All-solid-state lithium metal batteries (SS-LMBs) are expected to meet the strong requirements of the automotive sector in terms of performance and safety. Among the different solid electrolytes, poly(vinylidene fluoride) (PVDF)-based systems offer good performance in terms of ionic conductivity and stability at the anodic interface. However, despite the high polymer permittivity (ϵ′ ≈ 10-11) which should allow efficient salt dissociation, there is growing evidence that the ionic transport requires the presence of a non-negligible amount of residual, or permanent, solvent in the membrane. In this paper, we study the Li+ transport mechanism in a model system consisting of poly(vinylidene fluoride-co-hexafluoropropylene) (PFDF-HFP), lithium bis(fluorosulfonyl)imide (LiFSI) salt, and dimethylformamide (DMF) as permanent solvent, combining a large set of experimental techniques (thermal analysis, NMR, IR and Raman spectroscopy, impedance spectroscopy) and accurate density functional theory (DFT) modeling. We show that Li+-DMF interactions are predominant in these quasi-solid electrolytes (QSEs) and are the basis of the effective ion transport mechanism. Permanent solvent amounts on the order of [DMF]/[Li+] ∼ 2-3 are required to make QSEs able to practically work in a real environment.
Vallana, N., Carena, E., Ceribelli, N., Mezzomo, L., Di Liberto, G., Mauri, M., et al. (2024). Host–Guest Interactions and Transport Mechanism in Poly(vinylidene fluoride)-Based Quasi-Solid Electrolytes for Lithium Metal Batteries. ACS APPLIED ENERGY MATERIALS, 7(4), 1606-1617 [10.1021/acsaem.3c03046].
Host–Guest Interactions and Transport Mechanism in Poly(vinylidene fluoride)-Based Quasi-Solid Electrolytes for Lithium Metal Batteries
Vallana, NicholasPrimo
;Carena, Eleonora;Ceribelli, Nicole;Mezzomo, Lorenzo;Di Liberto, Giovanni;Mauri, Michele;Ferrara, Chiara;Lorenzi, Roberto;Giordano, Livia;Ruffo, Riccardo;Mustarelli, Piercarlo
Ultimo
2024
Abstract
All-solid-state lithium metal batteries (SS-LMBs) are expected to meet the strong requirements of the automotive sector in terms of performance and safety. Among the different solid electrolytes, poly(vinylidene fluoride) (PVDF)-based systems offer good performance in terms of ionic conductivity and stability at the anodic interface. However, despite the high polymer permittivity (ϵ′ ≈ 10-11) which should allow efficient salt dissociation, there is growing evidence that the ionic transport requires the presence of a non-negligible amount of residual, or permanent, solvent in the membrane. In this paper, we study the Li+ transport mechanism in a model system consisting of poly(vinylidene fluoride-co-hexafluoropropylene) (PFDF-HFP), lithium bis(fluorosulfonyl)imide (LiFSI) salt, and dimethylformamide (DMF) as permanent solvent, combining a large set of experimental techniques (thermal analysis, NMR, IR and Raman spectroscopy, impedance spectroscopy) and accurate density functional theory (DFT) modeling. We show that Li+-DMF interactions are predominant in these quasi-solid electrolytes (QSEs) and are the basis of the effective ion transport mechanism. Permanent solvent amounts on the order of [DMF]/[Li+] ∼ 2-3 are required to make QSEs able to practically work in a real environment.File | Dimensione | Formato | |
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