Fabrication, Facilitating Gas Permeability, and Molecular Simulations of Porous Hypercrosslinked Polymers Embedding 6FDA-Based Polyimide Mixed-Matrix Membranes.

Novel polymers applied in economic membrane technologies are a perennial hot topic in the fields of natural gas purification and O2 enrichment. Herein, novel hypercrosslinked polymers (HCPs) incorporating 6FDA-based polyimide (PI) MMMs were prepared via a casting method for enhancing transport of different gases (CO2, CH4, O2, and N2). Intact HCPs/PI MMMs could be obtained due to good compatibility between the HCPs and PI. Pure gas permeation experiments showed that compared with pure PI film, the addition of HCPs effectively promotes gas transport, increases gas permeability, and maintains ideal selectivity. The permeabilities of HCPs/PI MMMs toward CO2 and O2 were as high as 105.85 Barrer and 24.03 Barrer, respectively, and the ideal selectivities of CO2/CH4 and O2/N2 were 15.67 and 3.00, respectively. Molecular simulations further verified that adding HCPs was beneficial to gas transport. Thus, HCPs have potential utility in fabrication of MMMs for facilitating gas transport in the fields of natural gas purification and O2 enrichment.

Construction of greenly biodegradable bacterial cellulose/UiO-66-NH2 composite separators for efficient enhancing performance of lithium-ion battery.

The disposal of waste lithium batteries, especially waste separators, has always been a problem, incineration and burial will cause environmental pollution, therefore, the development of degradable and high-performance separators has become an important challenge. Herein, UiO-66-NH2 particles were successfully anchored onto bacterial cellulose (BC) separators by epichlorohydrin (ECH) as a crosslinker, then a BC/UiO-66-NH2 composite separator was prepared by vacuum filtration. The ammonia groups (-NH2) from UiO-66-NH2 can form hydrogen bonds with PF6- in the electrolyte, promoting lithium-ion transference. Additionally, UiO-66-NH2 can store the electrolyte and tune the porosity of the separator. The lithium ion migration number (0.62) of the battery assembled with BC/UiO-66-NH2 composite separator increased by 50 % compared to the battery assembled with commercial PP separator (0.45). The discharge specific capacity of the battery assembled with BC/UIO-66-NH2 composite separator after 50 charge and discharge cycles is 145.4 mAh/g, which is higher than the average discharge specific capacity of 114.3 mAh/g of the battery assembled with PP separator. When the current density is 2C, the minimum discharge capacity of the battery assembled with BC/UiO-66-NH2 composite separator is 85.3 mAh/g. The electrochemical performance of the BC/UiO-66-NH2 composite separator is significantly better than that of the commercial PP separator. In addition, -NH2 can offer a nitrogen source to facilitate degradation of the BC separators, whereby the BC/UiO-66-NH2 composite separator could be completely degraded in 15 days.

Bismuth oxychloride nanosheets anchored aramid separator with sponge-like structure for improved lithium-ion battery performance.

Functional modification of inorganic particles is an effective approach to tackle the issue of Li+ transport and the lithium dendrites formation in lithium-ion batteries (LIBs). In this study, PMIA/BiOCl composite separators are prepared by nonsolvent induce phase separation (NIPS) method using P-type semiconductor bismuth oxychloride (BiOCl) functionalized poly (m-phenylene isophthalamide) (PMIA) separators. Compared with the polypropylene (PP) separator, PMIA has superior thermal stability and the addition of BiOCl further enhances its flame retardancy. And the prepared PMIA/BiOCl separator presents improved porosity (66.47 %), enhanced electrolyte uptake rate (863 %) and higher ionic conductivity (0.49 mS∙cm-1). Besides, the incorporation of BiOCl can anchor PF6- to the three-dimensional network skeleton of the PMIA/BiOCl separators, enabling the desolvation of Li+ and selectively facilitating Li+ transport (the Li+ transfer number is 0.79). Moreover, the uniform porous structure of the PMIA/BiOCl separators and the efficient transport of Li+ uniformly deposite Li+, and minimize the growth of lithium dendrites. Batteries assembled with PMIA/BiOCl separators have a discharge specific capacity of 124.4 mAh∙g-1 and capacity retention of 96.7 % after 200 cycles at 0.2C. Therefore, this work provides an effective route in the design strategy of separators for LIBs.

Synthesis of PMIA/MIL-101(Cr) composite separators with high Li+ transmission for boosting safety and electrochemical performance of lithium-ion batteries.

Energy storage devices require separators with sufficient lithium-ion transfer and restrained lithium dendrite growth. Herein, PMIA separators tuned using MIL-101(Cr) (PMIA/MIL-101) were designed and fabricated by a one-step casting process. At 150 °C, the Cr3+ in the MIL-101(Cr) framework sheds two water molecules to form an active metal site that complexes with PF6- in the electrolyte on the solid/liquid interface, leading to improved Li+ transport. The Li+ transference number of the PMIA/MIL-101 composite separator was found to be 0.65, which is about 3 times higher than that of the pure PMIA separator (0.23). Additionally, MIL-101(Cr) can modulate the pore size and porosity of the PMIA separator, while its porous structure also functions as additional storage space for the electrolyte, enhancing the electrochemical performance of the PMIA separator. After 50 charge/discharge cycles, batteries assembled using the PMIA/MIL-101 composite separator and the PMIA separator presented a discharge specific capacity of 120.4 and 108.6 mAh/g, respectively. The battery assembled using PMIA/MIL-101 composite separator significantly outperformed both the batteries assembled from pure PMIA and commercial PP separators in terms of cycling performance at 2 C, displaying a discharge specific capacity of 1.5 times that of the battery assembled from PP separators. The chemical complexation of Cr3+ and PF6- plays a critical role to improve the electrochemical performance of the PMIA/MIL-101 composite separator. The tunability and enhanced properties of the PMIA/MIL-101 composite separator make it a promising candidate for use in energy storage devices.

Facile fabrication of PMIA composite separator with bi-functional sodium-alginate coating layer for synergistically increasing performance of lithium-ion batteries.

Lack of safety and unenough electrochemical performance have been known as a fundamental obstacle limiting the extensive application of lithium-ion batteries (LIBs). It is really preferable but challenging to fabricate thermal-response separator with shutdown function for high-performance LIBs. Herein, a thermal-response sodium-alginate modified PMIA (Na-Alg/PMIA) composite separator with shutdown function was designed and prepared by non-solvent phase induced separation (NIPs). PMIA and Na-Alg are combined by hydrogen bonding. While Na-Alg increases polar groups and makes Li+ easy to be transported, a small amount of Na+ can provide Li+ active sites, accelerate Li+ deposition coating and effectively inhibit the formation of Li dendrites. The as-prepared Na-Alg/PMIA composite separators can close pores at 200 °C and maintain dimensional integrity without obvious thermal shrinkage. In addition, the Na-Alg/PMIA composite separators has excellent wettability and ionic conductivity, resulting in high specific capacity and retention during the charge-discharge cycles. After 50 cycles, the capacity retention of cells with the Na-Alg/PMIA-20 composite separator is 84.3 %. At 2 C, cells with the Na-Alg/PMIA-20 composite separators still held 101.1 mAh g-1. This facile yet effective method improves the electrochemical performance while ensuring the safety of the LIBs, which provides ideas for the commercial application of PMIA separators.