Transport of Propylene Carbonate-LiTFSI Electrolytes in P(VDF-HFP)Using Time-resolved ATR-FTIR Spectroscopy:Diffusion Coefficients and Molecular Interactions

摘要

The time-resolved attenuated total reflectance-Fourier transform infrared(ATR-FTIR)spectroscopy is employed to investigate the transport mechanism of gel electrolytes by monitoring the diffusion behavior of propylene carbonate-lithium bis(trifluoromethylsulfonyl)imide(PC-LiTFSI)solution through poly(vinylidene fluoride-co-hexafluoropropylene)(P(VDF-HFP))films.Fickian behavior has been observed for both TFSr and PC.Higher temperature leads to faster diffusion of TFSI'and PC,which could be related to the increased free volume in P(VDF-HFP)matrix and rapid molecular movements upon heating.Various molecular interactions among LiTFSI,PC and P(VDF-HFP)have been recognized.During the diffusion process,PC molecules,in the form of small clusters,can firstly diffuse through the P(VDF-HFP)film and interact with P(VDF-HFP)by dipole-dipole interaction,acting as the plasticizer.Then,Li+diffuses into P(VDF-HFP)with the help of ion-dipole interactions between Li+and C=0 of PC.Meanwhile,TFSI-diffuses through the polymer matrix in solvation states.In addition,slight ion-dipole interactions between Li+and P(VDF-HFP)have been observed as well.Results in this work contribute to a better understanding of transport process in gel polymer electrolytes for lithium-ion batteries and support the development of improved gel polymer electrolytes by rationally regulating molecular interactions.