Influence of Solvent Evaporation Temperature on the Performance of Ternary Solid Polymer Electrolytes Based on Poly(vinylidene fluoride-co-hexafluoropropylene) Combining an Ionic Liquid and a Zeolite.

Solid polymer electrolytes (SPEs) will allow improving safety and durability in next-generation solid-state lithium-ion batteries (LIBs). Within the SPE class, ternary composites are a suitable approach as they provide high room-temperature ionic conductivity and excellent cycling and electrochemical stability. In this work, ternary SPEs based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) as a polymer host, clinoptilolite (CPT) zeolite, and 1-butyl-3-methylimidazolium thiocyanate ([Bmim][SCN])) ionic liquid (IL) as fillers were produced by solvent evaporation at different temperatures (room temperature, 80, 120, and 160 °C). Solvent evaporation temperature affects the morphology, degree of crystallinity, and mechanical properties of the samples as well as the ionic conductivity and lithium transference number. The highest ionic conductivity (1.2 × 10-4 S·cm-1) and lithium transference number (0.66) have been obtained for the SPE prepared at room temperature and 160 °C, respectively. Charge-discharge battery tests show the highest value of discharge capacity of 149 and 136 mAh·g-1 at C/10 and C/2 rates, respectively, for the SPE prepared at 160 °C. We conclude that the fine control of the solvent evaporation temperature during the preparation of the SPE allows us to optimize solid-state battery performance.

High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State 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.

Toward Sustainable Solid Polymer Electrolytes for Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) are the most widely used energy storage system because of their high energy density and power, robustness, and reversibility, but they typically include an electrolyte solution composed of flammable organic solvents, leading to safety risks and reliability concerns for high-energy-density batteries. A step forward in Li-ion technology is the development of solid-state batteries suitable in terms of energy density and safety for the next generation of smart, safe, and high-performance batteries. Solid-state batteries can be developed on the basis of a solid polymer electrolyte (SPE) that may rely on natural polymers in order to replace synthetic ones, thereby taking into account environmental concerns. This work provides a perspective on current state-of-the-art sustainable SPEs for lithium-ion batteries. The recent developments are presented with a focus on natural polymers and their relevant properties in the context of battery applications. In addition, the ionic conductivity values and battery performance of natural polymer-based SPEs are reported, and it is shown that sustainable SPEs can become essential components of a next generation of high-performance solid-state batteries synergistically focused on performance, sustainability, and circular economy considerations.

Lithium-Ion Battery Solid Electrolytes Based on Poly(vinylidene Fluoride)-Metal Thiocyanate Ionic Liquid Blends.

Solid polymer electrolytes (SPEs) are required to improve battery safety through the elimination of the liquid electrolyte solution in current batteries. This work is focused on the development of a hybrid SPE based on poly(vinylidene fluoride), PVDF, and 1-butyl-3-methylimidazolium cobalt(II) isothiocyanate, [BMIM]2[(SCN)4Co] magnetic ionic liquid (MIL), and its battery cycling behavior at room temperature. The addition of MIL in filler contents up to 40 wt % to the PVDF matrix does not influence the compact morphology of the samples obtained by solvent casting. The polar ß-phase of PVDF increases with increasing MIL content, whereas the degree of crystallinity, thermal degradation temperature, and mechanical properties of the MIL/PVDF blends decrease with increasing MIL content. The ionic conductivity of the MIL/PVDF blends increases both with temperature and MIL content, showing the highest ionic conductivity of 7 × 10-4 mS cm-1 at room temperature for the MIL/PVDF blend with 40 wt % of MIL. The cathodic half-cells prepared with this blend as SPE show good reversibility and excellent cycling behavior at different C-rates, with a discharge capacity of 80 mAh g-1 at a C/10-rate with a Coulombic efficiency of 99%. The developed magnetic SPE, with excellent performance at room temperature, shows potential for the implementation of sustainable lithium-ion batteries, which can be further tuned by the application of an external magnetic field.

High-Performance Room Temperature Lithium-Ion Battery Solid Polymer Electrolytes Based on Poly(vinylidene fluoride-co-hexafluoropropylene) Combining Ionic Liquid and Zeolite.

The demand for more efficient energy storage devices has led to the exponential growth of lithium-ion batteries. To overcome the limitations of these systems in terms of safety and to reduce environmental impact, solid-state technology emerges as a suitable approach. This work reports on a three-component solid polymer electrolyte system based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), the ionic liquid 1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN]), and clinoptilolite zeolite (CPT). The influences of the preparation method and of the dopants on the electrolyte stability, ionic conductivity, and battery performance were studied. The developed electrolytes show an improved room temperature ionic conductivity (1.9 × 10-4 S cm-1), thermal stability (up to 300 °C), and mechanical stability. The corresponding batteries exhibit an outstanding room temperature performance of 160.3 mAh g-1 at a C/15-rate, with a capacity retention of 76% after 50 cycles. These results represent a step forward in a promising technology aiming the widespread implementation of solid-state batteries.

Recent Advances in Poly(vinylidene fluoride) and Its Copolymers for Lithium-Ion Battery Separators.

The separator membrane is an essential component of lithium-ion batteries, separating the anode and cathode, and controlling the number and mobility of the lithium ions. Among the polymer matrices most commonly investigated for battery separators are poly(vinylidene fluoride) (PVDF) and its copolymers poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and poly(vinylidene fluoride-cochlorotrifluoroethylene) (PVDF-CTFE), due to their excellent properties such as high polarity and the possibility of controlling the porosity of the materials through binary and ternary polymer/solvent systems, among others. This review presents the recent advances on battery separators based on PVDF and its copolymers for lithium-ion batteries. It is divided into the following sections: single polymer and co-polymers, surface modification, composites, and polymer blends. Further, a critical comparison between those membranes and other separator membranes is presented, as well as the future trends on this area.