Cellulose acetate network via ion pre-anchored strategy for simultaneous regulation of uniform Mg2+ flux and ion conductivity.

Hybrid LiMg batteries stand out by combining the rapid lithium diffusion kinetics and the advantages of magnesium. However, the uneven Mg deposits may result in continuous parasitic reactions and penetrate the separator. Herein, cellulose acetate (CA), with functional groups, was applied to engineer coordination with MOFs and construct the evenly-distributed and ample nucleation sites. Moreover, the hierarchical MOFs@CA network was fabricated via the metal ion pre-anchored strategy to regulate the uniform Mg2+ flux and improve ion-conductivity simultaneously. Furthermore, the hierarchical CA networks with well-ordered MOFs provided efficient MOF-to-MOF ion-transportation channels and served as ion sieves to inhibit anion transportation, thereby mitigating polarization. The super dendrite-inhibition and interfacial compatibility was confirmed and the assembled Mo6S8//Mg batteries exhibited high capacity about 105 mAh g-1 and capacity decay of 4 % after 600 cycles at 30 C, which surpassed the state-of-the-art LMBs system employing Mo6S8 electrode. The fabricated GPE sheds fresh strategy for the design of CA-based GPEs and bright light on the promise of high-performance LMBs.

Simultaneously Suppressing Shuttle Effect and Dendrite Growth in Lithium-Sulfur Batteries via Building Dual-Functional Asymmetric-Cellulose Gel Electrolyte.

Polysulfides huttling and interfacial instability of Lithium-anode are the main technical issues hindering commercialization of high-energy-density lithium-sulfur batteries. Simply addressing the problem of polysulfide shuttling or lithium dendrite growth can result in safety hazards or short lifespan. To synchronously tackle the aforementioned issues, the authors have designed an asymmetric cellulose gel electrolyte, a defective and ionized UiO66/black phosphorus heterostructure coating layer (Di-UiO66/BP) and a cationic cellulose gelelectrolyte (QACA). Defective and ionized engineered UiO66 particles significantly enhances performance of UiO66/BP layer in anchoring free polysulfides, promoting smooth and effective polysulfide conversion and expediting the redox kinetics of sulfur cathode, therefore suppressing polysulfide shuttling. QACA electrolyte with numerous cationic groups can interact with anions via electrostatic adsorption, thus enhancing lithium-ion transference number and contributing to formation of stable solid electrolyte interface to suppress lithium dendrite growth. Owing to the superior performance of QACA/Di-UiO66/BP, the final cells exhibit outstanding electrochemical performance, presenting high sulfur utilization (1420.1 mAh g-1 at 0.1 C), high-rate capacity (665.4 mAh g-1 at 4 C) and long cycle lifespan. This work proposes a strategy of designing asymmetric electrolytes to simultaneously address the challenges in both S-cathode and Li-anode, which contributes to advanced Li-S batteries and their practical application.

All-cellulose gel electrolyte with black phosphorus based lithium ion conductors toward advanced lithium-sulfurized polyacrylonitrile batteries.

Sulfurized polyacrylonitrile (SPAN) have been regarded as a promising cathode in high-energy-density lithium-sulfur batteries. However, severe safety issues derived from the electrolyte leakage and the uncontrollable lithium dendrite growth have seriously hindered the practical usage of Li-SPAN batteries. To address these issues, an eco-friendly and porous cellulose gel electrolyte (GE) was designed and prepared by UV photopolymerization and phase inversion methods. Also, covalent functional black phosphorous nanosheets (denoted as BP-Li) were fabricated and chosen as superior Li+ conductors in cellulose GE, ensuring the rapid ion transmission and suppressing the growth of lithium dendrites. As expected, the cellulose/BP-Li GE exhibited satisfactory ionic conductivity up to 5.21 × 10-3 S cm-1 with the high lithium ion transference number of 0.72. The Li-SPAN battery assembled with cellulose/BP-Li GE delivered high capacity of 938.8 mAh g-1 after 500 cycles with the capacity retention of 72.8 %. Hence, the cellulose/BP-Li GE displayed its promising usage in Li-SPAN batteries.

Structure-controlled lignin complex for PLA composites with outstanding antibacterial, fluorescent and photothermal conversion properties.

Polylactic acid (PLA) is increasingly being considered as an ideal biodegradable candidate to replace petroleum-based polymers. However, its practical applications are often hampered by the poor mechanical robustness and solo functionality. Herein, based on the mechanical property improvement of PLA we proposed a simple process of assembling lignin-hybridized modifier and PLA matrix, as opposed to the traditional trade-off between mechanical strength and functionality, while anchoring a biofluorescent moiety onto lignin surfaces. Specifically, the fluorophore group could act as interfacial compatibilizer of complex and facilitate the shape-tailored hybrids for promoting functionality flexibility. With the bimetallic hetero-particles, the preferable lignin-assembled complex could be controllably configured as an antibacterial, fluorophore and photothermal agent. Thus, mechanical enhancement, fluorescence introduction and favorable photothermal ability of the resulting PLA composites were successfully achieved for integrated unification of structural robustness, geometric integrity and functional multiplicity, which was never seen in the other reports. The results showed that PLA composites containing 5 wt% modified lignin, 10 wt% zinc oxide, and 5 wt% silver presented excellent mechanical, fluorescent, photothermal conversion properties. By controlling the ZnO content and morphology, strong inhibition of Escherichia coli (Gram-negative) than that of Staphylococcus Aureus (Gram-positive) was also observed. The flake-shaped ZnO /Ag hybrids contributed to better overall performance of PLA composites than the rod-shaped ZnO/Ag. In this work we developed a facile strategy to assemble a bioderived fluorophore with lignin particles for constructing a structure-controlled complex as a multitasking modifier, featuring mechanical unity and functional adaptability. Specifically, the lignin reinforcement and bimetallic hybrids with different morphologies were explored as an effective fluorophore, antibacterial and photothermal agent. Through multiple dehydration reactions, a conjugating fluorophore was successfully grafted on lignin surfaces to serve as an interface modifier without physical changing its structural robustness. And morphology-tailored hybrid was advantageously immobilized on predefined hetero-particle carrier of fluorescent lignin and endowed composites with desirable antimicrobial properties. The developed strategy would expand the functional applications of PLA materials in food packaging, biopharmaceuticals and simple fluorescent anti-counterfeiting.

Ultralow loading mussel-inspired conductive hybrid as highly effective modifier for function-engineered poly(lactic acid) composites.

It remains a great challenge to prepare polylactic acid (PLA) composites with excellent mechanical properties, superior anti-bacteria, and highly effective electromagnetic interference (EMI) shielding using ultralow loading of functional fillers. Herein, lignin particles were uniformly nano-sized as the matrix reinforcement and the fillers carrier via green mechanochemistry for improved thermal properties of polymer matrix. Through one-pot approach to a multitasking engineered agent, hybridized ZnO/Ag particles were synthesized for multi-functionalities. Inspired by mussels, the bio-derived dopamine cross-linker was introduced to in-situ synthesize the polypyrrole (PPy-PDa) glutinous nanofibrils as an interfacial modifier and a particles dispersant to regulate surface free energy of nanoparticles and improve filler-matrix interactions. With effective constructed 3D conductive networks by glutinous nanofibrils and hybridized particles, the dramatic improvement in EMI shielding and electrical conductivity was accomplished using an ultralow content of the conductive particles modifier (0.29 vol% Ag). The resulted biobased composites presented outstanding anti-dripping properties, mechanical properties, electrical conductivity (104.2 S/cm), anti-bacteria, joule heating, photothermal conversion ability and EMI shielding effectiveness (48.6 dB at X-band), which are superior to those reported. This work will broaden the application prospects of PLA composites in the fields of wearable electronics, food packaging and medical devices.

Strong biodegradable cellulose materials with improved crystallinity via hydrogen bonding tailoring strategy for UV blocking and antioxidant activity.

It has been a huge challenge to obtain simultaneously excellent mechanical strength and desirable multifunctionality from the cellulose nanocrystals (CNC) based food packing materials. In this work, we demonstrated a hydrogen bonding tailoring strategy that can produce CNC/lignin films with UV blocking and antioxidant activity, while bypassing the loss of mechanical strength. Using a hyperbranched polyester, lignin was first functionalized to increase the amount of hydroxyl groups, thereby increasing the intermolecular interactions. By assembling the polyester modified lignin (H-lignin) into CNC matrix, the hydrogen bonding crosslinks between the H-lignin and CNC chains were successfully promoted, resulting in the CNC composites with the significantly improved mechanical strength, UV blocking and antioxidant activity. The phenolic structure and the hydrogen donation of H-lignin also endowed the resulting CNC composites with excellent UV blocking and antioxidant activity. The experimental results indicated that the H-lignin could bring about 34% and 63% increase in tensile strength and Young's modulus, respectively, higher than the reported ones. The CNC-based composites showed better thermal stability and improved crystallinity property. The H-lignin provides a new insight into the multifunctional exploration of CNC-based composite. This work opens a new avenue for the next generation's biodegradable food packing materials from cellulose-sourced composites.

Ultralight Programmable Bioinspired Aerogels with an Integrated Multifunctional Surface for Self-Cleaning, Oil Absorption, and Thermal Insulation via Coassembly.

Creating a configurable and controllable surface for structure-integrated multifunctionality of ultralight aerogels is of significance but remains a huge challenge because of the critical limitations of mechanical vulnerability and structural processability. Herein, inspired by Salvinia minima, the facile and one-step coassembly approach is developed to allow the structured aerogels to spontaneously replicate Salvinia-like textures for function-adaptable surfaces morphologically. The in situ superimposed construction of bioinspired topography and intrinsic topology is for the first time performed for programmable binary architectures with multifunctionality without engendering structural vulnerability and functional disruption. By introducing the binding groups for hydrophobicity tailoring, functionalized nanocellulose (f-NC) is prepared via mechanochemistry as a structural, functional, and topographical modifier for a multitasking role. The self-generated bioinspired surface with f-NC greatly maintains the structural unity and mechanical robustness, which enable self-adaptability and self-supporting of surface configurations. With fine-tuning of nucleation-driving, the binary microstructures can be controllably diversified for structure-adaptable multifunctionalities. The resulting ultralight S. minima-inspired aerogels (e.g., 0.054 g cm-3) presented outstanding temperature-endured elasticity (e.g., 90.7% high-temperature compress-recovery after multiple cycles), durable superhydrophobicity, anti-icing properties, oil absorbency efficiency (e.g., 60.2 g g-1), and thermal insulating (e.g., 0.075 W mK-1), which are superior to these reported on the overall performance. This coassembly strategy offers the opportunities for the design of ultralight materials with topography- and function-tailorable features to meet the increasing demands in many fields such as smart surfaces and self-cleaning coatings.

Cross-linking of poly(dimethylaminoethyl methacrylate) by phytic acid: pH-responsive adsorbent for high-efficiency removal of cationic and anionic dyes.

A new high-efficiency adsorbent for cationic and anionic dyes named PAGD was synthesized via polymerization of dimethylaminoethyl methacrylate by employing glycidyl-methacrylate-modified phytic acid as a cross-linker. The experiment demonstrated that PAGD is pH-sensitive, and the maximum adsorption capacities of anionic dye Reactive Red 24 (RR24) and cationic dye Fuchsin Basic (FB) were 1871.23 and 482.54 mg g-1, respectively. To the best of our knowledge, there has been no previous report on a dye adsorbent possessing an adsorption capacity of over 465 mg g-1 for RR24. The excellent adsorption abilities toward RR24 are due to the introduced phytic acid groups, which could promote protonation of tertiary amine groups under acid pH conditions. Moreover, PAGD is able to selectively remove RR24 in a mixed solution of cationic dye and RR24. The adsorption isotherms and kinetics of PAGD fit well with the Langmuir isotherm and pseudo-second-order kinetic model, respectively. These results imply that PAGD is a promising adsorbent for removal of both cationic and anionic dyes.