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

Hui-Xian Li; Lei Hou; Pei-Yi Wu

doi:10.1007/s10118-021-2571-6

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

ARTICLE | Updated：2021-06-04

- Transport of Propylene Carbonate-LiTFSI Electrolytes in P(VDF-HFP) Using Time-resolved ATR-FTIR Spectroscopy: Diffusion Coefficients and Molecular Interactions
- Chinese Journal of Polymer Science Vol. 39, Issue 8, Pages: 975-983(2021)
- Affiliations：
  
  1.National Engineering Research Center for Dyeing and Finishing of Textiles, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, China
- Author bio：
  
  houlei@dhu.edu.cn (L.H.)
  wupeiyi@dhu.edu.cn (P.Y.W.)
- Funds：
- DOI：10.1007/s10118-021-2571-6
  CLC：
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Hui-Xian Li, Lei Hou, Pei-Yi Wu. Transport of Propylene Carbonate-LiTFSI Electrolytes in P(VDF-HFP) Using Time-resolved ATR-FTIR Spectroscopy: Diffusion Coefficients and Molecular Interactions. [J]. Chinese Journal of Polymer Science 39(8):975-983(2021)
DOI：

Hui-Xian Li, Lei Hou, Pei-Yi Wu. Transport of Propylene Carbonate-LiTFSI Electrolytes in P(VDF-HFP) Using Time-resolved ATR-FTIR Spectroscopy: Diffusion Coefficients and Molecular Interactions. [J]. Chinese Journal of Polymer Science 39(8):975-983(2021) DOI： 10.1007/s10118-021-2571-6.

摘要

Abstract

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 TFSI,−, 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＝O 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.

关键词

Keywords

ATR-FTIR spectroscopyGel polymer electrolyteTransport mechanismMolecular interactionDiffusion coefficient

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