High output flexible polyvinylidene fluoride based piezoelectric device incorporating cellulose nanofibers/BaTiO3@TiO2 piezoelectric core-shell structure.

Flexible composite film has gained increasing attention in the fields of wearable devices and portable electronic products. In this work, a novel core-shell structure of cellulose nanofibers/BaTiO3@TiO2 (CNF/BTO@TiO2) was synthesized with the assistant of the biological macromolecule material of cellulose nanofibril (CNF), in which the CNF can improve the stability and dispersibility of BaTiO3 (BTO) in the aqueous phase and elevate the integrity of the core-shell structure. The agglomeration of nanoparticles and the structural defects of the composite film can be improved when the core-shell structure was uniformly dispersed in polyvinylidene fluoride (PVDF). Meanwhile, the core-shell structure can promote the polarization of the electric dipole and the formation of ß phase in PVDF due to the generated interface spatial polarization between the shell of TiO2 and the core of BTO. When the content of the core-shell structure was 5 wt%, the ß phase content reaches 61.89 %, and the piezoelectric coefficient of composite film reaches 84.29 pm/V. Thus the maximum output open-circuit voltage (VOC) and short-circuit current (ISC) of the piezoelectric composite film is as high as 13.10 V and 464.3 nA. In addition, its excellent pressure sensing capability allows for its application in various flexible electronic devices.

High thermal conductivity regenerated cellulose/carboxylated carbon nanotubes composite films with semi-insulating properties prepared via ionic coordination and hydrothermal synthesis of zinc oxide.

With the rapid development of miniaturization and integration of electronic products, its heat dissipation has become the focus of research. In order to improve the heat dissipation efficiency of electronic components, flexible thermal conduction materials are constantly studied. Cellulose has good flexibility and load capacity, which is often used in the preparation of thermal conduction materials. In this paper, carboxylated multi-walled carbon nanotubes (C-MWCNTs) were modified by metal ion coordination and hydrothermal synthesis of zinc oxide (ZnO) to prepare semi-insulating thermal conduction fillers, which were dispersed into regenerated cellulose (RC) to cast to be composite films. The results show that the two modification methods can reduce the probability of phonon scattering and block the electron transport path, so as to improve the thermal conductivity (TC) and electrical insulation properties of the composite films. Especially for the RC/C-MWCNTs@ZnO composite films, when the total filler content is 20 wt%, the in-plane TC can reach 11.89 ± 0.19 (W/(m·K)), and the surface electrical resistivity (ρs) is (5.24 ± 0.17) × 106 Ω. Compared with the RC/C-MWCNTs composite films, the in-plane TC and ρs of the RC/C-MWCNTs@ZnO composites films are increased by about 94.92 % and 555 %, respectively. Therefore, the developed RC-based composite film has broad application prospects in thermal management.

Flexible cellulose-based piezoelectric composite membrane involving PVDF and BaTiO3 synthesized with the assistance of TEMPO-oxidized cellulose nanofibrils.

High-performance flexible barium titanate (BaTiO3)-based piezoelectric devices have gained much attention. However, it is still a challenge to prepare flexible polymer/BaTiO3-based composite materials with uniform distribution and high performance due to the high viscosity of polymers. In this study, novel hybrid BaTiO3 particles were synthesized with assistance of TEMPO-oxidized cellulose nanofibrils (CNFs) via a low-temperature hydrothermal method and explored for their application in piezoelectric composites. Specifically, Ba2+ was adsorbed on uniformly dispersed CNFs with a large amount of negative charge on their surface, which nucleated, resulting in the synthesis of evenly dispersed CNF-BaTiO3. The obtained CNF-BaTiO3 possessed a uniform particle size, few impurities, high crystallinity and dispersity, high compatibility with the polymer substrate and surface activity due to the existence of CNFs. Subsequently, both polyvinylidene fluoride (PVDF) and TEMPO-oxidized CNFs were employed as piezoelectric substrates for the fabrication of a CNF/PVDF/CNF-BaTiO3 composite membrane with a compact structure, displaying the tensile strength of 18.61 ± 3.75 MPa and elongation at break of 3.06 ± 1.33%. Finally, a thin piezoelectric generator (PEG) was assembled, which output a considerable open-circuit voltage (4.4 V) and short-circuit current (200 nA), and could also power a light-emitting diode and charge a 1 µF capacitor to 3.66 V in 500 s. Its longitudinal piezoelectric constant (d 33) was 5.25 ± 1.04 pC N-1 even with a small thickness. It also exhibited high sensitivity to human movement, outputting a voltage of about 9 V and current of 739 nA for only a footstep. Thus, it exhibited good sensing property and energy harvesting property, presenting practical application prospects. This work provides a new idea for the preparation of hybrid BaTiO3 and cellulose-based piezoelectric composite materials.

Anisotropic Wooden Electromechanical Transduction Devices Enhanced by TEMPO Oxidization and PDMS.

In order to increase the number and contact probability of electric dipole on cellulose, acid and alkali treatment was employed to extract hemicellulose and lignin from original wood to gain a highly oriented cellulose frame. The combined means with 2,2,6,6-tetramethylpiperidine-1-oxyl-NaBr-NaClO oxidation and impregnation of PDMS with compression was subsequently used to enhance its mechanical performance and electromechanical conversion. The assembled wooden electromechanical device (10 mm × 10 mm × 1 mm) exhibits the maximum open-circuit voltage (V OC) of 11.75 V and short-circuit current (I SC) of 211.01 nA as stepped by foot. It can be sliced to fabricate a flexible sensor with high sensitivity displaying V OC of 2.88 V and I SC of 210.09 nA under the tapped state. Its highly oriented wood fiber makes it display significant anisotropy in terms of mechanical and electromechanical performance for multidirectional sense. This strategy will exactly provide reference for developing other high-performance piezoelectric devices.

Graphene oxide quantum dots attached on wood-derived nanocellulose to fabricate a highly sensitive humidity sensor.

Herein, cellulose nanofibril (CNF) with various carboxyl amounts were prepared via regulating its oxidation degree using TEMPO oxidation. The CNF dispersion was dropped onto the interdigital electrode to be capacitive humidity sensor by the subsequent vacuum freeze-drying. Pure CNF-7 (NaClO content of 7 mmol/g) humidity sensor involves in orderly porous structure, which displays better performance than other CNFs for its moderate carboxyl content and dimension. As uniformly adding appropriate content of graphene oxide quantum dots (GOQD) with larger surface area and active sites, it can be attached on the CNF to construct a three-dimensional interconnected porous structure for their excellent aqueous dispersity as well as differences in morphology and size. Consequently, the CNF/GOQD sensor exhibits the sensitivity as high as 51,840.91 pF/% RH, short response time (30 s)/recovery time (11 s) and excellent reproducibility. The proposed method can provide effective guidance for the design of humidity sensors based on nanomaterials.

Steady and Robust CNTs-Based Electric Heating Membrane Fabricated by Addition of Nanocellulose and Hot-Press Encapsulation.

Herein, a type of biomass-based electric heating membrane (EHM) with excellent stability was fabricated; this was achieved by incorporating carbon nanotubes (CNTs) into the nanofibrillated cellulose (NFC) as a natural dispersant and a biological substrate, as well as via the control of ultrasonic dispersion, grammage, and encapsulation using poly(dimethylsiloxane) (PDMS) with hot pressing. NFC entangles with CNTs in the form of an intertwined network and non-covalent interactions to fabricate a flexible EHM with steady electric heating performance; this formation is attributed to not only their similar morphology and surface-active groups but also the use of NFC that avoids additional disturbances in the overlapped interface among CNTs as far as possible. The obtained steady resistance varies as low as 5.1% under energized operation. In the encapsulated EHM (EM), PDMS was anchored on its surface by using hot pressing and an intertwined structure to enhance flexibility and robustness. The encapsulated membrane can be used in low-voltage applications, which require flexibility, waterproofing, and insulation.

Performance of the highly sensitive humidity sensor constructed with nanofibrillated cellulose/graphene oxide/polydimethylsiloxane aerogel via freeze drying.

A kind of capacitive humidity sensor with high sensitivity constructed with nanofibrillated cellulose (NFC), graphene oxide (GO) and polydimethylsiloxane (PDMS) is presented in this work, via a simple ultrasonic dispersion and freeze drying technology. The NFC and GO with a strong adsorption for water molecules were used as a substrate for the promotion of capacitive response of the humidity sensor. Moreover, anhydrous ethanol was added to inhibit the generation of big cracks in the humidity sensor in the freeze drying process, so as to obtain a regular network porous structure, then providing a great deal of conduction channels and active sites for molecular water. Also, the addition of PDMS can effectively enhance the flexibility and stability of its porous structure. The results confirmed that the humidity sensor with 30 wt% GO showed an excellent humidity sensitivity (6576.41 pF/% RH), remarkable reproducibility, low humidity hysteresis characteristic in 11-97% relative humidity (RH) at 25 °C, and short response/recovery times (57 s/2 s). In addition, the presented sensor exhibited small relative deviation of the measured relative humidity value compared with the commercial hygrometer. The realization of the high sensitivity can be attributed to the theories about interaction of the hydrophilic group, proton transfer of water molecules and the three-dimensional network transport structure model. Therefore, the NFC/GO/PDMS humidity sensor finally realizes stable, reproducible and fast humidity sensing via an eco-friendly process, exhibiting promising potential for wide practical application.

A Nanofibrillated Cellulose-Based Electrothermal Aerogel Constructed with Carbon Nanotubes and Graphene.

Nanofibrillated cellulose (NFC) as an environmentally friendly substrate material has superiority for flexible electrothermal composite, while there is currently no research on porous NFC based electrothermal aerogel. Therefore, this work used NFC as a skeleton, combined with multi-walled carbon nanotubes (MWCNTs) and graphene (GP), to prepare NFC/MWCNTs/GP aerogel (CCGA) via a simple and economic freeze-drying method. The electrothermal CCGA was finally assembled after connecting CCGA with electrodes. The results show that when the concentration of the NFC/MWCNTs/GP suspension was 5 mg mL-1 and NFC amount was 80 wt.%, the maximum steady-state temperature rise of electrothermal CCGA at 3000 W m-2 and 2000 W m-2 was of about 62.0 °C and 40.4 °C, respectively. The resistance change rate of the CCGA was nearly 15% at the concentration of 7 mg mL-1 under the power density of 2000 W m-2. The formed three-dimensional porous structure is conducive to the heat exchange. Consequently, the electrothermal CCGA can be used as a potential lightweight substrate for efficient electrothermal devices.

The use of nanofibrillated cellulose to fabricate a homogeneous and flexible graphene-based electric heating membrane.

Nanofibrillated cellulose (NFC) as a natural macromolecule, binder, dispersant, enhancer, was utilized to facilitate the assembly of graphene sheets, imparting a steady stacked structure by the sheets to the electric heating membrane with flexibility and uniform heating performance. Strong interface bonding formed in the membrane, which combined graphene sheets to be a steady conductive network structure for electric heating. The membrane attained an equilibrium temperature rise to 60°C in 3min under 2000Wm-2, which increased linearly with increasing power density and graphene content. Decreased resistance between two electrodes was caused by electric-heat coupling effect which led to a decrease in the membrane's oxygen-containing groups as conducting electrification. The temperature distributing on membrane surface, and that as bent and distorted to different angles even simultaneously at the electric heating status, were all characterized by infrared thermal imaging to indicate the uniform distribution and well bonding performance between NFC and graphene, as well as the great flexibility in the biomass membrane. This study would further broaden the utilization of the natural nanocellulose-graphene biomass composites.

Thin Electric Heating Membrane Constructed with a Three-Dimensional Nanofibrillated Cellulose⁻Graphene⁻Graphene Oxide System.

Nanofibrillated cellulose (NFC) and graphene oxide (GO) with reinforcing and film-forming properties were employed with graphene to develop a novel and thin electric heating membrane with heat dissipation controllability. A negative charge was found on the surface of GO and NFC in aqueous dispersions, which contributed to the homogeneous distribution of the graphene sheets. The membrane had a good laminated structure with three-dimensional interaction between GO and NFC, with embedded graphene sheets. Conductivity was characterized as a function of the amount of graphene, thus giving control over to the heating power by adjusting the ratio of graphene. Subsequent electric heating tests can remove irregularities on the GO and graphene sheet, improving the laminated structure further. The temperature on the surface of the membrane presented an exponential increasing regularity with time. Under the same power density and time, the stabilized temperature rise of membranes was higher when grammage was higher, which was characterized by the linear function of the power density. Low-grammage membranes (1 and 4 g·m-2) also exhibited regular and even stabilized temperature rises. The indicated structure and heating performance of the membrane, as well as the variation induced by Joule heating, would drive its applications.