The anti-freezing strategy of hydrogels and their self-healing structure are often contradictory,it is vital to break through the molecular structure to design and construct hydrogels with intrinsic anti-freezing/self...The anti-freezing strategy of hydrogels and their self-healing structure are often contradictory,it is vital to break through the molecular structure to design and construct hydrogels with intrinsic anti-freezing/self-healing for meeting the rapid development of flexible and wearable devices in diverse service conditions.Herein,we design a new hydrogel electrolyte(AF/SH-Hydrogel)with intrinsic anti-freezing/self-healing capabilities by introducing ethylene glycol molecules,dynamic chemical bonding(disulfide bond),and supramolecular interaction(multi-hydrogen bond)into the polyacrylamide molecular chain.Thanks to the exceptional freeze resistance(84%capacity retention at-20℃)and intrinsic self-healing capabilities(95%capacity retention after 5 cutting/self-healing cycles),the obtained AF/SH-Hydrogel makes the zinc||manganese dioxide cell an economically feasible battery for the state-of-the-art applications.The Zn||AF/SH-Hydrogel||MnO_(2)device offers a near-theoretical specific capacity of 285 m A h g^(-1)at 0.1 A g^(-1)(Coulombic efficiency≈100%),as well as good self-healing capability and mechanical flexibility in an ice bath.This work provides insight that can be utilized to develop multifunctional hydrogel electrolytes for application in next generation of self-healable and freeze-resistance smart aqueous energy storage devices.展开更多
Thermal softening is an inevitable process in the physical network.Polyurethane(PU),a typical commercial material,is constructed by physical networks,which undergoes the serious thermal decay on mechanical properties ...Thermal softening is an inevitable process in the physical network.Polyurethane(PU),a typical commercial material,is constructed by physical networks,which undergoes the serious thermal decay on mechanical properties at high temperature.Herein,a physically cross-linked PU with a unique thermal stiffening behavior has been developed by incorporating B–N coordination with reversible B–O bonds.The B–N coordination can significantly improve the mechanical properties of the PU.The reversible B–O bonds(temperature dependent reversible transformation between B–OH and B–O–B)are conducive to constructing more multicoordination macromolecular crosslinking points and more stable B–N coordination bonds at high temperature,endowing the PU with the special thermal stiffening behavior for the first time.Such thermal stiffening behavior compensates for the bond breakage and the network destruction caused by heat,significantly expands the rubbery plateau and delays the entire chain motion of the thermoplastic PU.As a result,the terminal flow occurs at a higher temperature up to 200°C.The modulus retention ratio of the materials is up to 87%even at 145oC,which is much higher than that of the existing PU elastomer with the physical network and even some covalent cross-link PU.Simultaneously,the physical network ensures the recyclability of the PU,and the thermal stiffening behavior is still obtained in recycled PU.This work provides a simple strategy to impart thermal stiffening behavior to the physically crosslinked PU,thereby significantly extending the operating temperature range of thermoplastic PU,which can potentially expand the scopes of PU in applications under harsh conditions.展开更多
Two novel coordination polymers with molecular structures(2MI)+[Zn(2MI)Cl3]-(1) and(2MI)+NO3-(2) based on ligand 2-methylimidazole(2MI) were synthesized under solution method. Compound 1 crystallizes in ...Two novel coordination polymers with molecular structures(2MI)+[Zn(2MI)Cl3]-(1) and(2MI)+NO3-(2) based on ligand 2-methylimidazole(2MI) were synthesized under solution method. Compound 1 crystallizes in the monoclinic system, space group Cc with a=7.489(2), b=13.448(4), c=13.983(4) , β=98.402(2)°, Z=4 and V=102.246(2) 3. Compound 2 crystallizes in the orthorhombic system, space group pnma with a=14.296(3), b=6.3180(12), c=7.3862(13) , β=90°, Z=4 and V=667.1(2) 3. Dielectric measurements show compounds 1 and 2 have reversible dielectric anomalous behaviors with variation frequencies at different temperature.展开更多
基金supported by the link project of the National Natural Science Foundation of China(52002052 and 22209020)the Key Research and Development Project of Science and Technology Department of Sichuan Province(2022YFSY0004)+2 种基金the Opening project of the State Key Laboratory of New Textile Materials and Advanced Processing Technology(FZ2021009)the Natural Science Foundation of Sichuan Province(2023NSFSC0995)the Natural Science Foundation of Hunan Province(2022JJ30227)。
文摘The anti-freezing strategy of hydrogels and their self-healing structure are often contradictory,it is vital to break through the molecular structure to design and construct hydrogels with intrinsic anti-freezing/self-healing for meeting the rapid development of flexible and wearable devices in diverse service conditions.Herein,we design a new hydrogel electrolyte(AF/SH-Hydrogel)with intrinsic anti-freezing/self-healing capabilities by introducing ethylene glycol molecules,dynamic chemical bonding(disulfide bond),and supramolecular interaction(multi-hydrogen bond)into the polyacrylamide molecular chain.Thanks to the exceptional freeze resistance(84%capacity retention at-20℃)and intrinsic self-healing capabilities(95%capacity retention after 5 cutting/self-healing cycles),the obtained AF/SH-Hydrogel makes the zinc||manganese dioxide cell an economically feasible battery for the state-of-the-art applications.The Zn||AF/SH-Hydrogel||MnO_(2)device offers a near-theoretical specific capacity of 285 m A h g^(-1)at 0.1 A g^(-1)(Coulombic efficiency≈100%),as well as good self-healing capability and mechanical flexibility in an ice bath.This work provides insight that can be utilized to develop multifunctional hydrogel electrolytes for application in next generation of self-healable and freeze-resistance smart aqueous energy storage devices.
基金supported by the National Natural Science Foundation of China(52203064 and 52373061)the China Postdoctoral Science Foundation(2023M732415)+1 种基金the Fundamental Research Funds for the Central Universities(2022SCU12011)the State Key Laboratory of Polymer Materials Engineering,Sichuan University。
文摘Thermal softening is an inevitable process in the physical network.Polyurethane(PU),a typical commercial material,is constructed by physical networks,which undergoes the serious thermal decay on mechanical properties at high temperature.Herein,a physically cross-linked PU with a unique thermal stiffening behavior has been developed by incorporating B–N coordination with reversible B–O bonds.The B–N coordination can significantly improve the mechanical properties of the PU.The reversible B–O bonds(temperature dependent reversible transformation between B–OH and B–O–B)are conducive to constructing more multicoordination macromolecular crosslinking points and more stable B–N coordination bonds at high temperature,endowing the PU with the special thermal stiffening behavior for the first time.Such thermal stiffening behavior compensates for the bond breakage and the network destruction caused by heat,significantly expands the rubbery plateau and delays the entire chain motion of the thermoplastic PU.As a result,the terminal flow occurs at a higher temperature up to 200°C.The modulus retention ratio of the materials is up to 87%even at 145oC,which is much higher than that of the existing PU elastomer with the physical network and even some covalent cross-link PU.Simultaneously,the physical network ensures the recyclability of the PU,and the thermal stiffening behavior is still obtained in recycled PU.This work provides a simple strategy to impart thermal stiffening behavior to the physically crosslinked PU,thereby significantly extending the operating temperature range of thermoplastic PU,which can potentially expand the scopes of PU in applications under harsh conditions.
基金Supported by the National Natural Science Foundation of China(No.21201087 and 21671084)NSF of Jiangsu Province(BK20131244 and BK20130460)+1 种基金the Foundation of Jiangsu Educational Committee(16KJB430011)the Qing Lan Project of Jiangsu Province and Jiangsu Overseas Research&Training Program for University Prominent Young&Middle-aged Teacher and Presidents,Six talent peaks project in Jiangsu Province(2014-XCL-008)
文摘Two novel coordination polymers with molecular structures(2MI)+[Zn(2MI)Cl3]-(1) and(2MI)+NO3-(2) based on ligand 2-methylimidazole(2MI) were synthesized under solution method. Compound 1 crystallizes in the monoclinic system, space group Cc with a=7.489(2), b=13.448(4), c=13.983(4) , β=98.402(2)°, Z=4 and V=102.246(2) 3. Compound 2 crystallizes in the orthorhombic system, space group pnma with a=14.296(3), b=6.3180(12), c=7.3862(13) , β=90°, Z=4 and V=667.1(2) 3. Dielectric measurements show compounds 1 and 2 have reversible dielectric anomalous behaviors with variation frequencies at different temperature.