Aqueous zinc metal batteries are noted for their costeffectiveness,safety and environmental friendliness.However,the water-induced notorious issues such as continuous electrolyte decomposition and uneven Zn electroche...Aqueous zinc metal batteries are noted for their costeffectiveness,safety and environmental friendliness.However,the water-induced notorious issues such as continuous electrolyte decomposition and uneven Zn electrochemical deposition remarkably restrict the development of the long-life zinc metal batteries.In this study,zwitterionic sulfobetaine is introduced to copolymerize with acrylamide in zinc perchlorate(Zn(ClO;);)solution.The designed gel framework with hydrophilic and charged groups can firmly anchor water molecules and construct ion migration channels to accelerate ion transport.The in situ generated hybrid interface,which is composed of the organic functionalized outer layer and inorganic Clcontaining inner layer,can synergically lower the mass transfer overpotential,reduce water-related side reactions and lead to uniform Zn deposition.Such a novel electrolyte configuration enables Zn//Zn cells with an ultra-long cycling life of over 3000 h and a low polarization potential(~0.03 V)and Zn//Cu cells with high Coulombic efficiency of 99.18%for 1000 cycles.Full cells matched with MnO;cathodes delivered laudable cycling stability and impressive shelving ability.Besides,the flexible quasi-solid-state batteries which are equipped with the anti-vandalism ability(such as cutting,hammering and soaking)can successfully power the LED simultaneously.Such a safe,processable and durable hydrogel promises significant application potential for long-life flexible electronic devices.展开更多
Aqueous zinc-ion batteries(ZIBs)have attracted much interest to realize safe rechargeable batteries with high safety and high energy density.However,it is still challenging to address dendrite growth and parasitic rea...Aqueous zinc-ion batteries(ZIBs)have attracted much interest to realize safe rechargeable batteries with high safety and high energy density.However,it is still challenging to address dendrite growth and parasitic reactions in zinc anodes.We propose herein the design concept of hydrogen bond-induced elastic polyzwitterion electrolytes with zincophilic groups for achieving robust ZIBs.Mussel-inspired autopolymerization has been developed to construct the polyzwitterion electrolytes at room temperature by inducing electron density delocalization atα-position of C=C bond in zwitterion monomer by Zn^(2+).Specifically,the zwitterionic functional groups construct ion transport channels,and the unique–NH–and SO_(3)^(-)groups co-compete with H_(2)O for coordination with Zn^(2+)and promote the desolvation of hydrated Zn^(2+),thus achieving a high room temperature ionic conductivity(6.7 mS cm^(-1))and an increased Zn^(2+)migration number(0.65)for the polyzwitterion electrolytes.In addition,various interactions such as hydrogen bonding and electrostatic interactions between electrolyte ions and zwitterionic groups impart high stretchability and strength to the polyzwitterion electrolytes,which,combined with SO_(3)^(-)philic(002)crystallographic properties,effectively inhibit the growth of zinc dendrites.As a result,rigid/wearable solid-state ZIBs exhibit excellent cycling and C-rate performances.We believe that the strategy of constructing polyzwitterionic electrolytes with zincophilic groups and ion transport channels opens up a new direction in polymer electrolyte engineering towards safe and high energy batteries.展开更多
Zn metal anode suffers from dendrite issues and passive byproducts,which severely plagues the practical application of aqueous Zn metal batteries.Herein,a polyzwitterionic cross-linked double network hydrogel electrol...Zn metal anode suffers from dendrite issues and passive byproducts,which severely plagues the practical application of aqueous Zn metal batteries.Herein,a polyzwitterionic cross-linked double network hydrogel electrolyte composed of physical crosslinking(hyaluronic acid)and chemical crosslinking(synthetic zwitterionic monomer copolymerized with acrylamide)is introduced to overcome these obstacles.On the one hand,highly hydrophilic physical network provides an energy dissipation channel to buffer stress and builds a H_(2)O-poor interface to avoid side reactions.On the other hand,the charged groups(sulfonic and imidazolyl)in chemical crosslinking structure build anion/cation transport channels to boost ions’kinetics migration and regulate the typical solvent structure[Zn(H_(2)O)_(6)]^(2+)to R-SO_(3)^(−)[Zn(H_(2)O)_(4)]^(2+),with uniform electric field distribution and significant resistance to dendrites and parasitic reactions.Based on the above functions,the symmetric zinc cell exhibits superior cycle stability for more than 420 h at a high current density of 5 mA·cm^(−2),and Zn||MnO_(2)full cell has a reversible specific capacity of 150 mAh·g^(−1)after 1000 cycles at 2 C with this hydrogel electrolyte.Furthermore,the pouch cell delivers impressive flexibility and cyclability for energy-storage applications.展开更多
In this work, by using coarse-grained molecular dynamics simulations, we found that poly（2-metha-cryloyloxyethyl phosphorylcholine）（PMPC） showed a strong solubility and a so-called antipolyelectrolyte effect（APE...In this work, by using coarse-grained molecular dynamics simulations, we found that poly（2-metha-cryloyloxyethyl phosphorylcholine）（PMPC） showed a strong solubility and a so-called antipolyelectrolyte effect（APE）in water. In contrast, obvious aggregations but no APE were found in n-butyl-substituted choline phosphatepolymers（PMBP） solutions. The underlying mechanisms for different solution behaviors of PMPC and PMBP wereinvestigated in detail. Our results indicate that the presence of butyl groups in PMBP enhances both the electrostaticinteractions and the hydrophobicity of PMBP molecules in the system. Both factors were found to contribute to theformations of aggregates in the PMBP system. Further researches revealed that hydrophobicity arising from the butylgroup plays a more important role than electrostatic interactions in inducing the PMBP aggregation. In addition, thestrong hydrophobicity in PMBP was found to be responsible for the absence of APE. These results are expected tocontribute to a better understanding and a better design of the solution properties of polyzwitterions.展开更多
Silicone elastomers-based materials have been extensively involved in the field of biomedical devices,while their use is extremely restricted due to the poor surface lubricity and inherent hydrophobicity.This paper de...Silicone elastomers-based materials have been extensively involved in the field of biomedical devices,while their use is extremely restricted due to the poor surface lubricity and inherent hydrophobicity.This paper describes a novel strategy for generating a robust layered soft matter lubrication coating on the surface of the polydimethylsiloxane(PDMS)silicone elastomer,by entangling thick polyzwitterionic polyelectrolyte brush of poly(sulfobetaine methacrylate)(PSBMA)into the sub-surface of the initiator-embedded stiff hydrogel coating layer of P(AAm-co-AA-co-HEMA-Br)/Fe,to achieve a unified low friction and high load-bearing properties.Meanwhile,the stiff hydrogel layer with controllable thickness is covalently anchored on the surface of PDMS by adding iron powder to provide catalytic sites through surface catalytically initiated radical polymerization(SCIRP)method and provides high load-bearing capacity,while the topmost brush/hydrogel composite layer is highly effective for aqueous lubrication.Their synergy effects are capable of attaining low friction coefficient(COFs)under wide range of loaded condition in water environment with steel ball as sliding pair.Furthermore,the influence of mechanical modulus of the stiff hydrogel layer on the lubrication performance of layered coating is investigated,for which the COF is the lowest only when the modulus of the stiff hydrogel layer well matches the PDMS substrate.Surprisingly,the COF of the modified PDMS could remain low friction(COF<0.05)stably after encountering 50,000 sliding cycles under 10 N load.Finally,the surface wear characterizations prove the robustness of the layered lubricating coating.This work provides a new route for engineering lubricious silicon elastomer with low friction,high load-bearing capacity,and considerable durability.展开更多
In this work,we demonstrate that the strength of anion specificities of thermosensitive polymers is determined by the affinity of direct anion binding to the polymers.We have prepared a series of thermosensitive stati...In this work,we demonstrate that the strength of anion specificities of thermosensitive polymers is determined by the affinity of direct anion binding to the polymers.We have prepared a series of thermosensitive statistical copolymers with distinct thermoresponsive behaviors.The anions can specifically interact with the different types of thermosensitive polymers in very different strengths.A similar strength of specific anion effects on thermoresponsive behaviors can be observed at very different salt concentrations for the different types of thermosensitive polymers.A stronger anion binding to the thermosensitive polymers gives rise to a more obvious anion specificity and vice versa.The work presented here opens up opportunities for the application of ion binding affinity to modulate the strength of ion specificities of thermosensitive polymers.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.51874362,52072411,51932011)the Natural Science Foundation of Hunan Province(Grant No.2021JJ20060)Open access funding provided by Shanghai Jiao Tong University
文摘Aqueous zinc metal batteries are noted for their costeffectiveness,safety and environmental friendliness.However,the water-induced notorious issues such as continuous electrolyte decomposition and uneven Zn electrochemical deposition remarkably restrict the development of the long-life zinc metal batteries.In this study,zwitterionic sulfobetaine is introduced to copolymerize with acrylamide in zinc perchlorate(Zn(ClO;);)solution.The designed gel framework with hydrophilic and charged groups can firmly anchor water molecules and construct ion migration channels to accelerate ion transport.The in situ generated hybrid interface,which is composed of the organic functionalized outer layer and inorganic Clcontaining inner layer,can synergically lower the mass transfer overpotential,reduce water-related side reactions and lead to uniform Zn deposition.Such a novel electrolyte configuration enables Zn//Zn cells with an ultra-long cycling life of over 3000 h and a low polarization potential(~0.03 V)and Zn//Cu cells with high Coulombic efficiency of 99.18%for 1000 cycles.Full cells matched with MnO;cathodes delivered laudable cycling stability and impressive shelving ability.Besides,the flexible quasi-solid-state batteries which are equipped with the anti-vandalism ability(such as cutting,hammering and soaking)can successfully power the LED simultaneously.Such a safe,processable and durable hydrogel promises significant application potential for long-life flexible electronic devices.
基金supported by the National Key Research and Development Program of China(2023YFB3608904)the National Natural Science Foundation of China(21835003,21674050,62274092)+8 种基金the Natural Science Foundation of Jiangsu Province(BK20210601,BE2019120)the Foundation of Key Laboratory of Flexible Electronics of Zhejiang Province(2023FE002)the Program for Jiangsu Specially-Appointed Professor(RK030STP15001)the Leading Talent of Technological Innovation of National Ten-Thousands Talents Program of Chinathe NUPT“1311 Project”and Scientific Foundation(NY219159,NY219021)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD,YX030003)the China Postdoctoral Science Foundation(2023M741624)the Project of State Key Laboratory of Organic Electronics and Information Displays(GZR2023010016)the Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY223079)。
文摘Aqueous zinc-ion batteries(ZIBs)have attracted much interest to realize safe rechargeable batteries with high safety and high energy density.However,it is still challenging to address dendrite growth and parasitic reactions in zinc anodes.We propose herein the design concept of hydrogen bond-induced elastic polyzwitterion electrolytes with zincophilic groups for achieving robust ZIBs.Mussel-inspired autopolymerization has been developed to construct the polyzwitterion electrolytes at room temperature by inducing electron density delocalization atα-position of C=C bond in zwitterion monomer by Zn^(2+).Specifically,the zwitterionic functional groups construct ion transport channels,and the unique–NH–and SO_(3)^(-)groups co-compete with H_(2)O for coordination with Zn^(2+)and promote the desolvation of hydrated Zn^(2+),thus achieving a high room temperature ionic conductivity(6.7 mS cm^(-1))and an increased Zn^(2+)migration number(0.65)for the polyzwitterion electrolytes.In addition,various interactions such as hydrogen bonding and electrostatic interactions between electrolyte ions and zwitterionic groups impart high stretchability and strength to the polyzwitterion electrolytes,which,combined with SO_(3)^(-)philic(002)crystallographic properties,effectively inhibit the growth of zinc dendrites.As a result,rigid/wearable solid-state ZIBs exhibit excellent cycling and C-rate performances.We believe that the strategy of constructing polyzwitterionic electrolytes with zincophilic groups and ion transport channels opens up a new direction in polymer electrolyte engineering towards safe and high energy batteries.
基金the Science Technology and Innovation Team in University of Henan Province(No.24IRTSTHN002)the National Natural Science Foundation of China(No.22279121)China Postdoctoral Science Foundation(No.2022M712863),and DFT calculations were supported by the National Supercomputing Centre in Zhengzhou and the funding of Zhengzhou University.
文摘Zn metal anode suffers from dendrite issues and passive byproducts,which severely plagues the practical application of aqueous Zn metal batteries.Herein,a polyzwitterionic cross-linked double network hydrogel electrolyte composed of physical crosslinking(hyaluronic acid)and chemical crosslinking(synthetic zwitterionic monomer copolymerized with acrylamide)is introduced to overcome these obstacles.On the one hand,highly hydrophilic physical network provides an energy dissipation channel to buffer stress and builds a H_(2)O-poor interface to avoid side reactions.On the other hand,the charged groups(sulfonic and imidazolyl)in chemical crosslinking structure build anion/cation transport channels to boost ions’kinetics migration and regulate the typical solvent structure[Zn(H_(2)O)_(6)]^(2+)to R-SO_(3)^(−)[Zn(H_(2)O)_(4)]^(2+),with uniform electric field distribution and significant resistance to dendrites and parasitic reactions.Based on the above functions,the symmetric zinc cell exhibits superior cycle stability for more than 420 h at a high current density of 5 mA·cm^(−2),and Zn||MnO_(2)full cell has a reversible specific capacity of 150 mAh·g^(−1)after 1000 cycles at 2 C with this hydrogel electrolyte.Furthermore,the pouch cell delivers impressive flexibility and cyclability for energy-storage applications.
文摘In this work, by using coarse-grained molecular dynamics simulations, we found that poly（2-metha-cryloyloxyethyl phosphorylcholine）（PMPC） showed a strong solubility and a so-called antipolyelectrolyte effect（APE）in water. In contrast, obvious aggregations but no APE were found in n-butyl-substituted choline phosphatepolymers（PMBP） solutions. The underlying mechanisms for different solution behaviors of PMPC and PMBP wereinvestigated in detail. Our results indicate that the presence of butyl groups in PMBP enhances both the electrostaticinteractions and the hydrophobicity of PMBP molecules in the system. Both factors were found to contribute to theformations of aggregates in the PMBP system. Further researches revealed that hydrophobicity arising from the butylgroup plays a more important role than electrostatic interactions in inducing the PMBP aggregation. In addition, thestrong hydrophobicity in PMBP was found to be responsible for the absence of APE. These results are expected tocontribute to a better understanding and a better design of the solution properties of polyzwitterions.
基金We gratefully acknowledge supports from the National Key Research and Development Program of China(2016YFC1100401)National Natural Science Foundation of China(22032006,52075522)+1 种基金F.Zhou thanks to the project support of the Key Research Program of the Chinese Academy of Sciences(XDPB2404)S.Ma thanks to the support by Youth Innovation Promotion Association(2019411).
文摘Silicone elastomers-based materials have been extensively involved in the field of biomedical devices,while their use is extremely restricted due to the poor surface lubricity and inherent hydrophobicity.This paper describes a novel strategy for generating a robust layered soft matter lubrication coating on the surface of the polydimethylsiloxane(PDMS)silicone elastomer,by entangling thick polyzwitterionic polyelectrolyte brush of poly(sulfobetaine methacrylate)(PSBMA)into the sub-surface of the initiator-embedded stiff hydrogel coating layer of P(AAm-co-AA-co-HEMA-Br)/Fe,to achieve a unified low friction and high load-bearing properties.Meanwhile,the stiff hydrogel layer with controllable thickness is covalently anchored on the surface of PDMS by adding iron powder to provide catalytic sites through surface catalytically initiated radical polymerization(SCIRP)method and provides high load-bearing capacity,while the topmost brush/hydrogel composite layer is highly effective for aqueous lubrication.Their synergy effects are capable of attaining low friction coefficient(COFs)under wide range of loaded condition in water environment with steel ball as sliding pair.Furthermore,the influence of mechanical modulus of the stiff hydrogel layer on the lubrication performance of layered coating is investigated,for which the COF is the lowest only when the modulus of the stiff hydrogel layer well matches the PDMS substrate.Surprisingly,the COF of the modified PDMS could remain low friction(COF<0.05)stably after encountering 50,000 sliding cycles under 10 N load.Finally,the surface wear characterizations prove the robustness of the layered lubricating coating.This work provides a new route for engineering lubricious silicon elastomer with low friction,high load-bearing capacity,and considerable durability.
基金financially supported by the National Natural Science Foundation of China(Nos.21873091,21622405,21574121 and 52033001)the Youth Innovation Promotion Association of CAS(No.Y201769)+1 种基金the National Synchrotron Radiation Laboratory(No.UN2018LHJJ)the Fundamental Research Funds for the Central Universities(No.WK2480000007)。
文摘In this work,we demonstrate that the strength of anion specificities of thermosensitive polymers is determined by the affinity of direct anion binding to the polymers.We have prepared a series of thermosensitive statistical copolymers with distinct thermoresponsive behaviors.The anions can specifically interact with the different types of thermosensitive polymers in very different strengths.A similar strength of specific anion effects on thermoresponsive behaviors can be observed at very different salt concentrations for the different types of thermosensitive polymers.A stronger anion binding to the thermosensitive polymers gives rise to a more obvious anion specificity and vice versa.The work presented here opens up opportunities for the application of ion binding affinity to modulate the strength of ion specificities of thermosensitive polymers.
