Transport of Propylene Carbonate-LiTFSI Electrolytes in P(VDF-HFP) Using Time-resolved ATR-FTIR Spectroscopy: Diffusion Coefficients and Molecular Interactions
Transport of Propylene Carbonate-LiTFSI Electrolytes in P(VDF-HFP) Using Time-resolved ATR-FTIR Spectroscopy: Diffusion Coefficients and Molecular Interactions
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使用时间分辨 ATR-FTIR 光谱传输 P(VDF-HFP) 中的碳酸丙烯酯-LiTFSI 电解质：扩散系数和分子相互作用
DOI：
10.1007/s10118-021-2571-6
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发表时间：
2021-06
影响因子：
4.3
通讯作者：
Wu Pei-Yi
中科院分区：
文献类型：
--
作者：
Li Hui-Xian;Hou Lei;Wu Pei-Yi
利用时间分辨衰减全反射傅里叶变换红外光谱(ATR-FTIR)研究了碳酸亚丙酯-双(三氟甲基磺酰亚胺)锂(PC-LiTFSI)溶液在聚偏氟乙烯-六氟丙烯(P(VDF-HFP))膜中的扩散行为，研究了凝胶电解质的传输机理。在TFSI−和PC中都观察到了费克行为。温度越高，TFSI−和PC的扩散速度越快，这可能与P(VDFHFP)基质中自由体积的增加和加热时分子的快速运动有关。LiTFSI、PC和P(VDF-HFP)之间的各种分子相互作用已经被认识到。在扩散过程中，PC分子以小团簇的形式首先通过P(VDF-HFP)膜扩散，并通过偶极-偶极相互作用与P(VDF-HFP)相互作用，起到增塑剂的作用。然后，Li+通过Li+与PC的C-O之间的离子-偶极相互作用扩散到P(VDF-HFP)中。同时，TFSI−以溶剂化状态通过聚合物基质扩散。此外，还观察到了Li+与P(VDF-HFP)之间轻微的离子-偶极相互作用。研究结果有助于更好地理解锂离子电池用凝胶聚合物电解液中的传输过程，并通过合理调节分子间的相互作用来支持改进的凝胶聚合物电解液的开发。
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.
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影响因子：
6.6
作者：
Babu, Binson;Shaijumon, M. M.
通讯作者：
Shaijumon, M. M.
DOI：
10.1021/acs.jpcb.9b11446
发表时间：
2020-02
期刊：
The journal of physical chemistry. B
影响因子：
--
作者：
Kyoungmin Kim;D. Hallinan
通讯作者：
Kyoungmin Kim;D. Hallinan
K2Nb8O21纳米管具有优异的电化学性能，可用于超稳定的锂存储
影响因子：
11.9
作者：
Xing Cheng;Haojie Zhu;Haoxiang Yu;Wuquan Ye;Runtian Zheng;Tingting Liu;Na Peng;Miao Shui;Jie Shu
通讯作者：
Jie Shu
DOI：
10.1002/anie.201712751
发表时间：
2018-06-18
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Baij L;Hermans JJ;Keune K;Iedema P
通讯作者：
Iedema P
影响因子：
27.8
作者：
Cheng, Hanlin;He, Xu;Ouyang, Jianyong
通讯作者：
Ouyang, Jianyong