Macroporous acrylonitrile-acrylic acid (AN-AA) copolymer hydrogels were synthesized by flee-radical solution polymerizations, using ammonium persulfate (APS)/N,N,N',N'-tetramethylethylenediamine (TEMED) redox ...Macroporous acrylonitrile-acrylic acid (AN-AA) copolymer hydrogels were synthesized by flee-radical solution polymerizations, using ammonium persulfate (APS)/N,N,N',N'-tetramethylethylenediamine (TEMED) redox initiator system and alcohols porogens. The morphology, temperature and pH sensitive swelling behavior, and swelling kinetics of the resulting hydrogels were investigated. It was found that alcohol type and concentration had great influences on the pore structure and porosity of hydrogels. The pore size of hydrogel increases with the moderate increase of the length of alcohol alkyl chain. However, a further increase of alkyl length would result in the formation of cauliflower-like structure and the decrease of pore size. The porosity of hydrogels increases with the increase of porogen concentration in the polymerization medium. The hydrogels with macroporous structure swell or shrink much faster in response to the change of pH in comparison with the conventional hydrogel without macroporous structure. Furthermore, the response rate is closely related to the porosity of the hydrogels, which could be easily controlled by modulating the concentration of the porogen in the medium. The circular swelling behavior of hydrogels indicated the formation of a relaxing three-dimensional network.展开更多
The actual manufacture of supercapacitors(SCs)is restricted by the inadequate energy density,and the energy density of devices can be properly promoted by assembling zinc-ion capacitors(ZICs)which used capacitive cath...The actual manufacture of supercapacitors(SCs)is restricted by the inadequate energy density,and the energy density of devices can be properly promoted by assembling zinc-ion capacitors(ZICs)which used capacitive cathode and battery-type anode.Two-dimensional(2D)MXene has brought great focuses in the electrode research on the foundation of large redox-active surface,but the specific capacitance is still affected by the tight stacking of interlaminations.Ti_(3)C_(2)T_(x)@polyaniline(PANI)heterostructures are prepared by uniformly depositing the conductive polymer PANI nanorods as the intercalation agent into the external of Ti_(3)C_(2)T_(x)nanosheets to inhibit stacking.Subsequently,by using graphene oxide(GO)-assisted low-temperature hydrothermal self-assembly manufacture,2D heterostructures are assembled into the three-dimensional(3D)porous crosslinked Ti_(3)C_(2)T_(x)@PANI-reduced graphene oxide(RGO)hydrogels.Attributed to the synergistic work of PANI nanorods,Ti_(3)C_(2)T_(X)nanosheets,and 3D crosslinking frameworks of RGO to match capacitive and battery effects,3D porous hierarchical Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels have rich ion transport channels,a large number of active sites,and excellent reaction kinetics.ZIC is assembled by using Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels as cathodes and zinc foil as anodes.In this work,Ti_(3)C_(2)T_(x)@PANI-RGO//Zn ZIC exhibits a wide working window(2.0 V),marked specific capacitance(589.89 F·g^(−1)at 0.5 A·g−1),salient energy density(327.71 Wh·kg^(−1)at 513.61 W·kg^(−1)and 192.20 Wh·kg^(−1)at 13,005.87 W·kg^(−1)),and durable cycling stability(97.87%capacitance retention after 10,000 cycles at 10 A·g^(−1)).This study emphasizes the device design of ZICs and the broad prospect of Ti_(3)C_(2)T_(x)-based hydrogels as viable cathodes for ZICs.展开更多
文摘Macroporous acrylonitrile-acrylic acid (AN-AA) copolymer hydrogels were synthesized by flee-radical solution polymerizations, using ammonium persulfate (APS)/N,N,N',N'-tetramethylethylenediamine (TEMED) redox initiator system and alcohols porogens. The morphology, temperature and pH sensitive swelling behavior, and swelling kinetics of the resulting hydrogels were investigated. It was found that alcohol type and concentration had great influences on the pore structure and porosity of hydrogels. The pore size of hydrogel increases with the moderate increase of the length of alcohol alkyl chain. However, a further increase of alkyl length would result in the formation of cauliflower-like structure and the decrease of pore size. The porosity of hydrogels increases with the increase of porogen concentration in the polymerization medium. The hydrogels with macroporous structure swell or shrink much faster in response to the change of pH in comparison with the conventional hydrogel without macroporous structure. Furthermore, the response rate is closely related to the porosity of the hydrogels, which could be easily controlled by modulating the concentration of the porogen in the medium. The circular swelling behavior of hydrogels indicated the formation of a relaxing three-dimensional network.
基金the National Key Research and Development Program of China(No.2022YFC2105900)the National Natural Science Foundation of China(No.52073022).
文摘The actual manufacture of supercapacitors(SCs)is restricted by the inadequate energy density,and the energy density of devices can be properly promoted by assembling zinc-ion capacitors(ZICs)which used capacitive cathode and battery-type anode.Two-dimensional(2D)MXene has brought great focuses in the electrode research on the foundation of large redox-active surface,but the specific capacitance is still affected by the tight stacking of interlaminations.Ti_(3)C_(2)T_(x)@polyaniline(PANI)heterostructures are prepared by uniformly depositing the conductive polymer PANI nanorods as the intercalation agent into the external of Ti_(3)C_(2)T_(x)nanosheets to inhibit stacking.Subsequently,by using graphene oxide(GO)-assisted low-temperature hydrothermal self-assembly manufacture,2D heterostructures are assembled into the three-dimensional(3D)porous crosslinked Ti_(3)C_(2)T_(x)@PANI-reduced graphene oxide(RGO)hydrogels.Attributed to the synergistic work of PANI nanorods,Ti_(3)C_(2)T_(X)nanosheets,and 3D crosslinking frameworks of RGO to match capacitive and battery effects,3D porous hierarchical Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels have rich ion transport channels,a large number of active sites,and excellent reaction kinetics.ZIC is assembled by using Ti_(3)C_(2)T_(x)@PANI-RGO heterostructure hydrogels as cathodes and zinc foil as anodes.In this work,Ti_(3)C_(2)T_(x)@PANI-RGO//Zn ZIC exhibits a wide working window(2.0 V),marked specific capacitance(589.89 F·g^(−1)at 0.5 A·g−1),salient energy density(327.71 Wh·kg^(−1)at 513.61 W·kg^(−1)and 192.20 Wh·kg^(−1)at 13,005.87 W·kg^(−1)),and durable cycling stability(97.87%capacitance retention after 10,000 cycles at 10 A·g^(−1)).This study emphasizes the device design of ZICs and the broad prospect of Ti_(3)C_(2)T_(x)-based hydrogels as viable cathodes for ZICs.