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Laser-induced graphitization (LIG) is a method of converting a carbon-rich precursor into a highly conductive graphite-like carbon by laser scribing. This method has shown great promise as a versatile and low-cost patterning technique. Here we show for the first time how an ink based on cellulose and lignin can be patterned using screen printing followed by laser graphitization. Screen printing is one of the most commonly used manufacturing techniques of printed electronics, making this approach compatible with existing processing of various devices. The use of forest-based materials opens the possibility of producing green and sustainable electronics. Pre-patterning of the ink enables carbon patterns without residual precursor between the patterns. We investigated the effect of the ink composition, laser parameters, and additives on the conductivity and structure of the resulting carbon and could achieve low sheet resistance of 3.8 Ω sq−1 and a high degree of graphitization. We demonstrated that the process is compatible with printed electronics and finally manufactured a humidity sensor which uses lignin as the sensing layer and graphitized lignin as the electrodes.

Redox flow batteries represent a remarkable alternative for grid-scale energy storage. They commonly employ carbon felts or carbon papers, which suffer from low activity towards the redox reactions involved, leading to poor performance. Here we propose the use of electrospun freestanding carbon materials derived from lignin as alternative sustainable electrodes for all-vanadium flow batteries. The lignin-derived carbon electrospun mats exhibited a higher activity towards the VO2+/VO2+ reaction than commercial carbon papers when tested in a three-electrode electrochemical cell (or half-cell), which we attribute to the higher surface area and higher amount of oxygen functional groups at the surface. The electrospun carbon electrodes also showed performance comparable to commercial carbon papers, when tested in a full cell configuration. The modification of the surface chemistry with the addition of phosphorous produced different effect in both samples, which needs further investigation. This work demonstrates for the first time the application of sustainably produced electrospun lignin-derived carbon electrodes in a redox flow cell, with comparable performance to commercial materials and establishes the great potential of biomass-derived carbons in energy devices.

In this study, a renewable reinforcement, namely cellulose nanocrystals (CNC), was used to develop a bio-based nanocomposite UV-cured coating system with improved performance. CNC was modified in order to be compatible with the nonpolar polymer matrix (acrylated epoxidized soybean oil (AESO)). The CNC was modified by two methods, with acryloyl chloride or a cationic surfactant (HDTMA). The mechanical properties and structure of bionanocomposites were evaluated. The addition of CNC increased modulus of elasticity (MOE) and tensile strength of the cured film coatings. Use of CNC modified by HDTMA and acrylated CNC led to a higher increase in tensile strength and MOE, relative to un-modified CNC. Best performance enhancement was in hardness and reduced elastic modulus (Er), measured by the nanoindentation technique, which were improved several fold by CNC addition. Hardness, Er, MOE and tensile strength increased with CNC loading level in the matrix. Hardness measurements of cured film coating by pencil hardness test methods confirmed that CNC improved the hardness of the films. Studying the morphology of the nanocomposites revealed that surface modification method of CNC affected nanocomposite film structure and thus the mechanical properties.

Demand for durable clear wood coatings is on the rise. Cellulose nanocrystals (CNC) constitute an organic nanomaterial widely studied in polymer composites for its reinforcing effect. In this study, CNC was used to enhance the performance of a UV curable high-solid content coating system intended for indoor environments. The CNC surface was modified by a cationic surfactant since the coating system was hydrophobic resin-based requiring hydrophobic nanomaterial reinforcement. Modified CNC was mixed with the coating system using a high-speed mixer and the ultrasonication technique. Mechanical, thermal and morphological properties and curing behavior of the newly developed UV-curing coatings were assessed. Inclusion of CNC in the coating increased the mechanical properties (hardness and reduced modulus) of the coating system to a large extent. Thermal stability of the coating system was also improved by CNC addition. The CNC did not affect the curing behavior of the coating, in contrast to most inorganic nanomaterials. The CNC dispersed well in the matrix at 1% loading. Results of this study show that CNC can be used successfully with high-solid content coating systems.

The process of stabilization is essential in the production of carbon fibers from lignins. During stabilization, the initially thermoplastic lignin polymer is converted to a thermoset polymer allowing for high-temperature treatment without a change in shape. In this work, hardwood (HKL) and softwood (SKL) Kraft lignins were stabilized in air at temperatures between 190 and 340 °C before carbonization at 800 °C in a nitrogen atmosphere. Due to the differences in side-chain linkages, functional groups and molar mass, the lignins exhibit different structural changes upon stabilization and hence develop different porosities upon carbonization. Both lignins undergo major crosslinking reactions in the side chains at low temperatures and degradation reactions at high temperatures during stabilization. Crosslinking gives rise to narrow pore size distributions with mainly (sub-) nanometer pores, whereas degradation reactions lead to a more open pore structure with additional mesoporosity (>2 nm). When both types of reactions take place simultaneously, highly accessible (sub-) nanoporosity can be effectively created, which boosts the performance of supercapacitors operating in 6 M KOH(aq). This effect terminates when the crosslinking reactions cease and mainly degradation reactions take place, which occurs in HKL at 340 °C. SKL shows both a lower degree of crosslinking and degradation and hence develops less specific surface area. The optimum performance in an aqueous alkaline supercapacitor is achieved with HKL stabilized at 310 °C. It shows a specific gravimetric capacitance of 164 F g−1 at 0.1 A g−1 and 119 F g−1 at 250 A g−1 with a capacitance retention of more than 90% after 10 000 cycles. M. J. M. L. and D. C. A. thank Spanish Ministry of Science, Innovation and Universities and FEDER (project RTI2018-095291-B-I00) for financial support. C. P. G. and C. O'K. thank Shell. MMT and PS thank RISE AB for co-funding Philipp Schlee's PhD position.

In this study, continuous lignin fibers from switchgrass have been successfully synthesized via multifilament melt-spinning and converted to carbon fibers using optimized stabilization and carbonization techniques. Unidirectional lignin carbon fiber reinforced composites are produced using a vacuum assisted resin transfer molding process for the first time. Produced lignin carbon fiber is evaluated in mechanical, interfacial, and microstructural areas. Single fiber mechanical properties are characterized using a unique MTS Bionix Nano-UTM. Interfacial properties and resin/fiber behavior are evaluated using single fiber fragmentation. Microstructural properties are determined using wide-angle x-ray diffraction. Mechanical results indicated an initial tensile modulus along fiber axis of 36 GPa and a failure stress of 600 MPa for single carbon fibers. Lignin carbon fibers demonstrate a nonlinear increase in modulus with applied tensile strain similar to recently observed for commercial poly-acrylonitrile (PAN) carbon fibers. Microscopy revealed few defects within and along the lignin carbon fibers, and the processed lignin fibers demonstrated minimal crystalline regions and crystallite alignment when compared to commercial PAN based fibers. Interfacial shear strength with epoxy resin was found to be 17 MPa with a fiber fracture length of 228 μm. Unidirectional composite coupons achieved tensile modulus of 9 GPa and a failure strength of 85 MPa at 1% failure strain. Lignin carbon fiber and composites produced are targeted for non-structural applications as mechanical properties are currently less than PAN carbon fibers and therefore are not suitable to replace PAN carbon fiber at this stage. Relatively low composite strength is the likely result of fiber layup, fiber fusing, and non-continuous fibers across the gage length of the composite. Nano-tensile and interface shear strength results presented here have important implications for lignin carbon fiber composite development to optimize fiber/resin bonding. In addition, composite manufacturing procedures detailed here are a major step forward in the development of sustainable carbon fiber composite production.

Lignin was extracted from Alamo switchgrass (Panicum virgatum) and yellow polar (Liriodendron tulipifera) by organosolv fractionation at different pretreatment temperatures, and its chemical structure was studied by means of elemental analysis and spectroscopy. Thermal properties of lignins were investigated using thermogravimetric analysis and differential scanning calorimetry. Lignin fibers were produced via melt-spinning by a twin-screw extruder with a custom spinneret. Fibers were thermostabilized at different rates and finally carbonized. In both species, lignin obtained from higher severity organosolv fractionation had fewer impurities, higher content of phenolic hydroxyl groups, and more condensed structures as a result of extensive cleavage of aryl ether linkages. Higher organosolv severity improved the ability to spin fibers; in the case of switchgrass, only the high severity sample was spinnable. High severity also decreased thermostabilization time and increased tensile strength and modulus of ...

A very simple method to enhance the low volumetric energy density of free-standing carbon nanofiber electrodes., We have discovered a very simple method to address the challenge associated with the low volumetric energy density of free-standing carbon nanofiber electrodes for supercapacitors by electrospinning Kraft lignin in the presence of an oxidizing salt (NaNO3) and subsequent carbonization in a reducing atmosphere. The presence of the oxidative salt decreases the diameter of the resulting carbon nanofibers doubling their packing density from 0.51 to 1.03 mg cm–2 and hence doubling the volumetric energy density. At the same time, the oxidative NaNO3 salt eletrospun and carbonized together with lignin dissolved in NaOH acts as a template to increase the microporosity, thus contributing to a good gravimetric energy density. By simply adjusting the process parameters (amount of oxidizing/reducing agent), the gravimetric and volumetric energy density of the resulting lignin free-standing carbon nanofiber electrodes can be carefully tailored to fit specific power to energy demands. The areal capacitance increased from 147 mF cm–2 in the absence of NaNO3 to 350 mF cm–2 with NaNO3 translating into a volumetric energy density increase from 949 μW h cm–3 without NaNO3 to 2245 μW h cm–3 with NaNO3. Meanwhile, the gravimetric capacitance also increased from 151 F g–1 without to 192 F g–1 with NaNO3.

Pure eucalyptus Kraft lignin derived carbon fiber mats were produced based on a model workflow. It covers the preparation and characterization of the lignin precursor and the carbon materials and its testing in the final application (supercapacitor). Sequential solvent extraction was employed to produce a eucalyptus Kraft lignin precursor which could be electrospun into lignin fibers without any additives. The fiber formation from low molecular weight lignin is assigned to strong intermolecular interactions via hydrogen bonding and π-π-stacking between individual lignin macromolecules which gives rise to association complexes in the electrospinning solution. By stabilization in air, carbonization in N2 and an activation step in CO2, free-standing microporous carbon fiber mats could be produced. These fiber mats possess mainly basic oxygen functional groups which proved to be beneficial when tested as free-standing electrodes in symmetric supercapacitors. Consequently, the CO2-activated fiber mats showed a high specific gravimetric capacitance of 155 F/g at 0.1 A/g, excellent rate capability with 113 F/g at 250 A/g and good capacitance retention of 94% after 6000 cycles when tested in 6 M KOH electrolyte. Therefore, we conclude that lignin itself is a promising precursor to produce microporous, oxygen functionalized carbon fibers serving as free-standing electrodes in aqueous supercapacitors. We would like to thank EPSRC (EP/R021554/1, EP/N509899/1, EP/P031323/1) for the financial support.

Organosolv fractionation is a promising pathway to separate cellulosic biomass into high purity cellulose, hemicelluloses, and lignin. This work specifically investigates the properties of lignins isolated at specific time points as fractionation progressed, with the intent of correlating fractionation time with lignin purity, yield, thermal and chemical properties. Yellow poplar (Liriodendron tulipifera) was fractionated using a mixture of methyl isobutyl ketone, ethanol, and water with sulfuric acid as catalyst at 140 °C over a two-hour period. Aliquots of the liquor were collected by sampling every 15 min during the fractionation to generate a series of lignins. The results showed that with increased fractionation time, lignin purity improved from 90.3 to 94.6% and the glass transition temperature increased from 117 to 137 °C. The loss of aliphatic OH and increase of phenolic OH with fractionation time led to an increase in condensed structures and increased polydispersity at times greater than 90 min. Principal component analysis of Fourier transform infrared spectroscopic data confirmed the shift to higher purity and more condensed chemical structures with increasing fractionation time. Overall, this study demonstrates that thermal and chemical properties of lignin change with the organosolv fractionation time.

Lignin/lignin blends were used to improve fiber spinning, stabilization rates, and properties of lignin-based carbon fibers. Organosolv lignin from Alamo switchgrass (Panicum virgatum) and yellow poplar (Liriodendron tulipifera) were used as blends for making lignin-based carbon fibers. Different ratios of yellow poplar:switchgrass lignin blends were prepared (50:50, 75:25, and 85:15 w/w). Chemical composition and thermal properties of lignin samples were determined. Thermal properties of lignins were analyzed using thermogravimetric analysis and differential scanning calorimetry. Thermal analysis confirmed switchgrass and yellow poplar lignin form miscible blends, as a single glass transition was observed. Lignin fibers were produced via melt-spinning by twin-screw extrusion. Lignin fibers were thermostabilized at different rates and subsequently carbonized. Spinnability of switchgrass lignin markedly improved by blending with yellow poplar lignin. On the other hand, switchgrass lignin significantly improved thermostabilization performance of yellow poplar fibers, preventing fusion of fibers during fast stabilization and improving mechanical properties of fibers. These results suggest a route towards a 100% renewable carbon fiber with significant decrease in production time and improved mechanical performance.

Replacing petroleum by biomass can be economically feasible by generating revenue from the three primary biomass constituents., The production of renewable chemicals and biofuels must be cost- and performance- competitive with petroleum-derived equivalents to be widely accepted by markets and society. We propose a biomass conversion strategy that maximizes the conversion of lignocellulosic biomass (up to 80% of the biomass to useful products) into high-value products that can be commercialized, providing the opportunity for successful translation to an economically viable commercial process. Our fractionation method preserves the value of all three primary components: (i) cellulose, which is converted into dissolving pulp for fibers and chemicals production; (ii) hemicellulose, which is converted into furfural (a building block chemical); and (iii) lignin, which is converted into carbon products (carbon foam, fibers, or battery anodes), together producing revenues of more than $500 per dry metric ton of biomass. Once de-risked, our technology can be extended to produce other renewable chemicals and biofuels.

The collision-activated fragmentation pathways and reaction mechanisms of 34 deprotonated model compounds representative of lignin degradation products were explored experimentally and computationally. The compounds were evaporated and ionized by using negative-ion mode electrospray ionization doped with NaOH to produce abundant deprotonated molecules. The ions were isolated and subjected to collision-activated dissociation (CAD). Their fragment ions were then isolated and also subjected to CAD. This was repeated until no further fragmentation was observed (up to MS6 ). This approach enabled the identification of characteristic reaction pathways and delineation of reasonable fragmentation mechanisms for deprotonated molecules containing various functional groups. The varying fragmentation patterns observed for different types of compounds allow for the identification of the functionalities in these compounds. This information was utilized to identify the presence of specific functionalities and their combinations in molecules in an organosolv lignin sample.

Organosolv switchgrass lignin (SGL) and hardwood lignin (HWL) polymers are used as precursors to prepare low cost carbon fibers (CFs). Lignin powder and fiber samples are stabilized and carbonized at different conditions to investigate the effect of HCl on thermal-oxidative stabilization time, mass yield, fiber diameter, and mechanical properties. The results show that HCl can accelerate stabilization and reduce the stabilization time from many hours to 75 min for the SGL fibers, and to 35 min for the HWL fiber. The rate of rapid stabilization in HCl/air is at least four times faster than conventional stabilization in air. The CFs prepared with two different stabilization methods have almost the same strength and modulus, but higher carbon yield is obtained with the rapid stabilization due to a short time of oxidation. Pores and defects observed on the surface and the cross-section of the CFs across all stabilization conditions contribute to low fiber strength. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45507.