Thermodynamics and kinetic analysis of membrane: Challenges and perspectives.

The ultimate structure of the membrane is determined using two important effects: (i) thermodynamic effect and (ii) kinetic effect. Controlling the mechanism of kinetic and thermodynamic processes in phase separation is essential for enhancing membrane performance. However, the relationship between system parameters and the ultimate membrane morphology is still largely empirical. This review focuses on the fundamental ideas behind thermally induced phase separation (TIPS) and nonsolvent-induced phase separation (NIPS) methods, including both kinetic and thermodynamic elements. The thermodynamic approach to understanding phase separation and the effect of different interaction parameters on membrane morphology has been discussed in detail. Furthermore, this review explores the capabilities and limitations of different macroscopic transport models used for the last four decades to explore the phase inversion process. The application of molecular simulations and phase field to understand phase separation has also been briefly examined. Finally, it discusses the thermodynamic approach to understanding phase separation and the consequence of different interaction parameters on membrane morphology, as well as possible directions for artificial intelligence to fill the gaps in the literature. This review aims to provide comprehensive knowledge and motivation for future modeling work for membrane fabrication via new techniques such as nonsolvent-TIPS, complex-TIPS, non-solvent assisted TIPS, combined NIPS-TIPS method, and mixed solvent phase separation.

Artificial intelligence and structural design of inorganic hollow fiber membranes: Materials chemistry.

A key challenge is to produce the uniform morphology and regular pore design of inorganic hollow fiber membranes (HFMs) due to involvement of multiple parameters including, fabrication process and materials chemistry. Inorganic HFMs required technical innovations via novel structural design and artificial intelligence (AI) to produce the uniform structure and regular pore design. Therefore, this review aims at critical analysis on the most recent and relevant approaches to tackle the issues related to tune the morphology and pore design of inorganic HFMs. Structural design and evaluation of routes towards the dope suspension, spinning, and sintering of inorganic HFMs are critically analysed. AI, driving forces and challenges involved for harnessing of materials are revealed in this review. AI programs used for the prediction of pore design and performance of HFMs have also been explained in this review. Overall, this review will provide the understanding to build the equilibrium in spinning and sintering processes to control the design of micro-channels, and structural properties of inorganic HFMs. This review has great significance to control the new design of membranes via AI programs. This review also explain the inorganic membrane efficiency as algal-bioreactor.

Highly Efficient Production of Nanoporous Block Copolymers with Arbitrary Structural Characteristics for Advanced Membranes.

The great significance of boosting the design of percolating nanopore structures in block copolymers (BCPs) for various cases has been widely demonstrated in the past several decades. However, it still remains challenging to prepare the desired porous structures in a rapid, facile, and universal manner. Here we have developed an unconventional and benchtop strategy to rapidly generate the nanoporous polystyrene-based BCPs with arbitrary structural characteristics regardless of the BCP bulk morphology. This universal pore-forming strategy enables the sustainable CO2 -based BCPs to form advanced membranes after 1 s soaking for efficiently rejecting 94.2 % brilliant blue R (826 g mol-1 ). Meanwhile, the water permeance retains around 1020 L (m2 h bar)-1 , which is 1-3 orders of magnitude higher than that of other membranes. This strategy may offer an excellent opportunity to introduce percolating pore structures in those newly developed BCPs with which the previously reported pore-forming methods may not deal.

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.

Synthesis of Sub-10 nm Two-Dimensional Covalent Organic Thin Film with Sharp Molecular Sieving Nanofiltration.

We demonstrated here a novel and facile synthesis of two-dimensional (2D) covalent organic thin film with pore size around 1.5 nm using a planar, amphiphilic and substituted heptacyclic truxene based triamine and a simple dialdehyde as building blocks by dynamic imine bond formation at the air/water interface using Langmuir-Blodgett (LB) method. Optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM), all unanimously showed the formation of large, molecularly thin and free-standing membrane that can be easily transferred on different substrate surfaces. The 2D membrane supported on a porous polysulfone showed a rejection rate of 64 and 71% for NaCl and MgSO4, respectively, and a clear molecular sieving at molecular size around 1.3 nm, which demonstrated a great potential in the application of pretreatment of seawater desalination and separation of organic molecules.

Surface modification of sulfur electrodes by chemically anchored cross-linked polymer coating for lithium-sulfur batteries.

Lithium-sulfur batteries suffer from severe self-discharge due to polysulfide dissolution into electrolytes. In this work, a chemically anchored polymer-coated (CAPC) sulfur electrode was prepared, through chemical bonding by coordinated Cu ions and cross-linking, to improve cyclability for Li/S batteries. This electrode retained specific capacities greater than 665 mAh g(-1) at high current density of 3.35 A g(-1) (2C rate) after 100 cycles with an excellent Coulombic efficiency of 100%.