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Triboelectric nanogenerators (TENGs) are ideal to meet the increasing need for green and efficient energy solutions, e.g., in small wireless and/or wearable applications. Regenerated cellulose is an exemplary material regarding both power output and mechanical performance, and it is environmentally friendly and economically favourable. To further improve the triboelectric performance of the cellulose, colour printing was done on the surface with conventional laser printing. Printer toners commonly contain substances with different triboelectric properties. [1] In this work, cellulose fibres were dissolved using a LiOH/urea solvent and regenerated in an ethanol bath and eventually dried under controlled conditions. Thereafter the resulting transparent cellulose films were run through a conventional laser paper printer to apply toners of different colour and patterns on the surface. Cyan, magenta, yellow and black was printed in one layer. In addition, black was printed in certain patterns from low to high coverage and in several layers to evaluate the effect of applied amount. The samples were analysed using SEM, AFM, XRD, FTIR and a TENG was assembled in the contact-separation mode to investigate the triboelectric performance. The printed cellulose films were found to give enhanced triboelectric output. The results show an interesting and simple processing route to enhance the performance of cellulose- based TENG materials that can be useful in the development of cheap and sustainable small wireless electrical generators or sensors. [1] Zhang, R.; Hummelgård, M.; Örtegren, J.; Andersson, H.; Olsen, M.; Chen, W.; Wang, P.; Eivazi, A.; Dahlström, C.; Norgren, M., Adv. Engin. Mater., 2023, in press, https://doi.org/10.1002/adem.202300107

nks and toners used for printing contain materials, such as polyester, with strong triboelectric properties to enhance the binding effects, making wastepaper, such as magazines and newspapers, good candidates for triboelectric materials. In this study, we report high- output power triboelectric nanogenerators (TENGs) that utilize wastepaper as triboelectric layers (wastepaper-based triboelectric nanogenerators (WP–TENGs)) [1]. Journal paper and office copy paper wastes are investigated. The results show that the maximum power densities of the WP–TENGs reach 43.5 W·m-2, which is approximately 250 times the previously reported output of the TENG with a recycled triboelectric layer made from wastepaper [2]. The maximum open circuit voltage (VOC) and short circuit current (ISC) are 774 V and 3.92 mA (784 mA m-2), respectively. These findings can be applied to extend the life cycle of printed papers for energy harvesting, and they can later be applied for materials recycling to enhance the sustainable development of our society. [1] Zhang, R., Hummelgård, M., Örtegren, J., Andersson, H., Olsen, M., Chen, W., Wang, P., Eivazi, A., Dahlström, C. & Norgren, M. Adv. Engin. Mater., in press, 2023; https://doi.org/10.1002/adem.202300107 [2] Zhang, Z., Jie, Y., Zhu, J., Zhu, Z., Chen, H, Lu, Q., Zeng, Y., Cao, X., Wang, N. & Wang, Z. Nano Res. 15, 1109, 2022; https://doi.org/10.1007/s12274-021-3612-8

In the history of cellulose chemistry, hydrogen bonding has been the predominant explanation when discussing intermolecular interactions between cellulose polymers. This is the general consensus in scholarly textbooks and in many research articles, and it applies to several other biomacromolecules’ interactions as well. This rather unbalanced description of cellulose has likely impacted the development of materials based on the processing of cellulose—for example, via dissolution in various solvent systems and regeneration into solid materials, such as films and fibers, and even traditional wood fiber handling and papermaking. In this review, we take as a starting point the questioning of the general description of the nature of cellulose and cellulose interactions initiated by Professor Björn Lindman, based on generic physicochemical reasoning about surfactants and polymers. This dispute, which became known as “the Lindman hypothesis”, highlights the importance of hydrophobic interactions in cellulose systems and that cellulose is an amphiphilic polymer. This paper elaborates on Björn Lindman’s contribution to the subject, which has caused the scientific community to revisit cellulose and reconsider certain phenomena from other perspectives.

Inks and toners used for printing contain materials, such as polyester, with strong triboelectric properties to enhance the binding effects, making wastepaper, such as magazines and newspapers, good candidates for triboelectric materials. Herein, high-output power triboelectric nanogenerators (TENGs) that utilize wastepaper as triboelectric layers (wastepaper-based triboelectric nanogenerators (WP–TENGs)) are reported. Journal paper and office copy paper wastes are investigated. The results show that the maximum power densities of the WP–TENGs reach 43.5 W m−2, which is approximately 250 times the previously reported output of the TENG with a recycled triboelectric layer made from wastepaper. The maximum open circuit voltage (V OC) and short circuit current (I SC) are 774 V and 3.92 mA (784 mA m−2), respectively. These findings can be applied to extend the life cycle of printed papers for energy harvesting, and they can later be applied for materials recycling to enhance the sustainable development of our society.

The triboelectric properties of the tribolayers are essential factors affecting the current density of triboelectric nanogenerators (TENGs). To enhance the current density, composites have been developed to tune their triboelectric properties. Previous studies have reported enhanced TENG performance with composite materials, primarily based on their composition, while chemical interactions between the components have been less analyzed. In this study, we report a novel approach to improve the current density of a TENG by introducing dipole-dipole interactions between a nylon filter membrane and graphene oxide (GO) through hydrogen bonds. The Raman spectroscopy confirmed the occurrence of the interactions resulting from hydrogen bonding. The enhancing mechanisms of hydrogen bonds were further analyzed by Kelvin probe force microscope (KPFM) measurement, which demonstrated that hydrogen bonding could influence the surface potential of the coated GO, leading to increased output of the nylon/GO@NFM TENG (NGN-TENG). Our results show that an ultrahigh current density of 1757 mA·m−2 was obtained with a 2 × 2 cm2 NGN-TENG. Additionally, we demonstrated the feasibility of using the NGN-TENG as a motion sensor to sense finger motions. These findings suggest that the introduction of hydrogen bonds in TENG composites can provide a promising route for improving their performance.

Triboelectric nanogenerators (TENGs) have attracted increasing attention because of their excellent energy conversion efficiency, the diverse choice of materials, and their broad applications in energy harvesting devices and self-powered sensors. New materials have been explored, including green materials, but their performances have not yet reached the level of that for fluoropolymers. Here, a high-performance, fully green TENG (FG-TENG) using cellulose-based tribolayers is reported. It is shown that the FG-TENG has an output power density of above 300 W m−2, which is a new record for green-material-based TENGs. The high performance of the FG-TENG is due to the high positive charge density of the regenerated cellulose. The FG-TENG is stable after more than 30 000 cycles of operations in humidity of 30%–84%. This work demonstrates that high-performance TENGs can be made using natural green materials for a broad range of applications.

The current work aims at understanding factors that influence the processability of nanographite-nanocellulose suspensions onto flexible substrates for production of conductive electrodes. A custom-built slot-die was used in a continuous rollto-roll process to coat the nanomaterial suspension onto substrates with varying surface smoothness, thickness, pore structure, and wet strength. The influence of a carboxymethyl cellulose (CMC) additive on suspension rheology, water release properties, and coating quality was probed. CMC addition reduced the suspension yield stress by 2 orders of magnitude and the average pore diameter of the coated electrodes by 70%. Sheet resistances of 5-9 Omega sq(-1) were obtained for the conductive coatings with a coat weight of 12-24 g m(-2). Calendering reduced the sheet resistance to 1-3 Omega sq(-1) and resistivity to as low as 12 mu Omega m. The coated electrodes were used to demonstrate a metal-free aqueous-electrolyte supercapacitor with a specific capacitance of 63 F g(-1). The results increase our understanding of continuous processing of nanographite-nanocellulose suspensions into electrodes, with potential uses in flexible, lightweight, and environmentally friendly energy devices.

Cellulose in different forms is increasingly used due to sustainability aspects. Even though cellulose itself is an isolating material, it might affect ion transport in electronic applications. This effect is important to understand for instance in the design of cellulose-based supercapacitors. To test the ion conductivity through membranes made from cellulose nanofibril (CNF) materials, different electrolytes chosen with respect to the Hofmeister series were studied. The CNF samples were oxidised to three different surface charge levels via 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), and a second batch was further cross-linked by periodate oxidation to increase wet strength and stability. The outcome showed that the CNF pre-treatment and choice of electrolyte are both crucial to the ion conductivity through the membranes. Significant specific ion effects were observed for the TEMPO-oxidised CNF. Periodate oxidated CNF showed low ion conductivity for all electrolytes tested due to an inhibited swelling caused by the crosslinking reaction. © 2020 Elsevier Ltd

A sustainable strategy for synergistic surface engineering of lignocellulose and cellulose fibers derived from wood by synergistic combination of metal‐free catalysis and renewable polyelectrolyte (PE) complexes is disclosed. The strategy allows for improvement and introduction of important properties such as strength, water resistance, and fluorescence to the renewable fibers and cellulosic materials. For example, the “green” surface engineering significantly increases the strength properties (up to 100% in Z‐strength) of chemi‐thermomechanical pulp (CTMP) and bleached sulphite pulp (BSP)‐derived sheets. Next, performing an organocatalytic silylation with a nontoxic organic acid makes the corresponding lignocellulose and cellulose sheets hydrophobic. A selective color modification of polysaccharides is developed by combining metal‐free catalysis and thiol‐ene click chemistry. Next, fluorescent PE complexes based on cationic starch (CS) and carboxymethylcellulose (CMC) are prepared and used for modification of CTMP or BSP in the presence of a metal‐free catalyst. Laser‐scanning confocal microscopy reveals that the PE‐strength additive is evenly distributed on the CTMP and heterogeneously on the BSP. The fluorescent CS distribution on the CTMP follows the lignin distribution of the lignocellulosic fibers.

In article number 1900018 by Armando Cordova and co‐workers, the novel combination of metal‐free catalysis and renewable polyelectrolyte complexes leads to synergistic surface engineering of lignocellulose and cellulose fibers derived from wood. This sustainable strategy allows for improvement and introduction of important properties such as strength (up to 100% in Z‐strength), water resistance, and fluorescence to the renewable fibers and cellulosic materials under eco‐friendly conditions.

In this study, Cu and Cu2O nanoparticles (NPs) were synthesized through chemical reduction of soluble copper-chelating ligand complexes using formaldehyde as a reducing agent. The influence of various chelating ligands, such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and a surface-active derivative of DTPA (C12-DTPA), as well as surfactants (i.e., hexadecyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium chloride (DoTAC), sodium dodecyl sulfate (SDS), and dimethyldodecylamine-N-oxide (DDAO)), on morphology and the composition of produced NPs was investigated. In the absence of surfactants, spherical copper particles with polycrystalline structure could be obtained. X-ray diffraction (XRD) analysis revealed that, in the presence of EDTA, the synthesized NPs are mainly composed of Cu with a crystallite size on the order of 35 nm, while with DTPA and C12-DTPA, Cu2O is also present in the NPs as a minority phase. The addition of ionic surfactants to the copper–EDTA complex solution before reduction resulted in smaller spherical particles, mainly composed of Cu. However, when DDAO was added, pure Cu2O nano-octahedrons were formed, as verified by high-resolution scanning electron microscopy (HR-SEM) and XRD. Furthermore, a hybrid material could be successfully prepared by mixing the octahedral Cu2O NPs with cellulose dissolved in a LiOH/urea solvent system, followed by spin-coating on silica wafers. It is expected that this simple and scalable route to prepare hybrid materials could be applied to a variety of possible applications.

Printed electronics are of increasing interest. The substrates used have primarily been plastics although the interest for cellulose-based substrates is increasing due to the environmental aspect as well as cost. The requirements of substrates for electronically active inks differs from graphical inks and therefore we have investigated a custom-made pigment based coated paper and compared it to commercial photo-papers and a coated PE film. Our goal with the study of different substrates was to select the most suitable substrate to print water based 2D materials inkjet inks for flexible electronics. The discovery of graphene, a layered material achieved from the exfoliation of graphite, has resulted in the study of other materials with similar properties to cover areas where graphene could not be used due to the absence of a bandgap in the material. For example in thin film transistors (TFT) a semiconductor layer is essential to enable turn on and off the device. This semiconductor layer can be achieved using various materials but particular interest have been dedicated to abundant and cheap 2D materials such as the transition metal dichalcogenide (TMD) molybdenum disulfide (MoS2). To date, most of the dispersions based on TMDs use organic solvents or water solutions of surfactants. Previously we focus on the study of environmental friendly inks produced by liquid phase exfoliation (LPE) of MoS2 in water using cellulose stabilizers such as ethyl cellulose (EC), cellulose nanofibrils (CNF) and nanofibrilcellulose (NFC). We have study various aspects of the ink fabrication includi ng pH range, the source of MoS2, nanosheets thickness, particle size distribution, ink stabilizers, ink concentration, viscosity and surface tension. These inks have very low concentration requiring a number of printing passes to cover the substrate. Therefore the substrate selection is crucial as a large amount of solvent is to be absorb by the substrate. Our goal was to use such an ink to, Proceedings will be published on the Elsevier Journal Thin Solid Films.

The sustainable improvement of the strength properties of chemimechanical pulp by eco-friendlycatalysis is disclosed. Significant research activities have been performed on the use of cationic starchand polyelectrolyte complexes for improving the strength properties of cellulose-based materials. Herewe apply an eco-friendly strategy based on catalysis for significantly improving the strength propertiesof sheets made from chemimechanical pulp (CTMP) and bleeched sulphite pulp (BSP) using sustainablepolyelectrolyte complexes as the strength additives and organocatalysis. This surface engineeringstrategy significantly increased the strength properties of the assembled sheets (up to 100% in the caseof Z-strength). We also developed a catalytic selective colour marking of the cationic potato starch (CS)and carboxymethylcellulose (CMC) in order to elucidated how the specific strength additives aredistributed on the sheets. It revealed that the strength additives were more evenly distributed on thesheets made from CTMP as compared to BSP sheets. This is most likely attributed to the presence oflignin in the former lignocellulosic material. It also contributes to the increase in strength (up to 100%,Z-strength) for the CTMP derived sheets. The selective colour marking method also revealed that morestrength additives had been bound to the pulps in the presence of the catalyst.

Paper products with active and functional coatings have attracted interest in recent years to counter the stagnating demand for traditional graphic paper grades. Conductive coatings have potential uses in various energy generation and storage applications, e.g. in batteries, supercapacitors, and photovoltaics. The current work aims to demonstrate large-scale production of flexible low-cost nanographite coatings on paper-based substrate. The large aspect ratio of graphene present in the suspension limits solids content to very low values, which makes it challenging to create thick coating layers required for high conductivity. The use of nanocellulose binder together with a custom-built slot-coating device enables roll-to-roll coating of thick conductive coatings on paper. The rheological and water-retention properties of nanographite-nanocellulose suspensions are reported. The influence of coat weight, carbon black addition, and calendering on coating structure and the resulting conductivity of the coatings is investigated. Impact of humidity and bending/creasing of coated samples on their electrical performance is explored as well. The lowest surface resistances obtained were in the range 1-2 Ohm/square, for 15 g m(-2) coat weight. Increasing the coat weight and calendering nip load resulted in higher conductivity of coatings. Carbon black addition deteriorated the conductivity somewhat, probably due to increased porosity of coatings. Moisture and creasing did not affect significantly the conductivity of high coat weight and calendered samples. The results reported are very encouraging for future research on further improving the electrical performance of such carbon coatings.

Invited lecture

Many solution processing methods of exfoliation of layered materials have been studied during the last few years; most of them are based on organic solvents or rely on surfactants andother funtionalization agents. Pure water should be an ideal solvent, however, it is generallybelieved, based on solubility theories that stable dispersions of water could not be achievedand systematic studies are lacking. Here we describe the use of water as a solvent and thestabilization process involved therein. We introduce an exfoliation method of molybdenumdisulfide (MoS2) in pure water at high concentration (i.e., 0.14±0.01 g L−1). This was achieved by thinning the bulk MoS2by mechanical exfoliation between sand papers and dis-persing it by liquid exfoliation through probe sonication in water. We observed thin MoS2nanosheets in water characterized by TEM, AFM and SEM images. The dimensions of thenanosheets were around 200 nm, the same range obtained in organic solvents. Electropho-retic mobility measurements indicated that electrical charges may be responsible for the sta-bilization of the dispersions. A probability decay equation was proposed to compare thestability of these dispersions with the ones reported in the literature. Water can be used as asolvent to disperse nanosheets and although the stability of the dispersions may not be ashigh as in organic solvents, the present method could be employed for a number of applications where the dispersions can be produced on site and organic solvents are not desirable., Paper Solar Cells

Symmetric electric double-layer capacitors (EDLCs) have equal masses of the same active material in both electrodes. However, having equal electrode masses may prevent the EDLC to have the largest possible specific capacitance if the sizes of the hydrated anions and cations in the electrolyte differ because the electrodes and the electrolyte may not be completely utilized. Here we demonstrate how this issue can be resolved by mass balancing. If the electrode masses are adjusted according to the size of the ions, one can easily increase an EDLC's specific capacitance. To that end, we performed galvanostatic cycling to measure the capacitances of symmetric EDLCs with different electrode mass ratios using four aqueous electrolytes-Na2SO4, H2SO4, NaOH, and KOH (all with a concentration of 1 M)-and compared these to the theoretical optimal electrode mass ratio that we calculated using the sizes of the hydrated ions. Both the theoretical and experimental values revealed lower-than-1 optimal electrode ratios for all electrolytes except KOH. The largest increase in capacitance was obtained for EDLCs with NaOH as electrolyte. Specifically, we demonstrate an increase of the specific capacitance by 8.6% by adjusting the electrode mass ratio from 1 to 0.86. Our findings demonstrate that electrode mass balancing is a simple and inexpensive method to increase the capacitance of EDLCs. Furthermore, our results imply that one can reduce the amount of unused material in EDLCs and thus decrease their weight, volume and cost.

Though research into nanofibrillated cellulose (NFC) has recently increased, few studies have considered co-utilising NFC and nanographite(NG) in composite films, and, it has, however been a challenge to use high-yield pulp fibres (mechanical pulps) to produce this nanofibrillar material. It is worth noting that there is a significant difference between chemical pulp fibres and high-yield pulp fibres, as the former is composed mainly of cellulose and has a yield of approximately 50 % while the latter is consist of cellulose, hemicellulose and lignin, and has a yield of approximately 90 %. NFC was produced by combining TEMPO (2,2,6,6-tetramethypiperidine-1-oxyl)-mediated oxidation with the mechanical shearing of chemi-thermomechanical pulp (CTMP) and sulphite pulp (SP); the NG was produced by mechanically exfoliating graphite. The different NaClO dosages in the TEMPO system differently oxidised the fibres, altering their fibrillation efficiency. NFC-NG films were produced by casting in a Petri dish. We examine the effect of NG on the sheet-resistance and mechanical properties of NFC films. Addition of 10 wt% NG to 90 wt% NFC of sample CC2 (5 mmol NaClO CTMP-NFC homogenised for 60 min) improved the sheet resistance, i.e. from that of an insulating pure NFC film to 180 Omega/sq. Further addition of 20 (CC3) and 25 wt% (CC4) of NG to 80 and 75 wt% respectively, lowered the sheet resistance to 17 and 9 Omega/sq, respectively. For the mechanical properties, we found that adding 10 wt% NG to 90 wt% NFC of sample HH2(5 mmol NaClO SP-NFC homogenised for 60 min) improved the tensile index by 28 %, tensile stiffness index by 20 %, and peak load by 28 %. The film's surface morphology was visualised using scanning electron microscopy, revealing the fibrillated structure of NFC and NG. This methodology yields NFC-NG films that are mechanically stable, bendable, and flexible.

MoS2 is a layered material which is abundant and non-toxic and has been increasingly studied during the last few years as a semiconducting alternative to graphene. While most studies have been performed on single MoS2 nanosheets, for example to demonstrate high-performance electronic transistors, more work is needed to explore the use of MoS2 in printed electronics. The importance of using MoS2 as a printed electronic material could be understood by considering the several orders higher electron mobility in MoS2, even in several nanometer thick layers, compared to the organic and other materials used today. In the few studies performed so far on printing MoS2, the developed dispersions used mainly organic solvents that might be detrimental for the environment. Here, we show an environmentally friendly liquid-based exfoliation method in water where the solution was stabilized by sodium dodecyl sulfate (SDS) surfactant. The dispersions consisted of very thin MoS2 nanosheets with average lateral size of about 150 nm, surface tension of 28 mN m(-1), and a shelf life of a year. Although both the concentration and viscosity was less than optimal, we were able to inkjet print the MoS2 solution on paper and on PET films, using multiple printing passes. By tuning the concentration/viscosity, this approach might lead to an environmentally friendly MoS2 ink suitable for printed electronics.

Invited lecture