RESUMEN
Solid-state polymer electrolytes (SPEs), such as poly(ethylene oxide) (PEO), have good flexibility when compared to ceramic-type solid electrolytes. Therefore, it could be an ideal solid electrolyte for zero-excess all-solid-state Li metal battery (ZESSLB), also known as anode-free all-solid-state Li battery, development by offering better contact to the Cu current collector. However, the low Coulombic efficiencies observed from polymer type solid-state Li batteries (SSLBs) raise the concern that PEO may consume the limited amount of Li in ZESSLB to fail the system. Here, we designed ZESSLBs by using all-ceramic half-cells and an extra PEO electrolyte interlayer to study the reactivity between PEO and freshly deposited Li under a real battery operating conduction. By shuttling active Li back from the anode to the cathode, the PEO SPEs can be separated from the ZESSLBs for experimental studies without the influence from cathode materials or possible contamination from the usage of Li foil as the anode. Electrochemical cycling of ZESSLBs shows that the capacities of ZESSLBs with solvent-free and solvent-casted PEO SPEs significantly degraded compared to the ones with Li metal as the anode for the all-solid-state Li batteries. The fast capacity degradation of ZESSLBs using different types of PEO SPEs is evidenced to be associated with Li reacting with PEO, residual solvent, and water in PEO and dead Li formation upon the presence or absence of residual solvent. The results suggest that avoiding direct contact between the PEO electrolyte and deposited lithium is necessary when there is only a limited amount of Li available in ZESSLBs.
RESUMEN
Solid-state batteries are considered the next big step towards the realization of intrinsically safer high-energy lithium batteries for the steadily increasing implementation of this technology in electronic devices and particularly, electric vehicles. However, so far only electrolytes based on poly(ethylene oxide) have been successfully commercialized despite their limited stability towards oxidation and low ionic conductivity at room temperature. Block copolymer (BCP) electrolytes are believed to provide significant advantages thanks to their tailorable properties. Thus, research activities in this field have been continuously expanding in recent years with great progress to enhance their performance and deepen the understanding towards the interplay between their chemistry, structure, electrochemical properties, and charge transport mechanism. Herein, we review this progress with a specific focus on the block-copolymer nanostructure and ionic conductivity, the latest works, as well as the early studies that are fr"equently overlooked by researchers newly entering this field. Moreover, we discuss the impact of adding a lithium salt in comparison to single-ion conducting BCP electrolytes along with the encouraging features of these materials and the remaining challenges that are yet to be solved.
RESUMEN
Three types of chloride-conducting membranes based on polyvinyl chloride, commercial gelatin, and polyvinyldifluoride-hexafluoropolymer are introduced in this report. The polymers are mixed with chloride-containing salts, such as tetrabutylammonium chloride, and cast to form membranes. We studied the structural properties, thermal stability, and electrochemical response of the membranes to understand chloride migration and transport. Finally, the membranes are tested in a prototype solid-state chloride-ion battery setup. The feasibility of the membranes for their potential use in anion batteries is discussed.
RESUMEN
One of the problems that arise with bifluoride- or fluoride-containing compounds is their poor solubility in non-aqueous solvents. We report herein a facile one-pot synthesis and the chemical analysis of fluoride/bifluoride-containing polymers, which are soluble in MeCN. Different polymers, such as Polyvinylacetate or Polyethylene imine and saccharides, such as maltodextrin, were complexed with ammonium (bi)fluoride using hydrogen bonds to form the desired (bi)fluoride-containing compounds. The newly formed hydrogen bonding (bi)fluoride-doped polymer matrices were analyzed using infrared and nuclear magnetic resonance spectroscopies, and X-ray diffraction. The promising materials also underwent impedance spectroscopy, conductivity measurements and preliminary tests as electrolytes for room temperature fluoride ion batteries along with an analysis of their performance.