Redox-active NiS@bacterial cellulose nanofiber composite separators with superior rate capability for lithium-ion batteries.

Separator is an essential component of lithium-ion batteries (LIBs), which is placed between the electrodes to impede their electrical contact and provide the transport channels for lithium ions. Traditionally, the separator contributes the overall mass of LIBs, thereby reducing the gravimetric capacity of the devices. Herein, a dual-layer redox-active cellulose separator is designed and fabricated to enhance the electrochemical performances of LIBs by introducing NiS. The presented separator is composed of an insulating bacterial cellulose (BC) nanofiber layer and a conductive, and redox-active NiS@BC/carbon nanotubes layer. By using the NiS@BC separator, the discharge capacity of the LiFePO4//Li half battery is enhanced to 117 mAh g-1 at a current of 2C owing to the redox-activity of NiS. Moreover, the functional separator-electrode interface can facilitate the homogenous Li stripping/plating and depress the polarization upon the repeated stripping/plating process. Consequently, the battery containing the redox-active separator exhibits outstanding cycle stability and rate capability. The present study contributes a novel strategy for the developments of functional separators to improve the electrochemical properties of LIBs.

Flexible, ultrathin and integrated nanopaper supercapacitor based on cationic bacterial cellulose.

Cellulose composite nanopaper is extensively employed in flexible energy storage systems owing to their light weight, good flexibility and high specific surface area. Nevertheless, achieving flexible and ultrathin nanopaper supercapacitors with excellent electrochemical performance remains a challenge. Herein, surface cationization of bacterial cellulose (BC) nanofibers was conducted using 2,3-epoxypropyltrimethylammonium chloride (EPTMAC). Anion-doped polypyrrole (PPy) was incorporated onto the surface of the cationic bacterial cellulose (BCE) nanofibers by an interfacial electrostatic self-assembly process. The obtained PPy@BCE electrode exhibited excellent electrochemical performance, including an areal capacitance of 3988 mF cm-2 at 1.0 mA cm-2 and a capacitance retention of 97 % after 10,000 cycles. A laminated paper-forming strategy was adopted to design and fabricate all-in-one integrated flexible supercapacitors (IFSCs) using PPy@BCE nanopaper as electrodes and BC nanopaper as a separator. The IFSCs showed superior areal capacitance (3669 mF cm-2 at 1 mA cm-2), high energy density (193.7 µWh cm-2 at a power density of 827.3 µW cm-2), and outstanding mechanical flexibility (with no significant capacitance attenuation after repeatedly bending for 1000 times). The present strategy paves a way for the large-scale production of paper-based energy storage devices.

Thermo-Responsive Poly(N-isopropylacrylamide)/Hydroxypropylmethyl Cellulose Hydrogel with High Luminous Transmittance and Solar Modulation for Smart Windows.

Thermochromic smart windows are considered to be promising energy-saving devices for reducing energy consumption in buildings. The ideal materials for thermochromic smart windows should have high transmittance, high solar modulation, low phase-transition temperature, and excellent high-temperature thermal stability, which are difficult to achieve simultaneously. This work reports a simple one-step low-temperature polymerization method to prepare a thermo-responsive poly(N-isopropylacrylamide)/hydroxypropylmethyl cellulose (PNIPAM/HPMC) hydrogel achieving the above performances simultaneously. The low-temperature polymerization environment endowed the hydrogel with a high luminous transmittance (Tlum) of 90.82%. HPMC as a functional material effectively enhanced the mechanical properties and thermal stability of the hydrogel. Meanwhile, the PNIPAM/HPMC hydrogel showed a low phase-transition temperature (∼32 °C) and high solar modulation (ΔTsol = 81.52%), which proved that it is an ideal material for thermochromic smart windows. Moreover, a PNIPAM/HPMC smart window exhibited high light transmittance (T380-760 = 86.27%), excellent light modulation (ΔT365 = 74.27%, ΔT380-760 = 86.17%, and ΔT940 = 63.93%), good indoor temperature regulation ability and stability, which indicated that it was an attractive candidate for application in reducing energy consumption in buildings. This work also provides an option and direction for modifying PNIPAM-based thermochromic smart windows.

Highly tough and ionic conductive starch/poly(vinyl alcohol) hydrogels based on a universal soaking strategy.

High-performance hydrogels with favorable mechanical strength, high modulus, sufficient ionic conductivity and freezing resistance have far-ranging applications in flexible electronic equipment. Nevertheless, it is challenging to combine admirable mechanical properties and high ionic conductivity into one hydrogel. Herein, a facile strategy was developed for the preparation of the hydrogel with excellent strength (1.45 MPa), super Young's modulus (8.85 MPa) and high conductivity (1.47 S/m) using starch and poly(vinyl alcohol) (PVA) as raw materials. The starch/PVA/Gly/Na3Cit (SPGN) gel was firstly cross-linked by crystalline regions of PVA upon freezing-thawing cycles. It was further immersed in the saturated Na3Cit solution to enhance the interaction between the substrates through the salting-out effect. The effect of soaking time on the crystallinity, intermolecular interactions, mechanical and electrical properties of SPGN gel was demonstrated by X-ray diffraction, Fourier transform infrared spectroscopy, tensile and impedance testing measurements. The introduction of glycerol and Na3Cit also endowed SPGN gels with favorable anti-freezing properties. The SPGN gel could maintain high mechanical flexibility and ionic conductivity at -15 °C.

Polypyrrole/SnCl2 modified bacterial cellulose electrodes with high areal capacitance for flexible supercapacitors.

Polypyrrole (PPy)/bacterial cellulose (BC) composite membranes are a promising kind of lightweight and flexible electrodes for supercapacitors. Herein, we explored a facile and efficient electrostatic self-assembly approach to uniformly depositing anion-doped PPy onto positively charged SnCl2-modifed BC (SBC). The obtained PPy@SBC electrode exhibited a high areal capacitance of 5718 mF cm-2 at a current density of 0.5 mA cm-2, a desirable capacitance retention of 83.1% at 5.0 mA cm-2 and excellent cycling stability (a capacitance retention of 86.8% after 10,000 cycles at 10 mA cm-2). A symmetric flexible supercapacitor was further assembled with the PPy@SBC electrodes, which delivered outstanding mechanical flexibility with negligible capacitance decay under different bent states. This study shows impressive potential in fabricating high-performance electrodes for flexible supercapacitors.

Dopamine-Modified Hyaluronic Acid Hydrogel Adhesives with Fast-Forming and High Tissue Adhesion.

Commercial or clinical tissue adhesives are currently limited due to their weak bonding strength on wet biological tissue surface, low biological compatibility, and slow adhesion formation. Although catechol-modified hyaluronic acid (HA) adhesives are developed, they suffer from limitations: insufficient adhesiveness and overfast degradation, attributed to low substitution of catechol groups. In this study, we demonstrate a simple and efficient strategy to prepare mussel-inspired HA hydrogel adhesives with improved degree of substitution of catechol groups. Because of the significantly increased grafting ratio of catechol groups, dopamine-conjugated dialdehyde-HA (DAHA) hydrogels exhibit excellent tissue adhesion performance (i.e., adhesive strength of 90.0 ± 6.7 kPa), which are significantly higher than those found in dopamine-conjugated HA hydrogels (∼10 kPa), photo-cross-linkable HA hydrogels (∼13 kPa), or commercially available fibrin glues (2-40 kPa). At the same time, their maximum adhesion energy is 384.6 ± 26.0 J m-2, which also is 40-400-fold, 2-40-fold, and ∼8-fold higher than those of the mussel-based adhesive, cyanoacrylate, and fibrin glues, respectively. Moreover, the hydrogels can gel rapidly within 60 s and have a tunable degradation suitable for tissue regeneration. Together with their cytocompatibility and good cell adhesion, they are promising materials as new biological adhesives.

Soft freezing-induced self-assembly of silk fibroin for tunable gelation.

Silk fibroin (SF) hydrogel is a promising candidate in biomaterial field; however its application is quite limited by long-gelation time. In the present study, we developed a novel strategy named soft freezing to accelerate the process and control the sol-gel transition of SF protein. SF protein was induced to self-assembly by soft freezing process for achieving the reconstructed SF solution with metastable structure. It was found that the soft freezing process triggers the structural transition from random structure to ordered structure-rich conformation. Gelation kinetics showed that the gelation time of SF protein could be regulated by changing freezing time and initial concentration. The reconstructed SF solution allowed enhanced sol-gel transition within 6 hours, even at extremely low concentration. The attractive features of the method described here include the accelerated gelation, free of chemical agents, and reducing processing complexity. The SF solution with short gelation time will be applicable as cell encapsulation and injectable applications for tissue engineering and regenerative medicine, which greatly expand the applications of SF hydrogels.

Photopolymerized maleilated chitosan/thiol-terminated poly (vinyl alcohol) hydrogels as potential tissue engineering scaffolds.

Photocrosslinkable hydrogels composed of natural materials exhibit great application potential in tissue engineering scaffolds. However, weak formation and poor mechanical property can usually be a limitation. Herein, the photo-clickable thiol-ene hydrogels based chitosan were synthesized using photopolymerization of maleic chitosan (MCS) and thiol-terminated poly (vinyl alcohol) (TPVA) in the presence of a biocompatible photoinitiator. Rheological property and absorbing behavior of the MCS/TPVA hydrogels could be tailored by varying the amount of TPVA in the feed. There was strong intermolecular hydrogen bonding between the molecules of MCS and TPVA. Notably, the MCS/TPVA hydrogel (MT-3) exhibited rapid gelation behavior (<120 s), improved stiff (G' = ∼5500 Pa) and compressive strength (0.285 ±â€¯0.014 MPa), which were important for hydrogel scaffolds, especially for injectable hydrogel scaffolds. Photocrosslinked MCS/TPVA hydrogels was cytocompatible and could promote the L929 cells attachment and proliferation, showing their potential as tissue engineering scaffolds.

Thermal-oxidative effect of Kraft lignin antioxidant in polypropylene: Uncovering the key factor using correlation analysis model.

Which factors are crucial to improving lignin antioxidant ability in polymers has been debated over years. Here, the structural effect of natural antioxidant from technical Kraft lignin (KL) on the oxidation induction time (OIT) of KL/polypropylene (PP) was quantitatively investigated using correlation analysis model instead of traditional linear fitting model. The correlation coefficient and significance value of their relationship clearly demonstrated the dominating role of non-condensed Phenolic OH (Ph-OH) in improving KL/PP thermal-oxidation stability, subsequently followed by M¯n, aliphatic OH/total Ph-OH, condensed Ph-OH and polydispersity. OIT is positive with non-condensed and total Ph-OH, while it declines with increase of the above other factors. Remarkably, the longest OIT (∼90min) was obtained even at extreme loading (0.5wt%), almost ∼911% and ∼201% huge increase in contrast to that of pure PP and crude KL/PP composite, respectively. Meanwhile, the mechanical properties of KL fractions/PP blends can be maintained at the same or better level than that of pure PP, due to strong interfacial adhesion strength.

Selective aminolysis of acetylated lignin: Toward simultaneously improving thermal-oxidative stability and maintaining mechanical properties of polypropylene.

Even with outstanding radical capturing ability, the utilization of lignin as a natural antioxidant in polypropylene (PP) still has been pended. Usually, the compatibility of its blends is improved based on the reaction of hydroxyl content, thus leading to the decreasing content of phenolic hydroxyl (Ph-OH) group and inferior thermal-oxidative stability of lignin blends. Here, the selective aminolysis of acetylated Kraft lignin (pyr-KL) was investigated, which structures were characterized using FTIR, 31P-NMR and GPC. The Ph-OH group of acetylated KL could be released by the addition of pyrrolidine; however the aliphatic hydroxyl group is still blocked. With the control of reaction conditions, the highest oxidation induction time of pyr-KL/PP (0.5wt% loading) reaches up to 22.6min, almost 2.6 times than that of pure PP. More importantly, the mechanical properties of PP were also maintained under the loading of pyr-KL, which is much better than that of curde KL/PP.

Regenerated egg white/silk fibroin composite films for biomedical applications.

Protein-based composites have always been desirable biomaterials as they can be fabricated into a wide range of biomaterials with tunable properties, including modulation of mechanical properties and control of cell responses. Both egg white protein (EW) and silk fibroin (SF) are biocompatible, biodegradable, non-toxic and naturally abundant biopolymers. In order to obtain biocompatible composite films with tunable performance, EW and SF were blended at various ratios. Raising the SF ratio in the composite films significantly increased breaking strength, but impaired flexibility. Conversely, increasing the EW ratio remarkably enhanced elasticity of the composite films. Furthermore, the biological assays based on endothelial cells showed that the incorporation of EW promoted cell viability. These make them potential materials with controllable mechanical property and enhanced bioactivity, providing useful options for the fabrication of tissue engineering scaffolds.

Non-isothermal crystallization kinetics of eucalyptus lignosulfonate/polyvinyl alcohol composite.

The nonisothermal crystallinization kinetic was performed on Polyvinyl alcohol (PVA) mixed with eucalyptus lignosulfonate calcuim (HLS) as the biobased thermal stabilizer, which was systematically analyzed based on Jeziorny model, Ozawa equation and the Mo method. The results indicated that the entire crystallization process took place through two main stages involving the primary and secondary crystallization processes. The Mo method described nonisothermal crystallization behavior well. Based on the results of the half time for completing crystallization, kc value in Jeziorny model, F(T) value in Mo method and crystallization activation energy, it was concluded that low loading of HLS accelerated PVA crystallization process, however, the growth rate of PVA crystallization was impeded at high content of HLS.

Lignosulfonate as reinforcement in polyvinyl alcohol film: Mechanical properties and interaction analysis.

Recently, there has been a growing research interest on renewable composite due to sustainability concerns. This work demonstrated the possibility of using eucalyptus lignosulfonate calcium (HLS) particles as reinforcement in polyvinyl alcohol (PVA) matrix. 41% and 384.7% improvement of pure PVA tensile strength and Young's modulus were achieved with incorporation of 5 wt% HLS. The above results were ascribed to specific intermolecular interactions between HLS and PVA, suggested by the increasing PVA glass transition and crystalline relaxations temperature, depression of melting point with HLS incorporation. Moreover, this interaction was quantitatively determined by q value of -62.4±10.0 in Kwei equation. Additionally, the remarkable red shift of wavenumber corresponding to hydroxyl group also indicated the formation of strong hydrogen bond in HLS/PVA blend. SEM characterization confirmed that HLS/PVA blends are at least miscible.

Graft polymers of eucalyptus lignosulfonate calcium with acrylic acid: synthesis and characterization.

The graft copolymerization of eucalyptus lignosulfonate calcium (HLS-Ca) from hardwood and acrylic acid (AA) was investigated by using Fenton agent as a coinitiator. The influences of reaction conditions on grafting parameters i.e. product yield (Y%), AA conversion (C%), grafting ratio (G%) and grafting efficiency (GE%) were carefully studied. The effects of the phenolic hydroxyl (Ph-OH) group on the polymerization of AA and grafting reaction were researched. Graft copolymers were identified by the new absorption at 1,727 cm(-1), more homogenized morphology and higher decomposition temperature after grafted with AA, as illustrated in FTIR, SEM and TG spectra. The optimum synthesis conditions are as follows: H2O2=25.2 mol/L, FeCl2=63.0 mol/L, T=50°C and t=2h and the optimum percentages of Y, C, G and GE are 97.61%, 95.23%, 71.29% and 78.85%, respectively. The Ph-OH group of HLS-Ca cannot inhibit the polymerization of AA and is involved in the grafting reaction as an active center.