Autor(es): Barbosa, João C. ; Correia, Daniela Maria Silva ; Fidalgo-Marijuan, Arkaitz ; Gonçalves, Renato Ferreira ; Ferdov, S. ; de Zea Bermudez, Verónica ; Lanceros-Méndez, S. ; Costa, Carlos Miguel Silva
Data: 2023
Identificador Persistente: https://hdl.handle.net/1822/93621
Origem: RepositóriUM - Universidade do Minho
Assunto(s): ternary composites; PVDF copolymers; lithium salt and ionic liquids; solid polymer electrolytes; lithium-ion batteries
Renewable energy sources require efficient energy storage systems. Lithium-ion batteries stand out among those systems, but safety and cycling stability problems still need to be improved. This can be achieved by the implementation of solid polymer electrolytes (SPE) instead of the typically used separator/electrolyte system. Thus, ternary SPEs have been developed based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene), P(VDF-TrFE-CFE) as host polymers, clinoptilolite (CPT) zeolite added to stabilize the battery cycling performance, and ionic liquids (ILs) (1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN])), 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([PMPyr][TFSI]) or lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), incorporated to increase the ionic conductivity. The samples were processed by doctor blade with solvent evaporation at 160 °C. The nature of the polymer matrix and fillers affect the morphology and mechanical properties of the samples and play an important role in electrochemical parameters such as ionic conductivity value, electrochemical window stability, and lithium-transference number. The best ionic conductivity (4.2 × 10–5 S cm–1) and lithium transference number (0.59) were obtained for the PVDF-HFP-CPT-[PMPyr][TFSI] sample. Charge–discharge battery tests at C/10 showed excellent battery performance with values of 150 mAh g–1 after 50 cycles, regardless of the polymer matrix and IL used. In the rate performance tests, the best SPE was the one based on the P(VDF-TrFE-CFE) host polymer, with a discharge value at C-rate of 98.7 mAh g–1, as it promoted ionic dissociation. This study proves for the first time the suitability of P(VDF-TrFE-CFE) as SPE in lithium-ion batteries, showing the relevance of the proper selection of the polymer matrix, IL type, and lithium salt in the formulation of the ternary SPE, in order to optimize solid-state battery performance. In particular, the enhancement of the ionic conductivity provided by the IL and the effect of the high dielectric constant polymer P(VDF-TrFE-CFE) in improving battery cyclability in a wide range of discharge rates must be highlighted.
