Fluorine-free proton exchange membranes(PEMs)capable of healing from physical damage are important for PEM fuel cells(PEMFCs)with extended service life and enhanced reliability.Herein,highly elastic fluorine-free PEMs...Fluorine-free proton exchange membranes(PEMs)capable of healing from physical damage are important for PEM fuel cells(PEMFCs)with extended service life and enhanced reliability.Herein,highly elastic fluorine-free PEMs with excellent self-healing ability and high proton conductivity are fabricated through complexation of phytic acid(PA)with sulfonated polyvinyl alcohol(SPVA),followed by subsequent grafting of SPVA with positively charged 4-(1H-imidazol-1-yl)benzenecarbaldehyde(IBZ).Compared with recast Nafion membranes,the as-prepared SPVA-IBZ/PA membranes exhibit an enhanced mechanical strength and elasticity and can spontaneously recover from a^50%strain to their initial states within^30 s at room temperature.Meanwhile,the SPVA-IBZ/PA membranes have a proton conductivity of^0.095 S cm-1at^70°C,which is higher than that of recast Nafion membranes.The hydrogen-powered PEMFCs using the SPVA-IBZ/PA membranes,which show an open circuit voltage of^0.98 V and maximum power density of^609 mW cm-2,exhibit a satisfactory cell performance.Importantly,the SPVA-IBZ/PA membranes can spontaneously heal mechanical damage of several tens of micrometers in size and restore their original proton conductivity and cell performance under the working conditions of PEMFCs.展开更多
Self-healing materials have attracted considerable attention because of their improved safety, lifetime, energy efficiency and environmental impact. Supramolecular interactions have been extensively considered in the ...Self-healing materials have attracted considerable attention because of their improved safety, lifetime, energy efficiency and environmental impact. Supramolecular interactions have been extensively considered in the field of self-healing materials due to their excellent reversibility and sensitive responsiveness to environmental stimuli. However,development of a polymeric material with good mechanical performance as well as self-healing capacity is very challenging. In this study, we report a robust self-healing polyurethane(PU) elastomer polypropylene glycol-2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol(PPG-mUPy) by integrating ureidopyrimidone(UPy) motifs with a PPG segment with a well-defined architecture and microphase morphology.To balance the self-healing capacity and mechanical performance, a thermal-triggered switch of H-bonding is introduced. The quadruple H-bonded UPy dimeric moieties in the backbone induce phase separation to form a hard domain as well as enable further aggregation into microcrystals by virtue of the stacking interactions, which are stable in ambient temperature. This feature endows the PU with high mechanical strength. Meanwhile, a high healing efficiency can be realized, when the reversibility of the H-bond was unlocked from the stacking at higher temperature. An optimized sample PPG1000-mUPy50%with a good balance of mechanical performance(20.62 MPa of tensile strength) and healing efficiency(93% in tensile strength) was achieved. This strategy will provide a new idea for developing robust self-healing polymers.展开更多
基金supported by the National Natural Science Foundation of China(21774049 and 21905105)。
文摘Fluorine-free proton exchange membranes(PEMs)capable of healing from physical damage are important for PEM fuel cells(PEMFCs)with extended service life and enhanced reliability.Herein,highly elastic fluorine-free PEMs with excellent self-healing ability and high proton conductivity are fabricated through complexation of phytic acid(PA)with sulfonated polyvinyl alcohol(SPVA),followed by subsequent grafting of SPVA with positively charged 4-(1H-imidazol-1-yl)benzenecarbaldehyde(IBZ).Compared with recast Nafion membranes,the as-prepared SPVA-IBZ/PA membranes exhibit an enhanced mechanical strength and elasticity and can spontaneously recover from a^50%strain to their initial states within^30 s at room temperature.Meanwhile,the SPVA-IBZ/PA membranes have a proton conductivity of^0.095 S cm-1at^70°C,which is higher than that of recast Nafion membranes.The hydrogen-powered PEMFCs using the SPVA-IBZ/PA membranes,which show an open circuit voltage of^0.98 V and maximum power density of^609 mW cm-2,exhibit a satisfactory cell performance.Importantly,the SPVA-IBZ/PA membranes can spontaneously heal mechanical damage of several tens of micrometers in size and restore their original proton conductivity and cell performance under the working conditions of PEMFCs.
基金financially supported by the National Natural Science Foundation of China(51773131,51811530149and 51721091)the International S&T Cooperation Project of Sichuan Province(2017HH0034)
文摘Self-healing materials have attracted considerable attention because of their improved safety, lifetime, energy efficiency and environmental impact. Supramolecular interactions have been extensively considered in the field of self-healing materials due to their excellent reversibility and sensitive responsiveness to environmental stimuli. However,development of a polymeric material with good mechanical performance as well as self-healing capacity is very challenging. In this study, we report a robust self-healing polyurethane(PU) elastomer polypropylene glycol-2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol(PPG-mUPy) by integrating ureidopyrimidone(UPy) motifs with a PPG segment with a well-defined architecture and microphase morphology.To balance the self-healing capacity and mechanical performance, a thermal-triggered switch of H-bonding is introduced. The quadruple H-bonded UPy dimeric moieties in the backbone induce phase separation to form a hard domain as well as enable further aggregation into microcrystals by virtue of the stacking interactions, which are stable in ambient temperature. This feature endows the PU with high mechanical strength. Meanwhile, a high healing efficiency can be realized, when the reversibility of the H-bond was unlocked from the stacking at higher temperature. An optimized sample PPG1000-mUPy50%with a good balance of mechanical performance(20.62 MPa of tensile strength) and healing efficiency(93% in tensile strength) was achieved. This strategy will provide a new idea for developing robust self-healing polymers.
