periodic air prism architecture increases light collection, and how it may be designed to maximize light collection over the widest range of incident angles.