Scalable fabrication of Solvent-Free composite solid electrolyte by a continuous Thermal-Extrusion process.

Composite solid-state electrolytes (CSEs) are regarded as a promising alternative for the next-generation lithium-ion batteries because they integrate the advantages of inorganic electrolytes and organic electrolytes. However, there are two issues faced by current CSEs: 1) a green and feasible approach to prepare CSEs in large scales is desired; and 2) the trace solvents, remaining from the preparation processes, lead to some serious concerns, such as safety hazard issues, electrolyte-electrode interfacial issues, and reduced durability of batteries. Here, a continuous thermal-extrusion process is presented to realize the large-scale fabrication of solvent-free CSE. A 38.7-meter CSE membrane was prepared as a demonstration in this study. Thanks to the elimination of residual solvents, the electrolyte membrane exhibited a high tensile strength of 3.85 MPa, satisfactory lithium transference number (0.495), and excellent electrochemical stability (5.15 V). Excellent long-term stability was demonstrated by operating the symmetric lithium cell at a stable current density of 0.1 mA cm-2 for over 3700 h. Solvent-free CSE lithium metal batteries showed a discharge capacity of 155.7 - 25.17 mAh g-1 at 0.1 - 2.0C, and the discharge capacity remained 78.1% after testing for 380cycles.

Preparation of Highly Porous Polymer Membranes with Hierarchical Porous Structures via Spinodal Decomposition of Mixed Solvents with UCST Phase Behavior.

The predominant method to prepare polymer membranes is based on phase inversion. However, this method always leads to a dense skin with low porosity when normal polymers are used. Using the self-assembly of certain block copolymers, it is possible to prepare uniform pores with high porosity, but the prices of these polymers are too high to be afforded in practical applications. Here, we report a novel strategy to prepare highly porous and asymmetric polymer membranes using the widely used poly(vinylidene fluoride) (PVDF) as a prototype. The method combines spinodal decomposition with phase inversion utilizing mixed solvents that have the unique upper critical solution temperature phase behavior. The spinodal decomposition generates a thin surface layer containing a high density of relatively uniform pores in the mesoporous range, and the phase inversion generates a thick bulk layer composed of macrovoids; the two types of structures are interconnected, yielding a highly permeable, selective, and mechanically strong porous membrane. The membranes show an order of magnitude higher water permeance than commercial membranes and efficient molecular sieving of macromolecules. Notably, our strategy provides a general toolbox to prepare highly porous membranes from normal polymers. By blending PVDF with cellulose acetate (CA), a highly porous PVDF/CA membrane was prepared and showed similarly high separation performance, but the higher hydrophilicity of CA improved the membrane flux in the presence of proteins.