Task-Specific Phosphonium Iongels by Fast UV-Photopolymerization for Solid-State Sodium Metal Batteries.

Sodium metal batteries are an emerging technology that shows promise in terms of materials availability with respect to lithium batteries. Solid electrolytes are needed to tackle the safety issues related to sodium metal. In this work, a simple method to prepare a mechanically robust and efficient soft solid electrolyte for sodium batteries is demonstrated. A task-specific iongel electrolyte was prepared by combining in a simple process the excellent performance of sodium metal electrodes of an ionic liquid electrolyte and the mechanical properties of polymers. The iongel was synthesized by fast (<1 min) UV photopolymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of a saturated 42%mol solution of sodium bis(fluorosulfonyl)imide (NaFSI) in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide (P111i4FSI). The resulting soft solid electrolytes showed high ionic conductivity at room temperature (≥10−3 S cm−1) and tunable storage modulus (104−107 Pa). Iongel with the best ionic conductivity and good mechanical properties (Iongel10) showed excellent battery performance: Na/iongel/NaFePO4 full cells delivered a high specific capacity of 140 mAh g−1 at 0.1 C and 120 mAh g−1 at 1 C with good capacity retention after 30 cycles.

Influence of Anion Structure on Thermal, Mechanical and CO2 Solubility Properties of UV-Cross-Linked Poly(ethylene glycol) Diacrylate Iongels.

Iongel-based CO2 separation membranes were prepared by fast (< 1 min) UV-initiated polymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of different ionic liquids (ILs) with the [C2mim]+ cation and anions such as [TFSI]-, [FSI]-, [C(CN)3]- and [B(CN)4]-. The four ILs were completely miscible with the non-ionic PEGDA network. Transparent and free-standing iongels containing between 60 and 90 %wt of IL were obtained and characterized by diverse techniques (FTIR, TGA, DSC, DMTA, SEM, CO2 solubility and pure gas permeability). The thermal and mechanical stability of the iongels, as well as CO2 solubility, were found to be strictly dependent on the IL content and the anion's nature. The TGA results indicated that the iongels mostly follow the thermal profile of the respective neat ILs. The DMTA analysis revealed that the iongels based on fluorinated anions have higher storage modulus than those of cyano-functionalized anions. Conversely, the PEGDA-C(CN)3 iongels presented the highest CO2 solubility values ranging from 72 to 80 mmol/g. Single CO2 permeabilities of 583 ± 29 Barrer and ideal CO2/N2 selectivities of 66 ± 3 were obtained with the PEGDA-70 C(CN)3 iongel membrane. This work demonstrates that the combination of PEGDA with high contents of the best performing ILs is a promising and simple strategy, opening up new possibilities in the design of high-performance iongel membranes for CO2 separation.

High Coulombic Efficiency Na-O2 Batteries Enabled by a Bilayer Ionogel/Ionic Liquid.

Sodium-oxygen (Na-O2) cells are a promising high energy density storage technology with a theoretical specific energy of 1605 Wh kg-1. However, this technology faces certain challenges in order to achieve both a high practical energy density as well as long-term cycling capability. In this Letter, a superior Coulombic cyclic efficiency, close to 100%, has been demonstrated by the use of a bilayer electrolyte composed of an ionogel and an ionic liquid electrolyte, reported herein for the first time. The presence of the ionogel plays a major role in the prevention of side reactions originating at the anode, providing a promising route to extend cell cycling, whereas the ionic liquid is essential to support high reaction rates at the cathode.