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High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State Lithium-Ion Batteries

[Image: see text] 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...

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Autores principales: Barbosa, João C., Correia, Daniela M., Fidalgo-Marijuan, Arkaitz, Gonçalves, Renato, Ferdov, Stanislav, de Zea Bermudez, Verónica, Lanceros-Mendez, Senentxu, Costa, Carlos M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10347132/
https://www.ncbi.nlm.nih.gov/pubmed/37379238
http://dx.doi.org/10.1021/acsami.3c03361
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author Barbosa, João C.
Correia, Daniela M.
Fidalgo-Marijuan, Arkaitz
Gonçalves, Renato
Ferdov, Stanislav
de Zea Bermudez, Verónica
Lanceros-Mendez, Senentxu
Costa, Carlos M.
author_facet Barbosa, João C.
Correia, Daniela M.
Fidalgo-Marijuan, Arkaitz
Gonçalves, Renato
Ferdov, Stanislav
de Zea Bermudez, Verónica
Lanceros-Mendez, Senentxu
Costa, Carlos M.
author_sort Barbosa, João C.
collection PubMed
description [Image: see text] 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.
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spelling pubmed-103471322023-07-15 High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State Lithium-Ion Batteries Barbosa, João C. Correia, Daniela M. Fidalgo-Marijuan, Arkaitz Gonçalves, Renato Ferdov, Stanislav de Zea Bermudez, Verónica Lanceros-Mendez, Senentxu Costa, Carlos M. ACS Appl Mater Interfaces [Image: see text] 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. American Chemical Society 2023-06-28 /pmc/articles/PMC10347132/ /pubmed/37379238 http://dx.doi.org/10.1021/acsami.3c03361 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Barbosa, João C.
Correia, Daniela M.
Fidalgo-Marijuan, Arkaitz
Gonçalves, Renato
Ferdov, Stanislav
de Zea Bermudez, Verónica
Lanceros-Mendez, Senentxu
Costa, Carlos M.
High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State Lithium-Ion Batteries
title High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State Lithium-Ion Batteries
title_full High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State Lithium-Ion Batteries
title_fullStr High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State Lithium-Ion Batteries
title_full_unstemmed High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State Lithium-Ion Batteries
title_short High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State Lithium-Ion Batteries
title_sort high performance ternary solid polymer electrolytes based on high dielectric poly(vinylidene fluoride) copolymers for solid state lithium-ion batteries
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10347132/
https://www.ncbi.nlm.nih.gov/pubmed/37379238
http://dx.doi.org/10.1021/acsami.3c03361
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