Solvent-Free Procedure for the Preparation under Controlled Atmosphere Conditions of Phase-Segregated Thermoplastic Polymer Electrolytes

Abstract

A solvent-free method that allows thermoplastic solid electrolytes based on poly(ethylene oxide) PEO to be obtained under controlled atmosphere conditions is presented. This method comprises two steps, the first one being the melt compounding of PEO with a filler, able to physically crosslink the polymer and its pelletizing, and the second the pellets’ swelling with an electroactive liquid phase. This method is an adaptation of the step described in previous publications of the preparation of thermoplastic electrolytes by a single melt compounding. In comparison to the single step extrusion methodology, this new method permits employing electroactive species that are very sensitive to atmospheric conditions. The two-step method can also be designed to produce controlled phase-segregated morphologies in the electrolyte, namely polymer-poor and polymer-rich phases, with the aim of increasing ionic conductivity over that of homogeneous electrolytes. An evaluation of the characteristics of the electrolytes prepared by single and two-step procedures is done by comparing membranes prepared by both methods using PEO as a polymeric scaffold and a solution of the room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EMI TFSI) and the bis(trifluoromethanesulfonyl) imide lithium salt (Li TFSI) as liquid phase. The electrolytes prepared by both methods have been characterized by Fourier transform infrared spectroscopy and optic microscopy profilometry, differential scanning calorimetry, self-creep experiments, and dielectric spectroscopy. In this way, the phase separation, rheology, and ionic conductivity are studied and compared. It is striking how the electrolytes prepared with this new method maintain their solid-like behavior even at 90 °C. Compared to the single step method, the two-step method produces electrolytes with a phase-separated morphology, which results in higher ionic conductivity.

Challenges in Solvent-Free Methods for Manufacturing Electrodes and Electrolytes for Lithium-Based Batteries

“…Finally, the pellets were compressed to form a film. This process resulted in amorphous PEO and a solid-polymer electrolyte above 90 • C. However, the ionic conductivity at 25 • C is of the same order of magnitude, i.e., 10 −4 S.cm −1 , as the one made with the one step procedure [49]. Moreover, the two-step procedure seems difficult to apply on an industrial scale.…”

“…Finally, the electrolyte was shaped by compression molding in a 1 mm thick mold at 120 • C [41]. Following this attempt, it appears that extrusion with Li salt was not performed until ten years later by Tiemblo's group, who has since become very active in improving their extrusion process [12,[42][43][44][45][46][47][48][49]. In 2014, Mejia et al physically pre-mixed PEO, LiTf, sepiolite (surface modified or not) and EC or a mixture of EC and PC.…”

“…The one step procedure consists of mixing and extruding all the components together while the twostep procedure begins with the extrusion and pelletization of PEO and sepiolite which is followed by swelling the pellets in a liquid mixture of EMITFSI + LiTFSI. Reprinted with permission of Polymers 2019, 11, 406 [49].…”

“…Extrusion processes used by Tiemblo's group for hybrid polymer electrolytes of poly (ethylene oxide) (PEO), EMITFSI (or PYR 14 TFSI), LiTFSI, and surface-modified sepiolite (TPGS-S).The one step procedure consists of mixing and extruding all the components together while the twostep procedure begins with the extrusion and pelletization of PEO and sepiolite which is followed by swelling the pellets in a liquid mixture of EMITFSI + LiTFSI. Reprinted with permission of Polymers 2019, 11, 406[49].…”

Roadmap for Competitive Production of Solid‐State Batteries: How to Convert a Promise into Reality

“…In order to avoid the use of toxic organic volatile solvents, dry powder to thin film melt processing based on extrusion is rising an unusually high interest attending to economic and environmental reasons. [46,47] Furthermore, solvent-free processing is a good option for large scale cell assembly production. [48] In brief, in the extrusion process, high quality raw materials are initially blended to create a homogenous mixture.…”