Cross-Linked and Shapeable Porous 3D Substrates from Freeze-Linked Cellulose Nanofibrils.

Chemically cross-linked highly porous nanocellulose aerogels with complex shapes have been prepared using a freeze-linking procedure that avoids common post activation of cross-linking reactions and freeze-drying. The aerogel shapes ranged from simple geometrical three-dimensional bodies to swirls and solenoids. This was achieved by molding or extruding a periodate oxidized cellulose nanofibril (CNF) dispersion prior to chemical cross-linking in a regular freezer or by reshaping an already prepared aerogel by plasticizing the structure in water followed by reshaping and locking the aerogel into its new shape. The new shapes were most likely retained by new cross-links formed between CNFs brought into contact by the deformation during reshaping. This self-healing ability to form new bonds after plasticization and redrying also contributed to the mechanical resilience of the aerogels, allowing them to be cyclically deformed in the dry state, reswollen with water, and redried with good retention of mechanical integrity. Furthermore, by exploiting the shapeability and available inner structure of the aerogels, a solenoid-shaped aerogel with all surfaces coated with a thin film of conducting polypyrrole was able to produce a magnetic field inside the solenoid, demonstrating electromagnetic properties. Furthermore, by biomimicking the porous interior and stiff exterior of the beak of a toucan bird, a functionalized aerogel was created by applying a 300 µm thick stiff wax coating on its molded external surfaces. This composite material displayed a 10-times higher elastic modulus compared to that of the plain aerogel without drastically increasing the density. These examples show that it is possible to combine advanced shaping with functionalization of both the inner structure and the surface of the aerogels, radically extending the possible use of CNF aerogels.

Electrochemical characteristics of lignin in CTMP for paper battery electrodes.

Lignin has been extensively researched as a cathode active material in secondary batteries. In the present work, the energy storage potential of lignin naturally present in papers made of chemi-thermomechanical pulp (CTMP) is explored. More specifically, effects from CTMP fines on the electrochemical characteristics have been studied. Compared to pulp fibers, fines are higher in lignin content and have higher specific surface area. It was expected that this would be positive for the electrode performance; however, the result points to the opposite. The fines do not significantly contribute to a higher lignin specific capacity, and they deteriorate the cycling stability. Higher fines content was found to result in a higher oxidative activity as well as more abundant competing reactions. These competing reactions are believed to be linked to the cycle stability. Therefore, we hypothesize that the electrochemical stability of lignin can be better understood by studying differences between fines and fiber lignin. As the theoretical specific capacity of this material is about 20 times larger than obtained here, identification of the reasons for this capacity discrepancy is needed to realize the full potential of lignin-based paper batteries.

Highly Conducting Nanographite-Filled Paper Fabricated via Standard Papermaking Techniques.

Eco-friendly and cost-effective materials and processes to manufacture functional substrates are crucial to further advance the area of printed electronics. One potential key component in the printed electronics platform is an electrically functionalized paper, produced by simply mixing common cellulosic pulp fibers with high-performance electroactive materials. Herein, an electronic paper including nanographite has been prepared using a standardized and scalable papermaking technique. No retention aid was needed to achieve a conducting nanographite loading as high as 50 wt %. The spontaneous retention that provides the integrity and stability of the nanographite paper, likely originates partially from an observed water-stable adhesion of nanographite flakes onto the fiber surfaces. The resulting paper exhibits excellent electrical characteristics, such as an in-plane conductivity of 107 S/cm and an areal capacitance of 9.2 mF/cm2, and was explored as the back-electrode in printed electrochromic displays.

A Multiparameter Pressure-Temperature-Humidity Sensor Based on Mixed Ionic-Electronic Cellulose Aerogels.

Pressure (P), temperature (T), and humidity (H) are physical key parameters of great relevance for various applications such as in distributed diagnostics, robotics, electronic skins, functional clothing, and many other Internet-of-Things (IoT) solutions. Previous studies on monitoring and recording these three parameters have focused on the integration of three individual single-parameter sensors into an electronic circuit, also comprising dedicated sense amplifiers, signal processing, and communication interfaces. To limit complexity in, e.g., multifunctional IoT systems, and thus reducing the manufacturing costs of such sensing/communication outposts, it is desirable to achieve one single-sensor device that simultaneously or consecutively measures P-T-H without cross-talks in the sensing functionality. Herein, a novel organic mixed ion-electron conducting aerogel is reported, which can sense P-T-H with minimal cross-talk between the measured parameters. The exclusive read-out of the three individual parameters is performed electronically in one single device configuration and is enabled by the use of a novel strategy that combines electronic and ionic Seebeck effect along with mixed ion-electron conduction in an elastic aerogel. The findings promise for multipurpose IoT technology with reduced complexity and production costs, features that are highly anticipated in distributed diagnostics, monitoring, safety, and security applications.

Flexible Lamination-Fabricated Ultra-High Frequency Diodes Based on Self-Supporting Semiconducting Composite Film of Silicon Micro-Particles and Nano-Fibrillated Cellulose.

Low cost and flexible devices such as wearable electronics, e-labels and distributed sensors will make the future "internet of things" viable. To power and communicate with such systems, high frequency rectifiers are crucial components. We present a simple method to manufacture flexible diodes, operating at GHz frequencies, based on self-adhesive composite films of silicon micro-particles (Si-µPs) and glycerol dispersed in nanofibrillated cellulose (NFC). NFC, Si-µPs and glycerol are mixed in a water suspension, forming a self-supporting nanocellulose-silicon composite film after drying. This film is cut and laminated between a flexible pre-patterned Al bottom electrode and a conductive Ni-coated carbon tape top contact. A Schottky junction is established between the Al electrode and the Si-µPs. The resulting flexible diodes show current levels on the order of mA for an area of 2 mm(2), a current rectification ratio up to 4 × 10(3) between 1 and 2 V bias and a cut-off frequency of 1.8 GHz. Energy harvesting experiments have been demonstrated using resistors as the load at 900 MHz and 1.8 GHz. The diode stack can be delaminated away from the Al electrode and then later on be transferred and reconfigured to another substrate. This provides us with reconfigurable GHz-operating diode circuits.

Thermoelectric Polymers and their Elastic Aerogels.

Electronically conducting polymers constitute an emerging class of materials for novel electronics, such as printed electronics and flexible electronics. Their properties have been further diversified to introduce elasticity, which has opened new possibility for "stretchable" electronics. Recent discoveries demonstrate that conducting polymers have thermoelectric properties with a low thermal conductivity, as well as tunable Seebeck coefficients - which is achieved by modulating their electrical conductivity via simple redox reactions. Using these thermoelectric properties, all-organic flexible thermoelectric devices, such as temperature sensors, heat flux sensors, and thermoelectric generators, are being developed. In this article we discuss the combination of the two emerging fields: stretchable electronics and polymer thermoelectrics. The combination of elastic and thermoelectric properties seems to be unique for conducting polymers, and difficult to achieve with inorganic thermoelectric materials. We introduce the basic concepts, and state of the art knowledge, about the thermoelectric properties of conducting polymers, and illustrate the use of elastic thermoelectric conducting polymer aerogels that could be employed as temperature and pressure sensors in an electronic-skin.

An Organic Mixed Ion-Electron Conductor for Power Electronics.

A mixed ionic-electronic conductor based on nanofibrillated cellulose composited with poly(3,4-ethylene-dioxythio-phene):-poly(styrene-sulfonate) along with high boiling point solvents is demonstrated in bulky electrochemical devices. The high electronic and ionic conductivities of the resulting nanopaper are exploited in devices which exhibit record values for the charge storage capacitance (1F) in supercapacitors and transconductance (1S) in electrochemical transistors.

Addition of silica nanoparticles to tailor the mechanical properties of nanofibrillated cellulose thin films.

Over the last decade, the use of nanocellulose in advanced technological applications has been promoted both due the excellent properties of this material in combination with its renewability. In this study, multilayered thin films composed of nanofibrillated cellulose (NFC), polyvinyl amine (PVAm) and silica nanoparticles were fabricated on polydimethylsiloxane (PDMS) using a layer-by-layer adsorption technique. The multilayer build-up was followed in situ by quartz crystal microbalance with dissipation, which indicated that the PVAm-SiO(2)-PVAm-NFC system adsorbs twice as much wet mass material compared to the PVAm-NFC system for the same number of bilayers. This is accompanied with a higher viscoelasticity for the PVAm-SiO(2)-PVAm-NFC system. Ellipsometry indicated a dry-state thickness of 2.2 and 3.4 nm per bilayer for the PVAm-NFC system and the PVAm-SiO(2)-PVAm-NFC system, respectively. Atomic force microscopy height images indicate that in both systems, a porous network structure is achieved. Young's modulus of these thin films was determined by the Strain-Induced Elastic Buckling Instability for Mechanical Measurements (SIEBIMM) technique. The Young's modulus of the PVAm/NFC films was doubled, from 1 to 2 GPa, upon incorporation of silica nanoparticles in the films. The introduction of the silica nanoparticles lowered the refractive index of the films, most probably due to an increased porosity of the films.