Ya He,Zhuo Chen,Junrun Feng,Jian Wang,Lun Zhang,Hao Gu,Lin Sheng,Pengfei Yao,Feng Ryan Wang,Zhangxiang Hao
Aqueous zinc-ion batteries (AZIBs) are considered one of the most promising next-generation energy storage devices due to cost-effectiveness and high safety. However, the uncontrolled dendrite growth and the intolerance against low temperatures hinder the application of AZIBs. Herein, hydrogen-bonding-rich dulcitol (DOL) is introduced into the ZnSO 4 , which reshaped the hydrogen-bond network in the electrolyte and optimized the solvation sheath structure, effectively reducing the amount of active water molecules and inhibiting hydrogen evolution and the parasitic reaction at the zinc anode. In addition, higher adsorption energy DOL preferentially adsorbs on the surface of the zinc anode, guiding the uniform deposition of Zn 2+ and inhibiting the formation of dendrites. DOL also enhances the interaction between free and free water and improves the resistance to freeze of the electrolyte. Consequently, the Zn//Zn symmetric cells assembled with DOL are extremely stable cycled for 2000 h at 2 mA cm −2 . The NH 4 V 4 O 10 (NVO)//Zn full cell showed more excellent specific capacity of 183.07 mAh g −1 after 800 cycles. Even at the low temperature of −10 °C, the cell still maintains 155.95 mAh g −1 capacity after 600 cycles. This work provides a new strategy for the subsequent study of AZIBs with high stability at low temperatures.
A facile and eco-friendly synthetic strategy has been developed to achieve a series of hydrogen bonding-rich bio-based thermosetting resins in this study. Using both safe and green solvents, we successfully synthesized target bio-based bisbenzoxazines (DcTa-fa, DcTa-sa, and DcTa-da) with high purity from five different naturally resourced raw materials. The chemical structures of the obtained bisbenzoxazine monomers were verified by nuclear magnetic resonance technology (including 1H and 13C NMR, two-dimensional 1H–1H nuclear Overhauser effect spectroscopy (NOESY), and 1H–13C heteronuclear multiple quantum coherence (HMQC)) and Fourier transform infrared spectroscopy (FT-IR). The polymerization processes were systematically investigated by differential scanning calorimetry (DSC) and in situ FT-IR analysis. Contact angle measurements were conducted and the corresponding results revealed tunable surface properties during the polymerization process of each bio-based bisbenzoxazine resin. In order to understand the relationship between the chemical structure and surface properties, more detailed FT-IR analyses were carried out to investigate the hydrogen bonding networks in the resulting polybenzoxazines. Notably, poly(DcTa-fa) presented excellent thermal stability (Td10 of 377 °C, Yc of 53.7 wt%) and strong adhesion strength (5.232 ± 0.26 MPa), while poly(DcTa-sa) and poly(DcTa-da) showed outstanding surface properties with very low surface free energy values (22.91 and 22.84 mJ m−2). These results highlight the utility of smart and sustainable benzoxazine chemistry and offer a facile and green synthetic approach to access hydrogen bonding-rich bio-based benzoxazine resins with many attractive properties.
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