Lignin-based materials for electrochemical energy storage devices

Lignin is the most abundant aromatic polymer in nature,which is rich in a large number of benzene ring structures and active functional groups.The molecular structure of lignin has unique designability and controllability,and is a class of functional materials with great application prospects in energy storage and conversion.Here,this review firstly focuses on the concept,classification,and physicochemical property of lignin.Then,the application research of lignin in the field of electrochemical storage materials and devices are summarized,such as lignin-carbon materials and lignin-carbon composites in supercapacitors and secondary batteries.Finally,this review points out the bottlenecks that need to be solved urgently and the prospects for future research priorities.

Lignin-based carbon fibers: Formation, modification and potential applications

As an aromatic polymer in nature, lignin has recently attracted gross attention because of its advantages of high carbon content, low cost and bio-renewability. However, most lignin is directly burnt for power generation to satisfy the energy demand of the pulp mills. As a result, only a handful of isolated lignin is used as a raw material. Thus, increasing value addition on lignin to expand its scope of applications is currently a challenge demanding immediate attention. Many efforts have been made in the valorization of lignin, including the preparation of precursors for carbon fibers. However, its complex structure and diversity significantly restrict the spinnability of lignin. In this review, we provide elaborate knowledge on the preparation of lignin-based carbon fibers ranging from the relationships among chemical structures, formation conditions and properties of fibers, to their potential applications. Specifically, control procedures for different spinning methods of lignin, including melt spinning, solution spinning and electrospinning, together with stabilization and carbonization are deeply discussed to provide an overall understanding towards the formation of lignin-based carbon fibers. We also offer perspectives on the challenges and new directions for future development of lignin-based carbon fibers.

Synthesis of Lignin-Based Polyacid in an Acidic Ionic Liquid: A Green Method to Improve the Performance of Lignin as Catalyst in Urea-Formaldehyde Resin

The aim of this research was to investigate the effect of ionic liquid treated lignin-based polyacid as a catalyst for urea-formaldehyde(UF)resins.Esterification of lignin was carried out,without any catalyst,with anhydride maleic and 1-butyl-3-methylimidazolium hydrogen sulfate[Bmim][HSO 4]as acidic ionic liquid to form maleated lignin-based polyacids(MA-IL).The performance of MA-IL as UF resin catalyst was respectively compared to hyroxymethylated lignin-based polyacid(MA-HL)and to NH 4 Cl.The FTIR analysis indicated that the propor-tion of-COOH and C-O bonds increased due to the esterification of lignin with ionic liquid rather than its hyr-oxymethylation.Physicochemical tests indicated that the gelation time of the UF resin was shorter by adding MA-IL when compared to NH 4 Cl and MA-HL,respectively.DSC analysis showed that the addition of MA-IL significantly decreased the temperature peak(Tp)of the UF resin;as the Tp of the UF resin with 2 wt%MA-IL was lower than with MA-HL and NH 4 Cl,respectively.The panel test results of plywood bonded with a UF resin with a MA-IL level increasing from 1%to 3%,effectively improved the mechanical strength,water resistance and formaldehyde emission even higher than with MA-HL and NH 4 Cl,respectively.

Reinforcement of Lignin-Based Phenol-Formaldehyde Adhesive with Nano-Crystalline Cellulose (NCC): Curing Behavior and Bonding Property of Plywood

The curing behavior of lignin-based phenol-formaldehyde (LPF) resin with different contents of nano-crystalline cellulose (NCC) was studied by differential scanning calorimetry (DSC) at different heating rates (5, 10 and 20&degC/min) and the bonding property was evaluated by the wet shear strength and wood failure of two-ply plywood panels after soaking in water (48 hours at room temperature and followed by 1-hour boiling). The test results indicated that the NCC content had little influence on the peak temperature, activation energy and the total heat of reaction of LPF resin at 5 and 10&degC/min. But at 20&degC/min, LPF0.00% (LPF resin without NCC) showed the highest total heat of reaction, while LPF0.25% (LPF resin containing 0.25% NCC content) and LPF0.50% (LPF resin containing 0.50% NCC content) gave the lowest value. The wet shear strength was affected by the NCC content to a certain extent. With regard to the results of one-way analysis of variance, the bonding quality could be improved by NCC and the optimum NCC content ranged from 0.25% to 0.50%. The wood failure was also affected by the NCC content, but the trend with respect to NCC content was not clear.

Synthesis and characterization of water-soluble PEGylated lignin-based polymers by macromolecular azo coupling reaction

Water-soluble PEG grafted lignin-based polymers （AL-azo-PEG） were efficiently synthesized by macromolecular azo coupling reaction between alkali lignin and PEG based macromolecular diazonium salts in alkaline water. This one-step PEGylation method showed many advantages such as high efficiency, controllable grafting radio, extremely mild conditions and without organic solvents. The prepared AL-azo-PEG polymers were well characterized by using various spectroscopic methods including UV-vis, FTIR and 1H NMR spectra. Experimental results showed that the synthesized polymers had good solubility both in water over a wide pH range （pH 2-12） and in the majority of organic solvents, which helped to easily fabricate self-assembly colloidal particles and nanofibers by vapor diffusion method and electrospinning method, respectively, The azobenzene linkages generated by the macromolecular azo coupling reaction also brought photo-responsive properties to the prepared polymers.

Production of chitosan-based composite film reinforced with lignin-rich lignocellulose nanofibers from rice husk

Lignocellulosic nanofibers(LCNFs),implying lignin-containing cellulose fibers,maintain the prop-erties of both lignin and cellulose,which are hydrophobic and hydrophilic,respectively.The pres-ence of hydrophobic lignin in LCNFs is expected to be an economical and attractive option that can improve the thermal and mechanical properties of polymers.Thus,this study was conducted to produce lignin-rich LCNFs from sugar-rich waste obtained from rice husks after acidic pretreat-ment.The LCNFs were produced from the lignin-rich solid fractions obtained after pretreatment and enzymatic hydrolysis,which were then incorporated as an additive into a chitosan-based film.The variations in lignin content in the range of approximately 50.6%-66.8%in differently obtained LCNFs gave significantly different optical strengths and mechanical properties.These controllable processes may allow for customized film formation.Additionally,the glucose-rich liquid fractions obtained after pretreatment and enzymatic hydrolysis were used as a substrate for ethanol fermentation to achieve total utilization of rice husk biomass waste.In conclusion,the lignin-rich biomass fraction holds promise as a suitable material for chitosan-LCNF film and has the potential to increase the economic feasibility of the biomaterial industry.