Innovative modification of cellulose fibers for paper-based electrode materials using metal-organic coordination polymers.

Cellulosic paper-based electrode materials have attracted increasing attention in the field of flexible supercapacitor. As a conductive polymer, polyaniline exhibits high theoretical pseudocapacitive capacitance and has been applied in paper-based electrode materials along with cellulose fibers. However, the stacking of polyaniline usually leads to poor performance of electrodes. In this study, metal-organic coordination polymers of zirconium-alizarin red S and zirconium-phytic acid are applied to modulate the polyaniline layer to obtain high-performance cellulosic paper-based electrode materials. Zirconium hydroxide is firstly loaded on cellulose fibers while alizarin red S and phytic acid are introduced to regulate the morphology of polyaniline through doping and coordination processes. The results show that the introduction of dual coordination polymers is effective to regulate the morphology of polyaniline on cellulose fibers. The performances of the paper-based electrode materials, including electrical conductivity and electrochemistry, are apparently improved. It provides a promising strategy for the potential development of economical and green electrode materials in the conventional paper-making process.

Sustainable Polyvinyl Chloride-Derived Soft Carbon Anodes for Potassium-Ion Storage: Electrochemical Behaviors and Mechanism.

Soft carbon is a promising anode material for potassium-ion batteries due to its favorable properties such as low cost, high conductivity, stable capacity, and low potential platform. Polyvinyl chloride, as a white pollutant, is a soft carbon precursor that can be carbonized at varying temperatures to produce soft carbons with controllable defect and crystal structures. This work investigates the effect of carbonization temperature on the crystalline structures of the obtained soft carbons. In situ Raman spectroscopy was used to elucidate the adsorption-intercalation charge storage mechanism of potassium ions in soft carbons. Soft carbons prepared at the temperature of 800 °C have a defect-rich, short-range ordered structure, which provides optimal intercalation and adsorption sites for potassium ions, resulting in a satisfactory capacity of 302 mAh g-1 . This work presents new possibilities for designing soft carbon materials from recycling plastics for potassium-ion batteries.

Zinc Vacancy Promotes Photo-Reforming Lignin Model to H2 Evolution and Value-Added Chemicals Production.

Lignin, rich in ß-O-4 bonds and aromatic structure, is a renewable and potential resource for value-added chemicals and promoting H2 evolution. However, direct photo-reforming lignin remains a huge challenge due to its recalcitrant structure. Herein, a collaborative strategy is proposed by dispersing Pt on zinc-vacancy-riched ZnIn2 S4 (Pt/VZn -ZIS) for revealing the effect of lignin structure during photo-reforming process with lignin models. And a series of theoretical calculations and experimental results show that lignin model substances with more nucleophilic group structures will have a stronger tendency to occur the photo-reforming reactions. In addition, benefiting of Pt-S electronic channel is formed by occupying Pt atom onto zinc vacancies in ZnIn2 S4 , which can effectively reduce the energy barrier of H2 evolution and accompany the selective oxidation of lignin model from Cα-OH to Cα = O under simulated sunlight. The natural lignin is used to further demonstrate this selective oxidation mechanism. The presented work demonstrates the photo-reforming lignin model mechanism and the influence of lignin-structure during the process of photo-reforming.

Structure and Interface Engineering of Ultrahigh-Rate 3D Bismuth Anodes for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have attracted tremendous attention as promising low-cost energy storage devices in future grid-scale energy management applications. Bismuth is a promising anode for SIBs due to its high theoretical capacity (386 mAh g-1 ). Nevertheless, the huge volume variation of Bi anode during (de)sodiation processes can cause the pulverization of Bi particulates and rupture of solid electrolyte interphase (SEI), resulting in quick capacity decay. It is demonstrated that rigid carbon framework and robust SEI are two essentials for stable Bi anodes. A lignin-derived carbonlayer wrapped tightly around the bismuth nanospheres provides a stable conductive pathway, while the delicate selection of linear and cyclic ether-based electrolytes enable robust and stable SEI films. These two merits enable the long-term cycling process of the LC-Bi anode. The LC-Bi composite delivers outstanding sodium-ion storage performance with an ultra-long cycle life of 10 000 cycles at a high current density of 5 A g-1 and an excellent rate capability of 94% capacity retention at an ultrahigh current density of 100 A g-1 . Herein, the underlying origins of performance improvement of Bi anode are elucidated, which provides a rational design strategy for Bi anodes in practical SIBs.

Status and Opportunities of Zinc Ion Hybrid Capacitors: Focus on Carbon Materials, Current Collectors, and Separators.

Zinc ion hybrid capacitors (ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.

Synergistic effect of nitrogen and oxygen dopants in 3D hierarchical porous carbon cathodes for ultra-fast zinc ion hybrid supercapacitors.

Zinc-ion hybrid supercapacitor is one of the most promising electrochemical energy storage devices for the applications needing both high energy densities and power densities. Nitrogen doping is an effective way to enhance the capacitive performance of porous carbon cathodes in zinc-ion hybrid supercapacitor. However, accurate evidence is yet needed to demonstrate how nitrogen dopants influence the charge storage of Zn2+ and H+ cations. Herein, we prepared 3D interconnected hierarchical porous carbon nanosheets by a one-step explosion method. The effect of nitrogen dopants on pseudocapacitance was analyzed by the electrochemical behaviors of as-prepared porous carbon samples with similar morphology and pore structure but different nitrogen and oxygen doping levels. Ex-situ XPS and DFT calculation demonstrate that nitrogen dopants promote the pseudocapacitive reactions by lowering the energy barrier for the change of oxidation states of carbonyl moieties. Owing to the improved pseudocapacitance by nitrogen/oxygen dopants and fast diffusion of Zn2+ ions in 3D interconnected hierarchical porous carbon matrix, the as-constructed ZIHCs show both high gravimetric capacitance (301 F g-1 at 0.1 A g-1) and excellent rate capability (a capacitance retention of 30% at 200 A g-1).

Defect Engineering of Disordered Carbon Anodes with Ultra-High Heteroatom Doping Through a Supermolecule-Mediated Strategy for Potassium-Ion Hybrid Capacitors.

Amorphous carbons are promising anodes for high-rate potassium-ion batteries. Most low-temperature annealed amorphous carbons display unsatisfactory capacities. Heteroatom-induced defect engineering of amorphous carbons could enhance their reversible capacities. Nevertheless, most lignocellulose biomasses lack heteroatoms, making it a challenge to design highly heteroatom-doped carbons (> 10 at%). Herein, we report a new preparation strategy for amorphous carbon anodes. Nitrogen/sulfur co-doped lignin-derived porous carbons (NSLPC) with ultra-high nitrogen doping levels (21.6 at% of N and 0.8 at% of S) from renewable lignin biomacromolecule precursors were prepared through a supramolecule-mediated pyrolysis strategy. This supermolecule/lignin composite decomposes forming a covalently bonded graphitic carbon/amorphous carbon intermediate product, which induces the formation of high heteroatom doping in the obtained NSLPC. This unique pyrolysis chemistry and high heteroatom doping of NSLPC enable abundant defective active sites for the adsorption of K+ and improved kinetics. The NSLPC anode delivered a high reversible capacity of 419 mAh g‒1 and superior cycling stability (capacity retention of 96.6% at 1 A g‒1 for 1000 cycles). Potassium-ion hybrid capacitors assembled by NSLPC anode exhibited excellent cycling stability (91% capacity retention for 2000 cycles) and a high energy density of 71 Wh kg-1 at a power density of 92 W kg-1.

Successive organic solvent fractionation and homogenization of technical lignin for polyurethane foam with high mechanical performance.

This work demonstrates an organic solvent fractionation method for lignin homogenization, which can effectively reduce the lignin heterogeneity and use each lignin fraction to prepare polyurethane foams (PUFs) with excellent mechanical properties. Such fractions were fully characterized by GPC, NMR (31P, 2D-HSQC), FTIR, and TG to obtain a detailed description of the structures and properties. The properties of PUFs from each lignin fraction showed higher compatibility than that from unfractionated industrial lignin, as studied by morphology and DSC analysis. The improvement of compatibility between the fractionated lignin fractions and polyethylene glycol can effectively enhance the mechanical properties of the prepared PUFs. The hysteresis loss (43.10%-51.85%) and resilience (95.81%-98.81%) of the fractionated lignin polyurethane foams (LPUFs) were better than that from the unfractionated LPUFs (hysteresis loss 41.64%, resilience 94.67%) at the lignin content of 5%. Subsequently, the strong relationships between lignin structures and PUF properties were demonstrated in detail. The suggested approach provides greater possibilities to prepare LPUFs with tunable properties based on real industrial lignin fractions, rather than modified lignin.

High-purity lignin fractions and nanospheres rich in phenolic hydroxyl and carboxyl groups isolated with alkaline deep eutectic solvent from wheat straw.

A combined pretreatment based on alkaline deep eutectic solvent (DES) of K2CO3 and glycerol and sequential acid fractionation was developed to extract reactive lignin from wheat straw biomass. This process exhibited excellent purification performance in lignin isolation, and the lignin fractionated at low pH displayed high reactivity, having hydroxyl and carboxyl groups up to 9.60 and 2.52 mmol/g, respectively. Silica was selectively separated and removed during the precipitation stage, avoiding the "silica interference". Moreover, DES-lignin nanospheres created by self-assembly using lignin fractions obtained by acid precipitation possessed a high zeta potential, large particle size and high content of hydrophilic groups. Overall, the findings related to the dissociation mechanism and fractionation of reactive lignin during alkaline DES pretreatment and the acid sequence precipitation are crucial for facilitating lignin valorization in high-added value products.

Differences in the Mechanisms of MnO2 Oxidation between Lignin Model Compounds with the p-Hydroxyphenyl, Guaiacyl, and Syringyl Nuclei.

The purpose of this study was to examine how the rate and mechanism of MnO2 oxidation differ between the p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) types of simple nonphenolic lignin model compounds as well as the p-ethylphenyl (E) type compounds. The oxidation was conducted using an excess amount of MnO2 in a sulfate buffer solution at a pH value of 1.5 at room temperature. MnO2 oxidized at least the G and S nuclei, although it commonly oxidizes alcohols present at the benzyl position. The oxidation rates of the benzyl alcohol derivatives were in the order of G- > S- ≫ H- > E-type, which suggests that the rates are determined by the electronic effects of their methoxy and ethyl functional groups on not only their benzyl positions but also their aromatic π-electron systems. The kinetic isotope effect was observed in the MnO2 oxidations of the same derivatives deuterated at their benzyl hydroxymethyl groups. The observed magnitudes were in the order of E- ≫ H- > G- ≫ S-type, suggesting that the contribution of oxidation of their aromatic nuclei, which is another reaction mode of the oxidation of their benzyl positions, increases in the reverse order.