Effects of LiBOB on salt solubility and BiF₃ electrode electrochemical properties in fluoride shuttle batteries

Abstract

Using lithium bis(oxalato)borate for a fluoride shuttle battery in organic solvents allowed a successful fluoride shuttle-based redox reaction.

Study of Behavior of Supporting Electrolyte Ion of Fluoride Shuttle Battery Using Anomalous X‐Ray Scattering

“…The interactions between fluoride ions and CH 2 groups were studied by NMR spectroscopy. [ 10,58,59 ] The 19 F NMR spectrum of 1‐methyl‐3‐phenyl‐1 H ‐naphtho[2,3‐ d ]imidazole and KPF 6 in CH 3 CN showed the peaks for free F − and (C–H) + ··· F − at −115.4 and −150.9 ppm. [ 59 ] Similar (C–H) + ··· F − ionic hydrogen‐bond interactions have been observed in the macrocyclic polyethers studied by 1 H and 19 F NMR spectroscopies.…”

“…The small signals at around −148 ppm of these three electrolytes may be attributed to the (C–H) + ··· F − interaction of F − ions with CH 2 groups of G4, as observed in the 19 F NMR spectra of the CsF/LiBOB/G4 electrolytes. [ 10 ] The low intensities of the signals suggest that the (C–H) + ··· F − interactions are not dominant in these electrolytes.…”

“…Liquid electrolytes also show high ionic conductivities as high as crystalline solid electrolytes. [ 7–10 ] Many types of electrolytes are investigated to find the best composition, which has high ionic conductivity, wide stability window range, high capacity, etc. A pair of an electrolyte compound of an organic solvent and a supporting electrolyte salt such as a fluoride compound should be selected by considering the electrochemical reaction in a liquid‐based electrolyte over a wide potential range.…”

“…[ 13 ] Moreover, lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(oxalato)borate (LiBOB) are added to improve solubility and ionic conductivity. [ 10,14–17 ] To develop efficient electrolytes for the FSB, it is necessary to understand the local structure of the electrolyte which is related to the electronic transfer.…”

Nanoscale Defluorination Mechanism and Solid Electrolyte Interphase of a MgF2 Anode in Fluoride-Shuttle Batteries

“…Fluoride-shuttle batteries, which utilize fluoride ion (F – ) transfer between electrodes, are one of the candidates as next-generation batteries due to their potential to achieve higher energy density than the lithium-ion batteries. , The concept of this battery was reported in 1970s. , Reddy and Fichtner in 2011 demonstrated the first reversible cycling performance in an all-solid-state fluoride-shuttle battery, and it has attracted significant attention ever since. − There are many types of metal/metal fluorides, thus making it possible to achieve a high voltage cell by exploring suitable combinations of cathode and anode materials with an appropriate fluoride ion conductivity electrolyte. Then, in a defluorination process based on a conversion reaction of metal/metal fluorides in the electrodes, multiple electron reactions can be promoted by moving single-charged anions of F – in electrolytes.…”