Preparation and Performance of Lignin-Based Multifunctional Superhydrophobic Coating.

Superhydrophobic coatings have drawn much attention in recent years for their widespread potential applications. However, there are challenges to find a simple and cost-effective approach to prepare superhydrophobic materials and coatings using natural polymer. Herein, we prepared a kraft lignin-based superhydrophobic powder via modifying kraft lignin through 1H, 1H, 2H, 2H-perfluorodecyl-triethoxysilane (PFDTES) substitution reaction, and constructed superhydrophobic coatings by direct spraying the suspended PFDTES-Lignin powder on different substrates, including glass, wood, metal and paper. The prepared lignin-based coatings have excellent repellency to water, with a water contact angle of 164.7°, as well as good friction resistance, acid resistance, alkali resistance, salt resistance properties and quite good self-cleaning performance. After 30 cycles of sand friction or being stayed in 2 mol/L HCl, 0.25 mol/L NaOH and 2 mol/L NaCl solution for 30 min, the coatings still retain super hydrophobic capability, with contact angles higher than 150°. The superhydrophobic performance of PFDTES-Lignin coatings is mainly attributed to the constructed high surface roughness and the low surface energy afforded by modified lignin. This lignin-based polymer coating is low-cost, scalable, and has huge potential application in different fields, providing a simple way for the value-added utilization of kraft lignin.

Halloysite nanotubes enhanced polyimide/oxidized-lignin nanofiber separators for long-cycling lithium metal batteries.

The high energy density and robust cycle properties of lithium-ion batteries contribute to their extensive range of applications. Polyolefin separators are often used for the purpose of storing electrolytes, hence ensuring the efficient internal ion transport. Nevertheless, the electrochemical performance of lithium-ion batteries is constrained by its limited interaction with electrolytes and poor capacity for cation transport. This work presents the preparation of a new bio-based nanofiber separator by combining oxidized lignin (OL) and halloysite nanotubes (HNTs) with polyimide (PI) using an electrospinning technique. Analysis was conducted to examine and compare the structure, morphology, thermal characteristics, and EIS of the separator with those of commercially available polypropylene separator (PP). The results indicate that the PI@OL and PI-OL@ 10 % HNTs separators exhibit higher lithium ion transference number and ionic conductivity. Moreover, the use of HNTs successfully impeded the proliferation of lithium dendrites, hence exerting a beneficial impact on both the cycle performance and multiplier performance of the battery. Consequently, after undergoing 300 iterations, the battery capacity of LiFePO4|PI-OL@ 10 % HNTs|Li stays at 92.1 %, surpassing that of PP (86.8 %) and PI@OL (89.6 %). These findings indicate that this new bio-based battery separator (PI-OL@HNTs) has the great potential to serve as a substitute for the commonly used PP separator in lithium metal batteries.

A novel high-performance electrospun of polyimide/lignin nanofibers with unique electrochemical properties and its application as lithium-ion batteries separators.

Polypropylene is currently one of the most widely used separators in lithium batteries because of its low cost and chemical stability. However, it also has some intrinsic flaws that hamper the battery performance, such as poor wettability, low ionic conductivity, and some safety issues. This work introduces a novel electrospun nanofibrous consisting of polyimide (PI) blended with lignin (L) to serve as a new class of bio-based separators for lithium-ion batteries. The morphology and properties of the prepared membranes were studied in detail and compared with those of a commercial polypropylene separator. Interestingly, the polar groups in lignin promoted the affinity to the electrolytes and improved the liquid absorption properties of the PI-L membrane. Besides, the PI-L separator showed a higher ionic conductivity (1.78 × 10-3 S/cm) and Li+ transference number (0.787). Furthermore, the battery's cycle and rate performance improved due to adding of lignin. The capacity retention of the assembled LiFePO4 | PI-L | Li Battery was 95.1 % after 100 cycles at 1C current density, which was higher than that of the PP (90 %). Based on the results, PI-L, a bio-based battery separator, can potentially replace the current PP separators in lithium metal batteries.

Effect of lignin-based monomer on controlling the molecular weight and physical properties of the polyacrylonitrile/lignin copolymer.

In this work, lignin was grafted with acrylonitrile to control the molecular weights and molecular architecture of polyacrylonitrile (PAN)/lignin copolymer. Lignin-acrylonitrile monomer (LA-AN) and its copolymers with AN were synthesized successfully. First, lignin was aminated (LA) and then grafted with 2-chloroacrylonitrile to prepare LA-AN. The copolymerization of LA-AN and AN was carried out using 2,2-azobis(2-methylpropionitrile) as initiator. The modification, grafting, and copolymerization were confirmed with Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and X-ray photoelectron spectroscopy. Contrary to the previous studies, gel permeation chromatography showed that the molecular weight of the copolymers was increased significantly due to the presence of lignin (up to 203,944). Viscosity analysis revealed that the addition of lignin reduces the viscosity of the copolymer solution. While thermogravimetric analysis showed improvement in the degradation temperature, and lowering of the melt temperature, as revealed by differential scanning calorimetry. These findings indicated that the attaching acrylonitrile on lignin molecules result in control of the molecular weight and molecular structure of PAN/Lignin copolymers which results in enhanced solubility, spinnability, and other properties associated with molecular weight.

Chemical modification of cellulose by in situ reactive extrusion in ionic liquid.

In order to prepare the spinning solution of cellulose with high concentration in environmentally friendly solvent, cellulose was chemically modified by in situ reactive extrusion with several chemicals, such as urea, phthalic anhydride (PA), maleic anhydride (MA) and butyl glycidyl ether (BGE) and with ionic liquid namely 1-N-butyl-3-methylimidazolium chloride (BMIMCl) as reaction medium. These four modifiers all in situ grafted onto cellulose and the modification effectiveness was found to decrease in the sequence, MA>PA>BGE>urea. The formation of side chain on cellulose backbone destroyed the regularity of cellulose chains and the hydrogen bond network efficiently. The concentration of modified cellulose in spinning solution can be up to 14-25%, comparing with 9% for unmodified cellulose in BMIMCl. The high solid content results in high efficiency and less energy consumption of fiber production and solvent recycle.