Advancing Fluoride-Ion Batteries with a Pb-PbF2 Counter Electrode and a Diluted Liquid Electrolyte.

Fluoride ion batteries (FIB) are a promising post lithium-ion technology thanks to their high theoretical energy densities and Earth-abundant materials. However, the flooded cells commonly used to test liquid electrolyte FIBs severely affect the overall performance and impede comparability across different studies, hindering FIB progress. Here, we report a reliable Pb-PbF2 counter electrode that enables the use of two-electrode coin cells. To test this setup, we first introduce a liquid electrolyte that combines the advantages of a highly concentrated electrolyte (tetramethylammonium fluoride in methanol) while addressing its transport and high-cost shortcomings by introducing a diluent (propionitrile). We then demonstrate the viability of this system by reporting a BiF3-Pb-PbF2 cell with the highest capacity retention to date.

Solvent-in-Salt Electrolytes for Fluoride Ion Batteries.

The fluoride ion battery (FIB) is a promising post-lithium ion battery chemistry owing to its high theoretical energy density and the large elemental abundance of its active materials. Nevertheless, its utilization for room-temperature cycling has been impeded by the inability to find sufficiently stable and conductive electrolytes at room temperature. In this work, we report the use of solvent-in-salt electrolytes for FIBs, exploring multiple solvents to show that aqueous cesium fluoride exhibited sufficiently high solubility to achieve an enhanced (electro)chemical stability window (3.1 V) that could enable high operating voltage electrodes, in addition to a suppression of active material dissolution that allows for an improved cycling stability. The solvation structure and transport properties of the electrolyte are also investigated using spectroscopic and computational methods.

Manipulating Frontal Polymerization and Instabilities with Phase-Changing Microparticles.

Recently presented as a rapid and eco-friendly manufacturing method for thermoset polymers and composites, frontal polymerization (FP) experiences thermo-chemical instabilities under certain conditions, leading to visible patterns and spatially dependent material properties. Through numerical analyses and experiments, we demonstrate how the front velocity, temperature, and instability in the frontal polymerization of cyclooctadiene are affected by the presence of poly(caprolactone) microparticles homogeneously mixed with the resin. The phase transformation associated with the melting of the microparticles absorbs some of the exothermic reaction energy generated by the FP, reduces the amplitude and order of the thermal instabilities, and suppresses the front velocity and temperatures. Experimental measurements validate predictions of the dependence of the front velocity and temperature on the microparticle volume fraction provided by the proposed homogenized reaction-diffusion model.

Rapid Synthesis of Elastomers and Thermosets with Tunable Thermomechanical Properties.

Rapid, solvent-free synthesis of poly(1,4-butadiene) in ambient conditions is demonstrated by frontal ring-opening metathesis polymerization (FROMP) of 1,5-cyclooctadiene (COD). Furthermore, cross-linked copolymers with a wide range of tunable properties are readily prepared by FROMP of mixtures of COD and dicyclopentadiene (DCPD). Specifically, glass transition temperature and tensile modulus are varied from -90 to 114 °C and 3.1 MPa to 1.9 GPa, respectively, by controlling the comonomer ratio. Copolymers with subambient glass transition temperature exhibit robust elastomeric behavior, with the ability to repeatedly recover from large elastic deformations. As a demonstration of the capability of this manufacturing strategy, gradient materials are fabricated in less than a minute with spatially controlled properties for multistage shape memory actuation. This simple yet powerful manufacturing strategy enables rapid synthesis of copolymers ranging from elastomers to thermosets with precise control over thermomechanical properties.