Molecular self-assembled cellulose enabling durable, scalable, high-power osmotic energy harvesting.

In recent years, renewable cellulose-based ion exchange membranes have emerged as promising candidates for capturing green, abundant osmotic energy. However, the low power density and structural/performance instability are challenging for such cellulose membranes. Herein, cellulose-molecule self-assembly engineering (CMA) is developed to construct environmentally friendly, durable, scalable cellulose membranes (CMA membranes). Such a strategy enables CMA membranes with ideal nanochannels (∼7 nm) and tailored channel lengths, which support excellent ion selectivity and ion fluxes toward high-performance osmotic energy harvesting. Finite element simulations also verified the function of tailored nanochannel length on osmotic energy conversion. Correspondingly, our CMA membrane shows a high-power density of 2.27 W/m2 at a 50-fold KCl gradient and super high voltage of 1.32 V with 30-pair CMA membranes (testing area of 22.2 cm2). In addition, the CMA membrane demonstrates long-term structural and dimensional integrity in saline solution, due to their high wet strength (4.2 MPa for N-CMA membrane and 0.5 MPa for P-CMA membrane), and correspondingly generates ultrastable yet high power density more than 100 days. The self-assembly engineering of cellulose molecules constructs high-performance ion-selective membranes with environmentally friendly, scalable, high wet strength and stability advantages, which guide sustainable nanofluidic applications beyond the blue energy.

Stretchable and Durable Bacterial Cellulose-Based Thermocell with Improved Thermopower Density for Low-Grade Heat Harvesting.

Low-grade heat exists ubiquitously in the environment, and gel-state thermogalvanic cells (GTCs) can directly convert thermal energy into electricity by a redox reaction. However, their low ionic conductivity and poor mechanical properties are still insufficient for their potential applications. Here, we designed a bacterial cellulose (BC) nanofiber-macromolecular entanglement network to balance the GTC's thermopower and mechanical properties. Therefore, the BC-GTC shows a Seebeck coefficient of 3.84 mV K-1, an ionic conductivity of 108.5 mS cm-1, and a high specific output power density of 1760 µW m-2 K-2, which are much higher than most current literature. Further connecting 15 units of BC-GTCs, the output voltage of 3.35 V can be obtained at a temperature gradient of 65 K, which can directly power electronic devices such as electronic calculators, thermohydrometers, fans, and light-emitting diodes (LEDs). This work offers a promising method for developing high-performance and durable GTC in sustainable green energy.

Advanced Bacterial Cellulose Ionic Conductors with Gigantic Thermopower for Low-Grade Heat Harvesting.

Ionic conductors such as polymer electrolytes and ionic liquids have high thermoelectric voltages several orders of magnitude higher than electronic thermoelectric materials, while their conductivity is much lower than the latter. This work reports a novel approach to achieve high-performance ionic conductors using calcium ion (Ca2+) coordinated bacterial cellulose (CaBC) through molecular channel engineering. Through the coordination of Ca2+ with cellulose molecular chain, the distance between the cellulose molecular chains is widened, so that ions can transport along the cellulose molecular chain. Therefore, we reported ionic thermoelectric (i-TE) material based on CaBC/NaCl with a relatively high ionic Seebeck coefficient of -27.2 mV K-1 and high ionic conductivity of 204.2 mS cm-1. This ionic hydrogel is promising in the design of high-thermopower i-TE materials for low-grade heat energy harvesting.

Crack-Based Core-Sheath Fiber Strain Sensors with an Ultralow Detection Limit and an Ultrawide Working Range.

With the booming development of flexible wearable sensing devices, flexible stretchable strain sensors with crack structure and high sensitivity have been widely concerned. However, the narrow sensing range has been hindering the development of crack-based strain sensors. In addition, the existence of the crack structure may reduce the interface compatibility between the elastic matrix and the sensing material. Herein, to overcome these problems, integrated core-sheath fibers were prepared by coaxial wet spinning with partially added carbon nanotube sensing materials in thermoplastic polyurethane elastic materials. Due to the superior interface compatibility and the change in the conductive path during stretching, the fiber strain sensor exhibits excellent durability (5000 tensile cycles), high sensitivity (>104), large stretchability (500%), a low detection limit (0.01%), and a fast response time of ∼60 ms. Based on these outstanding strain sensing performances, the fiber sensor is demonstrated to detect subtle strain changes (e.g., pulse wave and swallowing) and large strain changes (e.g., finger joint and wrist movement) in real time. Moreover, the fabric sensor woven with the core-sheath fibers has an excellent performance in wrist bending angle detection, and the smart gloves based on the fabric sensors also show exceptional recognition ability as a wireless sign language translation device. This integrated strategy may provide prospective opportunities to develop highly sensitive strain sensors with durable deformation and a wide detection range.

Hierarchically Designed Three-Dimensional Composite Structure on a Cellulose-Based Solar Steam Generator.

The emerging water purification technology represented by solar water evaporation has developed rapidly in recent years and is widely used in seawater desalination. However, the high reflectivity of sunlight and low efficiency of photothermal conversion greatly hinder its application prospects. In this paper, the hierarchical structure of the film was designed and optimized by the addition of carbon materials in the process of bacterial cellulose culture. A cellulose-based composite film material with a microporous structure was obtained, which can improve the photothermal evaporation rate and photothermal conversion efficiency from the structural principle to improve the stability of floating on the water. Bacterial cellulose (BC) as a three-dimensional carrier was combined with one-dimensional and two-dimensional (1D/2D) compounds of carbon nanotubes (CNT) and reduced graphene oxide (RGO) to form composite films for solar evaporation. By the addition of CNT-RGO (21.8 wt %), the composite showed prominent photothermal evaporation rate and photothermal conversion efficiency properties. Through in situ culture of BC, not only a tight structure can be obtained but also the surface of BC contains a large number of hydroxyl groups, which have many active sites to load photothermal materials. BC nanofibers, CNT, and RGO cooperate to form a porous network structure, which provides continuous double channels for the rapid transmission of water molecules and light paths, so as to form an excellent photothermal layer. The photothermal conversion efficiency is 90.2%, and the photothermal evaporation rate is 1.85 kg m-2 h-1 to achieve efficient solar interface evaporation. This is a high level of photothermal properties in a cellulose-based solar steam generator. The superior photothermal performance of this hybrid film possesses scalability and desalination ability.

Toward continuous high-performance bacterial cellulose macrofibers by implementing grading-stretching in spinning.

At present, the orderly assembly of bio-cellulose nanofibers (CNFs) with excellent mechanical properties in a simple and continuous manner still remains a challenge. Here, we propose a strategy of combining a wet spinning process with a self-made grading-stretching device to realize the continuous preparation of high-performance bacterial cellulose (BC) macrofibers. The macrofiber obtained by one-stage stretching at the optimum stretching ratio of 40% achieves the Young's modulus of 19.8 GPa and tensile strength of 544.5 MPa. Under two-stage stretching, wide-angle X-ray (WXRD) diffraction analysis revealed that the second orientation of nanofibers shows a higher degree of orientation than that under one-stage stretching. The maximum Young's modulus and tensile strength of the macrofiber can reach 33.2 GPa and 659.8 MPa, respectively, which are higher than most CNFs macrofibers obtained by spinning and post-stretching. This research is expected to provide a significant reference for the industrial spinning of nanocellulose.

TEMPO-Oxidized Bacterial Cellulose Nanofibers/Graphene Oxide Fibers for Osmotic Energy Conversion.

The large osmotic energy between river water and seawater is an inexhaustible blue energy source; however, the complicated manufacturing methods used for ion-exchange devices hinder the development of reverse electrodialysis (RED). Here, we use a wet-spinning method to continuously spin meter-scale 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized bacterial cellulose (TOBC) nanofiber filaments, which are then used to construct nanochannels for osmotic energy conversion. These are then used to build a nacre-like structure by adding graphene oxide (GO), which provides narrow nanochannels in one-dimensional and two-dimensional nanofluid systems for rapid ion transport. With a 50-fold concentration gradient, the nanochannels in the fibers generate electricity of 0.35 W m-2, with an ionic mobility of 0.94 and an energy conversion efficiency of 38%. The assembly of GO and TOBC results in a high power density of 0.53 W m-2 using artificial seawater and river water. The RED device fabricated from TOBC/GO fibers maintains a stable power density for 15 days. This research proposes a simple method to reduce the size of nanochannels to improve the ionic conductivity, ionic selectivity, and power density of cellulose-based nanofibers to increase the possibility of their application for the conversion of osmotic energy to electrical energy.

Anisotropic bacterial cellulose hydrogels with tunable high mechanical performances, non-swelling and bionic nanofluidic ion transmission behavior.

Water-rich hydrogels with tissue-like softness, especially ion conductive hydrogels with ion signal transfer systems similar to biological areas, are promising soft electrode materials, while too poor or unstable mechanical properties that come from uncontrollable swelling and biocompatibility issues caused by introducing high concentration ions are serious obstacles in practical applications. Herein, a simple method for fabricating strong, stable, ion-conductive, anisotropic bacterial cellulose hydrogels (ABCHs) is first reported. Relying on nanofibers with high aspect ratio in bacterial cellulose (BC), a tailor-made nanofiber-network-reinforced structure is constructed by controlled dissolution, followed by aligning them well via a simple fossilizing process under stretching. Therefore, tunable high mechanical performances can be achieved and the maximum tensile strength can reach 14.3 MPa with 70% water content. It is worth noting that ABCHs will not swell in water for 30 days and maintain 93% tensile strength. Most importantly, the unique nanofluid behaviors from nanochannels in nanofibers allow effective ion transport in ABCHs relying only on low concentrations of ions in body fluids (<300 mM), avoiding sacrificing biocompatibility to achieve useful conductivity. This facile strategy might be very scalable in fabricating high-strength, non-swelling, bio-ion conductive cellulose hydrogels for application in next-generation bio-interfacing and flexible implantable devices.

High-Strength Superstretchable Helical Bacterial Cellulose Fibers with a "Self-Fiber-Reinforced Structure".

As a hydrogel membrane grown on the gas-liquid interface by bacterial culture that can be industrialized, bacterial cellulose (BC) cannot give full play to the advantages of its natural nanofibers. Conversion to the properties of nanofibers from high-performance to macrofibers represents a difficult material engineering challenge. Herein, we construct high-strength BC macrofibers with a "self-fiber-reinforced structure" using a dry-wet spinning method by adjusting the BC dissolution and concentration. The macrofiber with a tensile strength of 649 MPa and a strain of 17.2% can be obtained, which is one of the strongest and toughest cellulose fibers. In addition, the macrofiber can be fabricated to a superstretchable helical fiber without adding other elastomers or auxiliary materials. When the helical diameter is 1.6 mm, the ultimate stretch reaches 1240%. Meanwhile, cyclic tests show that the mechanical properties and morphology of the fiber remained stable after 100 times of 100% cyclic stretching. It is exciting that the helical fiber also owns outstanding knittability, washability, scalability, and dyeability. Furthermore, superstretchable functional helical BC fibers can be fabricated by embedding functional materials (carbon materials, conductive polymers, etc.) on BC or in the spinning dope, which can be made to wearable devices such as fiber solid-state supercapacitors. This work provides a scalable way for high-strength superstretchable and multifunctional fibers applied in wearable devices.

A 3D-printable TEMPO-oxidized bacterial cellulose/alginate hydrogel with enhanced stability via nanoclay incorporation.

Three-dimensional (3D) printing offers a novel approach to manufacture repeatable personalized structures for mass customization in medical fields. Considering the resemblance of materials in composition and microstructure to biological tissues, polysaccharide-based hydrogel is a promising printing material. However, its long-term stability of structure has always been a problem. In this work, we showed a green nanocomposite printing ink based on 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-oxidized bacterial cellulose (TOBC), sodium alginate (SA) and laponite nanoclay (Xls). The TOBC/SA/Xls hydrogel prepared by the 3D printing ink not only exhibited structural stability, but also performed a long-term release behavior of protein which could be attractive in medical application of drug release, biomedical devices and tissue engineering.

A strategy of tailoring polymorphs and nanostructures to construct self-reinforced nonswelling high-strength bacterial cellulose hydrogels.

A serious decline in mechanical properties of polysaccharide hydrogels caused by swelling has always been a difficult problem which greatly limited their application especially in the medical field. Herein, nonswelling high-strength natural hydrogels based on self-reinforced double-crosslinked bacterial cellulose (SDBC) were prepared. Inspired by the concept of homogeneous composite materials, by regulating the ratio of LiOH/urea alkaline solvent, the aggregation structure and nanostructure of SDBC hydrogels can be controlled, thereby a unique nanofiber-network-self-reinforced (FNSR) structure was constructed and a new self-reinforcing mechanism is proposed. The prepared SDBC hydrogels have excellent mechanical properties at a high water content (>91%) for the combination of double-crosslinking and a unique FNSR structure, which can effectively prevent crack propagation and dissipate a large amount of energy. In particular, the compressive strength can reach 3.17 MPa which is 56 times that of native bacterial cellulose (BC). It is worth mentioning that no swelling occurs for the hydrogel, and the mechanical strength still remains in excess of 90% for 15 days in water, which is favorable for promising application in underwater equipment, implantable ionic devices, and tissue engineering scaffolds. This study also opens up a new horizon for the preparation of self-reinforced hydrogels.